Porous wall-shaped tin sulfide micron material and preparation method thereof

Abstract

The invention belongs to the technical field of functional material preparation, and particularly relates to a porous wall-shaped tin sulfide micron material and a preparation method thereof.The preparation method comprises the steps that a tin source precursor is added into an alcohol solvent to be stirred at the room temperature, then a sulfur source is added, stirring continues to be conducted at the room temperature to be evenly mixed, the obtained precursor mixed solution is subjected to a hydrothermal reaction at the temperature of 120-180 DEG C, and the porous wall-shaped tin sulfide micron material is obtained. And carrying out centrifugal washing and vacuum drying on the product after reaction and cooling to obtain the product. The single-component porous wall-shaped tin sulfide micron material prepared by the method has the characteristics of high specific surface area, rich surface active sites, adjustable mass transfer channels and the like due to the unique porous wall-shaped structure, has efficient catalytic degradation performance on methylene blue, and has important research value in the field of porous materials.

Description

Technical Field

[0001] This invention belongs to the field of functional material preparation technology, specifically relating to a porous wall-shaped tin sulfide micron material and its preparation method. Background Technology

[0002] Tin sulfide, belonging to the IV-VI group, is an important semiconductor material with a hexagonal crystal structure and two-dimensional van der Waals lamellar properties. Its band gap is approximately 2.3 eV and is tunable. It exhibits excellent light absorption response and electrical properties, making it widely used in photocatalysis, solar cells, lithium-ion batteries, and electronic devices. Compared to most semiconductor materials, tin sulfide is abundant and low in toxicity, with a highly stable chemical structure and properties. Both its preparation and recycling processes demonstrate significant advantages in terms of safety and ease of handling.

[0003] In recent years, the microstructure control of tin sulfide, as a functional material, has been extensively studied. Various preparation methods and morphology control strategies have been reported in the prior art. For example, patent CN 119929874 A discloses a tin sulfide / bismuth sulfide composite material and its preparation method, employing a solvothermal one-pot method to mix tin source, bismuth source, sulfur source, activator, acid solution, and solvent to prepare tin sulfide / bismuth sulfide composite materials with morphologies such as rods, hexagonal flakes, curved flakes, and strips. Patent CN 117263234 A discloses a defect-engineered method for preparing hollow mesoporous copper-doped tin sulfide nanospheres. Using a defect engineering strategy, hollow mesoporous copper sulfide is used as a template. Sulfur source, tin source, alkaline substance, and polyvinylpyrrolidone are added to deionized water, and tin sulfide is induced to crosslink and grow inside the porous nanospheres under high temperature and high pressure conditions, ultimately obtaining hollow mesoporous copper-doped tin sulfide nanospheres. Another Chinese patent, CN102412394 B, reports a method for preparing layered tin disulfide / silica core-shell nanorods for lithium batteries. The method involves sulfiding a pre-synthesized tin / silica core-shell material to obtain layered tin disulfide / silica core-shell nanorods. This structure is suitable for lithium battery electrode materials.

[0004] Existing technologies for controlling the morphology of tin sulfide materials mainly focus on strategies such as elemental doping or composites with carbon materials and oxides to optimize their electrochemical or catalytic performance. However, for the construction of the intrinsic microstructure of single-component tin sulfide materials, common morphologies achieved by existing technologies, such as hexagonal plates, rods, spherical particles, flower-like layers, and flower-like spheres, all have certain inherent defects. For example, dense or stacked hexagonal plates and rods often expose limited specific surface areas, and the ion diffusion paths are long, leading to sluggish reaction kinetics. Although the spherical structures formed by the stacking of nanoparticles increase the specific surface area to some extent, their poor internal connectivity is not conducive to sufficient electrolyte wetting and rapid ion transport. Flower-like layers or flower-like spheres formed by the self-assembly of nanosheets have high specific surface areas, but during cycling or reaction, secondary structural units (nanosheets) are prone to slippage, stacking, or even aggregation, leading to a reduction in active sites and decreased structural stability. These structural defects collectively limit the rate performance and long-term cycle stability of single tin sulfide materials in applications such as lithium / sodium ion battery anodes and electrocatalysis.

[0005] To date, no reports have been found in publicly available literature and patents regarding single-component tin sulfide materials with regular, self-supporting porous wall structures. This structural design promises to simultaneously provide tin sulfide materials with high specific surface area, abundant surface active sites, excellent electrolyte permeability, and shortened ion diffusion paths, thereby systematically overcoming the performance bottlenecks of the aforementioned traditional morphologies. Summary of the Invention

[0006] The purpose of this invention is to provide a porous, wall-shaped tin sulfide micron-sized material and its preparation method. This method eliminates the need for template agents or surfactants, and allows for the one-step hydrothermal preparation of a single-component tin sulfide material with a porous, wall-shaped morphology. Compared to common nanoparticle, sheet-like, or dense tin sulfide structures, the core advantage of this carefully constructed porous, wall-shaped tin sulfide material lies in its extremely high specific surface area and abundant surface active sites. The synergistic effect of the high specific surface area and hierarchical pores not only greatly promotes the adsorption and mass transfer efficiency of reactants but also significantly enhances its adsorption and catalytic performance in applications such as methylene blue degradation.

[0007] The present invention is specifically achieved through the following technical solution: a porous wall-shaped tin sulfide micromaterial is proposed according to the present invention. The tin sulfide micromaterial exhibits a porous wall-shaped structure, on which mesopores, macropores and micron-sized pits are widely distributed. Nanosheets are separated between the pores, and the diameter of the pits is about 0.5-5 μm.

[0008] The aforementioned porous, wall-shaped tin sulfide micromaterial was prepared according to the following method: (1) Add the tin source precursor to an alcohol solvent and stir at room temperature for 30-60 min to obtain a mixed system; (2) Under stirring conditions, the sulfur source precursor is added to the mixture obtained in step (1), and stirring is continued at room temperature for 30-60 min to obtain the precursor mixture. (3) Transfer the obtained precursor mixture into a polytetrafluoroethylene liner, seal the polytetrafluoroethylene liner in a stainless steel reactor, place the reactor in an oven, and react at a constant temperature of 120-180 ℃ for 18-24 h. After completion, allow it to cool naturally to room temperature. (4) After cooling the product in step (3), centrifuge the separated solid into a centrifuge tube, add double-distilled water, centrifuge, discard the supernatant and retain the precipitate; wash the precipitate with deionized water 3-5 times, then wash it with anhydrous ethanol 3-5 times, and finally vacuum dry the precipitate to obtain porous wall-shaped tin sulfide micron material.

[0009] The aforementioned porous wall-shaped tin sulfide micron material allows for the control of the amount of sulfur source precursor added, with a molar ratio of sulfur source to tin source greater than 2.

[0010] The aforementioned porous wall-shaped tin sulfide micron material, wherein the tin source is selected from at least one of tin chloride, stannous chloride, tin oxide, and tin acetate.

[0011] In the aforementioned porous wall-shaped tin sulfide micromaterial, the sulfur source is selected from at least one of sodium thiosulfate, thiourea, and sodium sulfide.

[0012] In the aforementioned porous wall-shaped tin sulfide micron material, the solvent is selected from at least one of glycerol, isopropanol, ethylene glycol, and thiols, and the thiols can be selected from at least one of n-dodecyl thiols, n-tetradecyl thiols, n-hexadecyl thiols, and n-octadecyl thiols.

[0013] The aforementioned porous wall-shaped tin sulfide micron material has a polytetrafluoroethylene liner with a filling degree controlled at 50-80%.

[0014] The aforementioned porous wall-shaped tin sulfide micron material is vacuum dried at a temperature of 50-80 °C for 8-12 h.

[0015] The aforementioned porous wall-shaped tin sulfide micron material is a yellowish-brown powder.

[0016] Compared with existing technologies, this invention has significant advantages and beneficial effects. Through the above technical solution, this invention achieves considerable technological advancement and practicality, and has broad application value, possessing at least the following advantages: (1) This invention does not require the introduction of surfactants such as polyvinylpyrrolidone, nor does it rely on a complex sacrificial template method. By simply adjusting the ratio of tin source to sulfur source precursors, a single-component tin sulfide micromaterial with a porous wall-like morphology can be directly synthesized. The entire preparation process is mild, uses inexpensive and safe raw materials, and is environmentally friendly. Subsequent steps of centrifugation, washing, and drying are sufficient to obtain high-purity, well-formed porous wall-like single-component tin sulfide micromaterials. This invention avoids the cumbersome template removal or surfactant cleaning process, simplifying the process and reducing production costs while embodying a green and efficient synthesis concept.

[0017] (2) The present invention has a relatively wide range of raw material selection. Specifically, it selects tin chloride, stannous chloride, tin oxide, tin acetate, etc. as tin source, sodium thiosulfate, thiourea, sodium sulfide, etc. as sulfur source, and glycerol, isopropanol, ethylene glycol, thiol, etc. as solvent and morphology regulator. It is low in toxicity and inexpensive.

[0018] (3) This invention controls the high-pressure environment required for the reaction by controlling the filling degree of the reactor, thus creating critical synthesis conditions for material growth. The essence of the entire reaction process is the synergistic effect of controlled decomposition of inorganic precursors, directional crystal assembly, and anisotropic growth induced by hydroxyl alcohols or thiols. Hydroxyl alcohols or thiols act as both solvents and structure guides. Their internal polar functional groups (hydroxyl or thiol groups) strongly coordinate with the tin species generated by the hydrolysis of the tin source, forming stable complex intermediates, which can finely control the release rate and reaction path of the sulfur-containing groups of the sulfur source. In the initial stage of the reaction, the sulfur-containing groups of the sulfur source combine with the tin complex intermediates to generate spherical or plate-like primary tin sulfide crystal nuclei. Hydroxyl alcohols or thiols, with the selective adsorption capacity generated by their internal polar functional groups (hydroxyl or thiol groups), can act differently on different crystal faces of the primary tin sulfide crystal nuclei, effectively adjusting the surface energy of each crystal face and driving the crystal nuclei to grow anisotropically along a specific direction. During this process, the primary tin sulfide nuclei are further fused and assembled through mechanisms such as orientation attachment and Ostwald ripening, ultimately forming a porous walled tin sulfide micromaterial with complex hierarchical channels and regular thick-walled morphology.

[0019] (4) The tin sulfide micron material synthesized in this invention has a porous wall-like morphology. The inner surface of the wall-like structure is widely distributed with dense mesopores and macropores, with nanosheets separating the pores. The pore structure is flat and extends inward. This porous wall-like structure is mainly formed by the growth of tin source precursor and sulfur source precursor under the action of alcohol solvent as morphology modifier. The inner surface of the wall-like structure also has pits with a diameter of about 0.5-5 μm, similar to meteorite craters. The outer surface of the wall-like structure exhibits a morphology that is non-porous but uneven. The single-component, porous wall-like tin sulfide micron material successfully prepared in this invention not only breaks through the limitations of traditional single tin sulfide morphologies (such as hexagonal plates, rods, etc.), but more importantly, its unique porous wall-like structure significantly increases the specific surface area of ​​the material, exposes more active sites, and optimizes the ion / electron transport pathway. This structural characteristic is crucial for fully leveraging the intrinsic advantages of tin sulfide as a semiconductor material, enabling it to demonstrate greater application potential than traditional morphological tin sulfide materials in fields such as high-performance photocatalysis (e.g., full-spectrum solar-driven reactions), high-sensitivity gas sensing, and next-generation high-efficiency energy storage devices (e.g., sodium / potassium ion battery anodes), thus opening up new pathways for functional enhancement and structural innovation of single-component semiconductor materials. Attached Figure Description

[0020] Figure 1 This is a SEM image of the porous walled tin sulfide synthesized in Example 1.

[0021] Figure 2 This is the XRD pattern of the porous walled tin sulfide synthesized in Example 1.

[0022] Figure 3 This is the absorbance curve of methylene blue over time in the experiment of catalytic degradation of methylene blue by porous walled tin sulfide synthesized in Example 1.

[0023] Figure 4 This is a SEM image of the porous walled tin sulfide synthesized in Example 2.

[0024] Figure 5 This is a SEM image of the porous walled tin sulfide synthesized in Example 3.

[0025] Figure 6 This is a SEM image of the porous walled tin sulfide synthesized in Example 4. Detailed Implementation

[0026] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below in conjunction with specific embodiments. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0027] The present invention will be described in detail below with reference to specific embodiments. Unless otherwise specified, all conditions in the embodiments are performed under conventional conditions or conditions recommended by the manufacturer. Raw materials and reagents whose manufacturers are not specified are all commercially available products.

[0028] Example 1: (1) Weigh 1.54 mmol of tin tetrachloride pentahydrate into a 50 mL beaker, add 30 mL of glycerol as a solvent, and stir at room temperature for 30 min to obtain a mixed system; (2) Under stirring conditions, 6.57 mmol of thiourea was slowly added to the mixture obtained in step (1), and stirring was continued at room temperature for 30 min to obtain the precursor mixture; (3) Transfer the obtained precursor mixture into a 50 mL polytetrafluoroethylene liner and seal the polytetrafluoroethylene liner in a stainless steel reactor, controlling the filling degree of the reactor to about 60%; then place the reactor in an oven and heat it to 180 °C, and react at this temperature for 18 h, and then let it cool naturally to room temperature after completion. (4) Centrifuge the product obtained in step (3), place the separated solid in a centrifuge tube, add double-distilled water, centrifuge, discard the supernatant and retain the precipitate; wash the precipitate three times with deionized water, then wash it three times with anhydrous ethanol, and finally place the centrifuge tube containing the precipitate in a vacuum drying oven at 50 ℃ for 12 h to dry. The resulting yellow-brown powder product is the tin sulfide sample.

[0029] The morphology and phase composition of the tin sulfide sample prepared in this embodiment were characterized. Figure 1 and Figure 2 These are the SEM and XRD patterns of the tin sulfide sample prepared in this embodiment, respectively. Figure 1 As can be seen, the tin sulfide samples exhibit a typical porous wall-like structure, with densely distributed mesopores, macropores, and micron-sized pits of approximately 0.5-5 μm in diameter and a certain depth. These mesopores, macropores, and micron-sized pits together constitute a multi-scale hierarchical pore system. Compared to common nanoparticle, lamellar, or dense tin sulfide structures, the core advantage of this carefully constructed porous wall-like morphology of tin sulfide lies in its extremely high specific surface area (tested to reach 32 m²). 2The high specific surface area and hierarchical pore system not only greatly promote the adsorption and mass transfer efficiency of reactants, but also significantly improve its catalytic performance.

[0030] from Figure 2 It can be seen that the XRD characteristic diffraction peaks of the sample are obvious and correspond to the diffraction peaks of tin sulfide, proving that tin sulfide was synthesized, and that the synthesized tin sulfide sample has high purity and high stability.

[0031] Application of the tin sulfide sample prepared in this embodiment in the catalytic degradation of organic dyes: 3 mL of a 0.05 mM methylene blue aqueous solution was mixed with 0.05 mL of a freshly prepared 50 mM potassium borohydride aqueous solution to obtain a mixed solution. The porous walled tin sulfide sample prepared in this example was dispersed in water to prepare a tin sulfide dispersion with a concentration of 0.25 mg / mL. 0.05 mL of the tin sulfide dispersion was added to the obtained mixed solution to obtain the degradation system. The degradation process of methylene blue was monitored at 664 nm using a UV-Vis spectrophotometer. The absorbance of the degradation system at 664 nm at different degradation times was measured, and the absorbance change curve over time was plotted. The results are shown below. Figure 3 As shown. From Figure 3 As observed, after the addition of tin sulfide dispersion, the absorbance of methylene blue at 664 nm gradually decreased over time. At 360 s, the absorbance of the solution was approximately 1.2, and then remained almost unchanged with further extension of time, proving that the methylene blue had been completely catalytically degraded. These experimental results demonstrate that the prepared porous wall-shaped tin sulfide micromaterial exhibits highly efficient catalytic degradation performance for methylene blue, with the reaction essentially completed within approximately 360 s (6 min), confirming the application potential of porous wall-shaped tin sulfide micromaterials in the rapid degradation of organic dyes. This excellent catalytic degradation efficiency is mainly attributed to the high specific surface area and abundant active sites resulting from the unique porous wall structure of the tin sulfide micromaterial, providing a reference for the development of high-performance catalytic materials.

[0032] Example 2: (1) Weigh 1.54 mmol of stannous chloride dihydrate into a 50 mL beaker, add 25 mL of isopropanol as a solvent, and stir at room temperature for 30 min to obtain a mixed system; (2) Under stirring conditions, 5.26 mmol of thiourea was slowly added to the mixture obtained in step (1), and stirring was continued at room temperature for 30 min to obtain the precursor mixture; (3) Transfer the obtained precursor mixture into a 50 mL polytetrafluoroethylene liner and seal the polytetrafluoroethylene liner in a stainless steel reactor, controlling the filling degree of the reactor to be about 50%; then place the reactor in an oven and heat it to 120 °C, and keep it at this temperature for 24 h. After completion, let it cool naturally to room temperature. (4) Centrifuge the product obtained in step (3), place the separated solid in a centrifuge tube, add double-distilled water, centrifuge, discard the supernatant and retain the precipitate; wash the precipitate three times with deionized water, then wash it three times with anhydrous ethanol, and finally place the centrifuge tube containing the precipitate in a vacuum drying oven at 60 ℃ for 10 h to dry. The resulting yellow-brown powder product is the tin sulfide sample.

[0033] Figure 4 This is a SEM image of the tin sulfide sample prepared in this embodiment. Figure 4 It can be observed that the morphology of the synthesized tin sulfide sample after changing the experimental conditions is similar to that of the original sample. Figure 1 The tin sulfide samples are quite similar, maintaining a porous wall structure with densely distributed mesopores, macropores and pits. The pit diameter is about 1-5 μm, and the pores are separated by nanosheets. Figure 4 It can also be observed that some of the holes attached to the wall-like structure do not penetrate the thick wall they are in.

[0034] Example 3: (1) Weigh 1.54 mmol of tin oxide and place it in a 50 mL beaker. Add 30 mL of ethylene glycol as a solvent and stir at room temperature for 30 min to obtain a mixed system. (2) Under stirring conditions, 6.57 mmol sodium thiosulfate was slowly added to the mixture obtained in step (1), and stirring was continued at room temperature for 30 min to obtain the precursor mixture; (3) Transfer the obtained precursor mixture into a 50 mL polytetrafluoroethylene liner and seal the polytetrafluoroethylene liner in a stainless steel reactor, controlling the filling degree of the reactor to about 60%; then place the reactor in an oven and heat it to 140 °C, and keep it at this temperature for 22 h. After completion, allow it to cool naturally to room temperature. (4) Centrifuge the product obtained in step (3), place the separated solid in a centrifuge tube, add double-distilled water, centrifuge, discard the supernatant and retain the precipitate; wash the precipitate three times with deionized water, then wash it three times with anhydrous ethanol, and finally place the centrifuge tube containing the precipitate in a vacuum drying oven at 50 ℃ for 12 h to dry. The resulting yellow-brown powder product is the tin sulfide sample.

[0035] Figure 5 This is a SEM image of the tin sulfide sample prepared in this embodiment. Figure 5It can be observed that the tin sulfide samples synthesized after changing the tin source, sulfur source, and solvent have similar morphologies to those synthesized in other samples. Figure 1 The tin sulfide samples showed similar morphologies, maintaining a porous wall structure with densely distributed mesopores and macropores, separated by nanosheets. Figure 5 Furthermore, it can be clearly observed that the material surface has pits similar to meteorite craters, with a diameter of approximately 1-5 μm. The pore distribution inside the pits is not as dense as that outside the pits, and the pores on the material surface as a whole exhibit a special structure with varying pore sizes and inward-extending channels.

[0036] Example 4: (1) Weigh 1.54 mmol of tin acetate and place it in a 50 mL beaker. Add 35 mL of n-dodecyl mercaptan as a solvent and stir at room temperature for 30 min to obtain a mixed system. In this step, n-dodecyl mercaptan is used as both a solvent and a sulfur source. (2) Transfer the obtained mixture into a 50 mL polytetrafluoroethylene liner and seal the polytetrafluoroethylene liner in a stainless steel reactor, controlling the filling degree of the reactor to be about 70%; then place the reactor in an oven and heat it to 160℃, and keep it at this temperature for 20 h. After completion, allow it to cool naturally to room temperature. (3) Centrifuge the product obtained in step (3), place the separated solid in a centrifuge tube, add double-distilled water, centrifuge, discard the supernatant and retain the precipitate; wash the precipitate three times with deionized water, then wash it three times with anhydrous ethanol, and finally place the centrifuge tube containing the precipitate in a vacuum drying oven at 70 ℃ for 8 h to dry. The resulting yellow-brown powder product is the tin sulfide sample.

[0037] Figure 6 This is a SEM image of the tin sulfide sample prepared in this embodiment. Figure 6 It can be observed that the synthesized tin sulfide samples, even after changing the experimental conditions, still maintained a porous wall-like structure. The inner surface of this wall-like structure is widely distributed with dense mesopores, macropores, and crater-like depressions approximately 1.5-5 μm in diameter. The interior of these depressions has fewer pores. Figure 6 It can also be observed that the outer surface of the wall-like structure does not have pores, but rather has uneven depressions, which is the surface morphology formed by crystal growth and fusion.

[0038] In other embodiments, the dodecyl mercaptan in Example 4 can be replaced with tetradecyl mercaptan, hexadecyl mercaptan, or octadecyl mercaptan.

[0039] The single-component, porous wall-shaped tin sulfide micromaterial successfully prepared by this invention not only breaks through the limitations of traditional single tin sulfide morphology (such as hexagonal plates, rods, etc.), but more importantly, its unique porous wall structure exhibits high specific surface area, abundant surface active sites, and tunable mass transfer channels, which has important research value in the field of porous materials, and is especially suitable for adsorption and separation, electrode materials for energy storage devices, catalytic degradation of pollutants, and sensitive sensing.

[0040] The above description is merely an embodiment of the present invention and is not intended to limit the present invention in any way. The present invention can also have other embodiments based on the above structure and function, which will not be listed hereafter. Therefore, any simple modifications, equivalent changes, and alterations made by those skilled in the art to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A porous wall-shaped tin sulfide micron-sized material, characterized in that, Tin sulfide micron-sized materials exhibit a porous wall-like structure, with mesopores, macropores, and micron-sized pits widely distributed on the wall-like structure. The pores are separated by nanosheets, and the pits have a diameter of 0.5-5 μm.

2. The porous wall-shaped tin sulfide micron material as described in claim 1, characterized in that, Prepared according to the following method: (1) Add the tin source precursor to an alcohol solvent and stir at room temperature for 30-60 min to obtain a mixed system; (2) Under stirring conditions, the sulfur source precursor is added to the mixture obtained in step (1), and stirring is continued at room temperature for 30-60 min to obtain the precursor mixture. (3) Transfer the obtained precursor mixture into a polytetrafluoroethylene liner, seal the polytetrafluoroethylene liner in a stainless steel reactor, place the reactor in an oven, and react at a constant temperature of 120-180 ℃ for 18-24 h. After completion, allow it to cool naturally to room temperature. (4) After cooling the product in step (3), centrifuge the separated solid into a centrifuge tube, add double-distilled water, centrifuge, discard the supernatant and retain the precipitate; wash the precipitate with deionized water 3-5 times, then wash it with anhydrous ethanol 3-5 times, and finally vacuum dry the precipitate to obtain porous wall-shaped tin sulfide micron material.

3. The porous wall-shaped tin sulfide material as described in claim 2, characterized in that, The molar ratio of sulfur source to tin source is greater than 2.

4. The porous wall-shaped tin sulfide material as described in claim 2 or 3, characterized in that, The tin source is selected from at least one of tin chloride, stannous chloride, tin oxide, and tin acetate.

5. The porous wall-shaped tin sulfide micron material as described in claim 2 or 3, characterized in that, The sulfur source is selected from at least one of sodium thiosulfate, thiourea, and sodium sulfide.

6. The porous wall-shaped tin sulfide micron material as described in claim 2 or 3, characterized in that, The solvent is selected from at least one of glycerol, isopropanol, ethylene glycol, and thiols.

7. The porous wall-shaped tin sulfide micron material as described in claim 6, characterized in that, The thiol is selected from at least one of dodecyl thiol, tetradecyl thiol, hexadecyl thiol, and octadecyl thiol.

8. The porous wall-shaped tin sulfide micron material as described in claim 2 or 3, characterized in that, The filling degree of the polytetrafluoroethylene liner is controlled at 50-80%.

9. The porous wall-shaped tin sulfide micron material as described in claim 2 or 3, characterized in that, The vacuum drying temperature is 50-80 ℃, and the drying time is 8-12 h.

10. The porous wall-shaped tin sulfide micron material as described in claim 2 or 3, characterized in that, The obtained porous wall-shaped tin sulfide micron material is a yellowish-brown powder.

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