CN113666434A - Preparation method of nickel-cobalt-manganese ternary precursor seed crystal - Google Patents
Preparation method of nickel-cobalt-manganese ternary precursor seed crystal Download PDFInfo
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- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000013078 crystal Substances 0.000 title claims abstract description 36
- 239000002243 precursor Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 104
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 93
- 239000007788 liquid Substances 0.000 claims abstract description 51
- 239000002002 slurry Substances 0.000 claims abstract description 48
- 239000002245 particle Substances 0.000 claims abstract description 43
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 34
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 34
- 239000000243 solution Substances 0.000 claims abstract description 33
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 31
- 239000012266 salt solution Substances 0.000 claims abstract description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 26
- 239000001301 oxygen Substances 0.000 claims abstract description 26
- 239000011572 manganese Substances 0.000 claims abstract description 17
- 238000000975 co-precipitation Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 230000003647 oxidation Effects 0.000 claims abstract description 5
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 5
- 150000002500 ions Chemical class 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- 239000002585 base Substances 0.000 claims description 11
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 1
- 239000012467 final product Substances 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 4
- 238000010899 nucleation Methods 0.000 abstract description 3
- 230000006911 nucleation Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- 238000001035 drying Methods 0.000 description 4
- 239000011265 semifinished product Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000012066 reaction slurry Substances 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- -1 manganese oxide ions Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
Classifications
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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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A preparation method of a nickel-cobalt-manganese ternary precursor seed crystal comprises the following steps: preparing a nickel-cobalt-manganese mixed salt solution, liquid caustic soda and an ammonia water solution; preparing reaction base liquid in a reaction kettle and introducing N2(ii) a Respectively and continuously introducing a nickel-cobalt-manganese mixed salt solution, liquid caustic soda and an ammonia water solution into a reaction kettle for coprecipitation reaction; the slurry generated by the coprecipitation reaction begins overflowing when the grain diameter D50 is 90-95% of the target grain diameter, and the N is stopped to be introduced2Then introducing oxygen into the residual slurry in the reaction kettle to lead Mn in the slurry to be2+By oxidation to Mn4+(ii) a And stopping introducing oxygen when the slurry D00 in the reaction kettle is less than 1.0 mu m and the radial distance D is more than or equal to 0.9, thus obtaining the nickel-cobalt-manganese ternary precursor seed crystal. The invention is characterized in that Mn in the feed liquid is added2+Oxidation to Mn with smaller solubility product4+The method has the advantages of simple operation, stable pH value in the reaction process, easy control of the balance between crystal nucleation and growth, small fluctuation of particle size distribution and good consistency of precursor particle morphology.
Description
Technical Field
The invention relates to the field of preparation of new energy battery material precursors, in particular to a preparation method of a nickel-cobalt-manganese ternary precursor seed crystal.
Background
The nickel-cobalt-manganese ternary precursor is the most important raw material for preparing the lithium ion battery anode material, the main preparation method of the ternary precursor is that a nickel-cobalt-manganese metal salt solution, liquid caustic soda and ammonia water are simultaneously added into a reaction kettle for coprecipitation reaction, in the process of preparing the ternary precursor by a continuous method (feeding and discharging at the same time), the particle size and the distribution of a target precursor are generally prepared by controlling reaction balance through adjusting the pH value of slurry of the reaction kettle, the concentration of ammonia, ternary flow and the like, the change of the pH value is realized through the addition of the liquid caustic soda in a certain time, if the pH adjustment amplitude is small, seed crystals cannot be excessively formed, the precursor particles in the reaction kettle are always agglomerated and grown, the particle size distribution is too narrow and cannot meet the requirement, if the pH adjustment amplitude is too large, the seed crystals can be explosively generated in a short time, the reaction balance is seriously damaged, and the material is scrapped, in addition, the primary particle crystallization of the precursor can be influenced by the pH period fluctuation, so that the morphology difference of the secondary particles of the precursor is large.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a nickel-cobalt-manganese ternary precursor seed crystal.
The invention is realized by the following technical scheme.
A preparation method of a nickel-cobalt-manganese ternary precursor seed crystal is characterized by comprising the following steps:
(1) preparing a nickel-cobalt-manganese mixed salt solution, liquid caustic soda and an ammonia water solution; preparing reaction base liquid in a reaction kettle and introducing N2；
(2) Continuously introducing the nickel-cobalt-manganese mixed salt solution, the liquid caustic soda and the ammonia water solution obtained in the step (1) into a reaction kettle respectively to carry out coprecipitation reaction;
(3) with continuous feeding, the particle size D50 of the slurry generated by the coprecipitation reaction is 90-95% of the target particle size and overflows, and the feeding of N is stopped at the moment2Then introducing oxygen into the residual slurry in the reaction kettle to lead Mn in the slurry to be2+By oxidation to Mn4+；
(4) And stopping introducing oxygen when the particle size D00 of the slurry in the reaction kettle is less than 1.0 mu m and the diameter distance D (D ═ D90-D10)/D50) is not less than 0.9, so as to obtain the nickel-cobalt-manganese ternary precursor seed crystal.
Furthermore, the concentration of the nickel-cobalt-manganese mixed salt solution is 80-130g/L, wherein the concentration of Ni ions is 30-70g/L, the concentration of Co ions is 10-30g/L, and the concentration of Mn ions is 20-40 g/L; the concentration of the liquid caustic soda is 25-35%, and the concentration of the ammonia water solution is 12-20%.
Further, the volume of the reaction bottom liquid in the step (1) is 1/2-5/6 of the volume of the reaction kettle.
Further, the reaction bottom liquid in the step (1) is prepared by mixing ammonia water and liquid alkali, wherein the ammonia concentration of the reaction bottom liquid is 8.0-12.0g/L, and the pH value is 10.0-12.0.
Further, said step (1) N2The flow rate of (A) is 0.2-1.5m3/h。
Further, the flow rates of the nickel-cobalt-manganese mixed salt solution, the liquid caustic soda and the ammonia water solution in the step (2) are respectively 600L/h, 60-350L/h and 20-70L/h.
Further, the oxygen concentration in the step (3) is 20-100%, and the flow rate is 0.05-0.5m3/h。
Further, when the grain diameter of the slurry in the reaction kettle continuously grows to D00 more than 1.0 mu m and D50 is 1.05-1.10 times of the target grain diameter of the finished product, stopping introducing N2And (5) continuously introducing oxygen, and repeating the step (3) and the step (4).
The invention has the beneficial technical effects that Mn in the feed liquid is added2+Oxidation to Mn with smaller solubility product4 +And then periodically nucleating and growing up to realize continuous production of the nickel-cobalt-manganese ternary precursor. The invention has small alkali flow regulating amplitude in the continuous production process, stable pH of reaction slurry, easy control of the balance between crystal nucleation and growth and small fluctuation of particle size distribution; critical parameter waves of pH, ammonia concentration, total alkalinity and the like of slurry in reaction processSmall movement, good consistency of the shape of precursor particles; avoiding fine grains or irregular flocculent precipitates generated when the pH fluctuation is large from entering the finished product slurry to finally influence the quality of the product.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
A preparation method of a nickel-cobalt-manganese ternary precursor seed crystal comprises the following steps:
(1) preparing a nickel-cobalt-manganese mixed salt solution, liquid caustic soda and an ammonia water solution; preparing reaction base liquid in a reaction kettle and introducing N2(ii) a Wherein the concentration of the nickel-cobalt-manganese mixed salt solution is 80-130g/L, the concentration of Ni ions is 30-70g/L, the concentration of Co ions is 10-30g/L, and the concentration of Mn ions is 20-40 g/L; the concentration of the liquid caustic soda is 25-35%, the concentration of the ammonia water solution is 12-20%, and the volume of the reaction bottom liquid is 1/2-5/6 of the volume of the reaction kettle; the reaction base solution is prepared by mixing ammonia water and liquid alkali, the ammonia concentration of the reaction base solution is 8.0-12.0g/L, and the pH value is 10.0-12.0; n is a radical of2The flow rate of (A) is 0.2-1.5m3/h；
(2) Continuously introducing the nickel-cobalt-manganese mixed salt solution, the liquid caustic soda and the ammonia water solution obtained in the step (1) into a reaction kettle respectively to carry out coprecipitation reaction; wherein the flow rates of the nickel-cobalt-manganese mixed salt solution, the liquid caustic soda and the ammonia water are respectively 600L/h, 60-350L/h and 20-70L/h;
(3) continuously feeding materials, continuously agglomerating and growing primary particles generated by coprecipitation reaction, and when the particle size D50 of the slurry is smaller than 90% of the target particle size, overflowing the reaction slurry from an overflow port of the reaction kettle to a semi-finished product tank, wherein the overflowing materials can be used as a bottom material of the reaction kettle;
(4) continuing the reaction, wherein the particle size D50 of the generated slurry is 90-95% of the target particle size of the finished product, overflowing the slurry from the reaction kettle to a finished product tank, and stopping introducing N2Introducing oxygen into the residual slurry in the reaction kettle to lead Mn to2+Oxidized to higher valence Mn4+Seed crystal is manufactured; wherein the oxygen concentration is 20% -100%, and the flow rate is 0.05-0.5m3/h。
(5) When the particle size of the slurry in the reaction kettle is D00 less than 1.0 μm and the diameter distance D (D ═ D90-D10)/D50) ≥ 0.9, stopping introducing oxygen, and reducing the generation of excessive seed crystals to obtain the required seed crystals.
(6) Introduction of N2Protecting secondary particles in the reaction slurry from continuously agglomerating and growing, and keeping the flow of ternary liquid, the flow of ammonia water, the flow of liquid alkali and the pH value stable in the process; stopping introducing N when the D00 is larger than 1.0 μm and the D50 is 1.05-1.10 times of the target particle size of the finished product as the particle size of the slurry in the reaction kettle continuously grows2Continuously introducing oxygen, making seed crystals by using manganese oxide ions, repeating the step (4) and the step (5), and keeping the particle size of the slurry in the reaction kettle to stably fluctuate; and washing and drying the slurry overflowing to the finished product tank to obtain the nickel-cobalt-manganese ternary precursor.
Example 1
A preparation method of a nickel-cobalt-manganese ternary precursor seed crystal comprises the following steps:
(1) preparing a nickel-cobalt-manganese mixed salt solution, liquid caustic soda and an ammonia water solution; preparing reaction base liquid in a reaction kettle and introducing N2(ii) a The concentration of the nickel-cobalt-manganese mixed salt solution is 90g/L, the concentration of Ni ions is 47g/L, the concentration of Co ions is 18g/L, the concentration of Mn ions is 25g/L, the concentration of liquid caustic soda is 30%, the concentration of an ammonia water solution is 14%, the volume of a reaction bottom solution is 1/2 of the volume of a reaction kettle, the concentration of ammonia of the reaction bottom solution is 9.5g/L, and the pH value is 10.0; n is a radical of2Flow rate of 0.5m3/h；
(2) Respectively introducing the nickel-cobalt-manganese mixed salt solution, the liquid caustic soda and the ammonia water solution obtained in the step (1) into a reaction kettle for coprecipitation reaction; wherein the flow rates of the nickel-cobalt-manganese mixed salt solution, the liquid caustic soda and the ammonia water solution are respectively 200L/h, 60L/h and 25L/h;
(3) with continuous feeding, slurry particles generated by coprecipitation reaction are continuously agglomerated and grow, the particle size D50 is less than 12.0 mu m, excessive materials in the reaction kettle flow into a semi-finished product groove from an overflow port of the reaction kettle, wherein overflow materials with the particle size D50 less than 12.0 mu m can be used as a bottom material of the reaction kettle;
(4) the reaction is continued, the particle size D50 of the generated slurry reaches 12.0 mu m (namely 92.0 percent of the target particle size), the slurry overflows from the reaction kettle to a finished product tank, and the N is stopped to be introduced2Introducing oxygen into the residual slurry in the reaction kettle to lead Mn to2+Oxidized to higher valence Mn4+Seed crystal is manufactured; wherein the oxygen concentration is 99 percent and the flow rate is 0.05m3/h；
(5) When the residual slurry D00 in the reaction kettle is less than 1.0 μm and the diameter distance D is 0.90-0.95, stopping introducing oxygen to obtain fine secondary balls formed by excessive seed crystals.
(6) Introduction of N2Protecting to enable the seed crystal to grow, and keeping the flow of the nickel-cobalt-manganese mixed salt solution, the flow of ammonia water, the flow of liquid caustic soda and the pH value stable in the process; when the D00 is larger than 1.0 μm and the D50 reaches 14.0 μm (i.e. 107.0% of the target particle size) with the continuous growth of the slurry in the reaction kettle, the introduction of N is stopped2Continuously introducing oxygen, continuously seeding the manganese oxide ions, repeating the step (4) and the step (5), and keeping the particle size of the slurry in the reaction kettle to stably fluctuate; and washing and drying the slurry overflowing to the finished product tank to obtain the nickel-cobalt-manganese ternary precursor.
Example 2
A preparation method of a nickel-cobalt-manganese ternary precursor seed crystal comprises the following steps:
(1) preparing a nickel-cobalt-manganese mixed salt solution, liquid caustic soda and an ammonia water solution; preparing reaction base liquid in a reaction kettle and introducing N2(ii) a The concentration of the nickel-cobalt-manganese mixed salt solution is 100g/L, the concentration of Ni ions is 50g/L, the concentration of Co ions is 20g/L, the concentration of Mn ions is 30g/L, the concentration of liquid caustic soda is 31%, the concentration of an ammonia water solution is 20%, the volume of a reaction bottom solution is 5/6 of the volume of a reaction kettle, the concentration of ammonia of the reaction bottom solution is 10.0g/L, and the pH value is 10.5; n is a radical of2Flow rate of 0.8m3/h；
(2) Respectively introducing the nickel-cobalt-manganese mixed salt solution, the liquid caustic soda and the ammonia water solution obtained in the step (1) into a reaction kettle for coprecipitation reaction; wherein the flow rates of the nickel-cobalt-manganese mixed salt solution, the liquid caustic soda and the ammonia water solution are respectively 260L/h, 88L/h and 38L/h;
(3) with continuous feeding, slurry particles generated by coprecipitation reaction are continuously agglomerated and grow, the particle size D50 is less than 12.5 mu m, excessive materials in the reaction kettle flow into a semi-finished product groove from an overflow port arranged on the reaction kettle, wherein the overflow material with the particle size D50 less than 12.5 mu m can be used as a bottom material of the reaction kettle;
(4) the reaction is continued until the particle size D50 of the slurry reaches 12.5 μm (93.0% of the target particle size), and the slurry begins to overflow to a finished product tank, at which time the introduction of N is stopped2Introducing oxygen into the residual slurry in the reaction kettle to lead Mn to2+Oxidized to higher valence Mn4+Seed crystal is manufactured; wherein the oxygen concentration is 49% and the flow rate is 0.3m3/h；
(5) When the residual slurry D00 in the reaction kettle is less than 1.0 μm and the diameter distance D is 0.95-1.00, stopping introducing oxygen to obtain fine secondary balls formed by excessive seed crystals.
(6) Introduction of N2Protecting to enable the seed crystal to grow, and keeping the flow of the nickel-cobalt-manganese mixed salt solution, the flow of ammonia water, the flow of liquid caustic soda and the pH value stable in the process; when the D50 reaches 14.5 mu m (i.e. 107.0 percent of the target particle size) as the slurry in the reaction kettle continuously grows until the D00 is more than 1.02Continuously starting oxygen, oxidizing manganese ions to seed, repeating the step (4) and the step (5), and keeping the particle size of the slurry in the reaction kettle to stably fluctuate; and washing and drying the slurry overflowing to the finished product tank to obtain the nickel-cobalt-manganese ternary precursor.
Example 3
A preparation method of a nickel-cobalt-manganese ternary precursor seed crystal comprises the following steps:
(1) preparing a nickel-cobalt-manganese mixed salt solution, liquid caustic soda and an ammonia water solution; preparing reaction base liquid in a reaction kettle and introducing N2(ii) a The concentration of the nickel-cobalt-manganese mixed salt solution is 130g/L, the concentration of Ni ions is 66g/L, the concentration of Co ions is 27g/L, the concentration of Mn ions is 37g/L, the concentration of liquid caustic soda is 35%, the concentration of ammonia water solution is 16%, the volume of reaction bottom liquid is 1/2 of the volume of a reaction kettle, the concentration of ammonia of the reaction bottom liquid is 10.7g/L, and the pH value is 11.8; n is a radical of2Flow rate of 1.5m3/h；
(2) Respectively introducing the nickel-cobalt-manganese mixed salt solution, the liquid caustic soda and the ammonia water solution obtained in the step (1) into a reaction kettle for coprecipitation reaction; wherein the flow rates of the nickel-cobalt-manganese mixed salt solution, the liquid caustic soda and the ammonia water solution are respectively 600L/h, 220L/h and 70L/h;
(3) with continuous feeding, slurry particles generated by coprecipitation reaction are continuously agglomerated and grow, the particle size D50 is less than 9.0 mu m, excessive materials in the reaction kettle flow into a semi-finished product groove from an overflow port of the reaction kettle, wherein overflow materials with the particle size D50 less than 9.0 mu m can be used as a bottom material of the reaction kettle;
(4) the reaction is continued to be carried out,slurry D50 reached 9.0 μm (i.e., 90.0% of the target particle size) and overflowed from the autoclave to the finishing tank, at which time N was turned off2Introducing oxygen into the residual slurry in the reaction kettle to lead Mn to2+Oxidized to higher valence Mn4+Seed crystal is manufactured; wherein the oxygen concentration is 29 percent and the flow rate is 0.5m3/h；
(5) When the residual slurry D00 in the reaction kettle is less than 1.0 μm, the diameter distance D is 0.93-0.98, and the D10 is 4.0-5.0 μm, the oxygen is closed, and fine secondary balls formed by excessive seed crystals are obtained.
(6) Introduction of N2Protecting to enable the seed crystal to grow, and keeping the flow of the nickel-cobalt-manganese mixed salt solution, the flow of ammonia water, the flow of liquid caustic soda and the pH value stable in the process; when the D00 is larger than 1.0 and the D50 reaches 11.0 mu m (namely 110.0 percent of the target particle size) with the continuous growth of the slurry in the reaction kettle, the N is closed2Continuously starting oxygen, oxidizing manganese ions to seed, repeating the step (4) and the step (5), and keeping the particle size of the slurry in the reaction kettle to stably fluctuate; and washing and drying the slurry overflowing to the finished product tank to obtain the nickel-cobalt-manganese ternary precursor.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention. It should be noted that other equivalent modifications can be made by those skilled in the art in light of the teachings of the present invention, and all such modifications can be made as are within the scope of the present invention.
Claims (8)
1. A preparation method of a nickel-cobalt-manganese ternary precursor seed crystal is characterized by comprising the following steps:
(1) preparing a nickel-cobalt-manganese mixed salt solution, liquid caustic soda and an ammonia water solution; preparing reaction base liquid in a reaction kettle and introducing N2；
(2) Continuously introducing the nickel-cobalt-manganese mixed salt solution, the liquid caustic soda and the ammonia water solution obtained in the step (1) into a reaction kettle respectively to carry out coprecipitation reaction;
(3) with continuous feeding, the particle size D50 of the slurry generated by the coprecipitation reaction is 90-95% of the target particle size and overflows, and the feeding of N is stopped at the moment2Then introducing oxygen into the residual slurry in the reaction kettle to lead Mn in the slurry to be2+By oxidation to Mn4+；
(4) And stopping introducing oxygen when the particle size D00 of the slurry in the reaction kettle is less than 1.0 mu m and the radial distance D is more than or equal to 0.9, thus obtaining the nickel-cobalt-manganese ternary precursor seed crystal.
2. The method for preparing the nickel-cobalt-manganese ternary precursor seed crystal according to claim 1, wherein the concentration of the nickel-cobalt-manganese mixed salt solution is 80-130g/L, wherein the concentration of Ni ions is 30-70g/L, the concentration of Co ions is 10-30g/L, and the concentration of Mn ions is 20-40 g/L; the concentration of the liquid caustic soda is 25-35%, and the concentration of the ammonia water solution is 12-20%.
3. The method for preparing the nickel-cobalt-manganese ternary precursor seed crystal according to claim 1, wherein the volume of the reaction base solution in the step (1) is 1/2-5/6 of the volume of the reaction kettle.
4. The method for preparing the nickel-cobalt-manganese ternary precursor seed crystal according to claim 1, wherein the reaction base solution in the step (1) is prepared by mixing ammonia water and liquid alkali, the concentration of the ammonia in the reaction base solution is 8.0-12.0g/L, and the pH is 10.0-12.0.
5. The method for preparing the nickel-cobalt-manganese ternary precursor seed crystal according to claim 1, wherein the step (1) is N2The flow rate of (A) is 0.2-1.5m3/h。
6. The method as claimed in claim 1, wherein the flow rates of the nickel-cobalt-manganese mixed salt solution, the liquid caustic soda and the ammonia solution in step (2) are respectively 200-600L/h, 60-350L/h and 20-70L/h.
7. The method for preparing nickel-cobalt-manganese ternary precursor seed crystal according to claim 1, wherein the oxygen concentration in the step (3) is 20-100%, and the flow rate is 0.05-0.5m3/h。
8. The method of claim 1, wherein the introduction of N is stopped when the slurry particle size in the reactor continuously grows to D00 > 1.0 μm and D50 is 1.05-1.10 times of the target particle size of the final product2And (5) continuously introducing oxygen, and repeating the step (3) and the step (4).
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114132972A (en) * | 2021-12-21 | 2022-03-04 | 天齐创锂科技(深圳)有限公司 | Method for controlling concentrated distribution of particle size of precursor of ternary cathode material |
| CN115043438A (en) * | 2022-05-24 | 2022-09-13 | 华友新能源科技（衢州）有限公司 | Ternary precursor and preparation method thereof |
| CN115893527A (en) * | 2022-12-26 | 2023-04-04 | 荆门市格林美新材料有限公司 | Method for synthesizing large-particle nickel-cobalt-manganese ternary precursor |
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| US20140011090A1 (en) * | 2011-03-28 | 2014-01-09 | Hiroyuki Toya | Nickel manganese composite hydroxide particles and manufacturing method thereof, cathode active material for a non-aqueous electrolyte secondary battery and manufacturing method thereof, and a non-aqueous electrolyte secondary battery |
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| CN115043438B (en) * | 2022-05-24 | 2023-09-26 | 华友新能源科技（衢州）有限公司 | Ternary precursor and preparation method thereof |
| CN115893527A (en) * | 2022-12-26 | 2023-04-04 | 荆门市格林美新材料有限公司 | Method for synthesizing large-particle nickel-cobalt-manganese ternary precursor |
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