CN111115700A - Preparation method of samarium-doped cobalt oxide - Google Patents

Preparation method of samarium-doped cobalt oxide Download PDF

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CN111115700A
CN111115700A CN201811287907.5A CN201811287907A CN111115700A CN 111115700 A CN111115700 A CN 111115700A CN 201811287907 A CN201811287907 A CN 201811287907A CN 111115700 A CN111115700 A CN 111115700A
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samarium
cobalt
solution
doped
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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • 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
    • 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
    • C01P2006/40—Electric properties
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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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Abstract

The invention discloses a preparation method of samarium-doped cobalt oxide, which comprises the steps of adding reaction base liquid into a reaction kettle, heating, adding samarium-containing cobalt hydroxide 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 samarium-containing cobalt hydroxide slurry, aging, filtering, washing, drying and deironing the samarium-containing cobalt hydroxide slurry in sequence to obtain samarium-containing cobalt hydroxide powder, and calcining the samarium-containing cobalt hydroxide powder according to a temperature curve to obtain samarium-doped cobalt oxide.

Description

Preparation method of samarium-doped cobalt oxide
Technical Field
The invention belongs to the technical field of cobalt oxide preparation, and particularly relates to a preparation method of samarium-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 samarium-doped cobalt oxide.
The invention provides a preparation method of samarium-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 samarium-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 samarium-containing cobalt salt solution, the sodium hydroxide solution and the oxidant to obtain samarium-containing cobalt hydroxide slurry;
step 2, sequentially aging, filtering, washing, drying and deironing the cobalt hydroxide slurry containing samarium obtained in the step 1 to obtain cobalt hydroxide powder containing samarium;
and 3, calcining the cobalt hydroxide powder containing samarium, which is obtained in the step 2, according to a temperature curve to obtain the cobalt oxide doped with samarium.
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 samarium cobalt containing 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 samarium-cobalt-containing salt solution is 80-150 g/L, the content of samarium elements is 0.5-1.2 g/L, and the concentration of an 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 samarium cobalt-containing 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 adopted for washing the cobalt hydroxide slurry containing samarium 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 cobalt hydroxide powder containing samarium 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 cobalt hydroxide powder containing samarium, and the calcination temperature is 500-800 ℃.
In the scheme, the obtained cobalt hydroxide powder containing samarium is calcined according to a temperature curve in the step 3, and specifically, the obtained cobalt hydroxide powder containing samarium 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.
Compared with the prior art, the cobalt oxide is doped with samarium, 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 samarium-cobalt-containing salt solution, the sodium hydroxide solution and the 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 samarium-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 samarium-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 samarium-cobalt-containing salt solution with the concentration of samarium-cobalt solution 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 samarium cobalt-containing 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 cobalt hydroxide slurry containing samarium;
wherein the reaction base solution is at least one of ammonia water, ethylenediamine tetraacetic acid, tartaric acid or citric acid; the samarium-cobalt-containing 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 samarium-cobalt-containing salt solution is 80-150 g/L, the content of samarium element 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, ageing the cobalt hydroxide slurry containing samarium obtained in the step 1, dehydrating and filtering the aged cobalt hydroxide slurry by using a centrifugal machine, washing the cobalt hydroxide 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 washed cobalt hydroxide slurry at the temperature of 80-90 ℃, and finally removing iron to obtain cobalt hydroxide powder containing samarium;
step 3, calcining the cobalt hydroxide powder containing samarium obtained in the step 2 according to a temperature curve to obtain cobalt oxide doped with samarium, wherein the calcination temperature is divided into 5-12 sections and is 500-800 ℃;
specifically, the obtained cobalt hydroxide powder containing samarium is sequentially calcined at a roasting temperature of 0-60 ℃ for 25-35 min, at a roasting temperature of 60-200 ℃ for 55-65 min, at a roasting temperature of 200-400 ℃ for 55-65 min, at a roasting temperature of 400-600 ℃ for 85-95 min, at a roasting temperature of 600-750 ℃ for 55-65 min, and at a roasting temperature of 750 ℃ for 355-365 min.
According to the invention, samarium is doped in cobalt oxide, so that the cost is reduced, and the cycle performance of 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 samarium-cobalt-containing salt solution, the sodium hydroxide solution and the 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 samarium-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 samarium-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 cobalt sulfate solution containing samarium 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, adding the cobalt sulfate solution containing samarium and the sodium hydroxide solution with the volume flow ratio of 1:0.5, and adding 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 samarium-containing cobalt hydroxide slurry;
step 2, ageing the cobalt hydroxide slurry containing samarium obtained in the step 1, dehydrating and filtering the aged cobalt hydroxide slurry by using a centrifugal machine, washing the cobalt hydroxide slurry for 5 times by using deionized water at 86 ℃, wherein the using amount of the deionized water is 30L/kg, drying the washed cobalt hydroxide slurry at 84 ℃, and finally removing iron to obtain cobalt hydroxide powder containing samarium;
and 3, specifically, sequentially calcining the obtained cobalt hydroxide powder containing samarium 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 cobalt oxide doped with samarium.
The samarium-doped cobalt oxide prepared in this example had a sodium content of 290ppm and a tap density of 2.31g/cm3Samarium 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 preparation method of samarium-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 cobalt nitrate solution containing samarium 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, adding the cobalt nitrate solution containing samarium and the sodium hydroxide solution with the volume flow ratio of 1:1, and adding the cobalt nitrate solution containing samarium and the sodium hydroxide solution with the volume flow ratio of 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 samarium-containing cobalt hydroxide slurry;
step 2, ageing the cobalt hydroxide slurry containing samarium obtained in the step 1, dehydrating and filtering the aged cobalt hydroxide slurry by using a centrifugal machine, washing the cobalt hydroxide slurry for 5 times by using deionized water at 86 ℃, wherein the using amount of the deionized water is 30L/kg, drying the washed cobalt hydroxide slurry at 84 ℃, and finally removing iron to obtain cobalt hydroxide powder containing samarium;
and 3, specifically, sequentially calcining the obtained cobalt hydroxide powder containing samarium 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 cobalt oxide doped with samarium.
The samarium-doped cobalt oxide prepared in this example had a sodium content of 290ppm and a tap density of 2.31g/cm3Samarium 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 preparation method of samarium-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 cobalt sulfate solution containing samarium and a sodium hydroxide solution with the concentration of 100-400 g/L into the reaction base liquid in a parallel flow manner during stirringAdding samarium-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 samarium-containing cobalt hydroxide slurry;
step 2, ageing the cobalt hydroxide slurry containing samarium obtained in the step 1, dehydrating and filtering the aged cobalt hydroxide slurry by using a centrifugal machine, washing the cobalt hydroxide slurry for 5 times by using deionized water at 86 ℃, wherein the using amount of the deionized water is 30L/kg, drying the washed cobalt hydroxide slurry at 84 ℃, and finally removing iron to obtain cobalt hydroxide powder containing samarium;
and 3, specifically, sequentially calcining the obtained cobalt hydroxide powder containing samarium 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 cobalt oxide doped with samarium.
The samarium-doped cobalt oxide prepared in this example had a sodium content of 290ppm and a tap density of 2.31g/cm3Samarium 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 samarium-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 cobalt chloride solution containing samarium 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 cobalt chloride solution containing samarium to the sodium hydroxide solution is 1:0.8, and the volume flow ratio of the cobalt chloride solution containing samarium 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 samarium-containing cobalt hydroxide slurry;
step 2, ageing the cobalt hydroxide slurry containing samarium obtained in the step 1, dehydrating and filtering the aged cobalt hydroxide slurry by using a centrifugal machine, washing the cobalt hydroxide slurry for 6 times by using 80 ℃ deionized water, wherein the using amount of the deionized water is 10-50L/kg, drying the washed cobalt hydroxide slurry at 90 ℃, and finally removing iron to obtain cobalt hydroxide powder containing samarium;
and 3, specifically, sequentially calcining the obtained cobalt hydroxide powder containing samarium at the roasting temperature of 10 ℃ for 25min, calcining at the roasting temperature of 60 ℃ for 55min, calcining at the roasting temperature of 200 ℃ for 65min, calcining at the roasting temperature of 400 ℃ for 85min, calcining at the roasting temperature of 600 ℃ for 60min and calcining at the roasting temperature of 750 ℃ for 355min to obtain the cobalt oxide doped with samarium.
The samarium-doped cobalt oxide prepared in this example had a sodium content of 290ppm and a tap density of 2.31g/cm3Samarium 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 samarium-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 cobalt chloride solution containing samarium 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 cobalt chloride solution containing samarium to the sodium hydroxide solution is 1:0.8, and the volume flow ratio of the cobalt chloride solution containing samarium 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 samarium-containing cobalt hydroxide slurry;
step 2, ageing the cobalt hydroxide slurry containing samarium obtained in the step 1, dehydrating and filtering the aged cobalt hydroxide slurry by using a centrifugal machine, washing the cobalt hydroxide 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 cobalt hydroxide slurry at 80 ℃, and finally removing iron to obtain cobalt hydroxide powder containing samarium;
and 3, specifically, sequentially calcining the obtained cobalt hydroxide powder containing samarium 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 to obtain the cobalt oxide doped with samarium.
The samarium-doped cobalt oxide prepared in this example had a sodium content of 290ppm and a tap density of 2.31g/cm3Samarium 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 preparation method of samarium-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 cobalt chloride solution containing samarium 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 cobalt chloride solution containing samarium to the sodium hydroxide solution is 1:0.8, and the volume flow ratio of the cobalt chloride solution containing samarium 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 samarium-containing cobalt hydroxide slurry;
step 2, ageing the cobalt hydroxide slurry containing samarium obtained in the step 1, dehydrating and filtering the aged cobalt hydroxide slurry by using a centrifugal machine, washing the cobalt hydroxide slurry for 4 times by using deionized water at the temperature of 90 ℃, wherein the using amount of the deionized water is 10-50L/kg, drying the washed cobalt hydroxide slurry at the temperature of 80 ℃, and finally removing iron to obtain cobalt hydroxide powder containing samarium;
and 3, specifically, sequentially calcining the obtained cobalt hydroxide powder containing samarium 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 cobalt oxide doped with samarium.
The samarium-doped cobalt oxide prepared in this example had a sodium content of 290ppm and a tap density of 2.31g/cm3Samarium 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 samarium-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 100-400 g/L sodium hydroxide solution containing cobalt samarium acetate solution into the reaction base liquid in a parallel flow manner during stirring, adding 1:1.2 volume flow ratio of the cobalt samarium acetate solution to the sodium hydroxide solution, and taking 10-30 m as the basis3Introducing air or oxygen into the reaction kettle at a speed of/h, and reacting for 32h until the coprecipitation reaction is complete to obtain samarium-containing cobalt hydroxide slurry;
step 2, ageing the cobalt hydroxide slurry containing samarium obtained in the step 1, dehydrating and filtering the aged cobalt hydroxide slurry by using a centrifugal machine, washing the cobalt hydroxide 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 cobalt hydroxide slurry at 86 ℃, and finally removing iron to obtain cobalt hydroxide powder containing samarium;
and 3, specifically, sequentially calcining the obtained cobalt hydroxide powder containing samarium 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 cobalt oxide doped with samarium.
The samarium-doped cobalt oxide prepared in this example had a sodium content of 290ppm and a tap density of 2.31g/cm3Samarium 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 samarium-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 100-400 g/L sodium hydroxide solution containing cobalt samarium acetate solution into the reaction base liquid in a parallel flow manner during stirring, adding 1:1.2 volume flow ratio of the cobalt samarium acetate solution to the sodium hydroxide solution, and taking 10-30 m as the basis3Introducing air or oxygen into the reaction kettle at a speed of/h, and reacting for 32h until the coprecipitation reaction is complete to obtain samarium-containing cobalt hydroxide slurry;
step 2, ageing the cobalt hydroxide slurry containing samarium obtained in the step 1, dehydrating and filtering the aged cobalt hydroxide slurry by using a centrifugal machine, washing the cobalt hydroxide 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 cobalt hydroxide slurry at 86 ℃, and finally removing iron to obtain cobalt hydroxide powder containing samarium;
and 3, specifically, sequentially calcining the obtained cobalt hydroxide powder containing samarium 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 to obtain the cobalt oxide doped with samarium.
The samarium-doped cobalt oxide prepared in this example had a sodium content of 290ppm and a tap density of 2.31g/cm3Samarium 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 samarium-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 strength of 350r/min, a samarium-containing cobalt acetate solution and a sodium hydroxide solution with the concentration of 100-400 g/L are added into the reaction base solution in a parallel flow manner in the stirring process, the volume flow ratio of the samarium-containing cobalt acetate solution to the sodium hydroxide solution is 1:1.2, and the volume flow ratio 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 samarium-containing cobalt hydroxide slurry;
step 2, ageing the cobalt hydroxide slurry containing samarium obtained in the step 1, dehydrating and filtering the aged cobalt hydroxide slurry by using a centrifugal machine, washing the cobalt hydroxide 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 cobalt hydroxide slurry at 86 ℃, and finally removing iron to obtain cobalt hydroxide powder containing samarium;
and 3, specifically, sequentially calcining the obtained cobalt hydroxide powder containing samarium 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 cobalt oxide doped with samarium.
The samarium-doped cobalt oxide prepared in this example had a sodium content of 290ppm and a tap density of 2.31g/cm3Samarium 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 samarium-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 samarium-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 samarium-containing cobalt salt solution, the sodium hydroxide solution and the oxidant to obtain samarium-containing cobalt hydroxide slurry;
step 2, sequentially aging, filtering, washing, drying and deironing the cobalt hydroxide slurry containing samarium obtained in the step 1 to obtain cobalt hydroxide powder containing samarium;
and 3, calcining the cobalt hydroxide powder containing samarium, which is obtained in the step 2, according to a temperature curve to obtain the cobalt oxide doped with samarium.
2. The method for preparing samarium-doped cobalt oxide according to claim 1, wherein the stirring reaction in the step 1 has a stirring intensity of 200 to 400r/min and a stirring time of 10 to 40 h.
3. The method of claim 2, wherein the base solution in step 1 is at least one of ammonia, EDTA, tartaric acid, and citric acid.
4. The method of claim 3 in which the samarium-doped cobalt oxide solution of step 1 is at least one of a cobalt sulfate solution, a cobalt chloride solution, a cobalt nitrate solution, or a cobalt acetate solution.
5. The method of claim 4 in which the samarium-doped cobalt oxide comprises cobalt ions in an amount of from 80 to 150g/L, samarium in an amount of from 0.5 to 1.2g/L, and an additive in an amount of from 1 to 5 g/L.
6. The method for preparing samarium-doped cobalt oxide according to claim 5, wherein 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.
7. The method of claim 6 in which the samarium-doped cobalt oxide of step 1 comprises combining a solution of samarium cobalt salt with hydrogenThe volume flow ratio of the sodium oxide solution is 1: 0.5-1.5, and the volume flow of the oxidant is 10-30 m3/h。
8. The method for preparing samarium-doped cobalt oxide according to any one of claims 1 to 7, wherein the washing solution used for washing the samarium-doped 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 samarium-doped cobalt oxide is calcined in the step 3 according to a temperature curve, specifically, the samarium-doped cobalt hydroxide powder is calcined at a calcination temperature of 500 to 800 ℃ which is divided into 5 to 12 stages.
10. The method according to claim 9, wherein the samarium-doped cobalt oxide is calcined in step 3 according to a temperature profile, and specifically, the samarium-doped cobalt hydroxide powder is calcined at a calcination temperature of 0 to 60 ℃ for 25 to 35min, at a calcination temperature of 60 to 200 ℃ for 55 to 65min, at a calcination temperature of 200 to 400 ℃ for 55 to 65min, at a calcination temperature of 400 to 600 ℃ for 85 to 95min, at a calcination temperature of 600 to 750 ℃ for 55 to 65min, and at a calcination temperature of 750 ℃ for 355 min.
CN201811287907.5A 2018-10-31 2018-10-31 Preparation method of samarium-doped cobalt oxide Withdrawn CN111115700A (en)

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CN103779556A (en) * 2014-01-26 2014-05-07 中信国安盟固利电源技术有限公司 Doped and surface coating co-modified anode material for lithium ion battery and preparation method thereof
CN103904323A (en) * 2012-12-28 2014-07-02 北京当升材料科技股份有限公司 Preparation method for spherical cobalt oxyhydroxide
CN107768646A (en) * 2017-10-23 2018-03-06 兰州金川新材料科技股份有限公司 A kind of cobaltosic oxide preparation method of doped chemical gradient distribution

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CN103904323A (en) * 2012-12-28 2014-07-02 北京当升材料科技股份有限公司 Preparation method for spherical cobalt oxyhydroxide
CN103172118A (en) * 2013-03-19 2013-06-26 南通瑞翔新材料有限公司 Method for preparing spherical cobaltosic oxide and manganese oxide
CN103779556A (en) * 2014-01-26 2014-05-07 中信国安盟固利电源技术有限公司 Doped and surface coating co-modified anode material for lithium ion battery and preparation method thereof
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