CN111717937B - Preparation method of nano-scale cobaltosic oxide - Google Patents
Preparation method of nano-scale cobaltosic oxide Download PDFInfo
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- CN111717937B CN111717937B CN202010438856.2A CN202010438856A CN111717937B CN 111717937 B CN111717937 B CN 111717937B CN 202010438856 A CN202010438856 A CN 202010438856A CN 111717937 B CN111717937 B CN 111717937B
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Abstract
The invention relates to the technical field of nano materials, and discloses a preparation method of nano cobaltosic oxide, which comprises the following steps: preparing porous spherical micron-sized cobaltosic oxide particles through a hydrothermal method and high-temperature calcination, wherein the cobaltosic oxide consists of a plurality of nano ions, and is fragile in structure and easy to break; the micron-sized cobaltosic oxide is further crushed into nano particles by a ball milling method, the conditions of a ball milling solvent, the diameter and the rotating speed of balls and the like are strictly controlled, the agglomeration of the nano particles can be effectively avoided, and the average particle size of the cobaltosic oxide is reduced to more than 100 nanometers; the method has simple process and is beneficial to industrial production.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a preparation method of nano cobaltosic oxide.
Background
The cobaltosic oxide belonging to the group VIII of P-type semiconductors has a relatively good empty electron orbit, so that an electron pair is easily fused with the cobaltosic oxide, and the cobaltosic oxide is a transition metal oxide with excellent performance and can be used as a catalyst. The existing research shows that the particle size and the morphology of the cobaltosic oxide have larger influence on the catalytic performance of the cobaltosic oxide, and the nano cobaltosic oxide is expected to obtain better performance than the large-particle cobaltosic oxide, and has important application value in the aspects of heterogeneous catalysis, anode materials of lithium ion storage batteries, solar energy absorption materials, pigments and the like.
The method for preparing nano cobaltosic oxide can be divided into a physical method and a chemical method. The physical method is simple to operate, and the obtained particles have high purity, good crystallinity, but the particle size is not easy to control, and the requirement on experimental conditions is higher. The chemical methods mainly include sol-gel method, electrochemical method, pyrolysis method, chemical precipitation method, and the like. The sol-gel method uses metal alkoxide as a raw material, so that the synthesis cost is high, the synthesis period is long, the sintering property is poor, and the drying shrinkage is large. Although the chemical precipitation method has industrial application prospect, the problem of agglomeration is the biggest problem in the preparation process. In general, cobaltosic oxide prepared by a hydrothermal method selects a cobalt salt and a precipitator as precursor solutions, the mixture is put into a reaction kettle (providing a high-temperature and high-pressure environment), cobalt carbonate with various shapes can be prepared, and then pure spherical cobaltosic oxide powder is prepared by high-temperature calcination; however, the following problems exist in this process: firstly, cobaltosic oxide nano particles are difficult to obtain by a general hydrothermal method; ② there is still a small amount of cobaltosic oxide that will cluster together.
Although the ball milling method can reduce the particle size, in the course of research, it was found that it is difficult to obtain nanoparticles with sufficiently small particle size by ball milling cobaltosic oxide by the conventional ball milling method, and the reason is presumed to be: 1) the structure of the micron cobaltosic oxide is compact, so that ball milling to the nanometer level is difficult, and high-rotation-speed ball milling is mostly adopted; 2) the cobaltosic oxide ball-milled to the nanometer level is easy to agglomerate.
Disclosure of Invention
In view of the above, the invention provides a method for preparing nano-scale cobaltosic oxide, which can effectively reduce the particle size of the cobaltosic oxide to about 100nm, has simple process and is beneficial to industrial production.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing nanometer cobaltosic oxide, which comprises the following steps:
s1, weighing cobalt chloride hexahydrate and urea, dissolving the cobalt chloride hexahydrate and urea in a mixed solution of deionized water and glycerol, stirring, standing until the mixture is transparent and bubble-free, transferring the mixture into a reaction kettle, reacting at 120-160 ℃ for 10-12 hours, cooling to room temperature, performing suction filtration, performing centrifugal washing for many times, and drying to obtain a cobalt carbonate precursor;
s2, calcining the cobalt carbonate prepared in the step S1 at high temperature, wherein the conditions are as follows: calcining for 8-10 hours at 600-650 ℃ to obtain cobaltosic oxide;
s3, placing the cobaltosic oxide prepared in the step S2 into a ball milling tank, adopting zirconia balls to fully pave the bottom of the ball milling tank, then adding absolute ethyl alcohol to submerge the small balls, wherein the ball milling time is 24-48h, the frequency of the ball mill is 25Hz, and the rotating speed is as follows: at 120-; the ratio of the different diameters of the zirconia balls is 1cm:0.8cm:0.5 cm-1: 1: 1.
Preferably, the mass volume ratio of the cobalt chloride hexahydrate, the urea, the deionized water and the glycerol is 1g:2g:10ml:30 ml.
Preferably, the temperature rise rate of the reaction kettle in the step S1 is: 2 ℃/min
Preferably, the temperature increase rate of the calcination process in step S2 is: 10 ℃/min
Preferably, the washing solution used in the washing in step S1 is absolute ethanol.
Preferably, the drying temperature in step S1 is 100 ℃.
The invention has the beneficial effects that: 1) the micron-sized cobaltosic oxide prepared by a hydrothermal method and calcination has a uniform particle size of about 12 microns, and can be found by electron microscope pictures to be porous and spherical and be stacked by a plurality of nano particles; 2) because the micron-sized cobaltosic oxide particle mechanism is very fragile, the structure of the micron-sized cobaltosic oxide particle mechanism is easy to break by external force, so that a large number of nano particles fall off, ball milling is promoted by setting ball milling conditions, adopting zirconia ground balls with a certain proportion of different particle diameters and a certain proportion of solvent, agglomeration of nano particles is avoided on the premise of effectively breaking the micron-sized cobaltosic oxide, the cobaltosic oxide with the average particle diameter of more than 100 nanometers is obtained, and the electrical property of the cobaltosic oxide is effectively improved.
Drawings
FIG. 1 shows spherical CoCO3XRD pattern of (a);
FIG. 2 shows spherical CoCO3SEM image at 5000 magnification;
FIG. 3 shows a spherical shape of Co3O4XRD pattern of (a);
FIG. 4 shows spherical Co before ball milling3O47000 magnification SEM image;
FIG. 5 shows the nano Co after ball milling3O4XRD pattern of (a);
FIG. 6 shows the ball milled Co with acetone as solvent3O4SEM image at 20000 magnification;
FIG. 7 shows the nano Co after ball milling with ethanol as solvent3O4SEM image at 8000 magnification;
fig. 8 is a statistical chart of particle size measurements using SMile software.
Detailed Description
In order that the invention may be better understood, it is further illustrated by the following specific examples, which are not to be construed as limiting the invention.
Example 1
(1) Firstly weighing 2g of red monoclinic system cobalt chloride hexahydrate, 4 g of rod-shaped crystal urea, 20 ml of pure deionized water and 60 ml of transparent glycerol, respectively adding the four samples into a beaker with the capacity of 100 ml, then placing the beaker on a stirrer, putting an olive-shaped magnetic stirrer on the stirrer, and fully stirring for 1 hour to obtain a pink solution; then placing the pink solution at room temperature, standing until the solution is transparent and bubble-free, transferring the solution into a bottle made of polytetrafluoroethylene with the capacity of 100 milliliters, then placing the bottle into a reaction kettle, transferring the bottle into a high-temperature furnace to provide a high-temperature and high-pressure environment for the solution so as to carry out hydrothermal reaction on a sample, setting the parameters of the high-temperature furnace to react for 12 hours at the temperature of 120 ℃, and setting the heating rate to be 2 ℃/min; then, after the temperature of the reaction kettle is reduced to room temperature, carrying out suction filtration on a product obtained after reaction in the reaction kettle by using a suction filter, wherein suction filtration can be carried out twice more for obtaining a pure sample; then transferring the filtrate into a 10ml centrifuge tube, placing the centrifuge tube in a centrifuge, and carrying out centrifugal washing for four times by using absolute ethyl alcohol; and finally, transferring the centrifugal product into a beaker, and drying the centrifugal product for 3 hours in a vacuum drying oven at the temperature of 100 ℃ to obtain the required product.
(2) And (3) placing the product obtained in the first step, namely the spherical cobaltous carbonate particles, in a ceramic crucible, placing the crucible in a muffle furnace for high-temperature calcination, setting the parameters of the high-temperature furnace to be 600 ℃ for calcination for 10 hours, and setting the heating rate to be 10 ℃/min to obtain the spherical cobaltosic oxide particles.
(3) Placing spherical cobaltosic oxide powder into a ball milling tank, adding absolute ethyl alcohol, adopting zirconia balls to fully cover the bottom of the ball milling tank, then adding the absolute ethyl alcohol until the small balls are submerged, wherein the ball milling time is 45 hours, the frequency of the ball mill is 25Hz, and the rotating speed is as follows: and (3) performing ball milling at 120 rpm, drying in a vacuum drying oven, and collecting a sample to obtain a target product, wherein an SEM (scanning Electron microscope) of the sample is shown in FIG. 7. Wherein the different diameters and the number ratio of the zirconia balls are 1cm:0.8cm:0.5 cm-1: 1: 1.
Example 2
(1) Firstly weighing 2g of red monoclinic system cobalt chloride hexahydrate, 4 g of rodlike crystal urea, 20 ml of pure deionized water and 60 ml of transparent glycerol, respectively adding the four samples into a beaker with the capacity of 100 ml, then placing the beaker on a stirrer, putting an olive-shaped magnetic stirrer, and fully stirring for 1 hour to obtain a pink solution; then placing the pink solution at room temperature, standing until the solution is transparent and bubble-free, transferring the solution into a bottle made of polytetrafluoroethylene with the capacity of 100 milliliters, then placing the bottle into a reaction kettle, transferring the bottle into a high-temperature furnace to provide a high-temperature and high-pressure environment for the solution so as to carry out hydrothermal reaction on a sample, wherein the parameter of the high-temperature furnace is set to react for 10 hours at the temperature of 160 ℃, and the heating rate is 5 ℃/min; then, after the temperature of the reaction kettle is reduced to room temperature, carrying out suction filtration on a product obtained after reaction in the reaction kettle by using a suction filter, wherein suction filtration can be carried out twice more for obtaining a pure sample; then transferring the filtrate into a 10ml centrifuge tube, placing the centrifuge tube in a centrifuge, and carrying out centrifugal washing for four times by using absolute ethyl alcohol; and finally, transferring the centrifugal product into a beaker, and drying the centrifugal product in a vacuum drying oven at the temperature of 80 ℃ for 3 hours to obtain the required product.
(2) And (2) placing the product obtained in the step (1), namely the spherical cobaltous carbonate particles, in a ceramic crucible, placing the crucible in a muffle furnace for high-temperature calcination, setting the parameters of the high-temperature furnace to be 650 ℃ for calcination for 8 hours, and setting the heating rate to be 7 ℃/min to obtain the spherical cobaltosic oxide particles.
(3) Placing spherical cobaltosic oxide powder in a ball milling tank, adopting zirconia balls to fully cover the bottom of the ball milling tank, then adding absolute ethyl alcohol until the ball is submerged and the upper part is 2 cm, wherein the ball milling time is 30h, the frequency of the ball mill is 25Hz, the rotating speed is 150 rpm, and drying after ball milling to obtain nano cobaltosic oxide; wherein the ratio of different diameters and the number of the zirconia balls is 1cm to 0.8cm to 0.5cm to 1:1: 1.
Comparative example 1
Steps (1) and (2) were the same as in example 1.
(3) Placing the obtained spherical cobaltosic oxide particles in a ball milling tank, adopting zirconia balls to fully cover the bottom of the ball milling tank, then adding acetone to a position 2 cm above the submerged small balls, wherein the ball milling time is 45h, the frequency of the ball milling machine is 25Hz, the rotating speed is 120 rpm, and drying after ball milling to obtain the nano cobaltosic oxide (an SEM picture is shown in figure 6); wherein the ratio of the different diameters and the number of the zirconia balls is 1cm:0.8cm:0.5 cm-1: 1: 1.
Comparative example 2
Steps (1) and (2) were the same as in example 1.
(3) Placing the obtained spherical cobaltosic oxide particles in a ball milling tank, adopting zirconia balls to fully cover the bottom of the ball milling tank, then adding absolute ethyl alcohol until the position 2 cm above the submerged small balls is reached, wherein the ball milling time is 45h, the frequency of the ball mill is 25Hz, the rotating speed is 120 rpm, and drying after ball milling to obtain nano cobaltosic oxide; wherein the zirconia balls have a diameter of 0.8cm or 0.5 cm.
Comparative example 3
Steps (1) and (2) were the same as in example 1.
(3) Placing the obtained spherical cobaltosic oxide particles in a ball milling tank, adopting zirconia balls to fully cover the bottom of the ball milling tank, then adding absolute ethyl alcohol until the position 2 cm above the submerged small balls is reached, wherein the ball milling time is 45h, the frequency of the ball mill is 25Hz, the rotating speed is 300 revolutions per minute, and drying after ball milling to obtain the nano cobaltosic oxide; the different diameters and the number ratio of the zirconia balls are 1cm to 0.8cm to 0.5cm to 1:1: 1.
Analysis of results
As shown in fig. 1-2, the product prepared by the hydrothermal method is cobalt carbonate, and the cobalt carbonate is spherical. As shown in figures 3-4, the product obtained by calcining cobalt carbonate at high temperature is spherical cobaltosic oxide, the average particle size is about 12 microns, the structure is very fragile, and the structure is easily broken by external force, so that a large number of nano particles fall off, the required nano particles are obtained, and the surface area of the particles is increased.
Ball milling is carried out on the cobaltosic oxide obtained by calcination, and the granularity of the obtained cobaltosic oxide is greatly reduced by controlling each ball milling parameter, and the granularity of the powder is about 135 nanometers. The mutual collision action among sample particles is continuously enhanced along with the increase of the powder ball milling time, so that the cobaltosic oxide powder is continuously ball-milled and crushed to obtain refined powder; the surfaces of the refined particles are a large number of fresh surfaces different from those before the refinement, so that the contact area between the powder particles is increased, the particle size and the components of the powder particles are more uniform, and the phenomenon is also beneficial to improving the performance of the material; meanwhile, the volume change caused by the small particle size is relatively reduced, so that the capacity loss caused by the collapse and crushing of the particle volume is reduced, the performance of the cobaltosic oxide material is improved, and the circulation stability of the material is improved. As can be seen from fig. 6 and 7, when the ball milling of the sample is performed using ethanol as the solvent, the sample is broken by simply taking acetone as the solvent in comparison with the ball milled sample. The cobaltosic oxide obtained by ball milling using zirconia of uniform particle size (comparative example 2) was found to be non-uniform in particle size and many remained as they were without being ground by the scanning electron microscope test. The agglomeration of the cobaltosic oxide was found to be serious by the observation of the scanning electron microscope using the cobaltosic oxide obtained by ball milling at 300 rpm (comparative example 3), and the reason is presumed to be: because the spherical cobaltosic oxide is spherical particles consisting of a plurality of nano particles, the spherical cobaltosic oxide can be crushed by only needing small force, and the agglomeration of the nano particles is promoted by the rotating speed of the ball mill.
Of course, the above is only a specific application example of the present invention, and the protection scope of the present invention is not limited in any way. In addition to the above embodiments, the present invention may have other embodiments. All technical solutions formed by using equivalent substitutions or equivalent transformations fall within the scope of the present invention.
Claims (6)
1. A method for preparing nanometer cobaltosic oxide is characterized by comprising the following steps:
s1, weighing cobalt chloride hexahydrate and urea, dissolving the cobalt chloride hexahydrate and the urea in a mixed solution of deionized water and glycerol, stirring, standing until the mixture is transparent and bubble-free, transferring the mixture into a reaction kettle, reacting at 120-160 ℃ for 10-12 hours, cooling to room temperature, performing suction filtration, performing centrifugal washing for many times, and drying to obtain a cobalt carbonate precursor;
s2, calcining the cobalt carbonate prepared in the step S1 at high temperature, wherein the conditions are as follows: calcining for 8-10 hours at 600-650 ℃ to obtain cobaltosic oxide;
s3, placing the cobaltosic oxide prepared in the step S2 into a ball milling tank, adopting zirconia balls to fully pave the bottom of the ball milling tank, then adding absolute ethyl alcohol to submerge the small balls, wherein the ball milling time is 24-48h, the frequency of the ball mill is 25Hz, and the rotating speed is as follows: at 120-; the ratio of the different diameters of the zirconia balls is 1cm:0.8cm:0.5 cm-1: 1: 1.
2. The method for preparing nano-scale cobaltosic oxide according to claim 1, wherein the mass volume ratio of the cobalt chloride hexahydrate, the urea, the deionized water and the glycerol is 1g:2g:10ml:30 ml.
3. The method for preparing nanometer-scale cobaltosic oxide according to claim 1, wherein the temperature rise rate of the reaction kettle in the step S1 is as follows: 2-5 ℃/min.
4. The method for preparing nanometer-scale cobaltosic oxide according to claim 1, wherein the temperature increase rate of the calcination process in the step S2 is as follows: 5 to 10 ℃/min.
5. The method for preparing nanometer-scale cobaltosic oxide according to claim 1, wherein the washing solution used in the washing in step S1 is absolute ethyl alcohol.
6. The method for preparing nano-scale cobaltosic oxide according to claim 1, wherein the drying temperature in step S1 is 80-100 ℃.
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