A simple method for preparing nano-petal-shaped spherical tin dioxide powder materials

Abstract

This invention discloses a simple method for preparing nano-petal-shaped spherical tin dioxide powder material. (1) Stannous sulfate powder is added to deionized water and mixed to obtain solution A; (2) Sodium carbonate or potassium carbonate is added to deionized water and completely dissolved to form solution B; (3) Solution A obtained in step (1) and solution B obtained in step (2) are thoroughly mixed and stirred continuously; (4) The solution obtained in step (3) is allowed to stand and separate into layers, the supernatant is removed, the concentrated high-concentration suspension is centrifuged and washed and the precipitate is collected, and the precipitate is dried to obtain precursor powder; (5) The precursor powder obtained in step (4) is calcined and heat-treated to completely transform the precursor powder into a stable tin dioxide phase structure, thereby obtaining high-purity and uniform nano-petal-shaped spherical tin dioxide powder. The method of this invention is simple, mild, and easy to realize large-scale industrial production.

Description

Technical Field

[0001] This invention relates to the field of design and preparation of nanostructured materials, specifically to a simple method for preparing nano-petal-shaped spherical tin dioxide powder. Background Technology

[0002] Nanoparticles, as functional materials with significant size effects, have always been a key focus of scientific research. Their unique nano-effects and flexible nanostructures endow them with broad application potential in functional fields such as optics, electronics, and heat. Therefore, designing and developing nanoscale assembled functional powder materials with special structures is of great significance to scientific progress.

[0003] Tin dioxide is an excellent n-type semiconductor material with wide applications in industrial energy storage, optical devices, and catalysis. In particular, the widely studied ITO thin film is primarily made from tin dioxide. Research on the structure of tin dioxide is crucial to the quality and performance of its downstream products; research on tin dioxide with special nanostructures contributes to the development of high-quality, high-performance downstream products. Currently, energy storage devices, optical devices, and gas-sensitive devices used in industry can all be manufactured using tin dioxide with a nano-petal-shaped structure as a raw material. While some patented methods for preparing petal-shaped tin dioxide exist, these methods suffer from drawbacks such as the presence of organic matter in the reactants, excessively high reaction temperatures, the need for high-pressure environments, and excessively large product sizes. These drawbacks significantly hinder its industrial application. The method described in this invention, however, employs a relatively mild preparation process, using raw materials completely free of organic matter. The resulting nano-petal-shaped tin dioxide powder possesses a rational three-dimensional structural design, maximizing the utilization of the material's surface area and effectively addressing these drawbacks. This invention achieves the preparation of high-quality, special nano-structured tin dioxide, facilitating its industrial synthesis. Summary of the Invention

[0004] The primary objective of this invention is to overcome the shortcomings and deficiencies of existing technologies and provide a simple, easy-to-control, green and environmentally friendly method for synthesizing high-quality nano-petal spherical tin dioxide powder under mild conditions, thereby promoting the industrial synthesis of nano-petal spherical tin dioxide powder.

[0005] The technical solution adopted in this invention is as follows:

[0006] A method for preparing nano-tin dioxide powder material includes the following steps:

[0007] (1) Add stannous sulfate or stannous chloride powder to deionized water and mix well to obtain solution A;

[0008] (2) Add sodium carbonate or potassium carbonate to deionized water and dissolve it completely to form solution B;

[0009] (3) Mix solution A obtained in step (1) and solution B obtained in step (2) thoroughly and continue stirring to react;

[0010] (4) The solution obtained from the reaction in step (3) was allowed to stand and separate into layers. The supernatant was removed, the concentrated high-concentration suspension was centrifuged, washed, and the precipitate was collected. The precipitate was dried to obtain nano precursor powder.

[0011] (5) The nano precursor powder obtained in step (4) is calcined and dehydrated to completely transform the precursor powder into a stable tin dioxide phase structure, thus obtaining nano tin dioxide powder material.

[0012] In step (1), the concentration of stannous sulfate in solution A is controlled to be 0.1–0.5 mol / L. The preferred concentration is 0.5 mol / L.

[0013] In step (1), when preparing solution A, ultrasonic dispersion should be performed for no less than 15 minutes, preferably 15-30 minutes.

[0014] In step (2), the concentration of sodium carbonate or potassium carbonate in solution B is controlled to be 0.4–2 mol / L. The preferred concentration corresponding to 0.5 mol / L solution A is 0.8 mol / L.

[0015] In step (3), solution A obtained in step (1) and solution B obtained in step (2) are thoroughly mixed and stirred in a 1:1 ratio. The stirring speed is controlled at 200-400 r / min, and the temperature is controlled at 0-50℃, preferably 25℃. The stirring reaction is continued for 2-8 hours. The preferred time is 6 hours.

[0016] Step (4) Wash the precipitate three times with deionized water at a speed of 4000-6000 r / min and collect the precipitate. Dry the precipitate in the air at a temperature of 40-80℃ for a time of not less than 12 hours.

[0017] Step (5) The nano-precursor powder obtained in step (4) is heat-treated in a muffle furnace at a temperature of 400-800°C for 2-8 hours. The preferred temperature is 800°C and the preferred time is 2-4 hours.

[0018] A second objective of this invention is to provide a nano-tin dioxide powder material prepared by the above-described method. The nano-tin dioxide powder material has a unique morphology of nano-petal-shaped spheres with a particle size between 5 and 8 μm.

[0019] A third objective of this invention is to provide applications of the aforementioned nano-tin dioxide powder material for the fabrication of energy storage devices, optical devices, and gas-sensitive devices.

[0020] Compared with existing methods for preparing tin dioxide nanospheres, the method of this invention is much simpler and more convenient, and no organic matter is involved in the reaction solvent, making it a green and pollution-free preparation method. Furthermore, the product prepared by this method has uniform particle size and a good flower-like structure, making it promising for direct application or as a supported carrier.

[0021] The method of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments, but the scope of protection of the method of the present invention is not limited to the content described. Attached Figure Description

[0022] Figure 1 This is a high-magnification scanning electron microscope (SEM) image of the precursor prepared in Example 6;

[0023] Figure 2 This is the X-ray diffraction (XRD) pattern of the precursor prepared in Example 6;

[0024] Figure 3 This is a high-magnification scanning electron microscope (SEM) image of the tin dioxide prepared in Example 6;

[0025] Figure 4 This is a low-magnification scanning electron microscope (SEM) image of the tin dioxide prepared in Example 6;

[0026] Figure 5 This is the X-ray diffraction (XRD) pattern of tin dioxide prepared in Example 6. Detailed Implementation

[0027] Example 1

[0028] A simple method for preparing nano-petal-shaped spherical tin dioxide powder, the steps of which are as follows:

[0029] (1) Add stannous sulfate powder to deionized water, control the concentration of stannous sulfate to be 0.1 mol / L, and ultrasonically disperse for 30 minutes to obtain solution A;

[0030] (2) Add sodium carbonate to deionized water at a concentration of 0.4 mol / L and stir vigorously until it is completely dissolved to form solution B;

[0031] (3) Mix solution A obtained in step (1) and solution B obtained in step (2) thoroughly in a 1:1 ratio and stir vigorously, keeping the temperature at 25°C and stirring continuously for 2 hours.

[0032] (4) Let the solution obtained in step (3) stand and separate into layers, remove the supernatant, wash the concentrated high-concentration suspension with deionized water at a speed of 5000 r / min 3 times and collect the precipitate, dry the precipitate in air at a temperature of 60℃ for 12 h to obtain the precursor powder.

[0033] (5) The precursor powder obtained in step (4) is heat-treated in a muffle furnace at 800°C for 2 hours to completely transform the precursor powder into a stable tin dioxide phase structure, thereby obtaining high-purity tin dioxide powder.

[0034] Example 2

[0035] A simple method for preparing petal-shaped spherical tin dioxide powder, the steps of which are as follows:

[0036] (1) Add stannous sulfate powder to deionized water, control the concentration of stannous sulfate to be 0.2 mol / L, and ultrasonically disperse for 30 minutes to obtain solution A;

[0037] (2) Add sodium carbonate to deionized water at a concentration of 0.4 mol / L and stir vigorously until it is completely dissolved to form solution B;

[0038] (3) Mix solution A obtained in step (1) and solution B obtained in step (2) thoroughly in a 1:1 ratio and stir vigorously, keeping the temperature at 25°C and stirring continuously for 2 hours.

[0039] (4) Let the solution obtained in step (3) stand and separate into layers, remove the supernatant, wash the concentrated high-concentration suspension with deionized water at a speed of 5000 r / min 3 times and collect the precipitate, dry the precipitate in air at a temperature of 60℃ for 12 h to obtain the precursor powder.

[0040] (5) The precursor powder obtained in step (4) is heat-treated in a muffle furnace at 800°C for 2 hours to completely transform the precursor powder into a stable tin dioxide phase structure, thereby obtaining high-purity tin dioxide powder.

[0041] Example 3

[0042] A simple method for preparing nano-petal-shaped spherical tin dioxide powder, the steps of which are as follows:

[0043] (1) Add stannous sulfate powder to deionized water, control the concentration of stannous sulfate to be 0.5 mol / L, and ultrasonically disperse for 30 minutes to obtain solution A;

[0044] (2) Add sodium carbonate to deionized water at a concentration of 0.4 mol / L and stir vigorously until it is completely dissolved to form solution B;

[0045] (3) Mix solution A obtained in step (1) and solution B obtained in step (2) thoroughly in a 1:1 ratio and stir vigorously, keeping the temperature at 25°C and stirring continuously for 2 hours.

[0046] (4) Let the solution obtained in step (3) stand and separate into layers, remove the supernatant, wash the concentrated high-concentration suspension with deionized water at a speed of 5000 r / min 3 times and collect the precipitate, dry the precipitate in air at a temperature of 60℃ for 12 h to obtain the precursor powder.

[0047] (5) The precursor powder obtained in step (4) is heat-treated in a muffle furnace at 800°C for 2 hours to completely transform the precursor powder into a stable tin dioxide phase structure, thereby obtaining high-purity tin dioxide powder.

[0048] Example 4

[0049] A simple method for preparing nano-petal-shaped spherical tin dioxide powder, the steps of which are as follows:

[0050] (1) Add stannous sulfate powder to deionized water, control the concentration of stannous sulfate to be 0.1 mol / L, and ultrasonically disperse for 30 minutes to obtain solution A;

[0051] (2) Add sodium carbonate to deionized water at a concentration of 0.8 mol / L and stir vigorously until it is completely dissolved to form solution B;

[0052] (3) Mix solution A obtained in step (1) and solution B obtained in step (2) thoroughly in a 1:1 ratio and stir vigorously, keeping the temperature at 25°C and stirring continuously for 2 hours.

[0053] (4) Let the solution obtained in step (3) stand and separate into layers, remove the supernatant, wash the concentrated high-concentration suspension with deionized water at a speed of 5000 r / min 3 times and collect the precipitate, dry the precipitate in air at a temperature of 80℃ for 12 h to obtain precursor powder.

[0054] (5) The precursor powder obtained in step (4) is heat-treated in a muffle furnace at 800°C for 2 hours to completely transform the precursor powder into a stable tin dioxide phase structure, thereby obtaining high-purity tin dioxide powder.

[0055] Example 5

[0056] A simple method for preparing nano-petal-shaped spherical tin dioxide powder, the steps of which are as follows:

[0057] (1) Add stannous sulfate powder to deionized water, control the concentration of stannous sulfate to be 0.2 mol / L, and ultrasonically disperse for 30 minutes to obtain solution A;

[0058] (2) Add sodium carbonate to deionized water at a concentration of 0.8 mol / L and stir vigorously until it is completely dissolved to form solution B;

[0059] (3) Mix solution A obtained in step (1) and solution B obtained in step (2) thoroughly in a 1:1 ratio and stir vigorously, keeping the temperature at 25°C and stirring continuously for 2 hours.

[0060] (4) The solution obtained in step (3) was allowed to stand and separate into layers. The supernatant was removed. The concentrated high-concentration suspension was washed three times by centrifugation with deionized water at a speed of 6000 r / min and the precipitate was collected. The precipitate was dried in air at a temperature of 40°C for 12 hours to obtain the precursor powder.

[0061] (5) The precursor powder obtained in step (4) is heat-treated in a muffle furnace at 800°C for 2 hours to completely transform the precursor powder into a stable tin dioxide phase structure, thereby obtaining high-purity tin dioxide powder.

[0062] Example 6

[0063] A simple method for preparing nano-petal-shaped spherical tin dioxide powder, the steps of which are as follows:

[0064] (1) Add stannous sulfate powder to deionized water, control the concentration of stannous sulfate to be 0.5 mol / L, and ultrasonically disperse for 30 minutes to obtain solution A;

[0065] (2) Add sodium carbonate to deionized water at a concentration of 0.8 mol / L and stir vigorously until it is completely dissolved to form solution B;

[0066] (3) Mix solution A obtained in step (1) and solution B obtained in step (2) thoroughly in a 1:1 ratio and stir vigorously, keeping the temperature at 25°C and stirring continuously for 2 hours.

[0067] (4) Let the solution obtained in step (3) stand and separate into layers, remove the supernatant, wash the concentrated high-concentration suspension with deionized water at a speed of 5000 r / min 3 times and collect the precipitate, dry the precipitate in air at a temperature of 80℃ for 12 h to obtain precursor powder.

[0068] (5) The precursor powder obtained in step (4) is heat-treated in a muffle furnace at 800°C for 2 hours to completely transform the precursor powder into a stable tin dioxide phase structure, thereby obtaining high-purity tin dioxide powder.

[0069] (6) The obtained powder sample was examined using a scanning electron microscope (SEM), and the results are as follows: Figure 1 , Figure 3 and Figure 4As shown, both the precursor powder and the final tin dioxide powder formed regularly shaped nanopetal-like spherical particles. The nanosheets of the spheres are composed of fine tin dioxide nanoparticles, which then assemble into the sphere-like structure. X-ray diffraction analysis of the sample phase structure yielded the following results: Figure 2 and Figure 5 As shown, the precursor powder is high-purity tin oxide, while the final sample phase structure is high-purity tin dioxide phase.

[0070] Example 7

[0071] A simple method for preparing nano-petal-shaped spherical tin dioxide powder, the steps of which are as follows:

[0072] (1) Add stannous sulfate powder to deionized water, control the concentration of stannous sulfate to be 0.1 mol / L, and ultrasonically disperse for 30 minutes to obtain solution A;

[0073] (2) Add sodium carbonate to deionized water at a concentration of 2 mol / L and stir vigorously until it is completely dissolved to form solution B;

[0074] (3) Mix solution A obtained in step (1) and solution B obtained in step (2) thoroughly in a 1:1 ratio and stir vigorously, keeping the temperature at 25°C and stirring continuously for 2 hours.

[0075] (4) Let the solution obtained in step (3) stand and separate into layers, remove the supernatant, wash the concentrated high-concentration suspension with deionized water at a speed of 4000 r / min 3 times and collect the precipitate, dry the precipitate in air at a temperature of 80℃ for 12 h to obtain precursor powder.

[0076] (5) The precursor powder obtained in step (4) is heat-treated in a muffle furnace at 800°C for 2 hours to completely transform the precursor powder into a stable tin dioxide phase structure, thereby obtaining high-purity tin dioxide powder.

[0077] Example 8

[0078] A simple method for preparing nano-petal-shaped spherical tin dioxide powder, the steps of which are as follows:

[0079] (1) Add stannous sulfate powder to deionized water, control the concentration of stannous sulfate to be 0.2 mol / L, and ultrasonically disperse for 30 minutes to obtain solution A;

[0080] (2) Add sodium carbonate to deionized water at a concentration of 2 mol / L and stir vigorously until it is completely dissolved to form solution B;

[0081] (3) Mix solution A obtained in step (1) and solution B obtained in step (2) thoroughly in a 1:1 ratio and stir vigorously, keeping the temperature at 25°C and stirring continuously for 2 hours.

[0082] (4) Let the solution obtained in step (3) stand and separate into layers, remove the supernatant, wash the concentrated high-concentration suspension with deionized water at a speed of 6000 r / min 3 times and collect the precipitate, dry the precipitate in air at a temperature of 80℃ for 12 h to obtain precursor powder.

[0083] (5) The precursor powder obtained in step (4) is heat-treated in a muffle furnace at 800°C for 2 hours to completely transform the precursor powder into a stable tin dioxide phase structure, thereby obtaining high-purity tin dioxide powder.

[0084] Example 9

[0085] A simple method for preparing nano-petal-shaped spherical tin dioxide powder, the steps of which are as follows:

[0086] (1) Add stannous sulfate powder to deionized water, control the concentration of stannous sulfate to be 0.5 mol / L, and ultrasonically disperse for 30 minutes to obtain solution A;

[0087] (2) Add sodium carbonate to deionized water at a concentration of 2 mol / L and stir vigorously until it is completely dissolved to form solution B;

[0088] (3) Mix solution A obtained in step (1) and solution B obtained in step (2) thoroughly in a 1:1 ratio and stir vigorously, keeping the temperature at 25°C and stirring continuously for 2 hours.

[0089] (4) Let the solution obtained in step (3) stand and separate into layers, remove the supernatant, wash the concentrated high-concentration suspension with deionized water at a speed of 4000 r / min 3 times and collect the precipitate, dry the precipitate in air at a temperature of 60℃ for 12 h to obtain the precursor powder.

[0090] (5) The precursor powder obtained in step (4) is heat-treated in a muffle furnace at 800°C for 2 hours to completely transform the precursor powder into a stable tin dioxide phase structure, thereby obtaining high-purity tin dioxide powder.

[0091] Example 10

[0092] A simple method for preparing nano-petal-shaped spherical tin dioxide powder, the steps of which are as follows:

[0093] (1) Add stannous sulfate powder to deionized water, control the concentration of stannous sulfate to be 0.5 mol / L, and ultrasonically disperse for 30 minutes to obtain solution A;

[0094] (2) Add potassium carbonate to deionized water at a concentration of 0.8 mol / L and stir vigorously until it is completely dissolved to form solution B;

[0095] (3) Mix solution A obtained in step (1) and solution B obtained in step (2) thoroughly in a 1:1 ratio and stir vigorously, keeping the temperature at 25°C and stirring continuously for 2 hours.

[0096] (4) The solution obtained in step (3) was allowed to stand and separate into layers. The supernatant was removed. The concentrated high-concentration suspension was washed three times by centrifugation with deionized water at a speed of 6000 r / min and the precipitate was collected. The precipitate was dried in air at a temperature of 40°C for 12 hours to obtain the precursor powder.

[0097] (5) The precursor powder obtained in step (4) is heat-treated in a muffle furnace at 800°C for 2 hours to completely transform the precursor powder into a stable tin dioxide phase structure, thereby obtaining high-purity tin dioxide powder.

[0098] The above examples are some implementation cases of this method, but this method is not limited to the above implementation cases. Any changes or adjustments to the parameters disclosed in this method should be considered as within the scope of protection of this method.

Claims

1. A method for preparing nano-petal-shaped spherical tin dioxide powder material, characterized in that, Includes the following steps: (1) Add stannous sulfate or stannous chloride powder to deionized water and mix well to obtain solution A; (2) Add sodium carbonate or potassium carbonate powder to deionized water and dissolve it completely to form solution B; (3) Mix solution A obtained in step (1) and solution B obtained in step (2) thoroughly and stir continuously for 2-8 h; (4) Let the solution obtained from the reaction in step (3) stand to separate into layers, remove the supernatant, centrifuge and wash the concentrated high-concentration suspension and collect the precipitate, and dry the precipitate to obtain precursor powder. (5) The precursor powder obtained in step (4) is calcined and dehydrated to completely transform the precursor powder into a stable tin dioxide phase structure, thus obtaining nano-petal spherical tin dioxide powder material. The nano-petal spherical tin dioxide powder material has a particle size between 5 and 8 μm; it is composed of fine tin dioxide nanoparticles forming petal nanosheets, which are then assembled into a petal spherical structure. In step (3), the stirring speed is controlled at 200~400 r / min and the temperature is controlled at 0~50℃.

2. The preparation method according to claim 1, characterized in that, In step (1), the concentration of stannous sulfate in solution A is controlled to be 0.1~0.5 mol / L.

3. The preparation method according to claim 1, characterized in that, In step (1), solution A is prepared by ultrasonic dispersion for no less than 15 minutes.

4. The preparation method according to claim 1, characterized in that, In step (2), the concentration of sodium carbonate or potassium carbonate in solution B is controlled to be 0.4~2 mol / L.

5. The preparation method according to claim 1, characterized in that, In step (3), the solution A obtained in step (1) and the solution B obtained in step (2) are thoroughly mixed in a 1:1 ratio and stirred vigorously.

6. The preparation method according to claim 1, characterized in that, Step (4) Wash the precipitate at least 3 times with deionized water at a speed of 4000~6000r / min and collect the precipitate. Dry the precipitate in the air at a temperature of 40~80℃ for a time of not less than 12 hours.

7. The preparation method according to claim 1, characterized in that, Step (5) Heat-treat the precursor powder obtained in step (4) in a muffle furnace at a temperature of 400~800℃ for 2~8 h.

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