CN113292106B - Three-time calcination preparation method of large-particle-size aluminum-doped cobaltosic oxide - Google Patents
Three-time calcination preparation method of large-particle-size aluminum-doped cobaltosic oxide Download PDFInfo
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Abstract
The invention belongs to the technical field of preparation methods of battery-grade cobaltosic oxide, and discloses a three-time calcination preparation method of aluminum-doped cobaltosic oxide with large particle size, which comprises the following steps: adding cobalt-aluminum solution and precipitant solution into a reaction kettle containing base solution simultaneously for precipitation reaction, and controlling the pH value to be 7.0-7.3 to obtain slurry seed crystals; precipitating the slurry seed crystal to obtain a precipitated slurry, adding a cobalt-aluminum solution and a precipitator solution into the precipitated slurry to continue the precipitation reaction, and controlling the pH value to be 7.3-7.5 to obtain a slurry finished product; centrifugally washing and dehydrating the slurry finished product to obtain a wet material finished product; and (3) carrying out low-temperature calcination on the wet material finished product in a roller kiln twice, and then carrying out high-temperature calcination in a rotary kiln to obtain the large-particle-size aluminum-doped cobaltosic oxide. The preparation method of the invention can produce the spherical large-particle-size aluminum-doped cobaltosic oxide with high tap density in large scale and batch without cracking phenomenon on the surface of the product.
Description
Technical Field
The invention belongs to the technical field of preparation methods of battery-grade cobaltosic oxide, and particularly relates to a three-time calcination preparation method of aluminum-doped cobaltosic oxide with large particle size.
Background
Along with the continuous development of society, the technological speed is increased, the informationized society has come, the continuous update of electronic products is promoted, and lithium battery products applied to the electronic aspect are also layered endlessly. Since the discharge capacity, voltage stability, cycle life, etc. of lithium cobaltate basically reach satisfactory states, lithium cobaltate is still used as a main stream product in lithium battery products nowadays.
The lithium cobaltate is mainly formed by sintering cobaltosic oxide and lithium carbonate or lithium hydroxide, wherein the cobaltosic oxide is obtained by roasting cobalt carbonate, so that the most main factors for determining the quality of the lithium cobaltate are the cobaltosic oxide, the tap density, the specific surface area, the morphology and other properties of the cobaltate have important influence on the final cathode material, but the stability of the lithium cobaltate is poor, the service life of the prepared lithium cobaltate battery is shorter, and various modification measures and methods are researched and adopted in order to solve the problems that the lithium cobaltate has higher requirements on the light weight, the high capacity and the like of digital products.
In which a metal element such as aluminum, magnesium, etc. is doped into tricobalt tetraoxide, which not only can reduce the application of cobalt metal, but also can improve the stability of lithium cobaltate lattice, so tricobalt tetraoxide doped with a metal element becomes a research hot spot.
The preparation methods of the metal element doped cobaltosic oxide commonly used by most manufacturers at present comprise a solid-phase thermal decomposition method, a hydrothermal method, a sol-gel method and the like, only a small number of suppliers can produce the metal element doped large-particle-size cobaltosic oxide with the particle size of more than 15 mu m, the production methods are difficult to produce in a large scale, the produced metal element doped large-particle-size cobaltosic oxide is uneven in sphericity and low in tap density, and more importantly, serious cracking phenomenon exists, which can influence the capacity of lithium cobaltate prepared by calcining the metal element doped large-particle-size cobaltosic oxide, and further influence the application of the metal element doped large-particle-size cobaltosic oxide in the aspect of lithium ion battery.
Disclosure of Invention
In view of the above, the present invention provides a three-time calcination preparation method of large-particle-size aluminum-doped cobaltosic oxide, in order to solve the problem that the surface cracking phenomenon of the large-particle-size aluminum-doped cobaltosic oxide prepared by the current production method is serious.
The invention is realized by adopting the following technical scheme: a three-time calcination preparation method of large-particle-size aluminum-doped cobaltosic oxide comprises the following steps:
s1, respectively preparing cobalt-aluminum solution containing cobalt ions and aluminum ions, and preparing precipitant solution containing carbonate ions for later use;
s2, adding pure water and a precipitant solution into a reaction kettle as base solution, stirring at 50-60 ℃, simultaneously adding the cobalt aluminum solution and the precipitant solution into the reaction kettle, performing precipitation reaction, adjusting the flow of the precipitant solution, controlling the pH of the reaction to be 7.0-7.3, adjusting the cobalt flow once every 4-8 hours of reaction at intervals, and adjusting the adjustment amount to be 40-60L/h each time until slurry seed crystals with target granularity are obtained;
s3, precipitating the slurry seed crystal to obtain a precipitated slurry, simultaneously adding the cobalt aluminum solution and the precipitant solution into the precipitated slurry to continue the precipitation reaction, controlling the pH of the reaction to be 7.3-7.5, adjusting the flow of the precipitant solution, adjusting the flow of the cobalt aluminum solution once every 12-16 h, and adjusting the amount of each time to be 40-60L/h until a slurry finished product with target granularity is obtained;
s4, centrifuging, washing and dehydrating the slurry finished product to obtain a wet material finished product;
s5, calcining the wet material finished product in a roller kiln at a low temperature twice to obtain an aluminum-doped cobaltosic oxide semi-finished product;
and S6, calcining the aluminum-doped cobaltosic oxide semi-finished product in a rotary kiln at high temperature to obtain the aluminum-doped cobaltosic oxide.
Preferably, the low temperature calcination conditions in S5 are: calcining for 4-6 h at 150-250 ℃; and calcining for 6-8 hours at 350-450 ℃ to obtain the aluminum-doped cobaltosic oxide semi-finished product.
Preferably, the high temperature calcination conditions in S6: calcining for 2-5 h at 700-750 ℃ to obtain aluminum-doped cobaltosic oxide.
Preferably, in the step S1, the concentration of cobalt ions in the cobalt-aluminum solution is 100 to 150g/L, and the concentration of aluminum ions is 0.5 to 1g/L.
Preferably, the precipitant solution is one or at least two of ammonium bicarbonate solution, ammonium carbonate solution, sodium bicarbonate solution and sodium carbonate solution, and the concentration of carbonate ions in the precipitant solution is 200-250 g/L.
Preferably, in the step S2, the flow rate of the cobalt-aluminum solution is 200-400L/h, and the flow rate of the precipitant solution is 900-1500L/h.
In a specific example, in the case of S2, the flow rate of the cobalt-aluminum solution before adjustment is usually ensured to be 200 to 400L/h, but in order to ensure the slurry seed particle size, the flow rate of the cobalt-aluminum solution after adjustment is also preferably ensured to be 200 to 400L/h.
Preferably, in the step S2, the process of preparing the base solution is as follows: 3-5 m 3 Adding pure water into a reaction kettle, heating to 50-60 ℃, adding 50-100L of the precipitant solution, and stirring at 1000-1500 rpm.
Preferably, in the step S3, the flow rate of the cobalt-aluminum solution is 200-300L/h, and the flow rate of the precipitant solution is 200-300L/h.
In a specific example, in the case of S3, the flow rate of the cobalt-aluminum solution before adjustment is usually ensured to be 200 to 300L/h, but in order to ensure the slurry seed particle size, the flow rate of the cobalt-aluminum solution after adjustment is also preferably ensured to be 200 to 300L/h.
Preferably, the step S3 further includes the following steps:
heating the precipitation slurry to 30-50 ℃, adding the precipitant solution, stirring at 100-500 rpm, and uniformly mixing for later use; wherein the volume ratio between the precipitation slurry and the precipitant solution is 1.5: (0.05-0.1).
Preferably, in the step S4, the slurry finished product is pumped to a centrifuge, washed for 3 to 6 times by adopting water with the temperature of 60 to 80 ℃ and dehydrated to obtain a wet material finished product.
Compared with the prior art, the invention has the beneficial effects that by adopting the scheme, the invention has the following advantages:
(1) Because the preparation method of the invention prepares the base solution, the reaction pH is controlled by controlling the flow of the precipitant solution, the granularity and sphericity of the product are controlled by controlling the flow of the cobalt-aluminum solution, and the large-grain-diameter aluminum-doped cobaltosic oxide can be successfully prepared by combining less parameters such as reaction time, reaction temperature and the like, so the preparation method of the invention is easy for batch and large-scale production; and the performance of the products generated in large scale is also relatively uniform;
(2) Firstly, preparing slurry seed crystals with target granularity, namely spherical aluminum-doped cobalt carbonate seed crystals; then, continuing to neutralize the precipitation reaction through the spherical aluminum-doped cobalt carbonate seed crystal to prepare a slurry finished product with target granularity, namely the spherical aluminum-doped cobalt carbonate slurry finished product; finally, the aluminum-doped cobaltosic oxide with large particle size is successfully prepared through low-temperature twice calcination and one-time high-temperature calcination. The detection shows that the large-particle-size aluminum-doped cobaltosic oxide prepared by the method is of a spherical structure, has good sphericity, has the particle size of about 18 mu m, is uniform in particle size distribution, has no cracking phenomenon on the surface of the product, and has high tap density.
Drawings
FIG. 1 is a scanning electron microscope image of large-particle-size aluminum-doped cobaltosic oxide prepared by the three-time calcination preparation method of large-particle-size aluminum-doped cobaltosic oxide in example 2 of the present invention;
FIG. 2 is another scanning electron microscope image of the large-particle-size aluminum-doped cobaltosic oxide prepared by the three-calcination preparation method of the large-particle-size aluminum-doped cobaltosic oxide of example 2 of the present invention;
FIG. 3 is a scanning electron microscope image of the large-particle-size aluminum-doped tricobalt tetraoxide prepared by the three-calcination preparation method of the large-particle-size aluminum-doped tricobalt tetraoxide of comparative example 1;
FIG. 4 is another scanning electron microscope image of the large-particle-diameter aluminum-doped tricobalt tetraoxide prepared by the three-calcination preparation method of the large-particle-diameter aluminum-doped tricobalt tetraoxide of comparative example 1.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In the following examples, cobalt salts which can be completely ionized in water such as cobalt chloride, cobalt sulfate or cobalt nitrate are used in preparing a cobalt-aluminum solution containing cobalt ions and aluminum ions; the aluminum salt used may be an aluminum salt capable of ionization in water such as aluminum sulfate.
In the following examples, a salt capable of ionizing carbonate ions in water is used as a solute in the preparation of a precipitant solution containing carbonate ions, and may be, for example, ammonium bicarbonate or sodium bicarbonate.
In the following embodiments, the flow rate of the cobalt-aluminum solution is adjusted every time at a certain interval, which means that the flow rate of the cobalt-aluminum solution is continuously increased on the basis of the original flow rate of the cobalt-aluminum solution; for example, the original flow rate of the cobalt-aluminum solution is 200L/h, the flow rate of the cobalt-aluminum solution is adjusted at intervals of 4h, the adjustment amount is 40L/h each time, and the flow rate of the adjusted cobalt-aluminum solution is 240L/h.
Example 1
The embodiment provides a three-time calcination preparation method of large-particle-size aluminum-doped cobaltosic oxide, which comprises the following steps:
s1, respectively preparing cobalt-aluminum solution containing cobalt ions and aluminum ions, and preparing ammonium bicarbonate solution with the concentration of 200g/L for later use; wherein, in the cobalt-aluminum solution, the concentration of cobalt ions is 100g/L, and the concentration of aluminum ions is 0.5g/L;
s2, selecting 8m 3 The reaction vessel was used as a reaction vessel, and 3m of the catalyst was charged into the reaction vessel 3 Heating to 50 ℃, adding 50L of ammonium bicarbonate solution prepared in the step S1 into a reaction kettle, and stirring at a rotating speed of 1000rpm for later use;
adding the cobalt-aluminum solution and the ammonium bicarbonate solution prepared in the step S1 into the reaction kettle at the same time, continuously stirring, and performing neutralization precipitation reaction, wherein the flow of the initial cobalt-aluminum solution is 200L/h, the flow of the ammonium bicarbonate is adjusted to 900-1500L/h, the reaction pH is controlled to 7.0-7.3, the flow of the cobalt-aluminum solution is adjusted once every 4h of reaction, and the adjustment (namely the increase) amount is 40L/h each time until slurry seed crystals with target granularity are obtained;
s3, precipitating the slurry seed crystal prepared in the step S2 to obtain precipitated slurry; will be 1.5m 3 Heating the precipitation slurry to 30 ℃, adding 50L of ammonium bicarbonate solution prepared in the step S1, and stirring and mixing uniformly at a rotating speed of 100 rpm; then, adding cobalt-aluminum solution and precipitant solution simultaneously to continue precipitation reaction, wherein the flow rate of the initial cobalt-aluminum solution is 200L/h, the flow rate of ammonium bicarbonate solution is adjusted to be 200-300L/h, the pH of the reaction is controlled to be 7.3-7.5, the flow rate of the cobalt-aluminum solution is adjusted once every 12h of reaction, and the adjustment is performed every timeI.e. increasing) the amount to 40L/h until a slurry finished product with target granularity is obtained;
s4, pumping the slurry finished product with complete reaction to a centrifugal machine, washing the centrifugal machine for five times according to a program, 5min each time, and using hot water for 2m 3 The temperature of the hot water is 60 ℃, and then the wet material finished product is obtained after dehydration;
s5, directly adding the wet material finished product into a sagger of a roller kiln, wherein the roller kiln comprises a temperature zone I and a temperature zone II, the temperature of the temperature zone I is 150 ℃, and the temperature of the temperature zone II is 350 ℃; the retention time of the sagger in the temperature zone I is 6 hours, and the retention time of the sagger in the temperature zone II is 8 hours, so that an aluminum-doped cobaltosic oxide semi-finished product is obtained; wherein, the sagger is from the temperature zone I to the temperature zone II at a speed of 1.8m/min, and each sagger is filled with 6-10 kg of wet material finished products;
s6, feeding the aluminum-doped cobaltosic oxide semi-finished product into a rotary kiln through a spiral feeding device at a feeding rate of 150kg/h, and performing high-temperature calcination, wherein the high-temperature calcination temperature is 700 ℃, the high-temperature calcination time is 5h, and then discharging, screening and removing iron to obtain the aluminum-doped cobaltosic oxide.
The aluminum-doped cobaltosic oxide prepared in the embodiment is detected, and the tap density is found to be 2.63g/cm 3 As can be seen from a scanning electron microscope used for shooting, the surface of the aluminum-doped cobaltosic oxide prepared by the embodiment has no cracking phenomenon, the particles are in a standard sphere shape, the particle size is about 18 mu m, and the aluminum-doped cobaltosic oxide prepared by the embodiment is large.
Example 2
The embodiment provides a three-time calcination preparation method of large-particle-size aluminum-doped cobaltosic oxide, which comprises the following steps:
s1, respectively preparing cobalt-aluminum solution containing cobalt ions and aluminum ions, and preparing ammonium bicarbonate solution with the concentration of 220g/L for later use; wherein, in the cobalt-aluminum solution, the concentration of cobalt ions is 130g/L, and the concentration of aluminum ions is 0.75g/L;
s2, selecting 8m 3 The reaction vessel was used as a reaction vessel, and 4m of the catalyst was charged into the reaction vessel 3 Heating to 55 ℃, adding 75L of ammonium bicarbonate solution prepared in the step S1 into a reaction kettle,stirring at 1200rpm for later use;
adding the cobalt-aluminum solution and the ammonium bicarbonate solution prepared in the step S1 into the reaction kettle at the same time, continuously stirring, and performing neutralization precipitation reaction, wherein the flow of the cobalt-aluminum solution is 200-400L/h in the reaction process, and the pH of the reaction is controlled to be 7.0-7.3 by adjusting the flow of the ammonium bicarbonate to 900-1500L/h, and in addition, the flow of the cobalt-aluminum solution is adjusted once every 6h of reaction at intervals, and the adjustment (namely the increase) amount is 50L/h each time until slurry seed crystals with target granularity are obtained;
s3, precipitating the slurry seed crystal prepared in the step S2 to obtain precipitated slurry; will be 1.5m 3 Heating the precipitation slurry to 40 ℃, adding 100L of ammonium bicarbonate solution prepared in the step S1, and stirring and mixing uniformly at a rotating speed of 300 rpm; then, simultaneously adding cobalt-aluminum solution and precipitant solution to continue the neutralization precipitation reaction, wherein the flow rate of the cobalt-aluminum solution in the reaction process is 200-300L/h, the reaction pH is controlled to be 7.3-7.5 by adjusting the flow rate of the ammonium bicarbonate solution to be 200-300L/h, and in addition, the flow rate of the cobalt-aluminum solution is adjusted once every 14h of reaction interval, and the adjustment (namely the increase) amount is 50L/h each time until a slurry finished product with target granularity is obtained;
s4, pumping the slurry finished product with complete reaction to a centrifugal machine, washing the centrifugal machine for five times according to a program, 5min each time, and using hot water for 2m 3 The temperature of the hot water is 70 ℃, and then the wet material finished product is obtained after dehydration;
s5, directly adding the wet material finished product into a sagger of a roller kiln, wherein the roller kiln comprises a temperature zone I and a temperature zone II, the temperature of the temperature zone I is 200 ℃, and the temperature of the temperature zone II is 400 ℃; the retention time of the sagger in the temperature zone I is 5 hours, and the retention time of the sagger in the temperature zone II is 7 hours, so that an aluminum-doped cobaltosic oxide semi-finished product is obtained; wherein, the sagger is from the temperature zone I to the temperature zone II at a speed of 1.8m/min, and each sagger is filled with 6-10 kg of wet material finished products;
s6, feeding the aluminum-doped cobaltosic oxide semi-finished product into a rotary kiln through a screw feeding device at a feeding rate of 200kg/h, and performing high-temperature calcination, wherein the high-temperature calcination temperature is 730 ℃, the high-temperature calcination time is 4h, and then discharging, screening and removing iron to obtain the aluminum-doped cobaltosic oxide.
The aluminum-doped cobaltosic oxide prepared in the embodiment is detected, and the tap density is found to be 2.51g/cm 3 As can be seen from a scanning electron microscope (shown in FIG. 1 and FIG. 2) used for photographing, the surface of the aluminum-doped cobaltosic oxide prepared by the embodiment has no cracking phenomenon, the particles are in a relatively standard sphere shape, and the particle size is about 18 mu m, namely, the aluminum-doped cobaltosic oxide prepared by the embodiment is large.
Example 3
The embodiment provides a three-time calcination preparation method of large-particle-size aluminum-doped cobaltosic oxide, which comprises the following steps:
s1, respectively preparing cobalt-aluminum solution containing cobalt ions and aluminum ions, and preparing ammonium bicarbonate solution with the concentration of 250g/L for later use; wherein, in the cobalt-aluminum solution, the concentration of cobalt ions is 150g/L, and the concentration of aluminum ions is 1g/L;
s2, selecting 8m 3 The reaction vessel of (2) was used as a reaction vessel, and 5m of the catalyst was added to the reaction vessel 3 Heating to 60 ℃, adding 100L of ammonium bicarbonate solution prepared in the step S1 into a reaction kettle, and stirring at a rotating speed of 1500rpm for later use;
adding the cobalt-aluminum solution and the ammonium bicarbonate solution prepared in the step S1 into the reaction kettle at the same time, continuously stirring, and performing neutralization precipitation reaction, wherein the flow of the initial cobalt-aluminum solution is 400L/h, the flow of the ammonium bicarbonate is adjusted to 900-1500L/h, the pH of the reaction is controlled to 7.0-7.3, the flow of the cobalt-aluminum solution is adjusted once every 8h of reaction, and the adjustment (namely the increase) amount is 60L/h each time until slurry seed crystals with target granularity are obtained;
s3, precipitating the slurry seed crystal prepared in the step S2 to obtain precipitated slurry; will be 1.5m 3 Heating the precipitation slurry to 50 ℃, adding 100L of ammonium bicarbonate solution prepared in the step S1, and stirring and mixing uniformly at a rotating speed of 500 rpm; then, adding cobalt-aluminum solution and precipitant solution at the same time to continue neutralization precipitation reaction, wherein the flow rate of the initial cobalt-aluminum solution is 300L/h, the flow rate of ammonium bicarbonate solution is adjusted to be 200-300L/h, the pH of the reaction is controlled to be 7.3-7.5, the flow rate of the cobalt-aluminum solution is adjusted once every 16h of reaction (namelyIncreasing the amount to 60L/h to obtain a slurry finished product;
s4, pumping the slurry finished product with complete reaction to a centrifugal machine, washing the centrifugal machine for five times according to a program, 5min each time, and using hot water for 2m 3 The temperature of the hot water is 80 ℃, and then the wet material finished product is obtained after dehydration;
s5, directly adding the wet material finished product into a sagger of a roller kiln, wherein the roller kiln comprises a temperature zone I and a temperature zone II, the temperature of the temperature zone I is 250 ℃, and the temperature of the temperature zone II is 450 ℃; the retention time of the sagger in the temperature zone I is 4 hours, and the retention time of the sagger in the temperature zone II is 6 hours, so that an aluminum-doped cobaltosic oxide semi-finished product is obtained; wherein, the sagger is from the temperature zone I to the temperature zone II at a speed of 1.8m/min, and each sagger is filled with 6-10 kg of wet material finished products;
s6, feeding the aluminum-doped cobaltosic oxide semi-finished product into a rotary kiln through a spiral feeding device at the feeding rate of 250kg/h, and performing high-temperature calcination, wherein the high-temperature calcination temperature is 750 ℃, the high-temperature calcination time is 2h, and then discharging, screening and removing iron to obtain the aluminum-doped cobaltosic oxide.
The aluminum-doped cobaltosic oxide prepared in the embodiment is detected, and the tap density is found to be 2.59g/cm 3 As can be seen from a scanning electron microscope used for shooting, the surface of the aluminum-doped cobaltosic oxide prepared by the embodiment has no cracking phenomenon, the particles are in a standard sphere shape, the particle size is about 18 mu m, and the aluminum-doped cobaltosic oxide prepared by the embodiment is large.
Comparative example 1
The comparative example provides a preparation method of large-particle-size aluminum-doped cobaltosic oxide, which comprises the following steps:
s1, respectively preparing cobalt-aluminum solution containing cobalt ions and aluminum ions, and preparing ammonium bicarbonate solution with the concentration of 220g/L for later use; wherein, in the cobalt-aluminum solution, the concentration of cobalt ions is 130g/L, and the concentration of aluminum ions is 0.75g/L;
s2, selecting 8m 3 The reaction vessel was used as a reaction vessel, and 4m of the catalyst was charged into the reaction vessel 3 Heating to 55deg.C, adding 75L ammonium bicarbonate solution prepared in step S1 into the reaction kettle, stirring at 1200rpm for use；
Adding the cobalt-aluminum solution and the ammonium bicarbonate solution prepared in the step S1 into the reaction kettle at the same time, continuously stirring, and performing neutralization precipitation reaction, wherein the flow of the cobalt-aluminum solution is 200-400L/h, the flow of the ammonium bicarbonate is adjusted to 900-1500L/h, the reaction pH is controlled to 7.0-7.3, the flow of the cobalt-aluminum solution is adjusted once every 16h interval, the flow adjustment (namely the increase) amount of the cobalt-aluminum solution is 40L/h every time, and the reaction is performed for 100h, so that spherical slurry seed crystals with target granularity are obtained;
s3, precipitating the slurry seed crystal prepared in the step S2 to obtain precipitated slurry; heating the precipitation slurry to 40 ℃, adding 100L of ammonium bicarbonate solution prepared in the step S1, and stirring and mixing uniformly at a rotating speed of 300 rpm; then, simultaneously adding cobalt-aluminum solution and precipitant solution to continue the neutralization precipitation reaction, wherein the flow rate of the cobalt-aluminum solution is 200-300L/h, the flow rate of ammonium bicarbonate solution is adjusted to be 200-300L/h, the pH of the reaction is controlled to be 7.3-7.5, the flow rate of the cobalt-aluminum solution is adjusted once every 22h, the flow rate of the cobalt-aluminum solution is adjusted every time, and the reaction is carried out for 100h to obtain a spherical slurry finished product with target granularity;
s4, pumping the slurry finished product with complete reaction to a centrifugal machine, washing the centrifugal machine for five times according to a program, 5min each time, and using hot water for 2m 3 The temperature of the hot water is 70 ℃, and then the wet material finished product is obtained after dehydration;
s5, throwing wet material finished products into a rotary kiln through a spiral feeding device, and adjusting the temperature of the rotary kiln to a temperature zone I:450 ℃; warm zone II:500 ℃; temperature zone III:630 ℃; temperature zone IV:730 deg.c; calcining the wet material finished product in the temperature zone 1-IV for 4h,5h,7h and 4h respectively, discharging after the calcining is finished, sieving by a 400-mesh vibrating screen, and removing iron to obtain the aluminum-doped cobaltosic oxide.
The aluminum-doped cobaltosic oxide prepared in comparative example 1 was tested and found to have a tap density of 2.2g/cm 3 As can be seen from a scanning electron microscope (FIGS. 3 and 4) photographed, although the aluminum-doped tricobalt tetraoxide prepared by the present example is relatively standard spherical and has a particle diameter of about 18 μm, the surface has an obvious cracking appearance, and as can be seen from FIG. 4, mostThe surface of several aluminum-doped tricobalt tetraoxides has the problem of cracking.
Comparing comparative example 2 with example 2, the main difference is that the post calcination process of the wet material finished product is different, and comparing the result of this comparative example with the result of example 2, it is clear that the aluminum-doped cobaltosic oxide prepared by the preparation method of this example has a relatively standard spherical appearance, a particle size of about 18 μm, that is, meets the requirement of large particle size of the aluminum-doped cobaltosic oxide in actual production, and more importantly, the surface of the aluminum-doped cobaltosic oxide prepared by the method of example 2 has no cracking phenomenon, and the tap density is higher than that of the product of comparative example 1.
Comparative example 2
The wet material finished product obtained in the step S4 of the embodiment 2 is calcined through the following procedures:
directly adding the wet material finished product into a roller kiln for three times of calcination, wherein the roller kiln comprises a temperature zone I, a temperature zone II and a temperature zone III, the temperature of the temperature zone I is 200, the temperature of the temperature zone II is 400, and the temperature of the temperature zone III is 730; the retention time of the sagger in the temperature zone I is 5h, the retention time of the sagger in the temperature zone II is 7h, and the retention time of the sagger in the temperature zone III is 4h, so that the aluminum-doped cobaltosic oxide is obtained; wherein, the sagger is from the temperature zone I to the temperature zone II and from the temperature zone II to the temperature zone III at the speed of 1.8m/min, and each sagger is filled with 6-10 kg of wet material finished products.
The aluminum-doped cobaltosic oxide prepared in comparative example 2 was examined to find that the tap density of the aluminum-doped cobaltosic oxide of comparative example 2 was 2.43g/cm 3 As can be seen from a photographed scanning electron microscope, the aluminum-doped tricobalt tetraoxide prepared by comparative example 2 has a poor sphericity and non-uniform particle size although it hardly has a cracking problem on the surface.
Comparative example 3
The wet material finished product obtained in the step S4 of the embodiment 2 is calcined through the following procedures:
directly adding the wet material finished product into a rotary kiln for three times of calcination, and firstly calcining for 5 hours under the condition of 200 finished products; then, at 400, calcining for 7 hours; finally, at 730, calcination is performed for 4 hours to obtain aluminum-doped cobaltosic oxide.
The aluminum-doped cobaltosic oxide prepared in comparative example 3 was examined to find that the tap density of the aluminum-doped cobaltosic oxide of comparative example 3 was 2.02g/cm 3 As can be seen from a scanning electron microscope used for shooting, the aluminum-doped cobaltosic oxide prepared in the comparative example 3 has good sphericity, uniform particle size and about 18 mu m particle size, but has a cracking phenomenon on the surface of part of spherical particles.
Comparative example 4
Comparative example 4 differs from example 2 only in S3, and all other steps are the same as in example 2.
S3 of comparative example 4 is:
s3, precipitating the slurry seed crystal prepared in the step S2 to obtain precipitated slurry; will be 1.5m 3 Heating the precipitation slurry to 40 ℃, adding 250L of ammonium bicarbonate solution prepared in the step S1, and stirring and mixing uniformly at a rotating speed of 800 rpm; then, simultaneously adding a cobalt-aluminum solution and a precipitator solution to continue the neutralization precipitation reaction, wherein the flow rate of the cobalt-aluminum solution is 250L/h, the flow rate of the ammonium bicarbonate solution is adjusted to be 200-300L/h, the pH of the reaction is controlled to be 7.3-7.5, the flow rate of the cobalt-aluminum solution is kept unchanged, and the reaction is carried out for 14h to obtain a slurry finished product;
the subsequent washing and calcination processes were exactly the same as in example 2.
The aluminum-doped cobaltosic oxide prepared in comparative example 4 was examined and found to have a tap density as high as 3.01g/cm 3 As can be seen from a scanning electron microscope used for shooting, the aluminum-doped cobaltosic oxide prepared in the comparative example 4 has a spherical structure with good sphericity, uniform particle size, but the particle size is about 10 mu m, and the surface of the particle has a severe cracking phenomenon.
As can be seen from the comparison of the comparative examples and examples, the large-particle-size aluminum-doped tricobalt tetraoxide with higher tap density, uniform particle size distribution, larger particle size (up to 18 μm), better sphericity and no cracking problem on the particle surface can be successfully prepared only by adopting the preparation method of the invention and controlling the reaction parameters within the range specified by the invention.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (5)
1. The three-time calcination preparation method of the large-particle-size aluminum-doped cobaltosic oxide is characterized by comprising the following steps of:
s1, respectively preparing cobalt-aluminum solution containing cobalt ions and aluminum ions, and preparing precipitant solution containing carbonate ions, wherein the concentration of the cobalt ions in the cobalt-aluminum solution is 100-150 g/L, and the concentration of the aluminum ions is 0.5-1 g/L for later use;
s2, adding pure water and a precipitant solution into a reaction kettle as base solution, stirring at 50-60 ℃, simultaneously adding the cobalt-aluminum solution and the precipitant solution into the reaction kettle, performing precipitation reaction, adjusting the flow of the precipitant solution, and controlling the pH of the reaction to 7.0-7.3; adjusting the flow of the cobalt-aluminum solution once every 4-8 hours, wherein the adjustment amount is 40-60L/h each time until slurry seed crystals with target granularity are obtained, the flow of the cobalt-aluminum solution is 200-400L/h, and the flow of the precipitant solution is 900-1500L/h;
s3, precipitating the slurry seed crystal to obtain a precipitated slurry, simultaneously adding the cobalt aluminum solution and the precipitator solution into the precipitated slurry to continue the precipitation reaction, adjusting the flow of the precipitator solution, controlling the pH of the reaction to be 7.3-7.5, adjusting the flow of the cobalt aluminum solution once every 12-16 h, and adjusting the flow of the cobalt aluminum solution every time to be 40-60L/h until a slurry finished product with target granularity is obtained, wherein the flow of the cobalt aluminum solution is 200-300L/h, and the flow of the precipitator solution is 200-300L/h;
s4, centrifuging, washing and dehydrating the slurry finished product to obtain a wet material finished product;
s5, calcining the wet material finished product in a roller kiln at a low temperature twice to obtain an aluminum-doped cobaltosic oxide semi-finished product, wherein the conditions of the two low-temperature calcination are as follows: calcining for 4-6 h at 150-250 ℃; calcining for 6-8 hours at 350-450 ℃ to obtain an aluminum-doped cobaltosic oxide semi-finished product;
s6, calcining the aluminum-doped cobaltosic oxide semi-finished product in a rotary kiln at a high temperature to obtain aluminum-doped cobaltosic oxide with large particle size, wherein the high temperature calcining condition is as follows: calcining at 700-750 deg.c for 2-5 hr to obtain large size aluminum doped cobaltosic oxide.
2. The method for preparing the large-particle-size aluminum-doped cobaltosic oxide by three times calcination according to claim 1, wherein the precipitant solution is one or at least two of ammonium bicarbonate solution, ammonium carbonate solution, sodium bicarbonate solution and sodium carbonate solution, and the concentration of carbonate ions in the precipitant solution is 200-250 g/L.
3. The method for preparing the large-particle-size aluminum-doped cobaltosic oxide by three-time calcination according to claim 1, wherein in the step S2, the process of preparing the base solution is as follows: 3-5 m 3 Adding pure water into a reaction kettle, heating to 50-60 ℃, adding 50-100L of the precipitant solution, and stirring at 1000-1500 rpm to obtain the base solution.
4. A process for the preparation of large particle size aluminum-doped tricobalt tetraoxide by three calcination according to any of claims 1 to 3, wherein S3 further comprises the steps of:
heating the precipitation slurry to 30-50 ℃, adding the precipitant solution, stirring at 100-500 rpm, and uniformly mixing for later use; wherein the volume ratio between the precipitation slurry and the precipitant solution is 1.5: (0.05-0.1).
5. The method for preparing the large-particle-size aluminum-doped cobaltosic oxide by three times calcination according to any one of claims 1 to 3, wherein in the step S4, the slurry finished product is pumped into a centrifuge, washed for 3 to 6 times by water with the temperature of 60 to 80 ℃ and dehydrated to obtain a wet material finished product.
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| CN113753966A (en) * | 2021-09-09 | 2021-12-07 | 荆门市格林美新材料有限公司 | Integrated device for producing doped cobaltosic oxide and production method |
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| CN114940515B (en) * | 2022-06-15 | 2023-11-03 | 荆门市格林美新材料有限公司 | Aluminum-doped cobalt carbonate and preparation method and application thereof |
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