CN110759387A - Preparation method of manganese-doped basic cobalt carbonate - Google Patents
Preparation method of manganese-doped basic cobalt carbonate Download PDFInfo
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Abstract
The invention discloses a preparation method of manganese-doped basic cobalt carbonate, which comprises the steps of adding a sodium carbonate solution and a cobalt chloride solution into a reaction kettle, controlling the pH value of a reaction system to be 6.0-7.8, controlling the reaction temperature to be 90-95 ℃, and stirring for 5-6 hours to obtain basic cobalt carbonate slurry; dehydrating the basic cobaltous carbonate slurry while the basic cobaltous carbonate slurry is hot, transferring the dehydrated basic cobaltous carbonate slurry into an immersion kettle, adding a saturated manganese chloride solution into the immersion kettle, stirring for reaction, and then sequentially performing filter pressing dehydration and drying to obtain manganese-doped basic cobaltous carbonate; thus, the basic cobalt carbonate is prepared by replacing ammonium bicarbonate with sodium carbonate and is used as a superfine cobalt powder precursor, ammonia-containing wastewater is not generated, the atmosphere is not polluted, the impurity content of the prepared precursor is low, and the production requirement of cobalt powder in the current market can be met; and moreover, the saturated manganese chloride is adopted to dope the basic cobalt carbonate, so that the conductivity of the basic cobalt carbonate precursor can be enhanced, and the stability can be improved.
Description
Technical Field
The invention belongs to the technical field of preparation of basic carbonate, and particularly relates to a preparation method of manganese-doped basic cobalt carbonate.
Background
The cobaltosic oxide product is an important transition metal oxide, and is usually used as a main raw material for producing hard alloy, lithium battery materials and electronic materials, as well as a colorant in the ceramic industry and a catalyst in the chemical industry; in the chemical industry, cobaltosic oxide is an efficient and durable catalyst; the basic cobaltous carbonate material is used as an important raw material for producing the lithium battery, namely a precursor material of cobaltosic oxide, and the production technology of the basic cobaltous carbonate material is crucial to the performance of the lithium battery.
The cobaltosic oxide is produced by a plurality of methods, usually, the cobaltosic oxide is produced by an oxalic acid precipitation method and then calcined, but the cost is higher; the method has the advantages that the method has low cost, but the micro-particle morphology of the basic cobaltous carbonate prepared by the method is needle-shaped or hetero-type loose structure, and the basic cobaltous carbonate is easy to form higher anion (mainly chloride ion, nitrate ion or sulfate ion) package among crystal nuclei; meanwhile, complex and double salt products containing anions are easily generated in the reaction; in general, the anionic retention of such basic cobalt carbonate material is 2% or more, and 6% or more in the case of high content, so that HCl and HNO are generated in the calcination step3Or H2SO4The acid gas and the acid gas overflow to cause serious corrosion of equipment and severe production environment.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method of manganese-doped basic cobalt carbonate.
The invention provides a preparation method of manganese-doped basic cobalt carbonate, which is implemented by the following steps:
step 1, adding a sodium carbonate solution and a cobalt chloride solution into a reaction kettle, controlling the pH value of a reaction system to be 6.0-7.8, controlling the reaction temperature to be 90-95 ℃, and reacting for 5-6 hours under stirring at a rotating speed of 200rmp/min to obtain basic cobalt carbonate slurry;
step 2, dehydrating the basic cobalt carbonate slurry obtained in the step 1 while the basic cobalt carbonate slurry is hot, transferring the slurry to an immersion kettle, adding a saturated manganese chloride solution into the immersion kettle, and stirring for reaction to obtain a manganese-doped basic cobalt carbonate crude product;
and 3, sequentially carrying out filter pressing dehydration and drying on the manganese-doped basic cobalt carbonate crude product obtained in the step 2 to obtain the manganese-doped basic cobalt carbonate.
In the scheme, the concentration of the sodium carbonate solution in the step 1 is 120g/L +/-5 g/L.
In the scheme, the concentration of the cobalt chloride solution in the step 1 is 120g/L +/-3 g/L.
In the scheme, the molar ratio of the saturated manganese chloride solution added in the step 2 to the basic cobalt carbonate slurry is 2: 1-3: 1.
In the scheme, the reaction temperature of the stirring reaction in the step 2 is 55-60 ℃.
In the scheme, the reaction time of the stirring reaction in the step 2 is 10-14 h.
In the scheme, the pressure of the filter pressing dehydration in the step 3 is 0.6 Mpa.
In the scheme, the drying temperature in the step 3 is 90-98 ℃.
Compared with the prior art, the invention provides a preparation method of manganese-doped basic cobalt carbonate, which comprises the steps of adding a sodium carbonate solution and a cobalt chloride solution into a reaction kettle, controlling the pH value of a reaction system to be 6.0-7.8, controlling the reaction temperature to be 90-95 ℃, and reacting for 5-6 hours under stirring at a rotating speed of 200rmp/min to obtain basic cobalt carbonate slurry; dehydrating the basic cobalt carbonate slurry while the basic cobalt carbonate slurry is hot, transferring the slurry to an immersion kettle, adding a saturated manganese chloride solution into the immersion kettle, and stirring for reaction to obtain a manganese-doped basic cobalt carbonate crude product; sequentially carrying out filter-pressing dehydration and drying on the manganese-doped basic cobalt carbonate crude product to obtain manganese-doped basic cobalt carbonate; thus, the basic cobalt carbonate is prepared by replacing ammonium bicarbonate with sodium carbonate and is used as a superfine cobalt powder precursor, ammonia-containing wastewater is not generated, the atmosphere is not polluted, the impurity content of the prepared precursor is low, and the production requirement of cobalt powder in the current market can be met; in addition, the saturated manganese chloride is adopted to dope the basic cobalt carbonate, so that the conductivity of the basic cobalt carbonate precursor can be enhanced, and the stability can be improved; in addition, the decomposition rate of sodium carbonate is controlled by controlling the reaction temperature, the shape of basic cobalt carbonate is directly controlled without using additives, dehydration is carried out after high-temperature reaction, sodium ions can be effectively desorbed after slurrying and washing, and the requirement can be met by washing with a small amount of hot pure water.
Drawings
Fig. 1 is a scanning electron microscope image of manganese-doped basic cobalt carbonate prepared by the method for preparing manganese-doped basic cobalt carbonate provided in embodiment 1 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 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 embodiment of the invention provides a preparation method of manganese-doped basic cobalt carbonate, which is implemented by the following steps:
step 1, adding a sodium carbonate solution with the concentration of 120g/L +/-5 g/L and a cobalt chloride solution with the concentration of 120g/L +/-3 g/L into a reaction kettle through a metering pump, strictly controlling the reaction temperature to be 90-95 ℃, controlling the pH value of a reaction system to be 6.0-7.8, reacting for 5-6 hours under stirring at the rotating speed of 200rmp/min, and stopping the reaction to obtain basic cobalt carbonate slurry;
step 2, dehydrating the basic cobalt carbonate slurry obtained in the step 1 by a centrifugal machine while the basic cobalt carbonate slurry is hot, transferring the dehydrated basic cobalt carbonate slurry into an immersion kettle, adding a saturated manganese chloride solution into the immersion kettle, wherein the molar ratio of the added saturated manganese chloride solution to the basic cobalt carbonate slurry is 2: 1-3: 1, and stirring and reacting at the reaction temperature of 55-60 ℃ for 10-14 hours to obtain a manganese-doped basic cobalt carbonate crude product;
and 3, performing filter pressing dehydration on the manganese-doped basic cobalt carbonate crude product obtained in the step 2 under the pressure of 0.6Mpa, and then drying the manganese-doped basic cobalt carbonate crude product at the temperature of 90-98 ℃ by using a disc dryer to obtain the manganese-doped basic cobalt carbonate.
The method adopts sodium carbonate to replace ammonium bicarbonate to prepare the basic cobalt carbonate which is used as a precursor of the superfine cobalt powder, does not generate ammonia-containing wastewater, has no pollution to the atmosphere, has low impurity content in the prepared precursor, and can meet the production requirement of the cobalt powder on the current market; and doping the basic cobalt carbonate with saturated manganese chloride, and doping Mn2+The conductive powder is uniformly distributed on the surface of the spherical basic cobaltosic carbonate, the appearance of the spherical cobaltosic oxide is not damaged, and meanwhile, the conductive performance of a basic cobaltosic carbonate precursor can be enhanced and the stability can be improved; in addition, the decomposition rate of sodium carbonate is controlled by controlling the reaction temperature, the shape of basic cobalt carbonate is directly controlled without using additives, dehydration is carried out after high-temperature reaction, sodium ions can be effectively desorbed after slurrying and washing, and the requirement can be met by washing with a small amount of hot pure water.
Example 1
Embodiment 1 of the present invention provides a preparation method of manganese-doped basic cobalt carbonate, which is implemented by the following steps:
step 1, adding a sodium carbonate solution with the concentration of 120g/L +/-5 g/L and a cobalt chloride solution with the concentration of 120g/L +/-3 g/L into a reaction kettle through a metering pump, strictly controlling the reaction temperature to be 90 ℃, controlling the pH value of a reaction system to be 6.0-7.8, reacting for 6 hours at the rotation speed of 200rmp/min, and stopping the reaction to obtain basic cobalt carbonate slurry;
step 2, dehydrating the basic cobalt carbonate slurry obtained in the step 1 by a centrifugal machine while the basic cobalt carbonate slurry is hot, transferring the dehydrated basic cobalt carbonate slurry into an immersion kettle, adding a saturated manganese chloride solution into the immersion kettle, stirring and reacting the added saturated manganese chloride solution and the basic cobalt carbonate slurry for 12 hours at a reaction temperature of 58 ℃ to obtain a manganese-doped basic cobalt carbonate crude product;
and 3, performing filter pressing dehydration on the manganese-doped basic cobalt carbonate crude product obtained in the step 2 under the pressure of 0.6Mpa, and then drying the manganese-doped basic cobalt carbonate crude product at the temperature of 94 ℃ by adopting a disc dryer to obtain the manganese-doped basic cobalt carbonate.
The impurity content of the manganese-doped basic cobalt carbonate obtained by the preparation method of the manganese-doped basic cobalt carbonate provided in embodiment 1 of the present invention is shown in the following table:
as can be seen from the above table, in the embodiment, sodium carbonate is used for replacing ammonium bicarbonate, ammonia gas is not generated to pollute air in the production process, ammonium ions do not exist in the mother liquor and the washing water, the wastewater treatment cost is reduced by 80%, and the method is green and environment-friendly and pollutes the water environment; meanwhile, the prepared cobalt powder precursor impurity meets the production requirement of cobalt powder.
As shown in fig. 1, it can be seen that Mn is doped in the scanning electron microscope image of the manganese-doped basic cobalt carbonate obtained by the preparation method of the manganese-doped basic cobalt carbonate provided in embodiment 1 of the present invention2+The sodium ion-containing cobalt oxide is uniformly distributed on the surface of the spherical basic cobaltosic carbonate, the appearance of the spherical cobaltosic oxide is not damaged, the process is simple and easy to control, after high-temperature reaction, the sodium ion content can be washed by a small amount of hot pure water through high-temperature dehydration, slurrying and washing, and the requirement of high-quality cobalt powder can be met; the amount of waste water produced is significantly reduced.
Example 2
Embodiment 2 of the present invention provides a preparation method of manganese-doped basic cobalt carbonate, which is implemented by the following steps:
step 1, adding a sodium carbonate solution with the concentration of 120g/L +/-5 g/L and a cobalt chloride solution with the concentration of 120g/L +/-3 g/L into a reaction kettle through a metering pump, strictly controlling the reaction temperature to be 92 ℃, controlling the pH value of a reaction system to be 6.0-7.8, reacting for 5.2 hours at the rotation speed of 200rmp/min, and stopping the reaction to obtain basic cobalt carbonate slurry;
step 2, dehydrating the basic cobalt carbonate slurry obtained in the step 1 by a centrifugal machine while the basic cobalt carbonate slurry is hot, transferring the dehydrated basic cobalt carbonate slurry into an immersion kettle, adding a saturated manganese chloride solution into the immersion kettle, stirring and reacting the added saturated manganese chloride solution and the basic cobalt carbonate slurry for 12 hours at a reaction temperature of 58 ℃ to obtain a manganese-doped basic cobalt carbonate crude product;
and 3, performing filter pressing dehydration on the manganese-doped basic cobalt carbonate crude product obtained in the step 2 under the pressure of 0.6Mpa, and then drying the manganese-doped basic cobalt carbonate crude product at the temperature of 94 ℃ by adopting a disc dryer to obtain the manganese-doped basic cobalt carbonate.
The impurity content of the manganese-doped basic cobalt carbonate obtained by the preparation method of the manganese-doped basic cobalt carbonate provided in embodiment 2 of the present invention is shown in the following table:
as can be seen from the above table, in the embodiment, sodium carbonate is used for replacing ammonium bicarbonate, ammonia gas is not generated to pollute air in the production process, ammonium ions do not exist in the mother liquor and the washing water, the wastewater treatment cost is reduced by 80%, and the method is green and environment-friendly and pollutes the water environment; meanwhile, the prepared cobalt powder precursor impurity meets the production requirement of cobalt powder.
Further, Mn is doped2+The sodium ion-containing cobalt oxide is uniformly distributed on the surface of the spherical basic cobaltosic carbonate, the appearance of the spherical cobaltosic oxide is not damaged, the process is simple and easy to control, after high-temperature reaction, the sodium ion content can be washed by a small amount of hot pure water through high-temperature dehydration, slurrying and washing, and the requirement of high-quality cobalt powder can be met; the amount of waste water produced is significantly reduced.
Example 3
Embodiment 3 of the present invention provides a preparation method of manganese-doped basic cobalt carbonate, which is implemented by the following steps:
step 1, adding a sodium carbonate solution with the concentration of 120g/L +/-5 g/L and a cobalt chloride solution with the concentration of 120g/L +/-3 g/L into a reaction kettle through a metering pump, strictly controlling the reaction temperature to be 95 ℃, controlling the pH value of a reaction system to be 6.0-7.8, reacting for 5 hours at the rotation speed of 200rmp/min, and stopping the reaction to obtain basic cobalt carbonate slurry;
step 2, dehydrating the basic cobalt carbonate slurry obtained in the step 1 by a centrifugal machine while the basic cobalt carbonate slurry is hot, transferring the dehydrated basic cobalt carbonate slurry into an immersion kettle, adding a saturated manganese chloride solution into the immersion kettle, stirring and reacting the added saturated manganese chloride solution and the basic cobalt carbonate slurry for 12 hours at a reaction temperature of 58 ℃ to obtain a manganese-doped basic cobalt carbonate crude product;
and 3, performing filter pressing dehydration on the manganese-doped basic cobalt carbonate crude product obtained in the step 2 under the pressure of 0.6Mpa, and then drying the manganese-doped basic cobalt carbonate crude product at the temperature of 94 ℃ by adopting a disc dryer to obtain the manganese-doped basic cobalt carbonate.
The impurity content of the manganese-doped basic cobalt carbonate obtained by the preparation method of the manganese-doped basic cobalt carbonate provided by the embodiment 3 of the invention is shown in the following table:
as can be seen from the above table, in the embodiment, sodium carbonate is used for replacing ammonium bicarbonate, ammonia gas is not generated to pollute air in the production process, ammonium ions do not exist in the mother liquor and the washing water, the wastewater treatment cost is reduced by 80%, and the method is green and environment-friendly and pollutes the water environment; meanwhile, the prepared cobalt powder precursor impurity meets the production requirement of cobalt powder.
Further, Mn is doped2+The sodium ion-containing cobalt oxide is uniformly distributed on the surface of the spherical basic cobaltosic carbonate, the appearance of the spherical cobaltosic oxide is not damaged, the process is simple and easy to control, after high-temperature reaction, the sodium ion content can be washed by a small amount of hot pure water through high-temperature dehydration, slurrying and washing, and the requirement of high-quality cobalt powder can be met; the amount of waste water produced is significantly reduced.
Example 4
Embodiment 4 of the present invention provides a method for preparing manganese-doped basic cobalt carbonate, which is implemented by the following steps:
step 1, adding a sodium carbonate solution with the concentration of 120g/L +/-5 g/L and a cobalt chloride solution with the concentration of 120g/L +/-3 g/L into a reaction kettle through a metering pump, strictly controlling the reaction temperature to be 92 ℃, controlling the pH value of a reaction system to be 6.0-7.8, reacting for 5.4 hours at the rotation speed of 200rmp/min, and stopping the reaction to obtain basic cobalt carbonate slurry;
step 2, dehydrating the basic cobalt carbonate slurry obtained in the step 1 by a centrifugal machine while the basic cobalt carbonate slurry is hot, transferring the dehydrated basic cobalt carbonate slurry into an immersion kettle, adding a saturated manganese chloride solution into the immersion kettle, stirring and reacting for 14 hours at a reaction temperature of 55 ℃ with the molar ratio of the added saturated manganese chloride solution to the basic cobalt carbonate slurry being 2:1, and obtaining a manganese-doped basic cobalt carbonate crude product;
and 3, performing filter pressing dehydration on the manganese-doped basic cobalt carbonate crude product obtained in the step 2 under the pressure of 0.6Mpa, and then drying the manganese-doped basic cobalt carbonate crude product at the temperature of 96 ℃ by adopting a disc type dryer to obtain the manganese-doped basic cobalt carbonate.
The impurity content of the manganese-doped basic cobalt carbonate obtained by the preparation method of the manganese-doped basic cobalt carbonate provided in embodiment 4 of the present invention is shown in the following table:
as can be seen from the above table, in the embodiment, sodium carbonate is used for replacing ammonium bicarbonate, ammonia gas is not generated to pollute air in the production process, ammonium ions do not exist in the mother liquor and the washing water, the wastewater treatment cost is reduced by 80%, and the method is green and environment-friendly and pollutes the water environment; meanwhile, the prepared cobalt powder precursor impurity meets the production requirement of cobalt powder.
Further, Mn is doped2+The sodium ion-containing cobalt oxide is uniformly distributed on the surface of the spherical basic cobaltosic carbonate, the appearance of the spherical cobaltosic oxide is not damaged, the process is simple and easy to control, after high-temperature reaction, the sodium ion content can be washed by a small amount of hot pure water through high-temperature dehydration, slurrying and washing, and the requirement of high-quality cobalt powder can be met; the amount of waste water produced is significantly reduced.
Example 5
Embodiment 5 of the present invention provides a method for preparing manganese-doped basic cobalt carbonate, which is implemented by the following steps:
step 1, adding a sodium carbonate solution with the concentration of 120g/L +/-5 g/L and a cobalt chloride solution with the concentration of 120g/L +/-3 g/L into a reaction kettle through a metering pump, strictly controlling the reaction temperature to be 92 ℃, controlling the pH value of a reaction system to be 6.0-7.8, reacting for 5.4 hours at the rotation speed of 200rmp/min, and stopping the reaction to obtain basic cobalt carbonate slurry;
step 2, dehydrating the basic cobalt carbonate slurry obtained in the step 1 by a centrifugal machine while the basic cobalt carbonate slurry is hot, transferring the dehydrated basic cobalt carbonate slurry into an immersion kettle, adding a saturated manganese chloride solution into the immersion kettle, stirring and reacting the added saturated manganese chloride solution and the basic cobalt carbonate slurry for 12 hours at a reaction temperature of 58 ℃ to obtain a manganese-doped basic cobalt carbonate crude product, wherein the molar ratio of the added saturated manganese chloride solution to the basic cobalt carbonate slurry is 2.4: 1;
and 3, performing filter pressing dehydration on the manganese-doped basic cobalt carbonate crude product obtained in the step 2 under the pressure of 0.6Mpa, and then drying the manganese-doped basic cobalt carbonate crude product at the temperature of 96 ℃ by adopting a disc type dryer to obtain the manganese-doped basic cobalt carbonate.
The impurity content of the manganese-doped basic cobalt carbonate obtained by the preparation method of the manganese-doped basic cobalt carbonate provided in embodiment 5 of the present invention is shown in the following table:
as can be seen from the above table, in the embodiment, sodium carbonate is used for replacing ammonium bicarbonate, ammonia gas is not generated to pollute air in the production process, ammonium ions do not exist in the mother liquor and the washing water, the wastewater treatment cost is reduced by 80%, and the method is green and environment-friendly and pollutes the water environment; meanwhile, the prepared cobalt powder precursor impurity meets the production requirement of cobalt powder.
Further, Mn is doped2+The sodium ion-containing cobalt oxide is uniformly distributed on the surface of the spherical basic cobaltosic carbonate, the appearance of the spherical cobaltosic oxide is not damaged, the process is simple and easy to control, after high-temperature reaction, the sodium ion content can be washed by a small amount of hot pure water through high-temperature dehydration, slurrying and washing, and the requirement of high-quality cobalt powder can be met; the amount of waste water produced is significantly reduced.
Example 6
Embodiment 6 of the present invention provides a method for preparing manganese-doped basic cobalt carbonate, which is implemented by the following steps:
step 1, adding a sodium carbonate solution with the concentration of 120g/L +/-5 g/L and a cobalt chloride solution with the concentration of 120g/L +/-3 g/L into a reaction kettle through a metering pump, strictly controlling the reaction temperature to be 92 ℃, controlling the pH value of a reaction system to be 6.0-7.8, reacting for 5.4 hours at the rotation speed of 200rmp/min, and stopping the reaction to obtain basic cobalt carbonate slurry;
step 2, dehydrating the basic cobalt carbonate slurry obtained in the step 1 by a centrifugal machine while the basic cobalt carbonate slurry is hot, transferring the dehydrated basic cobalt carbonate slurry into an immersion kettle, adding a saturated manganese chloride solution into the immersion kettle, stirring and reacting for 10 hours at a reaction temperature of 60 ℃ with the molar ratio of the added saturated manganese chloride solution to the basic cobalt carbonate slurry being 3:1, and obtaining a manganese-doped basic cobalt carbonate crude product;
and 3, performing filter pressing dehydration on the manganese-doped basic cobalt carbonate crude product obtained in the step 2 under the pressure of 0.6Mpa, and then drying the manganese-doped basic cobalt carbonate crude product at the temperature of 96 ℃ by adopting a disc type dryer to obtain the manganese-doped basic cobalt carbonate.
The impurity content of the manganese-doped basic cobalt carbonate obtained by the preparation method of the manganese-doped basic cobalt carbonate provided in embodiment 6 of the present invention is shown in the following table:
as can be seen from the above table, in the embodiment, sodium carbonate is used for replacing ammonium bicarbonate, ammonia gas is not generated to pollute air in the production process, ammonium ions do not exist in the mother liquor and the washing water, the wastewater treatment cost is reduced by 80%, and the method is green and environment-friendly and pollutes the water environment; meanwhile, the prepared cobalt powder precursor impurity meets the production requirement of cobalt powder.
Further, Mn is doped2+The sodium ion-containing cobalt oxide is uniformly distributed on the surface of the spherical basic cobaltosic carbonate, the appearance of the spherical cobaltosic oxide is not damaged, the process is simple and easy to control, after high-temperature reaction, the sodium ion content can be washed by a small amount of hot pure water through high-temperature dehydration, slurrying and washing, and the requirement of high-quality cobalt powder can be met; the amount of waste water produced is significantly reduced.
Example 7
Embodiment 7 of the present invention provides a method for preparing manganese-doped basic cobalt carbonate, which is implemented by the following steps:
step 1, adding a sodium carbonate solution with the concentration of 120g/L +/-5 g/L and a cobalt chloride solution with the concentration of 120g/L +/-3 g/L into a reaction kettle through a metering pump, strictly controlling the reaction temperature to be 92 ℃, controlling the pH value of a reaction system to be 6.0-7.8, reacting for 6 hours at the rotation speed of 200rmp/min, and stopping the reaction to obtain basic cobalt carbonate slurry;
step 2, dehydrating the basic cobalt carbonate slurry obtained in the step 1 by a centrifugal machine while the basic cobalt carbonate slurry is hot, transferring the dehydrated basic cobalt carbonate slurry into an immersion kettle, adding a saturated manganese chloride solution into the immersion kettle, stirring and reacting for 14 hours at a reaction temperature of 56 ℃ with the molar ratio of the added saturated manganese chloride solution to the basic cobalt carbonate slurry being 3:1, and obtaining a manganese-doped basic cobalt carbonate crude product;
and 3, performing filter pressing dehydration on the manganese-doped basic cobalt carbonate crude product obtained in the step 2 under the pressure of 0.6Mpa, and then drying the manganese-doped basic cobalt carbonate crude product at the temperature of 90 ℃ by adopting a disc dryer to obtain the manganese-doped basic cobalt carbonate.
The impurity content of the manganese-doped basic cobalt carbonate obtained by the preparation method of the manganese-doped basic cobalt carbonate provided in embodiment 7 of the present invention is shown in the following table:
as can be seen from the above table, in the embodiment, sodium carbonate is used for replacing ammonium bicarbonate, ammonia gas is not generated to pollute air in the production process, ammonium ions do not exist in the mother liquor and the washing water, the wastewater treatment cost is reduced by 80%, and the method is green and environment-friendly and pollutes the water environment; meanwhile, the prepared cobalt powder precursor impurity meets the production requirement of cobalt powder.
Further, Mn is doped2+Uniformly distributed on the surface of the spherical basic cobaltosic carbonate, does not destroy the appearance of the spherical cobaltosic oxide, has simple and easily controlled process, is dehydrated, pulped and washed at high temperature after high-temperature reaction, and can be washed by a small amount of hot pure water to achieve high-quality cobalt powderSolving; the amount of waste water produced is significantly reduced.
Example 8
Embodiment 8 of the present invention provides a method for preparing manganese-doped basic cobalt carbonate, which is implemented by the following steps:
step 1, adding a sodium carbonate solution with the concentration of 120g/L +/-5 g/L and a cobalt chloride solution with the concentration of 120g/L +/-3 g/L into a reaction kettle through a metering pump, strictly controlling the reaction temperature to be 92 ℃, controlling the pH value of a reaction system to be 6.0-7.8, reacting for 6 hours at the rotation speed of 200rmp/min, and stopping the reaction to obtain basic cobalt carbonate slurry;
step 2, dehydrating the basic cobalt carbonate slurry obtained in the step 1 by a centrifugal machine while the basic cobalt carbonate slurry is hot, transferring the dehydrated basic cobalt carbonate slurry into an immersion kettle, adding a saturated manganese chloride solution into the immersion kettle, stirring and reacting for 14 hours at a reaction temperature of 56 ℃ with the molar ratio of the added saturated manganese chloride solution to the basic cobalt carbonate slurry being 3:1, and obtaining a manganese-doped basic cobalt carbonate crude product;
and 3, performing filter pressing dehydration on the manganese-doped basic cobalt carbonate crude product obtained in the step 2 under the pressure of 0.6Mpa, and then drying the manganese-doped basic cobalt carbonate crude product at the temperature of 95 ℃ by adopting a disc dryer to obtain the manganese-doped basic cobalt carbonate.
The impurity content of the manganese-doped basic cobalt carbonate obtained by the preparation method of the manganese-doped basic cobalt carbonate provided in embodiment 8 of the present invention is shown in the following table:
as can be seen from the above table, in the embodiment, sodium carbonate is used for replacing ammonium bicarbonate, ammonia gas is not generated to pollute air in the production process, ammonium ions do not exist in the mother liquor and the washing water, the wastewater treatment cost is reduced by 80%, and the method is green and environment-friendly and pollutes the water environment; meanwhile, the prepared cobalt powder precursor impurity meets the production requirement of cobalt powder.
Further, Mn is doped2+Uniformly distributed on the surface of the spherical basic cobaltosic carbonate, does not destroy the appearance of the spherical cobaltosic oxide, has simple and easily controlled process, and is dehydrated at high temperature after high-temperature reactionSlurrying and washing, wherein the content of sodium ions can be washed by a small amount of hot pure water to meet the requirement of high-quality cobalt powder; the amount of waste water produced is significantly reduced.
Example 9
Embodiment 9 of the present invention provides a method for preparing manganese-doped basic cobalt carbonate, which is implemented by the following steps:
step 1, adding a sodium carbonate solution with the concentration of 120g/L +/-5 g/L and a cobalt chloride solution with the concentration of 120g/L +/-3 g/L into a reaction kettle through a metering pump, strictly controlling the reaction temperature to be 92 ℃, controlling the pH value of a reaction system to be 6.0-7.8, reacting for 6 hours at the rotation speed of 200rmp/min, and stopping the reaction to obtain basic cobalt carbonate slurry;
step 2, dehydrating the basic cobalt carbonate slurry obtained in the step 1 by a centrifugal machine while the basic cobalt carbonate slurry is hot, transferring the dehydrated basic cobalt carbonate slurry into an immersion kettle, adding a saturated manganese chloride solution into the immersion kettle, stirring and reacting for 14 hours at a reaction temperature of 56 ℃ with the molar ratio of the added saturated manganese chloride solution to the basic cobalt carbonate slurry being 3:1, and obtaining a manganese-doped basic cobalt carbonate crude product;
and 3, performing filter pressing dehydration on the manganese-doped basic cobalt carbonate crude product obtained in the step 2 under the pressure of 0.6Mpa, and then drying the manganese-doped basic cobalt carbonate crude product at the temperature of 98 ℃ by adopting a disc dryer to obtain the manganese-doped basic cobalt carbonate.
The impurity content of the manganese-doped basic cobalt carbonate obtained by the preparation method of the manganese-doped basic cobalt carbonate provided in embodiment 9 of the present invention is shown in the following table:
as can be seen from the above table, in the embodiment, sodium carbonate is used for replacing ammonium bicarbonate, ammonia gas is not generated to pollute air in the production process, ammonium ions do not exist in the mother liquor and the washing water, the wastewater treatment cost is reduced by 80%, and the method is green and environment-friendly and pollutes the water environment; meanwhile, the prepared cobalt powder precursor impurity meets the production requirement of cobalt powder.
Further, Mn is doped2+Uniformly distributed on the surface of the spherical basic cobalt carbonate without destroying the spherical shapeThe cobaltosic oxide has the appearance, the process is simple and easy to control, after high-temperature reaction, high-temperature dehydration, slurrying and washing are carried out, and the content of sodium ions can be washed by a small amount of hot pure water to meet the requirement of high-quality cobalt powder; the amount of waste water produced is significantly reduced.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention.
Claims (8)
1. A preparation method of manganese-doped basic cobalt carbonate is characterized by comprising the following steps:
step 1, adding a sodium carbonate solution and a cobalt chloride solution into a reaction kettle, controlling the pH value of a reaction system to be 6.0-7.8, controlling the reaction temperature to be 90-95 ℃, and reacting for 5-6 hours under stirring at a rotating speed of 200rmp/min to obtain basic cobalt carbonate slurry;
step 2, dehydrating the basic cobalt carbonate slurry obtained in the step 1 while the basic cobalt carbonate slurry is hot, transferring the slurry to an immersion kettle, adding a saturated manganese chloride solution into the immersion kettle, and stirring for reaction to obtain a manganese-doped basic cobalt carbonate crude product;
and 3, sequentially carrying out filter pressing dehydration and drying on the manganese-doped basic cobalt carbonate crude product obtained in the step 2 to obtain the manganese-doped basic cobalt carbonate.
2. The method for preparing manganese-doped basic cobalt carbonate according to claim 1, wherein the concentration of the sodium carbonate solution in the step 1 is 120g/L ± 5 g/L.
3. The method for preparing manganese-doped basic cobalt carbonate according to claim 1, wherein the concentration of the cobalt chloride solution in the step 1 is 120g/L +/-3 g/L.
4. The method for preparing manganese-doped basic cobalt carbonate according to claim 1, wherein the molar ratio of the saturated manganese chloride solution added in the step 2 to the basic cobalt carbonate slurry is 2: 1-3: 1.
5. The method for preparing manganese-doped basic cobalt carbonate according to claim 1, wherein the reaction temperature of the stirring reaction in the step 2 is 55-60 ℃.
6. The method for preparing manganese-doped basic cobalt carbonate according to claim 1, wherein the reaction time of the stirring reaction in the step 2 is 10-14 h.
7. The method for preparing basic cobalt carbonate doped with manganese according to any one of claims 1 to 6, wherein the pressure filtration dehydration in the step 3 is 0.6 MPa.
8. The method for preparing manganese-doped basic cobalt carbonate according to claim 5, wherein the drying temperature in the step 3 is 90-98 ℃.
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| CN111825125A (en) * | 2020-09-16 | 2020-10-27 | 金驰能源材料有限公司 | Doped basic cobalt carbonate/cobalt carbonate composite precursor and preparation method and application thereof |
| CN113292108A (en) * | 2020-02-24 | 2021-08-24 | 荆门市格林美新材料有限公司 | Preparation process of low-chlorine cobalt carbonate for superfine cobalt powder |
| CN114804222A (en) * | 2022-06-16 | 2022-07-29 | 荆门市格林美新材料有限公司 | Nickel-manganese bimetal doped large-particle cobalt carbonate and preparation method and application thereof |
| CN114956197A (en) * | 2022-06-20 | 2022-08-30 | 江西佳纳能源科技有限公司 | Spherical cobalt carbonate, preparation method thereof and lithium ion battery cathode material |
| WO2024016469A1 (en) * | 2022-07-22 | 2024-01-25 | 广东邦普循环科技有限公司 | Manganese-doped cobaltosic oxide, and preparation method therefor and use thereof |
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