CN112499693B - Spherical cobalt carbonate particles compositely stacked by oversized single crystals and preparation method thereof - Google Patents
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Abstract
The invention relates to the technical field of preparation of lithium ion battery anode materials, in particular to battery-grade cobalt carbonate and a preparation method thereof. The invention designs spherical cobalt carbonate particles which are formed by compositely stacking oversized single crystals, wherein micron-sized oversized cobalt carbonate crystal grains are taken as primary particles, the primary particles are strip-shaped single crystal particles with the width of 2-5 mu m and the thickness of 0.2-0.5 mu m, and the primary particles are regularly and densely stacked along the radial growth of spherical secondary particles to form the spherical cobalt carbonate particles. The invention solves the difficult problems of cracking and crushing in the conventional cobalt carbonate calcining process from the material per se, and avoids the defects of low equipment utilization rate, high cost and the like of a low-temperature pre-reaction-high-temperature calcining secondary calcining scheme. The method is applied to the preparation of Lithium Cobaltate (LCO), and the LCO is easier to be subjected to single crystallization and has higher volume energy density and electrochemical stability.
Description
Technical Field
The invention relates to the technical field of preparation of lithium ion battery anode materials, in particular to battery-grade cobalt carbonate and a preparation method thereof.
Background
The cobalt carbonate is used as an important precursor for producing lithium battery materials such as cobaltosic oxide, lithium cobaltate and the like, the property of the cobalt carbonate determines the performance of the materials for producing the batteries to a great extent, the development of 5G mobile phones puts higher requirements on the energy density of lithium cobaltate cathode materials, the particle size of large particles is further improved, the compaction density can be effectively improved, and further the volume energy density is increased, the particle size D50 of the large-particle-size cobaltosic oxide materials for producing the batteries which are used frequently at present is mostly 15-16 micrometers, the large-particle-size cobaltosic oxide materials are formed by calcining the cobalt carbonate with the particle size D50 of 18-20 micrometers, and the cobaltosic oxide in the particle size range is mainly used as a middle-end battery material. In recent years, research on battery materials shows that the battery materials produced by cobaltosic oxide with large particle size have better performance, have higher voltage platform and compaction density, and are more applied to the high-end field. The cobaltosic oxide with large particle size is mainly prepared by calcining cobaltous carbonate with large particle size, so that the quality of the cobaltous carbonate with large particle size plays a decisive role in the performance of the cobaltosic oxide and the battery material.
However, as the particle size of the cobalt carbonate particles increases, the stress generated by crystal transformation in the process of calcining to form cobaltosic oxide becomes large, and CO is decomposed to form CO 2 The impact of the release on the particles is more obvious, so that the cobalt carbonate with large particle size is easy to crack and break in the calcining process, and the product performance is seriously influenced.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, designs a cobalt carbonate precursor taking micron monocrystal granular cobalt carbonate as primary particles and spherical secondary particles, and solves the problem that the cobalt carbonate is easy to crack in the calcining process from the material, thereby avoiding the defects of low equipment utilization rate, high cost and the like of a low-temperature pre-reaction-high-temperature calcining secondary calcining scheme.
In order to achieve the purpose, the spherical cobalt carbonate particles formed by compositely stacking oversized single crystals are designed by taking micron-sized oversized cobalt carbonate crystal grains as primary particles, the primary particles are strip-shaped single crystal particles with the width of 2-5 mu m and the thickness of 0.2-0.5 mu m, and the primary particles are regularly and densely stacked along the radial growth of spherical secondary particles to form the spherical cobalt carbonate particles.
Another object of the present invention is to provide a method for preparing the above spherical cobalt carbonate particles. The method comprises the following specific steps:
step one, raw material preparation:
preparing a soluble cobalt salt into a solution A with the molar concentration of 1-3M, a carbonate solution B with the molar concentration of 2.5-3M and a carbonate solution C with the molar concentration of 1-1.5M;
step two, seed crystal molding:
adding 1-4m into a reaction kettle 3 Bottoming with low-concentration carbonate solution C, heating to 30-50 deg.C, maintaining the temperature, and stirring at high speed at 1-3m 3 Adding the solution A into the reaction kettle at a speed of/h, starting a PLC automatic control system to add the solution B after the pH value in the reaction kettle is reduced to 7.4-7.6, stably controlling the pH value to 7.4-7.6 by adjusting the flow rate of the solution B, stopping stirring after the feeding is finished when the granularity of the cobalt carbonate reaches 3-6 mu m, and completing the preparation of the dispersed sample. Standing and settling the dispersed sample slurry in the kettle, pumping out supernatant, vacating the space for continuous feeding, stopping feeding when the slurry in the kettle is full, standing and settling, pumping out supernatant, continuously feeding, and repeating the operations until the particle size of the seed crystal reaches 8-10 mu m;
step three, synthesizing and growing up:
performing first kettle separation on the seed crystal slurry, namely uniformly dividing two parts and transferring the two parts to a reaction kettle with frame stirring to perform primary grain growth and secondary particle balling repair growth; the two reaction kettles continue to stir for 1-3m under the mild stirring condition respectively 3 Adding the solution A into a reaction kettle at a speed of/h, starting a PLC automatic control system to add the solution B after the pH value in the kettle is reduced to 7.3-7.6, stably controlling the pH value to 7.3-7.6 by adjusting the flow speed of the solution B, and keeping the temperature at 50-60 ℃; stopping feeding after feeding for 2-4 hours, stopping stirring, standing for layering, extracting supernatant, starting stirring, continuing to feed the next round, circulating the feeding until the solid content of the cobalt carbonate slurry in the kettle reaches 600-800 g/L, then performing secondary kettle separation, keeping the reaction condition unchanged after kettle separation, continuing feeding, repeating the operation until the cobalt carbonate reaches the target granularity, obtaining spherical cobalt carbonate slurry after synthesis is finished, and washing, dehydrating and drying the slurry to obtain the spherical cobalt carbonate powder material.
Preferably, the soluble cobalt salt in the first step is one or more of cobalt sulfate, cobalt chloride, cobalt nitrate and the like.
Preferably, in the first step, the soluble carbonate is one or a mixture of sodium carbonate, sodium bicarbonate, ammonium bicarbonate, potassium carbonate, potassium bicarbonate and the like.
Preferably, the high-speed stirring in the step two is three-layer inclined blade propelling type paddle stirring, and the stirring speed is 100-200rpm.
Preferably, the mild stirring intensity in the third step is 20-30rpm.
The median particle diameter D50 of the cobalt carbonate is more than or equal to 18 mu m, the particle size distribution is uniform, the Tap Density (TD) is more than or equal to 1.8g/cm < 3 >, and the production requirement of the high-energy density lithium cobaltate can be met.
The primary single crystal particles of the product are staggered and superposed to form a network skeleton, so that the product has better structural strength; meanwhile, gaps formed by the superposition of primary single crystal particles provide deformation buffer for particle shrinkage caused by crystal form conversion during calcination, the processing performance is improved, the problems of cracking and crushing in the conventional cobalt carbonate calcination process are solved, and the method is applied to the preparation of Lithium Cobaltate (LCO), is easier to be subjected to single crystallization during the preparation of LCO, and has higher volume energy density and electrochemical stability.
In the preparation process, two carbonate solutions with different concentrations are adopted, wherein the low-concentration carbonate solution is used for bottoming to reduce the reaction speed, the nucleation speed is lower than the growth speed, and the sphericity and the particle size distribution uniformity are ensured; the solid content of the subsequent high-concentration carbonate solution is increased, and the productivity is improved. The invention can well control the size of primary single crystal particles and the particle size by adjusting the process conditions of proper temperature, pH value, rotating speed and the like, is favorable for the growth of the primary single crystal particles to obtain strip-shaped single crystal particles, and the primary particles are regularly and densely packed along the radial growth of spherical secondary particles to form spherical cobalt carbonate particles.
Drawings
FIG. 1 is a SEM photograph of example 1 of the present invention;
FIG. 2 is a graph showing a particle size distribution of example 1 of the present invention;
FIG. 3 is a SEM photograph of example 2 of the present invention;
FIG. 4 particle size distribution diagram of example 2 of the present invention.
Detailed Description
Example 1:
dissolving cobalt sulfate in deionized water to prepare a solution A, wherein the concentration of cobalt ions is 120g/L; dissolving ammonium bicarbonate in deionized water to prepare a solution B with the concentration of 220 g/L; dissolving ammonium bicarbonate in deionized water to prepare a solution C with the concentration of 120 g/L.
Priming with solution C, heating to 48 deg.C, circularly maintaining the temperature in water bath, stirring at 150rpm, and stirring at 1.5m 3 Independently adding the solution A at a flow rate of/h until the pH value in the kettle is reduced to 7.6, then starting a PLC automatic control system to add the solution B, stably controlling the pH value to 7.6 by adjusting the flow rate of the solution B, stopping stirring when the feeding is finished when the granularity of the cobalt carbonate reaches 4.3 mu m, and finishing the preparation of the dispersed sample. And standing and settling the dispersed sample slurry in the kettle, removing supernatant, vacating the space, continuing feeding according to the control conditions, stopping feeding when the slurry in the kettle is full, and then circularly and repeatedly carrying out the operations of standing and settling, supernatant extraction, feeding and stopping feeding when the kettle is full until the grain size of the seed crystal reaches 9.0 mu m.
And (3) performing first kettle separation on the seed crystal slurry, namely uniformly dividing two parts and transferring the two parts to a reaction kettle with frame type stirring to perform primary grain growth and secondary grain balling restoration growth. The stirring speed is reduced to 25rpm, the materials are continuously added, the pH value in the reaction process is controlled to be stable at 7.4, and the constant temperature is kept at 55 ℃; and stopping feeding after feeding for 4 hours, stopping stirring, standing for layering, extracting supernatant, starting stirring, continuing to feed the next round, circulating the feeding until the solid content of the cobalt carbonate slurry in the kettle reaches 730g/L, then performing secondary kettle separation, keeping the reaction condition unchanged after kettle separation, continuing feeding, repeating the operation until the cobalt carbonate reaches the target granularity, and obtaining the cobalt carbonate slurry after synthesis is finished.
Washing, dehydrating and drying the slurry to obtain a spherical cobalt carbonate powder material with a median particle diameter D50 of 20.8 mu m and a tap density TD of 1.91g/cm 3 The scanning electron microscope is shown in figure 1, and the particle size distribution is shown in figure 2.
Example 2:
dissolving cobalt chloride in deionized water to prepare a solution A, wherein the concentration of cobalt ions is 150g/L; dissolving ammonium bicarbonate in deionized water to prepare a solution B with the concentration of 220 g/L; dissolving ammonium bicarbonate in deionized water to prepare a solution C with the concentration of 120 g/L.
Bottoming with solution C, heating to 45 deg.C, circularly maintaining the temperature with water bath, stirring at 150rpm, and stirring at 2m 3 Independently adding the solution A at a flow rate of/h until the pH value in the kettle is reduced to 7.4, then starting a PLC automatic control system to add the solution B, stably controlling the pH value to 7.4 by adjusting the flow rate of the solution B, stopping stirring when the feeding is finished when the granularity of the cobalt carbonate reaches 4.0 mu m, and completing the preparation of the dispersed sample. Standing and settling the dispersed sample slurry in the kettle, removing supernatant, vacating space, continuing feeding according to the control conditions, stopping feeding when the slurry in the kettle is full, and then circularly repeating the operations of standing and settling, supernatant extracting, feeding, stopping feeding when the kettle is full, until the grain size of the seed crystal reaches 8.5 mu m.
And (3) performing first kettle separation on the seed crystal slurry, namely uniformly dividing two parts and transferring the two parts to a reaction kettle with frame type stirring to perform primary grain growth and secondary grain balling restoration growth. The stirring speed is reduced to 30rpm, the materials are continuously added, the pH value in the reaction process is controlled to be stable at 7.5, and the constant temperature is 60 ℃; and stopping feeding after feeding for 3 hours, stopping stirring, standing for layering, extracting supernatant, starting stirring, continuing to feed the next round, circulating the feeding until the solid content of the cobalt carbonate slurry in the kettle reaches 650g/L, then performing secondary kettle separation, keeping the reaction condition unchanged after kettle separation, continuing feeding, repeating the operation until the cobalt carbonate reaches the target granularity, and obtaining the cobalt carbonate slurry after synthesis is finished.
Washing, dehydrating and drying the slurry to obtain spherical cobalt carbonate powder material with the median particle diameter D50 of 18.5 mu m and the tap density TD of 1.83g/cm 3 The scanning electron microscope is shown in figure 3, and the particle size distribution is shown in figure 4.
Example 3:
dissolving cobalt sulfate in deionized water to prepare a solution A, wherein the concentration of cobalt ions is 90g/L; sodium bicarbonate is dissolved in deionized water to prepare a solution B with the concentration of 235g/L, and sodium bicarbonate is dissolved in deionized water to prepare a solution C with the concentration of 100 g/L.
Bottoming with solution C, heating to 50 deg.C, circularly maintaining the temperature with water bath, stirring at 150rpm, and stirring at 3m 3 Independently adding the solution A at a flow rate of/h until the pH value in the kettle is reduced to 7.5, then starting a PLC automatic control system to add the solution B, stably controlling the pH value to 7.5 by adjusting the flow rate of the solution B, stopping stirring when the feeding is finished when the granularity of the cobalt carbonate reaches 5.0 mu m, and completing the preparation of the dispersed sample. And standing and settling the dispersed sample slurry in the kettle, removing supernatant, vacating the space, continuing feeding according to the control conditions, stopping feeding when the slurry in the kettle is full, and then circularly and repeatedly carrying out the operations of standing and settling, supernatant extraction, feeding and stopping feeding when the kettle is full until the grain size of the seed crystal reaches 9.5 mu m.
Performing first kettle division on the seed crystal slurry, namely uniformly dividing two parts and transferring the two parts to a reaction kettle with frame type stirring for primary grain growth and secondary particle balling restoration growth, reducing the stirring speed to 30rpm, continuously feeding, controlling the pH value in the reaction process to be stable at 7.5, and keeping the temperature at 58 ℃; stopping feeding after feeding for 2 hours, stopping stirring, standing for layering, extracting supernatant, starting stirring, continuing to feed the next round, circulating the feeding until the solid content of the cobalt carbonate slurry in the kettle reaches 780g/L, then performing secondary kettle separation, keeping the reaction condition unchanged after kettle separation, continuing feeding, repeating the operation until the cobalt carbonate reaches the target granularity, and obtaining the cobalt carbonate slurry after synthesis is finished.
Washing, dehydrating and drying the slurry to obtain a spherical cobalt carbonate powder material with a median particle diameter D50 of 19.8 mu m and a tap density TD of 1.88g/cm 3 。
Claims (6)
1. A spherical cobalt carbonate particle formed by compound accumulation of oversized single crystals is characterized in that: micron-sized oversized cobalt carbonate crystal grains are used as primary particles, the primary particles are strip-shaped single crystal particles with the width of 2-5 mu m and the thickness of 0.2-0.5 mu m, and the primary particles grow regularly and densely along the radial direction of spherical secondary particles to form spherical cobalt carbonate particles.
2. The method for preparing the spherical cobalt carbonate particles compositely stacked by the ultra-large single crystals as claimed in claim 1, wherein the method comprises the following steps: the method comprises the following specific steps:
step one, raw material preparation:
preparing a soluble cobalt salt into a solution A with the molar concentration of 1-3M, a carbonate solution B with the molar concentration of 2.5-3M and a carbonate solution C with the molar concentration of 1-1.5M;
step two, seed crystal forming:
adding 1-4m into a reaction kettle 3 Bottoming with low-concentration carbonate solution C, heating to 30-50 deg.C, maintaining the temperature, and stirring at high speed at 1-3m 3 Adding the solution A into a reaction kettle at a speed of/h, starting a PLC automatic control system to add the solution B after the pH value in the kettle is reduced to 7.4-7.6, stably controlling the pH value to 7.4-7.6 by adjusting the flow rate of the solution B, stopping stirring after the feeding is finished when the granularity of the cobalt carbonate reaches 3-6 mu m, and finishing the preparation of a dispersed sample; standing and settling the dispersed sample slurry in the kettle, pumping out supernatant, vacating the space and continuing feeding, stopping feeding when the slurry in the kettle is full, standing and settling, pumping out supernatant, continuing feeding, and repeating the operations until the grain size of the seed crystal reaches 8-10 mu m;
step three, synthesizing and growing up:
performing first kettle separation on the seed crystal slurry, namely uniformly dividing two parts and transferring the two parts to a frame-type stirring reaction kettle to perform primary grain growth and secondary grain balling restoration growth; the two reaction kettles continue to stir for 1-3m under the mild stirring condition respectively 3 Adding the solution A into a reaction kettle at a speed of/h, starting a PLC automatic control system to add the solution B after the pH value in the kettle is reduced to 7.3-7.6, stably controlling the pH value to 7.3-7.6 by adjusting the flow speed of the solution B, and keeping the temperature at 50-60 ℃; stopping feeding after feeding for 2-4 hours, stopping stirring, standing for layering, extracting supernatant, starting stirring, continuing to feed the next round, circulating the feeding until the solid content of the cobalt carbonate slurry in the kettle reaches 600-800 g/L, then performing secondary kettle separation, keeping the reaction condition unchanged after kettle separation, continuing feeding, repeating the operation until the cobalt carbonate reaches the target granularity, obtaining spherical cobalt carbonate slurry after synthesis is finished, and washing, dehydrating and drying the slurry to obtain the spherical cobalt carbonate powder material.
3. The method for preparing the spherical cobalt carbonate particles compositely stacked by the ultra-large single crystals as claimed in claim 2, wherein the method comprises the following steps: in the first step, the soluble cobalt salt is one or a mixture of cobalt sulfate, cobalt chloride and cobalt nitrate.
4. The method for preparing the spherical cobalt carbonate particles compositely stacked by the ultra-large single crystals as claimed in claim 2, wherein the method comprises the following steps: in the step one, the carbonate is one or a mixture of more of sodium carbonate, sodium bicarbonate, ammonium bicarbonate, potassium carbonate and potassium bicarbonate.
5. The method for preparing the spherical cobalt carbonate particles compositely stacked by the ultra-large single crystals as claimed in claim 2, wherein the method comprises the following steps: the high-speed stirring in the step two is three-layer inclined blade propelling type paddle stirring, and the stirring speed is 100-200rpm.
6. The method for preparing the spherical cobalt carbonate particles compositely stacked by the ultra-large single crystals as claimed in claim 2, wherein: the mild stirring intensity in the third step is 20-30rpm.
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| CN113213558B (en) * | 2021-07-09 | 2021-09-14 | 金驰能源材料有限公司 | Large-particle spherical cobalt carbonate precursor, preparation method thereof and preparation method of cobaltosic oxide |
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