CN113526569A - Preparation method of ternary material precursor and material prepared by preparation method - Google Patents
Preparation method of ternary material precursor and material prepared by preparation method Download PDFInfo
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- CN113526569A CN113526569A CN202110674307.XA CN202110674307A CN113526569A CN 113526569 A CN113526569 A CN 113526569A CN 202110674307 A CN202110674307 A CN 202110674307A CN 113526569 A CN113526569 A CN 113526569A
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- 239000002243 precursor Substances 0.000 title claims abstract description 141
- 239000000463 material Substances 0.000 title claims abstract description 140
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 105
- 239000002245 particle Substances 0.000 claims abstract description 78
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 53
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 35
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 35
- VNTQORJESGFLAZ-UHFFFAOYSA-H cobalt(2+) manganese(2+) nickel(2+) trisulfate Chemical compound [Mn++].[Co++].[Ni++].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VNTQORJESGFLAZ-UHFFFAOYSA-H 0.000 claims abstract description 27
- 230000032683 aging Effects 0.000 claims abstract description 14
- 230000001681 protective effect Effects 0.000 claims abstract description 13
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 claims abstract description 9
- 230000000536 complexating effect Effects 0.000 claims abstract description 4
- 239000002244 precipitate Substances 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 79
- 239000007787 solid Substances 0.000 claims description 47
- 229910052757 nitrogen Inorganic materials 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 26
- 239000011163 secondary particle Substances 0.000 claims description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 19
- 239000002002 slurry Substances 0.000 claims description 17
- 239000013078 crystal Substances 0.000 claims description 16
- 238000010899 nucleation Methods 0.000 claims description 16
- 230000006911 nucleation Effects 0.000 claims description 16
- 239000011164 primary particle Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000012216 screening Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 238000010668 complexation reaction Methods 0.000 claims description 3
- 238000013461 design Methods 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
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 4
- 239000010935 stainless steel Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 29
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 10
- 229910001873 dinitrogen Inorganic materials 0.000 description 9
- 238000001000 micrograph Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 239000002585 base Substances 0.000 description 6
- 238000005056 compaction Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 4
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 238000010923 batch production Methods 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 229910001429 cobalt ion Inorganic materials 0.000 description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229910001437 manganese ion Inorganic materials 0.000 description 3
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000036632 reaction speed Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 241000276425 Xiphophorus maculatus Species 0.000 description 1
- XKGIZIQMMABGJQ-UHFFFAOYSA-N [Mn](=O)(=O)([O-])[O-].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [Mn](=O)(=O)([O-])[O-].[Mn+2].[Co+2].[Ni+2].[Li+] XKGIZIQMMABGJQ-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000012066 reaction slurry Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- 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
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- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01P2006/40—Electric properties
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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
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Abstract
The invention provides a preparation method of a ternary material precursor and the ternary material precursor prepared by the preparation method. Preparing a nickel-cobalt-manganese sulfate solution with a certain concentration, a sodium hydroxide solution and ammonia water, introducing the nickel-cobalt-manganese sulfate solution, the sodium hydroxide solution and the ammonia water into a reaction kettle with the ammonia water as a base solution, and finally reacting the nickel-cobalt-manganese sulfate solution with the ammonia water after complexing to generate nickel-cobalt-manganese hydroxide precipitate. The controllable particle size and morphology of the ternary material precursor are realized by controlling reaction conditions such as the temperature of the reaction kettle, the components of the reaction protective gas, the reaction PH, the feeding speed of the reaction raw materials and the like. Three nickel-cobalt-manganese hydroxides with different target particle sizes are precipitated in an aging kettle, stirred and mixed, and then washed, dried and sieved to obtain a target ternary material precursor with high tap density, wherein the high tap density refers to that the ternary material precursor passes through a 316L stainless steel screen with the screen mesh number of 200 plus 450 meshes.
Description
Technical Field
The invention relates to a preparation method of a lithium ion battery anode material and a material prepared by the same, in particular to a preparation method of a ternary material precursor and a material prepared by the same.
Background
With the rapid development of the lithium battery industry, the cathode material with higher energy density is gradually favored by various domestic cathode material enterprises in recent years. In order to meet the application of the nickel-cobalt-manganese ternary material in the power market in the future, the development direction of the NCM nickel-cobalt-manganese lithium manganate ternary material tends to develop in the direction of improving the charging voltage of a battery and the compaction density of the material, meanwhile, the compaction density of the nickel-cobalt-manganese ternary material and the compaction density of a precursor corresponding to the nickel-cobalt-manganese ternary material show high correlation, and the polycrystalline series ternary material with high compaction density is the key point of the later-stage lithium battery anode material industry for controversial research.
The nickel-cobalt-manganese ternary precursor is prepared by two main processes at the present stage, wherein one process is an intermittent process: the method mainly comprises two steps, wherein in the first step, nickel-cobalt-manganese solid salt is prepared into a mixed solution with a certain concentration and proportion, the mixed solution, a precipitator and a complexing agent are subjected to coprecipitation crystallization, crystals are controlled to reach a target granularity through a discharging and solid-lifting mode, and in the second step, the crystallization slurry is subjected to working procedures of aging, washing, drying, sieving, iron removal and the like to obtain a nickel-cobalt-manganese hydroxide precursor, namely a ternary cathode material precursor.
The second is a continuous process, the synthetic method is similar to the batch process, and the post-treatment of the obtained target slurry is the same as the batch process; but the biggest characteristic is that in the synthesis section, the overflow mode is adopted, and the pH of the reaction slurry is adjusted to maintain the D50 of the slurry to fluctuate within a set range, so that a precursor with wider radial distance and higher tap density than a batch process is obtained.
Although the above two processes are widely used by domestic manufacturers at present, due to the limitation of the processes, the tap density of the precursor can be improved by adjusting the parameters of the equipment and controlling the equipment, but the results are very limited, and due to the characteristics of the precursor produced by the continuous process, a large amount of fine powder exists in the process problem, overburning is caused when the anode material is sintered, and the acceptance of part of enterprises is deviated.
Disclosure of Invention
The invention provides a ternary material precursor and a preparation method thereof, which can effectively solve the problems.
The invention is realized by the following steps:
a preparation method of a ternary material precursor is characterized by comprising the following steps:
before the reaction of S1, preparing a reaction bottom liquid in a reaction kettle, using ammonia water with a certain volume and concentration as the reaction bottom liquid, simultaneously adjusting the pH of the bottom liquid to 11.5-13, and keeping nitrogen as a protective gas for the bottom liquid of the reaction kettle;
s2, introducing sulfuric acid solution with concentration of 1.0-2.2mol/L of nickel-cobalt-manganese three metals and 4-10mol/L of sodium hydroxide solution into a reaction kettle with ammonia water as a base solution, controlling corresponding reaction conditions according to the requirements of crystal nucleation target particle size and morphology to obtain a ternary material precursor with consistent primary particle morphology, namely controlling the air inlet flow of nitrogen, controlling the feeding flow of the nickel-cobalt-manganese solution, controlling the feeding flow of the sodium hydroxide solution, controlling the reaction PH to be 11.5-13, controlling the rotation speed of the reaction kettle, generating a ternary precursor crystal nucleus at a certain constant temperature, namely complexing the nickel-cobalt-manganese sulfate solution with the ammonia water, and finally reacting nickel-cobalt-manganese hydroxide with the sodium hydroxide, wherein the stage is a nucleation stage;
s3, opening a solid lifting groove connected with a reaction kettle, reducing the PH of the reaction to 9-11.5, introducing nitrogen and air which is treated by a carbon removal device in advance into the reaction kettle as a protective gas, controlling the flow of the protective gas, adjusting the concentration and the feeding flow of nickel-cobalt-manganese sulfate, and controlling the solid content of the target particle size slurry, so that the solid content of the target particle size slurry is improved, the ternary material precursor crystal nucleus grows uniformly and slowly at a constant temperature to reach the designed target particle size, and secondary particles are obtained, wherein the solid lifting growth stage is the solid lifting growth stage;
s4, stopping the reaction when the secondary particle growth reaches the target particle size;
s5 repeating S1-S4 to obtain ternary material precursor secondary particles with different target particle sizes and consistent primary particle morphology;
s6, mixing secondary particles with design target particle sizes of 13-14 microns D50, 5-6 microns D50 and 2.5-3.5 microns D50 obtained by S5 according to a preset mass ratio, aging and mixing in an aging kettle for more than or equal to 2 hours at the rotating speed of 80-300RPM, washing, drying at low temperature, screening and magnetically separating after aging reaction to obtain a finished product, wherein the finished product is the hydroxide precipitate of nickel, cobalt and manganese, namely the ternary material precursor.
Further, the preparation method of the ternary material precursor comprises the step S1, wherein a certain base solution is contained in the reaction kettle, the base solution is ammonia water, and the concentration of the ammonia water is 2-7g/L, preferably 2.5-5 g/L.
Further, the preparation method of the ternary material precursor is characterized in that the reaction temperature in the reaction kettle in the step S2 is 40-65 ℃.
Further, in the preparation method of the ternary material precursor, the ammonia water participating in the complexation reaction in step S2 is industrial ammonia water, and the mass percentage of the industrial ammonia water is 20%.
Further, in the preparation method of the ternary material precursor, the concentration of the nickel cobalt manganese sulfate in the step S2 is preferably 1.6-2.2 mol/L.
Further, in the preparation method of the ternary material precursor, the concentration of the sodium hydroxide salt in the step S2 is preferably 5-7 mol/L.
Further, the preparation method of the ternary material precursor, wherein the rotation speed of the reaction kettle in the nucleation stage of the step S2 is 1000-; the step S3 is to lower the rotation speed of the reaction kettle in the pH stripping growth stage to 100-600rpm, preferably to 230-450 rpm.
Further, in the preparation method of the ternary material precursor, in step S2, the PH of the nucleation stage is adjusted according to the target particle size, the PH of the generated large-particle-size primary particles is 11.5 to 12, the PH of the generated medium-particle-size primary particles is 12.0 to 12.5, and the PH of the generated small-particle-size primary particles is 12.5 to 13.
Further, in the preparation method of the ternary material precursor, in the step S3, the PH of the large-particle-size secondary particles generated in the solid-lifting stage is 9 to 11.5, the PH of the medium-particle-size secondary particles generated in the solid-lifting stage is 10.5 to 11.5, and the PH of the small-particle-size secondary particles generated in the solid-lifting stage is 11.1 to 11.5.
Further, in the preparation method of the ternary material precursor, in step S3, the feeding flow rate of the nickel-cobalt-manganese sulfate is controlled, and the feeding flow rates of the nickel-cobalt-manganese sulfate solutions in the low PH lift-solid growth process are different, wherein the feeding flow rate of the nickel-cobalt-manganese sulfate for the target D50 ═ 2.5-3.5um growth is 2-4L/h, and the feeding flow rate of the nickel-cobalt-manganese sulfate for the target D50 ═ 5-6um growth is 3-5L/h; target D50 ═ 13-14um growth the nickel cobalt manganese sulfate feed rate was 4-6L/h.
Further, the preparation method of the ternary material precursor comprises the step of introducing nitrogen as a protective gas into a reaction kettle of the step S2, wherein the purity of the nitrogen is more than 99.95%, and the flow rate of the nitrogen is 0-2m3The nitrogen flow is preferably 1-2m for further strictly controlling the morphology of the ternary material precursor3/h。
Further, the preparation method of the ternary material precursor comprises the step S3 of carrying out crystal growth reaction,reducing the PH value in the reaction kettle, opening a solid lifting groove connected with the reaction kettle, introducing the nitrogen gas serving as protective gas into the reaction kettle in a long term, wherein the purity of the nitrogen gas is 95-98.5%, and the flow rate is 0-2m3And h, introducing the nitrogen and air which is treated by a carbon removal device in advance, and controlling the appearance of the nickel-cobalt-manganese hydroxide secondary particles in the slurry by adjusting the ratio of the nitrogen to the compressed air, wherein the flow ratio of the nitrogen to the air is 0-0.05.
Further, in the preparation method of the ternary material precursor, step S3 is to discharge the supernatant of the material in the reaction kettle through the fixing lifting tank at a certain flow rate; the clear liquid velocity of the solid lifting groove is the sum of the flow velocities of the material flow, the alkali flow and the ammonia flow; keeping the solid content of the slurry with the target particle size in the reaction kettle to be less than or equal to 40%, and if the target particle size is not reached, carrying out material distribution to reduce the solid content; after the target particle size is reached, the solid content phase difference value of the reaction kettle is 0-0.3%;
further, in the preparation method of the ternary material precursor, in the washing in step S6, the adopted washing medium is deionized water.
Further, in the preparation method of the ternary material precursor, the low-temperature drying in the step S6 is performed at a temperature of 90-130 ℃, preferably 110-120 ℃.
Furthermore, the invention also discloses a ternary material precursor prepared by the method, wherein the ternary material precursor is formed by mixing three ternary material precursors with different particle sizes,
the particle size distribution range of the large-particle-size ternary material precursor is 13-14 mu m (D50),
the particle size distribution range of the medium-particle size ternary material precursor is D50-5-6 μm,
the particle size distribution range of the small-particle-size ternary material precursor is 2.5-3.5 mu m (D50),
according to the solid content weight ratio: m (2.5-3.5 um): m (5-6 um): m (13-14 um): (1-1.5): (2-2.5): (6-7) are matched,
the tap density of the ternary material precursor is that the ternary material precursor is sieved through a 316L stainless steel screen with 200-450 meshes,
the surface of the precursor particle of the ternary material is provided with fine whiskers which are orderly arranged in a directional rule,
the precursor of the ternary material has a chemical formula of (Ni)xCoyMnz)OH2Where x + y + z is 1, 1.0 > x.gtoreq.0.3, x is preferably 1.0 > x.gtoreq.0.5.
The invention has the beneficial effects that: the preparation method adopts the preparation process of the ternary material precursor of continuous and intermittent mixing materials for crystal growth, has the advantages of a continuous process and an intermittent process, can obtain the ternary material precursor with a wider particle size range, and reduces the risk of overburning caused by excessive fine powder when the subsequent ternary material precursor is processed into the ternary material by controlling the solid content to be less than or equal to 40 percent and controlling the content of the fine powder. The ternary material precursor with large particle size (13-14 microns), medium particle size (5-6 microns) and small particle size (2.5-3.5 microns) is matched, mixed, washed, dried and screened to obtain the ternary material precursor with high tap density, namely the ternary material precursor with the mesh number of 200-450 meshes of 316L stainless steel screen mesh is used, and the tap density of the ternary material precursor is highly related to the compaction density, so that the tap density of the ternary material precursor is improved, the compaction density of the ternary material precursor is correspondingly improved, and the volumetric energy density of the ternary material is favorably improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 shows a process flow diagram of a method for preparing a ternary material precursor according to an embodiment of the present invention;
fig. 2 is a scanning electron microscope image of a precursor of a ternary material with a target particle size of D50 ═ 2-3um prepared in example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of a ternary material precursor with a target particle size of D50 ═ 5-6um prepared in example 1 of the present invention
Fig. 4 is a scanning electron microscope image of the precursor of the ternary material with the target particle size of D50 ═ 13-14um prepared in example 1 of the present invention;
FIG. 5 is a scanning electron microscope image of a mixed ternary material precursor prepared in example 1 of the present invention;
fig. 6 is a scanning electron microscope image of a precursor product D50 ═ 2-3um with a target particle size prepared in example 2 of the present invention;
FIG. 7 is a scanning electron microscope image of a precursor product D50 ═ 5-6um with a target particle size prepared in example 2 of the present invention
Fig. 8 is a scanning electron microscope image of a precursor product of 13-14um with a target particle size D50 prepared in example 2 of the present invention;
FIG. 9 is a scanning electron microscope image of the mixed precursor product prepared in example 2 of the present invention.
FIG. 10 is a scanning electron microscope image of the ternary material precursor product prepared in comparative example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings of the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
In the description of the present invention, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
In conjunction with FIG. 1
A preparation method of a ternary material precursor is characterized by comprising the following steps:
before the reaction of S1, preparing a reaction bottom liquid in a reaction kettle, using ammonia water with a certain volume and concentration as the reaction bottom liquid, simultaneously adjusting the pH of the bottom liquid to 11.5-13, and keeping nitrogen gas introduced into the reaction kettle bottom liquid for a long time as a protective gas for the reaction;
s2, introducing sulfuric acid solution with concentration of 1.0-2.2mol/L of nickel-cobalt-manganese three metals and 4-10mol/L of sodium hydroxide solution into a reaction kettle with ammonia water as a base solution, controlling corresponding reaction conditions according to the requirements of crystal nucleation target particle size morphology to obtain a ternary material precursor with consistent primary particle morphology, namely controlling the air inlet flow of nitrogen, controlling the feeding flow of the nickel-cobalt-manganese solution, controlling the feeding flow of the sodium hydroxide solution, controlling the reaction PH to be 11.5-13, controlling the rotation speed of the reaction kettle, generating ternary precursor crystal nuclei with consistent primary particle morphology at a certain constant temperature, namely complexing the nickel-cobalt-manganese sulfate solution with the ammonia water, and finally reacting the nickel-cobalt-manganese hydroxide with the sodium hydroxide, wherein the stage is a nucleation stage;
s3, opening a solid lifting groove connected with a reaction kettle, reducing the PH of the reaction to 9-11.5, introducing nitrogen and air which is treated by a carbon removal device in advance into the reaction kettle as a protective gas, controlling the flow of the protective gas, adjusting the concentration and the feeding flow of nickel-cobalt-manganese sulfate, and controlling the solid content of the target particle size slurry, so that the solid content of the target particle size slurry is improved, the ternary material precursor crystal nucleus grows uniformly and slowly at a constant temperature to reach the designed target particle size, and secondary particles are obtained, wherein the solid lifting growth stage is the solid lifting growth stage;
s4 step S3 is carried out, and the reaction is stopped when the secondary particle growth reaches the target particle size;
s5, repeating the steps S1-S4 to obtain ternary precursors with different particle sizes, wherein the primary particles of the ternary precursors are consistent in appearance. (ii) a
S6 mixing materials, matching and mixing the secondary particles with the design target particle sizes of D50 being 13-14 microns, D50 being 5-6 microns and D50 being 2.5-3.5 microns obtained in the step S5 according to a preset mass ratio, aging and mixing in an aging kettle for more than or equal to 2 hours at the rotating speed of 80-300RPM, washing, drying at low temperature, screening and magnetically separating the mixture after aging and mixing to obtain a finished product, wherein the finished product is the hydroxide precipitate of nickel, cobalt and manganese, namely the ternary material precursor.
Further, the preparation method of the ternary material precursor comprises the step S1, wherein a certain base solution is contained in the reaction kettle, the base solution is ammonia water, and the concentration of the ammonia water is 2-7g/L, preferably 2.5-5 g/L.
Further, the preparation method of the ternary material precursor is characterized in that the reaction temperature in the reaction kettle in the step S2 is 40-65 ℃.
Further, in the preparation method of the ternary material precursor, the ammonia water participating in the complexation reaction in step S2 is industrial ammonia water, and the mass percentage of the industrial ammonia water is 20%.
Further, in the preparation method of the ternary material precursor, the concentration of the nickel-cobalt-manganese sulfate in the step S2 is preferably 1.6-2.2 mol/L.
Further, in the preparation method of the ternary material precursor, the concentration of the sodium hydroxide salt in the step S2 is preferably 5 to 7 mol/L.
Further, the method for preparing the ternary material precursor, wherein the rotation speed of the reaction kettle in the nucleation stage in the step S2 is 1000-; in step S3, the rotation speed of the reaction kettle in the low pH lift-solid growth stage is 100-600rpm, preferably 230-450 rpm.
Further, in the preparation method of the ternary material precursor, in step S2, the PH of the nucleation stage is adjusted according to the target particle size, the PH of the generated large-particle-size primary particles is 11.5 to 12, the PH of the generated medium-particle-size primary particles is 12.0 to 12.5, and the PH of the generated small-particle-size primary particles is 12.5 to 13.
Further, in the preparation method of the ternary material precursor, in the step S3, the PH of the large-particle-size secondary particles generated in the solid-lifting stage is 9 to 11.5, the PH of the medium-particle-size secondary particles generated in the solid-lifting stage is 10.5 to 11.5, and the PH of the small-particle-size secondary particles generated in the solid-lifting stage is 11.1 to 11.5.
Further, in the preparation method of the ternary material precursor, in step S3, the feeding flow rate of the nickel cobalt manganese sulfate is controlled, and the feeding flow rates of the nickel cobalt manganese sulfate solutions in the low PH lift-solid growth process are different, wherein the feeding flow rate of the nickel cobalt manganese sulfate for growth with a target D50 ═ 2.5-3.5um is 2-4L/h, and the feeding flow rate of the nickel cobalt manganese sulfate for growth with a target D50 ═ 5-6um is 3-5L/h; target D50 ═ 13-14um growth the nickel cobalt manganese sulfate feed rate was 4-6L/h.
Further, the preparation method of the ternary material precursor comprises the step of introducing nitrogen gas as a protective gas into the reaction kettle in the step S2, wherein the purity of the nitrogen gas is more than 99.95%, and the flow rate is 0-2m3The nitrogen flow is preferably 1-2m for further strictly controlling the morphology of the ternary material precursor3/h。
Further, the preparation method of the ternary material precursor comprises the step S3 of carrying out crystal growth reaction, reducing the PH value in the reaction kettle, opening a solid lifting groove connected with the reaction kettle, introducing the nitrogen into the reaction kettle as a protective gas, wherein the purity of the nitrogen is 95-98.5%, and the flow rate is 0-2m3And h, introducing the nitrogen and air treated by a decarbonization device in advance, controlling the appearance of the secondary particles of the precursor of the ternary material in the slurry by adjusting the proportion of the nitrogen to the air, and detecting the precursor particles of the ternary material by a scanning electron microscope to know that if the proportion of the air to the nitrogen is not controlled, the surface of the precursor particles of the ternary material cannot form the appearance with fine whiskers and the whiskers are arranged orderly in a directional rule. If only nitrogen is introduced, the surface of the ternary material precursor particles is in a thicker platy stacked morphology, and the platesLarger gaps exist among the shape stacks; if the ratio of the introduced air is higher than 0.05, the air and the ternary material precursor particles are subjected to peroxidation reaction due to the presence of oxygen, and holes are formed on the surfaces of the ternary material precursor particles. In order to ensure that the surface of the ternary material precursor particles is compact and the crystals are orderly arranged, and the ternary material prepared by secondary sintering is favorable for forming compact particles, the flow ratio of the nitrogen to the air is controlled to be 0-0.05 in the crystal growth stage of the step S3 of preparing the ternary material precursor. Preferably, the flow ratio of the nitrogen gas to the air is 0.001 to 0.005.
Further, in the preparation method of the ternary material precursor, in the step S3, the supernatant of the material in the reaction kettle is discharged through the fixing lifting tank at a certain flow rate; the clear liquid velocity of the solid lifting groove is the sum of the flow velocities of the material flow, the alkali flow and the ammonia flow; keeping the solid content of the slurry with the target particle size in the reaction kettle to be less than or equal to 40%, and if the target particle size is not reached, carrying out material distribution to reduce the solid content; after the target particle size is reached, the solid content phase difference value of the reaction kettle is 0-0.3%;
further, in the preparation method of the ternary material precursor, in the washing in step S6, the adopted washing medium is deionized water.
Further, in the preparation method of the ternary material precursor, the low-temperature drying in step S6 is performed at a temperature of 90-130 ℃, preferably 110-120 ℃.
The invention further discloses a ternary material precursor prepared by the method, wherein the ternary material precursor is formed by mixing three ternary material precursors with different particle sizes, wherein the particle size distribution range of the large-particle-size ternary material precursor is D50-14 mu m, the particle size distribution range of the medium-particle-size ternary material precursor is D50-5-6 mu m, and the particle size distribution range of the small-particle-size ternary material precursor is D50-2.5-3.5 mu m. According to the solid content weight ratio: m (2.5-3.5 um): m (5-6 um): m (13-14 um): (1-1.5): (2-2.5): (6-7), the tap density of the ternary material precursor is that the ternary material precursor passes through a 316L stainless steel screen with the screen mesh number of 200 and 450,the surface of the precursor particle of the ternary material is provided with fine whiskers which are arranged orderly in a directional rule, and the chemical formula of the precursor of the ternary material is (Ni)xCoyMnz)OH2Where x + y + z is 1, 1.0 > x.gtoreq.0.3, x is preferably 1.0 > x.gtoreq.0.5.
Example 1
Preparing a mixed solution of NiSO4, CoSO4 and MnSO4 with the concentration of 1.6mol/L according to the molar ratio of nickel ions, cobalt ions and manganese ions of 70:10:20, filtering the mixed solution, a 6mol/L sodium hydroxide solution and 20% of industrial ammonia water with 200-mesh filter cloth by using a precision metering pump, enabling the mixed solution, the 6mol/L sodium hydroxide solution and the 20% industrial ammonia water to flow into a reaction kettle with reaction bottom liquid in a parallel flow manner, in the first stage, enabling the stirring speed of the reaction kettle to be 1050r/min, and carrying out nucleation on precursors with the target particle sizes of D50-2-3 um, D50-5-6 um and D50-13-14 um by using the pH values of 12.60, 12.3 and 11.8 respectively, and keeping the nitrogen gas at 0.5m and the temperature of 55 DEG C3H, long-pass reaction, wherein the ammonia value is 3-4g/L, and the reaction lasts for 1.5h for nucleation; and in the second stage (solid extraction stage), 2.0mol/L mixed sulfate solution is used, the growth pH of the precursor with the target granularity of D50-3 um, D50-5-6 um and D50-13-14 um is controlled at 11.3, 11.1 and 10.90, the flow rates of the growth salt are respectively 3L/h, 4.5L/h and 6L/h, the ammonia value in the reaction kettle is stabilized, the reaction speed is controlled at 3-4g/L, the reaction speed is controlled at 430rpm, the flow rate of air and nitrogen is adjusted to 0.002, the mother solution is filtered by a solid extractor respectively to be concentrated so as to improve the solid content and adjust the clear rate of the solid extractor and control the solid content, a Dandongbeit model 2600 particle size analyzer is used for measuring that the particles reach the required target granularity, and the reaction is stopped. Mixing the slurry for 3h at 200RPM of an aging kettle, washing, drying and screening to obtain a precursor material Ni0.70Co0.10Mn0.20(OH)2。
Scanning electron microscope testing is carried out on the nickel-cobalt-manganese ternary precursor materials with different particle sizes obtained in the embodiment 1, the testing results are shown in figures 2, 3 and 4, and the materials obtained after mixing are the scanning electron microscope testing results carried out after the ternary precursors are mixed, and are shown in figure 5.
Example 2
Preparing NiSO4, CoSO4 and MnSO with the concentration of 1.5mol/L according to the molar ratio of nickel ions to cobalt ions to manganese ions of 80:10:104, mixing the mixed solution, 5mol/L sodium hydroxide solution and 20% industrial ammonia water filtered by 200-mesh filter cloth by using a precision metering pump, enabling the mixed solution, the 5mol/L sodium hydroxide solution and the 20% industrial ammonia water to flow into a reaction kettle with reaction bottom liquid in a parallel flow mode, carrying out nucleation on precursors with target particle sizes of D50 being 2-3um, D50 being 5-6um and D50 being 13-14um by using the reaction kettle with the stirring speed of 1100r/min and the pH values of 12.50, 12.2 and 11.8 respectively at the temperature of 55 ℃, and keeping nitrogen gas at 0.2m and the temperature of 55 DEG C3H, long-pass reaction, wherein the ammonia value is 3.5-4g/L, and the reaction lasts for 1.5h for nucleation; and in the second stage, 2.0mol/L mixed sulfate solution is used, precursor growth pH values of which the target particle sizes are D50-2-3 um, D50-5-6 um and D50-13-14 um are controlled at 11.1, 11.0 and 10.80, growth salt flow rates are 3.5L/h, 4.5L/h and 5.5L/h respectively, the ammonia value in the reaction kettle is stabilized, the ammonia value is controlled at 3.5-4g/L, the reaction rotating speed is controlled at 400rpm, the flow ratio of air to nitrogen is adjusted to 0.002, a lifting fixer is used for filtering mother liquor for concentration to improve the solid content and adjust the clear-out speed of the lifting fixer and control the solid content, a Dandongbeit model 2600 particle size instrument is used for measuring that the particles reach the required target particle size, and the reaction is stopped. Mixing the slurry for 3h at 200rpm of an aging kettle, washing, drying and screening to obtain a precursor material Ni0.80Co0.10Mn0.10(OH)2。
Scanning electron microscope tests are carried out on the nickel-cobalt-manganese ternary precursor materials with different particle sizes obtained in the embodiment 2, and the test results are shown in fig. 6, 7 and 8, and the scanning electron microscope test results after mixing are shown in fig. 9.
Comparative example 1
Preparing a mixed solution of NiSO4, CoSO4 and MnSO4 with the concentration of 1.6mol/L according to the molar ratio of nickel ions, cobalt ions and manganese ions of 70:10:20, filtering the mixed solution, a 6mol/L sodium hydroxide solution and 20% of industrial ammonia water with 200-mesh filter cloth by using a precision metering pump, enabling the mixed solution, the 6mol/L sodium hydroxide solution and the 20% industrial ammonia water to flow into a reaction kettle with reaction bottom liquid in a parallel flow manner, in the first stage, enabling the stirring speed of the reaction kettle to be 1050r/min, and carrying out nucleation on precursors with the target particle sizes of D50-2-3 um, D50-5-6 um and D50-13-14 um by using the pH values of 12.60, 12.3 and 11.8 respectively, and keeping the nitrogen gas at 0.5m and the temperature of 55 DEG C3H, long-pass reaction, wherein the ammonia value is 3-4g/L, and the reaction lasts for 1.5h for nucleation; the second stage (solid extraction stage) uses 2.0mol/L mixed sulfate solutionThe growth PH of the precursor with the target granularity of D50-3 um, D50-5-6 um and D50-13-14 um is controlled at 11.3, 11.1 and 10.90, the flow rates of the growth salt are 3L/h, 4.5L/h and 6L/h respectively, the ammonia value in the reaction kettle is stabilized and is controlled at 3-4g/L, the reaction speed is controlled at 430rpm, the flow ratio of air to nitrogen is adjusted to be 0, only nitrogen is introduced, mother liquor is filtered by a solid lifting device for concentration to improve the solid content and adjust the clear-out speed of the solid lifting device and control the solid content, a Dandongberts 2600 type particle size instrument is used for measuring that the particles reach the required target granularity, and the reaction is stopped. Mixing the slurry for 3h at 200RPM of an aging kettle, washing, drying and screening to obtain a precursor material Ni0.70Co0.10Mn0.20(OH)2. And (3) carrying out scanning electron microscope test on the ternary precursor obtained in the comparative example 1 to obtain a scanning electron microscope test chart as 10.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a ternary material precursor is characterized by comprising the following steps:
before the reaction of S1, preparing a reaction base solution in a reaction kettle, using ammonia water with a certain volume and concentration as the reaction base solution, simultaneously adjusting the pH of the base solution to 11.5-13, and keeping nitrogen as a protective gas for the base solution in the reaction kettle;
s2, leading 1.0-2.2mol/L sulfuric acid solution of three metals of nickel, cobalt and manganese, 4-10mol/L sodium hydroxide solution and ammonia water into the bottom liquid of the reaction kettle in the step S1 in a parallel flow manner, and simultaneously maintaining the pH value of the bottom liquid in the reaction kettle between 11.5 and 13, wherein the ammonia value and the temperature are in a certain range; obtaining a ternary material precursor crystal nucleus, namely complexing the nickel-cobalt-manganese sulfate solution with ammonia water, and finally reacting with sodium hydroxide to obtain nickel-cobalt-manganese hydroxide, wherein the stage is a nucleation stage;
s3, opening a solid lifting groove connected with a reaction kettle, reducing the PH of the reaction to 9-11.5, introducing nitrogen and air treated by a carbon removal device in advance into the reaction kettle as the atmosphere control of the growth reaction of precursor crystal nuclei, controlling the flow of the air and the nitrogen, controlling the feeding flow of nickel-cobalt-manganese sulfate, and controlling the solid content of the target particle size slurry, so that the solid content of the target particle size slurry is improved, the ternary material precursor crystal nuclei grow uniformly and slowly at constant temperature to reach the designed target particle size, and the ternary material precursor secondary particles with consistent primary particle morphology are obtained, wherein the solid lifting growth stage is the solid lifting growth stage;
s4 step S3 stopping the reaction when the secondary particle growth reaches the preset target particle size;
s5 repeating the steps S1-S4 to obtain ternary material precursor secondary particles with different preset target particle sizes, wherein the ternary material precursor secondary particles have primary particles with consistent appearances;
s6, mixing the secondary particles with the design target particle sizes of D50 being 13-14 μm, D50 being 5-6 μm and D50 being 2.5-3.5 μm respectively obtained in the step S5 according to a preset mass ratio, aging and mixing in an aging kettle for more than or equal to 2h at the rotation speed of 80-300RPM, and washing, drying at low temperature, screening and magnetically separating sequentially after the aging and mixing to obtain a finished product, wherein the finished product is nickel-cobalt-manganese hydroxide precipitate, namely a ternary material precursor.
2. The method for preparing a ternary material precursor according to claim 1, wherein the reaction temperature in the reaction kettle of step S2 is 40-65 ℃.
3. The method for preparing the ternary material precursor of claim 1, wherein a certain base solution is contained in the reaction kettle in step S2, wherein the base solution is ammonia water, and the concentration of the ammonia water is 2-7 g/L; s2, the ammonia water participating in the complexation reaction is industrial ammonia water, and the mass percentage of the industrial ammonia water is 20%.
4. The method for preparing a ternary material precursor as claimed in claim 1, wherein the rotation speed of the reaction kettle in the nucleation stage in step S2 is 1000-; in step S3, the rotation speed of the reaction kettle in the low pH lift-solid growth stage is 100-600rpm, preferably 230-450 rpm.
5. The method according to claim 1, wherein the PH in step S2 is adjusted according to the target particle size, the PH for forming the large-particle-size primary particles is 11.5 to 12, the PH for forming the medium-particle-size primary particles is 12.0 to 12.5, and the PH for forming the small-particle-size primary particles is 12.5 to 13.
6. The method according to claim 1, wherein the PH of the large-size secondary particles produced in step S3 is 9 to 11.5, the PH of the medium-size secondary particles produced is 10.5 to 11.5, and the PH of the small-size secondary particles produced is 11.1 to 11.5.
7. The method of claim 1, wherein the feeding flow rate of the nickel cobalt manganese sulfate is controlled, and the feeding flow rate of the nickel cobalt manganese sulfate solution in the low PH lift-up growth process in step S3 is different, wherein the feeding flow rate of the nickel cobalt manganese sulfate solution is 2-4L/h for target D50 ═ 2.5-3.5um growth, and the feeding flow rate of the nickel cobalt manganese sulfate solution is 3-5L/h for target D50 ═ 5-6um growth; target D50 ═ 13-14um growth the nickel cobalt manganese sulfate feed rate was 4-6L/h.
8. The preparation method of the ternary material precursor of claim 1, wherein the nickel-cobalt-manganese sulfate solution is prepared in step S2, the sodium hydroxide solution is introduced into a reaction kettle with a base solution of ammonia water, nitrogen is introduced into the reaction kettle as a shielding gas, the purity of the nitrogen is 99.95%, and the flow rate of the nitrogen is 0-2m3/h。
9. The method for preparing a ternary material precursor according to claim 1, wherein the ternary material precursor is prepared by a method comprising a step of adding a solution of a ternary material precursorStep S3 is to carry out crystal growth reaction, reduce the PH in the reaction kettle, open the solid lifting groove connected with the reaction kettle, introduce nitrogen as protective gas into the reaction kettle, the purity of the nitrogen is 95-98.5%, and the flow is 0-2m3And h, introducing the nitrogen and air which is treated by a carbon removal device in advance, and controlling the appearance of the nickel-cobalt-manganese hydroxide secondary particles in the slurry by adjusting the ratio of the nitrogen to the air, wherein the flow ratio of the nitrogen to the air is 0-0.05.
10. The ternary material precursor prepared by the method of any one of claims 1 to 9, wherein the ternary material precursor is prepared by mixing three ternary material precursors with different particle sizes,
the particle size distribution range of the large-particle-size ternary material precursor is 13-14 mu m (D50),
the particle size distribution range of the medium-particle size ternary material precursor is D50-5-6 μm,
the particle size distribution range of the small-particle-size ternary material precursor is 2.5-3.5 mu m (D50),
according to the solid content weight ratio: m (2.5-3.5 um): m (5-6 um): m (13-14 um): (1-1.5): (2-2.5): (6-7) are matched,
the surface of the precursor particle of the ternary material is provided with fine whiskers which are orderly arranged in a directional rule,
the precursor of the ternary material has a chemical formula of (Ni)xCoyMnz)OH2Wherein x + y + z is 1, and x is more than 1.0 and is more than or equal to 0.3.
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