A method for preparing ultra-high nickel narrow-distribution, high-specific-surface-area ternary precursors using a seed crystal method

Abstract

This invention pertains to the technical field of cathode NCM ultra-high nickel precursor materials, specifically a method for preparing ultra-high nickel narrow-distribution, high-specific-surface-area ternary precursors using a seed crystal method. The method involves controlling oxidation during the seed crystal preparation process to create a relatively porous ternary precursor. Small particles of this porous ternary precursor are then used as crystal slurry or seed crystals to obtain a ternary ultra-high nickel narrow-distribution, high-specific-surface-area NCM-type precursor. The precursor prepared by this invention has a simple process, is internally porous and free of penetrating cracks, exhibits good sphericity of secondary particles, and is composed of alternating stacks of fine needle-like primary particles without broken, flaky primary particles.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of positive electrode NCM ultra-high nickel (Ni≥90) precursor materials, and specifically provides a preparation method for preparing large-particle ultra-high nickel ternary precursor with narrow distribution and large specific surface area by preparing loose small-particle ternary precursor as crystal slurry or crystal seed. BACKGROUND

[0002] With the increasing demand for new energy vehicles worldwide and the implementation of strict carbon emission standard policies by the European Union, the market size of ternary materials is growing, and high nickelization, single crystallization and low cobaltization will inevitably 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 nickelization is an important direction for future development, and the market of high nickel ternary positive electrode materials is expected to grow rapidly, thereby occupying a larger share of the global market.

[0003] Ternary precursor is a key component of lithium battery positive electrode materials, and the technical content thereof 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, i.e., the physicochemical indexes of the ternary positive electrode material, and can be said to occupy a very important position. A precursor material with a larger specific surface area will provide more active sites, improve the activity of the material, and help to increase the initial capacity of the battery. In the process of charging and discharging, more channels are provided for the effective entry and transmission of lithium ions, thereby improving the ion diffusion rate. At the same time, the porous structure increases the contact area with the electrolyte, which also improves the charging and discharging performance of the battery. The positive electrode precursor obtained by the co-precipitation multi-element layering method disclosed in the existing patent (202410555844.6 CN 118479560A) has a larger specific surface area, but the steps described in the patent are complex. Therefore, there is still a need in the art to explore a method for obtaining a large specific surface area positive electrode precursor with simple operation and stable process. SUMMARY

[0004] The purpose of the present application is to provide a preparation method for preparing ultra-high nickel ternary precursor with narrow distribution and large specific surface area by crystal seed method on the basis of the existing ternary precursor preparation process. The method of the present application is to prepare large-particle ultra-high nickel ternary precursor with narrow distribution and large specific surface area by preparing loose small-particle ternary precursor as crystal slurry or crystal seed. The prepared ultra-high nickel NCM type ternary positive electrode precursor has a narrow particle size distribution, a large BET, an internal loose and porous structure, no through cracks, a good sphericity of secondary particles, and no broken flaky primary particles formed by the intercalation of fine needle-like primary particles.

[0005] To achieve the above purpose, the technical scheme adopted by the present application is as follows:

[0006] A preparation method of a seed crystal method for preparing a super-high nickel narrow distribution large specific surface area ternary precursor, comprising the following steps:

[0007] (1) A ternary metal salt solution of a certain concentration is prepared from soluble salts of nickel, cobalt and manganese; a complexing agent aqueous solution and a precipitant aqueous solution used synchronously in the coprecipitation reaction are configured;

[0008] (2) The ternary metal salt solution of a certain concentration, the complexing agent aqueous solution and the precipitant aqueous solution configured in step (1) are added to a reaction system composed of a reaction kettle and a concentration mechanism to perform a reaction, and the specific steps include:

[0009] a) Seed crystal or crystal slurry preparation in a seed crystal kettle: seed crystals or crystal slurry required for subsequent reactions are prepared in the seed crystal kettle, water is added to 60% to 70% of the effective volume of the reaction kettle before the coprecipitation reaction, and a bottom solution is prepared by adding the complexing agent aqueous solution and the precipitant aqueous solution; under certain reaction temperature, stirring intensity and gas inlet conditions, the ternary metal salt solution, the complexing agent aqueous solution and the precipitant aqueous solution are simultaneously introduced into the seed crystal kettle to perform a coprecipitation reaction, and after the reaction reaches a preset particle size, the required seed crystals or crystal slurry are obtained; wherein the gas inlet includes phased introduction of inert gas and oxidizing gas, and the phased proportion of inert gas and oxidizing gas in the gas inlet includes the following:

[0010] Scheme one: the phased proportion of inert gas and oxidizing gas flow is: one stage 1:0, two stages 50:1, three stages 100:3, and four stages 25:1;

[0011] Or scheme two: the phased proportion of inert gas and oxidizing gas flow is: one stage 1:0, two stages 25:1, three stages 40:3, and four stages 10:1;

[0012] Or scheme three: the phased proportion of inert gas and oxidizing gas flow is: one stage 1:0, two stages 25:2, three stages 20:3, and four stages 5:1;

[0013] b) Large particle preparation in a growth reaction kettle

[0014] Under the protection of an inert gas atmosphere, the growth reaction kettle is added with water to 60% to 70% of the effective volume of the reaction kettle, the seed crystals or crystal slurry prepared in step (2)a) are put in, and a bottom solution is prepared by adding the complexing agent aqueous solution; under certain reaction temperature, stirring intensity and inert gas protection atmosphere, the ternary metal salt solution, the complexing agent aqueous solution and the precipitant aqueous solution are introduced into the growth reaction kettle to perform a coprecipitation reaction, and the reaction reaches a preset particle size as the reaction endpoint;

[0015] (3) The large particle precursor with a preset particle size in step b) of step (2) is subjected to conventional post-treatment to obtain the required super-high nickel narrow distribution large specific surface area ternary precursor material.

[0016] By adopting the technical scheme, the application can increase the specific surface area of the required precursor by adjusting the oxidation degree in the core preparation process of the precursor in the seed crystal stage, changing the loose degree of the seed crystal, and then growing to the target particle size.

[0017] Preferably, the total molar concentration of metal ions in the ternary metal salt solution prepared in step (1) is 1.6-2.3 mol / L; more preferably, the ratio of nickel, cobalt and manganese in the ternary metal salt solution is according to the chemical formula Ni x Co y Mn (1-x-y) (OH)2; wherein X=0.90-0.96, Y=0.025-0.06, and 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, ammonium sulfate, ammonium sulfite, ammonium bisulfate and ammonium thiosulfate. More preferably, the concentration of the aqueous solution of the complexing agent is 4-9.8 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 aqueous solution of the precipitant is 5-10.8 mol / L.

[0020] Preferably, the effective volume of the seed crystal reactor used in step a) of step (2) is 750-1100 L.

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

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

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

[0024] More preferably, the step (2) in step a) of scheme one, scheme two, scheme three, the oxidation gas is introduced in the nucleation 4h, i.e. 0-4h of the first stage of the reaction.

[0025] More preferably, the step (2) in step a) of scheme one, scheme two, scheme three, the second stage of the reaction is 4-12h, the third stage of the reaction is 12-20h, and the fourth stage of the reaction is 20h to the end of the reaction.

[0026] More preferably, the step (2) in step a) of scheme one, scheme two, scheme three, the oxidation gas is compressed air.

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

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

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

[0030] Preferably, the solid content in the reactor is adjusted to 50-55g / L by adding the seed or crystal slurry prepared in step (2) in step b) of step (2).

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

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

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

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

[0035] More preferably, the aging process in step (3) needs to be soaked in alkali, and the temperature is preferably 60℃, and the soaking time is preferably 4-8h.

[0036] More preferably, after the aging process in step (3) reaches the end of the soaking time, the washing and post-processing stage should be entered quickly.

[0037] Preferably, the washing in step (3) can use one or more of a centrifuge, a filter press, and a filter tank.

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

[0039] Preferably, the drying equipment in step (3) can use one or more of a static box oven, a tray dryer, a vacuum dryer, and a flash dryer. More preferably, the back end of the drying equipment includes a screening machine, a magnetic separator, and the like.

[0040] Preferably, after the 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 should be 0-50 ppb.

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

[0042] Compared with the prior art, the present application has the following advantages: the present application provides a preparation method of narrow-distribution large specific surface area super-high nickel ternary precursor large particles by preparing loose ternary precursor small particles as crystal slurry or crystal seeds, which comprises the following steps: (1) using soluble salt nickel sulfate, cobalt sulfate and manganese sulfate as raw materials, preparing a ternary metal salt solution with a certain concentration; (2) under the atmosphere of appropriate inert gas and oxidizing gas, the ternary metal salt solution, a complexing agent and a precipitating agent are introduced into a reaction kettle through a metering pump at a constant flow rate to perform a coprecipitation reaction, so as to obtain nickel-cobalt-manganese ternary hydroxide seeds or crystal slurry; (3) the crystal slurry or crystal seeds are transferred to a growth reaction kettle to perform a growth stage from ternary hydroxide small particles to ternary hydroxide large particles; (4) under the protection of an inert gas atmosphere, the ternary hydroxide small particles are used as a base material, and a certain concentration of the ternary metal salt solution, the complexing agent and the precipitating agent are introduced into the growth reaction kettle through the metering pump at the same time to perform a coprecipitation reaction; (5) the ternary precursor material with a preset particle size is obtained through conventional post-treatment, thereby obtaining a NCM type precursor with a narrow distribution and a large specific surface area of super-high nickel. In the seed preparation stage, the present application increases the oxidizing gas and changes the proportion of the oxidizing gas and the inert gas, so as to facilitate the formation of loose and porous seeds, and in the subsequent large particle growth process, it is easier to form large particle precursor particles with a large specific surface area. Meanwhile, the preparation process provided by the present application is relatively simple, the internal structure is loose and porous, there is no penetrating crack, the secondary particle sphericity is good, the primary particles are formed by interlocking accumulation of fine needle-like primary particles, and there is no broken flaky primary particle. BRIEF DESCRIPTION OF DRAWINGS

[0043] Figure 1 FIG. 10.0k scanning electron microscope image of the nickel-cobalt-manganese hydroxide prepared in Example 3 of the present application;

[0044] Figure 1-1 FIG. 6.0k cross-sectional scanning electron microscope image of the nickel-cobalt-manganese hydroxide prepared in Example 1 of the present application;

[0045] Figure 1-2 FIG. 15.0k cross-sectional scanning electron microscope image of the nickel-cobalt-manganese hydroxide prepared in Example 1 of the present application;

[0046] Figure 2-1 FIG. 6.0k cross-sectional scanning electron microscope image of the nickel-cobalt-manganese hydroxide prepared in Example 2 of the present application;

[0047] Figure 2-2 FIG. 15.0k cross-sectional scanning electron microscope image of the nickel-cobalt-manganese hydroxide prepared in Example 2 of the present application;

[0048] Figure 3-1 FIG. 6.0k cross-sectional scanning electron microscope image of the nickel-cobalt-manganese hydroxide prepared in Example 3 of the present application;

[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 this 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 this invention. Detailed Implementation

[0054] To better clarify and understand the objectives, process solutions, and advantages of this invention, the technical solutions and implementation methods of this invention will be further described clearly, completely, and in detail below through specific embodiments and in conjunction with the accompanying drawings. It should be understood that the embodiments described in this invention are implemented under the premise of the technical solutions of this invention, providing detailed implementation methods and specific operating procedures, but are only some embodiments of this invention, not all embodiments. The specific implementation methods described are limited to illustrating and explaining this invention and do not limit this invention. Based on the embodiments of this invention, all other implementation methods obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0055] Unless otherwise specified, the experimental methods and conditions used in the embodiments of this invention are conventional methods and conditions. The materials, reagents, and instruments used in the embodiments, unless otherwise specified, can be obtained commercially or prepared by conventional methods. The reaction conditions described in the invention can all achieve the reactions and obtain the desired products. Due to space limitations, some embodiments are listed below to further illustrate the advantages of the technical solution of this invention.

[0056] Example 1

[0057] This embodiment provides a method for preparing ultra-high nickel narrow-distribution, large-specific-area ternary precursors using a seed crystal method, specifically including 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 was used to prepare 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 10 mol / L sodium hydroxide aqueous solution was prepared as the precipitant (hereinafter referred to as the precipitant), and a 9 mol / L ammonia solution was prepared as the complexing agent (hereinafter referred to as the complexing agent).

[0059] (2) Preparation of ternary precursor seed crystals or slurry: Add pure water accounting for 60% to 70% of the effective volume of the crystal seed reactor to a crystal seed reactor with an effective volume of 770L. Heat the reactor to 60℃ (±3) through the PLC reaction control system and continuously introduce nitrogen gas for 4h. The nitrogen gas flow rate is set to 2000L / h. Before the reaction starts, add ammonia water to the reactor to a concentration of 2.5 to 3.0g / L and add sodium hydroxide aqueous solution to a precipitant concentration of 0.20 to 0.4g / L. Adjust the pH of the solution to 10.72 to 11.02. Then introduce nickel-cobalt-manganese ternary salt solution to start the reaction.

[0060] Stirring: The stirring speed was maintained at 550 r / min during the first 0-10 hours of the reaction, and then linearly reduced to 300 r / min between 10-24 hours after the start of the reaction.

[0061] Feeding: At the start 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 rate of 2 / 5 of the ternary salt solution flow rate until the precipitant concentration in the system reaches 0.20 g / L. Simultaneously, a complexing agent is introduced at a rate of approximately 0.07-0.1 times the ternary salt solution flow rate until the complexing agent concentration in the system reaches 2.5-3.0 g / L. Simultaneously, after 8 hours from the start of the reaction, the ternary salt solution flow rate linearly increases to 40 L / h between 8 and 20 hours. Simultaneously, the precipitant and complexing agent concentrations are adjusted synchronously according to the ternary salt solution flow rate to maintain the complexing agent and precipitant concentrations in the system. When the slurry volume in the reactor reaches 70%-80% of the effective volume of the reactor, the slurry is concentrated and clarified using a thickener.

[0062] pH control: Simultaneously, within the first two hours of the reaction, the pH of the system is maintained at 10.72-11.02 by introducing a precipitant. After two hours of nucleation, the pH is gradually and manually reduced to 10.45-10.55.

[0063] Gas control: Nitrogen gas is continuously introduced at a rate of 2000 L / h throughout the reaction. During the reaction from 4 to 12 hours, compressed air is introduced at a rate of 40 L / h. During the reaction from 12 to 20 hours, the flow rate of compressed air is changed to 60 L / h. During the reaction from 20 hours to the end, the flow rate of compressed air is changed to 80 L / h.

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

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

[0066] Stirring: The stirring speed was initially increased to 300 r / min, and then the stirring speed was reduced from 300 r / min to 100 r / min within 1 to 20 hours of reaction.

[0067] Feeding: At the start of the reaction, add the seed crystals or slurry prepared in (2) to adjust the solid content in the reactor to 50-55 g / L, control the pH at 10.50-10.70, and pass the nickel-cobalt-manganese ternary salt solution at a rate of 10 L / h. Simultaneously, after the start of the reaction, pass the precipitant at a ratio of 0.19-0.37 times the flow rate of the nickel-cobalt-manganese ternary salt solution, control the pH at 10.60-10.80, and simultaneously, pass the complexing agent at a ratio of 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, start to concentrate and clear it through the thickener. After the reaction continues for 4 hours, the flow rate of the ternary salt solution increases linearly to 80 L / h between 4 and 44 hours of the reaction. Simultaneously, the precipitant and complexing agent are adjusted synchronously according to the flow rate of the ternary salt solution until the end of the reaction.

[0068] Gas control: Nitrogen gas is continuously supplied at a rate of 2000 L / h as a protective gas throughout the entire process;

[0069] Particle size: Under the above process, the particles are grown to 13.50μm~13.70μm, and the second stage of growth reaction synthesis is ended; the solid content of the reaction system is 300-350g / L;

[0070] (4) In the post-processing stage, the slurry is left in the reactor or transferred to the aging reactor with temperature control function. The temperature is adjusted to 60℃ (±3), the stirring speed is adjusted to 80r / min, and the aging is maintained for 4 to 8 hours. Nitrogen gas of 1000 to 2000L / h is continuously introduced as a protective gas. After subsequent washing, drying, sieving, and demagnetization, the required ternary precursor material is obtained. The drying temperature is controlled at 100 to 150℃, the mesh size of the screen is controlled at 200 to 400 mesh, and the magnetic field strength of the iron remover is not less than 12000Gs.

[0071] The final scanning electron microscope (SEM) results of the ternary precursor profile obtained in Embodiment 1 of this invention are as follows: Figure 1-1 ,1-2; The final particle size was 13.60 μm, the particle size distribution ((D(90)-D(10)) / D(50)) was 0.34, and the BET was 8.49 m. 2 / g, tap density is 1.97g / cm³ 3 The Na content in the solid is 267 ppm, and the S content in the solid is 2859 ppm.

[0072] Example 2: Changing the proportion of oxidizing atmosphere

[0073] (1) Preparation: Mix nickel sulfate solution, cobalt sulfate solution, and manganese sulfate solution according to the general chemical formula Ni x Co y Mn (1-x-y) (OH)₂ was used 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 10 mol / L sodium hydroxide aqueous solution was prepared as the precipitant, and a 9 mol / L ammonia solution was prepared as the complexing agent.

[0074] (2) Preparation of ternary precursor seed crystals or slurry: Add pure water accounting for 60% to 70% of the effective volume of the crystal seed reactor to a crystal seed reactor with an effective volume of 770L. Heat the reactor to 60℃ (±3) using a PLC reaction control system. Before the reaction starts, continuously introduce nitrogen gas for 4 hours at a flow rate of 2000L / h. Before the reaction starts, add ammonia water to the reactor to a concentration of 2.5 to 3.0g / L and sodium hydroxide aqueous solution to a precipitant concentration of 0.20 to 0.4g / L. Adjust the pH of the solution to 10.72 to 11.02. Then introduce a nickel-cobalt-manganese ternary salt solution to start the reaction.

[0075] Stirring: At the start of the reaction, the stirring speed was initially increased to 550 r / min and maintained for 10 h. Then, 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 start 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 rate of 2 / 5 of the ternary salt solution flow rate until the precipitant concentration in the system reaches 0.2 g / L. Simultaneously, a complexing agent is introduced at a rate of approximately 0.07-0.1 times the ternary salt solution flow rate until the complexing agent concentration in the system reaches 2.5-3.0 g / L. After the reaction continues for 8 hours, the ternary salt solution flow rate linearly increases to 40 L / h between 8 and 20 hours. Simultaneously, the precipitant and complexing agent are adjusted according to the ternary salt solution flow rate. When the slurry volume in the reactor reaches 70%-80% of the effective volume of the reactor, the slurry is concentrated and clarified using a thickener.

[0077] pH control: Simultaneously, within the first two hours of the reaction, the pH of the system is maintained at 10.72–11.02 by introducing a precipitant. After two hours of nucleation, the pH is gradually reduced manually to 10.45–10.55.

[0078] Gas control: Nitrogen gas is continuously introduced at a rate of 2000 L / h throughout the reaction. During the reaction period of 4 to 12 hours, compressed air at a rate of 80 L / h is introduced simultaneously. During the reaction period of 12 to 20 hours, the flow rate of compressed air is changed to 150 L / h. During the reaction period of 20 hours until the end of the reaction, the flow rate of compressed air is changed to 200 L / h.

[0079] Particle size: The reaction continues to grow particles to 4.90 μm to 5.10 μm under the above process, thus ending the first stage of seed crystal or slurry synthesis.

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

[0081] Stirring: The stirring speed was initially increased to 300 r / min, and then reduced to 100 r / min during the first 1 to 20 hours of reaction.

[0082] Feeding: At the start of the reaction, add the prepared seed crystals or slurry to adjust the solid content in the reactor to 50-55 g / L, and control the pH at 10.50-10.70. Introduce a nickel-cobalt-manganese ternary salt solution at a rate of 10 L / h. Simultaneously, after the reaction begins, introduce a precipitant at a ratio of 0.19-0.37 times the flow rate of the ternary salt solution, maintaining the pH at 10.60-10.80. Simultaneously, introduce a complexing agent at approximately 0.07-0.1 times the flow rate of the ternary salt solution until the complexing agent concentration in the system reaches 2.5-3.0 g / L. When the slurry volume in the reactor reaches 70%-80% of the effective volume, begin concentrating and purging using a thickener. After the reaction continues for 4 hours, the ternary salt solution flow rate linearly increases to 80 L / h between 4 and 44 hours. Simultaneously, adjust the precipitant and complexing agent flow rates according to the ternary salt solution flow rate until the reaction ends.

[0083] Gas control: Nitrogen gas is continuously supplied at a rate of 2000 L / h as a protective gas throughout the entire process;

[0084] Particle size: Under the above process, the particles are grown to 13.50 μm to 13.70 μm, and the second stage of growth reaction synthesis is completed.

[0085] (4) In the post-processing stage, the slurry is left in the reactor or transferred to the aging reactor with temperature control function. The temperature is adjusted to 60℃ (±3), the stirring speed is adjusted to 80r / min, and the aging is maintained for 4 to 8 hours. Nitrogen gas of 1000 to 2000L / h is continuously introduced as a protective gas. After subsequent washing, drying, sieving, and demagnetization, the required ternary precursor material is obtained. The drying temperature is controlled at 100 to 150℃, the mesh size of the screen is controlled at 200 to 400 mesh, and the magnetic field strength of the iron remover is not less than 12000Gs.

[0086] The final scanning electron microscope (SEM) results of the ternary precursor profile obtained in Embodiment 2 of this invention are as follows: Figure 2-1 ,2-2; The final particle size was 13.59 μm, the particle size distribution ((D(90)-D(10)) / D(50)) was 0.36, and the BET was 10.31 m. 2 / g, tap density is 1.95g / cm³ 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 proportion of oxidizing atmosphere

[0088] (1) Preparation: Mix nickel sulfate solution, cobalt sulfate solution, and manganese sulfate solution according to the general chemical formula Ni x Co y Mn (1-x-y)(OH)₂ was used 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 10 mol / L sodium hydroxide aqueous solution was prepared as the precipitant, and a 9 mol / L ammonia solution was prepared as the complexing agent.

[0089] (2) Preparation of ternary precursor seed crystals or slurry: Add pure water accounting for 60% to 70% of the effective volume of the crystal seed reactor to a crystal seed reactor with an effective volume of 770L. Heat the reactor to 60℃ (±3) using a PLC reaction control system. Before the reaction starts, continuously introduce nitrogen gas for 4 hours at a flow rate of 2000L / h. Before the reaction starts, add ammonia water to the reactor to a concentration of 2.5 to 3.0g / L and sodium hydroxide aqueous solution to a precipitant concentration of 0.20 to 0.4g / L. Adjust the pH of the solution to 10.72 to 11.02. Then introduce a nickel-cobalt-manganese ternary salt solution to start the reaction.

[0090] Stirring: At the start of the reaction, the stirring speed was initially increased to 550 r / min and maintained for 10 h. Then, 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 start 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 rate of 2 / 5 of the ternary salt solution flow rate until the precipitant concentration in the system reaches 0.2 g / L. Simultaneously, a complexing agent is introduced at a rate of approximately 0.07-0.1 times the ternary salt solution flow rate until the complexing agent concentration in the system reaches 2.5-3.0 g / L. After the reaction continues for 8 hours, the ternary salt solution flow rate linearly increases to 40 L / h between 8 and 20 hours. Simultaneously, the precipitant and complexing agent are adjusted according to the ternary salt solution flow rate. When the slurry volume in the reactor reaches 70%-80% of the effective volume of the reactor, the slurry is concentrated and clarified using a thickener.

[0092] pH control: Simultaneously, within the first two hours of the reaction, the pH of the system is maintained at 10.72–11.02 by introducing a precipitant. After two hours of nucleation, the pH is gradually reduced manually to 10.45–10.55.

[0093] Gas control: Nitrogen gas is continuously introduced at a rate of 1000 L / h throughout the reaction. During the reaction period of 4 to 12 hours, compressed air at a rate of 80 L / h is introduced simultaneously. During the reaction period of 12 to 20 hours, the flow rate of compressed air is changed to 150 L / h. During the reaction period of 20 hours until the end of the reaction, the flow rate of compressed air is changed to 200 L / h.

[0094] Particle size: The reaction continues to grow particles to 4.90 μm to 5.10 μm under the above process, thus ending the first stage of seed crystal or slurry synthesis.

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

[0096] Stirring: The stirring speed was initially increased to 300 r / min, and then reduced to 100 r / min during the first 1 to 20 hours of reaction.

[0097] Feeding: At the start of the reaction, add the prepared seed crystals or slurry to adjust the solid content in the reactor to 50-55 g / L, and control the pH at 10.50-10.70. Introduce a nickel-cobalt-manganese ternary salt solution at a rate of 10 L / h. Simultaneously, within the first hour of the reaction, introduce a precipitant at a rate of 0.19-0.37 times the flow rate of the ternary salt solution, maintaining the pH at 10.60-10.80. Simultaneously, introduce a complexing agent at approximately 0.07-0.1 times the flow rate of the ternary salt solution until the complexing agent concentration in the system reaches 2.5-3.0 g / L. When the slurry volume in the reactor reaches 70%-80% of the effective volume, begin concentrating and purging using a thickener. After the reaction continues for 4 hours, the flow rate of the ternary salt solution linearly increases to 80 L / h between 4 and 44 hours. Simultaneously, adjust the flow rates of the precipitant and complexing agent according to the ternary salt solution flow rate until the reaction ends.

[0098] Gas control: Nitrogen gas is continuously supplied at a rate of 2000 L / h as a protective gas throughout the entire process;

[0099] Particle size: Under the above process, the particles are grown to 13.50 μm to 13.70 μm, and the second stage of growth reaction synthesis is completed.

[0100] (4) In the post-processing stage, the slurry is left in the reactor or transferred to the aging reactor with temperature control function. The temperature is adjusted to 60℃ (±3), the stirring speed is adjusted to 80r / min, and the aging is maintained for 4 to 8 hours. Nitrogen gas of 1000 to 2000L / h is continuously introduced as a protective gas. After subsequent washing, drying, sieving, and demagnetization, the required ternary precursor material is obtained. The drying temperature is controlled at 100 to 150℃, the mesh size of the screen is controlled at 200 to 400 mesh, and the magnetic field strength of the iron remover is not less than 12000Gs.

[0101] The final ternary precursor scanning electron microscope obtained in Embodiment 3 of this invention is shown below. Figure 1 The results of the cross-sectional scanning electron microscopy test are as follows: Figure 3-1,3-2; The final particle size was 13.53 μm, the particle size distribution ((D(90)-D(10)) / D(50)) was 0.35, and the BET was 14.40 m. 2 / g, tap density is 1.91g / cm³ 3 The Na content in the solid is 258 ppm, and the S content in the solid is 2812 ppm.

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

[0103] (1) Preparation: Mix nickel sulfate solution, cobalt sulfate solution, and manganese sulfate solution according to the NixCoyMn standard. (1-x-y) (OH)₂ was used 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 10 mol / L sodium hydroxide aqueous solution was prepared as the precipitant, and a 9 mol / L ammonia solution was prepared as the complexing agent.

[0104] (2) Preparation of ternary precursor seed crystals or slurry: Add pure water accounting for 60% to 70% of the effective volume of the crystal seed reactor to a crystal seed reactor with an effective volume of 770L. Heat the reactor to 60℃ (±3) using a PLC reaction control system. Before the reaction starts, continuously introduce nitrogen gas for 4 hours with a nitrogen flow rate of 2000L / h. Before the reaction starts, add ammonia water to the reactor to a concentration of 2.5 to 3.0g / L and sodium hydroxide aqueous solution to a precipitant concentration of 1.00 to 1.20g / L. Adjust the pH of the solution to 11.42 to 11.50. Then introduce a nickel-cobalt-manganese ternary salt solution to start the reaction.

[0105] Stirring: During the first 0-10 hours of the reaction, the stirring speed was maintained at 550 r / min, and then linearly reduced to 300 r / min between 10 and 24 hours after the start of the reaction.

[0106] Feeding: At the start 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 rate of 2 / 5 of the ternary salt solution flow rate until the precipitant concentration in the system is 0-1.2 g / L. Simultaneously, a complexing agent is introduced at a rate of approximately 0.07-0.1 times the ternary salt solution flow rate until the complexing agent concentration in the system is 2.5-3.0 g / L. Simultaneously, after 8 hours from the start of the reaction, the ternary salt solution flow rate linearly increases to 40 L / h between 8 and 20 hours. Simultaneously, the precipitant and complexing agent are adjusted according to the ternary salt solution flow rate. When the slurry volume in the reactor reaches 70%-80% of the effective volume of the reactor, the slurry is concentrated and clarified using a thickener.

[0107] pH control: Simultaneously, within the first two hours of the reaction, the pH of the system is maintained at 11.42–11.50 by introducing a precipitant. After two hours of nucleation, the pH is gradually reduced to 10.42–10.72.

[0108] Gas control: Nitrogen gas is continuously introduced at a rate of 2000 L / h throughout the reaction process;

[0109] Particle size: Under the above process, the particles are grown to 4.90μm~5.10μm, and the first stage of seed crystal or slurry synthesis is completed; the seed crystal preparation process does not involve oxidation, and the concentration of precipitant is conventional, resulting in relatively dense seed crystals;

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

[0111] Stirring: The stirring speed was initially increased to 300 r / min, and then reduced to 100 r / min during the first 1 to 20 hours of reaction.

[0112] Feeding: At the start of the reaction, add the prepared seed crystals or slurry to adjust the solid content in the reactor to 50-55 g / L, and control the pH at 10.50-10.70. Introduce a nickel-cobalt-manganese ternary salt solution at a rate of 10 L / h. Simultaneously, within the first hour of the reaction, introduce a precipitant at a rate of 0.19-0.37 times the flow rate of the nickel-cobalt-manganese ternary salt solution, maintaining the pH at 10.60-10.80. Simultaneously, introduce a complexing agent at a rate of approximately 0.07-0.1 times the flow rate of the ternary salt solution until the complexing agent concentration in the system reaches 2.5-3.0 g / L. When the slurry volume in the reactor reaches 70%-80% of the effective volume, begin concentrating and purging using a thickener. After the reaction continues for 4 hours, the flow rate of the ternary salt solution linearly increases to 80 L / h between 4 and 44 hours. Simultaneously, the flow rates of the precipitant and complexing agent are adjusted according to the flow rate of the ternary salt solution until the reaction ends.

[0113] Gas control: Nitrogen gas is continuously supplied at a rate of 2000 L / h as a protective gas throughout the entire process;

[0114] Particle size: Under the above process, the particles are grown to 13.50 μm to 13.70 μm, and the second stage of growth reaction synthesis is completed.

[0115] (4) In the post-processing stage, the slurry is left in the reactor or transferred to the aging reactor with temperature control function. The temperature is adjusted to 60℃ (±3), the stirring speed is adjusted to 80r / min, and the aging is maintained for 4 to 8 hours. Nitrogen gas of 1000 to 2000L / h is continuously introduced as a protective gas. After subsequent washing, drying, sieving, and demagnetization, the required ternary precursor material is obtained. The drying temperature is controlled at 100 to 150℃, the mesh size of the screen is controlled at 200 to 400 mesh, and the magnetic field strength of the iron remover is not less than 12000Gs.

[0116] The final scanning electron microscope (SEM) results of the ternary precursor profile obtained in Comparative Example 1 of this 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 / cm³ 3 The Na content in the solid is 225 ppm, and the S content in the solid is 3674 ppm.

[0117] The proportions of oxidizing and inert gases maintained constant during the seed preparation process in Comparative Example 2:

[0118] (1) Preparation: Mix nickel sulfate solution, cobalt sulfate solution, and manganese sulfate solution according to the NixCoyMn standard. (1-x-y) (OH)₂ was used 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 10 mol / L sodium hydroxide aqueous solution was prepared as the precipitant, and a 9 mol / L ammonia solution was prepared as the complexing agent.

[0119] (2) Preparation of ternary precursor seed crystals or slurry: Add pure water accounting for 60% to 70% of the effective volume of the crystal seed reactor to a crystal seed reactor with an effective volume of 770L. Heat the reactor to 60℃ (±3) using a PLC reaction control system. Before the reaction starts, continuously introduce nitrogen gas for 4 hours with a nitrogen flow rate of 2000L / h. Before the reaction starts, add ammonia water to the reactor to a concentration of 2.5 to 3.0g / L and sodium hydroxide aqueous solution to a precipitant concentration of 1.00 to 1.20g / L. Adjust the pH of the solution to 11.42 to 11.50. Then introduce a nickel-cobalt-manganese ternary salt solution to start the reaction.

[0120] Stirring: During the first 0-10 hours of the reaction, the stirring speed was maintained at 550 r / min, and then linearly reduced to 300 r / min between 10 and 24 hours after the start of the reaction.

[0121] Feeding: At the start 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 rate of 2 / 5 of the ternary salt solution flow rate until the precipitant concentration in the system is 0-1.2 g / L. Simultaneously, a complexing agent is introduced at a rate of approximately 0.07-0.1 times the ternary salt solution flow rate until the complexing agent concentration in the system is 2.5-3.0 g / L. Simultaneously, after 8 hours from the start of the reaction, the ternary salt solution flow rate linearly increases to 40 L / h between 8 and 20 hours. Simultaneously, the precipitant and complexing agent are adjusted according to the ternary salt solution flow rate. When the slurry volume in the reactor reaches 70%-80% of the effective volume of the reactor, the slurry is concentrated and clarified using a thickener.

[0122] pH control: Simultaneously, within the first two hours of the reaction, the pH of the system is maintained at 11.42–11.50 by introducing a precipitant. After two hours of nucleation, the pH is gradually reduced manually to 10.42–10.72.

[0123] Gas control: Nitrogen gas is continuously introduced at a rate of 2000 L / h throughout the reaction. The reaction continues for 4 hours until the end of the reaction. Simultaneously, oxygen-containing gas is introduced at a rate of 60 L / h.

[0124] Particle size: Under the above process, the reaction maintains particle growth to 4.90μm~5.10μm, ending the first stage of seed crystal or slurry synthesis; the porosity of the seed crystal is adjusted by increasing the proportion of oxidizing atmosphere.

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

[0126] Stirring: The stirring speed was initially increased to 300 r / min, and then reduced to 100 r / min during the first 1 to 20 hours of reaction.

[0127] Feeding: At the start of the reaction, add the prepared seed crystals or slurry to adjust the solid content in the reactor to 50-55 g / L, and control the pH at 10.50-10.70. Introduce a nickel-cobalt-manganese ternary salt solution at a rate of 10 L / h. Simultaneously, within the first hour of the reaction, introduce a precipitant at a rate of 0.19-0.37 times the flow rate of the nickel-cobalt-manganese ternary salt solution, maintaining the pH at 10.60-10.80. Simultaneously, introduce a complexing agent at a rate of approximately 0.07-0.1 times the flow rate of the ternary salt solution until the complexing agent concentration in the system reaches 2.5-3.0 g / L. When the slurry volume in the reactor reaches 70%-80% of the effective volume, begin concentrating and purging using a thickener. After the reaction continues for 4 hours, the flow rate of the ternary salt solution linearly increases to 80 L / h between 4 and 44 hours. Simultaneously, the flow rates of the precipitant and complexing agent are adjusted according to the flow rate of the ternary salt solution until the reaction ends.

[0128] Gas control: Nitrogen gas is continuously supplied at a rate of 2000 L / h as a protective gas throughout the entire process;

[0129] Particle size: Under the above process, the particles are grown to 13.50 μm to 13.70 μm, and the second stage of growth reaction synthesis is completed.

[0130] (4) In the post-processing stage, the slurry is left in the reactor or transferred to the aging reactor with temperature control function. The temperature is adjusted to 60℃ (±3), the stirring speed is adjusted to 80r / min, and the aging is maintained for 4 to 8 hours. Nitrogen gas of 1000 to 2000L / h is continuously introduced as a protective gas. After subsequent washing, drying, sieving, and demagnetization, the required ternary precursor material is obtained. The drying temperature is controlled at 100 to 150℃, the mesh size of the screen is controlled at 200 to 400 mesh, and the magnetic field strength of the iron remover is not less than 12000Gs.

[0131] The final scanning electron microscope (SEM) results of the ternary precursor profile obtained in Comparative Example 2 of this 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 μm. 2 / g, tap density is 2.01g / cm³ 3 The Na content in the solid is 295 ppm, and the S content in the solid is 3140 ppm.

[0132] As can be seen from the comparison of the embodiments and the accompanying drawings, in the preparation process of seed crystals or slurries, 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 forming loose and porous seed crystals or slurries. In the subsequent large particle growth process, it is easier to form large-particle precursor particles with large porous surface area.

[0133] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the present invention in any way. Other variations and modifications are possible without departing from the technical solutions described in the claims.

Claims

1. A method for preparing a super-high nickel narrow distribution large specific surface area ternary precursor by a seed crystal method, characterized in that, The method comprises the following steps: (1) preparing a ternary metal salt solution with soluble salts of nickel, cobalt and manganese; configuring an aqueous complexing agent solution and an aqueous precipitant solution; (2) adding the ternary metal salt solution, the aqueous complexing agent solution and the aqueous precipitant solution into a reactor for reaction, and the specific steps comprise: a) preparing crystal seeds or crystal slurry in a seed reactor: adding water into the seed reactor to 60-70% of the effective volume of the reactor, and adding the aqueous complexing agent solution and the aqueous precipitant solution to prepare a bottom solution; under certain reaction temperature, stirring intensity and gas inlet conditions, the ternary metal salt solution, the aqueous complexing agent solution and the aqueous precipitant solution are simultaneously introduced into the seed reactor for co-precipitation reaction, and after the reaction reaches the preset particle size, the required crystal seeds or crystal slurry is obtained; wherein the phase proportion of inert gas and oxidizing gas in the gas inlet comprises the following: Scheme one: the phase proportion of inert gas and oxidizing gas flow is: one stage 1:0, two stages 50:1, three stages 100:3, and four stages 25:1; or scheme two: the phase proportion of inert gas and oxidizing gas flow is: one stage 1:0, two stages 25:1, three stages 40:3, and four stages 10:1; or scheme three: the phase proportion of inert gas and oxidizing gas flow is: one stage 1:0, two stages 25:2, three stages 20:3, and four stages 5:1; b) preparing large particles in a growth reactor: under the protection of inert gas atmosphere, the growth reactor is added with water to 60-70% of the effective volume of the reactor, and under certain reaction temperature, stirring intensity and inert gas protection atmosphere, the crystal seeds or crystal slurry is introduced, and the ternary metal salt solution, the aqueous complexing agent solution and the aqueous precipitant solution are introduced into the growth reactor for co-precipitation reaction, and the reaction reaches the preset particle size as the reaction endpoint; wherein, the effective volume of the growth reactor in step b) of step (2) is 750-1100 L, the reaction temperature is 55-65℃, the stirring speed is 100-300 r / min, the inert gas flow is 2000-3000 L / h, the reaction system PH is 10.40-10.90, and the reaction preset particle size is 13.50-13.70 μm (3) performing conventional post-treatment to obtain a ternary precursor material with ultra-high nickel and narrow distribution and large specific surface.

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

04.

3. The method according to claim 1, wherein the method is characterized by, The complexing agent prepared in step (1) is an ammonium complexing agent, and the concentration of the aqueous complexing agent solution is 4-9.8 mol / L; the precipitant is one or more of sodium hydroxide, sodium carbonate and sodium bicarbonate, and the concentration of the aqueous precipitant solution is 5-10.8 mol / L.

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

5. The method according to claim 1, wherein the method is characterized by, In step a) of step (2), the inert gas flow is 1000-2000 L / h, and the oxidizing gas flow is 40-80 L / h.

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

7. The method according to claim 1, wherein the method is characterized by, The preset particle size of the seed crystal reaction in step a) in step (2) is 4.90-5.10 μm.

8. The method according to claim 1, wherein the method for preparing the ultra-high nickel narrow distribution large specific surface area ternary precursor by the seed crystal method is characterized in that, The post-treatment in step (3) includes aging, washing, drying, screening, and iron removal of the existing precursor process.

9. A method for preparing a super-high nickel narrow distribution large specific surface area ternary precursor according to any one of claims 1-8, characterized in that, The prepared ternary precursor material has a particle size distribution ((D(90)-D(10)) / D(50)) of not more than 0.40, and a BET of 7-18 m 2 / g.

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