CN107150127B - Preparation method of spherical cobalt powder - Google Patents
Preparation method of spherical cobalt powder Download PDFInfo
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- CN107150127B CN107150127B CN201610122181.4A CN201610122181A CN107150127B CN 107150127 B CN107150127 B CN 107150127B CN 201610122181 A CN201610122181 A CN 201610122181A CN 107150127 B CN107150127 B CN 107150127B
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Abstract
The invention relates to the technical field of cobalt material preparation, and particularly discloses a preparation method of spherical cobalt powder. The method comprises at least the following steps: step S01, mixing a cobalt salt solution and a precipitator solution in a parallel flow manner, and carrying out precipitation reaction; s02, dynamically roasting the precipitate obtained by the reaction in the step S01 in an oxidizing atmosphere; step S03, calcining the product obtained in the step S02 in a reducing atmosphere; wherein the dynamic roasting temperature is 400-800 ℃, and the roasting time is 4-8 h. The spherical cobalt powder obtained by the method has the characteristics of high purity, good dispersity, small particles, uniform and controllable granularity, good sphericity, regular appearance and the like; the method is suitable for the industrial large-scale production of the spheroidized cobalt powder material.
Description
Technical Field
The invention relates to the technical field of cobalt material preparation, in particular to a preparation method of spherical cobalt powder.
Background
Cobalt powder is widely used in industries such as hard alloy and battery material because of its excellent physical and chemical properties. In both the hard alloy industry and the battery material industry, strict requirements are imposed on the purity, the dispersibility, the surface morphology and other physical states of the cobalt powder, and if the purity of the cobalt powder is not high, the dispersibility is poor or the morphology is dendritic or strip-shaped, the mechanical properties and the service life of the hard alloy can be influenced to a certain extent.
At present, the methods for preparing the superfine cobalt powder at home and abroad are more, and mainly comprise a polyol reduction method, an electrolysis method, a precipitation-thermal dissociation method, a hydrogen reduction method and the like. The hydrogen reduction method is relatively simple in process flow and relatively suitable for industrial production, and is one of the main methods for producing cobalt powder in China, but the cobalt powder prepared by the conventional method is mainly dendritic or short rod-shaped in appearance and poor in sphericity. The precursor has a great influence on the particle morphology of the cobalt powder reduced by the hydrogen, namely the precursor morphology and the cobalt powder morphology have certain inheritance. Therefore, researchers at home and abroad have conducted many studies on precursors of the hydrogen reduction method.
The invention patent with application number 200710075929.0 discloses a manufacturing process of superfine cobalt powder, which comprises the following steps: the cobalt carbonate is firstly subjected to high-energy ball milling to obtain an ultrafine cobalt carbonate precursor, and then the ultrafine spherical cobalt powder is prepared by reduction in the atmosphere of a reducing gas. However, the ball milling production process is easy to introduce impurities, and influences the quality of the cobalt powder.
For another example, patent application No. 201010196228.4 discloses a method for preparing a near-spherical aggregate cobalt powder. The method comprises the steps of taking ammonium bicarbonate as a precipitator, adding the ammonium bicarbonate and a cobalt salt solution into a reactor in a cocurrent manner to generate a precursor, and then placing the obtained cobalt carbonate into a reduction furnace for thermal decomposition hydrogen reduction, thereby obtaining the cobalt powder in a near-spherical aggregation state.
The method emphasizes on controlling the generation of the precursor, the control on the reduction process is not fine, and the obtained cobalt powder spheroidizing effect is not very ideal.
Disclosure of Invention
Aiming at the problems of poor appearance, non-ideal sphericity and the like in the prior art, the embodiment of the invention aims to provide a preparation method of spherical cobalt powder.
In order to achieve the above purpose, the embodiment of the present invention adopts the following technical solutions:
a preparation method of spherical cobalt powder at least comprises the following steps:
step S01, mixing a cobalt salt solution and a precipitator solution in a parallel flow manner, and carrying out precipitation reaction;
s02, dynamically roasting the precipitate obtained by the reaction in the step S01 in an oxidizing atmosphere;
step S03, calcining the product obtained in the step S02 in a reducing atmosphere;
wherein the dynamic roasting temperature is 400-800 ℃, and the roasting time is 4-8 h.
The preparation method of the spherical cobalt powder provided by the embodiment of the invention combines dynamic roasting and hydrogen reduction, does not need to add any surfactant, and can obtain a precursor (Co) with good fluidity only by dynamic roasting3O4) Therefore, a precursor with good fluidity is provided for hydrogen reduction calcination, and finally obtained cobalt powder has the characteristics of good dispersibility, small particles, uniform and controllable granularity, high spheroidization degree, regular appearance and the like.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a process flow diagram of a method for preparing spherical cobalt powder according to an embodiment of the present invention;
FIG. 2 shows Co prepared by the method for preparing spherical cobalt powder provided in example 1 of the present invention3O4SEM image of (d).
Fig. 3 is an SEM image of cobalt powder prepared by the method for preparing spherical cobalt powder provided in example 1 of the present invention.
FIG. 4 shows Co prepared by the method for preparing spherical cobalt powder provided in example 2 of the present invention3O4SEM image of (d).
Fig. 5 is an SEM image of cobalt powder prepared by the method for preparing spherical cobalt powder provided in example 2 of the present invention.
FIG. 6 shows Co prepared by the method for preparing spherical cobalt powder provided in example 3 of the present invention3O4SEM image of (d).
Fig. 7 is an SEM image of cobalt powder prepared by the method for preparing spherical cobalt powder provided in example 3 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and 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 embodiment of the invention provides a preparation method of spherical cobalt powder, which at least comprises the following steps:
step S01, mixing a cobalt salt solution and a precipitator solution in a parallel flow manner, and carrying out precipitation reaction;
s02, dynamically roasting the precipitate obtained by the reaction in the step S01 in an oxidizing atmosphere;
step S03, calcining the product obtained in the step S02 in a reducing atmosphere;
wherein the dynamic roasting temperature is 400-800 ℃, and the roasting time is 4-8 h.
In a preferred embodiment, the reaction device in step S01 is a reaction kettle. Because reation kettle is from taking agitated vessel, and stirring speed is even controllable, can realize quick homogeneous mixing and avoid the formation of large granule precursor to the reaction mixture liquid and have an important role. In the embodiment of the invention, the stirring speed is controlled to be 150-250 rpm.
In a preferred embodiment, the cobalt salt and the precipitant are mixed in a mass ratio of 1: (1.5-2.0) and controlling the amount of the precipitant to be slightly excessive, so as to be beneficial to the complexation of cobalt salt and the nucleation of cobalt carbonate.
In a preferred embodiment, the cobalt salt is prepared into a cobalt salt solution with a concentration of 80-120 g/L, and the precipitant is prepared into a precipitant solution with a concentration of 180-250 g/L.
In a preferred embodiment, the precipitant is ammonium bicarbonate, primarily because this type of precipitant eventually decomposes into gases without introducing impurities and adversely affecting the purity of the product.
Preferably, the cobalt salt is cobalt chloride, mainly considering that chloride ions are easy to clean after reaction, other substances are not easy to remove, and impurities are not introduced.
In a preferred embodiment, the reaction of step S01 needs to be maintained at 40-55 ℃, which can significantly improve the chemical activity of the reactants and increase the reaction rate.
In the whole reaction, the pH value of the reaction mixed liquid has certain influence on the realization of the technical effect of the invention. Therefore, in the reaction of the embodiment of the invention, the pH value needs to be adjusted to 6.98-7.30, so as to control the combination rate of the cobalt salt and the precipitant.
In any embodiment, in order to ensure that the obtained precursor cobaltosic oxide has good fluidity, in the dynamic roasting process, preheating and pre-decomposition are required to be performed orderly, and the product obtained in the step S01 is placed in a boiling furnace, a fluidized furnace or a rotary kiln and moves and decomposes under airflow flowing in the furnace, so that the effect of modifying the morphology of the precursor cobaltosic oxide is achieved, and the precursor cobaltosic oxide has good dispersibility. The flowing gas stream here is a gas stream having oxidizing properties, in particular air or oxygen.
In a preferred embodiment, the calcination temperature is 350-550 ℃, the calcination time is 1-4 h, and the cobaltosic oxide can be completely reduced into cobalt powder in the reducing atmosphere within the calcination temperature and the calcination time.
In the embodiment of the present invention, after the reaction is completed in step S01, the method further includes the step of subjecting the reaction product cobalt carbonate to centrifugation or filtration washing and drying treatment.
According to the preparation method of the spherical cobalt powder provided by the embodiment of the invention, no surfactant is required to be added, ammonium bicarbonate is used as a precipitator, no other impurities are introduced into a product, more importantly, a dynamic roasting process is added before reduction, the sphericity of a precursor is optimized, the irregularity of the powder is reduced, the prepared precursor powder has regular appearance, high sphericity and uniform particle size, and finally the cobalt powder obtained by reduction of the precursor has the characteristics of high purity, good dispersibility, small particles, uniform and controllable particle size, good sphericity, regular appearance and the like. Meanwhile, the process is simple and feasible, can adopt continuous production, has high production efficiency, can ensure the stability of the quality of the product batch, and is suitable for large-scale industrial production.
Further, the cobalt powder material synthesized by the preparation method of the spherical cobalt powder provided by the embodiment of the invention can be applied to the field of lithium ion batteries or hard alloys.
In order to better embody the preparation method of the spherical cobalt powder provided by the embodiment of the present invention, the following is further illustrated by a plurality of embodiments.
Example 1
(1) Preparing a cobalt chloride solution with the concentration of 80 g/L and an ammonium bicarbonate solution with the concentration of 180 g/L;
(2) adding the ammonium bicarbonate solution and the cobalt chloride solution into a reaction kettle in parallel according to the condition that the dosage of the ammonium bicarbonate is 2 times of that of the cobalt chloride, and heating to 45 ℃;
(3) stirring at a stirring speed of 200rpm, keeping the reaction temperature at 45 ℃ and the pH value at 7.0-7.1, and reacting for 2 hours to obtain superfine spherical cobalt carbonate precipitate;
(4) carrying out centrifugal separation, washing and drying on the superfine spherical cobalt carbonate, and then dynamically roasting at 400 ℃ for 8h in an oxygen atmosphere to obtain a black precursor Co3O4And (3) ultrafine powder. As a result of examination, the precursor Co obtained in example 13O4The grain size of the superfine powder is less than or equal to 1.0 mu m. And for the obtained Co3O4Scanning the superfine powder with SEM scanning result as shown in figure 2;
(5) co to be obtained3O4The superfine powder is placed in reducing atmosphere hydrogen and calcined for 2h at 420 ℃ to obtain superfine spherical cobalt powder with the granularity of about 0.5 mu m, and the shape of the superfine spherical cobalt powder is shown in figure 3 after SEM scanning.
Example 2
(1) Preparing a cobalt chloride solution with the concentration of 100 g/L and an ammonium bicarbonate solution with the concentration of 200 g/L;
(2) adding the ammonium bicarbonate solution and the cobalt chloride solution into a reaction kettle in a concurrent flow mode according to the condition that the dosage of the ammonium bicarbonate is 1.5 times of that of the cobalt chloride, and heating to 50 ℃;
(3) stirring at a stirring speed of 250rpm, keeping the reaction temperature at 50 ℃ and the pH value at 7.1-7.2, and reacting for 3 hours to obtain superfine spherical cobalt carbonate precipitate;
(4) mixing superfine spherical cobalt carbonatePerforming centrifugal separation, washing and drying, and then dynamically roasting at 800 ℃ for 4 hours in an oxygen atmosphere to obtain a black precursor Co3O4And (3) ultrafine powder. Through detection, the precursor Co obtained in the embodiment 23O4The grain size of the superfine powder is less than or equal to 1.0 mu m. And for the obtained Co3O4Scanning the superfine powder by SEM, wherein the scanning result is shown in figure 4 in the specification;
(5) co to be obtained3O4The superfine powder is placed in reducing atmosphere hydrogen and calcined for 2h at 420 ℃ to obtain superfine spherical cobalt powder with the granularity of about 0.5 mu m, and the shape of the superfine spherical cobalt powder is shown in figure 5 after SEM scanning.
Example 3
(1) Preparing a cobalt chloride solution with the concentration of 120 g/L and an ammonium bicarbonate solution with the concentration of 220 g/L;
(2) adding the ammonium bicarbonate solution and the cobalt chloride solution into a reaction kettle in a concurrent flow mode according to the condition that the dosage of the ammonium bicarbonate is 1.8 times of that of the cobalt chloride, and heating to 40 ℃;
(3) stirring at a stirring speed of 150rpm, keeping the reaction temperature at 40 ℃, keeping the pH value at 7.2-7.3, and reacting for 3 hours to obtain superfine spherical cobalt carbonate precipitate;
(4) centrifugally separating, washing and drying the superfine spherical cobalt carbonate, and then dynamically roasting at 550 ℃ for 7 hours in an oxygen atmosphere to obtain a black precursor Co3O4And (3) ultrafine powder. Through detection, the precursor Co obtained in the embodiment 33O4The grain size of the superfine powder is less than or equal to 1.0 mu m. And for the obtained Co3O4Scanning the superfine powder with SEM scanning result as shown in figure 6;
(5) co to be obtained3O4The superfine powder is placed in a reducing atmosphere hydrogen and calcined for 2 hours at 52 ℃ to obtain superfine spherical cobalt powder with the granularity of about 0.5 mu m, and the shape of the superfine spherical cobalt powder is shown in figure 7 after SEM scanning.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (7)
1. A preparation method of spherical cobalt powder at least comprises the following steps:
step S01, mixing a cobalt salt solution and a precipitator solution in a parallel flow manner, and carrying out precipitation reaction;
s02, dynamically roasting the precipitate obtained by the reaction in the step S01 in an oxidizing atmosphere;
step S03, calcining the product obtained in the step S02 in a reducing atmosphere;
wherein the dynamic roasting temperature is 400-800 ℃, and the roasting time is 4-8 h;
the dynamic roasting is to make the product obtained in the step S02 move and decompose under flowing airflow; the flowing gas flow is air or oxygen;
the precipitant is ammonium bicarbonate;
the calcination temperature is 350-550 ℃; the mass ratio of the cobalt salt to the precipitator is 1 (1.5-2.0).
2. The method for preparing spherical cobalt powder according to claim 1, wherein: the temperature of the precipitation reaction is 40-55 ℃.
3. The method for preparing spherical cobalt powder according to claim 1, wherein: the pH value of the reaction solution is controlled to be 6.98-7.30.
4. The method for preparing spherical cobalt powder according to claim 1, wherein: the reaction time is 2-3 h.
5. The method for preparing spherical cobalt powder according to claim 1, wherein: in the reaction process, a stirring treatment step is also carried out, wherein the stirring speed of the stirring treatment is 150-250 rpm.
6. The method for preparing spherical cobalt powder according to claim 1, wherein: the calcination time is 1-4 h.
7. The method for preparing spherical cobalt powder according to claim 1, wherein the concentration of the cobalt salt solution is 80-120 g/L, and/or the concentration of the precipitant is 180-250 g/L.
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| CN110935886A (en) * | 2018-09-21 | 2020-03-31 | 荆门市格林美新材料有限公司 | Class C60Preparation method of type cobalt powder |
| CN109550972A (en) * | 2019-01-22 | 2019-04-02 | 宇辰新能源材料科技无锡有限公司 | A kind of preparation method of high temperature cemented carbide cobalt powder |
| CN109622988B (en) * | 2019-01-22 | 2022-09-09 | 宇辰新能源材料科技无锡有限公司 | Preparation method of cobalt powder for corrosion-resistant hard alloy |
| CN111842921A (en) * | 2019-04-25 | 2020-10-30 | 荆门市格林美新材料有限公司 | Preparation method of small FSSS high-apparent-density cobalt powder |
| CN111702184A (en) * | 2020-06-30 | 2020-09-25 | 荆门市格林美新材料有限公司 | Preparation method of large FSSS cobalt powder |
| CN111922355A (en) * | 2020-06-30 | 2020-11-13 | 荆门市格林美新材料有限公司 | Preparation method of superfine cobalt powder |
| CN112355317A (en) * | 2020-10-19 | 2021-02-12 | 衢州华友钴新材料有限公司 | Preparation method of superfine spherical cobalt powder |
| CN112974823A (en) * | 2021-02-02 | 2021-06-18 | 安徽寒锐新材料有限公司 | Preparation method and preparation equipment of superfine spherical cobalt powder |
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