Hollow tubular ternary tin-selenium-sulfur composite carbon anode material, its preparation method and application

Abstract

This invention discloses a hollow tubular ternary tin-selenium-sulfur composite carbon anode material, its preparation method, and its application. The hollow tubular wall of the hollow tubular ternary tin-selenium-sulfur composite carbon anode material is made of SnSe. 0.5 S 0.5 Constructed from nanocrystals, polyvinylpyrrolidone is carbonized and coated onto hollow tubular SnSe. 0.5 S 0.5 The inner and outer wall surfaces. Prepared according to the following steps: First, prepare pure phase SnSe. 0.5 S 0.5 Nanocrystals; based on pure-phase SnSe 0.5 S 0.5 Nanocrystals, SnSe prepared by electrospinning 0.5 S 0.5 @PVP nanofibers; then SnSe 0.5 S 0.5 Hollow tubular ternary tin-selenium-sulfur composite carbon anode material was prepared by pre-oxidation and calcination of PVP nanofibers. This material is used in the fabrication of lithium-ion, sodium-ion, and potassium-ion batteries, exhibiting good cycle stability.

Description

Technical Field

[0001] This invention belongs to the field of ternary alloy preparation for potassium-ion battery anodes, and relates to a hollow tubular ternary tin-selenium-sulfur composite carbon anode material, its preparation method and application. Background Technology

[0002] Lithium-ion batteries (LIBs) are widely used in portable electronic devices such as mobile phones and laptops due to their high energy density, good cycle performance, safety, and high efficiency. However, the large-scale consumption of lithium resources and their limited storage capacity threaten the continued use of lithium-ion batteries. Therefore, researchers have had to find other electrochemical storage systems that can replace lithium-ion batteries.

[0003] Because potassium ions and lithium ions belong to the same main group, and their redox potentials are very close to those of lithium ions (K... + / K: -2.93V vs. Li + / Li: -3.04V). Therefore, potassium-ion batteries (PIBs) are one of the ideal alternatives to lithium-ion batteries. For both LIBs and PIBs, the anode material is a key factor affecting their electrochemical performance; therefore, developing high-performance anode materials is crucial for promoting the development of potassium-ion batteries.

[0004] Tin-based chalcogenides, including binary sulfides, selenides, and ternary sulfoselenides, possess advantages such as high theoretical capacity and good conductivity, and have therefore been widely studied as anode materials for lithium-ion batteries (LIBs). However, research on their application in polyimide batteries (PIBs) is limited. Theoretically, tin-based chalcogenides all have a two-dimensional layered structure with relatively large interlayer spacing, making them more suitable for large-radius Kc atoms compared to traditional carbon-based anode materials. + Free insertion and extraction are beneficial for obtaining good electrochemical performance. Therefore, it is of great significance to explore and develop tin-based chalcogenides for the anode of potassium-ion batteries.

[0005] Ternary SnSe in tin-based chalcogenides 0.5 S 0.5 In electrochemical storage reactions, it can react with K + The reaction generates intermediate phases such as Sn, K₂S, and K₂Se. The heterogeneous phase boundaries formed in the multiphase system can suppress the coarsening of elemental Sn, thereby achieving higher potassium storage activity. However, SnSe... 0.5 S 0.5 Similar to other tin-based alloy anode materials, SnSe undergoes significant volume expansion during charge and discharge, leading to… 0.5 S 0.5 The structure is damaged after repeated charge-discharge cycles. Two common modification methods are used to address this phenomenon: one is to prepare nanomaterials with special structures, such as hollow structures or multi-level core-shell structures. Hollow or multi-level core-shell structures can be SnSe.0.5 S 0.5 Volume changes provide a buffer space; secondly, composite materials with carbon are constructed, where carbon can act as a buffer matrix to alleviate SnSe. 0.5 S 0.5 Volume expansion. But for ternary SnSe... 0.5 S 0.5 In particular, preparing special structures with nanoscale dimensions and their composites with carbon is quite difficult because SnSe 0.5 S 0.5 The synthesis methods mainly focus on chemical vapor transport, chemical vapor deposition, and solid-state reaction methods. In these methods, the melting point decreases after the elemental Sn, Se, and S form an alloy, and SnSe is synthesized at higher solid-state reaction temperatures. 0.5 S 0.5 It melts into a block ingot, which severely limits the application of SnSe. 0.5 S 0.5 The preparation method hinders the development of SnSe. 0.5 S 0.5 The development and application of negative electrode materials in potassium-ion batteries. Summary of the Invention

[0006] The purpose of this invention is to provide a hollow tubular ternary tin-selenium-sulfur composite carbon anode material and its preparation method, so as to solve the problem of the current special structure of ternary SnSe 0.5 S 0.5 The difficulties in preparing SnSe and its composite materials with carbon, and the existing ternary SnSe 0.5 S 0.5 The problem of poor electrochemical performance as a negative electrode material.

[0007] Another objective of this invention is to provide an application of a hollow tubular ternary tin-selenium-sulfur composite carbon anode material.

[0008] The technical solution adopted in this embodiment of the invention is: a hollow tubular ternary tin-selenium-sulfur composite carbon anode material, wherein the hollow tube wall is made of SnSe 0.5 S 0.5 Constructed from nanocrystals, polyvinylpyrrolidone is carbonized and coated onto hollow tubular SnSe. 0.5 S 0.5 The inner and outer wall surfaces.

[0009] Furthermore, the hollow tubular ternary tin-selenium-sulfur composite carbon anode material described herein is orthorhombic SnSe, as indicated by powder diffraction card number 48-1225 published by JCPDS. 0.5 S 0.5 The structure is consistent.

[0010] Furthermore, the hollow tubular ternary tin-selenium-sulfur composite carbon anode material has an average diameter of 200 nm.

[0011] Another technical solution adopted in this embodiment of the invention is: a method for preparing the hollow tubular ternary tin-selenium-sulfur composite carbon anode material as described above, comprising the following steps:

[0012] Step S1: Preparation of pure phase SnSe 0.5 S 0.5 Nanocrystals;

[0013] Step S2: Based on pure phase SnSe 0.5 S 0.5 Nanocrystals, SnSe prepared by electrospinning 0.5 S 0.5 @PVP nanofibers;

[0014] Step S3: For SnSe 0.5 S 0.5 Hollow tubular ternary tin-selenium-sulfur composite carbon anode material was prepared by pre-oxidation-calcination treatment of PVP nanofibers.

[0015] Furthermore, the preparation process in step S1 includes:

[0016] Step S11: Weigh out the tin source and add it to the organic solvent. Stir until completely dissolved to obtain a tin-containing solvent for later use.

[0017] Step S12: Weigh out the selenium source and sulfur source respectively and add them to the reducing solvent. Stir continuously in a water bath at 50°C for 30-120 minutes. After stirring, a solvent containing selenium source and sulfur source is obtained.

[0018] Step S13: The obtained selenium source and sulfur source solvents are added dropwise to the tin source solvent over 5-10 minutes to obtain a mixed solution. The molar ratio of tin source, selenium source and sulfur source in the mixed solution is 1:0.5:0.5.

[0019] Step S14: Transfer the obtained mixed solution to a reaction vessel with an outer stainless steel vessel and an inner polytetrafluoroethylene vessel, and keep it in an oven at 150~240℃ for 4~36h.

[0020] Step S15: After cooling to room temperature, open the reaction vessel, stir the obtained solution evenly, pour it into a centrifuge tube and centrifuge at high speed. After discarding the supernatant, wash the remaining powder with ethanol and deionized water several times by centrifugation.

[0021] Step S16: After centrifugation and washing, pour the obtained powder into a clean petri dish, freeze-dry it, and obtain pure phase SnSe. 0.5 S 0.5 Nanocrystals.

[0022] Furthermore, the concentration of tin in the tin-containing solvent prepared in step S11 is 0.03~3.3 mol / L, and the tin source is a tin salt soluble in an organic solvent, such as ethylene glycol, glycerol, or ethanol.

[0023] In step S12, the concentrations of selenium and sulfur in the selenium source and sulfur source solvent are 0.17~10 mol / L, respectively. The sulfur source is sulfur powder, thiourea or thioacetamide, the selenium source is at least one of Se powder and SeO2, and the reducing solvent is hydrazine hydrate, ethylenediamine or oleylamine.

[0024] In step S15, high-speed centrifugation is performed at 5000~10000 rpm for 5~25 min;

[0025] In step S16, the freezing temperature for freeze drying is -40 to -20°C, the freezing time is 3 to 6 hours, the drying temperature is 40 to 80°C, and the drying time is 8 to 12 hours.

[0026] Furthermore, the preparation process in step S2 includes:

[0027] Step S21: Weigh polyvinylpyrrolidone and N,N-dimethylformamide in a mass ratio of 0.125~0.5:1, mix them in a beaker, and stir magnetically to obtain a transparent solution A;

[0028] Step S22: Weigh anhydrous ethanol into a beaker and add the pure phase SnSe prepared in step S1. 0.5 S 0.5 Nanocrystals were stirred at room temperature to obtain solution B;

[0029] Step S23: Pour solution B into solution A and continue stirring for 4-12 hours. After standing until there are no bubbles in the mixture, perform electrospinning and collect the fibers.

[0030] Step S24: After the spinning time is reached, immediately place the collected nanofibers into an oven and dry them at 40~80℃ for 8~24 hours to obtain uniformly distributed SnSe. 0.5 S 0.5 @PVP nanofibers.

[0031] Furthermore, in step S21, the magnetic stirring speed is 400~1000r, and the stirring time is 8~24h;

[0032] In step S22, the mixture is stirred at room temperature for 4-12 hours to obtain solution B, which contains anhydrous ethanol and pure phase SnSe. 0.5 S 0.5 The mass ratio of nanocrystals is 10 to 1:1;

[0033] In step S23, electrospinning is performed by injecting a bubble-free mixture into a plastic syringe equipped with a 16-25 gauge needle. The syringe needle is connected to a high-voltage power supply, the solution flow rate is set to 0.5-1.5 ml / h, and the spinning time is 4-12 h.

[0034] Furthermore, the preparation process in step S3 includes:

[0035] Step S31: Apply SnSe to the surface of the aluminum foil 0.5 S 0.5 The PVP nanofibers were removed with tweezers and placed into a clean ceramic boat. The boat was then placed in a muffle furnace and kept at 160-260℃ for 30-120 minutes to complete the SnSe process. 0.5 S 0.5 Pre-oxidation of PVP nanofibers;

[0036] Step S32: After cooling to room temperature, remove the ceramic boat and place it in a vacuum tube furnace. In an inert atmosphere, heat the material to 400-600℃ at a heating rate of 2-10℃ / min and hold for 30-180min. After the reaction is complete, collect the powder to obtain a hollow tubular ternary tin-selenium-sulfur composite carbon anode material.

[0037] Another technical solution adopted in the embodiments of the present invention is the application of the hollow tubular ternary tin-selenium-sulfur composite carbon anode material as described above, used to prepare lithium-ion batteries, sodium-ion batteries and potassium-ion batteries.

[0038] The beneficial effects of the embodiments of the present invention are:

[0039] (1) For the first time, a solvothermal method combined with electrospinning technology was used. The solvothermal method was first used to obtain pure phase SnSe with small size and uniform particle size. 0.5 S 0.5 Nanocrystals, using polyvinylpyrrolidone as the polymer, are used to obtain SnSe through electrospinning. 0.5 S 0.5 Embedded nanofibers are then processed using a pre-oxidation and special heat treatment process to obtain SnSe with a hollow tubular structure. 0.5 S 0.5 @C composite material, namely hollow tubular ternary tin-selenium-sulfur composite carbon anode material, not only expands the anode material system of potassium-ion batteries but also provides a special structure for SnS. 0.5 Se 0.5 A new method for preparing materials has been provided, which solves the current problem of ternary SnSe with special structures. 0.5 S 0.5 The difficulties in preparing composite materials with carbon;

[0040] (2) The hollow tube structure is made of SnSe 0.5 S 0.5Constructed from nanocrystals, polyvinylpyrrolidone is carbonized and coated onto the inner and outer surfaces of the hollow tube, forming SnSe with a special structure. 0.5 S 0.5 @C composite material, this special hollow tube structure and the carbon layers on its inner and outer walls can alleviate SnSe 0.5 S 0.5 The volume expansion during potassium storage, the SnSe 0.5 S 0.5 @C composite material exhibits good cycle stability as a negative electrode material for potassium-ion batteries, solving the problems of existing ternary SnSe... 0.5 S 0.5 The poor electrochemical performance of negative electrode materials has significant scientific implications for their application in potassium-ion battery electrode materials. Attached Figure Description

[0041] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0042] Figure 1 The pure-phase SnSe in Embodiment 3 of this invention 0.5 S 0.5 Scanning electron microscope image of nanocrystals.

[0043] Figure 2 The SnSe prepared in Example 3 of this invention 0.5 S 0.5 Scanning electron microscope image of PVP nanofibers.

[0044] Figure 3 The hollow tubular SnSe prepared in Example 3 of this invention 0.5 S 0.5 X-ray diffraction pattern of @C composite material.

[0045] Figure 4 The hollow tubular SnSe prepared in Example 3 of this invention 0.5 S 0.5 Scanning electron microscope image of the @C composite material.

[0046] Figure 5 The hollow tubular SnSe prepared in Example 3 of this invention 0.5 S 0.5 Cyclic performance curves of @C composite materials. Detailed Implementation

[0047] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0048] Example 1

[0049] A method for preparing hollow tubular ternary tin-selenium-sulfur composite carbon anode material includes the following steps:

[0050] Step S1: Preparation of pure phase SnSe 0.5 S 0.5 Nanocrystals:

[0051] Step S11: Weigh 0.012 mol of SnCl2·2H2O and add it to 60 mL of ethylene glycol. Stir until completely dissolved to obtain a tin-containing source solvent with a tin molar concentration of 0.2 mol / L for later use.

[0052] Step S12: Weigh 0.006 mol of selenium powder and sulfur powder respectively and add them to 8 mL of hydrazine hydrate with a concentration of 80%. Stir continuously in a water bath at 50°C for 60 min to obtain selenium source and sulfur source solvent with concentrations of 0.75 mol / L.

[0053] Step S13: Using a disposable dropper, add the obtained selenium source and sulfur source solvents dropwise to the tin source solvent over 8 minutes to obtain a mixed solution. The molar ratio of tin source, selenium source and sulfur source in the mixed solution is 1:0.5:0.5.

[0054] Step S14: Transfer the obtained mixed solution to a reaction vessel with an outer stainless steel vessel and an inner polytetrafluoroethylene vessel, and keep it in an oven at 240°C for 4 hours;

[0055] Step S15: After cooling to room temperature, open the reaction vessel, stir the obtained solution evenly and pour it into a centrifuge tube. Centrifuge at 9000 rpm for 5 minutes. After discarding the supernatant, wash the remaining powder with ethanol and deionized water three times each by centrifugation.

[0056] Step S16: After centrifugation and washing, the obtained powder is poured into a clean petri dish and dried in a vacuum freeze dryer to obtain pure phase SnSe. 0.5 S 0.5 Nanocrystals, freezing temperature -40℃, freezing time 3h, drying temperature 80℃, drying time 6h;

[0057] Step S2: Based on pure phase SnSe 0.5 S 0.5 Nanocrystals, SnSe prepared by electrospinning0.5 S 0.5 @PVP nanofibers:

[0058] Step S21: Weigh 2.5g of polyvinylpyrrolidone (PVP) and 10g of N,N-dimethylformamide (DMF), mix them in a beaker and stir magnetically at 600r for 16h to obtain a transparent solution A;

[0059] Step S22: Weigh 5g of anhydrous ethanol into a beaker and add 1.0g of pure SnSe prepared in step S1. 0.5 S 0.5 Nanocrystals were stirred at room temperature for 10 hours to obtain solution B.

[0060] Step S23: Pour solution B into solution A and continue stirring for 12 hours. After standing until there are no bubbles in the mixture, perform electrospinning. Inject the mixture into a plastic syringe equipped with a No. 22 needle. Connect the syringe needle to a high-voltage power supply. Set the solution flow rate to 1.2 ml / h and the spinning time to 6 hours. Use aluminum foil to collect the fibers.

[0061] Step S24: After the spinning time is reached, immediately place the fiber membrane in an oven at 50°C and dry for 24 hours to obtain uniformly distributed SnSe. 0.5 S 0.5 @PVP nanofibers;

[0062] Step S3: For SnSe 0.5 S 0.5 Hollow tubular ternary tin-selenium-sulfur composite carbon anode material was prepared by pre-oxidation-calcination treatment of PVP nanofibers.

[0063] Step S31: Apply SnSe to the surface of the aluminum foil 0.5 S 0.5 The PVP nanofibers were removed with tweezers and placed into a clean ceramic boat. The boat was then placed in a muffle furnace and kept at 160°C for 120 minutes to complete the SnSe process. 0.5 S 0.5 Pre-oxidation of PVP nanofibers;

[0064] Step S32: After cooling to room temperature, remove the ceramic boat and place it in a vacuum tube furnace. In an inert atmosphere, heat to 400℃ at a rate of 3℃ / min, hold for 120 min, and collect the powder after the reaction is complete to obtain hollow tubular SnSe. 0.5 S 0.5 @C composite material, namely hollow tubular ternary tin selenium sulfur composite carbon anode material.

[0065] Example 2

[0066] A method for preparing hollow tubular ternary tin-selenium-sulfur composite carbon anode material includes the following steps:

[0067] Step S1: Preparation of pure phase SnSe 0.5 S 0.5 Nanocrystals:

[0068] Step S11: Weigh 0.05 mol of SnCl2·2H2O and add it to 50 mL of glycerol. Stir until completely dissolved to obtain a tin-containing source solvent with a tin concentration of 1 mol / L for later use.

[0069] Step S12: Weigh 0.025 mol of selenium powder and thiourea and add them to 5 mL of ethylenediamine. Stir continuously in a water bath at 50 °C for 120 min. After stirring, a selenium source and a sulfur source solvent with a concentration of 5 mol / L are obtained.

[0070] Step S13: Using a disposable dropper, add the selenium source and sulfur source solvents dropwise to the tin source solvent over 6 minutes to obtain a mixed solution. The molar ratio of tin source, selenium source and sulfur source in the mixed solution is 1:0.5:0.5.

[0071] Step S14: Transfer the obtained mixed solution to a reaction vessel with an outer stainless steel vessel and an inner polytetrafluoroethylene vessel, and keep it in an oven at 200°C for 12 hours;

[0072] Step S15: After cooling to room temperature, open the reaction vessel, stir the obtained solution evenly and pour it into a centrifuge tube. Centrifuge at 10,000 rpm for 15 minutes. After discarding the supernatant, wash the remaining powder with ethanol and deionized water three times each by centrifugation.

[0073] Step S16: After centrifugation and washing, the obtained powder is poured into a clean petri dish and dried in a vacuum freeze dryer to obtain pure phase SnSe. 0.5 S 0.5 The freezing temperature is -30℃, the freezing time is 5 hours, the drying temperature is 60℃, and the drying time is 8 hours.

[0074] Step S2: Based on pure phase SnSe 0.5 S 0.5 Nanocrystals, SnSe prepared by electrospinning 0.5 S 0.5 @PVP nanofibers:

[0075] Step S21: Weigh 1.0g of polyvinylpyrrolidone (PVP) and 4.0g of N,N-dimethylformamide (DMF), mix them in a beaker and stir magnetically at 800 rpm for 8 hours to obtain a transparent solution A. Polyvinylpyrrolidone determines the viscosity of the spinning solution. If too little is added, the spinning solution will be too thin, making it difficult to obtain continuous fibers. If too much is added, the spinning solution will be too viscous, resulting in uneven fibers. Both of these will affect the structure of the obtained hollow tubular ternary tin selenium sulfur composite carbon anode material, thereby affecting its electrochemical performance.

[0076] Step S22: Weigh 2.0 g of anhydrous ethanol into a beaker and add 0.5 g of pure SnSe prepared in step S1. 0.5 S 0.5 The powder was stirred at room temperature for 8 hours to obtain solution B, and pure phase SnSe in anhydrous ethanol was added. 0.5 S 0.5 If the concentration of nanocrystals is too high, the SnSe in the spinning solution will be affected. 0.5 S 0.5 Excessive SnSe content can easily lead to two phenomena: First, SnSe 0.5 S 0.5 The particles disrupt the continuity of the fiber filaments, resulting in uneven fiber lengths, and even SnSe... 0.5 S 0.5 The particles cannot be completely encapsulated by polyvinylpyrrolidone (PVP) and thus agglomerate; secondly, even if it does not affect the spun fibers, SnSe may still agglomerate after the pre-oxidation-carbonization process. 0.5 S 0.5 Excessive particle aggregation prevents the formation of hollow tubular structures; pure phase SnSe in anhydrous ethanol 0.5 S 0.5 When the concentration of nanocrystals is too low, the SnSe formed after the spun fibers undergo a pre-oxidation-carbonization process... 0.5 S 0.5 SnSe in C composite materials 0.5 S 0.5 The content of SnSe is too low, making it unsuitable as an electrode material. 0.5 S 0.5 The capacity of the @C composite material is mainly determined by SnSe. 0.5 S 0.5 Contribution, SnSe 0.5 S 0.5 Too low a content will directly lead to the electrode material SnSe 0.5 S 0.5 @C has a relatively low overall capacity;

[0077] Step S23: Pour solution B into solution A and continue stirring for 6 hours. After standing until there are no bubbles in the solution, perform electrospinning. Inject the mixture into a plastic syringe equipped with a No. 21 needle. Connect the syringe needle to a high-voltage power supply. Set the solution flow rate to 0.9 ml / h and the spinning time to 10 hours. Use aluminum foil to collect the fibers.

[0078] Step S24: After the spinning time is reached, immediately place the aluminum foil containing the collected fibers into an oven at 80°C and dry for 8 hours to obtain uniformly distributed SnSe. 0.5 S 0.5 @PVP nanofibers;

[0079] Step S3: For SnSe 0.5 S 0.5 Hollow tubular ternary tin-selenium-sulfur composite carbon anode material was prepared by pre-oxidation-calcination treatment of PVP nanofibers.

[0080] Step S31: Apply SnSe to the surface of the aluminum foil 0.5 S 0.5 The PVP nanofibers were removed with tweezers and placed into a clean ceramic boat. The boat was then placed in a muffle furnace and kept at 200°C for 80 minutes to complete the SnSe process. 0.5 S 0.5 Pre-oxidation of PVP nanofibers;

[0081] Step S32: After cooling to room temperature, remove the ceramic boat and place it in a vacuum tube furnace. In an inert atmosphere, heat at 10°C / min. -1 The temperature was increased to 600℃ at a heating rate, held for 30 min, and the powder was collected after the reaction was completed to obtain hollow tubular SnSe. 0.5 S 0.5 @C composite material, namely hollow tubular ternary tin selenium sulfur composite carbon anode material.

[0082] Example 3

[0083] A method for preparing hollow tubular ternary tin-selenium-sulfur composite carbon anode material includes the following steps:

[0084] Step S1: Preparation of pure phase SnSe 0.5 S 0.5 Nanocrystals:

[0085] Step S11: Weigh 0.001 mol of SnCl4·5H2O and add it to 30 mL of glycerol. Stir until completely dissolved to obtain a tin-containing source solvent with a tin concentration of 0.03 mol / L for later use.

[0086] Step S12: Weigh 0.0005 mol of selenium powder and thioacetamide and add them to 3 mL of hydrazine hydrate. Stir continuously in a water bath at 50 °C for 90 min. After stirring, a selenium source and a sulfur source solvent with concentrations of 0.17 mol / L are obtained.

[0087] Step S13: Using a disposable dropper, add the selenium source and sulfur source solvents dropwise to the tin source solvent over 5 minutes to obtain a mixed solution. The molar ratio of tin source, selenium source and sulfur source in the mixed solution is 1:0.5:0.5.

[0088] Step S14: Transfer the obtained mixed solution to a reaction vessel with an outer stainless steel vessel and an inner polytetrafluoroethylene vessel, and keep it in an oven at 220°C for 24 hours;

[0089] Step S15: After cooling to room temperature, open the reaction vessel, stir the obtained solution evenly and pour it into a centrifuge tube. Centrifuge at 9000 rpm for 20 min. After discarding the supernatant, wash the remaining powder twice each with ethanol and deionized water by centrifugation.

[0090] Step S16: After centrifugation and washing, the obtained powder is poured into a clean petri dish and dried in a vacuum freeze dryer to obtain pure phase SnSe. 0.5 S 0.5 The freezing temperature is -20℃, the freezing time is 6 hours, the drying temperature is 40℃, and the drying time is 12 hours. Figure 1 As shown, pure-phase SnSe was observed using a field emission scanning electron microscope (S4800). 0.5 S 0.5 It exhibits uniformly sized, small nanoparticles;

[0091] Step S2: Based on pure phase SnSe 0.5 S 0.5 Nanocrystals, SnSe prepared by electrospinning 0.5 S 0.5 @PVP nanofibers:

[0092] Step S21: Weigh 0.05g of polyvinylpyrrolidone (PVP) and 0.25g of N,N-dimethylformamide (DMF), mix them in a beaker and stir magnetically at 500r for 10h to obtain a transparent solution A;

[0093] Step S22: Weigh 0.2 g of anhydrous ethanol into a beaker and add 0.1 g of pure SnSe prepared in step S1. 0.5 S 0.5 The powder was stirred at room temperature for 4 hours to obtain solution B;

[0094] Step S23: Pour solution B into solution A and continue stirring for 8 hours. After standing until there are no bubbles in the solution, perform electrospinning. Inject the mixture into a plastic syringe equipped with an 18-gauge needle. Connect the syringe needle to a high-voltage power supply. Set the solution flow rate to 0.8 ml / h and the spinning time to 12 hours. Use aluminum foil to collect the fibers.

[0095] Step S24: After the spinning time is reached, immediately place the aluminum foil containing the collected fibers into an oven at 60°C and dry for 10 hours to obtain SnSe. 0.5 S 0.5 @PVP nanofibers, such as Figure 2 As shown, SnSe was observed using a field emission scanning electron microscope (S4800). 0.5 S 0.5 @PVP was found to exhibit completely uniformly distributed nanofibers;

[0096] Step S3: For SnSe 0.5 S 0.5 Hollow tubular ternary tin-selenium-sulfur composite carbon anode material was prepared by pre-oxidation-calcination treatment of PVP nanofibers.

[0097] Step S31: Apply SnSe to the surface of the aluminum foil 0.5 S 0.5 The PVP nanofibers were removed with tweezers and placed into a clean ceramic boat. The boat was then placed in a muffle furnace and kept at 180°C for 90 minutes to complete the SnSe process. 0.5 S 0.5 Pre-oxidation of PVP nanofibers;

[0098] Step S32: After cooling to room temperature, remove the ceramic boat and place it in a vacuum tube furnace, where it is heated at 5°C / min in an inert atmosphere. -1 The temperature was increased to 500℃ at a heating rate, held for 60 min, and the powder was collected after the reaction was completed to obtain hollow tubular SnSe. 0.5 S 0.5 @C composite material, namely hollow tubular ternary tin selenium sulfur composite carbon anode material.

[0099] like Figure 3 As shown, the SnSe prepared in this embodiment was analyzed using a Rigaku X-ray diffractometer (Rigaku Ultima IV). 0.5 S 0.5 @C composite powder, which is orthorhombic SnSe with JCPDS number 48-1225 (JCPDS published powder diffraction card number 48-1225). 0.5 S 0.5 The structure (crystal structure) is consistent, and no diffraction peaks of carbon were observed. This may be due to the low degree of carbon graphitization, insufficient carbon content, or its diffraction peaks being obscured by SnSe.0.5 S 0.5 The reason for the obstruction of diffraction peaks. SnSe was observed using a field emission scanning electron microscope (S4800). 0.5 S 0.5 The morphology of the @C composite material, such as Figure 4 As shown, SnSe 0.5 S 0.5 The @C composite material exhibits a hollow tubular structure with an average diameter of 200 nm. The hollow tubular walls are composed of fine SnSe particles. 0.5 S 0.5 It is constructed of nanocrystals, with PVP carbonized and coated on hollow tubular SnSe. 0.5 S 0.5 The inner and outer wall surfaces. In this embodiment, the amount of tin source, selenium source, and sulfur source added is relatively small, and their concentration in the reactor is also relatively small. This results in less competition during nucleation, allowing for complete crystallization and growth, leading to better electrochemical performance of the obtained product. The cycling performance curve of the prepared hollow tubular SnSe0.5S0.5@C composite material is shown in the figure. Figure 5 As shown.

[0100] Example 4

[0101] A method for preparing hollow tubular ternary tin-selenium-sulfur composite carbon anode material includes the following steps:

[0102] Step S1: Preparation of pure phase SnSe 0.5 S 0.5 Nanocrystals:

[0103] Step S11: Weigh 0.2 mol of SnCl4·5H2O and add it to 60 mL of ethanol. Stir until completely dissolved to obtain a tin source solvent with a tin concentration of 3.3 mol / L for later use. 3.3 mol / L is the maximum solubility of the tin source in organic solvents. If the tin source concentration is too high, it will easily cause insufficient dissolution of the tin source. On the other hand, it will increase the probability of crystal nuclei colliding in the same space, which will easily form products with larger sizes, which is not conducive to the improvement of electrochemical performance.

[0104] Step S12: Weigh 0.1 mol of SeO2 and thiourea and add them to 10 mL of ethylenediamine. Stir continuously in a water bath at 50 °C for 30 min. After stirring, the concentrations of selenium and sulfur are 10 mol / L, respectively, to obtain selenium source and sulfur source solvents. 10 mol / L is the maximum solubility of selenium source and sulfur source in reducing solvent. If the concentration is too high, on the one hand, the selenium source and sulfur source will not dissolve sufficiently and will easily generate impurities; on the other hand, it will easily cause the recombination of dissolved ions.

[0105] Step S13: Using a disposable dropper, add the selenium source and sulfur source solvents dropwise to the tin source solvent over 10 minutes to obtain a mixed solution. The molar ratio of tin source, selenium source and sulfur source in the mixed solution is 1:0.5:0.5.

[0106] Step S14: Transfer the obtained mixed solution to a reaction vessel with an outer stainless steel vessel and an inner polytetrafluoroethylene vessel, and keep it in an oven at 160°C for 8 hours;

[0107] Step S15: After cooling to room temperature, open the reaction vessel, stir the obtained solution evenly and pour it into a centrifuge tube. Centrifuge at 5000 rpm for 25 min. After discarding the supernatant, wash the remaining powder three times each with ethanol and deionized water.

[0108] Step S16: After centrifugation and washing, the obtained powder is poured into a clean petri dish and freeze-dried in a vacuum freeze dryer to obtain pure phase SnSe. 0.5 S 0.5 The freezing temperature is -30℃, the freezing time is 4 hours, the drying temperature is 50℃, and the drying time is 10 hours.

[0109] Step S2: Based on pure phase SnSe 0.5 S 0.5 Nanocrystals, SnSe prepared by electrospinning 0.5 S 0.5 @PVP nanofibers:

[0110] Step S21: Weigh 0.6g of polyvinylpyrrolidone (PVP) and 2.5g of N,N-dimethylformamide (DMF), mix them in a beaker and stir magnetically at 1000r for 20h to obtain a transparent solution A;

[0111] Step S22: Weigh 1.0 g of anhydrous ethanol into a beaker and add 0.2 g of pure SnSe prepared in step S1. 0.5 S 0.5 The powder was stirred at room temperature for 12 hours to obtain solution B.

[0112] Step S23: Pour solution B into solution A and continue stirring for 10 hours. After standing until there are no bubbles in the solution, perform electrospinning. Inject the mixture into a plastic syringe equipped with a No. 25 needle. Connect the syringe needle to a high-voltage power supply. Set the solution flow rate to 1.5 ml / h and the spinning time to 4 hours. Use aluminum foil to collect the fibers.

[0113] Step S24: After the spinning time is reached, immediately place the aluminum foil containing the collected fibers into an oven at 70°C and dry for 12 hours to obtain SnSe. 0.5 S 0.5 @PVP nanofibers;

[0114] Step S3: For SnSe 0.5 S 0.5 Hollow tubular ternary tin-selenium-sulfur composite carbon anode material was prepared by pre-oxidation-calcination treatment of PVP nanofibers.

[0115] Step S31: Apply SnSe to the surface of the aluminum foil 0.5 S 0.5 The PVP nanofibers were removed with tweezers and placed into a clean ceramic boat. The boat was then placed in a muffle furnace and kept at 240°C for 60 minutes to complete the SnSe process. 0.5 S 0.5 Pre-oxidation of PVP nanofibers;

[0116] Step S32: After cooling to room temperature, remove the ceramic boat and place it in a vacuum tube furnace. In an inert atmosphere, heat at 2°C / min. -1 The temperature was increased to 400℃ at a heating rate, held for 180 min, and the powder was collected after the reaction was completed to obtain hollow tubular SnSe. 0.5 S 0.5 @C composite material, namely hollow tubular ternary tin selenium sulfur composite carbon anode material.

[0117] Example 5

[0118] A method for preparing hollow tubular ternary tin-selenium-sulfur composite carbon anode material includes the following steps:

[0119] Step S1: Preparation of pure phase SnSe 0.5 S 0.5 Nanocrystals:

[0120] Step S11: Weigh 0.1 mol of SnCl2·2H2O and add it to 80 mL of ethylene glycol. Stir until completely dissolved to obtain a tin-containing source solvent with a tin concentration of 1.25 mol / L for later use.

[0121] Step S12: Weigh 0.05 mol of SeO2 and sulfur powder respectively and add them to 5 mL of oleylamine. Stir continuously in a water bath at 50 °C for 60 min. After stirring, a selenium source and a sulfur source solvent with a concentration of 10 mol / L are obtained.

[0122] Step S13: Using a disposable dropper, add the selenium source and sulfur source solvents dropwise to the tin source solvent over 8 minutes to obtain a mixed solution. The molar ratio of tin source, selenium source and sulfur source in the mixed solution is 1:0.5:0.5.

[0123] Step S14: Transfer the obtained mixed solution to a reaction vessel with an outer stainless steel vessel and an inner polytetrafluoroethylene vessel, and keep it in an oven at 150°C for 36 hours;

[0124] Step S15: After cooling to room temperature, open the reaction vessel, stir the obtained solution evenly and pour it into a centrifuge tube. Centrifuge at 8000 rpm for 12 min. After discarding the supernatant, wash the remaining powder twice each with ethanol and deionized water by centrifugation.

[0125] Step S16: After centrifugation and washing, the obtained powder is poured into a clean petri dish and dried in a vacuum freeze dryer to obtain pure phase SnSe. 0.5 S 0.5 The freezing temperature is -40℃, the freezing time is 5 hours, the drying temperature is 70℃, and the drying time is 8 hours.

[0126] Step S2: Based on pure phase SnSe 0.5 S 0.5 Nanocrystals, SnSe prepared by electrospinning 0.5 S 0.5 @PVP nanofibers:

[0127] Step S21: Weigh 2.0g of polyvinylpyrrolidone (PVP) and 8.0g of N,N-dimethylformamide (DMF), mix them in a beaker and stir magnetically at 400r for 24h to obtain a transparent solution A;

[0128] Step S22: Weigh 3.0 g of anhydrous ethanol into a beaker and add 0.8 g of pure SnSe prepared in step S1. 0.5 S 0.5 The powder was stirred at room temperature for 6 hours to obtain solution B;

[0129] Step S23: Pour solution B into solution A and continue stirring for 4 hours. After standing until there are no bubbles in the solution, perform electrospinning. Inject the mixture into a plastic syringe equipped with a No. 16 needle. Connect the syringe needle to a high-voltage power supply. Set the solution flow rate to 0.5 ml / h and the spinning time to 8 hours. Use aluminum foil to collect the fibers.

[0130] Step S24: After the spinning time is reached, immediately place the aluminum foil containing the collected fibers into an oven at 40°C and dry for 16 hours to obtain SnSe. 0.5 S 0.5 @PVP nanofibers;

[0131] Step S3: For SnSe 0.5 S 0.5 Hollow tubular ternary tin-selenium-sulfur composite carbon anode material was prepared by pre-oxidation-calcination treatment of PVP nanofibers.

[0132] Step S31: Apply SnSe to the surface of the aluminum foil 0.5 S 0.5The PVP nanofibers were removed with tweezers and placed into a clean ceramic boat. The boat was then placed in a muffle furnace and kept at 260°C for 30 minutes to complete the SnSe process. 0.5 S 0.5 Pre-oxidation of PVP nanofibers;

[0133] Step S32: After cooling to room temperature, remove the ceramic boat and place it in a vacuum tube furnace. In an inert atmosphere, heat at 10°C / min. -1 The temperature was increased to 500℃ at a heating rate, held for 90 min, and the powder was collected after the reaction was completed to obtain hollow tubular SnSe. 0.5 S 0.5 @C composite material, namely hollow tubular ternary tin selenium sulfur composite carbon anode material.

[0134] Example 6

[0135] The difference between this embodiment and embodiment 3 is that the molar ratio of tin source, selenium source and sulfur source in the mixed solution of step S13 is 1:0.3:0.3.

[0136] Example 7

[0137] The difference between this embodiment and embodiment 3 is that the molar ratio of tin source, selenium source and sulfur source in the mixed solution of step S13 is 1:0.8:0.8.

[0138] Example 8

[0139] The difference between this embodiment and embodiment 3 is that the molar ratio of tin source, selenium source and sulfur source in the mixed solution of step S13 is 1:0.5:0.7.

[0140] Example 9

[0141] The difference between this embodiment and embodiment 3 is that the molar ratio of tin source, selenium source and sulfur source in the mixed solution of step S13 is 1:0.7:0.5.

[0142] Example 10

[0143] The difference between this embodiment and Embodiment 3 is that the concentration of tin in the tin-containing source solvent in step S11 is 0.2 mol / L.

[0144] Example 11

[0145] The difference between this embodiment and Embodiment 3 is that the concentration of tin in the tin-containing source solvent in step S11 is 1.25 mol / L.

[0146] Example 12

[0147] The difference between this embodiment and Embodiment 3 is that the concentration of tin in the tin-containing source solvent in step S11 is 3.3 mol / L.

[0148] Example 13

[0149] The difference between this embodiment and Embodiment 3 is that the concentrations of selenium and sulfur in the selenium source and sulfur source solvents in step S12 are 5 mol / L, respectively.

[0150] Example 14

[0151] The difference between this embodiment and embodiment 3 is that the concentrations of selenium and sulfur in the selenium source and sulfur source solvents in step S12 are 10 mol / L, respectively.

[0152] Example 15

[0153] The difference between this embodiment and embodiment 3 is that in step S13, the selenium source and sulfur source solvent are added dropwise to the tin source solvent within 7 minutes.

[0154] Example 16

[0155] The difference between this embodiment and embodiment 3 is that in step S13, the selenium source and sulfur source solvent are added dropwise to the tin source solvent over 10 minutes.

[0156] Example 17

[0157] The difference between this embodiment and embodiment 3 is that in step S21, 0.5g of polyvinylpyrrolidone (PVP) and 1g of N,N-dimethylformamide (DMF) are weighed, mixed, and placed in a beaker for magnetic stirring.

[0158] Example 18

[0159] The difference between this embodiment and embodiment 3 is that in step S21, 0.25g of polyvinylpyrrolidone (PVP) and 2g of N,N-dimethylformamide (DMF) are weighed, mixed, and placed in a beaker for magnetic stirring.

[0160] Example 19

[0161] The difference between this embodiment and embodiment 3 is that in step S21, 1.0g of polyvinylpyrrolidone (PVP) and 4.0g of N,N-dimethylformamide (DMF) are weighed, mixed, and placed in a beaker for magnetic stirring.

[0162] Example 20

[0163] The difference between this embodiment and Embodiment 3 is that in step S22, 2g of anhydrous ethanol is weighed into a beaker, and 2g of pure SnSe prepared in step S1 is added. 0.5 S 0.5 The powder was stirred at room temperature for 10 hours to obtain solution B.

[0164] Example 21

[0165] The difference between this embodiment and Embodiment 3 is that in step S22, 8.0 g of anhydrous ethanol is weighed into a beaker, and 0.8 g of pure SnSe prepared in step S1 is added. 0.5 S 0.5 The powder was stirred at room temperature for 6 hours to obtain solution B.

[0166] Example 22

[0167] The difference between this embodiment and Embodiment 3 is that in step S22, 1.0 g of anhydrous ethanol is weighed into a beaker, and 0.2 g of pure SnSe prepared in step S1 is added. 0.5 S 0.5 The powder was stirred at room temperature for 6 hours to obtain solution B.

[0168] Example 23

[0169] The difference between this embodiment and Embodiment 3 is that in step S23, solution B is poured into solution A and stirred for 4 hours, then allowed to stand until no bubbles remain before electrospinning. The mixture is injected into a plastic syringe equipped with a No. 16 needle, which is connected to a high-voltage power supply. The solution flow rate is set to 0.5 ml / h, and the spinning time is 8 hours. Aluminum foil is used to collect the fibers. In step S24, after the spinning time is reached, the aluminum foil containing the collected fibers is immediately placed in an oven at 40°C and dried for 16 hours to obtain SnSe. 0.5 S 0.5 @PVP nanofibers.

[0170] Example 24

[0171] The difference between this embodiment and Embodiment 3 is that in step S23, solution B is poured into solution A and stirred for 12 hours, then allowed to stand until the mixture is free of bubbles before electrospinning. The mixture is injected into a plastic syringe equipped with a No. 22 needle, which is connected to a high-voltage power supply. The solution flow rate is set to 1.2 ml / h, and the spinning time is 6 hours. Aluminum foil is used to collect the fibers. In step S24, after the spinning time is reached, the fiber membrane is immediately placed in an oven at 50°C and dried for 24 hours to obtain uniformly distributed SnSe. 0.5 S 0.5 @PVP nanofibers.

[0172] Example 25

[0173] The difference between this embodiment and Embodiment 3 is that in step S31, the temperature is maintained at 200°C for 80 minutes to complete the SnSe process. 0.5 S 0.5 Pre-oxidation of PVP nanofibers; in step S32, oxidation is carried out at 10 °C / min in an inert atmosphere.-1 The temperature was increased to 600℃ at a heating rate, held for 30 min, and the powder was collected after the reaction was completed to obtain hollow tubular SnSe. 0.5 S 0.5 @C composite material, namely hollow tubular ternary tin selenium sulfur composite carbon anode material.

[0174] Example 26

[0175] The difference between this embodiment and Embodiment 3 is that in step S31, the temperature is maintained at 160°C for 120 minutes to complete the SnSe process. 0.5 S 0.5 @Pre-oxidation of PVP nanofibers; in step S32, the temperature is increased to 400℃ at a heating rate of 3℃ / min in an inert atmosphere, and held for 120min. After the reaction is completed, the powder is collected to obtain hollow tubular SnSe. 0.5 S 0.5 @C composite material, namely hollow tubular ternary tin selenium sulfur composite carbon anode material.

[0176] The cycle performance data of the hollow tubular ternary tin-selenium-sulfur composite carbon anode materials prepared in Examples 1-26 are shown in Table 1. As can be seen from Table 1, the hollow tubular ternary tin-selenium-sulfur composite carbon anode materials prepared in the examples of the present invention have good electrochemical performance and can be used to prepare lithium-ion batteries, sodium-ion batteries and potassium-ion batteries.

[0177] Table 1. Cycle performance data of hollow tubular ternary tin-selenium-sulfur composite carbon anode materials prepared in Examples 1-26

[0178]

[0179] The above description is merely a preferred embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention are included within the scope of protection of the present invention.

Claims

1. A hollow tubular ternary tin-selenium-sulfur composite carbon anode material, characterized in that, Hollow tube wall is made of SnSe 0.5 S 0.5 Nanocrystals are constructed, and polyvinylpyrrolidone is coated on the inner and outer wall surfaces of hollow tubular SnSe 0.5 S 0.5 after carbonization.

2. The hollow tubular ternary tin-selenium-sulfur composite carbon anode material according to claim 1, characterized in that, The hollow tubular ternary tin-selenium-sulfur composite carbon anode material is orthorhombic SnSe according to powder diffraction card number 48-1225 published by JCPDS. 0.5 S 0.5 The structure is consistent.

3. The hollow tubular ternary tin-selenium-sulfur composite carbon anode material according to claim 1, characterized in that, The hollow tubular ternary tin-selenium-sulfur composite carbon anode material has an average diameter of 200 nm.

4. The method for preparing the hollow tubular ternary tin-selenium-sulfur composite carbon anode material according to any one of claims 1 to 3, characterized in that, Includes the following steps: Step S1: Preparation of pure phase SnSe 0.5 S 0.5 Nanocrystals; Step S2: Based on pure phase SnSe 0.5 S 0.5 Nanocrystals, SnSe prepared by electrospinning 0.5 S 0.5 @PVP nanofibers; Step S3: For SnSe 0.5 S 0.5 Hollow tubular ternary tin-selenium-sulfur composite carbon anode material was prepared by pre-oxidation-calcination treatment of PVP nanofibers.

5. The preparation method of the hollow tubular ternary tin-selenium-sulfur composite carbon anode material according to claim 4, characterized in that, The preparation process in step S1 includes: Step S11: Weigh out the tin source and add it to the organic solvent. Stir until completely dissolved to obtain a tin-containing solvent for later use. Step S12: Weigh out the selenium source and sulfur source respectively and add them to the reducing solvent. Stir continuously in a water bath at 50°C for 30-120 minutes. After stirring, a solvent containing selenium source and sulfur source is obtained. Step S13: The obtained selenium source and sulfur source solvents are added dropwise to the tin source solvent over 5-10 minutes to obtain a mixed solution. The molar ratio of tin source, selenium source and sulfur source in the mixed solution is 1:0.5:0.

5. Step S14: Transfer the obtained mixed solution to a reaction vessel with an outer stainless steel vessel and an inner polytetrafluoroethylene vessel, and keep it in an oven at 150~240℃ for 4~36h. Step S15: After cooling to room temperature, open the reaction vessel, stir the obtained solution evenly, pour it into a centrifuge tube and centrifuge at high speed. After discarding the supernatant, wash the remaining powder with ethanol and deionized water several times by centrifugation. Step S16: After centrifugation and washing, pour the obtained powder into a clean petri dish, freeze-dry it, and obtain pure phase SnSe. 0.5 S 0.5 Nanocrystals.

6. The preparation method of the hollow tubular ternary tin-selenium-sulfur composite carbon anode material according to claim 5, characterized in that, The concentration of tin in the tin-containing solvent prepared in step S11 is 0.03~3.3 mol / L. The tin source is a tin salt soluble in an organic solvent, such as ethylene glycol, glycerol, or ethanol. In step S12, the concentrations of selenium and sulfur in the selenium source and sulfur source solvent are 0.17~10 mol / L, respectively. The sulfur source is sulfur powder, thiourea or thioacetamide, the selenium source is at least one of Se powder and SeO2, and the reducing solvent is hydrazine hydrate, ethylenediamine or oleylamine. In step S15, high-speed centrifugation is performed at 5000~10000 rpm for 5~25 min; In step S16, the freezing temperature for freeze drying is -40 to -20°C, the freezing time is 3 to 6 hours, the drying temperature is 40 to 80°C, and the drying time is 8 to 12 hours.

7. The preparation method of the hollow tubular ternary tin-selenium-sulfur composite carbon anode material according to claim 4, characterized in that, The preparation process in step S2 includes: Step S21: Weigh polyvinylpyrrolidone and N,N-dimethylformamide in a mass ratio of 0.125~0.5:1, mix them in a beaker, and stir magnetically to obtain a transparent solution A; Step S22: Weigh anhydrous ethanol into a beaker and add the pure phase SnSe prepared in step S1. 0.5 S 0.5 Nanocrystals were stirred at room temperature to obtain solution B; Step S23: Pour solution B into solution A and continue stirring for 4-12 hours. After standing until there are no bubbles in the mixture, perform electrospinning and collect the fibers. Step S24: After the spinning time is reached, immediately place the collected nanofibers into an oven and dry them at 40~80℃ for 8~24 hours to obtain uniformly distributed SnSe. 0.5 S 0.5 @PVP nanofibers.

8. The preparation method of the hollow tubular ternary tin-selenium-sulfur composite carbon anode material according to claim 7, characterized in that, In step S21, the magnetic stirring speed is 400~1000r, and the stirring time is 8~24h; In step S22, the mixture is stirred at room temperature for 4-12 hours to obtain solution B, which contains anhydrous ethanol and pure phase SnSe. 0.5 S 0.5 The mass ratio of nanocrystals is 10 to 1:1; In step S23, electrospinning is performed by injecting a bubble-free mixture into a plastic syringe equipped with a 16-25 gauge needle. The syringe needle is connected to a high-voltage power supply, the solution flow rate is set to 0.5-1.5 ml / h, and the spinning time is 4-12 h.

9. The preparation method of the hollow tubular ternary tin-selenium-sulfur composite carbon anode material according to claim 4, characterized in that, The preparation process in step S3 includes: Step S31: Apply SnSe to the surface of the aluminum foil 0.5 S 0.5 The PVP nanofibers were removed with tweezers and placed into a clean ceramic boat. The boat was then placed in a muffle furnace and kept at 160-260℃ for 30-120 minutes to complete the SnSe process. 0.5 S 0.5 Pre-oxidation of PVP nanofibers; Step S32: After cooling to room temperature, remove the ceramic boat and place it in a vacuum tube furnace. In an inert atmosphere, heat the material to 400-600℃ at a heating rate of 2-10℃ / min and hold for 30-180min. After the reaction is complete, collect the powder to obtain a hollow tubular ternary tin-selenium-sulfur composite carbon anode material.

10. The application of the hollow tubular ternary tin-selenium-sulfur composite carbon anode material as described in any one of claims 1 to 3, characterized in that, Used in the manufacture of lithium-ion batteries, sodium-ion batteries, and potassium-ion batteries.

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