CN114620774A - Preparation method and application of core-shell structure high-nickel ternary precursor - Google Patents

Preparation method and application of core-shell structure high-nickel ternary precursor Download PDF

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CN114620774A
CN114620774A CN202210250956.1A CN202210250956A CN114620774A CN 114620774 A CN114620774 A CN 114620774A CN 202210250956 A CN202210250956 A CN 202210250956A CN 114620774 A CN114620774 A CN 114620774A
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shell structure
nickel
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precursor
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明磊
肖志明
欧星
张宝
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Central South University
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C—CHEMISTRY; METALLURGY
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    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes

Abstract

The invention belongs to the technical field of battery materials, and discloses a preparation method and application of a core-shell structure high-nickel ternary precursor, which is characterized in that an inner layer is NiM formed by coprecipitationp(OH)2A spherical inner core with an outer layer of NixCoyMnzMq(OH)2The protective shell, the inner layer element doping volume is greater than the skin. NiMp(OH)2The core may provide higher capacity, NixCoyMnzMq(OH)2Compared with the inner core, the shell has more stable structure and is more complete to the materialThe body structure can play a role in stabilization and protection. Particularly, the high-nickel ternary material prepared by the method is gradient doped with the M element in a bulk phase, so that the stability of an internal structure of the bulk phase can be greatly improved, and the generation of grain boundary cracks is inhibited; the surface layer is a low/medium nickel ternary material with a stable structure, so that the surface/interface problem of the high nickel ternary material can be improved, and the industrialization process of the high nickel ternary material is promoted. And finally, mixing and sintering the ternary precursor and a lithium source to obtain the ternary cathode material, wherein the ternary cathode material has high specific capacity and long cycle capacity, and the practical application value of the material is powerfully proved.

Description

Preparation method and application of core-shell structure high-nickel ternary precursor
Technical Field
The invention belongs to the field of lithium ion battery materials, and particularly relates to a preparation method and application of a core-shell structure high-nickel ternary precursor.
Background
With the rapid development of power automobiles, the nickel-cobalt-manganese ternary positive electrode material is widely applied due to the advantages of high capacity, high energy density and the like. In the nickel-cobalt-manganese ternary cathode material, the main capacity contribution comes from nickel, the higher the nickel content is, the higher the energy density is, and the high nickel material is the mainstream research and development trend at present. However, as the nickel content increases, the cycle stability and thermal stability of the material rapidly decrease, which severely hinders its large-scale commercial application.
The problem of the high nickel material is mainly divided into a bulk phase interior part and a surface part, and for the bulk phase interior part, because the material is synthesized by adopting a coprecipitation method mostly, primary particles are randomly distributed and agglomerated together, and can be subjected to the action of anisotropic stress in the discharging process, so that the structure is easy to break, and the material is inactivated; from the surface structure, the high nickel material has high surface alkalinity and is easy to absorb moisture and CO when exposed in the air2Reacts with residual lithium on the surface to form LiOH and Li2CO3This part lithium is "dead lithium" basically, can seriously influence the electrochemistry energy storage performance of ternary material, and simultaneously, in the charging and discharging process, the lithium that takes off of electrode material all begins from the top layer, high nickel material surface structure can take place H2 to H3 phase transition, lead to the structure to be changed into rock salt phase structure by lamellar structure, form the inert layer, can hinder lithium ion's quick transmission, the high valence nickel ion of the strong oxidizing property on high nickel material surface layer takes place serious side reaction with electrolyte simultaneously, increase polarization, also can make the capacity attenuate fast.
The modification strategies currently made to address the above issues are mainly doping and cladding modification of the positive electrode material. In terms of doping, the research on doping modification in the precursor stage is less, and the doping in the precursor stage is easier to realize the regulation and control of the distribution of doping elements, so that a precursor material with a stable structure is obtained; for coating modification, at present, materials such as metal oxides, fast ion conductors, carbon materials, phosphates and the like are mainly used for coating modification, sintering is carried out after coating, energy consumption can be increased, production efficiency is reduced, and if the structural design of the materials can be realized to achieve the effect of modifying the surfaces of the materials, the coating effect is achieved, so that the production benefit can be greatly improved, however, the research in the direction is very lacking at present.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and realize the preparation of the high-nickel anode material with long-cycle stability by designing the structure of the material body.
The further technical problem to be solved is to prepare the high-nickel ternary precursor with the core-shell structure.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a high-nickel ternary precursor with core-shell structure has a chemical formula of NiMp(OH)2·NixCoyMnzMq(OH)2Wherein x is more than or equal to 0.4 and less than or equal to 1, Y is more than or equal to 0.03 and less than or equal to 0.3, z is more than or equal to 0.02 and less than or equal to 0.4, p is more than or equal to 0 and less than or equal to 0.01, q is more than or equal to 0 and less than or equal to 0.008, x + Y + z is 1, M is one or more of Al, Zr, Ce, Mo, Mg, Ti, Ta, W, B, Nb, Y, Na, Zn, In, Sr and V, and the inner layer is NiM formed by coprecipitationp(OH)2A spherical inner core with an outer layer of NixCoyMnzMq(OH)2The doping amount of the inner layer element is larger than that of the outer layer.
The invention solves the technical problem by adopting the technical scheme that a preparation method and application of a core-shell structure high-nickel ternary precursor comprise the following steps:
(1) preparing a nickel salt solution; preparing a doped element salt solution; preparing a nickel, cobalt and manganese mixed salt solution according to a molar ratio; preparing complexing agent NH3·H2O solution; preparing a precipitator NaOH solution;
(2) preparing a reaction kettle bottom solution, introducing nitrogen, and respectively pumping the nickel salt solution, the doped element salt solution, the complexing agent solution and the precipitator solution prepared in the step (1) by using a peristaltic pumpPutting into a reaction kettle 1, controlling the adding proportion of nickel salt and doping element salt, the concentration of ammonia water, pH, temperature and the rotating speed of a stirrer in the system, carrying out particle size test by using a particle size tester, stopping feeding after the reaction time reaches 1-15 mu m, and forming Ni (OH)2A spherical inner core;
(3) NiM obtained in step (2)p(OH)2Placing the spherical core in a reaction kettle 2, introducing nitrogen, pumping the doped element salt solution, the mixed salt solution, the complexing agent solution and the precipitator solution by using a peristaltic pump respectively, adjusting reaction parameters in the kettle, and carrying out reaction in NiMp(OH)2Continuing to grow Ni on the spherical corexCoyMnzMq(OH)2And (3) testing the particle size of the shell by using a particle size tester, reacting for a period of time until the particle size reaches 1-20 mu m, and stopping feeding to obtain the precursor slurry with the core-shell structure.
(4) Carrying out solid-liquid separation on the precursor slurry obtained in the step (3), collecting solids, washing, drying, sieving and demagnetizing the solids to obtain a precursor with a core-shell structure;
(5) reacting LiOH & H2And ball-milling and mixing the O and the precursor with the core-shell structure, and sintering in an oxygen atmosphere to obtain the ternary cathode material.
Further, the diameter of the core-shell structure high-nickel ternary precursor material is 1-15 μm, and the thickness of the shell is 0-5 μm.
Further, in the step (2), the concentration of the metal ions in the doped element salt solution is 0.001-1 mol/L; complexing agent NH3·H2The O solution is 25% industrial ammonia water; the concentration of the precipitator NaOH solution is 2-10 mol/L.
Further, in the step (2), in the reaction kettle 1, the concentration of the complexing agent is 5.0-10.0 g/L, pH and is 12-13, the stirring speed is 300-600 r/min, and the temperature is 40-60 ℃.
Further, in the step (3), in the reaction kettle 2, the concentration of the complexing agent is 5.0-10.0 g/L, pH and is 10-12, the stirring speed is 400-800 r/min, and the temperature is 50-70 ℃.
Further, in the step (5), the sintering process is divided into two stages, wherein the first stage sintering temperature rise rate is 2-10 ℃/min, the sintering temperature is 350-; the temperature rise rate of the second-stage sintering is 2-9 ℃/min, the sintering temperature is 690-1100 ℃, and the temperature is kept for 10-30 h.
Compared with the prior art, the invention has the beneficial effects that:
(1) the preparation method realizes the preparation of the high-performance high-nickel material by carrying out gradient doping on the material and designing the core-shell structure of the body at the precursor stage. Gradient doping, wherein the core is doped with M element in a proper amount due to unstable structure, the structure is stabilized, the shell structure is relatively stable, the M element is doped in a micro-trace manner, and the amount of the M element doped in the inner layer is larger than that of the M element doped in the outer layer, so that the body structure can be effectively enhanced, and the generation of grain boundary cracks is reduced; and the core-shell structure design, the core provides main capacity for the nickel ball, and the shell has more stable structure compared with the core and can protect the surface of the material, so that the high-nickel ternary cathode material with high energy density and long-cycle stability is obtained.
(2) The invention provides a new idea for preparing a novel high-nickel electrode material, which is completely different from the surface coating modification means of the traditional positive electrode material.
(3) The preparation method is simple, does not need to additionally add other coating materials, has low production cost and high production efficiency, and is suitable for industrial production.
Drawings
FIG. 1 is an electron microscope image of a zirconium core-shell structure high-nickel ternary precursor in example 1 of the present invention
FIG. 2 is a diagram showing the electrochemical properties of the positive electrode material in example 1 of the present invention
FIG. 3 is an electron microscope image of a tungsten core-shell structure high-nickel ternary precursor in example 2 of the present invention
Detailed Description
The invention is further described with reference to the following figures and specific examples.
Example 1
The chemical equation of the precursor of the ternary cathode material with the core-shell structure is NiZr0.004(OH)2·Ni5Co2Mn3Zr0.002(OH)2。
In this embodiment, the ternary cathode material precursor core NiZr0.004(OH)212 to 13 μm in thickness and Ni as a shell5Co2Mn3Zr0.002(OH)22 to 3 μm.
The preparation method and application of the core-shell structure high-nickel ternary precursor comprise the following steps:
(1) preparing 1mol/L NiSO4·6H2O salt solution; preparing 0.04mol/L Zr (SO)4)2A salt solution; NiSO according to the molar ratio of 5:2:34·6H2O、CoSO4·7H2O, and MnSO4·H2O preparing a mixed salt solution with the metal ion concentration of 1 mol/L; preparing 8mol/LNaOH alkali solution precipitant.
(2) Preparing a base solution of the reaction kettle 1 by using hot pure water, industrial ammonia water and a precipitator, controlling the temperature of the reaction kettle to be 70 ℃, the pH value to be 12.5 and the ammonia concentration to be 6.8g/L, and introducing nitrogen. Then, the prepared NiSO with the concentration of 1mol/L is pumped by a peristaltic pump4·6H2O salt solution at a flow rate of 40mL/min, Zr (SO) at 0.04mol/L4)2Adding a salt solution into a reaction kettle 1 at a flow rate of 4mL/min, adjusting the rotating speed of a stirring paddle to be 400rpm/min, controlling the temperature of the reaction kettle to be 66 ℃, controlling the ammonia concentration in the system to be 6.6g/L, pH to be 11.5 by utilizing industrial ammonia water and a precipitator, sampling and testing the granularity every half hour until the diameter of the particle grows to 12-13 mu m, and stopping feeding to obtain pure nickel sphere precursor slurry.
(3) Carrying out solid-liquid separation on the nickel ball precursor slurry obtained in the step (2), transferring the nickel ball precursor slurry into a reaction kettle 2 with prepared base solution for continuous growth, and at the moment, carrying out continuous growth on the mixed salt solution at the flow rate of 40mL/min and Zr (SO) of 0.04mol/L4)2Adding salt solution at a flow rate of 2mL/min, adjusting the rotation speed of a stirring paddle to 600rpm/min, controlling the temperature of a reaction kettle to be 60 ℃, and controlling the ammonia concentration in the system to be 6.4g/L, pH ═ by using industrial ammonia water and a precipitatorAnd 11.2, sampling every half hour to test the granularity, and stopping feeding until the diameter of the particles grows to 14-16 mu m to obtain the precursor slurry with the core-shell structure.
(4) And (4) carrying out solid-liquid separation on the precursor slurry obtained in the step (3), collecting solids, and washing, drying, sieving and demagnetizing the solids to obtain the core-shell structure high-nickel ternary precursor.
(5) 1mol of the ternary precursor obtained in the step (4) and 1.05mol of LiOH. H2And O, mixing, uniformly ball-milling at the rotation speed of 150rpm for 2h, calcining at 400 ℃ for 3h at the temperature rise rate of 5 ℃/min in the oxygen atmosphere, and then calcining at 800 ℃ for 19h to obtain the ternary cathode material with the core-shell structure.
An electron microscope image of the zirconium element core-shell structure high-nickel ternary precursor is shown in fig. 1, the whole is spherical particles, and the particle size is 14-16 μm. Sintering the precursor into a positive electrode material, assembling the positive electrode material into a lithium ion button cell, and then carrying out electrochemical performance test, wherein the test result is shown in figure 2, and the first ring has 195.7mAh g in a voltage range of 2.7-4.3V at room temperature under the test condition of 0.1C-1The specific discharge capacity of the lithium battery is 84.94% of the coulomb efficiency of the first circle; the first circle of 1C has 177.1mAh g-1The specific capacity of the resin is 166.2mAh g after 200 cycles of circulation-1The specific capacity and the capacity retention rate of (2) were 93.85%.
Example 2
The chemical equation of the precursor of the ternary cathode material with the core-shell structure is NiW0.004(OH)2·Ni6Co2Mn2W0.002(OH)2。
The precursor core NiW of the ternary cathode material in this embodiment0.004(OH)213-14 μm, shell Ni6Co2Mn2W0.002(OH)2Is 1-2 μm.
The preparation method and application of the core-shell structure high-nickel ternary precursor comprise the following steps:
(1) preparing 1mol/L NiSO4·6H2O salt solution; 0.04mol/L of Na is prepared2WO4A salt solution; according to a molar ratio of 6:2:2NiSO4·6H2O、CoSO4·7H2O, and MnSO4·H2O, preparing a mixed salt solution with the metal ion concentration of 1 mol/L; preparing 8mol/L NaOH alkali solution precipitant.
(2) Preparing a base solution of the reaction kettle 1 by using hot pure water, industrial ammonia water and a precipitator, controlling the temperature of the reaction kettle to be 70 ℃, the pH value to be 12.5 and the ammonia concentration to be 6.8g/L, and introducing nitrogen. Then, the prepared NiSO with the concentration of 1mol/L is pumped by a peristaltic pump4·6H2O salt solution at a flow rate of 40mL/min, 0.04mol/L Na2WO4Adding a salt solution into a reaction kettle 1 at a flow rate of 4mL/min, adjusting the rotating speed of a stirring paddle to 410rpm/min, controlling the temperature of the reaction kettle to be 67 ℃, controlling the ammonia concentration in the system to be 6.7g/L, pH to 11.6 by using industrial ammonia water and a precipitator, sampling and testing the granularity every half hour until the diameter of the particle grows to 13-14 mu m, and stopping feeding to obtain pure nickel sphere precursor slurry.
(3) Carrying out solid-liquid separation on the nickel ball precursor slurry obtained in the step (2), transferring the nickel ball precursor slurry into a reaction kettle 2 with prepared base solution for continuous growth, and at the moment, carrying out continuous growth on the mixed salt solution at the flow rate of 40mL/min and Na of 0.04mol/L2WO4Adding a salt solution at a flow rate of 2mL/min, adjusting the rotating speed of a stirring paddle to be 620rpm/min, controlling the temperature of the reaction kettle to be 61 ℃, controlling the ammonia concentration in the system to be 6.5g/L, pH to be 11.3 by using industrial ammonia water and a precipitator, sampling every half hour to test the particle size, and stopping feeding until the particle diameter grows to 14-16 mu m to obtain the precursor slurry with the core-shell structure.
(4) And (4) performing solid-liquid separation on the precursor slurry obtained in the step (3), collecting solids, washing, drying, sieving and demagnetizing the solids to obtain the core-shell structure high-nickel ternary precursor.
An electron microscope image of the high-nickel ternary precursor with the tungsten element core-shell structure is shown in fig. 3, the whole is spherical particles, and the particle size is 14-16 μm.

Claims (7)

1. A high-nickel ternary precursor with a core-shell structure is characterized in that the chemical formula is NiMp(OH)2·NixCoyMnzMq(OH)2Wherein x is more than or equal to 0.4 and less than or equal to 1, Y is more than or equal to 0.03 and less than or equal to 0.3, z is more than or equal to 0.02 and less than or equal to 0.4, p is more than or equal to 0 and less than or equal to 0.01, q is more than or equal to 0 and less than or equal to 0.008, x + Y + z is 1, M is one or more of Al, Zr, Ce, Mo, Mg, Ti, Ta, W, B, Nb, Y, Na, Zn, In, Sr and V, and the inner layer is NiM formed by coprecipitationp(OH)2A spherical inner core with an outer layer of NixCoyMnzMq(OH)2The doping amount of the inner layer element is larger than that of the outer layer.
2. The core-shell structure high-nickel ternary precursor material according to claim 1, wherein the core diameter of the core-shell structure high-nickel ternary precursor material is between 1 and 15 μm, and the shell thickness is between 0 and 5 μm.
3. A preparation method and application of the core-shell structure high-nickel ternary precursor as claimed in claim 1 or 2, characterized by comprising the following steps:
(1) preparing a nickel salt solution; preparing a doped element salt solution; preparing a nickel, cobalt and manganese mixed salt solution according to a molar ratio; preparing complexing agent NH3·H2O solution; preparing a precipitator NaOH solution;
(2) preparing a reaction kettle bottom solution, introducing nitrogen, pumping the nickel salt solution, the doping element salt solution, the complexing agent solution and the precipitator solution prepared in the step (1) into the reaction kettle 1 by using a peristaltic pump, controlling the adding proportion of the nickel salt and the doping element salt in the system, the ammonia water concentration, the pH value, the temperature and the rotating speed of a stirrer, performing particle size test by using a particle size tester, stopping feeding after the reaction lasts for a period of time and the particles reach 1-15 mu m, and obtaining the NiMp(OH)2A spherical inner core;
(3) NiM obtained in step (2)p(OH)2Placing the spherical core in a reaction kettle 2, introducing nitrogen, pumping the doped element salt solution, the mixed salt solution, the complexing agent solution and the precipitator solution by using a peristaltic pump respectively, adjusting reaction parameters in the kettle, and carrying out reaction in NiMp(OH)2Continuing to grow Ni on the spherical corexCoyMnzMq(OH)2Outer casingPerforming particle size test by using a particle size tester, reacting for a period of time until the particles reach 1-20 mu m, and stopping feeding to obtain precursor slurry with a core-shell structure;
(4) carrying out solid-liquid separation on the precursor slurry obtained in the step (3), collecting solids, washing, drying, sieving and demagnetizing the solids to obtain a precursor with a core-shell structure;
(5) reacting LiOH & H2And ball-milling and mixing the O and the precursor with the core-shell structure, and sintering in an oxygen atmosphere to obtain the ternary cathode material.
4. The preparation method and application of the core-shell structure high-nickel ternary precursor according to claim 2 or 3, characterized in that in the step (2), the concentration of metal ions in the doped element salt solution is 0.001-1 mol/L; complexing agent NH3·H2The O solution is 25% industrial ammonia water; the concentration of the precipitator NaOH solution is 2-10 mol/L.
5. The preparation method and application of the core-shell structure high-nickel ternary precursor according to any one of claims 2 to 4, wherein in the step (2), the concentration of the complexing agent is 5.0 to 10.0g/L, pH and is 12 to 13, the stirring speed is 300 to 600r/min, and the temperature is 40 to 60 ℃ in the reaction kettle 1.
6. The preparation method and application of the core-shell structure high-nickel ternary precursor according to any one of claims 2 to 5, wherein in the step (3), the concentration of the complexing agent is 5.0 to 10.0g/L, pH and is 10 to 12, the stirring speed is 400 to 800r/min, and the temperature is 50 to 70 ℃ in the reaction kettle 2.
7. The preparation method and application of the core-shell structure high-nickel ternary precursor as claimed in any one of claims 2 to 6, wherein in the step (5), the sintering process is divided into two stages, the first stage sintering temperature rise rate is 2-10 ℃/min, the sintering temperature is 350-; the temperature rise rate of the second-stage sintering is 2-9 ℃/min, the sintering temperature is 690-1100 ℃, and the temperature is kept for 10-30 h.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115676913A (en) * 2022-10-14 2023-02-03 宜宾光原锂电材料有限公司 Zinc-doped core-shell structure high-nickel ternary precursor and preparation method thereof
CN115893520A (en) * 2022-11-17 2023-04-04 广东佳纳能源科技有限公司 Doped high-nickel ternary precursor and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103078109A (en) * 2013-01-16 2013-05-01 中南大学 Gradient coated LiNiO2 material and preparation method
CN108598441A (en) * 2018-05-29 2018-09-28 东莞理工学院 A kind of different grain size narrow ditribution ternary precursor and preparation method thereof
CN109301240A (en) * 2018-10-21 2019-02-01 圣戈莱（北京）科技有限公司 Nickelic multicomponent material presoma of cation doping gradient and its preparation method and application

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103078109A (en) * 2013-01-16 2013-05-01 中南大学 Gradient coated LiNiO2 material and preparation method
CN108598441A (en) * 2018-05-29 2018-09-28 东莞理工学院 A kind of different grain size narrow ditribution ternary precursor and preparation method thereof
CN109301240A (en) * 2018-10-21 2019-02-01 圣戈莱（北京）科技有限公司 Nickelic multicomponent material presoma of cation doping gradient and its preparation method and application

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115676913A (en) * 2022-10-14 2023-02-03 宜宾光原锂电材料有限公司 Zinc-doped core-shell structure high-nickel ternary precursor and preparation method thereof
CN115676913B (en) * 2022-10-14 2024-03-26 宜宾光原锂电材料有限公司 Zinc-doped core-shell structure high-nickel ternary precursor and preparation method thereof
CN115893520A (en) * 2022-11-17 2023-04-04 广东佳纳能源科技有限公司 Doped high-nickel ternary precursor and preparation method and application thereof

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