CN110336014B - Preparation method of amorphous nickel-cobalt-manganese ternary precursor - Google Patents

Preparation method of amorphous nickel-cobalt-manganese ternary precursor Download PDF

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CN110336014B
CN110336014B CN201910633063.3A CN201910633063A CN110336014B CN 110336014 B CN110336014 B CN 110336014B CN 201910633063 A CN201910633063 A CN 201910633063A CN 110336014 B CN110336014 B CN 110336014B
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cobalt
nickel
manganese
manganese ternary
reactor
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CN110336014A (en
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代杨
曹玉欣
许兆东
范建贵
雷应权
张琦
华东
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Guizhou Redstar Electronic Materials Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Abstract

The invention provides a preparation method of a nickel-cobalt-manganese ternary precursor, which comprises the following steps: (1) inputting a nickel-cobalt-manganese ternary sulfate solution and a sodium hydroxide solution into a reactor, stirring for reaction, and carrying out solid-liquid separation to obtain a nickel-cobalt-manganese hydroxide; (2) and washing the nickel-cobalt-manganese hydroxide, and drying to obtain the nickel-cobalt-manganese ternary precursor. The median particle size D50 of the nickel-cobalt-manganese ternary precursor prepared by the method is 3-5 mu m, and impurity elements of calcium and magnesium are effectively separated by water washing, so that the content of Ca in the nickel-cobalt-manganese ternary precursor is less than 50ppm, and the content of Mg in the nickel-cobalt-manganese ternary precursor is less than 70 ppm.

Description

Preparation method of amorphous nickel-cobalt-manganese ternary precursor
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a preparation method of an amorphous nickel-cobalt-manganese ternary precursor, and more particularly relates to a preparation method for reversely synthesizing an amorphous nickel-cobalt-manganese ternary lithium battery positive electrode material precursor.
Background
The nickel-cobalt-manganese ternary material gradually becomes the mainstream of the anode material of the lithium ion battery due to the advantages of good safety, high specific capacity, long cycle life and the like. The quality of the nickel-cobalt-manganese ternary precursor is important for the influence of the synthesized nickel-cobalt-manganese ternary cathode material. At present, a plurality of methods for synthesizing the nickel-cobalt-manganese ternary precursor are available, such as a hydrothermal method, a solid phase method, a sol-gel method, a spray drying method, a coprecipitation method and the like. Among them, the coprecipitation method is widely used because of controllability of a crystallization process of a precursor, morphology and size of particles. However, the coprecipitation method has several disadvantages: firstly, ammonia water is used in the reaction process, for example, the method disclosed in the Chinese patent application with the application number of 201710414860.3, or ammonium salt is used as a complexing agent, for example, the method disclosed in the Chinese patent application with the application number of 201710603691.8, the subsequent reaction liquid is difficult to treat, and the problem of serious environmental pollution is caused; secondly, the nickel-cobalt-manganese ternary precursor is formed by growing and stacking for a long time under the action of a complexing agent, so that the particles are spherical, have larger size and have lower reaction activity.
With the rapid development of the new energy automobile industry, the demand of the power lithium battery reaches 125GWh by 2020, and the scrappage reaches 32.2GWh, about 50 ten thousand tons; by 2023, the scrappage amount will reach 101GWh, about 116 ten thousand tons. If the scrapped power lithium battery is not properly disposed, the environment is greatly polluted. The waste power lithium battery has remarkable resource, wherein the potential value of cobalt and lithium is the highest. The recovery of the waste lithium ion battery is not slow.
Disclosure of Invention
The invention aims to provide a preparation method for reversely synthesizing an amorphous nickel-cobalt-manganese ternary lithium battery positive electrode material precursor aiming at the defects of the prior art.
The present invention achieves the above object by the following technical means.
A preparation method of a nickel-cobalt-manganese ternary precursor comprises the following steps:
(1) inputting a nickel-cobalt-manganese ternary sulfate solution and a sodium hydroxide solution into a reactor, stirring for reaction, and carrying out solid-liquid separation to obtain a nickel-cobalt-manganese hydroxide;
(2) and washing the nickel-cobalt-manganese hydroxide, and drying to obtain the nickel-cobalt-manganese ternary precursor.
Further, in the step (1), the nickel-cobalt-manganese ternary sulfate solution is obtained by recovering waste lithium ion batteries.
Further, in the step (1), the concentration of the nickel-cobalt-manganese ternary sulfate solution is 100-200g/L, preferably 150 g/L; the concentration of the sodium hydroxide solution is 150-250g/L, preferably 200 g/L.
Further, in the step (1), the stirring speed is 1800-.
Further, the reaction in step (1) is carried out under a protective atmosphere, preferably, the reaction in step (1) is carried out under a nitrogen protective atmosphere.
Further, in the step (2), the nickel cobalt manganese hydroxide is washed by the following method: pulping the nickel-cobalt-manganese hydroxide by using pure water, washing with water, and then carrying out solid-liquid separation; preferably, the washing temperature is 40-60 ℃ (more preferably 50 ℃), and the washing time is 1-3h (more preferably 2 h); more preferably, the nickel cobalt manganese hydroxide is washed twice.
Further, the preparation method is carried out by adopting an internal spiral microcavity continuous special reactor;
wherein, the reactor is a cylindrical device, and baffles regularly dispersed on the wall of the reactor are arranged at the upper end inside the reactor; the lower end in the reactor is provided with a cavity, a nickel-cobalt-manganese ternary sulfate solution cavity and an alkaline solution cavity, and outlets which are uniformly distributed are respectively arranged at the inner side part of the nickel-cobalt-manganese ternary sulfate solution cavity and the upper part of the alkaline solution cavity; the lower end of the outside of the reactor is respectively provided with an inlet of a nickel-cobalt-manganese ternary sulfate solution and an inlet of an alkaline solution, and the inlets are respectively connected with a flowmeter and a liquid storage tank in sequence; the upper end of the outside of the reactor is provided with a synthetic liquid outlet which is connected with a reaction kettle with a stirrer.
Further, the preparation method comprises the following steps:
(1) simultaneously feeding the nickel-cobalt-manganese ternary sulfate solution and the sodium hydroxide solution into a reactor through a flowmeter at a constant speed, controlling the stirring speed in the reactor at 2000r/min and the temperature at room temperature, when the liquid level in the reactor rises to a synthetic liquid outlet, overflowing the slurry in the reactor into a reaction kettle, and controlling the stirring speed in the reaction kettle at 60 r/min; and after the reaction is finished, stirring for 1h, and carrying out solid-liquid separation to obtain the first nickel-cobalt-manganese hydroxide.
(2) Pulping the first nickel-cobalt-manganese hydroxide by pure water at 50 ℃ and washing with water for 2h to obtain a second nickel-cobalt-manganese hydroxide; pulping the second nickel-cobalt-manganese hydroxide by pure water at 50 ℃ and washing with water for 2h to obtain a third nickel-cobalt-manganese hydroxide; and washing, drying and crushing the third nickel-cobalt-manganese hydroxide.
A nickel-cobalt-manganese ternary precursor is obtained by adopting the preparation method.
Further, the median particle size D of the nickel-cobalt-manganese ternary precursor503-5 μm, Ca content less than 50ppm, Mg less than 70 ppm.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) the synthesis raw material of the precursor is the waste lithium ion battery, the utilization rate of metal elements is improved, the synthesis process is free of ammoniation, and the sustainable development of resource environment is facilitated.
(2) The synthesis of the precursor is that the nickel-cobalt-manganese ternary sulfate solution and the alkali solution instantaneously react at the junction of three cavities, so that the diffusion of Ni, Co and Mn at different pH values is prevented, the distribution of all elements is more uniform, and the median particle size D50 of the prepared nickel-cobalt-manganese ternary precursor is 3-5 mu m.
(3) Impurity elements such as calcium and magnesium are effectively separated through water washing, the Ca content of the prepared nickel-cobalt-manganese ternary precursor is less than 50ppm, and the Mg content is less than 70 ppm.
Drawings
FIG. 1 is a schematic diagram of the front cross-sectional structure of an internal spiral microcavity continuous special reactor adopted in the present invention, wherein, 1-a stirring motor; 2-outlet of synthetic liquid; 3-a valve; 4-baffle plate; 5-a baffle plate; 6-outlet of mixed metal ion solution of nickel salt, manganese salt and cobalt salt; 7-sodium hydroxide solution outlet; 8-an inlet of mixed metal ion solution of nickel salt, manganese salt and cobalt salt; 9-sodium hydroxide solution inlet; 10-a cavity; 11-a mixed metal ion solution chamber of nickel salt, manganese salt and cobalt salt; 12-sodium hydroxide solution chamber.
FIG. 2 is a scanning electron micrograph of the ternary Ni-Co-Mn precursor prepared in example 1.
Detailed Description
The present invention will be described in detail with reference to the following embodiments in order to fully understand the objects, features and effects of the invention. The process of the present invention employs conventional methods or apparatus in the art, except as described below. The following noun terms have meanings commonly understood by those skilled in the art unless otherwise specified.
Aiming at the problems in the prior art, the invention provides a preparation method of a nickel-cobalt-manganese ternary precursor, which comprises the following steps: (1) inputting a nickel-cobalt-manganese ternary sulfate solution and a sodium hydroxide solution into a reactor, stirring for reaction, and carrying out solid-liquid separation to obtain a nickel-cobalt-manganese hydroxide; and (2) washing the nickel-cobalt-manganese hydroxide, and drying to obtain the nickel-cobalt-manganese ternary precursor.
The nickel-cobalt-manganese ternary precursor is NixCoyMn(1-x-y)(OH)2Wherein 0.65 > x > 0.33, 0.33 > y > 0.
Preferably, the nickel-cobalt-manganese ternary sulfate solution adopted by the preparation method is obtained by recycling waste lithium ion batteries, and specifically, the preparation method of the nickel-cobalt-manganese ternary sulfate solution is as follows:
1) weighing a certain mass of waste lithium battery pole pieces, and crushing the waste lithium battery pole pieces;
2) adding strong alkali solution (such as sodium hydroxide solution and potassium hydroxide solution), stirring until no gas is generated, and filtering;
3) pulping the filter residue with low concentration strong alkali solution, washing, and filtering;
4) adding the filter residue into a dilute sulfuric acid solution, and adding hydrogen peroxide while stirring;
5) and filtering to obtain the ternary compound sulfate solution after the reaction is complete.
Various specific conditions and parameters related to the above steps 1) to 5) can be reasonably determined by those skilled in the art in practical operation, and are not described herein again.
Preferably, in the step (1), the concentration of the nickel-cobalt-manganese ternary sulfate solution is 100-200g/L, more preferably 150 g/L; the concentration of the sodium hydroxide solution is 150-250g/L, more preferably 200 g/L.
Preferably, in step (1), the stirring speed is 1800-.
Preferably, the reaction in step (1) is carried out under a protective atmosphere, and preferably, the reaction in step (1) is carried out under a nitrogen protective atmosphere. By using a protective atmosphere, oxidation of manganese during the reaction can be prevented.
Preferably, in step (2), the nickel cobalt manganese hydroxide is washed 2 times. More preferably, the washing is carried out by: the nickel cobalt manganese hydroxide is subjected to water washing at 40 to 60 ℃, more preferably 50 ℃ for 1 to 3 hours, more preferably 2 hours by beating with pure water, followed by solid-liquid separation.
Preferably, the preparation method is carried out by adopting an internal spiral microcavity continuous special reactor; as shown in fig. 1, wherein the reactor is a cylindrical device, a stirring motor 1 is arranged inside, and baffle plates 4 are regularly dispersed on the upper side wall inside; the lower end of the inner part of the shell is provided with a cavity 10, a baffle 5, a mixed metal ion solution cavity 11 of nickel salt, manganese salt and cobalt salt and a sodium hydroxide solution cavity 12, and outlets which are uniformly distributed, namely a mixed metal ion solution outlet 6 of nickel salt, manganese salt and cobalt salt and a sodium hydroxide solution outlet 7, are arranged at the inner side part of the mixed metal ion solution cavity 11 of nickel salt, manganese salt and cobalt salt and the upper part of the sodium hydroxide solution cavity 12; the lower end of the outer part is provided with a mixed metal ion solution inlet 8 of nickel salt, manganese salt and cobalt salt and a sodium hydroxide solution inlet 9 which are respectively provided with a valve 3 and are respectively connected with a flowmeter and a liquid storage tank in sequence; the outer upper end is provided with a synthesis liquid outlet 2 and a valve 3.
The following describes a preferred embodiment of the process of the present invention with reference to the reactor of FIG. 1:
before preparing the nickel-cobalt-manganese ternary precursor, nitrogen is introduced into an alkali liquor storage tank, a nickel-cobalt-manganese ternary sulfate solution storage tank and a reaction kettle, and the aim is to prevent manganese from being oxidized in the reaction process. Before the reaction begins, a stirring motor 1 in the reactor is started, three valves 3 are started, nickel-cobalt-manganese ternary sulfate solution enters a mixed metal ion solution cavity 11 of nickel salt, manganese salt and cobalt salt from a mixed metal ion solution inlet 8 of the nickel salt, the manganese salt and the cobalt salt, and a sodium hydroxide solution inlet 9 enters the sodium hydroxide solution cavity. When the reaction starts, the sodium hydroxide solution in the sodium hydroxide solution cavity 12 is sprayed out from the sodium hydroxide solution outlet 7 at the bottom, the nickel-cobalt-manganese ternary sulfate solution in the nickel-cobalt-manganese mixed metal ion solution cavity 11 is sprayed out from the nickel-manganese mixed metal ion solution outlet 6 at the side, and the baffle 5 enables the nickel-cobalt-manganese ternary sulfate solution and the manganese mixed metal ion solution to be instantly solidified at the joint of the three cavities (namely the nickel-cobalt-manganese ternary sulfate solution cavity, the sodium hydroxide solution cavity and the cavity) to complete the reaction. Along with the reaction, when the liquid level in the reactor rises to the baffling baffle 4, the reaction mixed liquid is baffled and then is continuously stirred; when the liquid level in the reactor rises to the synthesis liquid outlet 2, the slurry overflows into a reaction kettle (not shown in figure 1); after the reaction is finished, stirring is continued for 1h, and then solid-liquid separation, washing, drying and crushing are sequentially carried out.
It should be understood that the preparation method of the present invention may be performed by using other equipment as long as the process conditions of the respective steps are satisfied.
The preparation method provided by the invention utilizes the nickel-cobalt-manganese ternary sulfate solution recovered from the waste lithium ion battery as a reaction raw material, no ammonia water or ammonium salt participates in the reaction, the reaction process is clean and environment-friendly, the reaction is carried out instantly, the synthesis time is short, and the synthesized nickel-cobalt-manganese ternary precursor particles are flaky, large in specific surface area and high in reaction activity. Specifically, the median particle size D of the nickel-cobalt-manganese ternary precursor obtained by the preparation method provided by the invention503-5 μm, Ca content less than 50ppm, Mg less than 70 ppm.
Examples
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. Experimental procedures without specifying specific conditions in the following examples were carried out according to conventional methods and conditions. The raw materials used in the following examples were all conventionally commercially available except for the nickel cobalt manganese sulfate solution.
The nickel cobalt manganese sulfate solutions used in the following examples 1 to 3 were prepared as follows:
1) weighing 500g of waste lithium battery pole pieces, and crushing the waste lithium battery pole pieces;
2) adding a sodium hydroxide solution with the concentration of 5mol/L, stirring until no gas is generated, and filtering;
3) pulping and washing filter residue by using 1mol/L sodium hydroxide solution, and filtering;
4) adding the filter residue into a dilute sulfuric acid solution, and adding hydrogen peroxide while stirring;
5) and filtering to obtain the nickel-cobalt-manganese sulfate solution after the reaction is complete.
Example 1: ni0.5Co0.2Mn0.3(OH)2Preparation of
(1) Reverse coprecipitation: the concentration of the nickel-cobalt-manganese sulfate solution recovered from the waste lithium ion battery is 150g/L, the molar ratio of nickel, cobalt and manganese is 5: 2: 3, and the NaOH solution is 200 g/L. Before the reaction starts, introducing nitrogen into the nickel-cobalt-manganese ternary liquid storage tank, the alkali liquor storage tank and the reaction kettle simultaneously; at the beginning of the reaction, the nickel-cobalt-manganese ternary sulfate solution is 2.7m3H and alkali liquor at 0.9m3Feeding the mixture into a reactor at a constant speed, controlling the stirring speed in the reactor at 2000r/min and the temperature at room temperature, controlling the pH of the synthesized filtrate to be 9.0-9.7, when the liquid level in the reactor reaches an outlet, overflowing the slurry in the reactor into a reaction kettle, and controlling the stirring speed in the reaction kettle to be 60 r/min; after the reaction is finished, stirring the synthetic solution in a reaction kettle for 1 hour, and then carrying out solid-liquid separation to obtain a first nickel-cobalt-manganese hydroxide material.
(2) First water washing: and (2) washing the first nickel-cobalt-manganese hydroxide material obtained in the step (1) with pure water, introducing nitrogen for protection in the washing process, controlling the temperature of the pure water to be 50 ℃, washing for 2 hours, and performing pressure filtration after washing to obtain a second nickel-cobalt-manganese hydroxide material.
(3) And (3) second water washing: and (3) washing the second nickel-cobalt-manganese hydroxide material obtained in the step (2) with pure water, introducing nitrogen for protection in the washing process, controlling the temperature of the pure water to be 50 ℃, washing for 2 hours, and performing pressure filtration after washing to obtain a third nickel-cobalt-manganese hydroxide material.
(4) Drying and crushing: and (4) drying and crushing the third nickel-cobalt-manganese hydroxide material obtained in the step (3), wherein the drying temperature is 110 ℃, the drying time is 12 hours, and the precursor for the nickel-cobalt-manganese ternary cathode material is obtained after crushing.
The nickel-cobalt-manganese ternary precursor prepared in example 1 is detected to obtain: d10＝0.70μm，D50＝3.05μm，D9018.45 μm, Ca content 40ppm, Mg content 38ppm, Na content 173 ppm; the scanning Electron microscope is shown in FIG. 2The nickel-cobalt-manganese ternary precursor particles are shown to be flaky.
Example 2: ni0.6sCo0.05Mn0.3(OH)2Preparation of
(1) Reverse coprecipitation: the concentration of the nickel-cobalt-manganese sulfate solution recovered from the waste lithium ion battery is 150g/L, the molar ratio of nickel, cobalt and manganese is 6.5: 0.5: 3, and the NaOH solution is 100 g/L. Before the reaction starts, introducing nitrogen into the nickel-cobalt-manganese ternary liquid storage tank, the alkali liquor storage tank and the reaction kettle simultaneously; at the beginning of the reaction, the nickel-cobalt-manganese ternary sulfate solution is 2.7m3H and alkali liquor at 0.9m3The slurry enters a reactor at a constant speed, the stirring speed in the reactor is controlled to 2200r/min, the temperature is room temperature, the pH of the synthetic filtrate is controlled to 9.0-9.7, when the liquid level in the reactor reaches an outlet, the slurry in the reactor overflows into a reaction kettle, and the stirring speed in the reaction kettle is controlled to 60 r/min; after the reaction is finished, stirring the synthetic solution in a reaction kettle for 1 hour, and then carrying out solid-liquid separation to obtain a first nickel-cobalt-manganese hydroxide material.
(2) First water washing: and (2) washing the first nickel-cobalt-manganese hydroxide material obtained in the step (1) with pure water, introducing nitrogen for protection in the washing process, controlling the temperature of the pure water to be 50 ℃, washing for 2 hours, and performing pressure filtration after washing to obtain a second nickel-cobalt-manganese hydroxide material.
(3) And (3) second water washing: and (3) washing the second nickel-cobalt-manganese hydroxide material obtained in the step (2) with pure water, introducing nitrogen for protection in the washing process, controlling the temperature of the pure water to be 50 ℃, washing for 2 hours, and performing pressure filtration after washing to obtain a third nickel-cobalt-manganese hydroxide material.
(4) Drying and crushing: and (4) drying and crushing the third nickel-cobalt-manganese hydroxide material obtained in the step (3), wherein the drying temperature is 110 ℃, the drying time is 12 hours, and the precursor for the nickel-cobalt-manganese ternary cathode material is obtained after crushing.
The nickel-cobalt-manganese ternary precursor prepared in example 2 is detected to obtain: d10＝1.02μm，D50＝4.41μm，D9018.01. mu.m, 35ppm of Ca, 52ppm of Mg and 166ppm of Na.
Example 3: ni0.3Co0.3Mn0.4(OH)2Preparation of
(1) Reverse coprecipitation: the concentration of the nickel-cobalt-manganese sulfate solution recovered from the waste lithium ion battery is 150g/L, the molar ratio of nickel, cobalt and manganese is 3: 4, and the NaOH solution is 150 g/L. Before the reaction starts, introducing nitrogen into the nickel-cobalt-manganese ternary liquid storage tank, the alkali liquor storage tank and the reaction kettle simultaneously; at the beginning of the reaction, the nickel-cobalt-manganese ternary sulfate solution is 2.7m3H and alkali liquor at 0.9m3The slurry enters a reactor at a constant speed, the stirring speed in the reactor is controlled to 2200r/min, the temperature is room temperature, the pH of the synthetic filtrate is controlled to 9.0-9.7, when the liquid level in the reactor reaches an outlet, the slurry in the reactor overflows into a reaction kettle, and the stirring speed in the reaction kettle is controlled to 60 r/min; after the reaction is finished, stirring the synthetic solution in a reaction kettle for 1 hour, and then carrying out solid-liquid separation to obtain a first nickel-cobalt-manganese hydroxide material.
(2) First water washing: and (2) washing the first nickel-cobalt-manganese hydroxide material obtained in the step (1) with pure water, introducing nitrogen for protection in the washing process, controlling the temperature of the pure water to be 50 ℃, washing for 2 hours, and performing pressure filtration after washing to obtain a second nickel-cobalt-manganese hydroxide material.
(3) And (3) second water washing: and (3) washing the second nickel-cobalt-manganese hydroxide material obtained in the step (2) with pure water, introducing nitrogen for protection in the washing process, controlling the temperature of the pure water to be 50 ℃, washing for 2 hours, and performing pressure filtration after washing to obtain a third nickel-cobalt-manganese hydroxide material.
(4) Drying and crushing: and (4) drying and crushing the third nickel-cobalt-manganese hydroxide material obtained in the step (3), wherein the drying temperature is 110 ℃, the drying time is 12 hours, and the precursor for the nickel-cobalt-manganese ternary cathode material is obtained after crushing.
The nickel-cobalt-manganese ternary precursor prepared in example 3 is detected to obtain: d10＝0.96μm，D50＝3.67μm，D9017.95 μm, a Ca content of 37ppm, a Mg content of 51ppm and a Na content of 147 ppm.
It can be seen from the product performance data of the above examples 1 to 3 that the nickel-cobalt-manganese ternary precursor prepared by the method of the present invention has the advantages of uniform distribution of each element, low content of calcium and magnesium impurities, and excellent product performance.

Claims (8)

1. A preparation method of a nickel-cobalt-manganese ternary precursor is characterized by comprising the following steps:
(1) simultaneously feeding the nickel-cobalt-manganese ternary sulfate solution and the sodium hydroxide solution into a reactor through a flowmeter at a constant speed, controlling the stirring speed in the reactor at 2000r/min and the temperature at room temperature, when the liquid level in the reactor rises to a synthetic liquid outlet, overflowing the slurry in the reactor into a reaction kettle, and controlling the stirring speed in the reaction kettle at 60 r/min; after the reaction is finished, stirring for 1h, and then carrying out solid-liquid separation to obtain a first nickel-cobalt-manganese hydroxide;
(2) pulping the first nickel-cobalt-manganese hydroxide by pure water at 50 ℃ and washing with water for 2h to obtain a second nickel-cobalt-manganese hydroxide; pulping the second nickel-cobalt-manganese hydroxide by pure water at 50 ℃ and washing with water for 2h to obtain a third nickel-cobalt-manganese hydroxide; washing, drying and crushing the third nickel-cobalt-manganese hydroxide;
the preparation method is carried out in an internal spiral microcavity continuous special reactor; wherein, the reactor is a cylindrical device, and baffles regularly dispersed on the wall of the reactor are arranged at the upper end inside the reactor; the lower end in the reactor is provided with a cavity, a nickel-cobalt-manganese ternary sulfate solution cavity and an alkaline solution cavity, and outlets which are uniformly distributed are respectively arranged at the inner side part of the nickel-cobalt-manganese ternary sulfate solution cavity and the upper part of the alkaline solution cavity; the lower end of the outside of the reactor is respectively provided with an inlet of a nickel-cobalt-manganese ternary sulfate solution and an inlet of an alkaline solution, and the inlets are respectively connected with a flowmeter and a liquid storage tank in sequence; the upper end of the outside of the reactor is provided with a synthetic liquid outlet which is connected with a reaction kettle with a stirrer;
when the reaction starts, the sodium hydroxide solution in the alkali solution cavity is sprayed out from an outlet arranged at the upper part of the alkali solution cavity, the nickel-cobalt-manganese ternary sulfate solution in the nickel-cobalt-manganese ternary sulfate solution cavity is sprayed out from an outlet arranged at the inner side part of the nickel-cobalt-manganese ternary sulfate solution cavity, and the baffle arranged at the upper end inside the reactor enables the nickel-cobalt-manganese ternary sulfate solution cavity and the alkali solution cavity to be instantly solidified at the joint of the nickel-cobalt-manganese ternary sulfate solution cavity, the alkali solution cavity and the cavity to complete.
2. The preparation method according to claim 1, wherein in the step (1), the nickel-cobalt-manganese ternary sulfate solution is obtained by recycling waste lithium ion batteries.
3. The method as claimed in claim 1, wherein in the step (1), the concentration of the Ni-Co-Mn ternary sulfate solution is 100-200 g/L; the concentration of the sodium hydroxide solution was 150-250 g/L.
4. The method according to claim 3, wherein in the step (1), the concentration of the nickel cobalt manganese ternary sulfate solution is 150 g/L; the concentration of the sodium hydroxide solution was 200 g/L.
5. The method according to claim 1, wherein the reaction in step (1) is carried out under a protective atmosphere.
6. The method according to claim 5, wherein the reaction in step (1) is carried out under a nitrogen atmosphere.
7. A nickel-cobalt-manganese ternary precursor, which is characterized by being obtained by the preparation method of any one of claims 1 to 6.
8. The nickel cobalt manganese ternary precursor of claim 7, wherein the nickel cobalt manganese ternary precursor has a median particle size D503 to 5 μm, Ca content<50ppm，Mg<70ppm。
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