CN108483513B - Preparation method of three-dimensional flower-like cobaltosic oxide - Google Patents
Preparation method of three-dimensional flower-like cobaltosic oxide Download PDFInfo
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- CN108483513B CN108483513B CN201810678883.XA CN201810678883A CN108483513B CN 108483513 B CN108483513 B CN 108483513B CN 201810678883 A CN201810678883 A CN 201810678883A CN 108483513 B CN108483513 B CN 108483513B
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Abstract
The invention discloses a preparation method of three-dimensional flower-shaped cobaltosic oxide, which is realized on the basis of a hydrothermal method, and is characterized in that a second component metal salt is added into a reactant to finally generate an oxide solid solution containing the second component, the solid solution powder is fine, a scanning electron microscope finds that the structure is in a uniform three-dimensional flower shape, and after high-quality performance metal is added, the electrochemical performance of the obtained cobaltosic oxide is greatly improved, so that the further application of the cobaltosic oxide is facilitated.
Description
Technical Field
The invention relates to a preparation method of three-dimensional flower-like cobaltosic oxide.
Background
With the rapid development of the economy and technology in the 21 st century, energy problems and environmental problems have become global focuses. How to make environmentally friendly and high performance materials is an ongoing problem for scientists. Natural energy such as solar energy, water energy, wind energy and the like are also influenced by factors such as environmental climate and the like, and meanwhile, high-efficiency energy storage materials are also needed to store the energy to provide energy for human life. The novel energy storage device can meet the basic requirements of people for developing society, and has important strategic significance for one country.
Cobaltosic oxide (Co)3O4) The Cobalt oxide is a black powder, and the structure of the Cobalt oxide belongs to a cubic crystal system as shown in figure 1, wherein divalent Cobalt ions occupy tetrahedral positions, trivalent Cobalt occupies octahedral positions, and oxygen atoms occupy hexahedral positions, so that the Cobalt oxide has strong stability. Co3O4The material is applied to the fields of electrochemical catalysis, lithium battery manufacturing and the like. The nanometer cobalt is the most important cobalt source of the current lithium ion battery, the appearance, the particle size, the purity and the like of the nanometer cobalt directly influence the electrochemical performance of the lithium ion material, and the nanometer cobalt has good electrochemical performance when being used as a negative electrode material of the lithium ion battery.
The preparation of the three-dimensional flower-shaped cobaltosic oxide is that the cobaltosic oxide with the conventional shape is limited in electrochemical application to different degrees due to the single shape, and the flower-shaped structure has greater advantages in electrochemical performance compared with the traditional shape due to the shape advantages of the flower-shaped structure.
There are various methods for preparing Co3O4Such as solid phase reaction method and liquid phase reaction method. The liquid phase reaction method also comprises a liquid phase precipitation method, a hydrothermal/solvothermal method, an electrochemical deposition method and a sol method.
The hydrothermal/solvothermal method is to put aqueous solution or other solution as reaction solvent into a closed container and make the solution react with the reaction solvent under the conditions of high temperature and high pressure, and has the advantages that: the product has high particle purity, good dispersibility and controllable morphology. The method adopted in the experiment is a hydrothermal method, and cobalt acetate is used as a cobalt source.
In the case of cobaltosic oxide alone, the electrochemical properties such as capacitance and the like are continuously attenuated with the time, so that the attempt is made to add a second component metal nitrate into the reactants during the preparation of the oxide, so that an oxide solid solution containing the second component is generated in the reaction process, and unlike a single-component substance, the two-component structural substance can exert the advantages and the characteristics of the two components well so that the advantages are no longer 1+ 1-2, but the advantages are amplified by geometric times. Like magnesium-aluminum alloy is applied to aviation industry, after high-quality metal is added as a core, the advantages of the alloy in electrochemistry are amplified, and therefore cobaltosic oxide is applied to more places.
Disclosure of Invention
The invention aims to provide a preparation method of three-dimensional flower-shaped cobaltosic oxide aiming at the defects of the prior art.
The preparation method of the three-dimensional flower-like cobaltosic oxide comprises the following steps:
weighing cobalt acetate tetrahydrate solid and SDS into a beaker, adding ethylene glycol and deionized water, and stirring until solid particles are completely dissolved (solution A); the second component metal nitrate and TBAB were weighed into another beaker and ethylene glycol was added and stirred until the solid particles were completely dissolved (solution B). Pouring the solution B into the solution A, continuously stirring for 30min, adding urea, continuously stirring for 60min, transferring the solution into a hydrothermal kettle, and heating in a drying oven at 180 ℃ for 8 h; and cooling, taking out the reaction liquid, pouring the reaction liquid into a centrifugal tube, centrifuging for 5min at the speed of 4000rad/s, washing the precipitate with deionized water, washing the precipitate with absolute ethyl alcohol for multiple times, drying the precipitate, and roasting in a muffle furnace at 300 ℃ for 180 min.
In the technical scheme, the metal nitrate of the second component is copper nitrate, nickel nitrate or cerium nitrate, and the added SDS and TBAB are ionic soft template agents.
The molar ratio of the cobalt acetate tetrahydrate solid to the SDS, the TBAB to the urea to the second component of the metal nitrate is 10: 6.5: 1.94: 6: 1.
the concentration of SDS is preferably 0.4 mmol/L.
The volume ratio of the ethylene glycol to the deionized water is 6: 1, the mass ratio of the ethylene glycol to the cobalt acetate tetrahydrate is 41.83: 1.
the roasting temperature rise rate is 3 ℃/min.
According to the method, the second component of metal salt is added into the reactant, the oxide solid solution containing the second component is finally generated, the solid solution powder is fine, the scanning electron microscope finds that the structure is in a uniform three-dimensional flower shape, and after the high-quality performance metal is added, the electrochemical performance of the obtained cobaltosic oxide is greatly improved, so that the cobaltosic oxide is further applied.
Drawings
FIG. 1Co3O4Schematic diagram of the spatial structure of (1);
FIG. 2 is an SEM electron micrograph of a product obtained by the method of the present invention;
FIG. 3 is an XRD pattern of a product made with the addition of a different second component metal;
FIG. 4 is a plot of cyclic voltammograms of the products obtained in examples 1, 2 and 4;
fig. 5 is a graph of LSV for different samples.
Detailed Description
Example 1
0.8g of cobalt acetate tetrahydrate solid and 0.6g of SDS were weighed into a beaker, 20ml of ethylene glycol and 5ml of deionized water were added, and stirring was carried out until stirring was completedThe solid particles were completely dissolved (solution a); second component metal nitrate (second component metal to cobalt molar ratio of 1:10) and 0.2g TBAB were weighed into another beaker and 10ml ethylene glycol was added and stirred until the solid particles were completely dissolved (solution B). And pouring the solution B into the solution A, continuously stirring for 30min, adding 1.15g of urea, continuously stirring for 60min, transferring the solution into a hydrothermal kettle, and heating in an air-blast drying oven at 180 ℃ for 8 h. After heating, the reaction solution was cooled overnight, taken out and poured into a centrifuge tube, and centrifuged at 4000rad/s for 5min using a low speed centrifuge. After centrifugation, the precipitate is washed twice by deionized water, and washed three times by absolute ethyl alcohol after washing. After the washing was completed, the precipitate was transferred into a crucible, and placed in a forced air drying oven to be dried at 60 ℃ for 6 hours to obtain a dried tricobalt tetroxide precursor Co (OH)2. After drying, the sample is roasted in a muffle furnace at 300 ℃ for 180min (the heating rate is 3 ℃/min). The nitrate in this example is nickel nitrate.
Example 2
The difference from example 1 is that the nitrate of the second component is cerium nitrate.
Example 3
The same as example 1, except that the nitrate of the second component was copper nitrate.
Example 4
The difference from example 1 is that no nitrate of the second component was added.
Through the research on the hydrothermal reaction conditions, the reaction can not be carried out at the temperature of less than 160 ℃, and the reaction temperature is higher than 220 ℃ due to Co2+Will preferentially incorporate the SDS-introduced SO4 2-In combination with the alcohol but not in combination with the alcohol, a cobalt sulfate solid is prepared, the color of the product is pink, and the appearance and the performance of the obtained product are both better when the method is carried out at 160-220 ℃, particularly 180 ℃.
The flower-like structure of the cobalt oxide is formed preliminarily when the reaction is carried out for 6h, but the structure is slightly incomplete and is mixed with a small amount of cobalt sulfate, the flower-like structure formed by self-assembly of the cobalt oxide continuously grows when the reaction is carried out for 8h, sulfate radicals are not combined with cobalt ions any more, the crystal structure is continuously perfected, a three-dimensional flower-like structure is formed, and the specific surface area is optimal. As the reaction continues, the flower-like structure begins to shrink and the cell undergoes destructive recombination.
TABLE 1 specific surface data of the product at different hydrothermal times
The appearance of the cobaltosic oxide is not greatly influenced by adding the second component metal salt, but the cobaltosic oxide is more compact, the XRD pattern of each product is shown in figure 3, a solid solution product formed after adding Ni is better, and a diffraction peak of nickel oxide is not shown. The nickel material proves to have a better effect on the formation of flower-like cobalt oxide solid solution.
FIG. 4 is a graph of cyclic voltammograms of the products obtained in examples 1, 2 and 4, and it can be seen by comparison that the redox peaks on the CV curves of cobaltosic oxide are not prominent when no second component material is added, but the redox peaks are increased to various degrees after the addition of the second component, wherein NiO/Co is used3O4The redox peak for the second component species is most elevated, while the NiO/Co can be found by cycling through the curves3O4The cycle curve of the material has no obvious attenuation, which shows that the electrochemical performance of the material has no obvious decline after long-term use, and NiO/Co is used3O4The maximum area enclosed by the curve (a) indicates that the product has a relatively high specific capacitance.
Pure Co without addition of a second component3O4The oxygen evolution potential of (2) is higher, while the oxygen uptake potential is obviously reduced after the second component nitrate is added and a two-component substance is formed (as shown in figure 5), and it can be seen that the current changes are unstable along with the rise of voltage after the second component is added, but NiO/Co3O4、CeO/Co3O4Two component product vs. Co3O4The graph of (1) tends to be stable at high voltage and has a stable point.
Claims (3)
1. A preparation method of three-dimensional flower-like cobaltosic oxide is characterized by comprising the following steps:
weighing cobalt acetate tetrahydrate solid and SDS (sodium dodecyl sulfate) in a beaker, adding ethylene glycol and deionized water, and stirring until solid particles are completely dissolved to obtain a solution A; weighing a second component of metal nitrate and TBAB in another beaker, adding ethylene glycol, and stirring until solid particles are completely dissolved to obtain a solution B; pouring the solution B into the solution A, continuously stirring for 30min, adding urea, continuously stirring for 60min, transferring the solution into a hydrothermal kettle, and heating in a drying oven at 180 ℃ for 8 h; cooling, taking out the reaction liquid, pouring the reaction liquid into a centrifugal tube, centrifuging for 5min at the speed of 4000rad/s, washing the precipitate with deionized water, washing the precipitate with absolute ethyl alcohol for multiple times, drying the precipitate, and roasting in a muffle furnace at 300 ℃ for 180 min; the second component metal nitrate is nickel nitrate, and the molar ratio of the cobalt acetate tetrahydrate solid, SDS, TBAB, urea and the second component metal nitrate is 10: 6.5: 1.94: 6: 1.
2. the method for preparing three-dimensional flower-like cobaltosic oxide according to claim 1, wherein the volume ratio of the ethylene glycol to the deionized water is 6: 1, the mass ratio of the ethylene glycol to the cobalt acetate tetrahydrate is 41.83: 1.
3. the method for preparing three-dimensional flower-like cobaltosic oxide according to claim 1, wherein the roasting temperature rise rate is 3 ℃/min.
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| CN107381660A (en) * | 2017-08-02 | 2017-11-24 | 上海纳米技术及应用国家工程研究中心有限公司 | Sb, Mn codope cobaltosic oxide nano flower-like microsphere preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107381660A (en) * | 2017-08-02 | 2017-11-24 | 上海纳米技术及应用国家工程研究中心有限公司 | Sb, Mn codope cobaltosic oxide nano flower-like microsphere preparation method |
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| Title |
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| Synthesis of flower-like Co3O4–CeO2 composite oxide and its application to catalytic degradation of 1,2,4-trichlorobenzene;Shijing Li等;《Applied Catalysis B: Environmental》;20120517;第440-447页 * |
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