Electrode material of hollow tire-like carbon material composite transition metal sulfoselenide

Abstract

The application discloses a hollow tire-shaped carbon material composite transition metal sulfur selenium compound electrode material, which comprises an aspergillus niger spore-derived carbon framework with a three-dimensional hollow tire-shaped structure and a transition metal sulfur selenium compound nanosheet material loaded on the carbon framework, and an outer layer of the nanosheet material is coated with a carbon layer; the electrode material has a chemical composition represented by ANDC@MSSe@C, wherein ANDC is an aspergillus niger-derived hollow tire-shaped carbon framework, and M is a metal element Sn, Mo or W. The electrode material has a high specific capacity, a good retention after 2000 cycles, a good and stable electrochemical performance, and a very good structural stability and cycle life under an ultrahigh rate. The raw material cost of the application is low, energy consumption is low, reaction conditions are easier to realize, and the application is convenient for commercial application, and the application shows a great application prospect in a sodium ion battery.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of sodium ion battery materials, and particularly relates to a hollow tire-shaped carbon material composite transition metal sulfide-selenide electrode material. BACKGROUND

[0002] Lithium ion batteries (LIBs) have attracted extensive research interest worldwide since their first commercialization in 1991. LIBs have been booming in emerging application fields due to their high energy density, strong safety, and long cycle life. However, the scarcity and uneven distribution of lithium resources make it difficult to sustain the demand for large-scale energy storage systems. In order to alleviate this situation, the development of an alternative rechargeable battery system has attracted widespread attention. Among the numerous candidate batteries, sodium ion batteries (SIBs) stand out with their abundant sources, suitable redox potential, and low cost, and are considered to be a good substitute for LIBs and a key technology for large-scale energy storage. In addition, cheaper, lighter, and more abundant aluminum (Al) foil can be used as the current collector for SIBs, while copper (Cu) is the only choice for LIBs, which means that SIBs have lower cost and greater commercial potential. Despite the many attractive advantages of SIBs, they also face many daunting challenges. The ionic radius (Na + For Li + For ) and molar mass (Na 22.99 gmol -1 , Li 6.94 g mol -1 ) are significantly larger than Li, which is not conducive to the diffusion kinetics of sodium ions during sodiumization / desodiation and the structural stability of electrode materials. Unfortunately, this means that most traditional electrode materials used for LIBs cannot be used for SIBs. Therefore, the key technology for developing SIBs lies in developing electrode materials with good electrochemical performance.

[0003] In the past few years, SIBs cathode materials have made encouraging progress, including layered materials, polyanionic compounds, and Prussian blue analogues. However, the development of anode materials with low electrochemical reaction platforms, relatively high reversible capacity, and stable structure is still insufficient. So far, the commonly used anode materials for SIBs are carbonaceous materials, titanium materials, alloy materials, metal oxides / sulfides / selenides, and organic materials, etc. Among them, metal chalcogenides with layered and non-layered structures have become a research hotspot due to their diverse material types. In particular, transition metal sulfides (TMS) with layered structure have the advantages of abundant reserves, low cost, stable performance, high theoretical capacity, etc. In addition, due to their multi-electron redox reactions and easy breaking of M-S bonds (M represents metal), they show higher theoretical capacity and faster ion diffusion rate. For example, the invention patent CN110600275B discloses a preparation method and application of a metal sulfide / carbon composite electrode material, in which the carbon and metal sulfide are uniformly compounded, having good electrical conductivity and stable bowl-shaped structure. The invention patent CN112349889B discloses a preparation method of a transition metal sulfide nanocomposite electrode material, which synthesizes MOFs precursor as a hard template, and through one-step carbonization and sulfuration, the structure characteristics of the MOFs precursor are maintained while the metal sulfide is prepared. However, most of them still suffer from the defects of inherent low electrical conductivity and severe volume expansion during long-term cycling, which will lead to poor rate performance and rapid capacity decay. In order to solve these thorny problems, people have made considerable efforts to build delicate nanostructures. Specifically, the introduction of exogenous anion ligands to form single-phase ternary metal disulfides plays an interface engineering role at the atomic level, providing a promising way to adjust their physical and chemical properties. Selenium (Se) has similar chemical properties to sulfur, but has a smaller band gap and larger atomic radius. Therefore, doping Se atoms into the lattice of layered TMSs forms S 2-x Se x interlayer ligands, which can improve electrical conductivity, expand interlayer spacing, enrich anion defect sites, and enhance the storage capacity of Na + . On the other hand, TMSs with hollow (internal void) structure and carbon modification can accommodate the volume expansion during Na + insertion, maintain structural stability and improve electrical conductivity, thereby ensuring extended service life and promoting Na +However, the existing composite layered structure metal disulfide electrode material still has the problem of repeated insertion of sodium ions, which causes the stacking, agglomeration and even the collapse of the structure of the ultra-thin nanosheet, thereby limiting the large-scale application of the electrode material in SIBs, and the performance is not satisfactory. Moreover, most of the metal disulfides reported so far involve relatively complex synthesis process, expensive instruments, uncontrollable anion concentration and other problems. Therefore, it is a very urgent challenge to develop an efficient and scalable method for large-scale preparation of transition metal-based sulfide selenide with fast charge transport characteristics and strong structure. SUMMARY

[0004] Therefore, the purpose of the present application is to provide a hollow tire-shaped carbon material composite transition metal sulfide selenide electrode material, which has ultra-high reversible capacity, ultra-long cycle life and good structural stability under ultra-high rate, and solves the problems of slow ion transport rate, serious volume expansion and repeated insertion of sodium ions, which causes the stacking, agglomeration and even the collapse of the structure of the ultra-thin nanosheet of the existing metal sulfide electrode material.

[0005] To achieve the above purpose, the present application provides the following technical scheme: a hollow tire-shaped carbon material composite transition metal sulfide selenide electrode material, comprising an Aspergillus Niger spores derived carbon framework with a three-dimensional hollow tire-shaped structure and a transition metal sulfide selenide nanosheet material loaded on the carbon framework, and an outer layer of the nanosheet material is coated with a carbon layer, and the outer layer of the carbon layer is a glucose (G), polypyrrole (PPy) or polydopamine (PDA) derived carbon layer. The outer layer of the carbon layer can effectively protect the structure of the material during the sodium ion extraction process and provide better conductivity; the electrode material has a chemical composition represented by ANDC@MSSe@C, wherein ANDC is an Aspergillus Niger derived hollow tire-shaped carbon framework, and M is a metal element Sn, Mo or W. Compared with M-S, the M-Se bond has a weak bond strength and is easy to break in the conversion reaction, and in the sodium ion extraction process, the formation of sodium polysulfide molecules is limited, thereby further enhancing the Na + kinetics and reversible sodium ion extraction. As a preferred, the M is a metal element Sn, and the outer layer of the carbon layer is a glucose derived carbon layer.

[0006] Another purpose of the present application is to provide a preparation method of the hollow tire-shaped carbon material composite transition metal sulfide selenide electrode material, comprising the following steps:

[0007] 1) ultrasonic treatment of Aspergillus Niger spores in deionized water and cleaning, drying;

[0008] 2) The Aspergillus niger spores obtained in step 1) are subjected to high-temperature carbonization treatment in a tube furnace with a protective atmosphere, and after the reaction is completed, the temperature is allowed to decrease naturally to obtain the Aspergillus niger spore-derived hollow tire-shaped carbon material ANDC;

[0009] 3) The ANDC material obtained in step 2) is placed in a solution containing a sulfur source and one of a tin source, a molybdenum source and a tungsten source, and is continuously stirred to obtain a mixed solution, and then the mixed solution is transferred into a high-pressure reaction kettle for high-temperature reaction, and after the reaction is completed, the temperature is allowed to decrease naturally, and then the product is washed with deionized water and anhydrous ethanol multiple times and is subjected to drying treatment to obtain the ANDC@MS2 composite material.

[0010] 4) The ANDC@MS2 composite material obtained in step 3) is added to an aqueous solution containing glucose and is continuously stirred to obtain a suspension, and then the suspension is transferred into a high-pressure reaction kettle for hydrothermal reaction, and after the reaction is completed, the temperature is allowed to decrease naturally to obtain the product ANDC@MS2@G; or the ANDC@MS2 composite material obtained in step 3) is added to an aqueous solution containing dopamine or pyrrole, and polymerization reaction occurs under room temperature conditions to obtain the product ANDC@MS2@PPy or ANDC@MS2@PDA;

[0011] 5) The product obtained in step 4) is washed with deionized water and anhydrous ethanol multiple times and is subjected to drying treatment, and then the dried product is placed in a tube furnace with a protective atmosphere for high-temperature carbonization treatment, and after the reaction is completed, the temperature is allowed to decrease naturally to obtain the ANDC@MS x @C (x = 1 or 2) composite material; when M is W and Mo, X is 2, that is, the loaded WS2 and MoS2 do not change after carbonization annealing; when M is Sn, X is 1, that is, the loaded SnS2 changes to SnS after carbonization annealing.

[0012] 6) The ANDC@MS x @C prepared in step 4) and selenium powder are respectively placed in a porcelain boat and wrapped with a tin foil, and then they are subjected to selenization treatment in a protective atmosphere, and after the reaction is completed, the temperature is allowed to decrease naturally to obtain the hollow tire-shaped carbon material composite transition metal sulfoselenide electrode material ANDC@MSSe@C.

[0013] Further, the high-temperature carbonization treatment in step 2) is to increase the temperature to 500-1000°C at a temperature increasing rate of 1-20°C / min, and to keep the temperature for 0.5-10 h; the high-temperature reaction in step 3) is at a temperature of 180-220°C for 12-24 h.

[0014] Further, the tin source in step 3) is tin tetrachloride or stannous chloride; the molybdenum source is sodium molybdate or ammonium molybdate; the tungsten source is sodium tungstate or ammonium tungstate; the sulfur source is sublimed sulfur, thioacetamide or thiourea; when the tin source is added in the mixed solution, the solution is an organic solvent, and the organic solution is ethylene glycol or isopropyl alcohol; when the molybdenum source or the tungsten source is added in the mixed solution, the solution is deionized water.

[0015] Further, the addition amount of ANDC in the mixed solution in step 3) is 1.0-10 mg / mL, and the molar ratio of the tin source, the molybdenum source or the tungsten source to the sulfur source is 1:2-1:4.

[0016] Further, the concentration of the glucose, dopamine or pyrrole in step 4) is 0.02-0.1 M; the temperature of the hydrothermal reaction is 150-200 ℃, and the time is 6-24 h.

[0017] Further, in step 5), the high-temperature carbonization treatment is to increase the temperature to 500-800 ℃ at a temperature increasing rate of 1-10 ℃ / min, and then keep the temperature for 1-6 h.

[0018] Further, in step 6), the selenium treatment is to increase the temperature to 350-450 ℃ at a temperature increasing rate of 1-5 ℃ / min, and then keep the temperature for 0.5-5 h; the mass ratio of the ANDC@MS x to selenium powder is 1:1-1:10.

[0019] Further, the protective atmosphere is argon or nitrogen; and the drying is treated at 25-90 ℃ for 8-12 h.

[0020] Another object of the present application also provides the application of the electrode material prepared by the above method in a sodium ion battery.

[0021] Compared with the prior art, the present application has the following beneficial effects:

[0022] 1. The hollow tire-shaped carbon material composite transition metal sulfur selenium compound electrode material provided by the present application utilizes a hollow tire-shaped carbon skeleton derived from Aspergillus niger spores to composite layered ternary transition metal sulfur selenium compound nanosheets. In this structure, the hollow tire-shaped carbon skeleton derived from Aspergillus niger spores can effectively induce the uniform growth of metal sulfur selenium compound nanosheets, thereby effectively inhibiting the structural damage, crushing and agglomeration of metal sulfur selenium compounds in the repeated sodium removal process of sodium ions, thereby exhibiting high specific capacity and good cycle life. At the same time, with the uniform substitution of Se atoms for S atoms, the rich crystal defects formed in situ in the metal sulfur selenium compound nanosheets not only can serve as convenient Na + diffusion sites, but also can effectively inhibit the structural damage of the metal sulfur selenium compound nanosheets in the repeated sodium removal process of sodium ions, thereby effectively inhibiting the structural damage of the metal sulfur selenium compound nanosheets in the repeated sodium removal process of sodium ions. +a fast insertion process, and can act as a propellant for the intermediate product nucleation process in the initial transformation state by effectively reducing the Gibbs free energy, resulting in the final product M 0 uniform distribution between the three of Na2S, Na2Se, and M (M is Sn, Mo, W). In addition, due to the rich interface and low Na + diffusion barrier, thereby greatly improving the diffusion kinetics of Na ions between the intermediate transformation-alloying reaction. Most importantly, the high-density grain boundaries of the M 0 / Na2S / Na2Se intermediate distribution help to stabilize the active ingredients and limit the volume change, thereby effectively inhibiting the agglomeration of M 0 in the phase transition, improving the integrity of the layered structure, and ultimately ensuring the reversibility of the transformation-alloying reaction in the long-term cycle. Therefore, the electrode material of the present application has a high specific capacity, and still has good retention after 2000 cycles, showing good and stable electrochemical performance, and still having good structural stability and cycle life at an ultra-high rate. The present application solves the problems of slow ion transport rate, severe volume expansion, and repeated insertion of sodium ions causing the stacking, agglomeration, and even the collapse of the structure of the ultra-thin nanosheet of the existing transition metal chalcogenide electrode material, and has good application prospects.

[0023] 2. The novel hollow tire-shaped carbon material composite transition metal sulfide-selenide electrode material prepared by the present application is prepared by using a carbon skeleton derived from black aspergillus spores as the main raw material, and through hydrothermal reaction, high-temperature carbonization, and selenization treatment. Compared with other synthetic methods of metal chalcogenide solid solutions, the raw material cost of the present application is low, the process is simple, the energy consumption is low, the reaction conditions are easier to achieve, and batch production is possible, which is convenient for commercial application.

[0024] 3. The hollow tire-shaped carbon material composite transition metal sulfide-selenide electrode material of the present application has a super-long cycle life, a large reversible specific capacity, and excellent rate performance. The full cell assembled by the ANDC@SnSSe@C electrode material and the positive electrode material Na3V2(PO4)3@C has an initial coulombic efficiency of more than 100%, a capacity retention rate of more than 78.8%, and also has good cycle life and rate performance, indicating that the ANDC@SnSSe@C composite electrode material of the present application has a huge application prospect in sodium ion batteries. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 The electron microscope images of the black aspergillus spores and the hollow tire-shaped carbon material in Example 1 are shown in Figures 1a, 1b, 1c, 1d, 1e, and 1f. Figures 1a and 1b are scanning electron microscope images of the black aspergillus spores, Figures 1c and 1d are scanning electron microscope images of the hollow tire-shaped carbon material, and Figures 1e and 1f are transmission electron microscope images of the hollow tire-shaped carbon material.

[0026] Figure 2 The images are scanning electron microscope (SEM) images of ANDC@SnS2 and ANDC@SnS@C in Example 1; a and b are ANDC@SnS2, and c and d are ANDC@SnS@C.

[0027] Figure 3 The images show scanning electron microscope (SEM) images (a, b) and transmission electron microscope (TEM) images (c, d) of the ANDC@SnSSe@C electrode material prepared in Example 1.

[0028] Figure 4 The image shows the X-ray diffraction pattern of the ANDC@SnSSe@C electrode material prepared in Example 1.

[0029] Figure 5 Thermogravimetric analysis (a) and electron paramagnetic resonance (e) spectra of the ANDC@SnSSe@C electrode material prepared in Example 1 are shown.

[0030] Figure 6 The image shows the X-ray photoelectron spectrum of the ANDC@SnSSe@C electrode material prepared in Example 1.

[0031] Figure 7 The CV curves of the battery assembled with ANDC@SnSSe@C electrode material at different scan rates are shown.

[0032] Figure 8 This is a graph showing the rate performance of a battery assembled using ANDC@SnSSe@C electrode materials.

[0033] Figure 9 To prepare a half-cell using ANDC@SnSSe@C electrode material at 1.0 A g -1 Charge-discharge curves at current density (a) and cycle stability test (b).

[0034] Figure 10 The half-cell fabricated using ANDC@SnSSe@C electrode material was tested at 20.0 Ag. -1 Cyclic stability test at current density.

[0035] Figure 11 Electrochemical performance testing of full cells prepared using ANDC@SnSSe@C electrode materials; (a) at 1.0 A g -1 (a) Cyclic volt-ampere curves at current density, (b) Cyclic stability test, (c) Charge-discharge curves at different current densities, (d) Rate performance test. Detailed Implementation

[0036] The preferred embodiments of the present application will be described in detail below with reference to the drawings, but the embodiments are not intended to limit the present application. The experimental methods not specified in the preferred embodiments are generally performed according to the conventional conditions, or the conditions suggested by the manufacturers of reagents.

[0037] 1. A method for preparing an electrode material of a hollow tire-like carbon material composite transition metal sulfide selenide

[0038] Example 1

[0039] 1) Preparation of a hollow tire-like carbon material

[0040] The black aspergillus spores were ultrasonically treated in deionized water and washed and dried. 5 g of the dried black aspergillus spores were placed in a porcelain boat and wrapped with tin foil, and then transferred into a high-temperature tube furnace under Ar atmosphere protection, then the temperature was raised to 700°C at a rate of 5°C / min, and held for 2 h, and finally naturally cooled to room temperature, to obtain a black aspergillus spore-derived hollow tire-like carbon material (ANDC).

[0041] 2) Preparation of an ANDC@SnS2 precursor

[0042] 0.385 g of SnCl2·2H2O and 0.056 g of sublimed sulfur were dissolved in 70 ml of ethylene glycol solution, and uniformly stirred for half an hour to obtain a mixed solution; then 0.3 g of the ANDC prepared in step 1) was added to the mixed solution, and ultrasonically stirred for half an hour to obtain a suspension; the suspension was then transferred into a 100 ml high-pressure reaction kettle and reacted at 180°C for 12 h, and after the reaction was completed, it was naturally cooled, and the obtained product was washed with deionized water and anhydrous ethanol three times in turn, and dried in a vacuum drying box at 80°C for 8 h, to obtain an ANDC@SnS2 material.

[0043] 3) Preparation of an ANDC@SnS2@G composite material

[0044] 0.3 g of the ANDC@SnS2 precursor prepared in step 2) was dispersed in 60 ml of a 0.075M glucose aqueous solution and ultrasonically stirred for 30 min, and then transferred into a 100 ml high-pressure reaction kettle and reacted at 180°C for 12 h, and after the reaction was completed, it was naturally cooled, and the obtained product was washed with deionized water and anhydrous ethanol three times in turn, and dried in a vacuum drying box at 80°C for 8 h, to obtain an ANDC@SnS2@G material.

[0045] 4) Preparation of an ANDC@SnS@C composite material

[0046] The ANDC@SnS2@G material prepared in step 3) is placed in a porcelain boat and wrapped with a tin foil, and then transferred into a high-temperature tube furnace under Ar atmosphere protection, and then the temperature is raised to 500℃ at a heating rate of 2℃ / min, and kept for 2h, and finally naturally cooled to room temperature to obtain the ANDC@SnS@C composite material.

[0047] 5) Preparation of ANDC@SnSSe@C composite material

[0048] 0.2g of the ANDC@SnS@C obtained in step 4) and 0.8g of selenium powder are respectively placed in two porcelain boats and wrapped with a tin foil, and then directly transferred into a tube furnace filled with argon, and heated to 400℃ at a heating rate of 2℃ / min and kept for 2h, and after the reaction is completed, it is naturally cooled to prepare the ANDC@SnSSe@C composite electrode material.

[0049] Example 2

[0050] 1) Preparation of hollow tire-like carbon material

[0051] The black aspergillus spores are ultrasonically treated in deionized water and washed and dried, 5g of the dried black aspergillus spores are placed in a porcelain boat and wrapped with a tin foil, and then transferred into a high-temperature tube furnace under Ar atmosphere protection, and then the temperature is raised to 700℃ at a heating rate of 5℃ / min - , and kept for 2h, and finally naturally cooled to room temperature to obtain the black aspergillus spore-derived hollow tire-like carbon material (ANDC).

[0052] 2) Preparation of ANDC@SnS2 precursor

[0053] 0.71g of SnCl4·4H2O and 0.60g of thioacetamide (TAA) are dissolved in 70ml of isopropyl alcohol solution, and stirred uniformly for half an hour to obtain a mixed solution; then 0.3g of the ANDC prepared in step 1) is added to the mixed solution, and ultrasonically treated for half an hour to obtain a suspension; then the suspension is transferred into a 100ml high-pressure reaction kettle and reacted at 180℃ for 6h, and after the reaction is completed, it is naturally cooled, and the obtained product is washed with deionized water and anhydrous ethanol three times in turn, and dried in a vacuum drying box at 80℃ for 8h to obtain the ANDC@SnS2 material.

[0054] 3) Preparation of ANDC@SnS2@G composite material

[0055] Take 0.3 g of ANDC@SnS2 precursor prepared in step 2) and disperse it in 60 ml of 0.075 M aqueous glucose solution and ultrasonically stir for 30 min, then transfer it to a 100 ml high-pressure reaction kettle and react at 180℃ for 12 h. After the reaction is completed, it is naturally cooled, then the obtained product is washed with deionized water and anhydrous ethanol three times in turn, and dried in a vacuum drying box at 80℃ for 8 h to obtain ANDC@SnS2@G material.

[0056] 4) Preparation of ANDC@SnS@C composite material

[0057] Place the ANDC@SnS2@G material prepared in step 3) in a porcelain boat and wrap it with a tin foil, then transfer it into a high-temperature tube furnace protected by Ar atmosphere. Then increase the temperature to 500℃ at a rate of 2℃ / min and keep it for 2 h, and finally naturally cool to room temperature to obtain the ANDC@SnS@C composite material.

[0058] 5) Preparation of ANDC@SnSSe@C composite material

[0059] Take 0.2 g of ANDC@SnS@C obtained in step 4) and 0.8 g of selenium powder, respectively place them in two porcelain boats and wrap them with a tin foil, then directly transfer them into a tube furnace filled with argon and heat to 400℃ at a rate of 2℃ / min and keep it for 2 h, after the reaction is completed, naturally cool to obtain the ANDC@SnSSe@C composite electrode material.

[0060] Example 3

[0061] 1) Preparation of hollow tire-like carbon material

[0062] Ultrasonically treat and clean the Aspergillus niger spores in deionized water and dry them, take 5 g of dried Aspergillus niger spores and place them in a porcelain boat and wrap them with a tin foil, then transfer them into a high-temperature tube furnace protected by Ar atmosphere. Then increase the temperature to 700℃ at a rate of 5℃ / min and keep it for 2 h, and finally naturally cool to room temperature to obtain the hollow tire-like carbon material (ANDC) derived from Aspergillus niger spores.

[0063] 2) Preparation of ANDC@SnS2 precursor

[0064] 0.596 g of SnCl4-4H2O and 0.131 g of thioacetamide (TAA) were dissolved in 70 ml of ethylene glycol solution, and stirred uniformly for half an hour to obtain a mixed solution; then 0.3 g of ANDC prepared in step 1) was added to the mixed solution and ultrasonically stirred for half an hour; then it was transferred into a 100 ml high-pressure reaction kettle and reacted at 180℃ for 6 h, after the reaction was completed, it was naturally cooled, the obtained product was washed with deionized water and anhydrous ethanol three times in turn, and dried in a vacuum drying box at 80℃ for 8 h, to obtain the ANDC@SnS2 material.

[0065] 3) Preparation of ANDC@SnS2@G composite material

[0066] 0.3 g of ANDC@SnS2 precursor prepared in step 2) was dispersed in 60 ml of 0.075 M glucose aqueous solution and ultrasonically stirred for 30 min to obtain a suspension, then the suspension was transferred into a 100 ml high-pressure reaction kettle and reacted at 180℃ for 12 h, after the reaction was completed, it was naturally cooled, the obtained product was washed with deionized water and anhydrous ethanol three times in turn, and dried in a vacuum drying box at 80℃ for 8 h, to obtain the ANDC@SnS2@G material.

[0067] 4) Preparation of ANDC@SnS@C composite material

[0068] The ANDC@SnS2@G material prepared in step 3) was placed in a porcelain boat and wrapped with a tin foil, then it was transferred into a high-temperature tube furnace protected by argon atmosphere, then the temperature was increased to 500℃ at a heating rate of 2℃ / min and kept for 2 h, and finally it was naturally cooled to room temperature, to obtain the ANDC@SnS@C composite material.

[0069] 5) Preparation of ANDC@SnSSe@C composite material

[0070] 0.2 g of ANDC@SnS@C obtained in step 4) and 0.8 g of selenium powder were respectively placed in two porcelain boats and wrapped with a tin foil, then they were directly transferred into a tube furnace filled with argon, and the temperature was increased to 400℃ at a heating rate of 2℃ / min and kept for 2 h, after the reaction was completed, it was naturally cooled, to obtain the ANDC@SnSSe@C composite electrode material.

[0071] Example 4

[0072] 1) Preparation of hollow tire-shaped carbon material

[0073] 5g of Aspergillus niger spores were placed in a porcelain boat and wrapped with tin foil, and then transferred into a high-temperature tube furnace under Ar atmosphere protection, and then the temperature was raised to 700°C at a rate of 5°C / min and kept for 2h, and finally naturally cooled to room temperature to obtain Aspergillus niger spore-derived hollow tire-like carbon material (ANDC).

[0074] 2) Preparation of ANDC@SnS2 precursor

[0075] 0.385g of SnCl2·2H2O and 0.056g of sublimed sulfur were dissolved in 70ml of isopropanol solution, and stirred uniformly for half an hour to obtain a mixed solution; then 0.3g of ANDC prepared in step 1) was added to the mixed solution and ultrasonically stirred for half an hour; then it was transferred into a 100ml high-pressure reaction kettle and reacted at 180°C for 12h, and after the reaction was completed, it was naturally cooled, and the obtained product was washed with deionized water and anhydrous ethanol three times in turn, and dried in a vacuum drying box at 80°C for 8h, to obtain ANDC@SnS2 material.

[0076] 3) Preparation of ANDC@SnS2@G composite material

[0077] 0.3g of ANDC@SnS2 precursor prepared in step 2) was dispersed in 60ml of 0.075M glucose aqueous solution and ultrasonically stirred for 30min to obtain a suspension, and then the suspension was transferred into a 100ml high-pressure reaction kettle and reacted at 180°C for 12h, and after the reaction was completed, it was naturally cooled, and the obtained product was washed with deionized water and anhydrous ethanol three times in turn, and dried in a vacuum drying box at 80°C for 8h, to obtain ANDC@SnS2@G material.

[0078] 4) Preparation of ANDC@SnS@C composite material

[0079] The ANDC@SnS2@G material prepared in step 3) was placed in a porcelain boat and wrapped with tin foil, and then transferred into a high-temperature tube furnace under Ar atmosphere protection, and then the temperature was raised to 500°C at a rate of 2°C / min and kept for 2h, and finally naturally cooled to room temperature to obtain ANDC@SnS@C composite material.

[0080] 5) Preparation of ANDC@SnSSe@C composite material

[0081] 0.2g of ANDC@SnS@C obtained in step 4) and 0.8g of selenium powder were respectively placed in two porcelain boats and wrapped with a piece of tin foil, and then directly transferred into a tube furnace filled with argon, and then the temperature was raised to 400°C at a rate of 2°C / min and kept for 2h, and after the reaction was completed, it was naturally cooled to obtain ANDC@SnSSe@C composite electrode material.

[0082] Example 5

[0083] 1) Preparation of hollow tire-like carbon material

[0084] The Aspergillus niger spores were ultrasonically treated in deionized water and washed, dried, 5 g of dried Aspergillus niger spores were placed in a porcelain boat and wrapped with tin foil, then transferred into a high-temperature tube furnace protected by Ar atmosphere, then the temperature was raised to 700℃ at a rate of 5℃ / min and kept for 2h, and finally naturally cooled to room temperature, to obtain the hollow tire-like carbon material derived from Aspergillus niger spores (ANDC).

[0085] 2) Preparation of ANDC@SnS2 precursor

[0086] 0.596 g of SnCl4·4H2O and 0.131 g of thiourea were dissolved in 70 ml of isopropanol solution, and stirred uniformly for half an hour to obtain a mixed solution; then 0.3 g of ANDC prepared in step 1) was added to the mixed solution and ultrasonically treated for half an hour; then it was transferred to a 100 ml high-pressure reaction kettle and reacted at 180℃ for 6h, after the reaction was completed, it was naturally cooled, the obtained product was washed with deionized water and anhydrous ethanol three times in turn, and dried in a vacuum drying box at 80℃ for 8h, to obtain the ANDC@SnS2 material.

[0087] 3) Preparation of ANDC@SnS2@G composite material

[0088] 0.3 g of ANDC@SnS2 precursor prepared in step 2) was dispersed in 60 ml of 0.075M glucose aqueous solution and ultrasonically stirred for 30 min to obtain a suspension, then the suspension was transferred to a 100 ml high-pressure reaction kettle and reacted at 180℃ for 12h, after the reaction was completed, it was naturally cooled, the obtained product was washed with deionized water and anhydrous ethanol three times in turn, and dried in a vacuum drying box at 80℃ for 8h, to obtain the ANDC@SnS2@G material.

[0089] 4) Preparation of ANDC@SnS@C composite material

[0090] The ANDC@SnS2@G material prepared in step 3) was placed in a porcelain boat and wrapped with tin foil, then transferred into a high-temperature tube furnace protected by Ar atmosphere, then the temperature was raised to 500℃ at a rate of 2℃ / min and kept for 2h, and finally naturally cooled to room temperature, to obtain the ANDC@SnS@C composite material.

[0091] 5) Preparation of ANDC@SnSSe@C composite material

[0092] ANDC@SnS@C and 0.8 g of selenium powder were placed in two porcelain boats respectively and wrapped with a tin foil paper, and then transferred into a tube furnace filled with argon gas, and heated to 400°C at a heating rate of 2°C / min and kept for 2 h, and after the reaction was completed, it was naturally cooled, to prepare the ANDC@SnSSe@C composite electrode material.

[0093] Example 6

[0094] 1) Preparation of hollow tire-like carbon material

[0095] The black aspergillus spores were ultrasonically treated in deionized water and washed, dried, 5 g of dried black aspergillus spores were placed in a porcelain boat and wrapped with a tin foil paper, and then transferred into an Ar atmosphere protected high temperature tube furnace, and then the temperature was raised to 700°C at a heating rate of 5°C / min and kept for 2 h, and finally naturally cooled to room temperature, to obtain a black aspergillus spore derived hollow tire-like carbon material (ANDC). -1

[0096] 2) Preparation of ANDC@SnS2 precursor

[0097] 0.596 g of SnCl2·2H2O and 0.131 g of thiourea were dissolved in 70 ml of ethylene glycol solution, and stirred uniformly for half an hour to obtain a mixed solution; then 0.3 g of ANDC prepared in step 1) was added to the mixed solution and ultrasonically stirred for half an hour; then it was transferred into a 100 ml high-pressure reaction kettle and reacted at 180°C for 12 h, and after the reaction was completed, it was naturally cooled, and the obtained product was washed with deionized water and anhydrous ethanol three times in turn, and dried in a vacuum drying box at 80°C for 8 h, to obtain the ANDC@SnS2 material.

[0098] 3) Preparation of ANDC@SnS2@G composite material

[0099] 0.3 g of ANDC@SnS2 precursor prepared in step 2) was dispersed in 60 ml of 0.075M glucose aqueous solution and ultrasonically stirred for 30 min to obtain a suspension, and then the suspension was transferred into a 100 ml high-pressure reaction kettle and reacted at 180°C for 12 h, and after the reaction was completed, it was naturally cooled, and the obtained product was washed with deionized water and anhydrous ethanol three times in turn, and dried in a vacuum drying box at 80°C for 8 h, to obtain the ANDC@SnS2@G material.

[0100] 4) Preparation of ANDC@SnS@C composite material

[0101] ​The ANDC@SnS2@G material prepared in step 3) is placed in a porcelain boat and wrapped with tin foil, and then transferred into a high-temperature tube furnace under Ar atmosphere protection, and then the temperature is raised to 500℃ at a heating rate of 2℃ / min and kept for 2h, and finally naturally cooled to room temperature to obtain the ANDC@SnS@C composite material.

[0102] 5) Preparation of ANDC@SnSSe@C composite material

[0103] 0.2g of ANDC@SnS@C obtained in step 4) and 0.8g of selenium powder are respectively placed in two porcelain boats and wrapped with a tin foil, and then directly transferred into a tube furnace filled with argon, and heated to 400℃ at a heating rate of 2℃ / min and kept for 2h, and after the reaction is completed, it is naturally cooled to prepare the ANDC@SnSSe@C composite electrode material.

[0104] Example 7

[0105] 1) Preparation of hollow tire-like carbon material

[0106] The black aspergillus spores are ultrasonically treated in deionized water and washed and dried, 5g of dried black aspergillus spores are placed in a porcelain boat and wrapped with tin foil, and then transferred into a high-temperature tube furnace under Ar atmosphere protection, and then the temperature is raised to 700℃ at a heating rate of 5℃ / min and kept for 2h, and finally naturally cooled to room temperature to obtain the hollow tire-like carbon material (ANDC) derived from black aspergillus spores.

[0107] 2) Preparation of ANDC@MoS2 precursor

[0108] 0.215g of Na2MoO4·2H2O and 0.31g of thioacetamide are dissolved in 60ml of deionized water solution, and stirred uniformly for half an hour to obtain a mixed solution; then 0.3g of ANDC prepared in step 1) is added to the mixed solution and ultrasonically treated for half an hour; then it is transferred into a 100ml high-pressure reaction kettle and reacted at 200℃ for 24h, and after the reaction is completed, it is naturally cooled, and the obtained product is washed with deionized water and anhydrous ethanol three times in turn, and dried in a vacuum drying box at 80℃ for 8h to obtain the ANDC@MoS2 material.

[0109] 3) Preparation of ANDC@MoS2@PDA composite material

[0110] The 0.3 g ANDC@SnS2 precursor prepared in step 2) was dispersed in 60 ml of 10 mM Tris aqueous solution with pH value of 8.0-8.5 and ultrasonically stirred for 30 min, then 0.15 g of dopamine was added and stirred at room temperature for 6 h, after the reaction was completed, the obtained product was washed with deionized water and anhydrous ethanol for three times, and dried at 80℃ in a vacuum drying box for 8 h to obtain the ANDC@MoS2@PDA material.

[0111] 4) Preparation of ANDC@MoS2@C composite material

[0112] The ANDC@MoS2@PDA material prepared in step 3) was placed in a porcelain boat and wrapped with a tin foil, and then transferred into a high-temperature tube furnace protected by Ar atmosphere, then the temperature was raised to 800℃ at a heating rate of 2℃ / min and kept for 2 h, and finally naturally cooled to room temperature to obtain the ANDC@MoS2@C composite material.

[0113] 5) Preparation of ANDC@MoSSe@C composite material

[0114] 0.2 g of ANDC@SnS@C obtained in step 4) and 0.8 g of selenium powder were respectively placed in two porcelain boats and wrapped with a tin foil, and then directly transferred into a tube furnace filled with argon, and heated to 400℃ at a heating rate of 2℃ / min and kept for 2 h, and after the reaction was completed, it was naturally cooled to obtain the ANDC@MoSSe@C composite material.

[0115] Example 8

[0116] 1) Preparation of hollow tire-like carbon material

[0117] The black aspergillus spores were ultrasonically treated in deionized water and washed and dried, 5 g of dried black aspergillus spores were placed in a porcelain boat and wrapped with a tin foil, and then transferred into a high-temperature tube furnace protected by Ar atmosphere, and then the temperature was raised to 700℃ at a heating rate of 5℃ / min and kept for 2 h, and finally naturally cooled to room temperature to obtain the hollow tire-like carbon material (ANDC) derived from black aspergillus spores.

[0118] 2) Preparation of ANDC@WS2 precursor

[0119] A mixture solution was prepared by dissolving 0.5 g of Na2WO4·2H2O, 0.5 g of thioacetamide and 0.5 g of NaBH4 in 60 ml of water solution and stirring uniformly for half an hour; then 0.3 g of ANDC prepared in step 1) was added to the mixture solution and ultrasonically stirred for half an hour; then it was transferred into a 100 ml high-pressure reaction kettle and reacted at 220℃ for 12 h, after the reaction was completed, it was naturally cooled, the obtained product was washed with deionized water and anhydrous ethanol for three times respectively, and dried in a vacuum drying box at 80℃ for 8 h, to obtain the ANDC@WS2 material.

[0120] 3) Preparation of ANDC@WS2@PPy composite material

[0121] The ANDC@SnS2 precursor prepared in step 2) was dispersed in 50 ml of deionized water and ultrasonically stirred for 30 min, then 0.5 g of sodium dodecyl benzene sulfonate, 0.4 g of FeCl3 and 0.2 ml of pyrrole monomer were added in sequence and stirred at room temperature for 5 h, after the reaction was completed, the obtained product was washed with deionized water and anhydrous ethanol for three times respectively, and dried in a vacuum drying box at 80℃ for 8 h, to obtain the ANDC@WS2@PPy material.

[0122] 4) Preparation of ANDC@WS2@C composite material

[0123] The ANDC@WS2@PPy material prepared in step 3) was placed in a porcelain boat and wrapped with a tin foil, then it was transferred into a high-temperature tube furnace protected by argon atmosphere, then the temperature was raised to 800℃ at a heating rate of 2℃ / min and kept for 2 h, and finally it was naturally cooled to room temperature, to obtain the ANDC@WS2@C composite material.

[0124] 5) Preparation of ANDC@WSSe@C composite material

[0125] 0.2 g of ANDC@WS2@C obtained in step 4) and 0.8 g of selenium powder were respectively placed in two porcelain boats and wrapped with a tin foil, then they were directly transferred into a tube furnace filled with argon, then the temperature was raised to 400℃ at a heating rate of 2℃ / min and kept for 2 h, after the reaction was completed, it was naturally cooled, to obtain the ANDC@WSSe@C composite electrode material.

[0126] II. Performance detection

[0127] 1. The morphology of the Aspergillus niger spores and the tire-shaped carbon material after high-temperature carbonization in Example 1 was observed under a scanning microscope and a projection microscope, and the results are shown in FIGS. 1 and 2. Figure 1

[0128] a and Figure 1 Figure 1 ​​bIt can be seen that a large number of A. niger spores exhibit monodisperse characteristics and have a tire-like double-concave morphology, and the surface of the A. niger spores is relatively smooth. After high-temperature carbonization treatment, the tire-like structure of the A. niger spores is still well maintained, but the surface of the tire-like carbon material has obvious wrinkles and grooves, and the average diameter is 3 μm Figure 1 cand Figure 1 d). And the tire-like carbon material has an obvious hollow structure Figure 1 eand Figure 1 f).

[0129] 2, The ANDC@SnS2 and ANDC@SnS@C electrode materials prepared in Example 1 were observed under a scanning electron microscope, and the results are shown in Figure 2 .

[0130] From Figure 2 aand 2b, it can be seen that after the tire-like carbon material is subjected to a hydrothermal reaction, a large number of SnS2nanosheets grow uniformly on the surface of the ANDC, forming a nanosheet-wrapped hollow double-concave structure. After further coating with a glucose-derived carbon layer, the nanosheet-wrapped hollow double-concave structure is still well maintained, and no obvious change in morphology occurs Figure 2 cand 2d).

[0131] 3, The ANDC@SnSSe@C composite electrode material prepared in Example 1 was observed under a scanning electron microscope and a transmission electron microscope, and the results are shown in Figure 3 .

[0132] From Figure 3 aand Figure 3 b, it can be seen that after the ANDC@SnS@C material is subjected to high-temperature selenization treatment, the obtained ANDC@SnSSe@C maintains almost the same morphology as the ANDC@SnS2 precursor sample, and a large number of nanosheets are still tightly wrapped on the hollow double-concave tire-like carbon structure, and no obvious agglomeration of the nanosheets or collapse of the structure occurs Figure 3 c). From Figure 3 d, it can be seen that a clear crystal lattice fringe with a spacing of 0.323 nm corresponding to the (100) crystal plane of SnSSe is exhibited in a region of about 10 nm.

[0133] 4, The ANDC@SnSSe@C electrode material prepared in Example 1 was subjected to X-ray diffraction, X-ray photoelectron spectroscopy, thermogravimetric analysis, and electron paramagnetic resonance spectrum analysis, and the results are shown in Figures 4-6 .

[0134] From Figure 4As can be seen from the X-ray diffraction pattern, all crystal planes of the ANDC@SnSSe@C electrode material prepared in this embodiment can be well matched with the standard SnSSe phase, similar to a hexagonal crystal.

[0135] from Figure 5 The thermogravimetric analysis (TGA) plot shows a mass loss from room temperature to 200℃, primarily due to the evaporation of adhering moisture within the sample. The mass loss from 200℃ to 700℃ is due to the reaction of S, Se, and C with oxygen in the air, producing SO2, SeO2, and CO2 gases. The final stability at 700℃ is due to the formation of SnO2. Based on the above data analysis, the mass percentage of SnSSe in the ANDC@SnSSe@C electrode material is approximately 40.9%. Figure 5 The electron paramagnetic resonance spectrum of b reveals the presence of numerous defects in the ANDC@SnSSe@C electrode material. Furthermore, the abundant crystal defects formed in situ within the metal sulfose selenide nanosheets can serve as a convenient source of Na... + diffusion sites, ensuring Na + It can facilitate rapid insertion and, by effectively reducing the Gibbs free energy, act as a propellant for the nucleation process of intermediate products in the initial transformation state.

[0136] from Figure 6 The X-ray photoelectron spectrum shows that the ANDC@SnSSe@C electrode material is mainly composed of five elements: Sn, S, Se, C, and S.

[0137] III. Application of ANDC@SnSSe@C composite electrode materials in sodium-ion batteries

[0138] The ANDC@SnSSe@C electrode material prepared in Example 1 was used as the negative electrode material and mixed with Ketjen Black and CMC binder at a mass percentage of 60:30:10. Then, an appropriate amount of deionized water was added, and the mixture was ground into a paste in an agate mortar. The paste was then coated onto a copper foil with a diameter of 13 mm. The copper foil was then vacuum dried at 80 °C for 12 h to obtain the negative electrode sheet of the sodium-ion battery. The negative electrode sheet was then transferred to an argon-filled glove box for the assembly of button batteries. The button battery model was CR2032. The sodium metal sheet was used as the counter electrode, the separator was glass fiber, and the electrolyte was a 1 mol / L NaCF3SO3 solution (the solvent was diethylene glycol dimethyl ether solution).

[0139] 1. Cyclic voltammetry (CV) tests were conducted on the CR2032 coin cells assembled with the above ANDC@SnSSe@C electrode materials at different scan rates from 0.2 to 2.0 mV / s (using an electrochemical workstation CHI-660E, voltage range 0.01–3.0 V, the same below). The results are as follows. Figure 7 As shown.

[0140] As can be seen from the figure, all the CV curves obtained detect the presence of 6 redox peaks, and the peak current gradually increases with the increase of the scan rate. In addition, with the increase of the scan rate, the curve shape still remains good, indicating that the ANDC@SnSSe@C material has good rate performance and small polarization rate.

[0141] 2. The CR2032 button cell assembled by the above-mentioned ANDC@SnSSe@C electrode material was measured for discharge specific capacity under the condition of a current density of 0.2-20.0 A g -1 . The results are shown in Figure 8 .

[0142] As can be seen from the figure, when the current density is 0.2, 0.5, 1.0, 2.0, 5.0, 10.0 and 20.0 A g -1 , the discharge capacity is 638.2, 516.2, 455.1, 409.6, 345.4, 292.8 and 235.4 mAh g -1 , respectively. When the current density gradually returns to 0.2 A g -1 , the capacity returns to 652.1 mAh g -1 , and the capacity retention rate is more than 100%, indicating that the ANDC@SnSSe@C electrode material has excellent rate performance.

[0143] 3. The CR2032 button cell assembled by the above-mentioned ANDC@SnSSe@C electrode material was tested for cycle stability under a current density of 1.0 A g -1 . The results are shown in Figure 9 .

[0144] As can be seen from Figure 9 a, the initial charge and discharge capacities of the ANDC@SnSSe@C electrode material prepared in the application are 641.9 mAh g -1 and 509.3 mAh g -1 , respectively, and the corresponding initial coulombic efficiency is 79.3%. As can be seen from Figure 9 b, after the electrode is cycled for 120 times, the discharge specific capacity is still 416.4 mAh g -1 , and the capacity retention is 64.9% of the initial discharge capacity, indicating that the material has large specific capacity and good cycle stability.

[0145] 4. The CR2032 button cell assembled by the above-mentioned ANDC@SnSSe@C electrode material was tested for cycle stability under a current density of 20.0 A g -1Cyclic stability tests were performed at current densities, and the results are as follows: Figure 10 As shown.

[0146] As can be seen from the figure, the initial discharge capacity of the ANDC@SnSSe@C electrode material prepared in this invention is 398.5 mAh g. -1 After 2000 cycles, its discharge specific capacity is still 293.0 mAh g. -1 The average capacity decay rate per cycle is only 0.05%, indicating that the material still has good structural stability and cycle life at ultra-high rates.

[0147] 5. A CR2032 coin cell was assembled using the above ANDC@SnSSe@C electrode material and the positive electrode material Na3V2(PO4)3@C. Its cycle life and rate performance were tested, and the results are as follows: Figure 11 As shown.

[0148] Depend on Figure 11 From a, we can know that the full cell is at 1.0 A g -1 When charged and discharged at current densities of [specific values], their initial charge and discharge capacities are 659.9 and 648.3 mAh g, respectively. -1 The initial Coulomb efficiency exceeds 100%. Figure 11 As can be seen from b, after 100 electrode cycles, its discharge specific capacity is still 243.3 mAh g. -1 .from Figure 11 As can be seen from c and 11d, when the current density is 0.2, 0.5, 1.0, 1.5, 3.0 and 5.0 A g -1 At those times, their discharge capacities were 622.6, 492.6, 430.7, 375.1, 275.4, and 180.1 mAh g, respectively. -1 When the current density gradually recovers to 0.2 A g -1 At that time, the capacity recovered to 490.9mAh g. -1 Its capacity retention rate exceeded 78.8%, indicating that the present invention ANDC@SnSSe@C has great commercial application prospects.

[0149] It should be noted that the composite electrode materials prepared in Examples 2 to 8 also have good and cycle-stable electrochemical performance, but they are not listed here.

[0150] Finally, it should be noted that the above preferred embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail through the above preferred embodiments, those skilled in the art should understand that various changes can be made to it in form and detail without departing from the scope defined by the claims of the present invention.

Claims

1. An electrode material composed of hollow tire-shaped carbon material and transition metal sulfoselenide, characterized in that, The electrode material comprises a carbon skeleton with a three-dimensional hollow tire-like structure derived from Aspergillus niger spores and layered ternary transition metal sulfoselenide nanosheets supported on the carbon skeleton, wherein the outer layer of the nanosheets is coated with a carbon layer, which is a carbon layer derived from glucose, polypyrrole, or polydopamine; the electrode material has a chemical composition represented by ANDC@MSSe@C, where ANDC is a hollow tire-like carbon skeleton derived from Aspergillus niger, and M is a metal element Sn, Mo, or W.

2. A method for preparing an electrode material of hollow tire-shaped carbon material composite transition metal sulfoselenide as described in claim 1, characterized in that, Includes the following steps: 1) The Aspergillus niger spores were ultrasonically treated in deionized water, then washed and dried; 2) The Aspergillus niger spores obtained in step 1) are subjected to high-temperature carbonization in a tube furnace with a protective atmosphere. After the reaction is completed, the temperature is naturally cooled to obtain the hollow tire-shaped carbon material ANDC derived from Aspergillus niger spores. The high-temperature carbonization process is carried out by raising the temperature to 500-1000℃ at a heating rate of 1-20℃ / min and then holding it at that temperature for 0.5-10h. 3) The ANDC material obtained in step 2) is placed in a solution containing a sulfur source and one of the following sources: tin, molybdenum, and tungsten, and stirred continuously until homogeneous to obtain a mixed solution. The mixed solution is then transferred to a high-pressure reactor for high-temperature reaction. After the reaction is completed, the mixture is allowed to cool naturally. The product is then washed several times with deionized water and anhydrous ethanol and dried to obtain the ANDC@MS2 composite material. The high-temperature reaction is carried out at a temperature of 180~220℃ for 12~24h. 4) The ANDC@MS2 composite material obtained in step 3) is added to an aqueous solution containing glucose and stirred continuously to obtain a suspension. Then, the suspension is transferred to a high-pressure reactor for hydrothermal reaction. After the reaction is completed, the product is obtained by natural cooling. Alternatively, the ANDC@MS2 composite material obtained in step 3) can be added to an aqueous solution containing dopamine or pyrrole, and the reaction can be carried out under continuous stirring at room temperature to obtain the product; 5) The product obtained in step 4) is washed several times with deionized water and anhydrous ethanol and dried. Then, the dried product is placed in a tube furnace with a protective atmosphere for high-temperature carbonization. After the reaction is completed, the temperature is naturally cooled to obtain ANDC@MSx@C composite material, where x=1 or 2. The high-temperature carbonization treatment is carried out by heating the temperature at a rate of 1~10℃ / min to 500~800℃ and holding it at that temperature for 1~6h. 6) Place the ANDC@MSx@C and selenium powder obtained in step 5) into a ceramic boat and wrap them with a piece of tin foil. Then, perform selenization treatment in a protective atmosphere. After the reaction is completed, allow the material to cool naturally to obtain the electrode material ANDC@MSSe@C, which is a hollow tire-shaped carbon material composite transition metal sulfose selenide.

3. The method for preparing the electrode material of hollow tire-shaped carbon material composite transition metal sulfoselenide according to claim 2, characterized in that, In step 3), the tin source is tin tetrachloride or stannous chloride; the molybdenum source is sodium molybdate or ammonium molybdate; the tungsten source is sodium tungstate or ammonium tungstate; the sulfur source is sublimed sulfur, thioacetamide, or thiourea; when a tin source is added to the mixed solution, the solvent in the solution is ethylene glycol or isopropanol; when a molybdenum source or a tungsten source is added to the mixed solution, the solvent in the solution is deionized water.

4. The method for preparing the electrode material of hollow tire-shaped carbon material composite transition metal sulfoselenide according to claim 2, characterized in that, Step 3) The amount of ANDC added to the mixed solution is 1.0~10 mg / mL, and the molar ratio of tin source, molybdenum source or tungsten source to sulfur source is 1:2~1:

4.

5. The method for preparing the electrode material of hollow tire-shaped carbon material composite transition metal sulfoselenide according to claim 2, characterized in that, In step 4), the concentration of glucose, dopamine, or pyrrole in the aqueous solution is 0.02~0.1M; the temperature of the hydrothermal reaction is 150~200℃, and the time is 6~24h.

6. The method for preparing the electrode material of hollow tire-shaped carbon material composite transition metal sulfoselenide according to claim 2, characterized in that, The selenization treatment in step 6) involves heating the temperature to 350-450℃ at a rate of 1-5℃ / min and then holding it at that temperature for 0.5-5h; the mass ratio of ANDC@MSx@C to selenium powder is 1:1-1:

10.

7. The method for preparing the electrode material of hollow tire-shaped carbon material composite transition metal sulfoselenide according to claim 2, characterized in that, The protective atmosphere is argon or nitrogen; the drying process is carried out at 25-90°C for 8-12 hours.

8. The application of the electrode material as described in claim 1 or the electrode material prepared by the method as described in any one of claims 3 to 7 in sodium-ion batteries.

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