Metal-doped spherical cobaltosic oxide and preparation method thereof

Abstract

The invention discloses metal-doped spherical cobaltosic oxide and a preparation method thereof.The preparation method comprises the steps that a cobalt salt solution containing doped metal elements and a precipitant solution are stirred and mixed, then stirring is stopped, and crystal nucleuses grow statically; collecting insoluble substances after static growth; and carrying out heat treatment on the insoluble substance to obtain the metal-doped spherical cobaltosic oxide. Different from a traditional method adopting continuous feeding, a method similar to one-pot boiling is adopted, doped metal elements and cobalt salt are prepared together and then stirred and mixed with a precipitant solution, a reaction system can be obtained, then the reaction system grows in a static state, complex reaction steps and equipment are not needed, and the method is suitable for industrial production. And a large amount of electric power cost and manpower maintenance cost are saved. The metal-doped spherical cobaltosic oxide prepared by the preparation method disclosed by the invention has a relatively regular spherical structure while being relatively good in dispersity, and doped metal elements are uniformly distributed.

Description

Technical Field

[0001] The invention discloses a cobalt oxide preparation method, and relates to the technical field, and in particular to a metal-doped spherical cobalt oxide and a preparation method thereof. Background Art

[0002] Cobalt tetroxide is widely used in sensors, energy storage, catalysis, adsorption and other fields due to its unique physical and chemical properties. Its preparation methods include uniform precipitation method, solid phase reaction method, mechanical ball milling method, wet precipitation-calcination method and hydrothermal method. At the same time, cobalt tetroxide with different morphological structures has certain special properties, such as crystal face effect, size effect, quantum effect, etc., which makes researchers turn their focus to the precise control of the morphology and size of cobalt tetroxide. How to regulate the kinetic and thermodynamic parameters to prepare micron-sized cobalt tetroxide with specific morphology has always been a difficult point.

[0003] In addition, appropriate metal element doping can improve the cyclic stability of cobalt tetroxide, improve the oxygen vacancies on the surface, enhance the binding sites on the surface, regulate the morphology, and improve the application potential of cobalt tetroxide. For example, CN115676906A discloses a bimetallic alternating doped cobalt tetroxide and its preparation method and application, wherein a cobalt source solution and a carbon ammonium solution are added to a base solution, and when the median particle size of the particles grows to 4-6 μm, a cobalt source solution, a carbon ammonium solution and an aluminum source solution or a cobalt source solution, a carbon ammonium solution and a magnesium source solution are alternately added, and the insoluble matter is collected and calcined to obtain a magnesium-aluminum-doped cobalt tetroxide. Although this method can grow a magnesium-aluminum-doped cobalt tetroxide with a particle size greater than 15 μm, it is necessary to strictly monitor the particle size of the intermediate particles and strictly control the continuous feeding of each raw material. CN108217753A discloses a gradient doped cobalt tetroxide material and a preparation method thereof, wherein a cobalt salt solution is mixed with a precipitant to obtain a preprecipitate A, and then a salt solution containing a doping element is added to the above reaction system to obtain a doped precipitate B, and finally the doped precipitate B is calcined at a specific temperature to obtain a gradient doped cobalt tetroxide. The doped cobalt tetroxide prepared by this method has a high surface doping amount and a low internal doping amount, however, different feed rates need to be controlled in the continuous stages of particle growth, which increases the instability of production line production.

[0004] It can be seen that the current precipitation-calcination method for preparing cobalt tetroxide doped with metal elements often requires continuous feeding, and the introduction rates of the doping metal salt, cobalt salt solution and precipitant solution need to be strictly controlled. It is necessary to provide a method that is more suitable for the production line. Summary of the invention

[0005] In order to solve the problems existing in the prior art, the present invention provides a method for preparing metal-doped spherical cobalt oxide, comprising: The cobalt salt solution containing the doped metal element and the precipitant solution are stirred and mixed, and then the stirring is stopped to allow the crystal nuclei to grow statically; After static growth, the insoluble matter was collected; The insoluble matter is heat treated to obtain metal-doped spherical cobalt oxide.

[0006] Furthermore, the volume ratio of the cobalt salt solution containing the doped metal element to the precipitant solution is 1:1-4; The concentration of cobalt salt in the cobalt salt solution containing doped metal elements is 90-150 g / L, and the concentration of doped metal elements is 200-15000 ppm; The precipitant solution is a soluble bicarbonate solution with a concentration of 80-160 g / L.

[0007] In the present invention, the types of doping metal elements, cobalt salts and soluble bicarbonate salts do not need to be strictly limited. For example, the doping metal element can be at least one of magnesium, aluminum, nickel, iron, manganese, copper, zirconium, titanium, yttrium, ruthenium, lanthanum, cerium, etc.; the cobalt salt can be at least one of cobalt sulfate, cobalt chloride, cobalt nitrate, etc.; the soluble bicarbonate salt can be at least one of potassium bicarbonate, sodium bicarbonate, ammonium bicarbonate, etc. The solvents of the cobalt salt solution and the precipitant solution do not need to be strictly limited, and are general solvents, such as at least one of water, ethanol, acetone, etc., preferably water.

[0008] Furthermore, the stirring is continued for 1-2 hours at a stirring speed of 300-500 rpm.

[0009] Furthermore, the static growth lasts for 5-25 hours at a temperature of 35-60°C.

[0010] Furthermore, the collection is performed by filter pressing and washing to wash the impurity ions to a concentration lower than 20 ppm.

[0011] Furthermore, the heat treatment is carried out at 120-180° C. for 4-6 hours, then the temperature is raised to 300-400° C. for 2-5 hours, and finally the temperature is raised to 620-800° C. for 3-8 hours.

[0012] The present invention also provides a metal-doped spherical cobalt oxide, which is obtained by using the above-mentioned preparation method of the metal-doped spherical cobalt oxide.

[0013] The present invention also provides the application of the metal-doped spherical cobalt tetroxide in the fields of adsorption, catalysis, targeted therapy, sensing, pigments and fillers, and energy storage.

[0014] Compared with the prior art, the present invention has the following beneficial effects: Different from the traditional method of continuous feeding, continuously introducing cobalt salt solution, doping metal solution and precipitant solution, strictly monitoring the particle size of the crystal nucleus or strictly controlling the different rates of introduction of raw materials during grain growth, the present invention adopts a method similar to "one pot cooking", in which the doping metal element and cobalt salt are prepared together and then stirred and mixed with the precipitant solution to obtain a reaction system, and then the reaction system is grown in a static state, without the need for complicated reaction steps and equipment, and also saving a lot of electricity costs and manpower maintenance costs.

[0015] The metal-doped spherical cobalt tetroxide prepared by the present invention has good dispersibility and a relatively regular spherical structure, and the doped metal elements are evenly distributed, and has potential application prospects in the fields of adsorption, catalysis, targeted therapy, sensing, pigments and fillers, and energy storage. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0017] Figure 1 The scanning electron microscope image of the aluminum-doped cobalt carbonate obtained in Example 1 is shown; Figure 2 The scanning electron microscope image of the metal-doped spherical cobalt oxide prepared in Example 1 is shown; Figure 3 The EDS image of the metal-doped spherical cobalt oxide prepared in Example 1 is shown; Figure 4 shows a scanning electron microscope image of nickel-doped cobalt carbonate obtained in Example 2; Figure 5 The scanning electron microscope image of the metal-doped spherical cobalt oxide prepared in Example 2 is shown; Figure 6 The EDS image of the metal-doped spherical cobalt oxide prepared in Example 2 is shown; Figure 7 The scanning electron microscope image of the zirconium-doped cobalt carbonate obtained in Example 3 is shown; Figure 8 The scanning electron microscope image of the metal-doped spherical cobalt oxide prepared in Example 3 is shown; Fig. 9 The EDS image of the metal-doped spherical cobalt oxide prepared in Example 3 is shown; Fig.10 shows a scanning electron microscope image of manganese-doped cobalt carbonate obtained in Example 4; Fig.11The scanning electron microscope image of the metal-doped spherical cobalt oxide prepared in Example 4 is shown; Fig.12 The EDS image of the metal-doped spherical cobalt oxide prepared in Example 4 is shown; Fig.13 shows a scanning electron microscope image of the magnesium-doped cobalt carbonate obtained in Example 5; Fig.14 The scanning electron microscope image of the metal-doped spherical cobalt oxide prepared in Example 5 is shown; Fig.15 The EDS image of the metal-doped spherical cobalt oxide prepared in Example 5 is shown; Fig.16 shows a scanning electron microscope image of titanium-doped cobalt carbonate obtained in Example 6; Fig.17 The scanning electron microscope image of the metal-doped spherical cobalt oxide prepared in Example 6 is shown; Fig.18 The EDS image of the metal-doped spherical cobalt oxide prepared in Example 6 is shown; Fig.19 shows a scanning electron microscope image of the aluminum- and lanthanum-doped cobalt carbonate obtained in Example 7; Fig. 20 The scanning electron microscope image of the metal-doped spherical cobalt oxide prepared in Example 7 is shown; Fig.21 The EDS image of the metal-doped spherical cobalt oxide prepared in Example 7 is shown; Fig. 22 The scanning electron microscope image of the cobalt carbonate obtained in Comparative Example 1 is shown; Fig.23 The scanning electron microscope image of the spherical cobalt oxide prepared in Comparative Example 1 is shown. DETAILED DESCRIPTION

[0018] The endpoints and any values ​​of the ranges disclosed in the present invention are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be regarded as specifically disclosed in the present invention.

[0019] The following will be combined with the specific embodiments of the present invention and the drawings of the specification to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0020] Example 1 A method for preparing metal-doped spherical cobalt oxide comprises the following steps: S1. A cobalt chloride solution containing 10000 ppm aluminum and a concentration of 110 g / L is prepared with aluminum chloride, cobalt chloride and water; an ammonium bicarbonate solution of 120 g / L is prepared with ammonium bicarbonate and water; S2, adding the aluminum-containing cobalt chloride solution and the ammonium bicarbonate solution into a reaction kettle at a volume ratio of 1:3, stirring at a stirring speed of 400 rpm for 1.5 hours to mix evenly, and then stopping stirring to obtain a reaction system; S3, closing the reactor, keeping the reaction system at 50°C for 15 hours for static growth, collecting the insoluble matter after the static growth, and pumping it into a filter press for filter pressing and washing, washing the impurity ion concentration to below 20 ppm, and obtaining a wet material; S4. The wet material is placed in a roller kiln for calcination, kept at 145°C for 5 hours, then heated to 360°C for 3 hours, and finally heated to 720°C for 5 hours, and finally naturally cooled to room temperature to obtain metal-doped spherical cobalt tetroxide.

[0021] Example 2 A method for preparing metal-doped spherical cobalt oxide comprises the following steps: S1. Prepare a cobalt chloride solution containing 1000 ppm nickel and a concentration of 110 g / L with nickel acetate, cobalt chloride and water; prepare a 120 g / L ammonium bicarbonate solution with ammonium bicarbonate and water; S2, adding the cobalt chloride solution containing nickel element and the ammonium bicarbonate solution into the reaction kettle at a volume ratio of 1:3, stirring at a stirring speed of 400 rpm for 1.5 hours to mix evenly, and then stopping stirring to obtain a reaction system; S3, closing the reactor, keeping the reaction system at 50°C for 15 hours for static growth, collecting the insoluble matter after the static growth, and pumping it into a filter press for filter pressing and washing, washing the impurity ion concentration to below 20 ppm, and obtaining a wet material; S4. The wet material is placed in a roller kiln for calcination, kept at 145°C for 5 hours, then heated to 360°C for 3 hours, and finally heated to 720°C for 5 hours, and finally naturally cooled to room temperature to obtain metal-doped spherical cobalt tetroxide.

[0022] Example 3 A method for preparing metal-doped spherical cobalt oxide comprises the following steps: S1. Prepare a cobalt chloride solution containing 1000 ppm zirconium and a concentration of 110 g / L with zirconium oxychloride, cobalt chloride and water; prepare a 120 g / L ammonium bicarbonate solution with ammonium bicarbonate and water; S2, adding the cobalt chloride solution containing zirconium element and the ammonium bicarbonate solution into the reaction kettle at a volume ratio of 1:3, stirring at a stirring speed of 400 rpm for 1.5 hours to mix evenly, and then stopping stirring to obtain a reaction system; S3, closing the reactor, keeping the reaction system at 50°C for 15 hours for static growth, collecting the insoluble matter after the static growth, and pumping it into a filter press for filter pressing and washing, washing the impurity ion concentration to below 20 ppm, and obtaining a wet material; S4. The wet material is placed in a roller kiln for calcination, kept at 145°C for 5 hours, then heated to 360°C for 3 hours, and finally heated to 720°C for 5 hours, and finally naturally cooled to room temperature to obtain metal-doped spherical cobalt tetroxide.

[0023] Example 4 A method for preparing metal-doped spherical cobalt oxide comprises the following steps: S1. Prepare a cobalt chloride solution containing 1000 ppm manganese and a concentration of 110 g / L with manganese acetate, cobalt chloride and water; prepare a 120 g / L ammonium bicarbonate solution with ammonium bicarbonate and water; S2, adding the cobalt chloride solution containing manganese element and the ammonium bicarbonate solution into the reaction kettle at a volume ratio of 1:3, stirring at a stirring speed of 400 rpm for 1.5 hours to mix evenly, and then stopping stirring to obtain a reaction system; S3, closing the reactor, keeping the reaction system at 50°C for 15 hours for static growth, collecting the insoluble matter after the static growth, and pumping it into a filter press for filter pressing and washing, washing the impurity ion concentration to below 20 ppm, and obtaining a wet material; S4. The wet material is placed in a roller kiln for calcination, kept at 145°C for 5 hours, then heated to 360°C for 3 hours, and finally heated to 720°C for 5 hours, and finally naturally cooled to room temperature to obtain metal-doped spherical cobalt tetroxide.

[0024] Example 5 A method for preparing metal-doped spherical cobalt oxide comprises the following steps: S1. Prepare a cobalt chloride solution containing 1000 ppm magnesium and a concentration of 110 g / L with magnesium chloride, cobalt chloride and water; prepare a 120 g / L ammonium bicarbonate solution with ammonium bicarbonate and water; S2, adding the cobalt chloride solution containing magnesium element and the ammonium bicarbonate solution into the reaction kettle at a volume ratio of 1:3, stirring at a stirring speed of 400 rpm for 1.5 hours to mix evenly, and then stopping stirring to obtain a reaction system; S3, closing the reactor, keeping the reaction system at 50°C for 15 hours for static growth, collecting the insoluble matter after the static growth, and pumping it into a filter press for filter pressing and washing, washing the impurity ion concentration to below 20 ppm, and obtaining a wet material; S4. The wet material is placed in a roller kiln for calcination, kept at 145°C for 5 hours, then heated to 360°C for 3 hours, and finally heated to 720°C for 5 hours, and finally naturally cooled to room temperature to obtain metal-doped spherical cobalt tetroxide.

[0025] Example 6 A method for preparing metal-doped spherical cobalt oxide comprises the following steps: S1. Prepare a cobalt chloride solution containing 1000 ppm titanium and a concentration of 110 g / L with titanium oxysulfate, cobalt chloride and ethanol; prepare a 120 g / L ammonium bicarbonate solution with ammonium bicarbonate and water; S2, adding the titanium-containing cobalt chloride solution and the ammonium bicarbonate solution into a reaction kettle at a volume ratio of 1:3, stirring at a stirring speed of 400 rpm for 1.5 hours to mix evenly, and then stopping stirring to obtain a reaction system; S3, closing the reactor, keeping the reaction system at 50°C for 15 hours for static growth, collecting the insoluble matter after the static growth, and pumping it into a filter press for filter pressing and washing, washing the impurity ion concentration to below 20 ppm, and obtaining a wet material; S4. The wet material is placed in a roller kiln for calcination, kept at 145°C for 5 hours, then heated to 360°C for 3 hours, and finally heated to 720°C for 5 hours, and finally naturally cooled to room temperature to obtain metal-doped spherical cobalt tetroxide.

[0026] Example 7 A method for preparing metal-doped spherical cobalt oxide comprises the following steps: S1. A cobalt chloride solution containing 10000 ppm aluminum and 1000 ppm lanthanum and a concentration of 110 g / L is prepared with aluminum chloride, lanthanum nitrate, cobalt chloride and water; an ammonium bicarbonate solution of 120 g / L is prepared with ammonium bicarbonate and water; S2, adding the cobalt chloride solution containing aluminum and lanthanum elements and the ammonium bicarbonate solution into a reaction kettle at a volume ratio of 1:3, stirring at a stirring speed of 400 rpm for 1.5 hours to mix evenly, and then stopping stirring to obtain a reaction system; S3, closing the reactor, keeping the reaction system at 50°C for 15 hours for static growth, collecting the insoluble matter after the static growth, and pumping it into a filter press for filter pressing and washing, washing the impurity ion concentration to below 20 ppm, and obtaining a wet material; S4. The wet material is placed in a roller kiln for calcination, kept at 145°C for 5 hours, then heated to 360°C for 3 hours, and finally heated to 720°C for 5 hours, and finally naturally cooled to room temperature to obtain metal-doped spherical cobalt tetroxide.

[0027] Comparative Example 1 A method for preparing spherical cobalt oxide comprises the following steps: S1, prepare a 110 g / L cobalt chloride solution with cobalt chloride and water; prepare a 120 g / L ammonium bicarbonate solution with ammonium bicarbonate and water; S2, adding the cobalt chloride solution and the ammonium bicarbonate solution into a reaction kettle at a volume ratio of 1:3, stirring at a stirring speed of 400 rpm for 1.5 hours to mix evenly, and then stopping stirring to obtain a reaction system; S3, closing the reactor, keeping the reaction system at 50°C for 15 hours for static growth, collecting the insoluble matter after the static growth, and pumping it into a filter press for filter pressing and washing, washing the impurity ion concentration to below 20 ppm, and obtaining a wet material; S4. The wet material is placed in a roller kiln for calcination, kept at 145°C for 5 hours, then heated to 360°C for 3 hours, and finally heated to 720°C for 5 hours, and finally naturally cooled to room temperature to obtain spherical cobalt tetroxide.

[0028] Test Case The microscopic morphologies of the wet materials (metal-doped cobalt carbonate and cobalt carbonate) and the prepared spherical cobalt oxide materials in the preparation process of Examples 1-7 of the present invention and Comparative Example 1 were observed by scanning electron microscopy. The structures are as follows: Figure 1 and Figure 2 , Figure 4 and Figure 5 , Figure 7 and Figure 8 , Fig.10 and Fig.11 , Fig.13 and Fig.14 , Fig.16 and Fig.17 , Fig.19 and Fig. 20 , Fig. 22 and Fig.23 As shown. Fig. 22 and Fig.23 It can be seen that in Comparative Example 1, in which no doping metal element is introduced, the cobalt carbonate obtained has a uniform size distribution, presents a relatively perfect spherical structure, and does not agglomerate. At the same time, the decomposition of the cobalt carbonate during the calcination process makes the product cobalt tetroxide particles present a spherical structure with a loose and porous surface, retains very good dispersibility, does not agglomerate, and the calcination does not destroy the relatively perfect spherical structure. The average particle size of cobalt tetroxide is about 5 μm. Figure 1 and Figure 2 It can be seen that after the introduction of aluminum, the particle size of cobalt carbonate increases significantly and also presents a spherical shape, but there are certain small particle agglomerations on the surface. After calcination, some aluminum-doped cobalt carbonate breaks, and aluminum-doped cobalt tetroxide presents irregular spherical shapes. Figure 4 and Figure 5 It can be seen from the figure that after the introduction of nickel, the particle size of cobalt carbonate decreased significantly, the particle distribution was not concentrated, and it showed irregular spherical shape, and there were tiny particles and particles of 100~300nm. After calcination, a large amount of nickel-doped cobalt carbonate was broken, and the obtained nickel-doped cobalt tetroxide showed porous nanoparticles. Figure 7 and Figure 8 It can be seen that after the introduction of zirconium, the structure of zirconium-doped cobalt carbonate has no obvious change compared with the comparative example 1 without the introduction. After calcination, the zirconium-doped cobalt carbonate is evenly cracked to obtain a loose and porous surface of zirconium-doped cobalt tetroxide. Fig.10 and Fig.11 It can be seen that after the introduction of manganese, the particle size of cobalt carbonate increased significantly, and the surface became rough. After calcination, the manganese-doped cobalt carbonate was evenly cracked to obtain spherical manganese-doped cobalt oxide with an average particle size of about 13.8μm. Fig.13 and Fig.14 It can be seen that after the introduction of magnesium, the particle size of cobalt carbonate is significantly increased, and the surface is smooth, the dispersion is very good, there is no agglomeration, and it presents a perfect spherical structure. After calcination, the magnesium-doped cobalt carbonate is evenly cracked to obtain magnesium-doped cobalt tetroxide with high dispersion, loose and porous surface, and perfect spherical shape with an average particle size of about 15.8μm. Fig.16 and Fig.17 It can be seen from the figure that the introduction of titanium is similar to magnesium, but the particle size of cobalt carbonate is not as significant as that of magnesium, and the average particle size of titanium-doped cobalt tetroxide is about 13μm. Fig.19 and Fig. 20 For Figure 1 and Figure 2 Adding a certain amount of lanthanum element on the basis of introducing aluminum can inhibit the cracking of aluminum-doped cobalt carbonate during the calcination process, so that the aluminum-lanthanum-doped cobalt tetroxide can still retain a good spherical structure.

[0029] The element distribution results of the metal-doped spherical cobalt oxide materials prepared in Examples 1-7 of the present invention were observed by EDS. Figure 3 , Figure 6 , Fig. 9 , Fig.12 , Fig.15 , Fig.18 , Fig. 22 These results illustrate that the elements in the metal-doped spherical cobalt oxide material prepared by the present invention are uniformly distributed.

[0030] In summary, unlike the traditional method of continuous feeding, continuous introduction of cobalt salt solution, doped metal solution and precipitant solution, strict monitoring of the particle size of the crystal nucleus or strict control of the different introduction rates of raw materials during grain growth, the present invention adopts a similar "one pot" method, and the doped metal element and cobalt salt are prepared together and stirred and mixed with the precipitant solution to obtain a reaction system, and then the reaction system is grown in a static state, without the need for complex reaction steps and equipment, and also saves a lot of electricity costs and manpower maintenance costs. The metal-doped spherical cobalt tetroxide prepared by the present invention has a relatively regular spherical structure while having good dispersibility, the particle size of the material ranges from nanometer level to micrometer level, and the doped metal element is evenly distributed, and has potential application prospects in the fields of adsorption, catalysis, targeted therapy, sensing, pigments and fillers, and energy storage.

[0031] Finally, it should be noted that the above is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, it is still possible for those skilled in the art to modify the technical solutions described in the aforementioned embodiments or to make equivalent substitutions for some of the technical features therein. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing metal-doped spherical cobalt oxide, characterized in that: include, The cobalt salt solution containing the doped metal element and the precipitant solution are stirred and mixed, and then the stirring is stopped to allow the crystal nuclei to grow statically; After static growth, the insoluble matter was collected; The insoluble matter is heat treated to obtain metal-doped spherical cobalt oxide.

2. The method for preparing metal-doped spherical cobalt oxide according to claim 1, characterized in that: The volume ratio of the cobalt salt solution containing doped metal elements to the precipitant solution is 1:1-4; The concentration of cobalt salt in the cobalt salt solution containing doped metal elements is 90-150 g / L, and the concentration of doped metal elements is 200-15000 ppm; The precipitant solution is a soluble bicarbonate solution with a concentration of 80-160 g / L.

3. The method for preparing metal-doped spherical cobalt oxide according to claim 1, characterized in that: The stirring is continued for 1-2 h at a stirring speed of 300-500 rpm.

4. The method for preparing metal-doped spherical cobalt oxide according to claim 1, characterized in that: The static growth lasts for 5-25 hours at a temperature of 35-60°C.

5. The method for preparing metal-doped spherical cobalt oxide according to claim 1, characterized in that: The collection is performed by filter pressing and washing to wash the impurity ions to a concentration lower than 20 ppm.

6. The method for preparing metal-doped spherical cobalt oxide according to claim 1, characterized in that: The heat treatment is carried out at 120-180° C. for 4-6 hours, then the temperature is raised to 300-400° C. for 2-5 hours, and finally the temperature is raised to 620-800° C. for 3-8 hours.

7. A metal-doped spherical cobalt oxide, characterized in that: The metal-doped spherical cobalt oxide is obtained by the preparation method of any one of claims 1 to 6.

8. An application of the metal-doped spherical cobalt oxide as claimed in claim 7 in the fields of adsorption, catalysis, targeted therapy, sensing, pigments and fillers, and energy storage.

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