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CN111115711A - A kind of preparation method of magnesium-doped cobalt oxide - Google Patents

A kind of preparation method of magnesium-doped cobalt oxide Download PDF

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CN111115711A
CN111115711A CN201811289931.2A CN201811289931A CN111115711A CN 111115711 A CN111115711 A CN 111115711A CN 201811289931 A CN201811289931 A CN 201811289931A CN 111115711 A CN111115711 A CN 111115711A
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magnesium
containing cobalt
cobalt
solution
doped
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李炳忠
张爱青
史齐勇
王博
许东伟
伍一根
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GEM Co Ltd China
Jingmen GEM New Material Co Ltd
Gem Jiangsu Cobalt Industry Co Ltd
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GEM Co Ltd China
Jingmen GEM New Material Co Ltd
Gem Jiangsu Cobalt Industry Co Ltd
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    • C01G51/00—Compounds of cobalt
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract

本发明公开了一种掺杂镁的氧化钴的制备方法，该方法为向反应釜中加入反应底液并加热，再向所述反应底液中并流加入含镁钴盐溶液、氢氧化钠溶液、氧化剂，并控制反应体系的pH值，之后，搅拌至反应完全，获得含镁氢氧化钴浆料，之后，将含镁氢氧化钴浆料依次进行陈化、过滤、洗涤、烘干以及除铁，获得含镁氢氧化钴粉末，将含镁氢氧化钴粉末按温度曲线进行煅烧，获得掺杂镁的氧化钴，这样，本发明通过在氧化钴中掺杂镁在降低成本的同时，提高了氧化钴作为电池材料的循环性能。The invention discloses a preparation method of magnesium-doped cobalt oxide. The method comprises the steps of adding a reaction bottom liquid into a reaction kettle and heating, and then adding a magnesium-containing cobalt salt solution and sodium hydroxide to the reaction bottom liquid in parallel solution and oxidant, and control the pH value of the reaction system, after that, stir until the reaction is complete to obtain magnesium-containing cobalt hydroxide slurry, and then sequentially perform aging, filtration, washing, drying and Iron is removed to obtain magnesium-containing cobalt hydroxide powder, and the magnesium-containing cobalt hydroxide powder is calcined according to a temperature curve to obtain magnesium-doped cobalt oxide. In this way, the present invention reduces costs by doping magnesium in cobalt oxide. The cycle performance of cobalt oxide as a battery material is improved.

Description

Preparation method of magnesium-doped cobalt oxide
Technical Field
The invention belongs to the technical field of preparation of cobalt oxide, and particularly relates to a preparation method of magnesium-doped cobalt oxide.
Background
3C electronic products are required to be light and small, and corresponding batteries are required to have high energy density. Lithium cobaltate is used as the most important anode material for 3C electronic products at present, and the energy density of lithium cobaltate determines the energy density of a lithium ion battery to a certain extent. The high-voltage lithium cobalt oxide has the characteristics of high gram capacity and high voltage, has higher energy density compared with the conventional lithium cobalt oxide, and is the main direction of research and development of the lithium cobalt oxide in the future. The high-voltage lithium cobaltate is formed by doping certain metal elements into lithium cobaltate, so that the crystal structure stability of the lithium cobaltate under high voltage is improved, and the doped lithium cobaltate has high specific capacity and good cycle performance under high voltage.
However, in the prior art, when the high-voltage lithium cobaltate is prepared by doping the cobaltosic oxide in a coating manner, lithium cobaltate without doping elements inside can be formed, the internal crystal structure is easy to collapse under high voltage, so that the capacity is quickly attenuated, the elements doped by the method are not easy to enter crystal lattices of the cobaltosic oxide, and a large part of the doping elements exist in cobaltosic oxide powder in a mixture manner, so that the charge and discharge performance of the battery is influenced.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method of magnesium-doped cobalt oxide.
The invention provides a preparation method of magnesium-doped cobalt oxide, which is implemented by the following steps:
step 1, adding a reaction base solution into a reaction kettle, heating to 50-80 ℃, adjusting and controlling the pH value of a reaction system to be 9.0-11.0, adding a magnesium-containing cobalt salt solution, a sodium hydroxide solution and an oxidant into the reaction base solution in a parallel flow manner under the stirring action, and controlling the volume flow of the magnesium-containing cobalt salt solution, the sodium hydroxide solution and the oxidant to obtain a magnesium-containing cobalt hydroxide slurry;
step 2, sequentially aging, filtering, washing, drying and removing iron on the magnesium-containing cobalt hydroxide slurry obtained in the step 1 to obtain magnesium-containing cobalt hydroxide powder;
and 3, calcining the magnesium-containing cobalt hydroxide powder obtained in the step 2 according to a temperature curve to obtain the magnesium-doped cobalt oxide.
In the scheme, the stirring intensity of the stirring reaction in the step 1 is 200-400 r/min, and the stirring time is 10-40 h.
In the scheme, the reaction base solution in the step 1 is at least one of ammonia water, ethylenediamine tetraacetic acid, tartaric acid or citric acid.
In the above scheme, the magnesium-containing cobalt salt solution in step 1 is at least one of a cobalt sulfate solution, a cobalt chloride solution, a cobalt nitrate solution, or a cobalt acetate solution.
In the scheme, the concentration of cobalt ions in the magnesium-containing cobalt salt solution is 80-150 g/L, the content of magnesium element is 0.5-1.2 g/L, and the concentration of the additive is 1-5 g/L.
In the scheme, the concentration of the reaction base solution is 0.1-1 g/L, and the concentration of the sodium hydroxide solution is 100-400 g/L.
In the scheme, the volume flow ratio of the magnesium-containing cobalt salt solution to the sodium hydroxide solution in the step 1 is 1: 0.5-1.5, and the volume flow of the oxidant is 10-30 m3/h。
In the scheme, the washing liquid used for washing the magnesium-containing cobalt hydroxide slurry in the step 2 is deionized water, the using amount of the washing liquid is 10-50L/kg, and the temperature of the washing liquid is 80-90 ℃.
In the scheme, the magnesium-containing cobalt hydroxide powder obtained in the step 3 is calcined according to a temperature curve, specifically, the calcination temperature is divided into 5-12 sections to calcine the magnesium-containing cobalt hydroxide powder, and the calcination temperature is 500-800 ℃.
In the scheme, the obtained magnesium-containing cobalt hydroxide powder is calcined according to a temperature curve in the step 3, and specifically, the obtained magnesium-containing cobalt hydroxide powder is calcined at a calcination temperature of 0-60 ℃ for 25-35 min, at a calcination temperature of 60-200 ℃ for 55-65 min, at a calcination temperature of 200-400 ℃ for 55-65 min, at a calcination temperature of 400-600 ℃ for 85-95 min, at a calcination temperature of 600-750 ℃ for 55-65 min, and at a calcination temperature of 750 ℃ for 355-365 min in sequence.
Compared with the prior art, the preparation method has the advantages that the magnesium is doped in the cobalt oxide, so that the cost is reduced, and the cycle performance of the cobalt oxide as a battery material is improved; in the reaction process, the pH value of a reaction system is adjusted by controlling the volume flow of the added magnesium-containing cobalt salt solution, the added sodium hydroxide solution and the added oxidant, and the calcining temperature curve is controlled, so that the doping elements can be perfectly embedded into the cobalt oxide crystal lattice, the uniformity of the magnesium-doped cobalt oxide is improved, and the cycle performance and the charge-discharge performance of the battery are improved.
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 magnesium-doped cobalt oxide, which is implemented by the following steps:
step 1, adding a reaction base solution with the concentration of 0.1-1 g/L into a reaction kettle, heating to 50-80 ℃, adjusting and controlling the pH value of a reaction system to be 9.0-11.0, stirring the reaction base solution with the stirring strength of 200-400 r/min, and adding a magnesium-containing cobalt salt solution with the concentration of 200-400 r/min into the reaction base solution in a parallel flow manner during stirring100-400 g/L of sodium hydroxide solution and oxidant, wherein the volume flow ratio of the magnesium-containing cobalt salt solution to the sodium hydroxide solution is 1: 0.5-1.5, and the volume flow of the oxidant is 10-30 m3Reacting for 10-40 hours until the coprecipitation reaction is complete to obtain magnesium-containing cobalt hydroxide slurry;
wherein the reaction base solution is at least one of ammonia water, ethylenediamine tetraacetic acid, tartaric acid or citric acid; the magnesium-containing cobalt salt solution is at least one of a cobalt sulfate solution, a cobalt chloride solution, a cobalt nitrate solution or a cobalt acetate solution, the concentration of cobalt ions in the magnesium-containing cobalt salt solution is 80-150 g/L, the content of magnesium is 0.5-1.2 g/L, the concentration of an additive is 1-5 g/L, and the additive is ammonia water, EDTA, tartaric acid, citric acid or hydrogen peroxide; the oxidant is air or oxygen;
step 2, aging the magnesium-containing cobalt hydroxide slurry obtained in the step 1, dehydrating and filtering the slurry by using a centrifugal machine after aging, washing the slurry for 4-6 times by using deionized water at the temperature of 80-90 ℃, wherein the using amount of the deionized water is 10-50L/kg, drying the slurry at the temperature of 80-90 ℃ after washing, and finally removing iron to obtain magnesium-containing cobalt hydroxide powder;
step 3, calcining the magnesium-containing cobalt hydroxide powder obtained in the step 2 according to a temperature curve to obtain magnesium-doped cobalt oxide, wherein the calcination temperature is divided into 5-12 sections and is 500-800 ℃;
specifically, the obtained magnesium-containing cobalt hydroxide powder is sequentially calcined at a calcination temperature of 0-60 ℃ for 25-35 min, at a calcination temperature of 60-200 ℃ for 55-65 min, at a calcination temperature of 200-400 ℃ for 55-65 min, at a calcination temperature of 400-600 ℃ for 85-95 min, at a calcination temperature of 600-750 ℃ for 55-65 min, and at a calcination temperature of 750 ℃ for 355-365 min.
The invention reduces the cost by doping magnesium in the cobalt oxide, and improves the cycle performance of the cobalt oxide as a battery material; in the reaction process, the pH value of a reaction system is adjusted by controlling the volume flow of the added magnesium-containing cobalt salt solution, the added sodium hydroxide solution and the added oxidant, and the calcining temperature curve is controlled, so that the doping elements can be perfectly embedded into the cobalt oxide crystal lattice, the uniformity of the magnesium-doped cobalt oxide is improved, and the cycle performance and the charge-discharge performance of the battery are improved.
Example 1
Embodiment 1 of the present invention provides a method for preparing magnesium-doped cobalt oxide, which is implemented by the following steps:
step 1, adding ammonia water with the concentration of 0.1-1 g/L into a reaction kettle as reaction base liquid, heating to 50 ℃, adjusting and controlling the pH value of a reaction system to be 9.0-11.0, stirring the reaction base liquid with the stirring strength of 200r/min, adding a magnesium-containing cobalt sulfate solution and a sodium hydroxide solution with the concentration of 100-400 g/L into the reaction base liquid in a parallel flow manner in the stirring process, adding the magnesium-containing cobalt sulfate solution and the sodium hydroxide solution with the volume flow ratio of 1:0.5, and adding the magnesium-containing cobalt sulfate solution and the sodium hydroxide solution with the volume flow ratio of 10m3Introducing air or oxygen into the reaction kettle at a speed of/h, and reacting for 40h until the coprecipitation reaction is complete to obtain magnesium-containing cobalt hydroxide slurry;
step 2, aging the magnesium-containing cobalt hydroxide slurry obtained in the step 1, dehydrating and filtering the slurry by using a centrifugal machine after aging, washing the slurry for 5 times by using deionized water at 86 ℃, wherein the using amount of the deionized water is 30L/kg, drying the slurry at 84 ℃ after washing, and finally removing iron to obtain magnesium-containing cobalt hydroxide powder;
and 3, specifically, calcining the obtained magnesium-containing cobalt hydroxide powder at the roasting temperature of 40 ℃ for 30min, at the roasting temperature of 120 ℃ for 60min, at the roasting temperature of 300 ℃ for 60min, at the roasting temperature of 500 ℃ for 90min, at the roasting temperature of 700 ℃ for 60min and at the roasting temperature of 750 ℃ for 360min in sequence to obtain the magnesium-doped cobalt oxide.
The magnesium-doped cobalt oxide prepared in this example had a sodium content of 290ppm and a tap density of 2.31g/cm3The magnesium content is 0.4211%, the cobalt content: 72.6-73%, specific surface area: 3.0 to 8.0m2The grain size is 4.0-4.5um, and the grain size is normally distributed.
Example 2
Embodiment 2 of the present invention provides a preparation method of magnesium-doped cobalt oxide, which is implemented by the following steps:
step 1, adding tartaric acid with the concentration of 0.1-1 g/L into a reaction kettle as reaction base liquid, heating to 68 ℃, adjusting and controlling the pH value of a reaction system to be 9.0-11.0, stirring the reaction base liquid with the stirring strength of 320r/min, adding a magnesium-containing cobalt nitrate solution and a sodium hydroxide solution with the concentration of 100-400 g/L into the reaction base liquid in a parallel flow manner during stirring, wherein the volume flow ratio of the magnesium-containing cobalt nitrate solution to the sodium hydroxide solution is 1:1, and the volume flow ratio is 20m3Introducing air or oxygen into the reaction kettle at a speed of/h, and reacting for 28h until the coprecipitation reaction is complete to obtain magnesium-containing cobalt hydroxide slurry;
step 2, aging the magnesium-containing cobalt hydroxide slurry obtained in the step 1, dehydrating and filtering the slurry by using a centrifugal machine after aging, washing the slurry for 5 times by using deionized water at 86 ℃, wherein the using amount of the deionized water is 30L/kg, drying the slurry at 84 ℃ after washing, and finally removing iron to obtain magnesium-containing cobalt hydroxide powder;
and 3, specifically, calcining the obtained magnesium-containing cobalt hydroxide powder at the roasting temperature of 40 ℃ for 30min, at the roasting temperature of 120 ℃ for 60min, at the roasting temperature of 300 ℃ for 60min, at the roasting temperature of 500 ℃ for 90min, at the roasting temperature of 700 ℃ for 60min and at the roasting temperature of 750 ℃ for 360min in sequence to obtain the magnesium-doped cobalt oxide.
The magnesium-doped cobalt oxide prepared in this example had a sodium content of 290ppm and a tap density of 2.31g/cm3The magnesium content is 0.4211%, the cobalt content: 72.6-73%, specific surface area: 3.0 to 8.0m2The grain size is 4.0-4.5um, and the grain size is normally distributed.
Example 3
Embodiment 3 of the present invention provides a method for preparing magnesium-doped cobalt oxide, which is implemented by the following steps:
step 1, adding ammonia water with the concentration of 0.1-1 g/L into a reaction kettle as reaction base liquid, heating to 80 ℃, adjusting and controlling the pH value of a reaction system to be 9.0-11.0, stirring the reaction base liquid with the stirring strength of 400r/min, and adding a magnesium-containing cobalt sulfate solution and a sodium hydroxide solution with the concentration of 100-400 g/L into the reaction base liquid in a parallel flow manner in the stirring processAdding magnesium-containing cobalt sulfate solution and sodium hydroxide solution at a volume flow ratio of 1:1.5 and 30m3Introducing air or oxygen into the reaction kettle at a speed of/h, and reacting for 10h until the coprecipitation reaction is complete to obtain magnesium-containing cobalt hydroxide slurry;
step 2, aging the magnesium-containing cobalt hydroxide slurry obtained in the step 1, dehydrating and filtering the slurry by using a centrifugal machine after aging, washing the slurry for 5 times by using deionized water at 86 ℃, wherein the using amount of the deionized water is 30L/kg, drying the slurry at 84 ℃ after washing, and finally removing iron to obtain magnesium-containing cobalt hydroxide powder;
and 3, specifically, calcining the obtained magnesium-containing cobalt hydroxide powder at the roasting temperature of 40 ℃ for 30min, at the roasting temperature of 120 ℃ for 60min, at the roasting temperature of 300 ℃ for 60min, at the roasting temperature of 500 ℃ for 90min, at the roasting temperature of 700 ℃ for 60min and at the roasting temperature of 750 ℃ for 360min in sequence to obtain the magnesium-doped cobalt oxide.
The magnesium-doped cobalt oxide prepared in this example had a sodium content of 290ppm and a tap density of 2.31g/cm3The magnesium content is 0.4211%, the cobalt content: 72.6-73%, specific surface area: 3.0 to 8.0m2The grain size is 4.0-4.5um, and the grain size is normally distributed.
Example 4
Embodiment 4 of the present invention provides a preparation method of magnesium-doped cobalt oxide, which is implemented by the following steps:
step 1, adding Ethylene Diamine Tetraacetic Acid (EDTA) with the concentration of 0.1-1 g/L into a reaction kettle as reaction base liquid, heating to 64 ℃, adjusting and controlling the pH value of a reaction system to be 9.0-11.0, stirring the reaction base liquid with the stirring strength of 330r/min, adding a magnesium-containing cobalt chloride solution and a sodium hydroxide solution with the concentration of 100-400 g/L into the reaction base liquid in a parallel flow manner during stirring, wherein the volume flow ratio of the magnesium-containing cobalt chloride solution to the sodium hydroxide solution is 1:0.8, and the volume flow ratio of the magnesium-containing cobalt chloride solution to the sodium hydroxide solution is 10-30 m3Introducing air or oxygen into the reaction kettle at a speed of/h, and reacting for 32h until the coprecipitation reaction is complete to obtain magnesium-containing cobalt hydroxide slurry;
step 2, aging the magnesium-containing cobalt hydroxide slurry obtained in the step 1, dehydrating and filtering the aged slurry by using a centrifugal machine, washing the slurry for 6 times by using 80 ℃ deionized water, wherein the using amount of the deionized water is 10-50L/kg, drying the washed slurry at 90 ℃, and finally removing iron to obtain magnesium-containing cobalt hydroxide powder;
and 3, specifically, sequentially calcining the obtained magnesium-containing cobalt hydroxide powder at the calcination temperature of 10 ℃ for 25min, 60 ℃ for 55min, 200 ℃ for 65min, 400 ℃ for 85min, 600 ℃ for 60min and 750 ℃ for 355min to obtain the magnesium-doped cobalt oxide.
The magnesium-doped cobalt oxide prepared in this example had a sodium content of 290ppm and a tap density of 2.31g/cm3The magnesium content is 0.4211%, the cobalt content: 72.6-73%, specific surface area: 3.0 to 8.0m2The grain size is 4.0-4.5um, and the grain size is normally distributed.
Example 5
Embodiment 5 of the present invention provides a method for preparing magnesium-doped cobalt oxide, which is implemented by the following steps:
step 1, adding Ethylene Diamine Tetraacetic Acid (EDTA) with the concentration of 0.1-1 g/L into a reaction kettle as reaction base liquid, heating to 64 ℃, adjusting and controlling the pH value of a reaction system to be 9.0-11.0, stirring the reaction base liquid with the stirring strength of 330r/min, adding a magnesium-containing cobalt chloride solution and a sodium hydroxide solution with the concentration of 100-400 g/L into the reaction base liquid in a parallel flow manner during stirring, wherein the volume flow ratio of the magnesium-containing cobalt chloride solution to the sodium hydroxide solution is 1:0.8, and the volume flow ratio of the magnesium-containing cobalt chloride solution to the sodium hydroxide solution is 10-30 m3Introducing air or oxygen into the reaction kettle at a speed of/h, and reacting for 32h until the coprecipitation reaction is complete to obtain magnesium-containing cobalt hydroxide slurry;
step 2, aging the magnesium-containing cobalt hydroxide slurry obtained in the step 1, dehydrating and filtering the aged slurry by using a centrifugal machine, washing the slurry for 5 times by using deionized water at 85 ℃, wherein the using amount of the deionized water is 10-50L/kg, drying the washed slurry at 80 ℃, and finally removing iron to obtain magnesium-containing cobalt hydroxide powder;
and 3, specifically, calcining the obtained magnesium-containing cobalt hydroxide powder at the roasting temperature of 30 ℃ for 35min, calcining at the roasting temperature of 60 ℃ for 60min, calcining at the roasting temperature of 200 ℃ for 60min, calcining at the roasting temperature of 480 ℃ for 85min, calcining at the roasting temperature of 680 ℃ for 60min and calcining at the roasting temperature of 750 ℃ for 360min in sequence to obtain the magnesium-doped cobalt oxide.
The magnesium-doped cobalt oxide prepared in this example had a sodium content of 290ppm and a tap density of 2.31g/cm3The magnesium content is 0.4211%, the cobalt content: 72.6-73%, specific surface area: 3.0 to 8.0m2The grain size is 4.0-4.5um, and the grain size is normally distributed.
Example 6
Embodiment 6 of the present invention provides a method for preparing magnesium-doped cobalt oxide, which is implemented by the following steps:
step 1, adding Ethylene Diamine Tetraacetic Acid (EDTA) with the concentration of 0.1-1 g/L into a reaction kettle as reaction base liquid, heating to 64 ℃, adjusting and controlling the pH value of a reaction system to be 9.0-11.0, stirring the reaction base liquid with the stirring strength of 330r/min, adding a magnesium-containing cobalt chloride solution and a sodium hydroxide solution with the concentration of 100-400 g/L into the reaction base liquid in a parallel flow manner during stirring, wherein the volume flow ratio of the magnesium-containing cobalt chloride solution to the sodium hydroxide solution is 1:0.8, and the volume flow ratio of the magnesium-containing cobalt chloride solution to the sodium hydroxide solution is 10-30 m3Introducing air or oxygen into the reaction kettle at a speed of/h, and reacting for 32h until the coprecipitation reaction is complete to obtain magnesium-containing cobalt hydroxide slurry;
step 2, aging the magnesium-containing cobalt hydroxide slurry obtained in the step 1, dehydrating and filtering the slurry by using a centrifugal machine after aging, washing the slurry for 4 times by using deionized water at 90 ℃, wherein the using amount of the deionized water is 10-50L/kg, drying the slurry at 80 ℃ after washing, and finally removing iron to obtain magnesium-containing cobalt hydroxide powder;
and 3, specifically, calcining the obtained magnesium-containing cobalt hydroxide powder at the roasting temperature of 25 ℃ for 35min, calcining at the roasting temperature of 100 ℃ for 65min, calcining at the roasting temperature of 250 ℃ for 65min, calcining at the roasting temperature of 480 ℃ for 95min, calcining at the roasting temperature of 680 ℃ for 65min and calcining at the roasting temperature of 750 ℃ for 365min in sequence to obtain the magnesium-doped cobalt oxide.
The magnesium-doped cobalt oxide prepared in this example had a sodium content of 290ppm and a tap density of 2.31g/cm3The magnesium content is 0.4211%, the cobalt content: 72.6-73%, specific surface area: 3.0 to 8.0m2The grain size is 4.0-4.5um, and the grain size is normally distributed.
Example 7
Embodiment 7 of the present invention provides a method for preparing magnesium-doped cobalt oxide, which is implemented by the following steps:
step 1, adding 0.1-1 g/L citric acid serving as reaction base liquid into a reaction kettle, heating to 64 ℃, adjusting and controlling the pH value of a reaction system to be 9.0-11.0, stirring the reaction base liquid with the stirring strength of 350r/min, adding a magnesium-containing cobalt acetate solution and a sodium hydroxide solution with the concentration of 100-400 g/L into the reaction base liquid in a parallel flow manner during stirring, wherein the volume flow ratio of the magnesium-containing cobalt acetate solution to the sodium hydroxide solution is 1:1.2, and the volume flow ratio of the magnesium-containing cobalt acetate solution to the sodium hydroxide solution is 10-30 m3Introducing air or oxygen into the reaction kettle at a speed of/h, and reacting for 26h until the coprecipitation reaction is complete to obtain magnesium-containing cobalt hydroxide slurry;
step 2, aging the magnesium-containing cobalt hydroxide slurry obtained in the step 1, dehydrating and filtering the aged slurry by using a centrifugal machine, washing the slurry for 5 times by using deionized water at 86 ℃, wherein the using amount of the deionized water is 10-50L/kg, drying the washed slurry at 86 ℃, and finally removing iron to obtain magnesium-containing cobalt hydroxide powder;
and 3, specifically, sequentially calcining the obtained magnesium-containing cobalt hydroxide powder at the roasting temperature of 0-45 ℃ for 20min, at the roasting temperature of 120 ℃ for 60min, at the roasting temperature of 260 ℃ for 60min, at the roasting temperature of 520 ℃ for 90min, at the roasting temperature of 700 ℃ for 60min and at the roasting temperature of 750 ℃ for 355min to obtain the magnesium-doped cobalt oxide.
The magnesium-doped cobalt oxide prepared in this example had a sodium content of 290ppm and a tap density of 2.31g/cm3The magnesium content is 0.4211%, the cobalt content: 72.6-73%, specific surface area: 3.0 to 8.0m2The grain size is 4.0-4.5um, and the grain size is normally distributed.
Example 8
Embodiment 8 of the present invention provides a method for preparing magnesium-doped cobalt oxide, which is implemented by the following steps:
step 1, adding 0.1-1 g/L citric acid serving as reaction base liquid into a reaction kettle, heating to 64 ℃, adjusting and controlling the pH value of a reaction system to be 9.0-11.0, stirring the reaction base liquid with the stirring strength of 350r/min, adding a magnesium-containing cobalt acetate solution and a sodium hydroxide solution with the concentration of 100-400 g/L into the reaction base liquid in a parallel flow manner during stirring, wherein the volume flow ratio of the magnesium-containing cobalt acetate solution to the sodium hydroxide solution is 1:1.2, and the volume flow ratio of the magnesium-containing cobalt acetate solution to the sodium hydroxide solution is 10-30 m3Introducing air or oxygen into the reaction kettle at a speed of/h, and reacting for 26h until the coprecipitation reaction is complete to obtain magnesium-containing cobalt hydroxide slurry;
step 2, aging the magnesium-containing cobalt hydroxide slurry obtained in the step 1, dehydrating and filtering the aged slurry by using a centrifugal machine, washing the slurry for 5 times by using deionized water at 86 ℃, wherein the using amount of the deionized water is 10-50L/kg, drying the washed slurry at 86 ℃, and finally removing iron to obtain magnesium-containing cobalt hydroxide powder;
and 3, specifically, calcining the obtained magnesium-containing cobalt hydroxide powder at the roasting temperature of 25 ℃ for 35min, calcining at the roasting temperature of 80 ℃ for 62min, calcining at the roasting temperature of 240 ℃ for 55min, calcining at the roasting temperature of 480 ℃ for 95min, calcining at the roasting temperature of 620 ℃ for 60min and calcining at the roasting temperature of 750 ℃ for 360min in sequence to obtain the magnesium-doped cobalt oxide.
The magnesium-doped cobalt oxide prepared in this example had a sodium content of 290ppm and a tap density of 2.31g/cm3The magnesium content is 0.4211%, the cobalt content: 72.6-73%, specific surface area: 3.0 to 8.0m2The grain size is 4.0-4.5um, and the grain size is normally distributed.
Example 9
Embodiment 9 of the present invention provides a method for preparing magnesium-doped cobalt oxide, which is implemented by the following steps:
step 1, adding citric acid with the concentration of 0.1-1 g/L into a reaction kettle as reaction base liquid, heating to 64 ℃, adjusting and controlling a reaction bodyThe pH value of the system is 9.0-11.0, the reaction base solution is stirred with the stirring intensity of 350r/min, magnesium-containing cobalt acetate solution and sodium hydroxide solution with the concentration of 100-400 g/L are added into the reaction base solution in a parallel flow mode in the stirring process, the volume flow ratio of the magnesium-containing cobalt acetate solution to the sodium hydroxide solution is 1:1.2, and the stirring intensity is 10-30 m3Introducing air or oxygen into the reaction kettle at a speed of/h, and reacting for 26h until the coprecipitation reaction is complete to obtain magnesium-containing cobalt hydroxide slurry;
step 2, aging the magnesium-containing cobalt hydroxide slurry obtained in the step 1, dehydrating and filtering the aged slurry by using a centrifugal machine, washing the slurry for 5 times by using deionized water at 86 ℃, wherein the using amount of the deionized water is 10-50L/kg, drying the washed slurry at 86 ℃, and finally removing iron to obtain magnesium-containing cobalt hydroxide powder;
and 3, specifically, sequentially calcining the obtained magnesium-containing cobalt hydroxide powder at the roasting temperature of 35 ℃ for 35min, at the roasting temperature of 128 ℃ for 65min, at the roasting temperature of 320 ℃ for 60min, at the roasting temperature of 500 ℃ for 85min, at the roasting temperature of 680 ℃ for 60min and at the roasting temperature of 750 ℃ for 355min to obtain the magnesium-doped cobalt oxide.
The magnesium-doped cobalt oxide prepared in this example had a sodium content of 290ppm and a tap density of 2.31g/cm3The magnesium content is 0.4211%, the cobalt content: 72.6-73%, specific surface area: 3.0 to 8.0m2The grain size is 4.0-4.5um, and the grain size is normally distributed.
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 (10)

1.一种掺杂镁的氧化钴的制备方法，其特征在于，其方法通过以下步骤实施：1. a preparation method of the cobalt oxide doped with magnesium, is characterized in that, its method is implemented by the following steps: 步骤1，向反应釜中加入反应底液并加热至50～80℃，调节并控制反应体系的pH值为9.0～11.0，在搅拌作用下向所述反应底液中并流加入含镁钴盐溶液、氢氧化钠溶液、氧化剂，并控制加入所述含镁钴盐溶液、氢氧化钠溶液、氧化剂的体积流量，获得含镁氢氧化钴浆料；Step 1, add the reaction bottom liquid to the reaction kettle and heat it to 50～80°C, adjust and control the pH value of the reaction system to be 9.0～11.0, and add magnesium-containing cobalt salts to the reaction bottom liquid under stirring. solution, sodium hydroxide solution, oxidant, and control the volume flow of the magnesium-containing cobalt salt solution, sodium hydroxide solution, and oxidant added to obtain magnesium-containing cobalt hydroxide slurry; 步骤2，将所述步骤1获得的含镁氢氧化钴浆料依次进行陈化、过滤、洗涤、烘干以及除铁，获得含镁氢氧化钴粉末；In step 2, the magnesium-containing cobalt hydroxide slurry obtained in the step 1 is sequentially subjected to aging, filtration, washing, drying and iron removal to obtain magnesium-containing cobalt hydroxide powder; 步骤3，将所述步骤2获得的含镁氢氧化钴粉末按温度曲线进行煅烧，获得掺杂镁的氧化钴。Step 3, calcining the magnesium-containing cobalt hydroxide powder obtained in the step 2 according to a temperature curve to obtain magnesium-doped cobalt oxide. 2.根据权利要求1所述的一种掺杂镁的氧化钴的制备方法，其特征在于，所述步骤1的搅拌反应的搅拌强度为200～400r/min，搅拌时间为10～40h。2 . The method for preparing magnesium-doped cobalt oxide according to claim 1 , wherein the stirring intensity of the stirring reaction in the step 1 is 200-400 r/min, and the stirring time is 10-40 h. 3 . 3.根据权利要求2所述的一种掺杂镁的氧化钴的制备方法，其特征在于，所述步骤1中反应底液为氨水、乙二胺四乙酸、酒石酸或柠檬酸中的至少一种。3. the preparation method of a kind of magnesium-doped cobalt oxide according to claim 2, is characterized in that, in described step 1, reaction bottom liquid is at least one in ammoniacal liquor, EDTA, tartaric acid or citric acid kind. 4.根据权利要求3所述的一种掺杂镁的氧化钴的制备方法，其特征在于，所述步骤1中含镁钴盐溶液为硫酸钴溶液、氯化钴溶液、硝酸钴溶液或者醋酸钴溶液中的至少一种。4. the preparation method of a kind of magnesium-doped cobalt oxide according to claim 3, is characterized in that, in described step 1, the magnesium-containing cobalt salt solution is cobalt sulfate solution, cobalt chloride solution, cobalt nitrate solution or acetic acid at least one of the cobalt solutions. 5.根据权利要求4所述的一种掺杂镁的氧化钴的制备方法，其特征在于，所述含镁钴盐溶液中钴离子的浓度为80～150g/L，镁元素含量为0.5～1.2g/L，添加剂的浓度为1～5g/L。5 . The method for preparing a magnesium-doped cobalt oxide according to claim 4 , wherein the concentration of cobalt ions in the magnesium-containing cobalt salt solution is 80 to 150 g/L, and the magnesium content is 0.5 to 100 g/L. 6 . 1.2g/L, the concentration of additives is 1～5g/L. 6.根据权利要求5所述的一种掺杂镁的氧化钴的制备方法，其特征在于，所述反应底液的浓度为0.1～1g/L，所述氢氧化钠溶液的浓度为100～400g/L。6 . The method for preparing a magnesium-doped cobalt oxide according to claim 5 , wherein the concentration of the reaction bottom solution is 0.1～1 g/L, and the concentration of the sodium hydroxide solution is 100～1 g/L. 7 . 400g/L. 7.根据权利要求6所述的一种掺杂镁的氧化钴的制备方法，其特征在于，所述步骤1中含镁钴盐溶液与氢氧化钠溶液的体积流量比为1:0.5～1.5，氧化剂的体积流量为10～30m3/h。7. the preparation method of a kind of magnesium-doped cobalt oxide according to claim 6, is characterized in that, in described step 1, the volume flow ratio of magnesium-containing cobalt salt solution and sodium hydroxide solution is 1:0.5～1.5 , the volume flow of oxidant is 10～30m 3 /h. 8.根据权利要求1-7任意一项所述的一种掺杂镁的氧化钴的制备方法，其特征在于，所述步骤2中对含镁氢氧化钴浆料进行洗涤采用的洗涤液为去离子水，洗涤液的用量为10～50L/kg，洗涤液的温度为80～90℃。8. the preparation method of a kind of magnesium-doped cobalt oxide according to any one of claim 1-7, it is characterized in that, in described step 2, the washing liquid that is used to wash magnesium-containing cobalt hydroxide slurry is: Deionized water, the dosage of the washing solution is 10-50L/kg, and the temperature of the washing solution is 80-90°C. 9.根据权利要求8所述的一种掺杂镁的氧化钴的制备方法，其特征在于，所述步骤3将获得的所述含镁氢氧化钴粉末按温度曲线进行煅烧，具体为，将焙烧温度分为5～12段对所述含镁氢氧化钴粉末进行煅烧，所述焙烧温度为500～800℃。9. the preparation method of a kind of magnesium-doped cobalt oxide according to claim 8, is characterized in that, described step 3 will obtain described magnesium-containing cobalt hydroxide powder to be calcined according to the temperature curve, specifically, will be The calcination temperature is divided into 5-12 stages to calcine the magnesium-containing cobalt hydroxide powder, and the calcination temperature is 500-800°C. 10.根据权利要求9所述的一种掺杂镁的氧化钴的制备方法，其特征在于，所述步骤3将所述获得的含镁氢氧化钴粉末按温度曲线进行煅烧，具体为，将所述获得的含镁氢氧化钴粉末依次在0～60℃的焙烧温度下煅烧25～35min、在60～200℃的焙烧温度下煅烧55～65min、在200～400℃的焙烧温度下煅烧55～65min、在400～600℃的焙烧温度下煅烧85～95min、在600～750℃的焙烧温度下煅烧55～65min以及在750℃的焙烧温度下煅烧355～365min。10 . The method for preparing a magnesium-doped cobalt oxide according to claim 9 , wherein in the step 3, the obtained magnesium-containing cobalt hydroxide powder is calcined according to a temperature curve, specifically, calcining the obtained magnesium-containing cobalt hydroxide powder according to a temperature curve. 11 . The obtained magnesium-containing cobalt hydroxide powder is successively calcined at a calcination temperature of 0-60 DEG C for 25-35 min, calcined at a calcination temperature of 60-200 DEG C for 55-65 min, and calcined at a calcination temperature of 200-400 DEG C for 55 minutes. ~65min, calcining at 400~600℃ for 85~95min, 600~750℃ for 55~65min, and 750℃ for 355~365min.
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