CN112723426B - Porous positive electrode material precursor, preparation method thereof and ternary positive electrode material - Google Patents

Porous positive electrode material precursor, preparation method thereof and ternary positive electrode material Download PDF

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CN112723426B
CN112723426B CN202011636978.9A CN202011636978A CN112723426B CN 112723426 B CN112723426 B CN 112723426B CN 202011636978 A CN202011636978 A CN 202011636978A CN 112723426 B CN112723426 B CN 112723426B
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CN112723426A (en
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许开华
李伟
李聪
李顺利
刘德宠
施杨
何锐
周晓燕
陈玉君
徐世国
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Greenmei Hubei New Energy Materials Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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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Abstract

The invention discloses a porous anode material precursor, a preparation method thereof and a ternary anode material. The preparation method of the porous anode material precursor is characterized by comprising the following steps: introducing a metal salt solution, a complexing agent and an alkali liquor into the reaction bottom liquid in a concurrent flow manner, controlling the pH value to 12-13, and carrying out heat preservation reaction for 4-6 h at the temperature of 50-80 ℃; then reducing the pH value to 10-11, starting to introduce a polycarboxylate dispersant solution, controlling the reaction temperature to be 50-80 ℃, and carrying out heat preservation reaction for 24-36 h; and after the reaction is finished, stopping feeding, aging at 40-60 ℃ for 20-30 h, and performing solid-liquid separation, washing and drying to obtain the porous anode material precursor. According to the invention, different surfactants are selected and pH is controlled at different stages of the preparation process of the precursor, so that the core-layer structure of the precursor is more compact and the shell-layer structure of the precursor is more loose, thereby being beneficial to improving the specific surface area, avoiding the obvious reduction of tap density and improving the rate capability and structural stability of the material.

Description

Porous positive electrode material precursor, preparation method thereof and ternary positive electrode material
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a porous positive electrode material precursor, a preparation method thereof and a ternary positive electrode material.
Background
With new energyThe market of source automobiles is continuously strong, the demand of power batteries is increasing day by day, and the demand of high-power materials is particularly strong in the market of electric tools. High nickel materials are sought after because of their higher energy density and lower cost advantages over low nickel materials. But the high nickel material is also due to Ni 2+ The high activity ensures that the precipitation speed of transition metal ions is too high in the coprecipitation process, so that primary particles of a precursor are tightly stacked, the pores in the particles are few, and the primary particles of the sintered anode material are compact, so that the lithium ion transmission is hindered, and the power performance of the material is influenced.
Generally, the specific surface area is increased by increasing the porosity of the precursor of the high-nickel cathode material, so that the cathode material with a loose porous structure can effectively improve the rate capability of the material. However, too large a specific surface area also reduces the structural stability of the material, resulting in a decrease in the cycle life of the battery.
Therefore, the ternary positive electrode material precursor which has higher specific surface and structural stability is significant.
Disclosure of Invention
In view of the above, it is necessary to provide a porous cathode material precursor, a preparation method thereof, and a ternary cathode material, so as to solve the technical problems of high specific surface area and poor structural stability of the cathode material in the prior art.
The first aspect of the present invention provides a method for preparing a porous positive electrode material precursor, comprising the steps of:
introducing a metal salt solution, a complexing agent and an alkali liquor into the reaction base solution in a parallel flow manner, controlling the pH value to 12-13, and carrying out heat preservation reaction for 4-6 h at the temperature of 50-80 ℃; wherein the reaction base solution is a mixed solution of ammonia water, sodium hydroxide and sodium dodecyl benzene sulfonate; the metal salt solution is a mixed salt solution of sulfates, nitrates or hydrochlorides corresponding to nickel, cobalt and manganese;
then reducing the pH value to 10-11, starting to introduce a polycarboxylate dispersant solution, controlling the reaction temperature to be 50-80 ℃, and keeping the temperature to react for 24-36 h;
and after the reaction is finished, stopping feeding, aging at 40-60 ℃ for 20-30 h, and performing solid-liquid separation, washing and drying to obtain the porous anode material precursor.
A second aspect of the present invention provides a porous cathode material precursor obtained by the method for preparing the porous cathode material precursor provided in the first aspect of the present invention.
The third aspect of the invention provides a ternary cathode material, which is obtained by uniformly mixing the porous cathode material precursor obtained by the first aspect of the invention with a lithium source and then sintering.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, different surfactants are selected and pH is controlled at different stages of the preparation process of the precursor, so that the core-layer structure of the precursor is more compact and the shell-layer structure of the precursor is more loose, thereby being beneficial to improving the specific surface area, avoiding the obvious reduction of tap density and improving the rate capability and structural stability of the material.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The first aspect of the invention provides a preparation method of a porous anode material precursor, which comprises the following steps:
s1: introducing a metal salt solution, a complexing agent and an alkali liquor into the reaction bottom liquid in a concurrent flow manner, controlling the pH value to 12-13, and carrying out heat preservation reaction for 4-6 h at the temperature of 50-80 ℃; wherein the reaction base solution is a mixed solution of ammonia water, sodium hydroxide and sodium dodecyl benzene sulfonate; the metal salt solution is a mixed salt solution of sulfate, nitrate or hydrochloride corresponding to nickel, cobalt and manganese.
S2: then reducing the pH value to 10-11, starting to introduce a polycarboxylate dispersant solution, controlling the reaction temperature to be 50-80 ℃, and carrying out heat preservation reaction for 24-36 h;
s3: and after the reaction is finished, stopping feeding, aging at 40-60 ℃ for 20-30 h, and performing solid-liquid separation, washing and drying to obtain the porous anode material precursor.
In the preparation process of the precursor, sodium dodecyl benzene sulfonate is added and the pH is strictly controlled, so that the sodium dodecyl benzene sulfonate is favorable for covering the surface of metal ions under high pH, the ionic acting force among particles is reduced to a certain degree, the dispersibility of the metal ions is improved, and the reaction nucleation is promoted; after the pH is reduced at the later stage, the high-activity Ni is delayed by polycarboxylate 2 + 、Co 2+ 、Mn 2+ The crystallization rate of the material inhibits the directional rapid growth of metal ions on the (101) crystal face, so that the compactness of particles is reduced, the porosity of the particles is increased, the specific surface area of the material is improved, the sintered loose and porous structure is favorable for the transmission of lithium ions, and the power performance of the material is improved.
According to the invention, different surfactants are selected and pH is controlled at different stages of the preparation process of the precursor, so that the core-layer structure of the precursor is more compact and the shell-layer structure of the precursor is more loose, thereby being beneficial to improving the specific surface area, avoiding the obvious reduction of tap density and improving the rate capability and structural stability of the material.
Further, the concentration of ammonia water in the reaction base solution is 0.2 to 0.6mol/L, and further 0.4mol/L; the concentration of the sodium hydroxide is 3 to 5mol/L, and further 4mol/L; the concentration of sodium dodecylbenzenesulfonate is 0.1 to 0.5mol/L, further 0.3mol/L.
Furthermore, the total concentration of metal ions corresponding to nickel, cobalt and manganese in the metal salt solution is 1-5 mol/L. Further, the molar ratio of nickel, cobalt and manganese is (0.8-0.88): (0.03-0.15): (0.03 to 0.1), and further 0.8:0.1:0.1. in the reaction process, the flow rate of the metal salt solution is 3-5L/h, and further 4L/h.
In this embodiment, the metal salt solution further includes a soluble salt corresponding to the doping element; further, the doping element is one or more of Zr, al, Y, ti and W; furthermore, the ratio of the doping element to the total molar weight of nickel, cobalt and manganese is (0.01-0.2): 100, preferably (0.05-0.15): 100.
in the invention, by adding the doping elements, the synergistic effect of the doping elements, sodium dodecyl benzene sulfonate and polycarboxylate dispersant can be fully exerted, the distribution uniformity of the doping elements is improved, and the structural stability is obviously improved; meanwhile, the method can reduce the use of the dopant and avoid the reduction of the battery capacity caused by adding too much dopant.
In the embodiment, the complexing agent is one or two of ammonia water and sodium citrate, and the concentration of the complexing agent is 0.3-0.5 mol/L, and further 0.4mol/L; the alkali liquor is one or two of sodium hydroxide solution and potassium hydroxide solution, and the concentration of the alkali liquor is 2-10 mol/L, and further 4mol/L.
Further, in the process of controlling the pH to 12-13, the flow rate of the alkali liquor is 6-10L/h, and further 8L/h; the flow rate of the complexing agent is 2-4L/h, and further 3L/h.
Further, in the process of controlling the pH to 10-11, the flow rate of the alkali liquor is 4-8L/h, and further 6L/h; the flow rate of the complexing agent is 1-3L/h, and further 2L/h.
In this embodiment, the polycarboxylate dispersant is SP-2700.SP-2700 is a comb polymerization anionic surfactant insensitive to electrolyte, and can be irreversibly adsorbed on the surface of a solid with high stability, so that the dispersibility is improved and the crystallization rate is reduced. Further, the concentration of the polycarboxylate dispersant solution is 0.01 to 0.1mol/L, further 0.05mol/L; the flow rate of the polycarboxylate solution is 0.1-1L/h, further 0.5L/h.
In the invention, the molar ratio of the metal salt solution to the sodium dodecyl benzene sulfonate to the polycarboxylate dispersant is 1: (0.001-0.05): (0.0001 to 0.005); further 1: (0.007-0.03): (0.0005 to 0.003).
In the present invention, the stirring rate is controlled to 500 to 1500rpm, and further 800rpm.
A second aspect of the present invention provides a porous positive electrode material precursor obtained by the method for preparing a porous positive electrode material precursor provided in the first aspect of the present invention.
The third aspect of the invention provides a ternary cathode material, which is obtained by uniformly mixing the porous cathode material precursor obtained by the first aspect of the invention with a lithium source and then sintering.
The high porosity of the precursor of the positive electrode material can greatly improve the dispersibility of a lithium source in the preparation process of the positive electrode material, so that lithium is uniformly distributed in the positive electrode material, and the rate capability and the cycling stability of the positive electrode material are further improved.
In the present embodiment, the lithium source is lithium hydroxide or lithium carbonate. Furthermore, the ratio of the lithium in the lithium source to the total molar amount of nickel, cobalt and manganese in the precursor of the porous cathode material is (1.01-1.15): 1.
In the embodiment, the temperature for mixing and sintering the porous cathode material precursor and the lithium source is 750-800 ℃, and the sintering time is 12-18 h.
Example 1
(1) Respectively introducing a metal salt solution, a 0.4mol/L ammonia water solution and a 4mol/L sodium hydroxide solution into 20L of reaction base solution at flow rates of 4L/h, 3L/h and 8L/h in parallel, controlling the pH to 12-13, and carrying out heat preservation reaction at 60 ℃ for 5h; wherein the reaction base solution is a mixed solution of ammonia water, sodium hydroxide and sodium dodecyl benzene sulfonate, the concentration of the ammonia water is 0.4mol/L, the concentration of the sodium hydroxide is 4mol/L, and the concentration of the sodium dodecyl benzene sulfonate is 0.3mol/L; the metal salt solution is a mixed salt solution prepared from nickel sulfate, cobalt sulfate, manganese sulfate and zirconium sulfate, the total concentration of metal ions corresponding to nickel, cobalt and manganese is 3mol/L, and the molar ratio of nickel, cobalt and manganese is 0.8:0.1:0.1; the ratio of the total molar weight of zirconium to the total molar weight of nickel, cobalt and manganese is 0.1;
(2) Then reducing the flow rate of ammonia water to 2L/h, reducing the flow rate of sodium hydroxide to 6L/h to control the pH value of the reaction to be 10-11, starting to introduce 0.05mol/L polycarboxylate dispersant solution (SP-2700) at the flow rate of 0.5L/h, and carrying out heat preservation reaction for 27h at the temperature of 60 ℃;
(3) After the reaction is finished, stopping feeding, aging at 50 ℃ for 28h, and carrying out solid-liquid separation, washing and drying to obtain a porous anode material precursor;
(4) 1000g of the porous anode material precursor and 480g of LiOHH 2 And uniformly mixing the O in a high-speed mixer, and then sintering at 800 ℃ for 12h to obtain the ternary cathode material.
Example 2
(1) Respectively introducing a metal salt solution, a 0.4mol/L ammonia water solution and a 4mol/L sodium hydroxide solution into 20L of reaction base solution at flow rates of 4L/h, 3L/h and 8L/h in parallel, controlling the pH to 12-13, and carrying out heat preservation reaction for 4h at the temperature of 80 ℃; wherein the reaction base solution is a mixed solution of ammonia water, sodium hydroxide and sodium dodecyl benzene sulfonate, the concentration of the ammonia water is 0.4mol/L, the concentration of the sodium hydroxide is 4mol/L, and the concentration of the sodium dodecyl benzene sulfonate is 0.1mol/L; the metal salt solution is a mixed salt solution prepared from nickel sulfate, cobalt sulfate, manganese sulfate and zirconium sulfate, the total concentration of metal ions corresponding to nickel, cobalt and manganese is 2mol/L, and the molar ratio of nickel, cobalt and manganese is 0.88:0.09:0.03; the ratio of zirconium to the total molar amount of nickel, cobalt and manganese is 0.05.
(2) Then reducing the flow rate of ammonia water to 2L/h, reducing the flow rate of sodium hydroxide to 6L/h to control the reaction pH to be 10-11, starting to introduce 0.01mol/L polycarboxylate dispersant solution (SP-2700) at the flow rate of 0.5L/h, and carrying out heat preservation reaction for 30h at the temperature of 80 ℃;
(3) And after the reaction is finished, stopping feeding, aging at 40 ℃ for 30h, and carrying out solid-liquid separation, washing and drying to obtain the porous anode material precursor.
(4) 1000g of the porous positive electrode material precursor and 480g of LiOH & H 2 And mixing the materials uniformly in a high-speed mixer, and then sintering the materials for 18 hours at 750 ℃ to obtain the ternary cathode material.
Example 3
(1) Respectively introducing a metal salt solution, a 0.4mol/L ammonia water solution and a 4mol/L sodium hydroxide solution into 20L of reaction base solution at flow rates of 4L/h, 3L/h and 8L/h in a parallel flow manner, controlling the pH value to 12-13, and carrying out heat preservation reaction at 50 ℃ for 6h; wherein the reaction base solution is a mixed solution of ammonia water, sodium hydroxide and sodium dodecyl benzene sulfonate, the concentration of the ammonia water is 0.4mol/L, the concentration of the sodium hydroxide is 4mol/L, and the concentration of the sodium dodecyl benzene sulfonate is 0.5mol/L; the metal salt solution is a mixed salt solution prepared from nickel sulfate, cobalt sulfate, manganese sulfate and zirconium sulfate, the total concentration of metal ions corresponding to nickel, cobalt and manganese is 4mol/L, and the molar ratio of nickel, cobalt and manganese is 0.83:0.12:0.05; the ratio of the total molar weight of zirconium to the total molar weight of nickel, cobalt and manganese is 0.15;
(2) Then reducing the flow rate of ammonia water to 2L/h, reducing the flow rate of sodium hydroxide to 6L/h to control the reaction pH to be 10-11, starting to introduce 0.1mol/L polycarboxylate dispersant solution (SP-2700) at the flow rate of 0.5L/h, and carrying out heat preservation reaction at 50 ℃ for 24h;
(3) After the reaction is finished, stopping feeding, aging at 60 ℃ for 20h, and carrying out solid-liquid separation, washing and drying to obtain a porous anode material precursor;
(4) 1000g of the porous positive electrode material precursor and 480g of LiOH & H 2 And uniformly mixing the O in a high-speed mixer, and then sintering at 780 ℃ for 15h to obtain the ternary cathode material.
Example 4
In comparison with example 1, no zirconium sulfate was added to example 4.
Comparative example 1
In comparison to example 1, no SP-2700 was added to comparative example 1.
Comparative example 2
In comparison with example 1, in comparative example 2, sodium dodecylbenzenesulfonate was not added.
Comparative example 3
In contrast to example 1, the pH of the reaction in comparative example 3 was always 10 to 11.
Test group 1
Specific surface areas and tap densities of the porous positive electrode material precursors and the ternary positive electrode materials obtained in examples 1 to 4 of the present invention and comparative examples 1 to 3 were measured, and the results are shown in table 1.
TABLE 1
Figure BDA0002878763240000081
Test group 2
The positive electrode materials obtained in the embodiments 1 to 4 and the comparative examples 1 to 3 are uniformly mixed in NMP (N-methyl pyrrolidone) according to the mass ratio of the positive electrode material, the conductive agent SuperP and the binder PVDF of 92Drying the lithium ion battery slurry in a blast box, and drying in a vacuum box at 120 ℃. Taking the dried pole piece as a positive electrode, lithium metal as a negative electrode and a polyethylene film as a diaphragm, and adopting 1mol/L LiPF 6 The solution was used as an electrolyte (EC: EMC volume ratio in solvent 3) and the above materials were prepared into 2032 button cells in a glove box and tested for electrical properties on a LAND button tester. The results are shown in Table 2.
TABLE 2
Figure BDA0002878763240000082
Figure BDA0002878763240000091
As can be seen from tables 1 and 2, the positive electrode material precursor obtained by the invention has higher specific surface area and tap density; the obtained cathode material has good rate performance and cycle performance.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.

Claims (8)

1. A preparation method of a porous positive electrode material precursor is characterized by comprising the following steps:
introducing a metal salt solution, a complexing agent and an alkali liquor into the reaction base solution in a parallel flow manner, controlling the pH to be 12 to 13, and carrying out heat preservation reaction for 4 to 6h at the temperature of 50 to 80 ℃; wherein the reaction base solution is a mixed solution of ammonia water, sodium hydroxide and sodium dodecyl benzene sulfonate; in the reaction base solution, the concentration of ammonia water is 0.2-0.6 mol/L, the concentration of sodium hydroxide is 3-5 mol/L, and the concentration of sodium dodecyl benzene sulfonate is 0.1-0.5 mol/L; the metal salt solution is a mixed salt solution of sulfates, nitrates or hydrochlorides corresponding to nickel, cobalt and manganese; in the metal salt solution, the total concentration of metal ions corresponding to nickel, cobalt and manganese is 1 to 5mol/L; the complexing agent is one or two of ammonia water or sodium citrate, and the concentration of the complexing agent is 0.3 to 0.5mol/L; the alkali liquor is one or two of sodium hydroxide solution or potassium hydroxide solution, and the concentration of the alkali liquor is 2-10mol/L;
then, reducing the pH value to 10 to 11, starting to introduce a polycarboxylate dispersant solution, controlling the reaction temperature to be 50 to 80 ℃, and carrying out heat preservation reaction for 24 to 36h; the polycarboxylate dispersant is SP-2700, and the concentration of the polycarboxylate dispersant solution is 0.01 to 0.1mol/L;
and after the reaction is finished, stopping feeding, aging at 40 to 60 ℃ for 20 to 30h, and carrying out solid-liquid separation, washing and drying to obtain the porous cathode material precursor.
2. The method for preparing the precursor of the porous cathode material according to claim 1, wherein the molar ratio of nickel, cobalt and manganese in the metal salt solution is (0.8 to 0.88): (0.03 to 0.15): (0.03 to 0.1); in the reaction process, the flow rate of the metal salt solution is 3 to 5L/h.
3. The preparation method of the precursor of the porous cathode material according to claim 1, wherein the metal salt solution further comprises a soluble salt corresponding to a doping element, wherein the doping element is one or more of Zr, al, Y, ti, and W; the ratio of the doping element to the total molar weight of the nickel, the cobalt and the manganese is (0.01 to 0.2): 100.
4. The preparation method of the precursor of the porous cathode material according to claim 1, wherein in the process of controlling the pH to 12 to 13, the flow rate of the alkali liquor is 6 to 10L/h, and the flow rate of the complexing agent is 2 to 4L/h; and in the process of controlling the pH to 10 to 11, the flow rate of the alkali liquor is 4 to 8L/h, and the flow rate of the complexing agent is 1 to 3L/h.
5. The preparation method of the porous cathode material precursor according to claim 1, wherein the flow rate of the polycarboxylate solution is 0.1 to 1L/h.
6. The method for preparing the precursor of the porous cathode material according to claim 1, wherein the molar ratio of the metal salt solution to the sodium dodecyl benzene sulfonate to the polycarboxylate dispersant is 1: (0.001 to 0.05): (0.0001. About.0.005).
7. A porous positive electrode material precursor, which is obtained by the preparation method of the porous positive electrode material precursor according to any one of claims 1 to 6.
8. A ternary cathode material is characterized in that the ternary cathode material is obtained by uniformly mixing the porous cathode material precursor obtained in any one of claims 1 to 6 with a lithium source and then sintering.
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CN109516510B (en) * 2018-12-13 2021-07-06 华友新能源科技（衢州）有限公司 Nickel-cobalt-manganese hydroxide with special micro-nano structure and preparation method thereof
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