CN115745017A - Method for preparing narrow-distribution small-particle-size high-nickel ternary precursor by using continuous reactor system and method for preparing narrow-distribution small-particle-size high-nickel ternary precursor - Google Patents
Method for preparing narrow-distribution small-particle-size high-nickel ternary precursor by using continuous reactor system and method for preparing narrow-distribution small-particle-size high-nickel ternary precursor Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 78
- 239000002243 precursor Substances 0.000 title claims abstract description 66
- 238000009826 distribution Methods 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 172
- 239000002245 particle Substances 0.000 claims description 113
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 63
- 239000007864 aqueous solution Substances 0.000 claims description 55
- 239000002002 slurry Substances 0.000 claims description 55
- 239000008139 complexing agent Substances 0.000 claims description 39
- 229910052751 metal Inorganic materials 0.000 claims description 38
- 239000002184 metal Substances 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 38
- 239000012266 salt solution Substances 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 28
- 230000001681 protective effect Effects 0.000 claims description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 15
- 229910017052 cobalt Inorganic materials 0.000 claims description 15
- 239000010941 cobalt Substances 0.000 claims description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 15
- 239000011572 manganese Substances 0.000 claims description 15
- 239000012716 precipitator Substances 0.000 claims description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 11
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 238000003541 multi-stage reaction Methods 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000009472 formulation Methods 0.000 claims description 2
- 238000010924 continuous production Methods 0.000 abstract description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- 230000006911 nucleation Effects 0.000 abstract description 5
- 238000010899 nucleation Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000010405 anode material Substances 0.000 abstract description 2
- 238000000975 co-precipitation Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000013078 crystal Substances 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 229910021529 ammonia Inorganic materials 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000003513 alkali Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 238000005054 agglomeration Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- 150000001868 cobalt Chemical class 0.000 description 4
- 229940044175 cobalt sulfate Drugs 0.000 description 4
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 4
- 150000002696 manganese Chemical class 0.000 description 4
- 229940099596 manganese sulfate Drugs 0.000 description 4
- 239000011702 manganese sulphate Substances 0.000 description 4
- 235000007079 manganese sulphate Nutrition 0.000 description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 4
- 150000002815 nickel Chemical class 0.000 description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 4
- 229940053662 nickel sulfate Drugs 0.000 description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 4
- 230000000087 stabilizing effect Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910006178 NixCoyMn(1-x-y)(OH)2 Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of lithium ion battery anode materials, in particular to a narrow-distribution small-particle-size high-nickel ternary precursor prepared by a continuous reactor system and a method thereof. The method is characterized in that coprecipitation reaction is carried out in a continuous reactor system, reaction parameters in each reaction kettle are controlled, so that nucleation is continuously carried out in the first reaction kettle through the continuous reactor system, nucleation is avoided in the second reaction kettle and the third reaction kettle, and continuous growth is carried out, so that continuous production is realized, the production yield and the production efficiency are greatly improved, the method is suitable for industrial production, and the prepared ternary precursor is good in sphericity, narrow in distribution and high in tap density.
Description
Technical Field
The invention relates to the technical field of lithium ion battery anode materials, in particular to a narrow-distribution small-particle-size high-nickel ternary precursor prepared by a continuous reactor system and a method thereof.
Background
Lithium ion batteries have been widely used in the fields of portable electronic devices, energy storage base stations, electric vehicles, national defense and military industry, etc., due to their advantages of high energy density, high voltage, long cycle life, etc. The performance of the lithium ion battery is directly determined by the quality of the cathode material, and the nickel-cobalt-manganese ternary cathode material has the advantages of stable chemical structure, low price, high capacity and the like, and is a mainstream in all lithium ion battery cathode materials.
The key technology of the ternary cathode material lies in the preparation of a ternary precursor, the higher the nickel content is, the higher the specific capacity of the ternary cathode material is, but the difficulty in preparing the ternary precursor is also higher. Particularly, the preparation of the small-particle-size high-nickel ternary precursor is required to have good particle consistency, good sphericity without agglomeration, high tap density and narrow distribution, and the requirements greatly limit the continuous production process of the small-particle-size high-nickel ternary precursor and reduce the production efficiency.
Disclosure of Invention
The invention aims to solve the technical problems that the small-particle-size high-nickel ternary precursor is uninterruptedly synthesized, the continuous production is realized, and the synthesized small-particle-size high-nickel ternary precursor has good sphericity, high consistency, high tap density and narrow distribution in the prior art. The invention aims to provide a narrow-distribution small-particle-size high-nickel ternary precursor, and the invention aims to provide a preparation method of the narrow-distribution small-particle-size high-nickel ternary precursor.
The technical scheme adopted by the invention for solving the technical problem is as follows:
one of the purposes of the invention is to provide a method for preparing a narrow-distribution small-particle-size high-nickel ternary precursor by using a continuous reactor system, wherein the method adopts the continuous reactor system to carry out continuous reaction, the continuous reactor system comprises a plurality of stages of reaction kettles, ternary mixed metal salt solution containing nickel, cobalt and manganese, complexing agent aqueous solution and precipitator aqueous solution are continuously introduced into each stage of reaction kettle to carry out reaction, the reaction conditions in each stage of reaction kettle are controlled to ensure that slurry in each stage of reaction kettle reaches corresponding preset particle size, the slurry reaching the preset particle size sequentially flows into the next reaction kettle to carry out corresponding reaction, and the slurry in the last reaction kettle flows out after reaching the preset particle size to carry out post-treatment to obtain a high-nickel ternary precursor material; the majority of the multistage reaction kettle is at least larger than 1, and the corresponding preset particle sizes of the multistage reaction kettle are sequentially increased, namely the preset particle size of the slurry in the initial reaction kettle is the minimum, and after the preset particle sizes are sequentially increased, the preset particle size of the slurry in the final reaction kettle is the maximum, so that the high-nickel ternary precursor with narrow distribution and small particle size is obtained.
Preferably, multistage reation kettle is mostly 2-5, and multistage reation kettle is second grade reation kettle, tertiary reation kettle, level four reation kettle promptly, or five-stage reaction cauldron.
Preferably, the method specifically comprises the following steps:
(1) Preparing a ternary mixed metal salt solution containing nickel, cobalt and manganese by using soluble salts of nickel, cobalt and manganese; preparing a complexing agent aqueous solution; preparing a precipitant aqueous solution;
(2) And (2) introducing the ternary mixed metal salt solution, the complexing agent aqueous solution and the precipitator aqueous solution obtained in the step (1) into a continuous reactor system for reaction, and specifically comprising the following steps:
a) Under the protective atmosphere, adding deionized water with the effective volume of 50% of that of the first reaction kettle into the first reaction kettle, controlling the reaction temperature, simultaneously introducing a ternary mixed metal salt solution, a precipitator aqueous solution and a complexing agent aqueous solution, controlling the pH to be the first pH, and carrying out stirring reaction to enable the average particle size of the slurry to reach a first preset particle size;
b) Under the protection atmosphere, slurry of the first reaction kettle reaching a first preset particle size flows to a second reaction kettle, the reaction temperature is controlled, meanwhile, a ternary mixed metal salt solution, a precipitator aqueous solution and a complexing agent aqueous solution are introduced into the second reaction kettle to react, the slurry flowing into the second reaction kettle is used as a seed crystal, the pH is controlled to be a second pH, stirring reaction is carried out, new crystal nucleus generation is inhibited, particle growth is kept, and the average particle size of the slurry reaches a second preset particle size;
c) Under the protective atmosphere, flowing the slurry of the second reaction kettle reaching a second preset particle size to a third reaction kettle, controlling the reaction temperature, introducing a ternary mixed metal salt solution, a precipitator aqueous solution and a complexing agent aqueous solution into the third reaction kettle for reaction, controlling the pH to be a third pH, and carrying out stirring reaction to enable the average particle size of the slurry to reach a third preset particle size;
(3) And ageing the slurry of the third reaction kettle reaching a third preset particle size, and performing post-treatment to obtain the high-nickel ternary precursor material.
Preferably, the soluble salts of nickel, cobalt and manganese in the step (1) comprise sulfate, acetate, hydrochloride and nitrate; more preferably, the soluble salts of nickel, cobalt and manganese comprise soluble nickel salt, soluble cobalt salt and soluble manganese salt, the soluble nickel salt is any one or more of nickel sulfate, nickel acetate, nickel chloride and nickel nitrate, the soluble cobalt salt is any one or more of cobalt sulfate, cobalt acetate, cobalt chloride and cobalt nitrate, and the soluble manganese salt is any one or more of manganese sulfate, manganese acetate, manganese chloride and manganese nitrate.
Preferably, the total concentration of the metal ions (Me: ni, co, mn) in the ternary mixed metal salt solution in the step (1) is 1.4-2.4 mol/L.
Preferably, in the ternary mixed metal salt solution in the step (1), the nickel, cobalt and manganese metal ions are Ni x Co y Mn (1-x-y) (OH) 2 A formulation was prepared wherein x =0.75 to 0.90, y =0.03 to 0.22.
Preferably, the concentration of the complexing agent in the complexing agent aqueous solution in the step (1) is 1 to 10mol/L.
Preferably, the concentration of the precipitant in the precipitant aqueous solution in the step (1) is 4 to 10mol/L.
Preferably, the complexing agent aqueous solution in the step (1) is ammonia water, an ammonium sulfate solution, an EDTA solution, an oxalic acid solution, or an ammonium bicarbonate solution.
Preferably, the aqueous solution of the precipitant in step (1) is a sodium hydroxide solution, a sodium carbonate solution, or a potassium hydroxide solution.
Preferably, the protective atmosphere in step (2) is any one of a nitrogen atmosphere and an argon atmosphere or a mixture of the two.
Preferably, the flow of the precipitant aqueous solution in each reaction kettle in the step (2) is automatically adjusted by a pH automatic control system, so as to control the pH in the corresponding reaction kettle to reach the target pH value.
Preferably, in the step (2), the concentration of the complexing agent in the slurry in the first reaction kettle, the concentration of the complexing agent in the slurry in the second reaction kettle and the concentration of the complexing agent in the slurry in the third reaction kettle are the same by controlling the flow rate of the aqueous solution of the complexing agent in each reaction kettle, and the concentration of the complexing agent is kept between 2 and 10g/L.
Preferably, the pH in step (2) is, from high to low: a first pH, a second pH, a third pH; more preferably, the first pH in a) in the step (2) is controlled to 11.5 to 12.0, the second pH in b) is controlled to 11.0 to 11.5, and the third pH in c) is controlled to 10.5 to 11.0.
Preferably, the stirring speed in the step (2) a) is 1000-1200 rpm; b) The medium stirring speed is 900-1000rpm, and the medium stirring speed is 700-900 rpm.
Preferably, the reaction temperature in the step (2) a), the reaction temperature in the step (b), and the reaction temperature in the step (c) are the same, and the reaction temperature is 50 to 70 ℃.
Preferably, the particle size in step (2) is from small to large: a first preset particle size, a second preset particle size and a third preset particle size; more preferably, the first preset particle size in the step (2) a) is 1.5-2.0 μm; b) The second preset grain diameter is 2.0-3.0 μm; c) The third preset grain diameter is 3.2-3.8 μm.
Preferably, the final particle size distribution of the slurry in the first reaction kettle in the step (2) a) is controlled to be 1.3-1.7, the final particle size distribution of the slurry in the second reaction kettle in the step (b) is controlled to be 0.9-1.3, and the final particle size distribution of the slurry in the third reaction kettle in the step (c) is controlled to be 0.6-1.0.
Preferably, the post-treatment in the step (3) comprises aging, alkali washing, centrifuging and drying, and more preferably, the post-treatment further comprises mixing, screening and iron removal, wherein the mixing refers to mixing different dried batches of materials to keep the uniformity of the materials; screening and iron removal are respectively for removing large-size foreign matters and magnetic foreign matters in the material, and are conventional technical means in the field. .
Preferably, the aging time in the step (3) is 1 to 2 hours.
Preferably, the alkali solution for alkali washing in the step (3) is a sodium hydroxide solution with the concentration of 0.05 mol/L-0.5 mol/L.
Preferably, the alkali washing time in the step (3) is 30-60 min.
Preferably, the drying temperature in the step (3) is 100-150 ℃.
Preferably, the D50 of the high-nickel ternary precursor in the step (3) is 3.2-3.8 μm.
Preferably, the particle size distribution of the high-nickel ternary precursor in the step (3) is 0.6-1.0.
Preferably, the tap density of the high-nickel ternary precursor in the step (3) is 1.6-1.9 g/cm 3 。
The invention also aims to provide the narrow-distribution small-particle-size high-nickel ternary precursor prepared by the method for preparing the narrow-distribution small-particle-size high-nickel ternary precursor by using the continuous reactor system, wherein the D50 of the high-nickel ternary precursor is 3.2-3.8 mu m, the particle size distribution is 0.6-1.0, and the tap density is 1.6-1.9 g/cm 3 The sphericity is good and the particle consistency is high.
In the technical scheme, the ternary mixed metal salt solution, the complexing agent aqueous solution and the precipitant aqueous solution are continuously introduced into the first reaction kettle, the second reaction kettle and the third reaction kettle, so that the three kettles are subjected to uninterrupted synthesis operation, and continuous production is realized;
in the technical scheme, only the first reaction kettle generates new crystal nuclei and forms small particles by maintaining high reaction pH, the second reaction kettle and the third reaction kettle inhibit the nucleation rate by maintaining low pH, artificial balling is avoided, and the small particles flowing from the previous reaction kettle are kept growing step by step to narrow the particle size distribution of the whole particles;
in the technical scheme, except for the reaction pH and the stirring speed, the first reaction kettle, the second reaction kettle and the third reaction kettle are kept consistent in control parameters, such as temperature, the concentration of the introduced ternary mixed metal salt solution, the concentration of the introduced precipitant aqueous solution, the concentration of the introduced complexing agent aqueous solution and the like, so that good consistency of particles is realized.
Compared with the prior art, the invention has the beneficial effects that: the invention provides a method for preparing a narrow-distribution small-particle-size high-nickel ternary precursor by a continuous reactor, which is characterized in that a continuous reactor system is used for continuously nucleating in a first reaction kettle, and nucleation and continuous growth are avoided in a second reaction kettle and a third reaction kettle, so that continuous production is realized, the production yield and efficiency are greatly improved, and the prepared ternary precursor has good sphericity, narrow distribution and high tap density.
Drawings
FIG. 1 is a scanning electron micrograph of a high nickel ternary precursor material prepared in example 1;
FIG. 2 is a particle size distribution plot of the high nickel ternary precursor material prepared in example 1;
FIG. 3 is a scanning electron micrograph of the high nickel ternary precursor material prepared in example 2;
FIG. 4 is a particle size distribution plot of the high nickel ternary precursor material prepared in example 2; .
Detailed Description
The technical solution of the present invention is further specifically described below by way of specific examples in conjunction with the accompanying drawings.
The invention provides a method for preparing a narrow-distribution small-particle-size high-nickel ternary precursor by using a continuous reactor system, which comprises the following steps of:
(1) Preparing ternary mixed metal salt solution containing nickel, cobalt and manganese by using soluble salts of nickel, cobalt and manganese, wherein metal ions of nickel, cobalt and manganese are as Ni x Co y Mn (1-x-y) (OH) 2 Preparing, wherein x = 0.75-0.90, y = 0.03-0.22; preparing a complexing agent aqueous solution; preparing a precipitant aqueous solution;
(2) And (2) introducing the ternary mixed metal salt solution, the complexing agent aqueous solution and the precipitator aqueous solution obtained in the step (1) into a continuous reactor system for reaction, and specifically comprising the following steps:
a) Under the protective atmosphere, adding deionized water with the effective volume of 50% of that of the first reaction kettle into the first reaction kettle, controlling the reaction temperature, simultaneously introducing a ternary mixed metal salt solution, a precipitator aqueous solution and a complexing agent aqueous solution, controlling the pH to be the first pH, and carrying out stirring reaction to enable the average particle size of the slurry to reach a first preset particle size;
b) Under the protection atmosphere, slurry of the first reaction kettle reaching a first preset particle size flows to a second reaction kettle, the reaction temperature is controlled, meanwhile, a ternary mixed metal salt solution, a precipitator aqueous solution and a complexing agent aqueous solution are introduced into the second reaction kettle to react, the slurry flowing into the second reaction kettle is used as a seed crystal, the pH is controlled to be a second pH, stirring reaction is carried out, new crystal nucleus generation is inhibited, particle growth is kept, and the average particle size of the slurry reaches a second preset particle size;
c) Under the protective atmosphere, flowing the slurry of the second reaction kettle reaching a second preset particle size to a third reaction kettle, controlling the reaction temperature, introducing a ternary mixed metal salt solution, a precipitator aqueous solution and a complexing agent aqueous solution into the third reaction kettle for reaction, controlling the pH to be a third pH, and carrying out stirring reaction to enable the average particle size of the slurry to reach a third preset particle size;
(3) And ageing the slurry of the third reaction kettle reaching a third preset particle size, and performing post-treatment to obtain the high-nickel ternary precursor material.
In the embodiment of the invention, the soluble salts of nickel, cobalt and manganese in the step (1) comprise sulfate, acetate, hydrochloride and nitrate; in an embodiment of the present invention, the soluble salts of nickel, cobalt, and manganese include soluble nickel salts, soluble cobalt salts, and soluble manganese salts, the soluble nickel salts are any one or more of nickel sulfate, nickel acetate, nickel chloride, and nickel nitrate, the soluble cobalt salts are any one or more of cobalt sulfate, cobalt acetate, cobalt chloride, and cobalt nitrate, and the soluble manganese salts are any one or more of manganese sulfate, manganese acetate, manganese chloride, and manganese nitrate.
In the embodiment of the invention, the total concentration of metal ions (Me: ni, co, mn) in the ternary mixed metal salt solution in the step (1) is 1.4-2.4 mol/L.
In the embodiment of the present invention, the concentration of the complexing agent in the aqueous complexing agent solution in the step (1) is 1 to 10mol/L.
In the embodiment of the invention, the concentration of the precipitant in the precipitant aqueous solution in the step (1) is 4-10 mol/L.
In an embodiment of the present invention, the complexing agent aqueous solution in step (1) is ammonia, an ammonium sulfate solution, an EDTA solution, an oxalic acid solution, or an ammonium bicarbonate solution.
In an embodiment of the present invention, the aqueous precipitant solution in step (1) is a sodium hydroxide solution, a sodium carbonate solution, or a potassium hydroxide solution.
In the embodiment of the present invention, the protective atmosphere in step (2) is any one of a nitrogen atmosphere and an argon atmosphere, or a mixture of two.
In the embodiment of the invention, the flow rate of the precipitant aqueous solution in each reaction kettle in the step (2) is automatically adjusted by a pH automatic control system, so as to control the pH in the corresponding reaction kettle to reach the target pH value.
In the embodiment of the invention, in the step (2), the concentration of the complexing agent in the slurry in the first reaction kettle, the second reaction kettle and the third reaction kettle is the same by controlling the flow of the aqueous solution of the complexing agent in each reaction kettle, and the concentration of the complexing agent is kept to be 2-10 g/L.
In an embodiment of the present invention, the pH in step (2) is from high to low: a first pH, a second pH, a third pH; more preferably, the first pH in a) in the step (2) is controlled to 11.5 to 12.0, the second pH in b) is controlled to 11.0 to 11.5, and the third pH in c) is controlled to 10.5 to 11.0.
In the embodiment of the invention, the stirring speed in the step (2) a) is 1000-1200 rpm; b) The medium stirring speed is 900-1000rpm, and the medium stirring speed is 700-900 rpm.
In the embodiment of the present invention, the reaction temperature in the step (2) a), the reaction temperature in the step (b), and the reaction temperature in the step (c) are the same, and the reaction temperature is 50 to 70 ℃.
In the embodiment of the invention, the particle size in the step (2) is as follows from small to large: a first preset particle size, a second preset particle size and a third preset particle size; more preferably, the first preset particle size in the step (2) a) is 1.5-2.0 μm; b) The second preset grain diameter is 2.0-3.0 μm; c) The third preset grain diameter is 3.2-3.8 mu m.
In the embodiment of the invention, the final particle size distribution of the slurry in the first reaction kettle in the step (2) a) is controlled to be 1.3-1.7, the final particle size distribution of the slurry in the second reaction kettle is controlled to be 0.9-1.3, and the final particle size distribution of the slurry in the third reaction kettle is controlled to be 0.6-1.0.
In the embodiment of the present invention, the post-treatment in step (3) includes aging, alkaline washing, centrifugation, and drying, which are conventional technical means in the field, and a person skilled in the art can adjust the post-treatment according to actual conditions, and more preferably, the post-treatment further includes mixing, screening, and removing iron, which are conventional technical means in the field, and a person skilled in the art can adjust the post-treatment according to actual conditions, wherein mixing refers to mixing different batches of materials after drying, and uniformity of the materials is maintained; screening and iron removal are respectively to remove large-size foreign matters and magnetic foreign matters in the material. .
In the embodiment of the present invention, the aging time in the step (3) is 1 to 2 hours.
In the embodiment of the invention, the alkali solution for alkali washing in the step (3) is a sodium hydroxide solution with the concentration of 0.05 mol/L-0.5 mol/L.
In the embodiment of the present invention, the alkali washing time in the step (3) is 30 to 60min.
In the embodiment of the invention, the drying temperature in the step (3) is 100-150 ℃.
In the embodiment of the invention, the D50 of the high-nickel ternary precursor in the step (3) is 3.2-3.8 μm.
In the embodiment of the invention, the particle size distribution of the high-nickel ternary precursor in the step (3) is 0.6-1.0.
In the embodiment of the invention, the tap density of the high-nickel ternary precursor in the step (3) is 1.6-1.9 g/cm 3 。
The invention also provides a narrow-distribution small-particle-size high-nickel ternary precursor prepared by the method for preparing the narrow-distribution small-particle-size high-nickel ternary precursor by using the continuous reactor system, wherein the D50 of the high-nickel ternary precursor is 3.2-3.8 mu m, the particle size distribution is 0.6-1.0, and the tap density is 1.6-1.9 g/cm 3 The sphericity is good and the particle consistency is high.
In the technical scheme, the ternary mixed metal salt solution, the complexing agent aqueous solution and the precipitating agent aqueous solution are continuously introduced into the first reaction kettle, the second reaction kettle and the third reaction kettle, so that uninterrupted synthesis operation of the three kettles is realized, and continuous production is realized;
in the technical scheme, only the first reaction kettle generates new crystal nuclei and forms small particles by maintaining high reaction pH, the second reaction kettle and the third reaction kettle inhibit the nucleation rate by maintaining low pH, artificial balling is avoided, and the small particles flowing from the previous reaction kettle are kept growing step by step to narrow the particle size distribution of the whole particles;
in the technical scheme, the first reaction kettle, the second reaction kettle and the third reaction kettle keep consistent parameters except the pH value of the reaction and the stirring speed, such as temperature, the concentration of the introduced ternary mixed metal salt solution, the concentration of the introduced precipitant aqueous solution, the content of the complexing agent and the like, and the good consistency of the particles is realized.
The present invention is described in further detail with reference to the specific embodiments, it is obvious that the following embodiments are only some embodiments of the present invention, not all embodiments, and it should be noted that those skilled in the art can make all embodiments without departing from the main concept of the present invention and without substantial changes, and still fall within the protection scope of the present invention;
the invention provides a method for preparing a narrow-distribution small-particle-size high-nickel ternary precursor by using a continuous reactor system, which comprises the following steps of:
(1) Nickel cobalt manganese soluble metal salt is prepared according to a general formula NixCoyMn (1-x-y) (OH) 2 by molar ratio, wherein x = 0.75-0.90, y = 0.03-0.22, and a ternary mixed metal salt solution with the total concentration of 1.4-2.4 mol/L is prepared; preparing ammonia water with the concentration of 1-10 mol/L as a complexing agent aqueous solution; preparing sodium hydroxide with the concentration of 4-10 mol/L as a precipitator aqueous solution;
(2) Adding pure water with the effective volume of 50 percent into a reaction kettle 1, continuously introducing nitrogen as protective gas, controlling the reaction temperature to be 50-70 ℃, the stirring speed to be 1000-1200 rpm, the ammonia concentration to be 2-10 g/L, introducing the prepared mixed metal salt solution, sodium hydroxide solution and ammonia water to react, controlling the pH to be 11.5-12.0, maintaining the average particle size of the slurry to be 1.5-2.0 mu m, and controlling the particle size distribution to be 1.3-1.7; the slurry in the reaction kettle 1 overflows to the reaction kettle 2 through an overflow pipeline; continuously introducing nitrogen as protective gas into the reaction kettle 2, controlling the reaction temperature to be 50-70 ℃, the stirring speed to be 900-1000 rpm, the ammonia concentration to be 2-10 g/L, introducing the prepared mixed metal salt solution, sodium hydroxide solution and ammonia water for reaction, controlling the pH of the reaction kettle 2 to be 11.0-11.5 by using the overflow slurry of the reaction kettle as seed crystal, inhibiting the generation of new crystal nuclei, keeping the generation of particles, stabilizing the average particle size to be 2.0-3.0 mu m, and controlling the particle size distribution to be 0.9-1.3; the slurry in the reaction kettle 2 overflows to the reaction kettle 3 through an overflow pipeline; continuously introducing nitrogen as protective gas into the reaction kettle 3, controlling the reaction temperature to be 50-70 ℃, the stirring speed to be 700-900 rpm, the ammonia concentration to be 2-10 g/L, adding the prepared mixed metal salt solution, sodium hydroxide solution and ammonia water to react, controlling the pH to be 10.5-11.0, controlling the stable average particle size to be 3.2-3.8 mu m, and controlling the particle size distribution to be 0.6-1.0;
(3) After the slurry in the reaction kettle 3 completely overflows to Chen Huafu, the slurry is aged for 1 to 2 hours, washed by 0.05mol/L to 0.5mol/L sodium hydroxide alkali for 30 to 60 minutes, centrifuged, dried at 100 to 150 ℃, mixed, screened and deironized, and then the high-nickel ternary precursor material is obtained;
example 1
Nickel sulfate, cobalt sulfate and manganese sulfate are mixed according to the proportion of Ni: co: preparing a ternary mixed metal salt solution with the total metal ion concentration of 1.8mol/L according to the Mn molar ratio of 84; preparing ammonia water with the concentration of 10 mol/L; preparing a sodium hydroxide solution with the concentration of 5 mol/L;
adding pure water with the effective volume of 50% into a reaction kettle 1, continuously introducing nitrogen as protective gas, controlling the reaction temperature to be 65 ℃, stirring at 1100rpm, introducing the prepared ternary mixed metal salt solution (with the flow controlled to be 300L/h), sodium hydroxide solution and ammonia water to react, controlling the ammonia concentration to be 6g/L (by adjusting the flow of the ammonia water), controlling the pH to be 11.6-11.7 (by adjusting the flow of the sodium hydroxide), and maintaining the average particle size of the slurry to be 1.8 mu m of a first preset particle size and the particle size distribution to be 1.5;
overflowing the slurry of the reaction kettle 1 reaching the first preset particle size to the reaction kettle 2 through an overflow pipeline, continuously introducing nitrogen into the reaction kettle 2 as protective gas, controlling the reaction temperature to be 65 ℃, the stirring speed to be 1000rpm, simultaneously introducing the prepared mixed metal salt solution, sodium hydroxide solution and ammonia water for reaction, controlling the ammonia concentration to be 6g/L and the pH to be 11.3-11.4 by using the slurry of the reaction kettle 1 as seed crystals, inhibiting the generation of new crystal nuclei, keeping the generation of particles, stabilizing the average particle size to reach the second preset particle size of 2.5 mu m, and controlling the particle size distribution to be 1.2 by using the slurry of the reaction kettle 1 as seed crystals;
the slurry in the reaction kettle 2 reaching the second preset particle size overflows to the reaction kettle 3 through an overflow pipeline; continuously introducing nitrogen as a protective gas into the reaction kettle 3, controlling the reaction temperature to be 65 ℃, the stirring speed to be 800rpm, simultaneously introducing the prepared mixed metal salt solution, sodium hydroxide solution and ammonia water for reaction, controlling the ammonia concentration to be 6g/L, controlling the pH to be 10.9-11.0, stabilizing the average particle size to reach a third preset particle size of 3.5 mu m, and controlling the particle size distribution to be 0.7;
the slurry in the reaction kettle 3 reaching the third preset particle size completely overflows to Chen Huafu, is aged for 2 hours, washed with 0.1mol/L sodium hydroxide for 40 minutes, centrifuged, dried at 130 ℃, mixed, sieved and deironized to obtain the high-nickel ternary precursor material;
scanning electron microscope test is carried out on the high-nickel ternary precursor material prepared in the embodiment 1 of the invention, and the test result is shown in fig. 1, so that the high-nickel ternary precursor material prepared in the embodiment 1 of the invention has good sphericity, high particle consistency and no agglomeration;
the particle size test of the high-nickel ternary precursor material prepared in the embodiment 1 of the invention is carried out, and the test result is shown in fig. 2, so that the particle size D50 of the high-nickel ternary precursor material prepared in the embodiment 1 of the invention is 3.48 μm, the particle size distribution is 0.65, the particle size distribution is narrow, and no agglomeration exists;
the tap density of the high-nickel ternary precursor material prepared in the embodiment 1 of the invention is 1.85g/cm 3 。
Example 2
Nickel sulfate, cobalt sulfate and manganese sulfate are mixed according to the proportion of Ni: co: preparing a ternary mixed metal salt solution with the total concentration of 2.0mol/L according to the Mn molar ratio of 83; preparing ammonia water with the concentration of 10 mol/L; preparing a sodium hydroxide solution with the concentration of 8 mol/L;
adding pure water with the effective volume of 50% into a reaction kettle 1, continuously introducing nitrogen as protective gas, controlling the reaction temperature to be 60 ℃, stirring at the rotating speed of 1000rpm, introducing prepared mixed metal salt solution, sodium hydroxide solution and ammonia water for reaction, controlling the pH to be 11.4-11.5 and maintaining the average particle size of the slurry to be 1.8 mu m and the particle size distribution to be 1.5, wherein the ammonia concentration is 8 g/L;
the slurry in the reaction kettle 1 overflows to the reaction kettle 2 through an overflow pipeline, nitrogen is continuously introduced into the reaction kettle 2 to serve as protective gas, the reaction temperature is controlled to be 60 ℃, the stirring speed is 900rpm, the prepared mixed metal salt solution, sodium hydroxide solution and ammonia water are introduced to carry out reaction, the slurry in the reaction kettle 2 serves as seed crystal, the ammonia concentration is 8g/L, the pH is controlled to be 11.2-11.3, new crystal nucleus generation is inhibited, particle generation is maintained, the stable average particle size is 2.4 mu m, and the particle size distribution is 1.2;
the slurry in the reaction kettle 2 overflows to the reaction kettle 3 through an overflow pipeline; continuously introducing nitrogen as protective gas into the reaction kettle 3, controlling the reaction temperature to be 60 ℃, the stirring speed to be 800rpm, adding the prepared mixed metal salt solution, sodium hydroxide solution and ammonia water to react, controlling the ammonia concentration to be 8g/L, the pH to be 10.8-10.9, stabilizing the average particle size to be 3.3 mu m, and distributing the particle size to be 0.8;
overflowing the slurry in the reaction kettle 3 to Chen Huafu, aging for 2h, washing with 0.3mol/L sodium hydroxide for 40min, centrifuging, drying at 120 ℃, mixing, screening and removing iron to obtain a high-nickel ternary precursor material;
scanning electron microscope test is carried out on the high-nickel ternary precursor material prepared in the embodiment 2 of the invention, and the test result is shown in fig. 3, so that the high-nickel ternary precursor material prepared in the embodiment 2 of the invention has good sphericity, high particle consistency and no agglomeration;
the particle size test of the high-nickel ternary precursor material prepared in the embodiment 2 of the present invention is performed, and the test result is shown in fig. 4, which shows that the particle size D50 of the high-nickel ternary precursor material prepared in the embodiment 2 of the present invention is 3.35 μm, the particle size distribution is 0.81, the particle size distribution is narrow, and no agglomeration exists;
the tap density of the high-nickel ternary precursor material prepared in the embodiment 1 of the invention is 1.71g/cm 3 。
The above-described embodiments are merely preferred embodiments of the present invention, which is not intended to be limiting in any way, and other variations and modifications are possible without departing from the scope of the invention as set forth in the appended claims.
Claims (10)
1. A method for preparing a narrow-distribution small-particle-size high-nickel ternary precursor is characterized in that the continuous reactor system comprises a plurality of stages of reaction kettles, ternary mixed metal salt solution containing nickel, cobalt and manganese, complexing agent aqueous solution and precipitator aqueous solution are introduced into each stage of reaction kettle to react, the reaction conditions in each stage of reaction kettle are controlled to enable slurry in each stage of reaction kettle to reach the corresponding preset particle size, then the slurry sequentially flows into the next reaction kettle to carry out corresponding reaction, and the slurry finally flows out to be subjected to post-treatment to obtain a high-nickel ternary precursor material; wherein, most of the multistage reaction kettle is at least more than 1, and the corresponding preset particle sizes of the multistage reaction kettle are sequentially increased.
2. The method for preparing the narrow-distribution small-particle-size high-nickel ternary precursor according to claim 1, which specifically comprises the following steps:
(1) Preparing a ternary mixed metal salt solution containing nickel, cobalt and manganese by using soluble salts of nickel, cobalt and manganese; preparing a complexing agent aqueous solution; preparing a precipitant aqueous solution;
(2) And (2) introducing the ternary mixed metal salt solution, the complexing agent aqueous solution and the precipitator aqueous solution obtained in the step (1) into a continuous reactor system for reaction, and specifically comprising the following steps:
a) Adding 50% of water by volume into a first reaction kettle under a protective atmosphere, controlling the reaction temperature, introducing a ternary mixed metal salt solution, a precipitator aqueous solution and a complexing agent aqueous solution, controlling the pH to be a first pH, and carrying out stirring reaction to enable the average particle size of the slurry to reach a first preset particle size;
b) Under the protective atmosphere, flowing the slurry of the step a) to a second reaction kettle, controlling the reaction temperature, introducing a ternary mixed metal salt solution, a precipitator aqueous solution and a complexing agent aqueous solution, controlling the pH to be a second pH, and carrying out stirring reaction to enable the average particle size of the slurry to reach a second preset particle size;
c) Under the protective atmosphere, flowing the slurry of b) to a third reaction kettle, controlling the reaction temperature, introducing a ternary mixed metal salt solution, a precipitator aqueous solution and a complexing agent aqueous solution, controlling the pH to be a third pH, and carrying out stirring reaction to enable the average particle size of the slurry to reach a third preset particle size;
wherein, the grain diameter is from small to big: a first preset particle size, a second preset particle size and a third preset particle size;
(3) Aging the slurry of c) and then carrying out post-treatment to obtain the high-nickel ternary precursor material.
3. The method for preparing the narrow-distribution small-particle-size high-nickel ternary precursor according to claim 2, wherein the total concentration of metal ions in the ternary mixed metal salt solution in the step (1) is 1.4-2.4 mol/L; nickel, cobalt and manganese metal ions according to Ni x Co y Mn (1-x-y) (OH) 2 A formulation was prepared wherein x =0.75 to 0.90, y =0.03 to 0.22.
4. The method for preparing the narrow-distribution small-particle-size high-nickel ternary precursor according to claim 2, wherein the complexing agent aqueous solution in the step (1) is ammonia water, an ammonium sulfate solution, an EDTA solution, an oxalic acid solution or an ammonium bicarbonate solution; the concentration of the complexing agent in the complexing agent aqueous solution is 1-10 mol/L.
5. The method for preparing the narrow-distribution small-particle-size high-nickel ternary precursor according to claim 2, wherein the aqueous precipitant solution in the step (1) is a sodium hydroxide solution, a sodium carbonate solution or a potassium hydroxide solution, and the concentration of the precipitant in the aqueous precipitant solution is 4 to 10mol/L.
6. The method for preparing the narrow-distribution small-particle-size high-nickel ternary precursor according to claim 2, wherein the pH value in the step (2) is from high to low as: a first pH, a second pH, a third pH.
7. The method for preparing the narrow-distribution small-particle-size high-nickel ternary precursor according to claim 6, wherein the first pH value in step (2) is controlled to be 11.5-12.0 in a), the second pH value is controlled to be 11.0-11.5 in b), and the third pH value is controlled to be 10.5-11.0 in c).
8. The method for preparing the narrow-distribution small-particle-size high-nickel ternary precursor according to claim 2, wherein the first preset particle size in step (2) a) is 1.5-2.0 μm; b) The second preset grain diameter is 2.0-3.0 μm; c) The third preset grain diameter is 3.2-3.8 μm.
9. The method for preparing the narrow-distribution small-particle-size high-nickel ternary precursor according to claim 2, wherein the reaction temperature in step (2) a), the reaction temperature in step (b), and the reaction temperature in step (c) are the same, and the reaction temperature is 50-70 ℃; the stirring speed in the step (2) a) is 1000-1200 rpm; b) The medium stirring speed is 900-1000rpm, and the medium stirring speed is 700-900 rpm.
10. A narrow-distribution small-particle-size high-nickel ternary precursor prepared by the method for preparing the narrow-distribution small-particle-size high-nickel ternary precursor according to any one of claims 1 to 9, characterized in that the D50 of the high-nickel ternary precursor is 3.2 to 3.8 μm, the particle size distribution is 0.6 to 1.0, and the tap density is 1.6 to 1.9g/cm 3 。
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