Tin disulfide crystal as well as preparation method and application thereof
By controlling the temperature and time of high-temperature solid-phase reaction, tin disulfide crystals with a lateral size of 2 to 6 mm were prepared, which solved the problem of insufficient size in the existing technology, achieved efficient and environmentally friendly preparation of tin disulfide crystals, and improved conductivity and optical properties.
Patent Information
- Application Number
- CN202510838956.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-23
- Publication Date
- 2025-09-16
AI Technical Summary
It is difficult to prepare tin disulfide crystals with a lateral size of more than 1 mm by the existing technology through the solid-phase reaction method, and the chemical vapor transport method is costly, the equipment is complex and toxic.
By controlling the calcination temperature, holding time and cooling program of the high-temperature solid-phase reaction, tin disulfide crystals with a lateral size of 2 to 6 mm were prepared, avoiding the use of toxic transfer agents and complex equipment.
The preparation of large-sized tin disulfide crystals with good crystallinity and high purity was achieved, which reduced equipment costs and improved conductivity and optical properties.
Smart Images
Figure CN120649152A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the field of tin disulfide preparation, and specifically comprises a tin disulfide crystal, a preparation method and an application thereof. Background Art
[0002] Two-dimensional layered semiconductor materials are a class of materials with unique structures and excellent properties, enjoying widespread and important applications in optoelectronic devices, energy storage devices, sensors, flexible electronics, catalysis, and other fields. Tin disulfide (SnS2) has become a research hotspot in recent years due to its unique layered crystal structure and ability to absorb visible light, resulting in a rich variety of physical properties.
[0003] Studies have shown that SnS2 nanosheets with lateral dimensions of millimeters or above have higher light absorption efficiency and faster charge carrier diffusion, which significantly improves the light response performance and response speed; it is more convenient to build large-scale devices; and after large-size crystals are peeled off, a larger area of 2D material can be obtained. Its high specific area can increase light absorption and reaction sites, and has great application potential in the fields of electronics, optoelectronics, and catalysis.
[0004] The preparation methods of tin disulfide generally include solid phase reaction method, chemical vapor deposition method (CVD) and chemical vapor transport method (CVT).
[0005] The CVT method utilizes a solid raw material that is difficult to enter the vapor phase. This reacts chemically with another reactant that readily enters the vapor phase, allowing it to enter the vapor phase. This reactant then undergoes a reversible reaction in the growth zone, redepositing to form crystals. Existing techniques using iodine as a transport agent and chemical vapor transport have yielded large lateral sizes of tin disulfide, reaching 5-10 mm. However, the CVT method also has the following disadvantages: 1. High equipment cost: vacuum systems, high-temperature furnaces, gas flow control devices, and reaction chambers are required; 2. The production process is demanding and sensitive, resulting in poor experimental reproducibility: even small fluctuations in parameters such as temperature, pressure, gas flow rate, and deposition time can lead to significant discrepancies in results; 3. Transport agents are often toxic and corrosive: Commonly used transport agents, such as Cl₂, Br₂, and HCl gases, are highly corrosive and environmentally polluting.
[0006] The solid-phase reaction method, in which all reactants are in solid form, directly produces the desired product after reaction. It requires no solvent, has simple equipment, and offers controllable reactions. However, the size of tin disulfide produced by conventional solid-phase reaction methods is relatively small, typically not exceeding 1 mm. For example, a Chinese patent discloses a method for preparing single-crystal tin disulfide nanosheets, comprising the following steps: placing a substrate, SnS2 powder in one container, and sulfur powder in another container in a horizontal tube furnace, heating the furnace to 650-750°C in an inert gas atmosphere, and reacting for 5-30 minutes. The tin disulfide nanosheets are then deposited on the substrate. Optical microscopy images show that the maximum lateral dimension of the tin disulfide nanosheets produced by this method is approximately 0.5 mm, with most sizes concentrated between 0.1 and 0.5 mm. Therefore, the production of tin disulfide nanosheets larger than 1 mm using the solid-phase reaction method is a technical problem that urgently needs to be addressed in the field. Summary of the Invention
[0007] The present invention aims to overcome the defects and shortcomings of the existing solid-phase reaction method that cannot produce tin disulfide crystals with a lateral size of more than 1 mm, and provides a method for producing tin disulfide crystals. By controlling specific reaction conditions, tin disulfide crystals with a lateral size of more than 1 mm can be produced using the solid-phase reaction method.
[0008] Another object of the present invention is to provide a tin disulfide crystal.
[0009] Another object of the present invention is to provide applications of tin disulfide crystals.
[0010] To achieve the above object, the present invention is achieved by the following steps: A method for preparing tin disulfide crystals comprises the following steps: uniformly mixing sulfur powder and tin powder, and calcining in a vacuum environment to obtain tin disulfide crystals; The calcination treatment comprises: heating the temperature to 960-1040°C at a heating rate of 1-2°C / min, maintaining the temperature at 960-1040°C for 1-3 hours; then slowly cooling the temperature to 580-620°C over 80-120 hours, and then slowly cooling the temperature to 480-520°C over 150-350 hours.
[0011] The present invention prepares tin disulfide crystals through a high-temperature solid-phase reaction, and controls the crystal size of the tin disulfide crystals by controlling the calcination temperature, the holding time, and the cooling program. The preparation method of the tin disulfide crystals of the present invention is simple to operate.
[0012] The present invention's method for preparing tin disulfide crystals eliminates the need for toxic and corrosive transfer agents, which are required in the CVT method, thereby preventing environmental pollution. Furthermore, the method eliminates the need for reaction devices such as gas flow control devices used in the CVT method, thereby reducing equipment costs.
[0013] The tin disulfide crystals prepared by the method of the present invention have a lamellar structure, and the lateral size of the tin disulfide crystals is 2 to 6 mm. In addition, the prepared tin disulfide crystals have good crystallinity, high purity, and large size, which is conducive to reducing electron scattering and improving conductivity, and have significant advantages in the fields of optics and electricity.
[0014] In the present invention, the calcination temperature is too low to obtain tin disulfide crystals.
[0015] In the present invention, after the heat preservation treatment, the cooling time significantly affects the size of the tin disulfide crystals. If the cooling time is too short, large-sized tin disulfide crystals cannot be obtained.
[0016] In the present invention, after slowly cooling to 480-520° C., the temperature can be naturally cooled to room temperature.
[0017] In the present invention, the heat treatment may be performed at 960°C, 970°C, 980°C, 990°C, 1000°C, 1010°C, 1020°C, 1030°C or 1040°C.
[0018] In the present invention, the holding time may be 1 h, 1.2 h, 1.4 h, 1.6 h, 1.8 h, 2 h, 2.2 h, 2.4 h, 2.6 h, 2.8 h or 3 h.
[0019] In the present invention, the temperature can be slowly lowered to 580-600° C. over 80 h, 85 h, 90 h, 95 h, 100 h, 105 h, 110 h, 115 h or 120 h.
[0020] In the present invention, the temperature can be slowly lowered to 480-520° C. over 150 h, 180 h, 200 h, 220 h, 240 h, 260 h, 280 h, 300 h, 320 h or 350 h.
[0021] Preferably, the holding time is 2 to 3 hours. A longer holding time can produce larger tin disulfide crystals.
[0022] Preferably, the calcination treatment is carried out at a temperature of 1000-1020° C. A higher calcination temperature is conducive to obtaining larger tin disulfide crystals.
[0023] Preferably, the molar ratio of sulfur powder to tin powder is (2-4):1.
[0024] Preferably, the molar ratio of sulfur powder to tin powder is (2-3):1.
[0025] Preferably, the preparation method comprises the following steps: S1. Grind and mix the sulfur powder and tin powder, press the mixed powder into a tablet and place it in a crucible, place the crucible in a quartz tube, and seal the quartz tube; S2. Vacuum seal the quartz tube; S3. Place the quartz tube in a muffle furnace and begin calcining to obtain tin disulfide crystals.
[0026] Preferably, step S1 is performed in an atmosphere in which both the water content and the oxygen content are lower than 0.1 ppm.
[0027] Preferably, in step S1, the purity of the sulfur powder is ≥99.99% and the purity of the tin powder is ≥99.99%.
[0028] Preferably, in step S1, the crucible is an alumina crucible.
[0029] Preferably, in step S1, after placing the crucible in the quartz tube, the step further includes laying appropriate amounts of quartz wool above and below the crucible to protect the sample.
[0030] Preferably, in step S1, the quartz tube is sealed with a sealing film on the top of the quartz tube.
[0031] Preferably, step S1 is performed in a glove box with water content and oxygen content both lower than 0.1 ppm.
[0032] Preferably, in step S2, a vacuum tube sealing machine is used to wash and vacuum the quartz tube containing the mixed powder, and then seal the tube.
[0033] Preferably, in step S3, the quartz tube is placed vertically in a muffle furnace, and after insulating bricks are placed near the quartz tube, the calcination process is started.
[0034] The present invention also protects the tin disulfide crystals prepared by any of the above methods for preparing tin disulfide crystals.
[0035] Preferably, the tin disulfide crystals are in a lamellar structure, and the lateral size of the tin disulfide crystals is 2-6 mm.
[0036] The present invention also protects the use of the above-mentioned tin disulfide crystals in electrocatalysis or the preparation of photoelectric devices, energy storage devices, sensors, flexible electronic devices, and ferroelectric voltage devices.
[0037] Larger SnS2 crystals themselves have a thin sheet structure that can be bent and integrated into wearable devices such as smart watches while maintaining optoelectronic properties. Therefore, they can be used in the preparation of flexible electronic devices.
[0038] Larger-sized SnS2 crystals are stacked with graphene, hexagonal boron nitride (h-BN), etc. to form heterojunctions, which can be used to prepare high-frequency electronic chips, transistors and other optoelectronic devices.
[0039] The application of tin disulfide crystals in electrocatalysis is mainly due to the fact that larger SnS2 crystals have fewer defects, a longer lifetime of photogenerated carriers, reduced recombination, and improved hydrogen production efficiency. Large crystals have a larger specific surface area and a larger contact area with the reactants, resulting in higher catalytic efficiency.
[0040] Compared with the prior art, the present invention has the following beneficial effects: The present invention provides a method for preparing tin disulfide crystals. The method prepares the tin disulfide crystals through a high-temperature solid-phase reaction, and controls the crystal size of the tin disulfide crystals by controlling the calcination temperature, holding time, and cooling program. The method for preparing the tin disulfide crystals of the present invention is simple to operate.
[0041] The present invention's method for preparing tin disulfide crystals eliminates the need for toxic and corrosive transfer agents, which are required in the CVT method, thereby preventing environmental pollution. Furthermore, the method eliminates the need for reaction devices such as gas flow control devices used in the CVT method, thereby reducing equipment costs.
[0042] The tin disulfide crystals prepared by the method of the present invention have a lamellar structure, a lateral size of 2 to 6 mm, good crystallinity, high purity, and large size, which are beneficial for reducing electron scattering and improving conductivity, and have significant advantages in the fields of optics and electricity. BRIEF DESCRIPTION OF THE DRAWINGS
[0043] Figure 1 This is a physical picture of the sample obtained in Example 1.
[0044] Figure 2 This is a physical picture of the sample obtained in Example 2.
[0045] Figure 3 is the X-ray diffraction pattern of the sample obtained in Example 1.
[0046] Figure 4 This is the X-ray diffraction pattern of the sample obtained in Example 2.
[0047] Figure 5 This is the Raman map of the sample obtained in Example 1.
[0048] Figure 6 The voltage-current (IV) diagrams of the sample obtained in Example 1 under dark conditions and light conditions, respectively.
[0049] Figure 7 This is a current-time (IT) graph of the sample obtained in Example 1 when irradiated with a 365 nm light source at a voltage of 2 V. DETAILED DESCRIPTION
[0050] The present invention will be further described below with reference to the accompanying drawings and specific examples, but the examples do not limit the present invention in any way. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.
[0051] Unless otherwise specified, the reagents and materials used in the following examples were commercially available.
[0052] Example 1 A method for preparing tin disulfide crystals comprises the following steps: S1. In a glove box with a water and oxygen content below 0.1 ppm, weigh 1.187g of tin powder and 0.641g of sulfur powder (molar ratio of sulfur to tin:2:1). Grind the powder in a mortar until uniformly mixed. Press the ground powder into tablets using a tablet press and transfer them to a cleaned corundum crucible. Next, place the crucible containing the sample at the bottom of a quartz tube, placing an appropriate amount of quartz wool above and below the crucible to protect the sample. Seal the quartz tube with parafilm and remove from the glove box.
[0053] S2. Install the quartz tube on a vacuum tube sealing machine and seal it.
[0054] S3. Place the sealed quartz tube upright in a muffle furnace and place insulating bricks near the sample. Set the heating program to slowly increase the temperature from room temperature to 1020°C over 10 hours at a rate of 1-2°C / min. Hold for 2 hours, then slowly cool to 600°C over 100 hours. Then, slowly cool to 500°C over 300 hours. After cooling naturally to room temperature, SnS crystals will form on the inner and outer walls of the alumina crucible and the inner wall of the quartz tube.
[0055] The actual picture of the prepared tin disulfide crystal is as follows Figure 1 As shown, it can be seen that the tin disulfide crystals are golden flakes with a lateral size between 5 and 6 mm.
[0056] Example 2 A method for preparing tin disulfide crystals, which differs from Example 1 in that: The mass of sulfur powder is 1.282g.
[0057] That is, the molar ratio of sulfur powder to tin powder is 4:1.
[0058] The rest is the same as in Example 1 and will not be described again here.
[0059] The actual picture of the prepared tin disulfide crystal is as follows Figure 2 As shown, it can be seen that the tin disulfide crystals are golden flakes with a lateral size between 5 and 6 mm.
[0060] Example 3 A method for preparing tin disulfide crystals, which differs from Example 1 in that: S3. Place the sealed quartz tube upright in a muffle furnace and place insulation bricks near the sample. Set the heating program to slowly increase the temperature from room temperature to 1020°C over 10 hours, hold for 1 hour, then slowly decrease the temperature to 600°C over 100 hours, then slowly decrease the temperature to 500°C over 300 hours, and then naturally cool to room temperature.
[0061] The rest is the same as in Example 1 and will not be described again here.
[0062] The lateral size of the prepared tin disulfide crystals is 3~4mm.
[0063] Example 4 A method for preparing tin disulfide crystals, which differs from Example 1 in that: S3. Place the sealed quartz tube upright in a muffle furnace and place insulation bricks near the sample. Set the heating program to slowly increase the temperature from room temperature to 980°C over 10 hours, hold for 2 hours, then slowly decrease the temperature to 600°C over 100 hours, then slowly decrease the temperature to 500°C over 300 hours, and then naturally cool to room temperature. SnS2 crystals will form on the inner and outer walls of the alumina crucible and the inner wall of the quartz tube.
[0064] The rest is the same as in Example 1 and will not be described again here.
[0065] The lateral size of the prepared tin disulfide crystals is 3~4mm.
[0066] Comparative Example 1 A method for preparing tin disulfide crystals, which differs from Example 1 in that: S3. Place the sealed quartz tube vertically in a muffle furnace and place insulation bricks near the sample. Set the heating program to slowly increase the temperature from room temperature to 700°C over 10 hours, hold for 10 hours, then slowly decrease the temperature to 500°C over 300 hours, and then naturally cool to room temperature.
[0067] The rest is the same as in Example 1 and will not be described again here.
[0068] The result showed that no tin disulfide crystals were generated.
[0069] Comparative Example 2 A method for preparing tin disulfide crystals, which differs from Example 1 in that: S3. Place the sealed quartz tube upright in a muffle furnace and place insulation bricks near the sample. Set the heating program to slowly increase the temperature from room temperature to 1020°C over 10 hours, hold for 2 hours, then slowly decrease the temperature to 600°C over 50 hours, then slowly decrease the temperature to 500°C over 300 hours, and then naturally cool to room temperature. SnS2 crystals will form on the inner and outer walls of the alumina crucible and the inner wall of the quartz tube.
[0070] The rest is the same as in Example 1 and will not be described again here.
[0071] The lateral size of the obtained tin disulfide crystals is less than 1 mm.
[0072] Comparative Example 3 A method for preparing tin disulfide crystals, which differs from Example 1 in that: S3. Place the sealed quartz tube upright in a muffle furnace and place insulation bricks near the sample. Set the heating program to slowly increase the temperature from room temperature to 1020°C over 10 hours, hold for 2 hours, then slowly decrease the temperature to 600°C over 100 hours, then slowly decrease the temperature to 500°C over another 100 hours, and then naturally cool to room temperature. SnS crystals will form on the inner and outer walls of the alumina crucible and the inner wall of the quartz tube.
[0073] The rest is the same as in Example 1 and will not be described again here.
[0074] The lateral size of the obtained tin disulfide crystals is less than 1 mm.
[0075] Performance Testing (1) XRD test: Figure 3 This is the X-ray diffraction pattern of the tin disulfide crystals in Example 1. Figure 4 This is the X-ray diffraction pattern of the tin disulfide crystals of Example 2.
[0076] The XRD data show that the peaks of the tin disulfide crystals in Examples 1 and 2 are sharp, indicating that the crystals are large in size. Furthermore, there are no impurity peaks in the data, indicating that the samples are of very high purity.
[0077] Figure 3 The numerical intensity ratio of the highest peak Figure 4 The numerical intensity of the highest peak is one order of magnitude greater, indicating that the tin disulfide crystals prepared in Example 1 have higher crystallinity.
[0078] (2) Raman spectroscopy: Figure 5 This is the Raman spectrum of Example 1. At 313 cm -1 There is a peak at A corresponding to tin disulfide 1g The peaks indicate that the material is tin disulfide crystals.
[0079] (3) Photoelectric response test: The voltage-current (IV) diagrams of the sample obtained in Example 1 under dark conditions and light conditions are shown in FIG. Figure 6 The UV light source is a UV LED curing device (UV-P60). As can be seen in the IV curve, compared with the dark state, the 365nm light source is applied and the instantaneous power density is 23.5mW / cm 2 , applying 2V voltage, the current has increased significantly.
[0080] Figure 7 This is a current-time (IT) graph of the sample obtained in Example 1 when irradiated with a 365 nm light source at a voltage of 2 V.
[0081] As can be seen from the IT curve, SnS2 crystals have a clear response to light and have clear photoelectric response characteristics. Its characteristics are fast light response speed and stable cycle performance.
[0082] Obviously, the above embodiments of the present invention are merely examples for the purpose of clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Those skilled in the art will appreciate that other variations or modifications can be made based on the above description. It is not necessary and impossible to enumerate all embodiments here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the claims of the present invention.
Claims
1. A method for preparing tin disulfide crystals, characterized in that: The method comprises the following steps: uniformly mixing sulfur powder and tin powder, and calcining in a vacuum environment to obtain tin disulfide crystals; The calcination treatment comprises: heating the temperature to 960-1040°C at a heating rate of 1-2°C / min, maintaining the temperature at 960-1040°C for 1-3 hours; then slowly cooling the temperature to 580-620°C over 80-120 hours, and then slowly cooling the temperature to 480-520°C over 150-350 hours.
2. The method for preparing tin disulfide crystals according to claim 1, wherein The insulation time is 2~3h.
3. The method for preparing tin disulfide crystals according to claim 1, wherein Heat preservation treatment at 1000~1020℃.
4. The method for preparing tin disulfide crystals according to claim 1, wherein The molar ratio of sulfur powder to tin powder is (2~4):
1.
5. The method for preparing tin disulfide crystals according to claim 4, wherein: The molar ratio of sulfur powder to tin powder is (2~3):
1.
6. The method for preparing tin disulfide crystals according to any one of claims 1 to 5, characterized in that: The preparation method comprises the following steps: S1. Grind and mix the sulfur powder and tin powder, press the mixed powder into a tablet and place it in a crucible, place the crucible in a quartz tube, and seal the quartz tube; S2. Vacuum seal the quartz tube; S3. Place the quartz tube in a muffle furnace and begin calcining to obtain tin disulfide crystals.
7. The method for preparing tin disulfide crystals according to claim 6, characterized in that: Step S1 is performed in an atmosphere in which both the water content and the oxygen content are less than 0.1 ppm.
8. Tin disulfide crystals prepared by the method for preparing tin disulfide crystals according to any one of claims 1 to 7.
9. The tin disulfide crystal according to claim 8, characterized in that The tin disulfide crystals have a lamellar structure, and the lateral size of the tin disulfide crystals is 2 to 6 mm.
10. Use of the tin disulfide crystal according to claim 8 or 9 in electrocatalysis or the preparation of optoelectronic devices, energy storage devices, sensors, flexible electronic devices, and ferroelectric devices.