CN111115709A - Preparation method of titanium-doped cobalt oxide - Google Patents

Preparation method of titanium-doped cobalt oxide Download PDF

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Publication number
CN111115709A
CN111115709A CN201811289893.0A CN201811289893A CN111115709A CN 111115709 A CN111115709 A CN 111115709A CN 201811289893 A CN201811289893 A CN 201811289893A CN 111115709 A CN111115709 A CN 111115709A
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titanium
solution
containing cobalt
cobalt
reaction
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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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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/04—Oxides; Hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/11—Powder tap density
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Inorganic Chemistry (AREA)
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Abstract

The invention discloses a preparation method of titanium-doped cobalt oxide, which comprises the steps of adding reaction base liquid into a reaction kettle, heating, adding titanium-containing cobalt salt solution, sodium hydroxide solution and oxidant into the reaction base liquid in a concurrent flow manner, controlling the pH value of a reaction system, stirring until the reaction is complete to obtain titanium-containing cobalt hydroxide slurry, then sequentially aging, filtering, washing, drying and deironing the titanium-containing cobalt hydroxide slurry to obtain titanium-containing cobalt hydroxide powder, and calcining the titanium-containing cobalt hydroxide powder according to a temperature curve to obtain the titanium-doped cobalt oxide.

Description

Preparation method of titanium-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 titanium-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 titanium-doped cobalt oxide.
The invention provides a preparation method of titanium-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 titanium-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 added titanium-containing cobalt salt solution, the added sodium hydroxide solution and the added oxidant to obtain a titanium-containing cobalt hydroxide slurry;
step 2, sequentially aging, filtering, washing, drying and removing iron on the titanium-containing cobalt hydroxide slurry obtained in the step 1 to obtain titanium-containing cobalt hydroxide powder;
and 3, calcining the titanium-containing cobalt hydroxide powder obtained in the step 2 according to a temperature curve to obtain titanium-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 titanium-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 titanium-containing cobalt salt solution is 80-150 g/L, the content of titanium 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 titanium-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 titanium-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 titanium-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 titanium-containing cobalt hydroxide powder, and the calcination temperature is 500-800 ℃.
In the scheme, the obtained titanium-containing cobalt hydroxide powder is calcined according to a temperature curve in the step 3, and specifically, the obtained titanium-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 cobalt oxide is doped with titanium, 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 titanium-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 cobalt oxide lattices, the uniformity of the titanium-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 titanium-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, adding a titanium-containing cobalt salt solution, a sodium hydroxide solution with the concentration of 100-400 g/L and an oxidant into the reaction base solution in a parallel flow manner during stirring, and adding the volume flow ratio of the titanium-containing cobalt salt solution to the sodium hydroxide solution1: 0.5-1.5, and the volume flow of the introduced oxidant is 10-30 m3Reacting for 10-40 hours until the coprecipitation reaction is complete to obtain titanium-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 titanium-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 titanium-containing cobalt salt solution is 80-150 g/L, the content of titanium elements 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 titanium-containing cobalt hydroxide slurry obtained in the step 1, dehydrating and filtering the aged slurry by using a centrifugal machine, washing the slurry for 4-6 times by using 80-90 ℃ deionized water, wherein the using amount of the deionized water is 10-50L/kg, drying the washed slurry at 80-90 ℃, and finally removing iron to obtain titanium-containing cobalt hydroxide powder;
step 3, calcining the titanium-containing cobalt hydroxide powder obtained in the step 2 according to a temperature curve to obtain titanium-doped cobalt oxide, wherein the calcination temperature is divided into 5-12 sections and is 500-800 ℃;
specifically, the obtained titanium-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 titanium 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 titanium-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 cobalt oxide lattices, the uniformity of the titanium-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 titanium-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 titanium-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 titanium-containing cobalt sulfate solution and the sodium hydroxide solution with the volume flow ratio of 1:0.5, and adding 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 titanium-containing cobalt hydroxide slurry;
step 2, aging the titanium-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 86 ℃ deionized water, wherein the using amount of the deionized water is 30L/kg, drying the washed slurry at 84 ℃, and finally removing iron to obtain titanium-containing cobalt hydroxide powder;
and 3, specifically, sequentially calcining the obtained titanium-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 to obtain the titanium-doped cobalt oxide.
The titanium-doped cobalt oxide prepared in this example had a sodium content of 290ppm and a tap density of 2.31g/cm3Titanium content 0.4211%, 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 method for preparing titanium-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 and addingHeating to 68 ℃, adjusting and controlling the pH value of the reaction system to be 9.0-11.0, stirring the reaction base solution with the stirring strength of 320r/min, adding a titanium-containing cobalt nitrate solution and a sodium hydroxide solution with the concentration of 100-400 g/L into the reaction base solution in a concurrent flow manner in the stirring process, adding the titanium-containing cobalt nitrate solution and the sodium hydroxide solution with the volume flow ratio of 1:1, and controlling the volume flow ratio to be 20m3Introducing air or oxygen into the reaction kettle at a speed of/h, and reacting for 26h until the coprecipitation reaction is complete to obtain titanium-containing cobalt hydroxide slurry;
step 2, aging the titanium-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 86 ℃ deionized water, wherein the using amount of the deionized water is 30L/kg, drying the washed slurry at 84 ℃, and finally removing iron to obtain titanium-containing cobalt hydroxide powder;
and 3, specifically, sequentially calcining the obtained titanium-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 to obtain the titanium-doped cobalt oxide.
The titanium-doped cobalt oxide prepared in this example had a sodium content of 290ppm and a tap density of 2.31g/cm3Titanium content 0.4211%, 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 titanium-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, adding a titanium-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 titanium-containing cobalt sulfate solution and the sodium hydroxide solution with the volume flow ratio of 1:1.5 and 30m3H ofIntroducing air or oxygen into the reaction kettle at a speed, and reacting for 10 hours until the coprecipitation reaction is complete to obtain titanium-containing cobalt hydroxide slurry;
step 2, aging the titanium-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 86 ℃ deionized water, wherein the using amount of the deionized water is 30L/kg, drying the washed slurry at 84 ℃, and finally removing iron to obtain titanium-containing cobalt hydroxide powder;
and 3, specifically, sequentially calcining the obtained titanium-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 to obtain the titanium-doped cobalt oxide.
The titanium-doped cobalt oxide prepared in this example had a sodium content of 290ppm and a tap density of 2.31g/cm3Titanium content 0.4211%, 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 method for preparing titanium-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 titanium-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 titanium-containing cobalt chloride solution to the sodium hydroxide solution is 1:0.8, and the volume flow ratio of the titanium-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 22h until the coprecipitation reaction is complete to obtain titanium-containing cobalt hydroxide slurry;
step 2, aging the titanium-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 titanium-containing cobalt hydroxide powder;
and 3, specifically, sequentially calcining the obtained titanium-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 titanium-doped cobalt oxide.
The titanium-doped cobalt oxide prepared in this example had a sodium content of 290ppm and a tap density of 2.31g/cm3Titanium content 0.4211%, 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 titanium-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 titanium-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 titanium-containing cobalt chloride solution to the sodium hydroxide solution is 1:0.8, and the volume flow ratio of the titanium-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 22h until the coprecipitation reaction is complete to obtain titanium-containing cobalt hydroxide slurry;
step 2, aging the titanium-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 titanium-containing cobalt hydroxide powder;
and 3, specifically, calcining the obtained titanium-containing cobalt hydroxide powder at the roasting temperature of 30 ℃ for 35min, at the roasting temperature of 60 ℃ for 60min, at the roasting temperature of 200 ℃ for 60min, at the roasting temperature of 480 ℃ for 85min, at the roasting temperature of 680 ℃ for 60min, and at the roasting temperature of 750 ℃ for 360min in sequence to obtain the titanium-doped cobalt oxide.
The titanium-doped cobalt oxide prepared in this example had a sodium content of 290ppm and a tap density of 2.31g/cm3Titanium content 0.4211%, 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 titanium-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 titanium-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 titanium-containing cobalt chloride solution to the sodium hydroxide solution is 1:0.8, and the volume flow ratio of the titanium-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 22h until the coprecipitation reaction is complete to obtain titanium-containing cobalt hydroxide slurry;
step 2, aging the titanium-containing cobalt hydroxide slurry obtained in the step 1, dehydrating and filtering the aged slurry by using a centrifugal machine, 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 washed slurry at 80 ℃, and finally removing iron to obtain titanium-containing cobalt hydroxide powder;
and 3, specifically, sequentially calcining the obtained titanium-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 to obtain the titanium-doped cobalt oxide.
The titanium-doped cobalt oxide prepared in this example had a sodium content of 290ppm,the tap density is 2.31g/cm3Titanium content 0.4211%, 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 titanium-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 titanium-containing cobalt acetate solution and a 100-400 g/L sodium hydroxide solution into the reaction base liquid in a parallel flow manner during stirring, wherein the volume flow ratio of the titanium-containing cobalt acetate solution to the sodium hydroxide solution is 1:1.2, and the volume flow ratio of the titanium-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 32h until the coprecipitation reaction is complete to obtain titanium-containing cobalt hydroxide slurry;
step 2, aging the titanium-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 86 ℃ deionized water, wherein the using amount of the deionized water is 10-50L/kg, drying the washed slurry at 86 ℃, and finally removing iron to obtain titanium-containing cobalt hydroxide powder;
and 3, specifically, sequentially calcining the obtained titanium-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 titanium-doped cobalt oxide.
The titanium-doped cobalt oxide prepared in this example had a sodium content of 290ppm and a tap density of 2.31g/cm3Titanium content 0.4211%, 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 titanium-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 titanium-containing cobalt acetate solution and a 100-400 g/L sodium hydroxide solution into the reaction base liquid in a parallel flow manner during stirring, wherein the volume flow ratio of the titanium-containing cobalt acetate solution to the sodium hydroxide solution is 1:1.2, and the volume flow ratio of the titanium-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 32h until the coprecipitation reaction is complete to obtain titanium-containing cobalt hydroxide slurry;
step 2, aging the titanium-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 86 ℃ deionized water, wherein the using amount of the deionized water is 10-50L/kg, drying the washed slurry at 86 ℃, and finally removing iron to obtain titanium-containing cobalt hydroxide powder;
and 3, specifically, calcining the obtained titanium-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 titanium-doped cobalt oxide.
The titanium-doped cobalt oxide prepared in this example had a sodium content of 290ppm and a tap density of 2.31g/cm3Titanium content 0.4211%, 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 titanium-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 the pH value of a reaction system to be 9.0-11.0, stirring the reaction base liquid with the stirring intensity of 350r/min, and reacting in the stirring processAdding a titanium-containing cobalt acetate solution and a sodium hydroxide solution with the concentration of 100-400 g/L into the base solution in a parallel flow manner, wherein the volume flow ratio of the titanium-containing cobalt acetate solution to the sodium hydroxide solution is 1:1.2 and 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 titanium-containing cobalt hydroxide slurry;
step 2, aging the titanium-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 86 ℃ deionized water, wherein the using amount of the deionized water is 10-50L/kg, drying the washed slurry at 86 ℃, and finally removing iron to obtain titanium-containing cobalt hydroxide powder;
and 3, specifically, sequentially calcining the obtained titanium-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 titanium-doped cobalt oxide.
The titanium-doped cobalt oxide prepared in this example had a sodium content of 290ppm and a tap density of 2.31g/cm3Titanium content 0.4211%, 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. A preparation method of titanium-doped cobalt oxide is characterized by comprising 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 titanium-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 added titanium-containing cobalt salt solution, the added sodium hydroxide solution and the added oxidant to obtain a titanium-containing cobalt hydroxide slurry;
step 2, sequentially aging, filtering, washing, drying and removing iron on the titanium-containing cobalt hydroxide slurry obtained in the step 1 to obtain titanium-containing cobalt hydroxide powder;
and 3, calcining the titanium-containing cobalt hydroxide powder obtained in the step 2 according to a temperature curve to obtain titanium-doped cobalt oxide.
2. The method for preparing titanium-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. The method as claimed in claim 2, wherein the reaction solution in step 1 is at least one of ammonia, ethylenediamine tetraacetic acid, tartaric acid and citric acid.
4. The method as claimed in claim 3, wherein the cobalt salt solution containing titanium in step 1 is at least one of cobalt sulfate solution, cobalt chloride solution, cobalt nitrate solution and cobalt acetate solution.
5. The method according to claim 4, wherein the concentration of cobalt ions in the solution containing titanium cobalt salt is 80-150 g/L, the content of titanium element is 0.5-1.2 g/L, and the concentration of additive is 1-5 g/L.
6. The method 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 100-400 g/L.
7. The method according to claim 6, wherein the volume flow ratio of the titanium-containing cobalt salt solution to the sodium hydroxide solution in step 1 is 1: 0.5-1.5, and the volume flow of the oxidant is 10-30 m3/h。
8. The method for preparing titanium-doped cobalt oxide according to any one of claims 1 to 7, wherein the washing solution used for washing the titanium-containing cobalt hydroxide slurry in the step 2 is deionized water, the amount of the washing solution is 10 to 50L/kg, and the temperature of the washing solution is 80 to 90 ℃.
9. The method according to claim 8, wherein the titanium-containing cobalt hydroxide powder obtained in step 3 is calcined according to a temperature curve, specifically, the calcination temperature is divided into 5 to 12 stages and the titanium-containing cobalt hydroxide powder is calcined, and the calcination temperature is 500 to 800 ℃.
10. The method for preparing titanium-doped cobalt oxide according to claim 9, wherein the obtained titanium-containing cobalt hydroxide powder is calcined according to a temperature curve in the step 3, and specifically, the obtained titanium-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.
CN201811289893.0A 2018-10-31 2018-10-31 Preparation method of titanium-doped cobalt oxide Pending CN111115709A (en)

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