CN111196613B - 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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CN111196613B
CN111196613B CN202010109284.3A CN202010109284A CN111196613B CN 111196613 B CN111196613 B CN 111196613B CN 202010109284 A CN202010109284 A CN 202010109284A CN 111196613 B CN111196613 B CN 111196613B
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seed crystal
reaction kettle
high sphericity
valve
ternary precursor
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CN111196613A (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
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2004/32—Spheres
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    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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Abstract

The invention relates to a preparation method of a high sphericity ternary precursor seed crystal and a method for preparing the high sphericity ternary precursor by using the seed crystal, wherein the preparation method of the high sphericity ternary precursor seed crystal can prepare seed crystals with good sphericity and realize continuous production, the prepared high sphericity seed crystal can be used as seed crystal for producing the high sphericity precursor in the next step after being stored continuously for producing the high sphericity precursor, and can be used as a precursor with small particle diameter after being processed independently; a method for preparing high sphericity ternary precursor by using seed crystal is characterized by that the produced high sphericity seed crystal is introduced, and the reaction condition is controlled so as to make the seed crystal gradually grow up, so that the high sphericity precursor meeting the required grain size can be obtained, and its production period can be 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 ternary positive electrode material precursors 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
The lithium ion battery is used as a novel green power supply and is widely applied to the fields of 3C digital electronic products, electric tools, electric vehicles, energy storage and the like. Ternary positive electrode materials are hot spots for competitive development of various large enterprises at present, and ternary precursors have a critical influence on the performance of the positive electrode materials.
Sphericity is one of the key dimensions of the precursor being evaluated. The high sphericity can improve the tap density, the multiplying power performance, the cycle performance and the like of the anode material. Therefore, how to improve the sphericity of the precursor is an important technique. According to the current precursor synthesis technology, higher sphericity is easier to obtain when the particle size is greater than 4 μm. In contrast, when the particle size is less than 4. Mu.m, the sphericity of the particles is poor.
Chinese patent CN108946827a discloses a method for preparing ultra-small particle size nickel cobalt manganese hydroxide, which adopts an ammonia-free organic complexing agent to synthesize ultra-small particles with a particle size of less than 2 μm, and has high sphericity and dispersibility. Although the method has the advantages of environmental protection and capability of synthesizing small particle products with high sphericity and dispersity, the complete switching of the system exists, and the method is not compatible with the current wastewater treatment process of main stream industrialization, so that the popularization and development of the method also have a long road.
Chinese patent CN104201367B discloses a high-density small-particle-size nickel cobalt manganese hydroxide and a preparation method thereof, adopts a complexation control crystallization coprecipitation method, and solves the problems of uneven distribution, poor particle appearance, loose surface, difficult particle size control, non-uniformity, low tap density and the like of small-particle-size nickel cobalt manganese hydroxide elements prepared by the prior method by carrying out coprecipitation reaction on nickel cobalt manganese soluble salt aqueous solution and sodium hydroxide aqueous solution under the complexation of ammonia under the special process flows of nucleation and growth and continuous friction and collision of particles under the continuously improved solid-to-liquid ratio. The method has the agglomeration phenomenon when preparing the precursor with small particle size, and the sphericity is improved, but the requirement of downstream customers on high sphericity can not be met.
Chinese patent CN107640792A and Chinese patent CN103253717B synthesize small particles with good dispersibility by adopting mother liquor with the pH value adjusted and the complexing agent content as base liquor, and the small particles have remarkable agglomeration phenomenon although the sphericity is greatly improved, and the agglomeration 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 hard microspheres are added, and under the action of strong stirring, the collision frequency and the collision times of a nickel cobalt manganese ternary precursor product in the growth process are increased, so that the small-particle nickel cobalt manganese ternary precursor is promoted to have higher sphericity in a shorter growth time, and after the reaction is finished, the suspension of the hard microspheres is separated from slurry by natural sedimentation, thereby obtaining the high sphericity nickel cobalt manganese ternary precursor. The method is a batch reaction, cannot be continuously produced, and needs to periodically stop the reaction and separate the seed crystal and the particles, so that the production efficiency is low, and when the precursor with small particle size is prepared, the growth period is very short, so that the production practicability is low.
Because the updating iteration speed of the lithium battery industry is extremely high, the ternary precursor material does not have a value maintaining function, manufacturers cannot stock too many ternary precursor materials, and the stock often means loss.
However, when the customer needs the product urgently, the production period of the product is longer, the required product is difficult to obtain in a short time, so that the product cannot be delivered on time, or the product is updated and replaced after being produced, and the value of the product is reduced.
Disclosure of Invention
The invention provides a preparation method of a high sphericity ternary precursor seed crystal, which can prepare seed crystals with good sphericity, realize continuous production, continuously provide seed crystals with high sphericity for a production precursor, store the prepared seed crystals with high sphericity, then use the seed crystals as seed crystals for producing the high sphericity precursor in the next step, and also can be independently used as a precursor with small particle size after processing;
the second purpose of the invention is to provide a method for preparing the high sphericity ternary precursor by using the seed crystal, which is characterized in that the seed crystal is gradually grown up by introducing the produced high sphericity seed crystal and controlling the reaction condition, so that the high sphericity precursor meeting the required particle size is obtained, the production period is greatly shortened, and the development and use progress of downstream users can be quickly followed by the product.
In order to achieve the above 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 microporous 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 the inlet of the peristaltic pump, the outlet of the peristaltic pump is connected with the inlet of the concentrator, and the outlet of the concentrator is connected with the top of the seed crystal collecting tank; a stirrer, a feed pipe, a nitrogen guide pipe and a liquid level meter are arranged in the seed crystal reaction kettle; the stirrer stretches into the bottom of the reaction kettle from the top of the center of the seed crystal reaction kettle; one end of the feed pipe is connected with the upstream batching procedure, and the other end of the feed 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 guide pipe is connected with the nitrogen main pipe, and the other end of the nitrogen guide pipe extends into the bottom of the seed crystal reaction kettle through the top of the seed crystal reaction kettle; the liquid level meter stretches into the bottom of the seed crystal reaction kettle from the top of the seed crystal reaction kettle; the method comprises the following steps:
step 1, preparing a mixed salt solution with the total concentration of metal ions of 1.0 mol/L-2.5 mol/L by taking soluble salts of nickel, cobalt and manganese as raw materials and pure water according to the required molar ratio of nickel, cobalt and manganese in the ternary precursor seed crystal with high sphericity;
step 2, preparing sodium hydroxide solution with the concentration of 4.0mol/L to 11.0 mol/L;
step 3, preparing ammonia water with the concentration of 6.0mol/L to 12.0mol/L as a complexing agent;
step 4, opening a jacket of the seed crystal reaction kettle for water inflow 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 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 for starting up the reaction;
step 6, adding a certain amount of solid which is insoluble in the base solution, wherein the diameter of the solid which is insoluble in the base solution is always larger than the diameter of the filtering holes of the microporous filtering pipe, adjusting the solid content to be 80-1000 g/L, and enabling small seed crystals generated by reaction to be difficult to aggregate under the dispersion action of solid particles by improving the solid content in the base solution, avoiding the aggregation phenomenon of the small seed crystals, enabling each small seed crystal to independently grow, and enabling the seed crystals to continuously collide with the solid particles in the growth process under the strong stirring action so as to promote the seed crystals to be formed into a higher sphericity in a shorter growth time;
step 7, stirring is started, the prepared mixed salt solution, sodium hydroxide solution and ammonia water solution are added into a seed crystal reaction kettle in parallel flow for reaction, the pH value is controlled to be 11.00-12.30, the ammonia value is controlled to be 0.5-10.0 g/L, and the temperature is controlled to be 45-70 ℃;
step 8, after the materials fed into the seed crystal reaction kettle continuously pass through the microporous filter pipe by 500-1000 mm according to the step 7, opening the valve V1 and the valve V2, opening the peristaltic pump to pump the slurry, starting the thickener to concentrate the materials, and enabling the concentrated materials to enter a seed crystal collecting tank and mother liquor to enter a mother liquor water treatment process; controlling the peristaltic pump flow to be interlocked with the liquid level of the seed crystal reaction kettle, so that the liquid level of the seed crystal reaction kettle is maintained within 500-1000 mm after passing through the microporous filter pipe until the feeding is finished;
and 9, after the feeding is finished, sequentially closing the valve V1, the valve V2, the peristaltic pump and the concentrator, wherein the materials in the seed crystal collecting tank are the obtained high sphericity ternary precursor seed crystals.
The microporous filter tube is a detachable filter tube, and the microporous filter tube with the filter hole diameter of 1.0-5.0 μm is selected according to the size of the required seed crystal particle diameter.
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 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.
The preparation method of the high sphericity ternary precursor seed crystal has the diameter of solid insoluble in base liquid of 3.0-300 microns.
According to the preparation method of the high sphericity ternary precursor seed crystal, the outlet of a microporous filter tube is connected with a nitrogen storage tank with the pressure of 0.20-0.30 MPa through a valve V3; the valve V3 is interlocked with the peristaltic pump flow, the valve V1 and the valve V2, when the valve V1 and the valve V2 are fully opened, the peristaltic pump flow is reduced, the valve V1 and the valve V2 are immediately closed, the valve V3 is opened for 0.5-1 s, the reverse blowing is carried out on the microporous filter tube, the valve V3 is closed, the valve V1 and the valve V2 are opened, and the interlocking can not only stabilize the liquid level in the kettle, but also avoid the blockage of the microporous filter tube.
According to the preparation method of the high sphericity ternary precursor seed crystal, sphericity index phi of the prepared high sphericity ternary precursor seed crystal is 1.0-1.6, wherein phi=di/Dc, di is the radius of the extremely large inscribed sphere of the particle, and Dc is the radius of the extremely small inscribed sphere of the same particle.
The invention provides a method for preparing a high sphericity ternary precursor by using seed crystals, which comprises the following steps:
step 1, preparing a mixed salt solution with the total concentration of metal ions of 1.0 mol/L-2.5 mol/L by using soluble salts of nickel, cobalt and manganese as raw materials and pure water according to the required molar ratio of nickel, cobalt and manganese in the high sphericity ternary precursor;
step 2, preparing sodium hydroxide solution with the concentration of 4.0mol/L to 11.0 mol/L;
step 3, preparing ammonia water with the concentration of 6.0mol/L to 12.0mol/L as a complexing agent;
step 4, opening a jacket of the precursor reaction kettle for water inflow 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 the 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 base solution 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 quantity;
step 7, stirring is started, the prepared mixed salt solution, sodium hydroxide solution and ammonia water solution are added into a precursor reaction kettle in parallel flow for reaction, the pH value is controlled to be 10.50-12.00, the ammonia value is controlled to be 0.5-15.0 g/L, and the temperature is controlled to be 45-70 ℃;
step 8, stopping feeding when the D50 of the materials in the reaction kettle reaches 3.0-20.0 mu m, and continuing stirring and ageing for 1-2 hours;
and 9, adding the aged slurry in the step 8 into filter-pressing washing equipment for washing and filter-pressing, and then sending the slurry to a drying procedure, and sieving and demagnetizing the slurry in sequence after the drying procedure is finished to obtain the high sphericity ternary precursor.
According to the method for preparing the high sphericity ternary precursor by using the seed crystal, sphericity index phi of the prepared high sphericity ternary precursor is 1.0-1.6, wherein phi=di/Dc, di is the radius of the extremely large inscribed sphere of the particle, and Dc is the radius of the extremely small inscribed sphere of the same particle.
The invention has the beneficial effects that: the preparation method of the high sphericity ternary precursor seed crystal comprises the steps of adding solid particles insoluble in a base solution into a reaction synthesis base solution, improving the solid content in the base solution, enabling small seed crystals generated by the reaction to be difficult to aggregate under the dispersion action of the solid particles, avoiding the aggregation phenomenon of the small seed crystals, enabling each small seed crystal to independently grow, enabling the seed crystals to continuously collide with the solid particles in the growth process under the strong stirring action, enabling the seed crystals to be formed with higher sphericity in a shorter growth time, combining with the adjustment of the pH value and the ammonia value range, enabling the small particle seed crystals to be continuously generated in the synthesis process, extracting slurry through a microporous filter tube capable of penetrating the small particle seed crystals, separating the small particle seed crystals meeting the required granularity in a reaction kettle, namely obtaining the high sphericity ternary precursor seed crystal, realizing continuous production, continuously providing the high sphericity seed crystals for the precursor, and improving the production efficiency; the prepared high sphericity seed crystal can be used as seed crystal for producing small/medium/large granularity precursor with high sphericity in the next step after being stored, and can also be used as small granularity precursor after being processed; a method for preparing high sphericity ternary precursor by using seed crystal includes such steps as introducing the produced high sphericity seed crystal, controlling reaction condition to make seed crystal grow up gradually to obtain high sphericity precursor meeting the required granularity, greatly shortening production period, high productivity, ensuring delivery of product on time and in advance, and avoiding the damage to product value caused by too fast updating and substitution. The two methods of the invention can be widely applied to the production process of nickel cobalt manganese hydroxide, in particular to the preparation process of the high sphericity ternary precursor seed crystal and the process of 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 according to the present invention;
FIG. 2 is a FESEM image of a high sphericity ternary precursor seed prepared in example 1;
FIG. 3 is a FESEM image of a high sphericity ternary precursor seed prepared in example 2;
FIG. 4 is a FESEM image of a high sphericity ternary precursor seed prepared in example 3;
in fig. 1, 1 is a microporous filter tube, 2 is a seed crystal reaction kettle, 3 is a liquid level meter, 4 is a feed pipe, 5 is a nitrogen gas guide pipe, 6 is a valve V3, 7 is a seed crystal collecting tank, 8 is a concentrator, 9 is a peristaltic pump, 10 is a valve V2, 11 is a valve V1, 12 is a stirrer.
Detailed Description
The following examples will enable those skilled in the art to more fully understand the present invention and are not intended to limit the same in any way.
Example 1
The chemical formula is Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 The preparation method of the high sphericity ternary precursor seed crystal with the particle size smaller than 2.5 mu m comprises the following steps:
step 1, preparing a mixed salt solution with the total concentration of metal ions of 2.0mol/L by taking nickel, cobalt and manganese sulfate as raw materials and pure water according to the required molar ratio of nickel, cobalt and manganese in the high sphericity ternary precursor seed crystal of 8:1:1;
step 2, preparing 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 inflow 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 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 with 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 ℃ for starting up the reaction;
step 6, adding NCM811 hydroxide with the granularity of 7 mu m into the base solution, and adjusting the solid content to 400g/L;
step 7, stirring is started, the prepared mixed salt solution, sodium hydroxide solution and ammonia water solution are added into a seed crystal reaction kettle in parallel flow for reaction, the pH value is controlled to be 11.00-12.30, the ammonia value is controlled to be 0.5-10.0 g/L, and the temperature is controlled to be 45-70 ℃;
step 8, after the materials fed into the seed crystal reaction kettle continuously pass through the microporous filter pipe by 500-1000 mm according to the step 7, opening the valve V1 and the valve V2, opening the peristaltic pump to pump the slurry, starting the thickener to concentrate the materials, and enabling the concentrated materials to enter a seed crystal collecting tank and mother liquor to enter a mother liquor water treatment process; controlling the peristaltic pump flow to be interlocked with the liquid level of the seed crystal reaction kettle, so that the liquid level of the seed crystal reaction kettle is maintained within 500-1000 mm after passing through the microporous filter pipe until the feeding is finished;
step 9, after the feeding is finished, sequentially closing a valve V1, a valve V2, a peristaltic pump and a concentrator, wherein the material in the seed crystal collecting tank is the obtained chemical formula of Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 High sphericity ternary precursor seed crystal with particle size less than 2.5 microns.
According to the preparation method of the high sphericity ternary precursor seed crystal, the microporous filter tube is a detachable filter tube, and the microporous filter tube is a microporous filter tube with the filter hole diameter of 2.5 mu m according to the size of the required seed crystal particle size.
According to the preparation method of the high sphericity ternary precursor seed crystal, the outlet of a microporous filter tube is connected with a nitrogen storage tank with the pressure of 0.20-0.30 MPa through a valve V3; the valve V3 is interlocked with the peristaltic pump flow, the valve V1 and the valve V2, when the valve V1 and the valve V2 are fully opened, the peristaltic pump flow is reduced, the valve V1 and the valve V2 are immediately closed, the valve V3 is opened for 0.5-1 s, the back blowing is carried out on the microporous filter tube, the back blowing is finished, the valve V3 is closed, and the valve V1 and the valve V2 are opened.
According to the preparation method of the high sphericity ternary precursor seed crystal, sphericity index phi of the prepared high sphericity ternary precursor seed crystal is 1.0-1.6, wherein phi=di/Dc, di is the radius of the extremely large inscribed sphere of the particle, and Dc is the radius of the extremely small inscribed sphere of the same particle.
The chemical formula is Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 A method for preparing a high sphericity ternary precursor with d50=8.9 μm, comprising the steps of:
step 1, preparing a mixed salt solution with the total concentration of metal ions of 2.0mol/L by taking nickel, cobalt and manganese sulfate as raw materials and pure water according to the required molar ratio of nickel, cobalt and manganese in the high sphericity ternary precursor seed crystal of 8:1:1;
step 2, preparing 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 inflow 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 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 with 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 ℃ for starting up the reaction;
step 6, adding the high sphericity ternary precursor seed crystal prepared in the step into the base solution according to the required material quantity;
step 7, stirring is started, the prepared mixed salt solution, sodium hydroxide solution and ammonia water solution are added into a precursor reaction kettle in parallel flow for reaction, the pH value is controlled to be 11.30 plus or minus 0.05, the ammonia value is controlled to be 9.0 plus or minus 0.5g/L, and the temperature is controlled to be 55 plus or minus 0.2 ℃;
step 8, stopping feeding when the D50 of the materials in the reaction kettle reaches 8.9 mu m, and continuing stirring and ageing for 1-2 hours;
step 9, adding the aged slurry in the step 8 into filter-pressing washing equipment to carry out washing and filter-pressing, then delivering to a drying process, and after the drying process is finished, sieving and demagnetizing sequentially to obtain the Ni-based catalyst with the chemical formula of Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 D50=8.9 μm.
The sphericity index phi of the prepared high sphericity ternary precursor is 1.0-1.6, wherein phi=di/Dc, di is the radius of the extremely large inscribed sphere of the particles, and Dc is the radius of the extremely small inscribed sphere of the same particle.
Example 2
The chemical formula is Ni 0.6 Co 0.2 Mn 0.2 (OH) 2 The preparation method of the high sphericity ternary precursor seed crystal with the particle size smaller than 1.6 mu m comprises the following steps:
step 1, preparing a mixed salt solution with the total concentration of metal ions of 2.0mol/L by taking nickel, cobalt and manganese sulfate 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 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 inflow 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 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 with 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 ℃ for starting up the reaction;
step 6, adding polystyrene microspheres with granularity of 10 mu m into the base solution, and adjusting the solid content to 600g/L;
step 7, stirring is started, the prepared mixed salt solution, sodium hydroxide solution and ammonia water solution are added into a seed crystal reaction kettle in parallel flow for reaction, the pH value is controlled to be 11.30 plus or minus 0.05, the ammonia value is controlled to be 2.0 plus or minus 0.5g/L, and the temperature is controlled to be 50 plus or minus 0.2 ℃;
step 8, after the materials fed into the seed crystal reaction kettle continuously pass through the microporous filter pipe by 500-1000 mm according to the step 7, opening the valve V1 and the valve V2, opening the peristaltic pump to pump the slurry, starting the thickener to concentrate the materials, and enabling the concentrated materials to enter a seed crystal collecting tank and mother liquor to enter a mother liquor water treatment process; controlling the peristaltic pump flow to be interlocked with the liquid level of the seed crystal reaction kettle, so that the liquid level of the seed crystal reaction kettle is maintained within 500-1000 mm after passing through the microporous filter pipe until the feeding is finished;
step 9, after the feeding is finished, sequentially closing a valve V1, a valve V2, a peristaltic pump and a concentrator, wherein the material in the seed crystal collecting tank is the obtained chemical formula of Ni 0.6 Co 0.2 Mn 0.2 (OH) 2 High sphericity ternary precursor seed crystal with particle size less than 1.6 microns.
According to the preparation method of the high sphericity ternary precursor seed crystal, the microporous filter tube is a detachable filter tube, and the microporous filter tube is a microporous filter tube with the filter hole diameter of 1.6 mu m according to the size of the required seed crystal particle size.
According to the preparation method of the high sphericity ternary precursor seed crystal, the outlet of a microporous filter tube is connected with a nitrogen storage tank with the pressure of 0.20-0.30 MPa through a valve V3; the valve V3 is interlocked with the peristaltic pump flow, the valve V1 and the valve V2, when the valve V1 and the valve V2 are fully opened, the peristaltic pump flow is reduced, the valve V1 and the valve V2 are immediately closed, the valve V3 is opened for 0.5-1 s, the back blowing is carried out on the microporous filter tube, the back blowing is finished, the valve V3 is closed, and the valve V1 and the valve V2 are opened.
According to the preparation method of the high sphericity ternary precursor seed crystal, sphericity index phi of the prepared high sphericity ternary precursor seed crystal is 1.0-1.6, wherein phi=di/Dc, di is the radius of the extremely large inscribed sphere of the particle, and Dc is the radius of the extremely small inscribed sphere of the same particle.
The chemical formula is Ni 0.6 Co 0.2 Mn 0.2 (OH) 2 A method for preparing a high sphericity ternary precursor with d50=2.6 μm, comprising the steps of:
step 1, preparing a mixed salt solution with the total concentration of metal ions of 2.0mol/L by taking nickel, cobalt and manganese sulfate as raw materials and pure water according to the required molar ratio of nickel, cobalt and manganese in the high sphericity ternary precursor seed crystal of 8:1:1;
step 2, preparing 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 inflow 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 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 with 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 ℃ for starting up the reaction;
step 6, adding the high sphericity ternary precursor seed crystal prepared in the step into the base solution according to the required material quantity;
step 7, stirring is started, the prepared mixed salt solution, sodium hydroxide solution and ammonia water solution are added into a precursor reaction kettle in parallel flow for reaction, the pH value is controlled to be 10.9 plus or minus 0.05, the ammonia value is controlled to be 3.0 plus or minus 0.5g/L, and the temperature is controlled to be 50 plus or minus 0.2 ℃;
step 8, stopping feeding when the D50 of the materials in the reaction kettle reaches 2.6 mu m, and continuing stirring and ageing for 1-2 hours;
step 9, stepAdding the aged slurry in the step 8 into filter-pressing washing equipment for washing and filter-pressing, then delivering to a drying process, and sequentially sieving and demagnetizing after the drying is finished to obtain the compound with the chemical formula of Ni 0.6 Co 0.2 Mn 0.2 (OH) 2 D50=2.6 μm.
The sphericity index phi of the prepared high sphericity ternary precursor is 1.0-1.6, wherein phi=di/Dc, di is the radius of the extremely large inscribed sphere of the particles, and Dc is the radius of the extremely small inscribed sphere of the same particle.
Example 3
The chemical formula is Ni 0.9 Co 0.05 Mn 0.05 (OH) 2 The preparation method of the high sphericity ternary precursor seed crystal with the particle size smaller than 1.2 mu m comprises the following steps:
step 1, preparing a mixed salt solution with the total concentration of metal ions of 2.0mol/L by taking nickel, cobalt and manganese sulfate as raw materials and pure water according to the required molar ratio of nickel, cobalt and manganese in the high sphericity ternary precursor seed crystal of 9:0.5:0.5;
step 2, preparing 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 inflow 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 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 with 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 ℃ for starting up the reaction;
step 6, adding titanium nitride microspheres with granularity of 5 mu m into the base solution, and adjusting the solid content to 700g/L;
step 7, stirring is started, the prepared mixed salt solution, sodium hydroxide solution and ammonia water solution are added into a seed crystal reaction kettle in parallel flow for reaction, the pH value is controlled to be 11.80 plus or minus 0.05, the ammonia value is controlled to be 1.5 plus or minus 0.5g/L, and the temperature is controlled to be 50 plus or minus 0.2 ℃;
step 8, after the materials fed into the seed crystal reaction kettle continuously pass through the microporous filter pipe by 500-1000 mm according to the step 7, opening the valve V1 and the valve V2, opening the peristaltic pump to pump the slurry, starting the thickener to concentrate the materials, and enabling the concentrated materials to enter a seed crystal collecting tank and mother liquor to enter a mother liquor water treatment process; controlling the peristaltic pump flow to be interlocked with the liquid level of the seed crystal reaction kettle, so that the liquid level of the seed crystal reaction kettle is maintained within 500-1000 mm after passing through the microporous filter pipe until the feeding is finished;
step 9, after the feeding is finished, sequentially closing a valve V1, a valve V2, a peristaltic pump and a concentrator, wherein the material in the seed crystal collecting tank is the obtained chemical formula of Ni 0.9 Co 0.05 Mn 0.05 (OH) 2 High sphericity ternary precursor seed crystal with particle size less than 1.2 microns.
According to the preparation method of the high sphericity ternary precursor seed crystal, the microporous filter tube is a detachable filter tube, and the microporous filter tube is selected according to the size of the required seed crystal grain diameter, and the filter hole diameter is 1.2 mu m.
According to the preparation method of the high sphericity ternary precursor seed crystal, the outlet of a microporous filter tube is connected with a nitrogen storage tank with the pressure of 0.20-0.30 MPa through a valve V3; the valve V3 is interlocked with the peristaltic pump flow, the valve V1 and the valve V2, when the valve V1 and the valve V2 are fully opened, the peristaltic pump flow is reduced, the valve V1 and the valve V2 are immediately closed, the valve V3 is opened for 0.5-1 s, the back blowing is carried out on the microporous filter tube, the back blowing is finished, the valve V3 is closed, and the valve V1 and the valve V2 are opened.
According to the preparation method of the high sphericity ternary precursor seed crystal, sphericity index phi of the prepared high sphericity ternary precursor seed crystal is 1.0-1.6, wherein phi=di/Dc, di is the radius of the extremely large inscribed sphere of the particle, and Dc is the radius of the extremely small inscribed sphere of the same particle.
The chemical formula is Ni 0.9 Co 0.05 Mn 0.05 (OH) 2 A method for preparing a high sphericity ternary precursor with d50=3.8 μm, comprising the steps of:
step 1, preparing a mixed salt solution with the total concentration of metal ions of 1.0mol/L by taking nickel, cobalt and manganese sulfate as raw materials and pure water according to the required molar ratio of nickel, cobalt and manganese in the high sphericity ternary precursor seed crystal of 8:1:1;
step 2, preparing 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 inflow 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 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 with 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 ℃ for starting up the reaction;
step 6, adding the high sphericity ternary precursor seed crystal prepared in the step into the base solution according to the required material quantity;
step 7, stirring is started, the prepared mixed salt solution, sodium hydroxide solution and ammonia water solution are added into a precursor reaction kettle in parallel flow for reaction, the pH value is controlled to be 11.20 plus or minus 0.05, the ammonia value is controlled to be 3.0 plus or minus 0.5g/L, and the temperature is controlled to be 50 plus or minus 0.2 ℃;
step 8, stopping feeding when the D50 of the materials in the reaction kettle reaches 3.8 mu m, and continuing stirring and ageing for 1-2 hours;
step 9, adding the aged slurry in the step 8 into filter-pressing washing equipment to carry out washing and filter-pressing, then delivering to a drying process, and after the drying process is finished, sieving and demagnetizing sequentially to obtain the Ni-based catalyst with the chemical formula of Ni 0.09 Co 0.05 Mn 0.05 (OH) 2 D50=3.8 μm.
The sphericity index phi of the prepared high sphericity ternary precursor is 1.0-1.6, wherein phi=di/Dc, di is the radius of the extremely large inscribed sphere of the particles, and Dc is the radius of the extremely small inscribed sphere of the same particle.

Claims (7)

1. The preparation method of the ternary precursor seed crystal with high sphericity is characterized by comprising 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 microporous 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 the inlet of the peristaltic pump, the outlet of the peristaltic pump is connected with the inlet of the concentrator, and the outlet of the concentrator is connected with the top of the seed crystal collecting tank; a stirrer, a feed pipe, a nitrogen guide pipe and a liquid level meter are arranged in the seed crystal reaction kettle; the stirrer stretches into the bottom of the reaction kettle from the top of the center of the seed crystal reaction kettle; one end of the feed pipe is connected with the upstream batching procedure, and the other end of the feed 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 guide pipe is connected with the nitrogen main pipe, and the other end of the nitrogen guide pipe extends into the bottom of the seed crystal reaction kettle through the top of the seed crystal reaction kettle; the liquid level meter stretches into the bottom of the seed crystal reaction kettle from the top of the seed crystal reaction kettle; the method comprises the following steps:
step 1, preparing a mixed salt solution with the total concentration of metal ions of 1.0 mol/L-2.5 mol/L by taking soluble salts of nickel, cobalt and manganese as raw materials and pure water according to the required molar ratio of nickel, cobalt and manganese in the ternary precursor seed crystal with high sphericity;
step 2, preparing sodium hydroxide solution with the concentration of 4.0mol/L to 11.0 mol/L;
step 3, preparing ammonia water with the concentration of 6.0mol/L to 12.0mol/L as a complexing agent;
step 4, opening a jacket of the seed crystal reaction kettle for water inflow 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 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 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 the filter holes of the microporous filter tube, and the solid content is adjusted to be 400-1000 g/L; the solids insoluble in the base fluid include, but are not limited to, hydroxide microspheres, zirconium microspheres, polystyrene microspheres, titanium nitride microspheres, boron nitride microspheres, tungsten nitride microspheres;
step 7, stirring is started, the prepared mixed salt solution, sodium hydroxide solution and ammonia water solution are added into a seed crystal reaction kettle in parallel flow for reaction, the pH value is controlled to be 11.00-12.30, the ammonia value is controlled to be 0.5-10.0 g/L, and the temperature is controlled to be 45-70 ℃;
step 8, after the materials fed into the seed crystal reaction kettle continuously pass through the microporous filter pipe by 500-1000 mm according to the step 7, opening the valve V1 and the valve V2, opening the peristaltic pump to pump the slurry, starting the thickener to concentrate the materials, and enabling the concentrated materials to enter a seed crystal collecting tank and mother liquor to enter a mother liquor water treatment process; controlling the peristaltic pump flow to be interlocked with the liquid level of the seed crystal reaction kettle, so that the liquid level of the seed crystal reaction kettle is maintained within 500-1000 mm after passing through the microporous filter pipe until the feeding is finished;
and 9, after the feeding is finished, sequentially closing the valve V1, the valve V2, the peristaltic pump and the concentrator, wherein the materials in the seed crystal collecting tank are the obtained high sphericity ternary precursor seed crystals.
2. The method for preparing the ternary precursor seed crystal with high sphericity according to claim 1, wherein the microporous filter tube is a detachable filter tube, and the microporous filter tube has a filter hole diameter of 1.0-5.0 μm according to the size of the required seed crystal particle diameter.
3. The method for preparing ternary precursor seed crystals with high sphericity according to claim 1, wherein in the step 1, the soluble salts of nickel, cobalt and manganese are 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 the step 5, the pH value in the base solution is 11.0-12.3, and the ammonia concentration is 0.5-15.0 g/L.
5. The method for preparing a ternary precursor seed crystal with high sphericity according to claim 1, wherein the diameter of the solid insoluble in the base liquid is 3.0-300 μm.
6. The method for preparing the ternary precursor seed crystal with high sphericity according to claim 1, wherein 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; the valve V3 is interlocked with the peristaltic pump flow, the valve V1 and the valve V2, when the valve V1 and the valve V2 are fully opened, the peristaltic pump flow is reduced, the valve V1 and the valve V2 are immediately closed, the valve V3 is opened for 0.5-1 s, the back blowing is carried out on the microporous filter tube, the back blowing is finished, the valve V3 is closed, and the valve V1 and the valve V2 are opened.
7. A method for preparing a high sphericity ternary precursor using seed crystals, comprising the steps of:
step 1, preparing a high sphericity ternary precursor seed crystal by adopting the preparation method of claim 1;
step 2, according to the required molar ratio of nickel, cobalt and manganese in the high sphericity ternary precursor, preparing a mixed salt solution with the total concentration of metal ions of 1.0 mol/L-2.5 mol/L by using soluble salts of nickel, cobalt and manganese as raw materials and pure water;
step 3, preparing sodium hydroxide solution with the concentration of 4.0mol/L to 11.0 mol/L;
step 4, preparing ammonia water with the concentration of 6.0mol/L to 12.0mol/L as a complexing agent;
step 5, opening a jacket of the precursor reaction kettle for water inflow and water return, introducing nitrogen into the precursor reaction kettle for atmosphere protection, and keeping nitrogen protection in the whole reaction process;
step 6, adding pure water into the precursor reaction kettle until the pure water overflows the bottom stirring paddle, and then adding a certain amount of the sodium hydroxide solution prepared in the step 3 and the ammonia water prepared in the step 4 to form a reaction starting base solution 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 7, adding the high sphericity ternary precursor seed crystal prepared in the step 1 into the base solution according to the required material quantity;
step 8, stirring is started, the prepared mixed salt solution, sodium hydroxide solution and ammonia water solution are added into a precursor reaction kettle in parallel flow for reaction, the pH value is controlled to be 10.50-12.00, the ammonia value is controlled to be 0.5-15.0 g/L, and the temperature is controlled to be 45-70 ℃;
step 9, stopping feeding when the D50 of the materials in the reaction kettle reaches 3.0-20.0 mu m, and continuing stirring and ageing for 1-2 hours;
and step 10, adding the aged slurry in the step 9 into filter-pressing washing equipment for washing and filter-pressing, and then sending the slurry to a drying procedure, and sieving and demagnetizing the slurry in sequence after the drying procedure is finished to obtain the high sphericity ternary precursor.
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