CN114506880A - Full-continuous synthesis process for preparing large-particle nickel-cobalt-manganese ternary precursor - Google Patents

Full-continuous synthesis process for preparing large-particle nickel-cobalt-manganese ternary precursor Download PDF

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CN114506880A
CN114506880A CN202210100856.0A CN202210100856A CN114506880A CN 114506880 A CN114506880 A CN 114506880A CN 202210100856 A CN202210100856 A CN 202210100856A CN 114506880 A CN114506880 A CN 114506880A
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slurry
grading
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reaction kettle
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顾春芳
朱用
朱涛
李佰康
张文静
蒋鸿波
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Nantong Kington Energy Storage Power New Material 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes

Abstract

A full-continuous synthesis process for preparing large-particle Ni-Co-Mn ternary precursor, wherein the prepared large-particle ternary precursor product is NixCoyMnz(OH)2X + y + z =1, x is more than 0 and less than 1, D50 is more than 10um, and the Span value is 1.0-1.3. The method comprises the steps of continuously producing the master batch with the D50 particle size of 7-9 um and the Span value of 1.3-1.6 in a reaction kettle, and then carrying out multistage classification treatment on the master batch to obtain a large-particle product. The large-particle nickel-cobalt-manganese ternary precursor prepared by the invention has the advantages of no adhesion of small particle sphericity, no cracking of large particles, stable product quality and the like, and is a full-continuous synthesis process, high in capacity and simple in production operation.

Description

Full-continuous synthesis process for preparing large-particle nickel-cobalt-manganese ternary precursor
Technical Field
The invention relates to the technical field of lithium ion battery material preparation, in particular to a full-continuous synthesis process for preparing a large-particle nickel-cobalt-manganese ternary precursor.
Background
The global new energy automobile market and the power battery market maintain a high-prospect state, and the nickel-cobalt-manganese ternary material is used as a main raw material for the lithium ion battery, so that the market demand is strong. The yield of the ternary cathode material in China is 16.6 ten thousand tons in 1-6 months in 2021, and the yield is increased by 112 percent on a par. In 2021, the yield of the Chinese ternary precursor is 26.05 ten thousand tons in 1-6 months, and the yield is increased by 125 percent on a year-by-year basis. The total demand of ternary positive electrode materials is expected to reach 100 ten thousand tons in 2025. Under a wide market prospect, the new energy automobile market spans into a rapid growth period, higher requirements are put forward on the energy density, the endurance mileage, the safety and the cost of a power battery, and the development of the ternary precursor industry to the directions of high nickel and low cobalt, single crystal high voltage and the like is guided.
The ternary material is developed towards high nickel and low cobalt, the energy density is obviously improved, but the cycle performance of the battery is reduced due to the improvement of the nickel content and the reduction of the cobalt content. The ternary material of large particles of more than 10 microns of D50 has lower activity and relatively better cycle performance, so that the high-nickel ternary polycrystalline material selects the large particles of more than 10 microns as a main material, and a certain amount of small particle products of D50 < 6 microns are matched to fill gaps among the large particles so as to improve the pole piece compaction density and the energy density of the battery. The large and small particle mixing process includes the steps of preparing two products, namely a large particle ternary precursor with narrow distribution and a small particle ternary precursor with narrow distribution, performing lithium mixing sintering on the large particle ternary precursor and the small particle ternary precursor respectively, and finally performing dry physical mixing on the sintered large particle ternary cathode material and the sintered small particle ternary cathode material according to a certain proportion. The production process of the process route is complicated, the production energy consumption is high, the cost is high, and meanwhile, due to the fact that the narrow-distribution large and small particle ternary precursor synthesis processes are different and the sintering processes are different, the performance difference of the large and small particle ternary precursors is large in fluctuation, and the performance consistency of the finally mixed finished product is poor. In addition, because a dry physical mixing mode is finally adopted, the problems of uneven mixing of large and small-particle cathode materials, uneven battery slurry homogenizing, coating and layering of pole pieces and the like also exist.
In order to improve the energy density and the cycle performance of the polycrystalline high-nickel ternary battery, the industry tries to develop and use a wide-distribution large-particle ternary material, and a single-kettle continuous synthesis process is adopted to prepare a ternary precursor with D50 being more than 10um and Span being more than 1.0. The wide-distribution large-particle ternary precursor product prepared by the single-kettle continuous synthesis process has the advantages that large particles and small particles are carried out under the same synthesis process, the product consistency is good, the particle size distribution is uniform, and the problems of nonuniform battery slurry homogenization, pole piece coating layering and the like can be well solved. Meanwhile, the process route also has the advantages of simple and convenient production process, low cost and the like. At present, the demand for large-particle ternary precursors with wide distribution is increasingly enlarged in the industry, but the process for preparing the ternary precursors with D50 being more than 10 microns and Span being more than 1.0 in a full-continuous mode in a single kettle is not mature, and mainly reflects that the lowest stirring strength matched with products with different particle sizes in the single kettle cannot be balanced, the stirring rotating speed matched with small-particle products is high, the stirring rotating speed matched with large particles is low, and therefore the problems of small-particle adhesion, large-particle cracking and the like easily occur in the synthesis process.
Therefore, how to solve the above-mentioned deficiencies of the prior art is a problem to be solved by the present invention.
Disclosure of Invention
The invention aims to provide a full-continuous synthesis process for preparing a large-particle nickel-cobalt-manganese ternary precursor.
In order to achieve the purpose, the invention adopts the technical scheme that:
a full-continuous synthesis process for preparing a large-particle nickel-cobalt-manganese ternary precursor comprises a master batch preparation stage and a grading treatment stage;
in the preparation stage of the master batch, the master batch of the ternary precursor is prepared by a reaction kettle, and the chemical formula is NixCoyMnz(OH)2Wherein x + y + z is 1, x is more than 0 and less than 1, D50 of the master batch is 7-9 um, and the Span value is 1.2-1.6;
in the stage of grading treatment, grading collection of different granularities is carried out on product slurry through n grades of particle size grading devices which are connected in series, and each grading device is provided with a feed inlet on the side part, a discharge outlet on the upper end and a feed outlet; the classified large-particle slurry enters a finished product collecting tank, and the small-particle slurry enters a tailing collecting tank;
the master batch obtained in the master batch preparation stage overflows to an ageing tank through an overflow port of a reaction kettle, the ageing tank is sequentially connected with n-grade granularity grading devices in series, and in the grading treatment stage, large-particle slurry with the D50 of more than 10 microns and the Span value of 1.0-1.3, which is graded by each grading device, is transferred to a finished product collecting tank to be treated as a finished product;
wherein the masterbatch preparation stage comprises the steps of:
step one, adding pure water and ammonia water into a reaction kettle to serve as base liquid, and controlling the reaction temperature to be 40-70 ℃; continuously introducing protective gas into the reaction kettle to ensure that the oxygen concentration of the whole reaction system in the reaction kettle is less than or equal to 200 ppm;
continuously adding the salt solution of nickel, cobalt and manganese into a reaction kettle through a metering pump, and simultaneously continuously adding the alkali solution and the ammonia water into the reaction kettle through the metering pump for reaction, wherein the stirring speed is maintained at 200-800 r/min;
the pH value of the reaction system is maintained at 11.00-12.50 by adjusting the addition amount of the alkali solution; the ammonia concentration in the reaction kettle is maintained to be 0.1-1.0 mol/L by adjusting the adding amount of ammonia water;
step three, when the granularity of the product in the reaction kettle grows to 8-10 um, increasing the addition amount of the alkali solution to enable the pH of the reaction system to rise by 0.2-0.6 for secondary nucleation, and maintaining the secondary nucleation for 0.5-10 h;
after the secondary nucleation is finished, reducing the addition of the alkali solution, slowly reducing the pH value of the reaction system, stopping reducing the addition of the alkali solution for adjustment when the granularity in the reaction kettle reaches D50 of 7-9 um and the Span value of 1.2-1.6, subsequently maintaining the pH fluctuation range of the reaction kettle to be less than 0.10, starting the upper layer overflow of the reaction kettle for continuous discharging, and starting a grading treatment stage;
wherein the stage of the classification process comprises the steps of:
step one, continuously overflowing the slurry in the reaction kettle to an ageing tank, then starting a pump from the ageing tank to a feed inlet of a first grading device, and allowing the slurry in the ageing tank to enter the first grading device for grading treatment; slurry discharged from a discharge port at the upper end of the first grading device is transferred to a finished product collecting tank, and the slurry discharged from a discharge port at the upper end of the first grading device enters a first transfer tank; after the sizing agent in the ageing tank is classified, closing the pump from the ageing tank to the first classification device, and stopping the classification operation of the first classification device;
step two, after the first grading device stops grading operation, measuring and adjusting the slurry density of the first transfer tank, pumping the slurry in the first transfer tank into a second grading device after the adjustment of the slurry density of the first transfer tank is finished, and continuously grading the slurry in the first transfer tank through the second grading device;
transferring the slurry discharged from a discharge port of the second grading device into a finished product collecting tank, and feeding the slurry discharged from a discharge port at the upper end into a second transfer tank; after the density adjustment of the slurry in the second transfer tank is finished, pumping the slurry in the second transfer tank into a third grading device, and continuously grading the slurry in the second transfer tank through the third grading device;
step four, classifying the slurry in the third transit tank by a fourth classifying device according to the step three; sampling slurry discharged from a feed opening of the fourth grading device after grading is finished, measuring the granularity, if D50 is larger than 10 mu m and the Span value is 1.0-1.3, transferring the slurry into a finished product collecting tank, feeding the slurry discharged from a discharge opening at the upper end of the fourth grading device into a fourth transfer tank, and continuing the next grading operation according to the third step;
if the granularity D50 of the slurry discharged from the feed opening of the fourth grading device is less than 10 mu m, transferring the slurry to a tailing collecting tank completely, and simultaneously transferring the slurry discharged from the discharge opening at the upper end to the tailing collecting tank completely;
and step five, pumping the small-particle slurry in the tailing collecting tank back to the reaction kettle for continuous reaction.
The relevant content in the above technical solution is explained as follows:
1. in the scheme, n of the n-stage grain size grading devices connected in series is more than 3.
2. In the scheme, in the first step of the master batch preparation stage, the volume ratio of the ammonia water to the pure water in the base solution is 0.05-0.2.
3. In the scheme, in the second step of the master batch preparation stage, the salt solution of nickel, cobalt and manganese is continuously added into the reaction kettle through a metering pump, so that the liquid inlet flow rate is less than or equal to 40L/min; the alkali solution is sodium hydroxide or potassium hydroxide solution.
4. In the above scheme, in the fourth step of the masterbatch preparation stage, after the secondary nucleation is completed, the addition amount of the alkali solution may be reduced in a stepwise manner, and the specific pH reduction step may be: and reducing the pH value in a range of 0.05-0.2 every hour until the D50 is not reduced any more, and stopping reducing the pH value. The final pH value is reduced by 0.2-0.6 compared with the pH value of secondary nucleation.
5. In the above scheme, starting from the fourth grading device, the feed openings are respectively connected to the finished product collecting tank and the tailings collecting tank, and the transfer tank is connected to the tailings collecting tank.
6. In the scheme, each transfer tank is provided with a densimeter and an automatic pure water supplementing device, and the slurry density of the transfer tank is tested and adjusted to keep the slurry density range of the transfer tank within 1.2-1.5 g/cm3。
7. In the above scheme, the protective gas is nitrogen or inert gas.
8. In the above scheme, the salt solution of nickel, cobalt and manganese is one or more of a sulfate solution, a nitrate solution or a chloride solution.
9. In the scheme, the speed of overflowing the reaction kettle to the ageing tank is u0, the speed of pumping the small particle slurry of the tailing collecting tank into the reaction kettle is u1, and u1 is not more than u 0.
10. In the scheme, the volume of the slurry overflowing from the reaction kettle to the aging tank is V0, and the feeding volume pumped into the first grading device by the aging tank per minute is V1, wherein V0 is not more than 10V1, and preferably V0 is not more than 5V 1.
11. In the scheme, the operation time of the second grading device is less than or equal to 30min, preferably 0.5-15 min.
The working principle and the advantages of the invention are as follows:
the invention relates to a full-continuous synthesis process for preparing a large-particle nickel-cobalt-manganese ternary precursor, and the prepared large-particle nickel-cobalt-manganese ternary precursorThe product is NixCoyMnz(OH)2X + y + z is 1, x is more than 0 and less than 1, D50 is more than 10um, and the Span value is 1.0-1.3. The method comprises the steps of continuously producing the master batch with the D50 particle size of 7-9 um and the Span value of 1.3-1.6 in a reaction kettle, and then carrying out multistage classification treatment on the master batch to obtain a large-particle product. The large-particle nickel-cobalt-manganese ternary precursor prepared by the invention has the advantages of no adhesion of small particle sphericity, no cracking of large particles, stable product quality and the like, and is a full-continuous synthesis process, high in capacity and simple in production operation.
Compared with the prior art, the single-kettle full-continuous synthesis process is adopted to prepare the product D50 with the particle size of 7-9 microns, the Span value of 1.2-1.6 and the product D50 of less than 10 microns, so that the stirring speed can be effectively increased, the matched lowest stirring speed can meet the requirements that small particles are not adhered and large particles are not cracked, and the prepared product has excellent sphericity and wide particle size distribution; meanwhile, the stirring speed of the reaction kettle is high, the product granularity is small, the nucleation in the continuous synthesis process is facilitated, the nucleation amount in the master batch synthesis process is stable, and the quality of the master batch product discharged continuously is stable.
In addition, through carrying out multistage particle size grading to the masterbatch, final output finished product D50 > 10um, Span value 1.0~1.3, other characteristics inherit the masterbatch characteristic, have advantages such as little granule does not have the adhesion, the big granule does not have the fracture and product quality is stable. Meanwhile, the method can carry out recovery reaction on the tailings with multi-stage particle size grading, and has the advantages of simple production operation, zero slurry loss and the like.
The invention has the advantages of large product with wide distribution of large particles, uniform distribution of small particles, no adhesion of small particles, no cracking of large particles and the like.
Drawings
FIG. 1 is a schematic diagram of the structure produced by an embodiment of the present invention;
FIG. 2 is a PSD chart of masterbatches, finished products and finished comparative products according to examples of the present invention;
FIG. 3 is a SEM image I of a masterbatch according to an embodiment of the invention;
FIG. 4 is SEM image two of a masterbatch according to an embodiment of the invention;
FIG. 5 is a SEM image of a first finished product according to an embodiment of the invention;
FIG. 6 is a SEM image of a second finished product of the embodiment of the invention;
FIG. 7 is a SEM image of a finished product of a comparative example of the present invention;
FIG. 8 is SEM image II of the finished product of comparative example of the present invention.
Detailed Description
The invention is further described with reference to the following figures and examples:
the present disclosure will be described in detail and with reference to the drawings, and it is to be understood that various changes and modifications can be made by those skilled in the art without departing from the spirit and scope of the present disclosure.
As used herein, the terms "comprising," "including," "having," and the like are open-ended terms that mean including, but not limited to.
As used herein, the term (terms), unless otherwise indicated, shall generally have the ordinary meaning as commonly understood by one of ordinary skill in the art, in this written description and in the claims. Certain words used to describe the disclosure are discussed below or elsewhere in this specification to provide additional guidance to those skilled in the art in describing the disclosure.
Example (b): referring to the attached figure 1, a full-continuous synthesis process for preparing a large-particle nickel-cobalt-manganese ternary precursor is characterized in that pure water and ammonia water are added into a reaction kettle as base solution, and the reaction temperature is 50 ℃.
Continuously introducing nitrogen into the reaction kettle to ensure that the oxygen concentration of the whole reaction system in the reaction kettle is kept less than or equal to 200 ppm; and then continuously adding the salt solution of nickel, cobalt and manganese into the reaction kettle through a metering pump, and simultaneously continuously adding the alkali solution and the ammonia water into the reaction kettle through the metering pump for reaction, wherein the stirring speed is maintained at 600 r/min.
The pH value of the reaction kettle is maintained at 11.80 by adjusting the adding speed of the alkali solution; adjusting the adding speed of ammonia water to maintain the ammonia concentration in the reaction kettle at 0.35 mol/L;
when the granularity in the reaction kettle grows to 8um, increasing the adding amount of the alkali solution to control the pH to be 12.30, maintaining for 3 hours, and gradually reducing the adding amount of the alkali after 3 hours until the reaction pH reaches 11.80; the stirring speed is reduced to 400r/min, the pH fluctuation range of the reaction kettle is maintained to be less than 0.10 subsequently, and the upper layer overflow of the reaction kettle is started to continuously discharge the master batch.
The master batch overflows to an ageing tank, when the liquid level of the ageing tank reaches 90%, the ageing tank is started to a first grading device for grading treatment, and the grading operation time is 2 min; and then, sequentially starting the second, third and fourth grading devices to carry out grading treatment, wherein the grading operation time is 2 min.
And (3) sampling and measuring the granularity of slurry discharged from a feed opening of the fourth grading device, and if the granularity result shows that D50 is 9.75um < 10um, finishing the granularity grading, transferring all the slurry discharged from the feed openings of the first, second and third grading devices to a finished product collecting tank to be processed into a finished product, and transferring all the slurry discharged from the feed opening of the fourth grading device and the slurry of a fourth transfer tank to a tail material collecting tank.
And after the tailing collecting tank feeds, starting a pump from the tailing collecting tank to the reaction kettle, and slowly transferring to the reaction kettle at the speed of 5L/min to continue the reaction.
Comparative example:
adding pure water and ammonia water as base solution into a reaction kettle, wherein the reaction temperature is 50 ℃;
continuously introducing nitrogen into the reaction kettle to ensure that the oxygen concentration of the whole reaction system in the reaction kettle is kept less than or equal to 200 ppm; then continuously adding the salt solution of nickel, cobalt and manganese into the reaction kettle through a metering pump, and simultaneously continuously adding the alkali solution and the ammonia water into the reaction kettle through the metering pump for reaction, wherein the stirring speed is maintained at 600 r/min;
the pH value of the reaction kettle is maintained at 11.80 by adjusting the adding speed of the alkali solution; adjusting the adding speed of ammonia water to maintain the ammonia concentration in the reaction kettle at 0.35 mol/L;
when the granularity in the reaction kettle grows to 12um, increasing the adding amount of the alkali solution to control the pH to be 12.30, maintaining for 3 hours, and gradually reducing the adding amount of the alkali after 3 hours until the reaction pH reaches 11.80; the stirring speed is reduced to 300r/min, the pH fluctuation range of the reaction kettle is maintained to be less than 0.10, and the upper layer overflow of the reaction kettle is started to continuously discharge finished products.
TABLE 1 example- -comparative example slurry particle size data
Figure BDA0003492413990000061
Figure BDA0003492413990000071
As can be seen from Table 1 and attached figure 2, the masterbatch can produce a wide-distribution large-particle ternary precursor finished product after multi-stage classification treatment, and D50 reaches 15 micrometers and the Span value is greater than 1.0, which reaches the same level of a single-kettle continuous process.
As shown in the attached drawings 3-6, the wide-distribution large-particle ternary precursor finished product produced by the method inherits the morphological characteristics of the master batch in the reaction kettle, and has excellent sphericity and no spherical crack on the particle surface.
As can be seen from the accompanying FIGS. 7-8, the large-particle products with wide distribution prepared by the comparative example have serious surface open, and the small particles are attached to the surface of the large particles, so if the rotating speed is reduced to improve the surface open condition, the small particles are easy to adhere to the large particles, which results in the reduction of the sphericity of the products.
According to the invention, a single-kettle full-continuous synthesis process is adopted to prepare the product D50 with the particle size of 7-9 um, the Span value of 1.2-1.6, the D50 of the product is less than 10 microns, the stirring speed can be effectively increased, the matched lowest stirring speed can meet the requirements that small particles are not adhered and large particles are not cracked, and the prepared product has excellent sphericity and wide particle size distribution; meanwhile, the stirring speed of the reaction kettle is high, the product granularity is small, the nucleation in the continuous synthesis process is facilitated, the nucleation amount in the master batch synthesis process is stable, and the quality of the master batch product discharged continuously is stable.
In addition, through carrying out multistage particle size grading to the masterbatch, final output finished product D50 > 10um, Span value 1.0~1.3, other characteristics inherit the masterbatch characteristic, have advantages such as little granule does not have the adhesion, the big granule does not have the fracture and product quality is stable. Meanwhile, the method can be used for carrying out recovery reaction on tailings with multistage particle size grading, and has the advantages of simple production operation, zero slurry loss and the like.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered in the protection scope of the present invention.

Claims (9)

1. A full-continuous synthesis process for preparing a large-particle nickel-cobalt-manganese ternary precursor is characterized by comprising the following steps of:
comprises a master batch preparation stage and a grading treatment stage;
in the preparation stage of the master batch, the master batch of the ternary precursor is prepared by a reaction kettle, and the chemical formula is NixCoyMnz(OH)2Wherein x + y + z =1, x is more than 0 and less than 1, D50 of the master batch is 7-9 um, and the Span value is 1.2-1.6;
in the stage of grading treatment, grading collection of different granularities is carried out on product slurry through n grades of particle size grading devices which are connected in series, and each grading device is provided with a feed inlet on the side part, a discharge outlet on the upper end and a feed outlet; the classified large-particle slurry enters a finished product collecting tank, and the small-particle slurry enters a tailing collecting tank;
the master batch obtained in the master batch preparation stage overflows to an ageing tank through an overflow port of a reaction kettle, the ageing tank is sequentially connected with n-grade granularity grading devices in series, and in the grading treatment stage, large-particle slurry with the D50 of more than 10 microns and the Span value of 1.0-1.3, which is graded by each grading device, is transferred to a finished product collecting tank to be treated as a finished product;
wherein the masterbatch preparation stage comprises the steps of:
step one, adding pure water and ammonia water into a reaction kettle to serve as base liquid, and controlling the reaction temperature to be 40-70 ℃; continuously introducing protective gas into the reaction kettle to ensure that the oxygen concentration of the whole reaction system in the reaction kettle is less than or equal to 200 ppm;
continuously adding the salt solution of nickel, cobalt and manganese into a reaction kettle through a metering pump, and simultaneously continuously adding the alkali solution and the ammonia water into the reaction kettle through the metering pump for reaction, wherein the stirring speed is maintained at 200-800 r/min;
the pH value of the reaction system is maintained at 11.00-12.50 by adjusting the addition amount of the alkali solution; the ammonia concentration in the reaction kettle is maintained to be 0.1-1.0 mol/L by adjusting the adding amount of ammonia water;
step three, when the granularity of the product in the reaction kettle grows to 8-10 um, increasing the addition amount of the alkali solution to enable the pH of the reaction system to rise by 0.2-0.6 for secondary nucleation, and maintaining the secondary nucleation for 0.5-10 h;
after the secondary nucleation is finished, reducing the addition of the alkali solution, slowly reducing the pH value of the reaction system, stopping reducing the addition of the alkali solution for adjustment when the granularity in the reaction kettle reaches D50 of 7-9 um and the Span value of 1.2-1.6, subsequently maintaining the pH fluctuation range of the reaction kettle to be less than 0.10, starting the upper layer overflow of the reaction kettle for continuous discharging, and starting a grading treatment stage;
wherein the stage of the classification process comprises the steps of:
step one, continuously overflowing the slurry in the reaction kettle to an ageing tank, then starting a pump from the ageing tank to a feed inlet of a first grading device, and allowing the slurry in the ageing tank to enter the first grading device for grading treatment; slurry discharged from a discharge port of the first grading device is transferred into a finished product collecting tank, and slurry discharged from a discharge port at the upper end enters a first transfer tank; after the sizing agent in the ageing tank is classified, closing the pump from the ageing tank to the first classification device, and stopping the classification operation of the first classification device;
step two, after the first grading device stops grading operation, measuring and adjusting the slurry density of the first transfer tank, pumping the slurry in the first transfer tank into a second grading device after the adjustment of the slurry density of the first transfer tank is finished, and continuously grading the slurry in the first transfer tank through the second grading device;
transferring the slurry discharged from a discharge port of the second grading device into a finished product collecting tank, and feeding the slurry discharged from a discharge port at the upper end into a second transfer tank; after the adjustment of the slurry density of the second transfer tank is finished, pumping the slurry in the second transfer tank into a third grading device, and continuously grading the slurry in the second transfer tank through the third grading device;
step four, classifying the slurry in the third transit tank by a fourth classifying device according to the step three; sampling slurry discharged from a feed opening of the fourth grading device after grading is finished, measuring the granularity, if D50 is larger than 10 mu m and the Span value is 1.0-1.3, transferring the slurry into a finished product collecting tank, feeding the slurry discharged from a discharge opening at the upper end of the fourth grading device into a fourth transfer tank, and continuing the next grading operation according to the third step;
if the granularity D50 of the slurry discharged from the feed opening of the fourth grading device is less than 10um, transferring the slurry to a tailing collecting tank completely, and simultaneously transferring the slurry discharged from the discharge opening at the upper end of the fourth grading device to the tailing collecting tank completely;
and step five, pumping the small-particle slurry in the tailing collecting tank back to the reaction kettle for continuous reaction.
2. The fully continuous synthesis process according to claim 1, characterized in that: the n of the serially connected n-stage grain size grading devices is more than 3.
3. The fully continuous synthesis process according to claim 1, characterized in that: and starting from the fourth grading device, the feed openings are respectively connected to the finished product collecting tank and the tailing collecting tank, and the transfer tank is connected to the tailing collecting tank.
4. The fully continuous synthesis process according to claim 1, characterized in that: each transfer tank is provided with a densimeter and an automatic pure water supplementing device for testing and adjusting the slurry density of the transfer tank, so that the slurry density range of the transfer tank is kept between 1.2 and 1.5g/cm3。
5. The fully continuous synthesis process according to claim 1, characterized in that: the protective gas is nitrogen or inert gas.
6. The fully continuous synthesis process according to claim 1, characterized in that: the salt solution of nickel cobalt manganese is one or more of sulfate solution, nitrate solution or chloride solution.
7. The fully continuous synthesis process according to claim 1, characterized in that: the speed of overflowing the reaction kettle to the ageing tank is u0, the speed of pumping the small particle slurry in the tailing collecting tank into the reaction kettle is u1, and u1 is not more than u 0.
8. The fully continuous synthesis process according to claim 1, characterized in that: the volume of the slurry overflowing to the aging tank from the reaction kettle is V0, and the feeding volume pumped into the first grading device by the aging tank per minute is V1, wherein V0 is not more than 10V 1.
9. The fully continuous synthesis process according to claim 1, characterized in that: the grading operation time is less than or equal to 30min from the operation of the second grading device.
CN202210100856.0A 2022-01-27 2022-01-27 Full-continuous synthesis process for preparing large-particle nickel-cobalt-manganese ternary precursor Pending CN114506880A (en)

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CN108987682A (en) * 2017-06-02 2018-12-11 杉杉能源（宁夏）有限公司 It can prevent the preparation method of the Ni-based persursor material of richness of breakage of particles
CN109422297A (en) * 2017-08-28 2019-03-05 湖南杉杉能源科技股份有限公司 Regulate and control the method for nucleation in a kind of nickel cobalt manganese presoma crystallization process
CN113120974A (en) * 2021-04-01 2021-07-16 广东邦普循环科技有限公司 Preparation method and application of high-nickel ternary precursor
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CN105355902A (en) * 2015-11-23 2016-02-24 兰州金川新材料科技股份有限公司 Preparation method for continuously synthesizing lithium ion positive electrode material precursor
CN108987682A (en) * 2017-06-02 2018-12-11 杉杉能源（宁夏）有限公司 It can prevent the preparation method of the Ni-based persursor material of richness of breakage of particles
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