CN115432742A - Preparation method of composite precursor material - Google Patents
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Abstract
The invention relates to a preparation method of a composite precursor material, which comprises the following steps: (1) Mixing soluble cobalt salt, alkali metal hydroxide, a dispersing agent and EDTA (ethylene diamine tetraacetic acid), allowing the mixture to flow into a reaction kettle with a base solution and a large amount of air for constant-temperature co-precipitation, and performing full reaction to obtain a cobalt oxyhydroxide precursor material with the granularity of 3 mu m; (2) On the basis, preparing a mixed solution of manganese chloride, nickel chloride and aluminum chloride according to the molar ratio of Mn to Ni to Al =80 0.8 Ni 0.15 Al 0.05 (OH) 2 Is a composite precursor of the shell.
Description
Technical Field
The invention relates to the field of precursor production processes, in particular to a preparation method of a composite precursor material.
Background
The traditional method for preparing lithium cobaltate has been commercialized as early as many years ago, gradually occupies the market of traditional 3C, and how to effectively release more capacity of lithium cobaltate at present is a problem which is commonly solved by all the requirements of traditional 3C products and technical research and development personnel. The technical route for solving the problem is to select a liquid-phase coprecipitation method to dope salt solutions of Al, mg, ti and the like, or to coat metal oxides and carbon by a solid-phase sintering method. But the method has the defects of difficult industrialization, high process preparation requirement, complex technical difficulty and difficult guarantee of product consistency.
At present, the preparation route of the lithium cobaltate for industrial industrialization comprises the synthesis of cobalt carbonate and the lithium doping by sintering cobaltic; synthesizing cobalt hydroxide, and sintering to obtain the final product. The invention mainly adopts hydroxyl cobalt oxide to synthesize, wherein, the cobalt content of the finished product reaches 70.5 percent by controlling a crystallization method, and the direct lithium-doped sintering is carried out. The advantages are that the sintering process is reduced, more lithium carbonate is used, and the lithium carbonate is just combined with the lithium-rich manganese-based precursor.
CN 114436341A discloses a method for preparing single crystal mixed oxideThe precursor is spherical or spheroidal particle and consists of a single crystal anode material and an oxide layer, and the structure contains the single crystal anode material with higher strength, so that the problem that secondary particles are easy to break is solved. CN 112909231A discloses a preparation method of a lithium ion battery anode composite material precursor, which comprises the steps of putting any two or three salt solid raw materials of nickel, cobalt and manganese with crystal water into a reactor, and heating to a molten state; introducing ammonia gas under the protection of inert gas, pressurizing to 1.2-1.4Mpa, properly supplementing a small amount of water or not adding water according to the solubility of the above salts at different temperatures, and reacting while stirring; after the reaction is completed, evaporating out ammonium salt, taking out solid, and drying to obtain an amorphous binary or ternary positive electrode composite material precursor; CN 114436342A discloses a precursor of hydroxide coated on single crystal outer layer and a preparation method thereof, wherein a selected single crystal positive electrode material is subjected to acid treatment to form an uneven surface, so that primary hydroxide particles generated in a subsequent coprecipitation reaction can be better attached to the surface of the single crystal positive electrode material to prepare precursor particles with a core-shell structure, the particles are composed of an inner core and an outer shell, the inner core is the single crystal positive electrode material, and the outer shell of the particles is formed by aggregating primary nickel-containing composite hydroxide particles, so that the cycle performance, the integral packing density and the specific capacity of the material can be further improved by the structure; meanwhile, the shell layer of the particles is different according to application fields, and the primary particles are flaky, blocky, spindle-shaped or needle-shaped, so that the tap density of the material is further improved, and the electrochemical properties such as the rate capability, the cycle performance and the like of the lithium ion battery are improved. The invention is based on the difference of the processes that the precursor is prepared into the single crystal with the layered structure, and the high tap is 2.5-2.6g/cm 3 The lithium-rich manganese-based precursor is different from a lithium manganate precursor in that the lithium-rich manganese-based precursor is of a layered crystal structure, and lithium manganate is of a spinel crystal structure, so that the lithium manganese oxide is more beneficial to compounding.
Disclosure of Invention
The invention aims to provide a preparation method of a composite precursor material, which is used for preparing small-particle monocrystal cobalt oxyhydroxide by a controlled crystallization method, wherein the cobalt content reaches 70.5 percent, and the tap density is more than or equal to 2.5g/cm 3 Coating Mn with this as a core 0.8 Ni 0.15 Al 0.05 (OH) 2 Is a composite precursor of the shell, reduces the process, has high efficiency and can be applied to production in large scale. The specific process is as follows:
a, synthesizing a cobalt oxyhydroxide precursor
Mixing soluble cobalt salt, alkali metal hydroxide, a dispersing agent and EDTA, and allowing the mixture to flow into a reaction kettle with a base solution and a large amount of air for constant-temperature co-precipitation, and after full reaction, obtaining a cobalt oxyhydroxide precursor material with the diameter of 3 mu m; the amount of air introduced is not less than 5m 3 The reaction kettle is started and the aeration is carried out for 2 hours in advance, and the pH is controlled to be 10.0-12.5;
b. synthesis of manganese-rich precursor
Taking 3 mu m cobalt oxyhydroxide precursor slurry as a core, preparing a mixed solution of manganese chloride, nickel chloride, cobalt chloride and aluminum chloride according to the molar ratio of Mn to Ni to Al =80 0.8 Ni 0.15 Al 0.05 (OH) 2 Is a composite precursor of the shell.
In the step a, soluble cobalt salt is cobalt chloride solution, and the preparation concentration is 2.0 mol/L; the alkali metal hydroxide is sodium hydroxide, and the concentration is 8.0 mol/L; the concentration of EDTA is 0.04 mol/L; the dispersant is sodium dodecyl sulfate.
In the step a, the reaction temperature is 70 ℃, the stirring is carried out, the stirring speed is 550 r/min, and the air quantity is 5m 3 The flow ratio is 5. Wherein the relationship among the ventilation volume, the rotating speed and the flow rate is ensured to ensure that the content of the product cobaltosic oxide in the cobalt oxyhydroxide is more than or equal to 69.5 percent by using a crystallization control method under the premise of high pH.
In the step a, a spiral jet-shaped stirring paddle is adopted for stirring, and the diameter of an annular air hole on the paddle is 3-5nm, so that the uniform dispersion can be realized, and the oxidizability of the cobalt content is ensured.
In the step (b), manganese chloride, nickel chloride and aluminum chloride are mixed according to the molar ratio of Mn to Ni to Al = 80.
In the step (b), the reaction synthesis temperature is 52 ℃, the stirring speed is 650 r/min, and the nitrogen introduction amount is 2.5m 3 The pH value is controlled to be 11.5, the concentration of ammonium ions in the solution is 10g/L, and the material of the reaction kettle is stainless steel.
And (c) washing the composite precursor obtained in the step (b) for five times, and drying to ensure that the conductivity is less than or equal to 10 mu s/cm and the drying temperature is 105 ℃.
The invention gives full play to the strictness of the preparation process of the cobalt oxyhydroxide precursor, and the cobalt content is 70.5 percent and the high tap density is more than or equal to 2.5g/cm by controlling the crystallization method 3 The characteristic of (c). Coating Mn for the core on the basis 0.8 Ni 0.15 Al 0.05 (OH) 2 Is a composite precursor of the shell, reduces the process, has high efficiency and can be applied to production in large scale. The specific innovation points are embodied in the following aspects:
(1) The sintering process is reduced: the precursor prepared by controlling the crystallization method and the special stirring mode can directly ensure that the cobalt content is 70.5 percent, reduce the process of re-sintering the cobaltosic oxide and greatly reduce the cost.
(2) The composite property of the layered material: after the manganese-rich lithium-based precursor is selected to be doped with aluminum, the manganese-rich lithium-based precursor and the cobalt oxyhydroxide are all layered crystal structures without interface compatibility problems in the coating process, so that the defects of the materials are well complemented.
Drawings
FIG. 1 is an SEM photograph of a layered cobalt oxyhydroxide prepared according to example 1;
FIG. 2 is an XRD pattern of the layered cobalt oxyhydroxide prepared in example 1;
FIG. 3 is a diagram of example l preparation of CoOOH @ Mn 0.8 Ni 0.15 Al 0.05 (OH) 2 SEM image of composite precursor;
FIG. 4 preparation of CoOOH @ Mn as example 0.8 Ni 0.15 Al 0.05 (OH) 2 Composite precursor EDS energy spectrogram;
FIG. 5 is a preparation of CoOOH @ Mn in example 1 0.8 Ni 0.15 Al 0.05 (OH) 2 Particle size distribution diagram.
Detailed Description
The invention provides a preparation method of a composite precursor material, which is implemented by the following steps:
comparative example 1
Firstly, carrying out synthetic reaction on a mixed solution of 2mol/L cobalt chloride solution and 0.04mol/L EDTA and 8.0mol/L sodium hydroxide solution at the reaction synthetic temperature of 70 ℃, the stirring speed of 550 r/min and the air amount of 5m 3 The flow ratio is 5, the pH is controlled to be 11.0-12.5, and the material of the reaction kettle is titanium alloy. Two of the key factors are that the reactor is started and the aeration needs to be injected 2h in advance. By using a controlled crystallization method, the solid content in the kettle is observed to be about 35 percent, and the air quantity is large enough under the premise of high pH, so that the cobalt content (the main content of cobaltosic oxide is more than or equal to 90 percent) in the cobalt oxyhydroxide can be ensured to be 70.5 percent. The experimental scheme was carried out to prepare small particle, single crystal layered structured materials of cobalt oxyhydroxide particles up to 6 μm.
Comparative example 2
Preparing a mixed solution with the concentration of 2.0 mol/L, the concentration of sodium hydroxide of 8.0mol/L, the mixed concentration of EDTA and ammonia water of 0.4 mol/L, the reaction synthesis temperature of 52 ℃, the stirring speed of 650 r/min and the nitrogen amount of 2.5m by using manganese chloride, nickel chloride and aluminum chloride according to the molar ratio of Mn to Ni to Al =80 3 H, controlling the pH value to be 11.5, controlling the concentration of ammonium ions in the solution to be 10g/L, and using stainless steel as a reaction kettle material. Washing for five times, ensuring that the conductivity is less than or equal to 10 mu s/cm, drying at 105 ℃, and sieving to prepare the precursor rich in manganese and doped with aluminum.
Example 1
Firstly, carrying out synthetic reaction on a mixed solution of 2mol/L cobalt chloride solution and 0.04mol/L EDTA and 8.0mol/L sodium hydroxide solution at the reaction synthetic temperature of 70 ℃ and the stirring speed of 550 r/min (the stirring adopts a spiral jet-shaped stirring blade, the diameter of an annular air hole on the blade is 3-5nm, the stirring blade can be uniformly dispersed, and the oxidizability of the cobalt content is ensured), and the air inlet amount is 5m 3 Flow rate,/hThe ratio is 5, 1, the pH is controlled to be 11.0-12.5, and the material of the reaction kettle is titanium alloy. Two key factors are that the startup of the reaction kettle (the startup is carried out after the reaction kettle is added with 1.538g/L sodium dodecyl sulfate and the pH is adjusted by liquid caustic soda as a base solution) and the aeration quantity needs to be injected for 2 hours in advance. By using a controlled crystallization method, the solid content in the kettle is observed to be about 35 percent, and the air quantity is large enough under the premise of high pH, so that the cobalt content (the main content of cobaltosic oxide is more than or equal to 90 percent) in the cobalt oxyhydroxide is ensured to be 70.5 percent, and the granularity is made to be 3 mu m. Manganese chloride, nickel chloride and aluminum chloride are mixed according to the molar ratio of Mn to Ni to Al =80 3 H, controlling the pH value to be 11.5, controlling the concentration of ammonium ions in the solution to be 10g/L, and using stainless steel as a reaction kettle material. Taking a cobalt oxyhydroxide precursor as a core to prepare Mn 0.8 Ni 0.15 Al 0.05 (OH) 2 Is a composite precursor of the shell, the granularity is made to be 6 mu m, and the slurry is subjected to solid-liquid separation, aging, centrifugation and drying. Washing for five times, ensuring that the conductivity is less than or equal to 10 mu s/cm and the drying temperature is 105 ℃. Sieving to obtain CoOOH @ LiMn 0.8 Ni 0.15 Al 0.05 (OH) 2 A composite precursor material.
Example 2
Firstly, carrying out synthetic reaction on a mixed solution of 2mol/L cobalt chloride solution and 0.04mol/L EDTA and 8.0mol/L sodium hydroxide solution at the reaction synthesis temperature of 70 ℃ and the stirring speed of 550 r/min (a spiral jet-shaped stirring blade is adopted for stirring, the diameter of a circular air hole on the blade is 3-5nm, uniform dispersion can be realized, the oxidizability of the cobalt content is ensured), and the air inlet amount is 5m 3 H, the flow ratio is 5, the pH is controlled to be 11.0-12.5, and the material of the reaction kettle is titanium alloy. Two key factors are that the startup of the reaction kettle (the startup is carried out after the reaction kettle is added with 1.538g/L sodium dodecyl sulfate and the pH is adjusted by liquid caustic soda as a base solution) and the aeration quantity needs to be injected for 2 hours in advance. By using a controlled crystallization method, the solid content in the kettle is observed to be about 35 percent, and the air quantity is enough to ensure that hydroxyl groups can be ensured on the premise of high pHThe cobalt content in the cobalt oxide (the main content of cobaltosic oxide is more than or equal to 90 percent) is 70.5 percent, and the particle size is 3 mu m. Manganese chloride, nickel chloride and aluminum chloride are mixed according to the molar ratio of Mn to Ni to Al =80 3 The pH value is controlled to be 11.5, the concentration of ammonium ions in the solution is 10g/L, and the material of the reaction kettle is stainless steel. Taking a hydroxyl cobalt oxide precursor as a core to prepare Mn 0.8 Ni 0.15 Al 0.05 (OH) 2 Is a composite precursor of the shell, the granularity is made to be 6 mu m, and the slurry is subjected to solid-liquid separation, aging, centrifugation and drying. Washing for five times, ensuring that the conductivity is less than or equal to 10 mu s/cm and the drying temperature is 105 ℃. Sieving to obtain CoOOH @ LiMn 0.8 Ni 0.15 Al 0.05 (OH) 2 A composite precursor material. The proportions of nickel and aluminium were increased to 10% and 10%, respectively, compared to example 1.
Example 3
Firstly, carrying out synthetic reaction on a mixed solution of 2mol/L cobalt chloride solution and 0.04mol/L EDTA and 8.0mol/L sodium hydroxide solution at the reaction synthesis temperature of 70 ℃ and the stirring speed of 550 r/min (a spiral jet-shaped stirring blade is adopted for stirring, the diameter of a circular air hole on the blade is 3-5nm, uniform dispersion can be realized, the oxidizability of the cobalt content is ensured), and the air inlet amount is 5m 3 The flow ratio is 5, the pH is controlled to be 11.0-12.5, and the material of the reaction kettle is titanium alloy. Two key factors are that the startup of the reaction kettle (the startup of the reaction kettle after 1.538g/L sodium dodecyl sulfate is added into the reaction kettle and the pH is adjusted by liquid caustic soda as a base solution) and the ventilation volume need to be injected in advance for 2 hours. By using a controlled crystallization method, the solid content in the kettle is observed to be about 35 percent, and the air quantity is enough under the premise of high pH, so that the cobalt content (the main content of cobaltosic oxide is more than or equal to 90 percent) in the cobalt oxyhydroxide is ensured to be 70.5 percent, and the particle size is 3 mu m. Manganese chloride, nickel chloride and aluminum chloride are mixed according to the molar ratio of Mn to Ni to Al =7550 r/min, the amount of nitrogen introduced is 2.5m 3 The pH value is controlled to be 11.5, the concentration of ammonium ions in the solution is 10g/L, and the material of the reaction kettle is stainless steel. Taking a cobalt oxyhydroxide precursor as a core to prepare Mn 0.8 Ni 0.15 Al 0.05 (OH) 2 Is a composite precursor of the shell, the granularity is made to be 6 mu m, and the slurry is subjected to solid-liquid separation, aging, centrifugation and drying. Washing for five times, ensuring that the conductivity is less than or equal to 10 mu s/cm and the drying temperature is 105 ℃. Sieving to obtain CoOOH @ LiMn 0.8 Ni 0.15 Al 0.05 (OH) 2 A composite precursor material. Compared to examples 1 and 2, manganese chloride, nickel chloride and aluminum chloride were prepared in a ratio of Mn: ni: al = 75.
Example 4
Firstly, carrying out synthetic reaction on a mixed solution of 2mol/L cobalt chloride solution and 0.04mol/L EDTA and 8.0mol/L sodium hydroxide solution, wherein the reaction synthesis temperature is 70 ℃, the stirring speed is 550 r/min, the introduced air amount is 2-3m < 3 >/h, the flow ratio is 5, the pH is controlled to be 11.0-12.5, and the reaction kettle is made of titanium alloy. Two key factors are that the startup of the reaction kettle (the startup is carried out after the reaction kettle is added with 1.538g/L sodium dodecyl sulfate and the pH is adjusted by liquid caustic soda as a base solution) and the aeration quantity needs to be injected for 2 hours in advance. By using a controlled crystallization method, the solid content in the kettle is observed to be about 35 percent, and the air quantity is enough under the premise of high pH, so that the cobalt content (the main content of cobaltosic oxide is more than or equal to 90 percent) in the cobalt oxyhydroxide is ensured to be 65.9 percent, and the particle size is 3 mu m. Manganese chloride, nickel chloride and aluminum chloride are prepared into a mixed solution with the concentration of 2.0 mol/L, the concentration of sodium hydroxide of 8.0mol/L, the mixed concentration of EDTA-2Na and ammonia water of 0.4 mol/L according to the mol ratio of Mn to Ni to Al = 80. Taking a cobalt oxyhydroxide precursor as a core to prepare Mn 0.8 Ni 0.15 Al 0.05 (OH) 2 Is a composite precursor of the shell, the granularity is made to be 6 mu m, and the slurry is subjected to solid-liquid separation, aging, centrifugation and drying. Washing for five times, ensuring that the conductivity is less than or equal to 10 mu s/cm and the drying temperature is 105 ℃. Sieving to obtainCoOOH＠LiMn 0.8 Ni 0.15 Al 0.05 (OH) 2 A composite precursor material. The main difference between the processes of examples 1,2 and 3 is that the air ventilation in the synthesis process of cobalt oxyhydroxide is poor, the ventilation mode adopts normal stirring, and the cobalt content is obviously reduced.
Example 5
Firstly, carrying out synthetic reaction on a mixed solution of 2mol/L cobalt chloride solution and 0.04mol/L EDTA and 8.0mol/L sodium hydroxide solution, wherein the reaction synthesis temperature is 70 ℃, the stirring speed is 550 r/min, the introduced air amount is 2-3m < 3 >/h, the flow ratio is 5, the pH is controlled to be 9.4-9.8, and the reaction kettle is made of titanium alloy. Two key factors are that the startup of the reaction kettle (the startup of the reaction kettle after 1.538g/L sodium dodecyl sulfate is added into the reaction kettle and the pH is adjusted by liquid caustic soda as a base solution) and the ventilation volume need to be injected in advance for 2 hours. By using a controlled crystallization method, the solid content in the kettle is observed to be about 35 percent, and the air quantity is large enough under the premise of high pH, so that the cobalt content (the main content of cobaltosic oxide is more than or equal to 90 percent) in the cobalt oxyhydroxide is ensured to be 61 percent, and the particle size is made to be 3 mu m. Manganese chloride, nickel chloride and aluminum chloride are prepared into a mixed solution with the concentration of 2.0 mol/L, the concentration of sodium hydroxide of 8.0mol/L, the mixed concentration of EDTA-2Na and ammonia water of 0.4 mol/L according to the mol ratio of Mn to Ni to Al = 80. Taking a hydroxyl cobalt oxide precursor as a core to prepare Mn 0.8 Ni 0.15 Al 0.05 (OH) 2 Is a composite precursor of the shell, the granularity is made to be 6 mu m, and the slurry is subjected to solid-liquid separation, aging, centrifugation and drying. Washing for five times, ensuring that the conductivity is less than or equal to 10 mu s/cm and the drying temperature is 105 ℃. Sieving to obtain CoOOH @ LiMn 0.8 Ni 0.15 Al 0.05 (OH) 2 A composite precursor material. The main difference between the processes of examples 1,2,3, 4 and 5 is that the pH value is controlled to be 9.4-9.8 in the synthesis process of cobalt oxyhydroxide, the pH value of the manganese-rich coating is in the range of 10.5, a large amount of waste of salt solution occurs, the content of CI-ions is higher, and the cobalt content of the finished product is reduced.
Example 6
Firstly, carrying out synthetic reaction on a mixed solution of 2mol/L cobalt chloride solution and 0.04mol/L EDTA and 8.0mol/L sodium hydroxide solution, wherein the reaction synthesis temperature is 52 ℃, the stirring speed is 550 r/min, the introduced air amount is 2-3m < 3 >/h, the flow ratio is 5, the pH is controlled to be 10.2-10.5, and the reaction kettle is made of titanium alloy. The reactor was started (the reactor was started after 1.538g/L sodium lauryl sulfate was added and the pH was adjusted by caustic soda solution as a base solution) and the aeration rate was advanced by 1 hour. By using a controlled crystallization method, the solid content in the kettle is observed to be about 35 percent, and the air quantity is large enough under the premise of high pH, so that the cobalt content (the main content of cobaltosic oxide is more than or equal to 90 percent) in the cobalt oxyhydroxide is ensured to be 58.01 percent, and the granularity is made to be 3 mu m. Manganese chloride, nickel chloride and aluminum chloride are prepared into a mixed solution with the concentration of 2.0 mol/L, the concentration of sodium hydroxide of 8.0mol/L, the mixed concentration of EDTA-2Na and ammonia water of 0.4 mol/L according to the mol ratio of Mn to Ni to Al = 80. Taking a cobalt oxyhydroxide precursor as a core to prepare Mn 0.8 Ni 0.15 Al 0.05 (OH) 2 Is a composite precursor of the shell, the granularity is made to be 6 mu m, and the slurry is subjected to solid-liquid separation, aging, centrifugation and drying. Washing for five times, ensuring that the conductivity is less than or equal to 10 mu s/cm and the drying temperature is 105 ℃. Sieving to obtain CoOOH @ LiMn 0.8 Ni 0.15 Al 0.05 (OH) 2 A composite precursor material. The main process to distinguish between examples 1,2,3, 4 and 5 is the synthesis of cobalt oxyhydroxide and manganese rich coatings at a reaction temperature of 52 ℃ with reduced aeration oxidation time, which results in a reduction of the cobalt content.
TABLE I shows the comparison of the physicochemical parameters of the respective proportions and examples
The above-described embodiments are only a part of examples of the present invention, not all examples, and are not intended to limit the scope of the present invention.
Claims (7)
1. The preparation method of the composite precursor material is characterized by comprising the following specific steps of:
synthesis of cobalt oxyhydroxide precursor
Mixing soluble cobalt salt, alkali metal hydroxide, a dispersing agent and EDTA (ethylene diamine tetraacetic acid), allowing the mixture to flow into a reaction kettle with a base solution and a large amount of air for constant-temperature co-precipitation, and reacting fully to obtain a cobalt oxyhydroxide precursor material with the particle size of 3 microns; the amount of air introduced is not less than 5m 3 The reaction kettle is started and the aeration is carried out for 2 hours in advance, and the pH is controlled to be 10.0-12.5;
synthesis of manganese-rich precursor
Taking 3 mu m cobalt oxyhydroxide precursor slurry as a core, preparing a mixed solution of manganese chloride, nickel chloride, cobalt chloride and aluminum chloride according to the molar ratio of Mn to Ni to Al =80 0.8 Ni 0.15 Al 0.05 (OH) 2 Is a composite precursor of the shell.
2. The method according to claim 1, wherein in step a, the soluble cobalt salt is a cobalt chloride solution with a preparation concentration of 2.0 mol/L; the alkali metal hydroxide is sodium hydroxide, and the concentration is 8.0 mol/L; the concentration of EDTA is 0.04 mol/L; the dispersant is sodium dodecyl sulfate.
3. The method for preparing a composite precursor material according to claim 1, wherein in the step a, the reaction temperature is 70 ℃, stirring is carried out, the stirring speed is 550 r/min, and the air inlet amount is 5m 3 The flow ratio is 5.
4. The method according to claim 3, wherein in step a, the stirring is performed by a spiral jet-shaped stirring blade, and the diameter of the circular air hole passing through the stirring blade is 3-5nm.
5. A method of preparing a composite precursor material according to claim 1, wherein: in the step (b), manganese chloride, nickel chloride and aluminum chloride are mixed according to the molar ratio of Mn to Ni to Al = 80.
6. A method of preparing a composite precursor material according to claim 1, wherein: in the step (b), the reaction synthesis temperature is 52 ℃, the stirring speed is 650 r/min, and the nitrogen introduction amount is 2.5m 3 The pH value is controlled to be 11.5, the concentration of ammonium ions in the solution is 10g/L, and the material of the reaction kettle is stainless steel.
7. A method of preparing a composite precursor material according to claim 1, wherein: and (c) washing the composite precursor obtained in the step (b) for five times, and drying to ensure that the conductivity is less than or equal to 10 mu s/cm and the drying temperature is 105 ℃.
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