Method for preparing ultrahigh-nickel narrow-distribution large-specific-area ternary precursor through seed crystal method

Abstract

The invention belongs to the technical field of positive electrode NCM ultrahigh nickel precursor materials, and relates to a method for preparing an ultrahigh nickel narrow-distribution large-specific-area ternary precursor through a seed crystal method. According to the method, a loose ternary precursor is prepared through regulation and control of an oxidation means in the seed crystal preparation process, and the ternary NCM type precursor with ultrahigh nickel narrow distribution and large specific surface is prepared by taking loose ternary precursor small particles as crystal slurry or the seed crystal. The precursor prepared by the method is relatively simple in process, loose and porous in interior, free of penetrative cracks, relatively good in secondary particle sphericity, and free of crushed flaky primary particles, and is formed by alternately stacking fine needle-shaped primary particles.

Description

Technical Field

[0001] The present invention relates to the technical field of positive electrode NCM ultra-high nickel (Ni≥90) precursor materials, and specifically provides a preparation method for preparing narrow distribution and large specific surface area ultra-high nickel ternary precursor large particles by preparing relatively loose ternary precursor small particles as slurry or seeds. Background Art

[0002] With the growth of global demand for new energy vehicles and the implementation of strict carbon emission standards by the European Union, the market size of ternary materials is growing. High nickel, single crystal and low cobalt are bound to become one of the development trends of power battery technology. High nickel ternary materials can provide higher energy density, thereby improving the endurance of new energy vehicles. Therefore, high nickel is an important direction for future development. The market for high nickel ternary positive electrode materials is expected to grow rapidly, thereby occupying a larger share of the global market.

[0003] The ternary precursor is a key component of the positive electrode material of lithium batteries. The technical content will affect the performance of the final ternary positive electrode material. The particle size distribution, specific surface area, impurity content, and tap density of the precursor will directly determine the subsequent sintering product, that is, the physical and chemical indicators of the ternary positive electrode material, which can be said to occupy a very important position. Precursor materials with a larger specific surface area will provide more active sites, improve material activity, and help increase the initial capacity of the battery. During the charge and discharge process, more channels will be provided for the effective entry and transmission of lithium ions, thereby increasing the ion diffusion rate; at the same time, the porous structure increases the contact area with the electrolyte, and also simultaneously improves the charge and discharge performance of the battery. The existing patent (202410555844.6CN 118479560A) A multi-element doped positive electrode precursor and its preparation method, positive electrode material, battery and electrical equipment discloses a co-precipitation multi-element layered doping method to obtain a positive electrode precursor with a larger specific surface area, but the steps described in the patent are more complicated. Therefore, this field still needs to explore a method for obtaining a large specific surface area positive electrode precursor with simple operation and stable process. Summary of the invention

[0004] The purpose of the present invention is to provide a method for preparing an ultra-high nickel narrow distribution large ratio ternary precursor by a seed method on the basis of the existing ternary precursor preparation process. The method of the present invention is to prepare relatively loose ternary precursor small particles as slurry or seeds to prepare narrow distribution large ratio ultra-high nickel ternary precursor large particles. The obtained precursor for ultra-high nickel NCM type ternary positive electrode has a narrow controlled particle size distribution, a large BET, a loose and porous interior, no penetrating cracks, and a good sphericity of secondary particles. It is formed by the interactive accumulation of fine needle-shaped primary particles, and there are no broken flaky primary particles.

[0005] In order to achieve the above purpose, the technical solution adopted by the present invention is:

[0006] A method for preparing an ultra-high nickel narrow distribution large ratio ternary precursor by a seed crystal method, comprising the following steps:

[0007] (1) preparing a ternary metal salt solution of a certain concentration using soluble salts of nickel, cobalt and manganese; preparing a complexing agent aqueous solution and a precipitant aqueous solution for simultaneous coprecipitation reaction;

[0008] (2) adding the ternary metal salt solution, complexing agent aqueous solution and precipitant aqueous solution of a certain concentration prepared in step (1) to a reaction system consisting of a reaction kettle and a concentrator to react, the specific steps comprising:

[0009] a) Preparing seeds or slurry in a seed reactor: preparing seeds or slurry required for subsequent reactions in a seed reactor, adding water to the reactor to 60% to 70% of the effective volume of the reactor before the coprecipitation reaction, and adding a complexing agent aqueous solution and a precipitating agent aqueous solution to prepare a base solution; under certain reaction temperature, stirring intensity, and gas introduction conditions, the ternary metal salt solution, the complexing agent aqueous solution, and the precipitating agent aqueous solution are simultaneously introduced into the seed reactor for coprecipitation reaction, and after the reaction reaches a preset particle size, the desired seeds or slurry are obtained; wherein the introduced gas includes the staged introduction of an inert gas and an oxidizing gas, and the staged proportions of the inert gas and the oxidizing gas in the introduced gas include the following:

[0010] Scheme 1: The flow ratio of inert gas and oxidizing gas is: 1:0 in the first stage, 50:1 in the second stage, 100:3 in the third stage, and 25:1 in the fourth stage;

[0011] Or scheme 2: the phased ratio of inert gas and oxidizing gas flow is: 1:0 in the first stage, 25:1 in the second stage, 40:3 in the third stage, and 10:1 in the fourth stage;

[0012] Or scheme three: the phased ratio of inert gas and oxidizing gas flow is: 1:0 in the first stage, 25:2 in the second stage, 20:3 in the third stage, and 5:1 in the fourth stage;

[0013] b) Growth reactor to prepare large particles

[0014] In an inert gas protective atmosphere, water is added to the growth reactor to 60% to 70% of the effective volume of the reactor, the seed crystals or crystal slurry prepared in step (2) a) are added, and a complexing agent aqueous solution is added to prepare a base solution; under a certain reaction temperature, stirring intensity, and inert gas protective atmosphere, a ternary metal salt solution, a complexing agent aqueous solution, and a precipitant aqueous solution are introduced into the growth reactor to carry out a coprecipitation reaction, and the reaction reaches a preset particle size, which is the reaction endpoint;

[0015] (3) performing conventional post-treatment on the large particle precursor of step (2) in step b) that reaches a preset particle size to obtain the desired ternary precursor material with ultra-high nickel narrow distribution and large ratio.

[0016] By adopting the technical solution, the present invention mainly adjusts the degree of oxidation during the preparation of the precursor core at the seed stage, changes the looseness of the seed crystal, and then subsequently grows to the target particle size, thereby achieving the purpose of increasing the required precursor specific surface area.

[0017] Preferably, the total molar concentration of metal ions in the ternary metal salt solution prepared in step (1) is 1.6 to 2.3 mol / L; more preferably, the ratio of nickel, cobalt and manganese in the ternary metal salt solution is in accordance with the chemical formula Ni x Co y Mn (1-x-y) (OH)2; wherein X = 0.90-0.96, Y = 0.025-0.06, Z = 0.01-0.04. More preferably, the soluble salts of nickel, cobalt and manganese are nickel sulfate, cobalt sulfate and manganese sulfate.

[0018] Preferably, the complexing agent prepared in step (1) is an ammonium complexing agent, more preferably one or more of ammonia water, ammonium sulfate, ammonium sulfite, ammonium hydrogen sulfate, and ammonium thiosulfate. More preferably, the concentration of the complexing agent aqueous solution is 4 mol / L to 9.8 mol / L.

[0019] Preferably, the precipitant prepared in step (1) is one or more of sodium hydroxide, sodium carbonate, and sodium bicarbonate. More preferably, the concentration of the precipitant aqueous solution is 5 mol / L to 10.8 mol / L.

[0020] Preferably, the effective volume of the seed reaction kettle used in step a) in step (2) is 750L to 1100L.

[0021] Preferably, the inert gas in step (2) is one or more of nitrogen, argon and helium.

[0022] Preferably, in step (2), the reaction temperature in step a) is 55°C to 65°C, the stirring speed is 300r / min to 550r / min, the concentration of the complexing agent in the bottom liquid is 2 to 4g / L; the concentration of the precipitant in the bottom liquid is 0.15 to 0.4g / L, and the pH of the bottom liquid is controlled to be 10.59 to 11.30 by the precipitant. During the reaction, the concentration of the complexing agent and the concentration of the precipitant in the system are consistent with those of the bottom liquid, and the pH is 10.45 to 11.10.

[0023] Preferably, in step (2) the inert gas flow rate in step a) is 1000 to 2000 L / h, and the oxidizing gas flow rate is 40 to 80 L / h.

[0024] More preferably, in step (2) in scheme 1, scheme 2 and scheme 3, the oxidizing gas is introduced 4 hours after nucleation, that is, the first stage is 0 to 4 hours of reaction.

[0025] More preferably, in step a) of step (2), the second stage in scheme 1, scheme 2, and scheme 3 is 4 to 12 hours of reaction, the third stage is 12 to 20 hours of reaction, and the fourth stage is 20 hours of reaction until the end of the reaction.

[0026] More preferably, in said step (2), in scheme 1, scheme 2 and scheme 3, the oxidizing gas is compressed air.

[0027] Preferably, in step (2), the flow rate of the ternary metal salt solution in step a) is 10 to 60 L / h.

[0028] Preferably, in the step (2), the preset particle size of the seed crystal reaction in step a) is 4.90 μm to 5.10 μm, and the solid content of the reaction system is 100-125 g / L.

[0029] Preferably, the effective volume of the growth reactor used in step b) of step (2) is 750L to 1100L.

[0030] Preferably, in step (2), the seed crystals or slurry prepared in step (2) are added in step b) to adjust the solid content in the kettle to 50-55 g / L.

[0031] Preferably, the reaction temperature in step b) of step (2) is 55°C to 65°C, more preferably 60°C, the stirring speed is 100r / min to 300r / min, the gas flow rate of the inert gas is 2000 to 3000L / h, the concentration of the bottom liquid complexing agent is 2 to 4g / L, and the pH of the growth reaction system is adjusted to 10.40 to 10.90 by a precipitant. During the reaction, the concentration of the complexing agent in the system is consistent with that of the bottom liquid.

[0032] Preferably, the flow rate of the ternary metal salt solution in step b) in step (2) is 10 to 100 L / h.

[0033] Preferably, in step (2), the preset particle size of the growth reaction in step b) is between 13.50 μm and 13.70 μm, and the solid content of the reaction system is between 300 and 350 g / L.

[0034] Preferably, the post-treatment in step (3) includes the steps of aging, washing, drying, screening, iron removal, packaging, etc. of the existing precursor process.

[0035] More preferably, when the aging process in step (3) requires natron, it needs to be kept warm, the temperature is preferably 60° C., and the insulation time is preferably 4 to 8 hours.

[0036] More preferably, after the natron time of the aging process in step (3) is reached, the washing and post-treatment stage should be quickly entered.

[0037] Preferably, in step (3), the washing may be performed using one or more of a centrifuge, a filter press, and a filter press tank.

[0038] Preferably, the washing in step (3) is water washing.

[0039] Preferably, the drying equipment in step (3) can be selected from one or more of a static box oven, a disk dryer, a vacuum dryer, and a flash dryer. More preferably, the rear end of the drying equipment includes a screening machine, an iron remover, and other equipment.

[0040] Preferably, after drying in step (3), the Na content in the solid should be 200-400 ppm, the S content in the solid should be 2000-4000 ppm, the moisture content should be 0.00-0.50 wt%, and the magnetic foreign matter content should be 0-50 ppb.

[0041] Preferably, the particle size of the ternary precursor material prepared in step (3) is between 13.50 μm and 13.70 μm, the particle size distribution ((D(90)-D(10)) / D(50)) is not higher than 0.40, and the material tap density is between 1.8 and 2.1 g / cm 3 , BET is between 7 and 18m 2 / g.

[0042] Compared with the prior art, the present invention has the following beneficial effects: the present invention provides a method for preparing large particles of narrow distribution and large specific surface area ultra-high nickel ternary precursor by preparing relatively loose small particles of ternary precursor as slurry or seed crystals, which comprises the following steps: (1) preparing a ternary metal salt solution of a certain concentration using soluble salts of nickel sulfate, cobalt sulfate and manganese sulfate as raw materials; (2) introducing the ternary metal salt solution, a complexing agent and a precipitant into a reactor at a constant flow rate through a metering pump under an atmosphere of appropriate inert gas and oxidizing gas to perform a co-precipitation reaction to obtain nickel, cobalt and manganese sulfate. Ternary hydroxide seed or slurry; (3) the slurry or seed is transferred to the growth reactor to carry out the growth stage of ternary hydroxide small particles to ternary hydroxide large particles; (4) under the protection atmosphere of inert gas, with ternary hydroxide small particles as the base material, a certain concentration of ternary metal salt solution is simultaneously introduced into the growth reactor through a metering pump to carry out a co-precipitation reaction with a complexing agent and a precipitant; (5) the ternary precursor material reacted to a preset particle size is subjected to conventional post-treatment to obtain a ternary ultra-high nickel narrow distribution large-ratio NCM type precursor. The present invention is conducive to forming loose and porous seed by increasing the oxidizing gas and changing the proportion of the oxidizing gas and the inert gas in the seed preparation stage, and it is easier to form porous large-ratio large-particle precursor particles in the subsequent large-particle growth process; at the same time, the precursor process provided by the present invention is relatively simple, the interior is loose and porous, there are no penetrating cracks, the secondary particles have good sphericity, and are formed by the alternating accumulation of fine needle-shaped primary particles, without broken flaky primary particles. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 This is a 10.0k scanning electron microscope image of the nickel-cobalt-manganese hydroxide prepared in Example 3 of the present invention;

[0044] Figure 1-1 This is a 6.0k cross-sectional scanning electron microscope image of the nickel-cobalt-manganese hydroxide prepared in Example 1 of the present invention;

[0045] Figure 1-2 This is a 15.0k cross-sectional scanning electron microscope image of the nickel-cobalt-manganese hydroxide prepared in Example 1 of the present invention;

[0046] Figure 2-1 This is a 6.0k cross-sectional scanning electron microscope image of the nickel-cobalt-manganese hydroxide prepared in Example 2 of the present invention;

[0047] Figure 2-2 This is a 15.0k cross-sectional scanning electron microscope image of the nickel-cobalt-manganese hydroxide prepared in Example 2 of the present invention;

[0048] Figure 3-1 This is a 6.0k cross-sectional scanning electron microscope image of the nickel-cobalt-manganese hydroxide prepared in Example 3 of the present invention;

[0049] Figure 3-2This is a 15.0k cross-sectional scanning electron microscope image of the nickel-cobalt-manganese hydroxide prepared in Example 3 of the present invention;

[0050] Figure 4-1 This is a 6.0k cross-sectional scanning electron microscope image of the nickel-cobalt-manganese hydroxide prepared in Comparative Example 1 of the present invention;

[0051] Figure 4-2 This is a 15.0k cross-sectional scanning electron microscope image of the nickel-cobalt-manganese hydroxide prepared in Comparative Example 1 of the present invention;

[0052] Figure 5-1 This is a 6.0k cross-sectional scanning electron microscope image of the nickel-cobalt-manganese hydroxide prepared in Comparative Example 2 of the present invention;

[0053] Figure 5-2 This is a 15.0k cross-sectional scanning electron microscope image of the nickel-cobalt-manganese hydroxide prepared in Comparative Example 2 of the present invention. DETAILED DESCRIPTION

[0054] In order to better clarify and understand the purpose, process scheme and advantages of the present invention, the technical scheme and implementation method of the present invention are further described clearly, completely and in detail through specific examples and in combination with the accompanying drawings. It should be noted that the embodiments described in the present invention are implemented on the premise of the technical scheme of the present invention, and detailed implementation methods and specific operating processes are given, but they are only part of the embodiments of the present invention, not all of the embodiments. The specific implementation methods described are limited to explaining and interpreting the present invention, and do not limit the present invention. Based on the embodiments in the present invention, all other implementation methods obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0055] The experimental methods and conditions used in the embodiments of the present invention are conventional methods and conventional conditions unless otherwise specified. The materials, reagents or instruments used in the embodiments, unless otherwise specified, can be obtained from commercial sources or prepared by conventional methods. The reaction conditions embodied in the content of the invention of the present invention can achieve the reaction and obtain the product of the expected effect. Due to space limitations, some embodiments are listed below to further illustrate the advantages of the technical solution of the present invention.

[0056] Example 1

[0057] This embodiment provides a method for preparing an ultra-high nickel narrow distribution large ratio ternary precursor by a seed crystal method, which specifically includes the following steps.

[0058] (1) Preparation: Mix nickel sulfate solution, cobalt sulfate solution, and manganese sulfate solution according to Ni x Co y Mn (1-x-y)(OH)2 is mixed to form a nickel-cobalt-manganese ternary salt solution (hereinafter referred to as the ternary salt solution) with a molar ratio of Ni:Co:Mn=0.955:0.03:0.015 and a total metal ion concentration of 2.1 mol / L. A sodium hydroxide aqueous solution with a concentration of 10 mol / L is prepared as a precipitant aqueous solution (hereinafter referred to as the precipitant), and an ammonia aqueous solution with a concentration of 9 mol / L is prepared as a complexing agent aqueous solution (hereinafter referred to as the complexing agent).

[0059] (2) Preparation of ternary precursor seed crystals or slurry: pure water accounting for 60% to 70% of the effective volume of the reactor was added to a seed reactor with an effective volume of 770 L, and the temperature was raised to 60° C. (±3) through a PLC reaction control system. Nitrogen was continuously introduced for 4 h, and the nitrogen flow rate was set to 2000 L / h. Before the reaction started, ammonia water was added to the reactor to a concentration of 2.5 to 3.0 g / L, and sodium hydroxide aqueous solution was added to the reactor to a precipitant concentration of 0.20 to 0.4 g / L. The pH of the solution was adjusted to 10.72 to 11.02, and then a nickel-cobalt-manganese ternary salt solution was introduced to start the reaction;

[0060] Stirring: The stirring speed is maintained at 550 r / min during the first 0 to 10 hours of the reaction, and then gradually reduced to 300 r / min between 10 and 24 hours after the reaction begins;

[0061] Feeding: At the beginning of the reaction, a nickel-cobalt-manganese ternary salt solution is introduced at a rate of 10 L / h. Simultaneously, a precipitant is introduced at a ratio of 2 / 5 of the flow rate of the ternary salt solution until the system precipitant concentration is 0.20 g / L. Simultaneously, a complexing agent is introduced at about 0.07-0.1 times the flow rate of the ternary salt solution until the complexing agent concentration in the system is 2.5-3.0 g / L. Simultaneously, 8 hours after the start of the reaction, the ternary salt solution is linearly increased to 40 L / h between 8 and 20 hours. Simultaneously, the precipitant and the complexing agent are synchronously adjusted according to the flow rate of the ternary salt solution to maintain the complexing agent concentration and the precipitant concentration in the system. The slurry volume in the reactor reaches 70%-80% of the effective volume of the reactor, and the slurry is concentrated and cleared through the concentrator.

[0062] pH control: Synchronously, within two hours after the start of the reaction, the system pH was maintained at 10.72-11.02 by introducing a precipitant. Two hours after nucleation, the pH was gradually manually reduced to 10.45-10.55;

[0063] Gas control: 2000L / h of nitrogen was continuously introduced throughout the reaction, and the reaction lasted for 4-12h. At the same time, 40L / h of compressed air above the liquid was introduced, and the reaction lasted for 12-20h. The flow rate of compressed air above the liquid was changed to 60L / h. After 20h of reaction, the flow rate of compressed air above the liquid was changed to 80L / h.

[0064] Particle size: The reaction maintains the growth of particles to 4.90 μm to 5.10 μm under the above process, ending the first stage of seed crystal or slurry synthesis; slurry is obtained with a solid content of about 100-125 g / L; the slurry can be further filtered to obtain seed crystals;

[0065] (3) Preparation of growth reactor: The effective volume of the growth reactor is 770 L. 60% to 70% pure water is added in advance. The temperature is raised to 60° C. (±3) by the PLC reaction control system in advance. Nitrogen with a gas flow rate of 2000 L / h for 4 hours is introduced as a protective atmosphere before the reaction starts. The complexing agent is introduced, and after the concentration of the complexing agent reaches 2.5-3.0 g / L, seed crystals or slurry are added under stirring at 300 r / min, and a nickel-cobalt-manganese ternary salt solution is added to start the reaction. The reaction process is controlled as follows:

[0066] Stirring: The stirring speed is increased to 300 r / min in advance, and then the stirring speed is reduced from 300 r / min to 100 r / min within 1 to 20 hours of reaction;

[0067] Adding materials: adding the seed crystals or slurry prepared in (2) at the beginning of the reaction to adjust the solid content in the reactor to 50-55 g / L, controlling the pH value at 10.50-10.70, introducing the nickel-cobalt-manganese ternary salt solution at a rate of 10 L / h, synchronously introducing the precipitant at a ratio of 0.19-0.37 times the flow rate of the nickel-cobalt-manganese ternary salt solution after the reaction begins, controlling the pH value at 10.60-10.80, synchronously introducing the complexing agent at about 0.07-0.1 times the flow rate of the ternary salt solution until the complexing agent concentration in the system is 2.5-3.0 g / L; when the slurry volume in the reactor reaches 70%-80% of the effective volume of the reactor, the slurry is concentrated and cleared by a concentrator; after the reaction continues for 4 hours, the flow rate of the ternary salt solution is linearly increased to 80 L / h between 4 and 44 hours of the reaction, synchronously, the precipitant and the complexing agent are synchronously adjusted according to the flow rate of the ternary salt solution until the reaction is completed;

[0068] Gas control: 2000L / h of nitrogen is continuously introduced as protective gas throughout the process;

[0069] Particle size: The reaction maintains the above process to keep the particles growing to 13.50μm~13.70μm, ending the second stage of growth reaction synthesis; the solid content of the reaction system is 300-350g / L;

[0070] (4) In the post-treatment stage, the slurry is left in the reaction kettle or transferred to an aging kettle with a temperature regulating function, the temperature is adjusted to 60°C (±3), the stirring speed is adjusted to 80r / min, and the aging is carried out for 4 to 8 hours. 1000 to 2000L / h of nitrogen is continuously introduced as a protective gas. After subsequent washing, drying, screening, and demagnetization, the required ternary precursor material is obtained. Among them, the drying temperature is controlled at 100 to 150°C, the mesh number of the drying screen is controlled at 200 to 400 meshes, and the magnetic field strength of the iron remover is not less than 12000Gs.

[0071] The scanning electron microscope test results of the ternary precursor cross section finally obtained in Example 1 of the present invention are as follows: Figure 1-1 ,1-2; the final particle size is 13.60μm, the particle size distribution ((D(90)-D(10)) / D(50)) is 0.34, and the BET is 8.49m 2 / g, tap density is 1.97g / cm 3 , the Na content in the solid is 267ppm, and the S content in the solid is 2859ppm.

[0072] Example 2: Changing the Oxidizing Atmosphere Ratio

[0073] (1) Preparation: Nickel sulfate solution, cobalt sulfate solution, and manganese sulfate solution are prepared according to the chemical formula Ni x Co y Mn (1-x-y) (OH)2 was mixed to prepare a nickel-cobalt-manganese ternary salt solution with a molar ratio of Ni:Co:Mn=0.955:0.03:0.015 and a total metal ion concentration of 2.1 mol / L. A sodium hydroxide aqueous solution with a concentration of 10 mol / L was prepared as a precipitant aqueous solution, and an ammonia aqueous solution with a concentration of 9 mol / L was prepared as a complexing agent aqueous solution.

[0074] (2) Preparation of ternary precursor seed crystals or slurry: pure water accounting for 60% to 70% of the effective volume of the reactor was added to a seed reactor with an effective volume of 770 L, and the temperature was raised to 60° C. (±3) through a PLC reaction control system. Nitrogen was continuously introduced for 4 h before the reaction began, and the nitrogen flow rate was set to 2000 L / h. Ammonia water was added to the reactor to a concentration of 2.5 to 3.0 g / L before the reaction began, and sodium hydroxide aqueous solution was added to the reactor to a precipitant concentration of 0.20 to 0.4 g / L. The pH of the solution was adjusted to 10.72 to 11.02, and then a nickel-cobalt-manganese ternary salt solution was introduced to start the reaction;

[0075] Stirring: At the beginning of the reaction, the stirring speed was first increased to 550 r / min and maintained for 10 h. Between 10 h and 24 h after the start of the reaction, the stirring speed was linearly reduced to 300 r / min.

[0076] Feeding: At the beginning of the reaction, a nickel-cobalt-manganese ternary salt solution is introduced at a rate of 10 L / h. Simultaneously, a precipitant is introduced at a ratio of 2 / 5 of the flow rate of the ternary salt solution until the system precipitant concentration is 0.2 g / L. Simultaneously, a complexing agent is introduced at about 0.07-0.1 times the flow rate of the ternary salt solution until the system complexing agent concentration is 2.5-3.0 g / L. After the reaction continues for 8 hours, the ternary salt solution is linearly increased to 40 L / h between 8 and 20 hours. Simultaneously, the precipitant and the complexing agent are synchronously adjusted according to the flow rate of the ternary salt solution. The slurry volume in the reactor reaches 70% to 80% of the effective volume of the reactor, and the slurry is concentrated and cleared through the concentrator;

[0077] pH control: Synchronously, within two hours after the start of the reaction, the system pH is maintained at 10.72-11.02 by introducing a precipitant. Two hours after nucleation, the pH is gradually lowered to 10.45-10.55;

[0078] Gas control: 2000L / h of nitrogen was continuously introduced throughout the reaction, and the reaction lasted for 4-12h. At the same time, 80L / h of compressed air above the liquid was introduced, and the reaction lasted for 12-20h. The flow rate of compressed air above the liquid was changed to 150L / h. After 20h of reaction, the flow rate of compressed air above the liquid was changed to 200L / h.

[0079] Particle size: The reaction maintains the particle growth to 4.90μm-5.10μm under the above process, ending the first stage of seed crystal or slurry synthesis;

[0080] (3) Preparation of growth reactor: The effective volume of the growth reactor is 770 L. 60% to 70% pure water is added in advance. The temperature is raised to 60° C. (±3) by the PLC reaction control system in advance. Nitrogen with a gas flow rate of 2000 L / h for 4 hours is introduced in advance as a protective atmosphere. The complexing agent is introduced. After the concentration of the complexing agent reaches 2.5-3.0 g / L, seed crystals or slurry are added under stirring at 300 r / min, and a nickel-cobalt-manganese ternary salt solution is added to start the reaction. The reaction process is controlled as follows:

[0081] Stirring: The stirring speed is increased to 300r / min in advance, and the stirring speed is reduced from 300r / min to 100r / min within 1 to 20 hours of reaction.

[0082] Feeding: at the beginning of the reaction, the prepared seed crystals or slurry are added to adjust the solid content in the reactor to 50-55 g / L, the pH is controlled at 10.50-10.70, and the nickel-cobalt-manganese ternary salt solution is introduced at a rate of 10 L / h. Synchronously, after the reaction starts, a precipitant is introduced at a ratio of 0.19-0.37 times the flow rate of the ternary salt solution, and the pH is 10.60-10.80. Synchronously, a complexing agent is introduced at about 0.07-0.1 times the flow rate of the ternary salt solution until the concentration of the complexing agent in the system is 2.5-3.0 g / L; the slurry volume in the reactor reaches 70%-80% of the effective volume of the reactor, and the concentrator is used to concentrate and clear the slurry; after the reaction lasts for 4 hours, the ternary salt solution is linearly increased to 80 L / h between 4 and 44 hours, and the precipitant and the complexing agent are synchronously adjusted according to the flow rate of the ternary salt solution until the reaction is completed;

[0083] Gas control: 2000L / h of nitrogen is continuously introduced as protective gas throughout the process;

[0084] Particle size: The reaction maintains the particle growth to 13.50μm~13.70μm under the above process, ending the second stage growth reaction synthesis stage;

[0085] (4) In the post-treatment stage, the slurry is left in the reaction kettle or transferred to an aging kettle with a temperature regulating function, the temperature is adjusted to 60°C (±3), the stirring speed is adjusted to 80r / min, and the aging is carried out for 4 to 8 hours. 1000 to 2000L / h of nitrogen is continuously introduced as a protective gas. After subsequent washing, drying, screening, and demagnetization, the required ternary precursor material is obtained. Among them, the drying temperature is controlled at 100 to 150°C, the mesh number of the drying screen is controlled at 200 to 400 meshes, and the magnetic field strength of the iron remover is not less than 12000Gs.

[0086] The scanning electron microscope test results of the ternary precursor cross section finally obtained in Example 2 of the present invention are as follows: Figure 2-1 ,2-2; the final particle size is 13.59μm, the particle size distribution ((D(90)-D(10)) / D(50)) is 0.36, and the BET is 10.31m 2 / g, tap density is 1.95g / cm 3 , the Na content in the solid is 231 ppm, and the S content in the solid is 2635 ppm.

[0087] Example 3: Changing the Oxidizing Atmosphere Ratio

[0088] (1) Preparation: Nickel sulfate solution, cobalt sulfate solution, and manganese sulfate solution are prepared according to the chemical formula Ni x Co y Mn (1-x-y)(OH)2 was mixed to prepare a nickel-cobalt-manganese ternary salt solution with a molar ratio of Ni:Co:Mn=0.955:0.025:0.02 and a total metal ion concentration of 2.1 mol / L. A sodium hydroxide aqueous solution with a concentration of 10 mol / L was prepared as a precipitant aqueous solution, and an ammonia aqueous solution with a concentration of 9 mol / L was prepared as a complexing agent aqueous solution.

[0089] (2) Preparation of ternary precursor seed crystals or slurry: pure water accounting for 60% to 70% of the effective volume of the reactor was added to a seed reactor with an effective volume of 770 L, and the temperature was raised to 60° C. (±3) through a PLC reaction control system. Nitrogen was continuously introduced for 4 h before the reaction began, and the nitrogen flow rate was set to 2000 L / h. Ammonia water was added to the reactor to a concentration of 2.5 to 3.0 g / L before the reaction began, and sodium hydroxide aqueous solution was added to the reactor to a precipitant concentration of 0.20 to 0.4 g / L. The pH of the solution was adjusted to 10.72 to 11.02, and then a nickel-cobalt-manganese ternary salt solution was introduced to start the reaction;

[0090] Stirring: At the beginning of the reaction, the stirring speed was first increased to 550 r / min and maintained for 10 h. Between 10 h and 24 h after the start of the reaction, the stirring speed was linearly reduced to 300 r / min.

[0091] Feeding: At the beginning of the reaction, a nickel-cobalt-manganese ternary salt solution is introduced at a rate of 10 L / h. Simultaneously, a precipitant is introduced at a ratio of 2 / 5 of the flow rate of the ternary salt solution until the system precipitant concentration is 0.2 g / L. Simultaneously, a complexing agent is introduced at about 0.07-0.1 times the flow rate of the ternary salt solution until the system complexing agent concentration is 2.5-3.0 g / L. After the reaction continues for 8 hours, the ternary salt solution is linearly increased to 40 L / h between 8 and 20 hours. Simultaneously, the precipitant and the complexing agent are synchronously adjusted according to the flow rate of the ternary salt solution. The slurry volume in the reactor reaches 70% to 80% of the effective volume of the reactor, and the slurry is concentrated and cleared through the concentrator;

[0092] pH control: Synchronously, within two hours after the start of the reaction, the system pH is maintained at 10.72-11.02 by introducing a precipitant. Two hours after nucleation, the pH is gradually lowered to 10.45-10.55;

[0093] Gas control: 1000L / h of nitrogen was continuously introduced throughout the reaction, and the reaction lasted for 4-12h. At the same time, 80L / h of compressed air above the liquid was introduced, and the reaction lasted for 12-20h. The flow rate of compressed air above the liquid was changed to 150L / h. After 20h of reaction, the flow rate of compressed air above the liquid was changed to 200L / h.

[0094] Particle size: The reaction maintains the particle growth to 4.90μm-5.10μm under the above process, ending the first stage of seed crystal or slurry synthesis;

[0095] (3) Preparation of growth reactor: The effective volume of the growth reactor is 770 L. 60% to 70% pure water is added in advance. The temperature is raised to 60° C. (±3) by the PLC reaction control system in advance. Nitrogen with a gas flow rate of 2000 L / h for 4 hours is introduced in advance as a protective atmosphere. A complexing agent is introduced. When the concentration of the complexing agent reaches 2.5-3.0 g / L, seed crystals or slurry are added under stirring at 300 r / min, and a nickel-cobalt-manganese ternary salt solution is added to start the reaction. The reaction process is controlled as follows:

[0096] Stirring: The stirring speed is increased to 300r / min in advance, and the stirring speed is reduced from 300r / min to 100r / min within 1 to 20 hours of reaction.

[0097] Feeding: at the beginning of the reaction, the prepared seed crystals or slurry are added to adjust the solid content in the reactor to 50-55 g / L, the pH is controlled at 10.50-10.70, and the nickel-cobalt-manganese ternary salt solution is introduced at a rate of 10 L / h. Synchronously, within 1 hour after the start of the reaction, a precipitant is introduced at a ratio of 0.19-0.37 times the flow rate of the ternary salt solution, and the pH is 10.60-10.80. Synchronously, a complexing agent is introduced at about 0.07-0.1 times the flow rate of the ternary salt solution until the concentration of the complexing agent in the system is 2.5-3.0 g / L; when the slurry volume in the reactor reaches 70%-80% of the effective volume of the reactor, the slurry is concentrated and cleared by a concentrator; after the reaction lasts for 4 hours, the ternary salt solution is linearly increased to 80 L / h between 4 and 44 hours, and synchronously, the precipitant and the complexing agent are synchronously adjusted according to the flow rate of the ternary salt solution until the reaction is completed;

[0098] Gas control: 2000L / h of nitrogen is continuously introduced as protective gas throughout the process;

[0099] Particle size: The reaction maintains the particle growth to 13.50μm~13.70μm under the above process, ending the second stage growth reaction synthesis stage;

[0100] (4) In the post-treatment stage, the slurry is left in the reaction kettle or transferred to an aging kettle with a temperature regulating function, the temperature is adjusted to 60°C (±3), the stirring speed is adjusted to 80r / min, and the aging is carried out for 4 to 8 hours. 1000 to 2000L / h of nitrogen is continuously introduced as a protective gas. After subsequent washing, drying, screening, and demagnetization, the required ternary precursor material is obtained. Among them, the drying temperature is controlled at 100 to 150°C, the mesh number of the drying screen is controlled at 200 to 400 meshes, and the magnetic field strength of the iron remover is not less than 12000Gs.

[0101] The scanning electron microscopy of the ternary precursor finally obtained in Example 3 of the present invention is as follows Figure 1 , the cross-section SEM test results are as follows Figure 3-1,3-2; the final particle size is 13.53μm, the particle size distribution ((D(90)-D(10)) / D(50)) is 0.35, and the BET is 14.40m 2 / g, tap density is 1.91g / cm 3 , the Na content in the solid is 258ppm, and the S content in the solid is 2812ppm.

[0102] Comparative Example 1: No oxidizing gas was introduced during the seed preparation process:

[0103] (1) Preparation: Nickel sulfate solution, cobalt sulfate solution, and manganese sulfate solution were prepared according to the NixCoyMn (1-x-y) (OH)2 was mixed to prepare a nickel-cobalt-manganese ternary salt solution with a molar ratio of Ni:Co:Mn=0.955:0.03:0.015 and a total metal ion concentration of 2.1 mol / L. A sodium hydroxide aqueous solution with a concentration of 10 mol / L was prepared as a precipitant aqueous solution, and an ammonia aqueous solution with a concentration of 9 mol / L was prepared as a complexing agent aqueous solution.

[0104] (2) Preparation of ternary precursor seed crystals or slurry: pure water accounting for 60% to 70% of the effective volume of the reactor was added to a seed reactor with an effective volume of 770 L, and the temperature was raised to 60° C. (±3) through a PLC reaction control system. Nitrogen was continuously introduced for 4 h before the reaction began, and the nitrogen flow rate was set to 2000 L / h. Ammonia water was added to the reactor to a concentration of 2.5 to 3.0 g / L before the reaction began, and sodium hydroxide aqueous solution was added to the reactor to a precipitant concentration of 1.00 to 1.20 g / L. The pH of the solution was adjusted to 11.42 to 11.50, and then a nickel-cobalt-manganese ternary salt solution was introduced to start the reaction;

[0105] Stirring: 0-10h after the reaction, the stirring speed is maintained at 550r / min, and linearly reduced to 300r / min between 10h and 24h after the reaction starts;

[0106] Feeding: At the beginning of the reaction, a nickel-cobalt-manganese ternary salt solution is introduced at a rate of 10 L / h. Simultaneously, a precipitant is introduced at a ratio of 2 / 5 of the flow rate of the ternary salt solution until the system precipitant concentration is 0-1.2 g / L. Simultaneously, a complexing agent is introduced at about 0.07-0.1 times the flow rate of the ternary salt solution until the system complexing agent concentration is 2.5-3.0 g / L. Simultaneously, 8 hours after the start of the reaction, the ternary salt solution is linearly increased to 40 L / h between 8 and 20 hours. Simultaneously, the precipitant and the complexing agent are synchronously adjusted according to the flow rate of the ternary salt solution. The slurry volume in the reactor reaches 70% to 80% of the effective volume of the reactor, and the slurry is concentrated and cleared through the concentrator.

[0107] pH control: Synchronously, within two hours after the start of the reaction, the system pH is maintained at 11.42-11.50 by introducing a precipitant. Two hours after nucleation, the pH is gradually lowered to 10.42-10.72;

[0108] Gas control: 2000L / h of nitrogen was continuously introduced during the reaction;

[0109] Particle size: The reaction maintains the growth of particles to 4.90 μm to 5.10 μm under the above process, ending the first stage of seed crystal or slurry synthesis; the seed crystal preparation process does not involve oxidation, and the precipitant concentration is a conventional concentration, so that relatively dense seed crystals are obtained;

[0110] (3) Preparation of growth reactor: The effective volume of the growth reactor is 770 L. 60% to 70% pure water is added in advance. The temperature is raised to 60° C. (±3) by the PLC reaction control system in advance. Nitrogen with a gas flow rate of 2000 L / h for 4 hours is introduced in advance as a protective atmosphere. The complexing agent is introduced. After the concentration of the complexing agent reaches 2.5-3.0 g / L, seed crystals or slurry are added under stirring at 300 r / min, and a nickel-cobalt-manganese ternary salt solution is added to start the reaction. The reaction process is controlled as follows:

[0111] Stirring: The stirring speed is increased to 300r / min in advance, and the stirring speed is reduced from 300r / min to 100r / min within 1 to 20 hours of reaction.

[0112] Feeding: at the beginning of the reaction, the prepared seed crystals or slurry are added to adjust the solid content in the reactor to 50-55 g / L, the pH is controlled at 10.50-10.70, and the nickel-cobalt-manganese ternary salt solution is introduced at a rate of 10 L / h. Synchronously, a precipitant is introduced at a ratio of 0.19-0.37 times the flow rate of the nickel-cobalt-manganese ternary salt solution within 1 hour after the reaction starts, and the pH is 10.60-10.80. Synchronously, a complexing agent is introduced at about 0.07-0.1 times the flow rate of the ternary salt solution until the concentration of the complexing agent in the system is 2.5-3.0 g / L; when the slurry volume in the reactor reaches 70%-80% of the effective volume of the reactor, the slurry is concentrated and cleared by a concentrator; after the reaction continues for 4 hours, the ternary salt solution is linearly increased to 80 L / h between 4 and 44 hours, and synchronously, the precipitant and the complexing agent are synchronously adjusted according to the flow rate of the ternary salt solution until the reaction is completed;

[0113] Gas control: 2000L / h of nitrogen is continuously introduced as protective gas throughout the process;

[0114] Particle size: The reaction maintains the particle growth to 13.50μm~13.70μm under the above process, ending the second stage growth reaction synthesis stage;

[0115] (4) In the post-treatment stage, the slurry is left in the reaction kettle or transferred to an aging kettle with a temperature regulating function, the temperature is adjusted to 60°C (±3), the stirring speed is adjusted to 80r / min, and the aging is carried out for 4 to 8 hours. 1000 to 2000L / h of nitrogen is continuously introduced as a protective gas. After subsequent washing, drying, screening, and demagnetization, the required ternary precursor material is obtained. Among them, the drying temperature is controlled at 100 to 150°C, the mesh number of the drying screen is controlled at 200 to 400 meshes, and the magnetic field strength of the iron remover is not less than 12000Gs.

[0116] The scanning electron microscope test results of the ternary precursor cross section finally obtained in Comparative Example 1 of the present invention are as follows: Figure 4-1 , 4-2 The final particle size was 13.60 μm, the particle size distribution ((D(90)-D(10)) / D(50)) was 0.32, and the BET was 7.37 m 2 / g, tap density is 2.05g / cm 3 , the Na content in the solid is 225ppm, and the S content in the solid is 3674ppm.

[0117] Comparative Example 2 The ratio of oxidizing gas to inert gas was kept constant during the seed preparation process:

[0118] (1) Preparation: Nickel sulfate solution, cobalt sulfate solution, and manganese sulfate solution were prepared according to the NixCoyMn (1-x-y) (OH)2 was mixed to prepare a nickel-cobalt-manganese ternary salt solution with a molar ratio of Ni:Co:Mn=0.955:0.03:0.015 and a total metal ion concentration of 2.1 mol / L. A sodium hydroxide aqueous solution with a concentration of 10 mol / L was prepared as a precipitant aqueous solution, and an ammonia aqueous solution with a concentration of 9 mol / L was prepared as a complexing agent aqueous solution.

[0119] (2) Preparation of ternary precursor seed crystals or slurry: pure water accounting for 60% to 70% of the effective volume of the reactor was added to a seed reactor with an effective volume of 770 L, and the temperature was raised to 60° C. (±3) through a PLC reaction control system. Nitrogen was continuously introduced for 4 h before the reaction began, and the nitrogen flow rate was set to 2000 L / h. Ammonia water was added to the reactor to a concentration of 2.5 to 3.0 g / L before the reaction began, and sodium hydroxide aqueous solution was added to the reactor to a precipitant concentration of 1.00 to 1.20 g / L. The pH of the solution was adjusted to 11.42 to 11.50, and then a nickel-cobalt-manganese ternary salt solution was introduced to start the reaction;

[0120] Stirring: 0-10h after the reaction, the stirring speed is maintained at 550r / min, and linearly reduced to 300r / min between 10h and 24h after the reaction starts;

[0121] Feeding: At the beginning of the reaction, a nickel-cobalt-manganese ternary salt solution is introduced at a rate of 10 L / h. Simultaneously, a precipitant is introduced at a ratio of 2 / 5 of the flow rate of the ternary salt solution until the system precipitant concentration is 0-1.2 g / L. Simultaneously, a complexing agent is introduced at about 0.07-0.1 times the flow rate of the ternary salt solution until the system complexing agent concentration is 2.5-3.0 g / L. Simultaneously, 8 hours after the start of the reaction, the ternary salt solution is linearly increased to 40 L / h between 8 and 20 hours. Simultaneously, the precipitant and the complexing agent are synchronously adjusted according to the flow rate of the ternary salt solution. The slurry volume in the reactor reaches 70% to 80% of the effective volume of the reactor, and the slurry is concentrated and cleared through the concentrator.

[0122] pH control: Synchronously, within two hours after the start of the reaction, the system pH is maintained at 11.42-11.50 by introducing a precipitant. Two hours after nucleation, the pH is gradually lowered to 10.42-10.72;

[0123] Gas control: 2000 L / h of nitrogen was continuously introduced throughout the reaction, and 60 L / h of oxygen-containing gas was introduced simultaneously from the reaction time of 4 h to the end of the reaction;

[0124] Particle size: The reaction maintains the growth of particles to 4.90μm-5.10μm under the above process, ending the first stage of seed crystal or slurry synthesis; the looseness of the seed crystal is adjusted by increasing the proportion of oxidizing atmosphere;

[0125] (3) Preparation of growth reactor: The effective volume of the growth reactor is 770 L. 60% to 70% pure water is added in advance. The temperature is raised to 60° C. (±3) by the PLC reaction control system in advance. Nitrogen with a gas flow rate of 2000 L / h for 4 hours is introduced in advance as a protective atmosphere. The complexing agent is introduced. After the concentration of the complexing agent reaches 2.5-3.0 g / L, seed crystals or slurry are added under stirring at 300 r / min, and a nickel-cobalt-manganese ternary salt solution is added to start the reaction. The reaction process is controlled as follows:

[0126] Stirring: The stirring speed is increased to 300r / min in advance, and the stirring speed is reduced from 300r / min to 100r / min within 1 to 20 hours of reaction.

[0127] Feeding: at the beginning of the reaction, the prepared seed crystals or slurry are added to adjust the solid content in the reactor to 50-55 g / L, the pH is controlled at 10.50-10.70, and the nickel-cobalt-manganese ternary salt solution is introduced at a rate of 10 L / h. Synchronously, a precipitant is introduced at a ratio of 0.19-0.37 times the flow rate of the nickel-cobalt-manganese ternary salt solution within 1 hour after the reaction starts, and the pH is 10.60-10.80. Synchronously, a complexing agent is introduced at about 0.07-0.1 times the flow rate of the ternary salt solution until the concentration of the complexing agent in the system is 2.5-3.0 g / L; when the slurry volume in the reactor reaches 70%-80% of the effective volume of the reactor, the slurry is concentrated and cleared by a concentrator; after the reaction continues for 4 hours, the ternary salt solution is linearly increased to 80 L / h between 4 and 44 hours, and synchronously, the precipitant and the complexing agent are synchronously adjusted according to the flow rate of the ternary salt solution until the reaction is completed;

[0128] Gas control: 2000L / h of nitrogen is continuously introduced as protective gas throughout the process;

[0129] Particle size: The reaction maintains the particle growth to 13.50μm~13.70μm under the above process, ending the second stage growth reaction synthesis stage;

[0130] (4) In the post-treatment stage, the slurry is left in the reaction kettle or transferred to an aging kettle with a temperature regulating function, the temperature is adjusted to 60°C (±3), the stirring speed is adjusted to 80r / min, and the aging is carried out for 4 to 8 hours. 1000 to 2000L / h of nitrogen is continuously introduced as a protective gas. After subsequent washing, drying, screening, and demagnetization, the required ternary precursor material is obtained. Among them, the drying temperature is controlled at 100 to 150°C, the mesh number of the drying screen is controlled at 200 to 400 meshes, and the magnetic field strength of the iron remover is not less than 12000Gs.

[0131] The scanning electron microscope test results of the ternary precursor cross section finally obtained in Comparative Example 2 of the present invention are as follows: Figure 5-1 , 5-2 The final particle size was 13.54 μm, the particle size distribution ((D(90)-D(10)) / D(50)) was 0.37, and the BET was 7.91 m 2 / g, tap density is 2.01g / cm 3 , the Na content in the solid is 295ppm, and the S content in the solid is 3140ppm.

[0132] From the comparison of the embodiments and the accompanying drawings, it can be seen that in the process of preparing seeds or slurry, changing the proportion of the protective atmosphere and the oxidizing atmosphere in the reaction and increasing the proportion of the oxidizing atmosphere is beneficial to the formation of loose and porous seeds or slurry, and in the subsequent large particle growth process, it is easier to form porous and large-scale large-particle precursor particles.

[0133] The above-described embodiments are only preferred solutions of the present invention and are not intended to limit the present invention in any form. There are other variations and modifications without exceeding the technical solutions described in the claims.

Claims

1. A method for preparing an ultra-high nickel narrow distribution large ratio ternary precursor by a seed crystal method, characterized in that: The following steps are involved: (1) preparing a ternary metal salt solution using soluble salts of nickel, cobalt and manganese; preparing a complexing agent aqueous solution and a precipitating agent aqueous solution; (2) adding a ternary metal salt solution, a complexing agent aqueous solution, and a precipitant aqueous solution into a reaction kettle for reaction, the specific steps comprising: a) Preparing seed crystals or crystal slurry in a seed reactor: adding water to the reactor to 60% to 70% of the effective volume of the reactor, and adding a complexing agent aqueous solution and a precipitant aqueous solution to prepare a base solution; under certain reaction temperature, stirring intensity, and gas introduction conditions, the ternary metal salt solution, the complexing agent aqueous solution, and the precipitant aqueous solution are simultaneously introduced into the seed reactor for co-precipitation reaction, and after the reaction reaches a preset particle size, the desired seed crystals or crystal slurry are obtained; wherein the phased proportions of the inert gas and the oxidizing gas in the introduced gas include the following: Scheme 1: The flow ratio of inert gas and oxidizing gas is: 1:0 in the first stage, 50:1 in the second stage, 100:3 in the third stage, and 25:1 in the fourth stage; Or scheme 2: the phased ratio of inert gas and oxidizing gas flow is: 1:0 in the first stage, 25:1 in the second stage, 40:3 in the third stage, and 10:1 in the fourth stage; Or scheme three: the phased ratio of inert gas and oxidizing gas flow is: 1:0 in the first stage, 25:2 in the second stage, 20:3 in the third stage, and 5:1 in the fourth stage; b) Preparation of large particles in a growth reactor: In an inert gas protection atmosphere, water is added to the growth reactor to 60% to 70% of the effective volume of the reactor, and at a certain reaction temperature, stirring intensity, and inert gas protection atmosphere, seed crystals or crystal slurry are added, and a ternary metal salt solution, a complexing agent aqueous solution, and a precipitant aqueous solution are introduced into the growth reactor for co-precipitation reaction. The reaction ends when the reaction reaches a preset particle size; (3) Perform conventional post-treatment to obtain a ternary precursor material with ultra-high nickel, narrow distribution and large specific surface area.

2. The method for preparing a ternary precursor with ultra-high nickel narrow distribution and large ratio by a seed crystal method according to claim 1, characterized in that: The total molar concentration of metal ions in the ternary metal salt solution prepared in step (1) is 1.6 to 2.3 mol / L; the ratio of nickel, cobalt and manganese is based on the chemical formula Ni x Co y Mn (1-x-y) (OH)2 is used for the mixing; wherein X=0.90-0.96, Y=0.025-0.06, and Z=0.01-0.

04.

3. The method for preparing a ternary precursor with ultra-high nickel narrow distribution and large ratio by a seed crystal method according to claim 1, characterized in that: The complexing agent prepared in the step (1) is an ammonium complexing agent, and the concentration of the complexing agent aqueous solution is 4mol / L to 9.8mol / L; the precipitating agent is one or more of sodium hydroxide, sodium carbonate, and sodium bicarbonate, and the concentration of the precipitating agent aqueous solution is 5mol / L to 10.8mol / L.

4. The method for preparing a ternary precursor with ultra-high nickel narrow distribution and large ratio by a seed crystal method according to claim 1, characterized in that: In the step (2), the effective volume of the seed reaction kettle in step a) is 750L-1100L, the reaction temperature is 55°C-65°C, and the stirring speed is 300r / min-550r / min; the pH of the bottom liquid is controlled by adding a precipitant aqueous solution, the pH is 10.59-11.30, and the concentration of the complexing agent in the bottom liquid is 2-4g / L.

5. The method for preparing an ultra-high nickel narrow distribution large ratio ternary precursor by a seed crystal method according to claim 1, characterized in that: In the step (2), the inert gas flow rate in step a) is 1000-2000 L / h, and the oxidizing gas flow rate is 40-80 L / h.

6. The method for preparing a ternary precursor with ultra-high nickel narrow distribution and large ratio by a seed crystal method according to claim 1, characterized in that: In the step (2), the first stage in step a) is 0 to 4 hours of reaction, the second stage is 4 to 12 hours of reaction, the third stage is 12 to 20 hours of reaction, and the fourth stage is 20 hours of reaction until the end of the reaction.

7. The method for preparing an ultra-high nickel narrow distribution large ratio ternary precursor by a seed crystal method according to claim 1, characterized in that: In the step (2), the preset particle size of the seed crystal reaction in step a) is 4.90 μm to 5.10 μm.

8. The method for preparing a ternary precursor with ultra-high nickel narrow distribution and large ratio by a seed crystal method according to claim 1, characterized in that: In the step (2), the effective volume of the growth reactor in step b) is 750L-1100L, the reaction temperature is 55°C-65°C, the stirring speed is 100r / min-300r / min, the gas flow rate of the inert gas is 2000-3000L / h, the pH of the reaction system is 10.40-10.90, and the preset particle size of the reaction is 13.50μm-13.70μm.

9. The method for preparing a ternary precursor with ultra-high nickel narrow distribution and large ratio by a seed crystal method according to claim 1, characterized in that: The post-treatment in step (3) includes aging, washing, drying, screening and iron removal of the existing precursor process.

10. A method for preparing an ultra-high nickel narrow distribution large ratio ternary precursor by a seed crystal method according to any one of claims 1 to 9, characterized in that: The particle size distribution ((D(90)-D(10)) / D(50)) of the prepared ternary precursor material is not higher than 0.40, and the BET is between 7 and 18 m 2 / g.

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