CN111196613A - Preparation method of high-sphericity ternary precursor seed crystal and method for preparing high-sphericity ternary precursor by using seed crystal - Google Patents

Preparation method of high-sphericity ternary precursor seed crystal and method for preparing high-sphericity ternary precursor by using seed crystal Download PDF

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CN111196613A
CN111196613A CN202010109284.3A CN202010109284A CN111196613A CN 111196613 A CN111196613 A CN 111196613A CN 202010109284 A CN202010109284 A CN 202010109284A CN 111196613 A CN111196613 A CN 111196613A
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seed crystal
sphericity
reaction kettle
valve
ternary precursor
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CN111196613B (en
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王娟
邱天
王宏刚
高炯信
向波
周勤俭
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Huayou New Energy Technology Quzhou Co ltd
Zhejiang Huayou Cobalt Co Ltd
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Huayou New Energy Technology Quzhou Co ltd
Zhejiang Huayou Cobalt Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • 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

Abstract

The invention relates to a preparation method of a high-sphericity ternary precursor seed crystal and a method for preparing a high-sphericity ternary precursor by using the seed crystal, wherein the preparation method of the high-sphericity ternary precursor seed crystal can be used for preparing the seed crystal with better sphericity, realizing continuous production, continuously providing the high-sphericity seed crystal for the production precursor, storing the prepared high-sphericity seed crystal to be used as the seed crystal for the next production of the high-sphericity precursor, and processing the high-sphericity seed crystal to be independently used as a precursor with small particle size; a method for preparing a high-sphericity ternary precursor by using a seed crystal comprises the steps of introducing the produced high-sphericity seed crystal, controlling reaction conditions, and gradually growing the seed crystal to obtain the high-sphericity precursor with the required particle size, so that the production period is shortened.

Description

Preparation method of high-sphericity ternary precursor seed crystal and method for preparing high-sphericity ternary precursor by using seed crystal
Technical Field
The invention belongs to the technical field of precursors of ternary cathode materials of lithium ion batteries, and particularly relates to a preparation method of a high-sphericity ternary precursor seed crystal and a method for preparing a high-sphericity ternary precursor by using the seed crystal.
Background
As a novel green power source, the lithium ion battery is widely applied to the fields of 3C digital electronic products, electric tools, electric vehicles, energy storage and the like. The ternary cathode material is a hot spot of competitive development of various large enterprises at present, and the ternary precursor has a crucial influence on the performance of the cathode material.
Sphericity is one of the key dimensions for evaluating the precursor. The high sphericity can improve the tap density, rate capability, cycle performance and the like of the anode material. Therefore, how to improve the sphericity of the precursor is an important technology. According to the current precursor synthesis technology, when the particle size is larger than 4 μm, higher sphericity can be obtained easily. On the contrary, when the particle size is less than 4 μm, the sphericity of the particles is poor.
Chinese patent CN108946827A discloses a nickel-cobalt-manganese hydroxide with ultra-small particle size and a preparation method thereof, wherein an organic complexing agent without ammonia is adopted to synthesize ultra-small particles with the particle size of less than 2 mu m, and the ultra-small particles have high sphericity and dispersibility. Although the method is green and environment-friendly, and can synthesize small-particle products with high sphericity and dispersity, complete system switching exists, and the method is not compatible with the current mainstream industrialized wastewater treatment process, so that the popularization and development of the method have a long way.
Chinese patent CN104201367B discloses a high-density small-particle-size nickel-cobalt-manganese hydroxide and a preparation method thereof, wherein a complex control crystallization coprecipitation method is adopted, and a nickel-cobalt-manganese soluble salt aqueous solution and a sodium hydroxide aqueous solution are subjected to coprecipitation reaction under the complexation of ammonia through the special process flow of nucleation, growth and continuous particle friction and collision under the continuously improved solid-liquid ratio to obtain a small-particle-size nickel-cobalt-manganese hydroxide precipitate with uniform element distribution, good sphericity, uniform particle size distribution and high tap density. The method has agglomeration phenomenon when preparing the precursor with small particle size, and although the sphericity is improved, the method still cannot meet the requirement of downstream customers on high sphericity.
In the chinese patent CN107640792A and the chinese patent CN103253717B, the mother solution with the pH adjusted and the content of the complexing agent is used as the base solution, so that small particles with good dispersibility are synthesized, although the sphericity is greatly improved, the aggregation phenomenon still occurs significantly, and the aggregation at the initial stage of the reaction is more serious.
Chinese patent CN110040790A discloses a high sphericity nickel-cobalt-manganese ternary precursor and a preparation method thereof, wherein the collision frequency and the collision frequency of a nickel-cobalt-manganese ternary precursor product in the growth process are increased by adding hard microspheres and under the action of strong stirring, so that a small-particle nickel-cobalt-manganese ternary precursor is formed with higher sphericity within a shorter growth time, and after the reaction is finished, natural sedimentation is utilized to separate hard microsphere turbid liquid from slurry, so that the high sphericity nickel-cobalt-manganese ternary precursor is obtained. The method is an intermittent reaction, cannot realize continuous production, needs to periodically stop the reaction and separate the seed crystal from the particles, and has low production efficiency, and the growth period is very short when preparing the precursor with small particle size, so that the production practicability is low.
Because the update iteration speed of the lithium battery industry is extremely high, the ternary precursor material does not have the value-keeping function, and manufacturers cannot stock too many ternary precursor materials, so that the stock usually means loss.
However, when the customer demands the product urgently, the production cycle of the product is long, and it is difficult to obtain the required product in a short time, so that the product cannot be delivered on time, or the product is replaced by a new product after being produced, and the product value is greatly reduced.
Disclosure of Invention
One of the purposes of the invention is to provide a preparation method of a high-sphericity ternary precursor seed crystal, which can prepare a seed crystal with better sphericity, realize continuous production, continuously provide the high-sphericity seed crystal for a precursor for production, store the prepared high-sphericity seed crystal and use the seed crystal as the seed crystal for the next high-sphericity precursor for production, and process the seed crystal and use the seed crystal as a precursor with small particle size;
the second purpose of the invention is to provide a method for preparing a high-sphericity ternary precursor by using a seed crystal, which comprises the steps of introducing the produced high-sphericity seed crystal, controlling reaction conditions, and gradually growing up the seed crystal so as to obtain the high-sphericity precursor meeting the required particle size, thereby greatly shortening the production period and enabling the product to quickly follow the development and use progress of downstream users.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of a high-sphericity ternary precursor seed crystal, which comprises a seed crystal reaction kettle, a microporous filter tube, a peristaltic pump, a concentrator and a seed crystal collecting tank which are connected in sequence; the micropore filter pipe is arranged in the seed crystal reaction kettle and penetrates through the kettle wall of the seed crystal reaction kettle to be connected with an inlet of a peristaltic pump through a pipeline, an outlet of the peristaltic pump is connected with an inlet of a thickener, and an outlet of the thickener is connected with the top of a seed crystal collecting tank; a stirrer, a feeding pipe, a nitrogen guide pipe and a liquid level meter are arranged in the seed crystal reaction kettle; the stirrer extends into the bottom of the reaction kettle from the top of the center of the seed crystal reaction kettle; one end of the feeding pipe is connected with the upstream batching process, and the other end of the feeding pipe extends into the bottom of the seed crystal reaction kettle through the top of the seed crystal reaction kettle; one end of the nitrogen conduit is connected with the nitrogen header pipe, and the other end of the nitrogen conduit extends into the bottom of the seed crystal reaction kettle through the top of the seed crystal reaction kettle; the liquid level meter extends from the top of the seed crystal reaction kettle to the bottom of the seed crystal reaction kettle; the method comprises the following steps:
step 1, according to the mole ratio of nickel, cobalt and manganese in the required high-sphericity ternary precursor seed crystal, selecting soluble salts of nickel, cobalt and manganese as raw materials and preparing a mixed salt solution with the total metal ion concentration of 1.0-2.5 mol/L with pure water;
step 2, preparing a sodium hydroxide solution with the concentration of 4.0 mol/L-11.0 mol/L;
step 3, preparing ammonia water with the concentration of 6.0 mol/L-12.0 mol/L as a complexing agent;
step 4, opening a jacket of the seed crystal reaction kettle for water inlet and water return, introducing nitrogen into the seed crystal reaction kettle for atmosphere protection, and keeping nitrogen protection in the whole reaction process;
step 5, adding pure water into the seed crystal reaction kettle until the pure water overflows the bottom layer stirring paddle, and adding a certain amount of the sodium hydroxide solution prepared in the step 2 and the ammonia water prepared in the step 3 to form a bottom solution for starting up the reaction;
step 6, adding a certain amount of solid insoluble in the base solution into the base solution, wherein the diameter of the solid insoluble in the base solution is always larger than the diameter of a filter hole of the microporous filter tube, adjusting the solid content to be 80-1000 g/L, and increasing the solid content in the base solution to ensure that small seed crystals generated by reaction are difficult to aggregate under the dispersion action of solid particles, so that the agglomeration phenomenon of the small seed crystals is avoided, each small seed crystal can grow independently, and the seed crystals continuously collide with the solid particles in the growth process under the action of strong stirring to ensure that the seed crystals are formed in a shorter growth time and have higher sphericity;
step 7, starting stirring, adding the prepared mixed salt solution, sodium hydroxide solution and ammonia water solution into a seed crystal reaction kettle in a parallel flow manner for reaction, and controlling the pH value to be 11.00-12.30, the ammonia value to be 0.5-10.0 g/L and the temperature to be 45-70 ℃;
step 8, continuously feeding materials into the seed crystal reaction kettle according to the step 7, after the materials submerge 500-1000 mm of the microporous filter pipe, opening a valve V1 and a valve V2, opening a peristaltic pump to extract slurry, simultaneously starting a concentrator to concentrate the materials, enabling the concentrated materials to enter a seed crystal collecting tank, and enabling mother liquor to enter a mother liquor water treatment process; controlling the flow of the peristaltic pump to be interlocked with the liquid level of the seed crystal reaction kettle, and maintaining the liquid level of the seed crystal reaction kettle within 500-1000 mm of the liquid level of the seed crystal reaction kettle, until the feeding is finished;
and 9, after the feeding is finished, closing the valve V1, the valve V2, the peristaltic pump and the thickener in sequence, wherein the material in the seed crystal collecting tank is the obtained high-sphericity ternary precursor seed crystal.
The preparation method of the high sphericity ternary precursor seed crystal comprises the step of selecting the microporous filter pipe with the filtering hole diameter of 1.0-5.0 mu m according to the size of the required seed crystal particle diameter by using the microporous filter pipe as a detachable filter pipe.
In the preparation method of the high sphericity ternary precursor seed crystal, in the step 1, the soluble salt of nickel, cobalt and manganese is one or more of chloride, nitrate, sulfate and acetate.
In the step 5, the pH value of the base solution is 11.0-12.3, and the ammonia concentration is 0.5-15.0 g/L.
In the preparation method of the high-sphericity ternary precursor seed crystal, in the step 6, the solid insoluble in the base solution includes, but is not limited to, hydroxide microspheres, zirconium microspheres, polystyrene microspheres, titanium nitride microspheres, boron nitride microspheres, and tungsten nitride microspheres.
According to the preparation method of the high-sphericity ternary precursor seed crystal, the diameter of a solid insoluble in a base solution is 3.0-300 microns.
In the preparation method of the high-sphericity ternary precursor seed crystal, the outlet of the microporous filter tube is connected with a nitrogen storage tank with the pressure of 0.20-0.30 MPa through a valve V3; valve V3 is interlocked with peristaltic pump flow, valve V1 and valve V2, when valve V1 and valve V2 are fully opened, the peristaltic pump flow becomes small, valve V1 and valve V2 are immediately closed, valve V3 is opened for 0.5-1 s, the microporous filter pipe is subjected to back flushing, and after the back flushing is finished, valve V3 is closed, valve V1 and valve V2 are opened, so that the liquid level in the kettle can be stabilized, and the blockage of the microporous filter pipe can be avoided.
The sphericity index phi of the high-sphericity ternary precursor seed crystal prepared by the method is 1.0-1.6, wherein phi = Di/Dc, Di is the maximum inscribed sphere radius of a particle, and Dc is the minimum inscribed sphere radius of the same particle.
The invention provides a method for preparing a high-sphericity ternary precursor by using a seed crystal, which comprises the following steps:
step 1, according to the mole ratio of nickel, cobalt and manganese in the required high-sphericity ternary precursor, selecting soluble salts of nickel, cobalt and manganese as raw materials and pure water to prepare a mixed salt solution with the total metal ion concentration of 1.0-2.5 mol/L;
step 2, preparing a sodium hydroxide solution with the concentration of 4.0 mol/L-11.0 mol/L;
step 3, preparing ammonia water with the concentration of 6.0 mol/L-12.0 mol/L as a complexing agent;
step 4, opening a jacket of the precursor reaction kettle for water inlet and water return, introducing nitrogen into the precursor reaction kettle for atmosphere protection, and keeping nitrogen protection in the whole reaction process;
step 5, adding pure water into the precursor reaction kettle until the pure water overflows a bottom stirring paddle, and then adding a certain amount of the sodium hydroxide solution prepared in the step 2 and the ammonia water prepared in the step 3 to form a reaction starting bottom liquid with the pH value of 10.50-12.00, the ammonia value of 0.5-15.0 g/L and the temperature of 45-70 ℃;
step 6, adding the high-sphericity ternary precursor seed crystal prepared in the step into the base solution according to the required material amount;
step 7, starting stirring, adding the prepared mixed salt solution, sodium hydroxide solution and ammonia water solution into a precursor reaction kettle in a parallel flow manner for reaction, and controlling the pH value to be 10.50-12.00, the ammonia value to be 0.5-15.0 g/L and the temperature to be 45-70 ℃;
step 8, stopping feeding when the D50 of the materials in the reaction kettle is detected to reach 3.0-20.0 microns, and continuing stirring and aging for 1-2 hours;
and 9, adding the slurry aged in the step 8 into filter pressing washing equipment, washing and filter pressing the slurry, and sending the slurry to a drying process, and after drying is finished, sequentially sieving and demagnetizing the slurry to obtain the high-sphericity ternary precursor.
According to the method for preparing the high-sphericity ternary precursor by using the seed crystal, the sphericity index phi of the prepared high-sphericity ternary precursor is 1.0-1.6, wherein phi = Di/Dc, Di is the maximum inscribed sphere radius of a particle, and Dc is the minimum inscribed sphere radius of the same particle.
The invention has the beneficial effects that: a method for preparing high sphericity ternary precursor seed crystal includes adding solid particles insoluble in base liquid to synthetic base liquid, raising solid content in base liquid, making small seed crystal generated by reaction difficult to aggregate under dispersion action of solid particles, avoiding aggregation of small seed crystal, making each small seed crystal independently grow, making seed crystal continuously collide with solid particles in growth process under action of strong stirring to make seed crystal form higher sphericity in shorter growth time, regulating pH value and ammonia value range to make seed crystal continuously generate small particle seed crystal in synthetic process, extracting slurry through microporous filter tube of small particle seed crystal to separate out small particle seed crystal in required size in reaction kettle, obtaining high sphericity ternary precursor seed crystal and realizing continuous production, the production efficiency is improved; the prepared high sphericity seed crystal can be stored and used as the seed crystal for producing a high sphericity small/medium/large particle size precursor in the next step, and can also be processed and independently used as a small particle size precursor; a method for preparing high sphericity ternary precursor by using crystal seed includes such steps as introducing the high sphericity crystal seed, controlling reaction condition to make the crystal seed grow up gradually to obtain high sphericity precursor with needed grain size, greatly shortening production period, high productivity, ensuring on-time delivery of product and avoiding the loss of product value. The two methods can be widely applied to the production process of the nickel-cobalt-manganese hydroxide, and are particularly suitable for the preparation process of the high-sphericity ternary precursor seed crystal and the process for preparing the high-sphericity ternary precursor by using the seed crystal.
Drawings
FIG. 1 is a process flow diagram of a method for preparing a high sphericity ternary precursor seed crystal according to the present invention;
FIG. 2 is a FESEM image of a high sphericity ternary precursor seed crystal prepared in example 1;
FIG. 3 is a FESEM image of a high sphericity ternary precursor seed crystal prepared in example 2;
FIG. 4 is a FESEM image of a high sphericity ternary precursor seed crystal prepared in example 3;
in FIG. 1, 1 is a microporous filter tube, 2 is a seed reaction vessel, 3 is a liquid level meter, 4 is a feed pipe, 5 is a nitrogen conduit, 6 is a valve V3, 7 is a seed collection tank, 8 is a thickener, 9 is a peristaltic pump, 10 is a valve V2, 11 is a valve V1, and 12 is a stirrer.
Detailed Description
The following examples are presented to enable those skilled in the art to more fully understand the present invention and are not intended to limit the invention in any way.
Example 1
Has a chemical formula of Ni0.8Co0.1Mn0.1(OH)2The preparation method of the high-sphericity ternary precursor seed crystal with the particle size of less than 2.5 mu m comprises the following steps:
step 1, preparing a mixed salt solution with the total metal ion concentration of 2.0mol/L by using nickel, cobalt and manganese sulfates as raw materials and pure water according to the molar ratio of nickel, cobalt and manganese in the required high-sphericity ternary precursor seed crystal of 8:1: 1;
step 2, preparing a sodium hydroxide solution with the concentration of 6.0 mol/L;
step 3, preparing ammonia water with the concentration of 10.0mol/L as a complexing agent;
step 4, opening a jacket of the seed crystal reaction kettle for water inlet and water return, introducing nitrogen into the seed crystal reaction kettle for atmosphere protection, and keeping nitrogen protection in the whole reaction process;
step 5, adding pure water into the seed crystal reaction kettle until the pure water overflows a bottom stirring paddle, and then adding a certain amount of the sodium hydroxide solution prepared in the step 2 and the ammonia water prepared in the step 3 to form a base solution which has the pH value of 11.80 +/-0.05, the ammonia value of 3.0 +/-0.5 g/L and the temperature of 55 +/-0.2 ℃ and is started up in a reaction manner;
step 6, adding NCM811 hydroxide with the particle size of 7 mu m into the base solution, and adjusting the solid content to 400 g/L;
step 7, starting stirring, adding the prepared mixed salt solution, sodium hydroxide solution and ammonia water solution into a seed crystal reaction kettle in a parallel flow manner for reaction, and controlling the pH value to be 11.00-12.30, the ammonia value to be 0.5-10.0 g/L and the temperature to be 45-70 ℃;
step 8, continuously feeding materials into the seed crystal reaction kettle according to the step 7, after the materials submerge 500-1000 mm of the microporous filter pipe, opening a valve V1 and a valve V2, opening a peristaltic pump to extract slurry, simultaneously starting a concentrator to concentrate the materials, enabling the concentrated materials to enter a seed crystal collecting tank, and enabling mother liquor to enter a mother liquor water treatment process; controlling the flow of the peristaltic pump to be interlocked with the liquid level of the seed crystal reaction kettle, and maintaining the liquid level of the seed crystal reaction kettle within 500-1000 mm of the liquid level of the seed crystal reaction kettle, until the feeding is finished;
and 9, after the feeding is finished, closing the valve V1, the valve V2, the peristaltic pump and the concentrator in sequence, wherein the material in the seed crystal collecting tank is the obtained material with the chemical formula of Ni0.8Co0.1Mn0.1(OH)2And the high sphericity ternary precursor seed crystal with the grain diameter less than 2.5 microns.
The preparation method of the high sphericity ternary precursor seed crystal is characterized in that the microporous filter tube is a detachable filter tube, and the microporous filter tube with the filtering hole diameter of 2.5 mu m is selected according to the grain size of the required seed crystal.
In the preparation method of the high-sphericity ternary precursor seed crystal, the outlet of the microporous filter tube is connected with a nitrogen storage tank with the pressure of 0.20-0.30 MPa through a valve V3; and the valve V3 is interlocked with the flow rate of the peristaltic pump, the valve V1 and the valve V2, when the flow rate of the peristaltic pump is reduced when the valve V1 and the valve V2 are fully opened, the valve V1 and the valve V2 are immediately closed, the valve V3 is opened for 0.5-1 s continuously, the microporous filter pipe is subjected to back flushing, the valve V3 is closed after the back flushing is finished, and the valve V1 and the valve V2 are opened.
The sphericity index phi of the high-sphericity ternary precursor seed crystal prepared by the method is 1.0-1.6, wherein phi = Di/Dc, Di is the maximum inscribed sphere radius of a particle, and Dc is the minimum inscribed sphere radius of the same particle.
Has a chemical formula of Ni0.8Co0.1Mn0.1(OH)2D50=8.9 μm method for preparing a high sphericity ternary precursor comprising the steps of:
step 1, preparing a mixed salt solution with the total metal ion concentration of 2.0mol/L by using nickel, cobalt and manganese sulfates as raw materials and pure water according to the molar ratio of nickel, cobalt and manganese in the required high-sphericity ternary precursor seed crystal of 8:1: 1;
step 2, preparing a sodium hydroxide solution with the concentration of 6.0 mol/L;
step 3, preparing ammonia water with the concentration of 10.0mol/L as a complexing agent;
step 4, opening a jacket of the seed crystal reaction kettle for water inlet and water return, introducing nitrogen into the seed crystal reaction kettle for atmosphere protection, and keeping nitrogen protection in the whole reaction process;
step 5, adding pure water into the seed crystal reaction kettle until the pure water overflows a bottom stirring paddle, and then adding a certain amount of the sodium hydroxide solution prepared in the step 2 and the ammonia water prepared in the step 3 to form a base solution which has the pH value of 11.30 +/-0.05, the ammonia value of 9.0 +/-0.5 g/L and the temperature of 55 +/-0.2 ℃ and is started up in a reaction manner;
step 6, adding the high-sphericity ternary precursor seed crystal prepared in the step into the base solution according to the required material amount;
step 7, starting stirring, adding the prepared mixed salt solution, sodium hydroxide solution and ammonia water solution into a precursor reaction kettle in a parallel flow manner for reaction, and controlling the pH value to be 11.30 +/-0.05, the ammonia value to be 9.0 +/-0.5 g/L and the temperature to be 55 +/-0.2 ℃;
step 8, stopping feeding when the D50 of the materials in the reaction kettle is detected to reach 8.9 microns, and continuing stirring and aging for 1-2 hours;
step 9, adding the slurry aged in the step 8 into filter pressing washing equipment for washing and filter pressing, and then sending the slurry to a drying process, and after the drying is finished, sequentially carrying out sieving and demagnetizing to obtain the slurry with the chemical formula of Ni0.8Co0.1Mn0.1(OH)2D50=8.9 μm high sphericity ternary precursor.
The sphericity index phi of the prepared high-sphericity ternary precursor is 1.0-1.6, wherein phi = Di/Dc, Di is the maximum inscribed sphere radius of the particles, and Dc is the minimum inscribed sphere radius of the same particles.
Example 2
Has a chemical formula of Ni0.6Co0.2Mn0.2(OH)2High sphericity ternary precursor seed crystal with grain size less than 1.6 micronThe preparation method comprises the following steps:
step 1, preparing a mixed salt solution with the total metal ion concentration of 2.0mol/L by using nickel, cobalt and manganese sulfates as raw materials and pure water according to the molar ratio of nickel, cobalt and manganese in the required high-sphericity ternary precursor seed crystal of 6:2: 2;
step 2, preparing a sodium hydroxide solution with the concentration of 10.0 mol/L;
step 3, preparing ammonia water with the concentration of 10.0mol/L as a complexing agent;
step 4, opening a jacket of the seed crystal reaction kettle for water inlet and water return, introducing nitrogen into the seed crystal reaction kettle for atmosphere protection, and keeping nitrogen protection in the whole reaction process;
step 5, adding pure water into the seed crystal reaction kettle until the pure water overflows a bottom stirring paddle, and then adding a certain amount of the sodium hydroxide solution prepared in the step 2 and the ammonia water prepared in the step 3 to form a base solution which has the pH value of 11.30 +/-0.05, the ammonia value of 2.0 +/-0.5 g/L and the temperature of 50 +/-0.2 ℃ and is started up in a reaction manner;
step 6, adding polystyrene microspheres with the particle size of 10 microns into the base solution, and adjusting the solid content to 600 g/L;
step 7, starting stirring, adding the prepared mixed salt solution, sodium hydroxide solution and ammonia water solution into a seed crystal reaction kettle in a parallel flow manner for reaction, and controlling the pH value to be 11.30 +/-0.05, the ammonia value to be 2.0 +/-0.5 g/L and the temperature to be 50 +/-0.2 ℃;
step 8, continuously feeding materials into the seed crystal reaction kettle according to the step 7, after the materials submerge 500-1000 mm of the microporous filter pipe, opening a valve V1 and a valve V2, opening a peristaltic pump to extract slurry, simultaneously starting a concentrator to concentrate the materials, enabling the concentrated materials to enter a seed crystal collecting tank, and enabling mother liquor to enter a mother liquor water treatment process; controlling the flow of the peristaltic pump to be interlocked with the liquid level of the seed crystal reaction kettle, and maintaining the liquid level of the seed crystal reaction kettle within 500-1000 mm of the liquid level of the seed crystal reaction kettle, until the feeding is finished;
and 9, after the feeding is finished, closing the valve V1, the valve V2, the peristaltic pump and the concentrator in sequence, wherein the material in the seed crystal collecting tank is the obtained material with the chemical formula of Ni0.6Co0.2Mn0.2(OH)2High sphericity of less than 1.6 μmAnd (4) ternary precursor seed crystal.
The preparation method of the high sphericity ternary precursor seed crystal is characterized in that the microporous filter tube is a detachable filter tube, and the microporous filter tube with the filtering hole diameter of 1.6 mu m is selected according to the grain size of the required seed crystal.
In the preparation method of the high-sphericity ternary precursor seed crystal, the outlet of the microporous filter tube is connected with a nitrogen storage tank with the pressure of 0.20-0.30 MPa through a valve V3; and the valve V3 is interlocked with the flow rate of the peristaltic pump, the valve V1 and the valve V2, when the flow rate of the peristaltic pump is reduced when the valve V1 and the valve V2 are fully opened, the valve V1 and the valve V2 are immediately closed, the valve V3 is opened for 0.5-1 s continuously, the microporous filter pipe is subjected to back flushing, the valve V3 is closed after the back flushing is finished, and the valve V1 and the valve V2 are opened.
The sphericity index phi of the high-sphericity ternary precursor seed crystal prepared by the method is 1.0-1.6, wherein phi = Di/Dc, Di is the maximum inscribed sphere radius of a particle, and Dc is the minimum inscribed sphere radius of the same particle.
Has a chemical formula of Ni0.6Co0.2Mn0.2(OH)2D50=2.6 μm method for preparing a high sphericity ternary precursor, comprising the steps of:
step 1, preparing a mixed salt solution with the total metal ion concentration of 2.0mol/L by using nickel, cobalt and manganese sulfates as raw materials and pure water according to the molar ratio of nickel, cobalt and manganese in the required high-sphericity ternary precursor seed crystal of 8:1: 1;
step 2, preparing a sodium hydroxide solution with the concentration of 10.0 mol/L;
step 3, preparing ammonia water with the concentration of 8.0mol/L as a complexing agent;
step 4, opening a jacket of the seed crystal reaction kettle for water inlet and water return, introducing nitrogen into the seed crystal reaction kettle for atmosphere protection, and keeping nitrogen protection in the whole reaction process;
step 5, adding pure water into the seed crystal reaction kettle until the pure water overflows a bottom stirring paddle, and then adding a certain amount of the sodium hydroxide solution prepared in the step 2 and the ammonia water prepared in the step 3 to form a base solution which has the pH value of 10.90 +/-0.05, the ammonia value of 3.0 +/-0.5 g/L and the temperature of 50 +/-0.2 ℃ and is started up in a reaction manner;
step 6, adding the high-sphericity ternary precursor seed crystal prepared in the step into the base solution according to the required material amount;
step 7, starting stirring, adding the prepared mixed salt solution, sodium hydroxide solution and ammonia water solution into a precursor reaction kettle in a parallel flow manner for reaction, and controlling the pH value to be 10.9 +/-0.05, the ammonia value to be 3.0 +/-0.5 g/L and the temperature to be 50 +/-0.2 ℃;
step 8, stopping feeding when the D50 of the materials in the reaction kettle is detected to reach 2.6 microns, and continuing stirring and aging for 1-2 hours;
step 9, adding the slurry aged in the step 8 into filter pressing washing equipment for washing and filter pressing, and then sending the slurry to a drying process, and after the drying is finished, sequentially carrying out sieving and demagnetizing to obtain the slurry with the chemical formula of Ni0.6Co0.2Mn0.2(OH)2D50=2.6 μm high sphericity ternary precursor.
The sphericity index phi of the prepared high-sphericity ternary precursor is 1.0-1.6, wherein phi = Di/Dc, Di is the maximum inscribed sphere radius of the particles, and Dc is the minimum inscribed sphere radius of the same particles.
Example 3
Has a chemical formula of Ni0.9Co0.05Mn0.05(OH)2The preparation method of the high-sphericity ternary precursor seed crystal with the particle size of less than 1.2 mu m comprises the following steps:
step 1, preparing a mixed salt solution with the total metal ion concentration of 2.0mol/L by using nickel, cobalt and manganese sulfates as raw materials and pure water according to the molar ratio of nickel, cobalt and manganese in the required high-sphericity ternary precursor seed crystal of 9:0.5: 0.5;
step 2, preparing a sodium hydroxide solution with the concentration of 5.0 mol/L;
step 3, preparing ammonia water with the concentration of 7.0mol/L as a complexing agent;
step 4, opening a jacket of the seed crystal reaction kettle for water inlet and water return, introducing nitrogen into the seed crystal reaction kettle for atmosphere protection, and keeping nitrogen protection in the whole reaction process;
step 5, adding pure water into the seed crystal reaction kettle until the pure water overflows a bottom stirring paddle, and then adding a certain amount of the sodium hydroxide solution prepared in the step 2 and the ammonia water prepared in the step 3 to form a base solution which has the pH value of 11.80 +/-0.05, the ammonia value of 1.5 +/-0.5 g/L and the temperature of 50 +/-0.2 ℃ and is started up in a reaction manner;
step 6, adding titanium nitride microspheres with the particle size of 5 microns into the base solution, and adjusting the solid content to 700 g/L;
step 7, starting stirring, adding the prepared mixed salt solution, sodium hydroxide solution and ammonia water solution into a seed crystal reaction kettle in a parallel flow manner for reaction, and controlling the pH value to be 11.80 +/-0.05, the ammonia value to be 1.5 +/-0.5 g/L and the temperature to be 50 +/-0.2 ℃;
step 8, continuously feeding materials into the seed crystal reaction kettle according to the step 7, after the materials submerge 500-1000 mm of the microporous filter pipe, opening a valve V1 and a valve V2, opening a peristaltic pump to extract slurry, simultaneously starting a concentrator to concentrate the materials, enabling the concentrated materials to enter a seed crystal collecting tank, and enabling mother liquor to enter a mother liquor water treatment process; controlling the flow of the peristaltic pump to be interlocked with the liquid level of the seed crystal reaction kettle, and maintaining the liquid level of the seed crystal reaction kettle within 500-1000 mm of the liquid level of the seed crystal reaction kettle, until the feeding is finished;
and 9, after the feeding is finished, closing the valve V1, the valve V2, the peristaltic pump and the concentrator in sequence, wherein the material in the seed crystal collecting tank is the obtained material with the chemical formula of Ni0.9Co0.05Mn0.05(OH)2And the high sphericity ternary precursor seed crystal with the grain diameter less than 1.2 mu m.
The preparation method of the high sphericity ternary precursor seed crystal is characterized in that the microporous filter tube is a detachable filter tube, and the microporous filter tube with the filtering hole diameter of 1.2 mu m is selected according to the grain size of the required seed crystal.
In the preparation method of the high-sphericity ternary precursor seed crystal, the outlet of the microporous filter tube is connected with a nitrogen storage tank with the pressure of 0.20-0.30 MPa through a valve V3; and the valve V3 is interlocked with the flow rate of the peristaltic pump, the valve V1 and the valve V2, when the flow rate of the peristaltic pump is reduced when the valve V1 and the valve V2 are fully opened, the valve V1 and the valve V2 are immediately closed, the valve V3 is opened for 0.5-1 s continuously, the microporous filter pipe is subjected to back flushing, the valve V3 is closed after the back flushing is finished, and the valve V1 and the valve V2 are opened.
The sphericity index phi of the high-sphericity ternary precursor seed crystal prepared by the method is 1.0-1.6, wherein phi = Di/Dc, Di is the maximum inscribed sphere radius of a particle, and Dc is the minimum inscribed sphere radius of the same particle.
Has a chemical formula of Ni0.9Co0.05Mn0.05(OH)2D50=3.8 μm method for preparing a high sphericity ternary precursor, comprising the steps of:
step 1, preparing a mixed salt solution with the total metal ion concentration of 1.0mol/L by using nickel, cobalt and manganese sulfates as raw materials and pure water according to the molar ratio of nickel, cobalt and manganese in the required high-sphericity ternary precursor seed crystal of 8:1: 1;
step 2, preparing a sodium hydroxide solution with the concentration of 10.0 mol/L;
step 3, preparing ammonia water with the concentration of 8.0mol/L as a complexing agent;
step 4, opening a jacket of the seed crystal reaction kettle for water inlet and water return, introducing nitrogen into the seed crystal reaction kettle for atmosphere protection, and keeping nitrogen protection in the whole reaction process;
step 5, adding pure water into the seed crystal reaction kettle until the pure water overflows a bottom stirring paddle, and then adding a certain amount of the sodium hydroxide solution prepared in the step 2 and the ammonia water prepared in the step 3 to form a base solution which has the pH value of 11.20 +/-0.05, the ammonia value of 3.0 +/-0.5 g/L and the temperature of 50 +/-0.2 ℃ and is started up in a reaction manner;
step 6, adding the high-sphericity ternary precursor seed crystal prepared in the step into the base solution according to the required material amount;
step 7, starting stirring, adding the prepared mixed salt solution, sodium hydroxide solution and ammonia water solution into a precursor reaction kettle in a parallel flow manner for reaction, and controlling the pH value to be 11.20 +/-0.05, the ammonia value to be 3.0 +/-0.5 g/L and the temperature to be 50 +/-0.2 ℃;
step 8, stopping feeding when the D50 of the materials in the reaction kettle is detected to reach 3.8 mu m, and continuing stirring and aging for 1-2 hours;
step 9, adding the slurry aged in the step 8 into filter pressing washing equipment for washing, filter pressing and dryingThe working procedure is that after the drying is finished, the chemical formula of Ni is obtained after the sieving and the demagnetization are carried out in sequence0.09Co0.05Mn0.05(OH)2D50=3.8 μm high sphericity ternary precursor.
The sphericity index phi of the prepared high-sphericity ternary precursor is 1.0-1.6, wherein phi = Di/Dc, Di is the maximum inscribed sphere radius of the particles, and Dc is the minimum inscribed sphere radius of the same particles.

Claims (10)

1. A preparation method of a high sphericity ternary precursor seed crystal is characterized by comprising a seed crystal reaction kettle, a microporous filter tube, a peristaltic pump, a thickener and a seed crystal collecting tank which are connected in sequence; the micropore filter pipe is arranged in the seed crystal reaction kettle and penetrates through the kettle wall of the seed crystal reaction kettle to be connected with an inlet of a peristaltic pump through a pipeline, an outlet of the peristaltic pump is connected with an inlet of a thickener, and an outlet of the thickener is connected with the top of a seed crystal collecting tank; a stirrer, a feeding pipe, a nitrogen guide pipe and a liquid level meter are arranged in the seed crystal reaction kettle; the stirrer extends into the bottom of the reaction kettle from the top of the center of the seed crystal reaction kettle; one end of the feeding pipe is connected with the upstream batching process, and the other end of the feeding pipe extends into the bottom of the seed crystal reaction kettle through the top of the seed crystal reaction kettle; one end of the nitrogen conduit is connected with the nitrogen header pipe, and the other end of the nitrogen conduit extends into the bottom of the seed crystal reaction kettle through the top of the seed crystal reaction kettle; the liquid level meter extends from the top of the seed crystal reaction kettle to the bottom of the seed crystal reaction kettle; the method comprises the following steps:
step 1, according to the mole ratio of nickel, cobalt and manganese in the required high-sphericity ternary precursor seed crystal, selecting soluble salts of nickel, cobalt and manganese as raw materials and preparing a mixed salt solution with the total metal ion concentration of 1.0-2.5 mol/L with pure water;
step 2, preparing a sodium hydroxide solution with the concentration of 4.0 mol/L-11.0 mol/L;
step 3, preparing ammonia water with the concentration of 6.0 mol/L-12.0 mol/L as a complexing agent;
step 4, opening a jacket of the seed crystal reaction kettle for water inlet and water return, introducing nitrogen into the seed crystal reaction kettle for atmosphere protection, and keeping nitrogen protection in the whole reaction process;
step 5, adding pure water into the seed crystal reaction kettle until the pure water overflows the bottom layer stirring paddle, and adding a certain amount of the sodium hydroxide solution prepared in the step 2 and the ammonia water prepared in the step 3 to form a bottom solution for starting up the reaction;
step 6, adding a certain amount of solid insoluble in the base solution into the base solution, wherein the diameter of the solid insoluble in the base solution is always larger than the diameter of a filtration hole of the microporous filtration tube, and adjusting the solid content to 80-1000 g/L;
step 7, starting stirring, adding the prepared mixed salt solution, sodium hydroxide solution and ammonia water solution into a seed crystal reaction kettle in a parallel flow manner for reaction, and controlling the pH value to be 11.00-12.30, the ammonia value to be 0.5-10.0 g/L and the temperature to be 45-70 ℃;
step 8, continuously feeding materials into the seed crystal reaction kettle according to the step 7, after the materials submerge 500-1000 mm of the microporous filter pipe, opening a valve V1 and a valve V2, opening a peristaltic pump to extract slurry, simultaneously starting a concentrator to concentrate the materials, enabling the concentrated materials to enter a seed crystal collecting tank, and enabling mother liquor to enter a mother liquor water treatment process; controlling the flow of the peristaltic pump to be interlocked with the liquid level of the seed crystal reaction kettle, and maintaining the liquid level of the seed crystal reaction kettle within 500-1000 mm of the liquid level of the seed crystal reaction kettle, until the feeding is finished;
and 9, after the feeding is finished, closing the valve V1, the valve V2, the peristaltic pump and the thickener in sequence, wherein the material in the seed crystal collecting tank is the obtained high-sphericity ternary precursor seed crystal.
2. The method for preparing the high-sphericity ternary precursor seed crystal according to claim 1, wherein the microporous filter tube is a detachable filter tube, and the microporous filter tube with a filter hole diameter of 1.0-5.0 μm is selected according to the size of the desired seed crystal particle diameter.
3. The method for preparing the ternary precursor seed crystal with high sphericity according to claim 1, wherein in the step 1, the soluble salt of nickel, cobalt and manganese is one or more of chloride, nitrate, sulfate and acetate.
4. The method for preparing a ternary precursor seed crystal with high sphericity according to claim 1, wherein in step 5, the pH value in the base solution is 11.0 to 12.3, and the ammonia concentration is 0.5g/L to 15.0 g/L.
5. The method for preparing a ternary precursor seed crystal with high sphericity according to claim 1, wherein in step 6, the solid insoluble in the base solution includes, but is not limited to, hydroxide microspheres, zirconium microspheres, polystyrene microspheres, titanium nitride microspheres, boron nitride microspheres, and tungsten nitride microspheres.
6. The method for preparing a ternary precursor seed crystal with high sphericity according to claim 5, wherein the diameter of the solid insoluble in the base solution is 3.0 to 300 μm.
7. The preparation method of the high-sphericity ternary precursor seed crystal according to claim 1, wherein an outlet of the microporous filter tube is connected with a nitrogen storage tank with a pressure of 0.20-0.30 MPa through a valve V3; and the valve V3 is interlocked with the flow rate of the peristaltic pump, the valve V1 and the valve V2, when the flow rate of the peristaltic pump is reduced when the valve V1 and the valve V2 are fully opened, the valve V1 and the valve V2 are immediately closed, the valve V3 is opened for 0.5-1 s continuously, the microporous filter pipe is subjected to back flushing, the valve V3 is closed after the back flushing is finished, and the valve V1 and the valve V2 are opened.
8. The preparation method of the high-sphericity ternary precursor seed crystal according to any one of claims 1 to 7, wherein the sphericity index Φ of the prepared high-sphericity ternary precursor seed crystal is 1.0 to 1.6, where Φ = Di/Dc, Di is the maximum inscribed sphere radius of a particle, and Dc is the minimum inscribed sphere radius of the same particle.
9. A method for preparing a high sphericity ternary precursor using a seed crystal, comprising the steps of:
step 1, according to the mole ratio of nickel, cobalt and manganese in the required high-sphericity ternary precursor, selecting soluble salts of nickel, cobalt and manganese as raw materials and pure water to prepare a mixed salt solution with the total metal ion concentration of 1.0-2.5 mol/L;
step 2, preparing a sodium hydroxide solution with the concentration of 4.0 mol/L-11.0 mol/L;
step 3, preparing ammonia water with the concentration of 6.0 mol/L-12.0 mol/L as a complexing agent;
step 4, opening a jacket of the precursor reaction kettle for water inlet and water return, introducing nitrogen into the precursor reaction kettle for atmosphere protection, and keeping nitrogen protection in the whole reaction process;
step 5, adding pure water into the precursor reaction kettle until the pure water overflows a bottom stirring paddle, and then adding a certain amount of the sodium hydroxide solution prepared in the step 2 and the ammonia water prepared in the step 3 to form a reaction starting bottom liquid with the pH value of 10.50-12.00, the ammonia value of 0.5-15.0 g/L and the temperature of 45-70 ℃;
step 6, adding the high-sphericity ternary precursor seed crystal prepared in the claim 1 into the base solution according to the required material amount;
step 7, starting stirring, adding the prepared mixed salt solution, sodium hydroxide solution and ammonia water solution into a precursor reaction kettle in a parallel flow manner for reaction, and controlling the pH value to be 10.50-12.00, the ammonia value to be 0.5-15.0 g/L and the temperature to be 45-70 ℃;
step 8, stopping feeding when the D50 of the materials in the reaction kettle is detected to reach 3.0-20.0 microns, and continuing stirring and aging for 1-2 hours;
and 9, adding the slurry aged in the step 8 into filter pressing washing equipment, washing and filter pressing the slurry, and sending the slurry to a drying process, and after drying is finished, sequentially sieving and demagnetizing the slurry to obtain the high-sphericity ternary precursor.
10. The method for preparing the high-sphericity ternary precursor by using the seed crystal according to claim 9, wherein the sphericity index Φ of the prepared high-sphericity ternary precursor is 1.0-1.6, where Φ = Di/Dc, Di is the maximum inscribed sphere radius of the particle, and Dc is the minimum inscribed sphere radius of the same particle.
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