Preparation method of six-element high-entropy nanotube for sodium ion battery negative electrode material

Abstract

The invention belongs to the technical field of high-entropy derivatives, and relates to a preparation method of a six-membered high-entropy nanotube for a sodium-ion battery negative electrode material, and the method comprises the following steps: carrying out a first hydrothermal reaction on melamine, trimesic acid, boric acid and phosphoric acid; then adding nickel acetate, ferric chloride, cobalt acetate, zinc acetate and manganese acetate into the reaction solution, carrying out a second hydrothermal reaction to obtain NiCoFeMnZn-MOF, and then calcining the NiCoFeMnZn-MOF to obtain a five-membered high-entropy nanotube; then adding the five-membered high-entropy nanotube, tris (hydroxymethyl) aminomethane and dopamine hydrochloride into deionized water, reacting to obtain a carbon-coated five-membered high-entropy nanotube, uniformly mixing the carbon-coated five-membered high-entropy nanotube with selenium powder, and calcining to obtain the six-membered high-entropy nanotube. According to the method, solvothermal and selenylation are combined, the preparation process is easy to operate, a large number of high-entropy nanotubes with uniform sizes can be synthesized, and the electrochemical performance and stability of the high-entropy material are guaranteed.

Description

Technical Field

[0001] The present invention belongs to the technical field of high-entropy derivatives, and particularly relates to a preparation method of a six-element high-entropy nanotube for a negative electrode material of a sodium-ion battery. Background Art

[0002] Due to its unique four effects: high-entropy effect, lattice distortion effect, slow diffusion effect, and cocktail effect, high-entropy materials have high strength, corrosion resistance, high stability, high catalytic activity, etc., and have shown broad application potential in multiple fields in recent years, including the nuclear energy field, optoelectronic and magnetic materials, biomedicine, and the electrochemical field, etc. Currently, the most widely used preparation method of high-entropy materials is granular high-entropy spinel oxides.

[0003] Since the first successful preparation of single-phase high-entropy oxides (HEOs) in 2015, the preparation methods of high-entropy materials have experienced a rapid development from traditional high-temperature sintering to diversified and precise technologies. The synthesis of early high-entropy materials mainly relied on high-temperature sintering and mechanical alloying. With the improvement of the requirements for material morphology and performance, new synthesis strategies have emerged continuously, such as co-precipitation method, laser ablation, solvothermal method, etc., and nanoscale high-entropy materials can already be prepared. However, laser ablation and the like rely on precision equipment, resulting in a relatively high production cost for large-scale production of nanoscale high-entropy materials.

[0004] In order to prepare high-performance high-entropy energy storage materials, various methods have been adopted to prepare nanoscale high-entropy materials. For example: forming solid materials by the sol-gel method, and preparing high-entropy spinel ferrite nanofibers by electrospinning. Although the above methods have been able to prepare nanoscale high-entropy materials, they all face some challenges. The first is elemental uniformity. During the material preparation process, various elements may not be evenly dispersed in the material structure, which will affect the performance of the material, because uneven element distribution may lead to local structural defects or performance differences. The second is high-temperature stability. The material may undergo structural changes, element volatilization, or changes in interactions, etc. in a high-temperature environment, thus affecting its stability and performance. Moreover, the process complexity. These preparation methods often involve multiple steps, complex equipment, and strict process condition control, which not only increases the production cost but also may lead to low production efficiency. The emergence of these problems makes the prepared high-entropy materials lose their original excellent electrochemical properties, especially the cycle stability brought by entropy stability. The entropy stability of high-entropy materials helps to maintain the stability of structure and performance during the cycle of use, but the defects of the preparation method prevent this advantage from being fully exerted, affecting the application and performance of high-entropy materials in the field of energy storage and other fields.

[0005] In the prior art, a patent application for an invention with a publication number of CN 119461274 A discloses a method for preparing high-entropy phosphide nanotubes, which uses a hydrothermal reaction to obtain a uniform and size-controlled hollow nanotube structure; however, the high-entropy phosphide nanotubes prepared by this method are in an amorphous structure, which still affects the electrochemical properties of the material. At present, the research on high-entropy materials in the energy storage field is still in its early stage, and there is still great room for performance improvement. Therefore, there is an urgent need to find a new method for preparing nanoscale high-entropy materials. Summary of the Invention

[0006] To solve the problem of damage to the electrochemical properties of high-entropy materials during the preparation process of high-entropy materials in the prior art, the present invention provides a method for preparing a six-component high-entropy nanotube for a sodium-ion battery negative electrode material. This method is simple to operate and can synthesize a large number of high-entropy nanotubes with uniform sizes, showing high rate performance and excellent cycle stability in terms of electrochemical properties.

[0007] To solve the above problems, the technical solution of the present invention is as follows: A method for preparing a six-component high-entropy nanotube for a sodium-ion battery negative electrode material, comprising the following steps: Step 1: Add melamine, trimesic acid, boric acid, and phosphoric acid into an organic solvent, mix evenly to obtain a precursor solution; then perform a first hydrothermal reaction on the precursor solution; after the first hydrothermal reaction is completed, a mixed solution containing one-dimensional HOF nanowires (hydrogen-bonded organic frameworks) is obtained; hydrogen-bonded organic framework (HOF) nanowires are one-dimensional nanomaterials with a regular pore structure formed by organic molecules through hydrogen bond interactions, having a large specific surface area and a unique pore structure, providing an ordered structural template for the introduction of multi-metal ions and the formation of composite materials. In this step, during the first hydrothermal reaction process, the reaction system is in a high-temperature and high-pressure environment. Such conditions help the movement and diffusion of molecules, making the collisions between molecules such as melamine and trimesic acid more frequent, promoting the formation, breaking, and recombination of hydrogen bonds, accelerating the nucleation and growth of HOF nanowires, and finally obtaining a mixed solution containing one-dimensional HOF nanowires.

[0008] Step 2: Add a nickel source, an iron source, a cobalt source, a zinc source, and a manganese source into the mixed solution containing one-dimensional HOF nanowires obtained in Step 1, mix evenly, and then perform a second hydrothermal reaction; after the reaction is completed, wash and dry the reaction product to obtain NiCoFeMnZn-MOF; in this step, a coordination reaction occurs between the metal salt and the one-dimensional HOF nanowires to form NiCoFeMnZn-MOF.

[0009] Step 3: Calcinate the NiCoFeMnZn-MOF obtained in Step 2 in an inert gas atmosphere to obtain a quinary high-entropy nanotube; in this step, the organic ligand is removed by high-temperature treatment to form a quinary high-entropy nanotube.

[0010] Step 4: Add the quinary high-entropy nanotube, tris(hydroxymethyl)aminomethane, and dopamine hydrochloride obtained in Step 3 to deionized water and react to obtain a carbon-coated quinary high-entropy nanotube; in the present invention, carbon coating of the quinary high-entropy nanotube can better confine selenium elements in the nanomaterial and better maintain the rate and cycle stability of the material.

[0011] Step 5: After uniformly mixing the carbon-coated quinary high-entropy nanotube obtained in Step 4 with selenium powder, calcinate it in an inert gas atmosphere to obtain a hexary high-entropy nanotube. Selenization transforms the quinary amorphous structure of the high-entropy nanotube into a hexary crystal structure. The ordered crystal structure provides a clear sodium ion diffusion channel. At the same time, selenization introduces additional active sites, making the material more stable during the cycling of the sodium-ion battery and providing a higher pseudocapacitance contribution.

[0012] Further, the organic solvent in Step 1 is methanol, and the molar ratio of melamine, trimesic acid, boric acid, and phosphoric acid is 3:2:2:3.

[0013] Further, in Step 1, melamine, trimesic acid, boric acid, and phosphoric acid are added to the organic solvent and mixed uniformly by ultrasonic method. The ultrasonic power is 900 W and the time is 1 h.

[0014] The first hydrothermal reaction in Step 1 is carried out at a temperature of 150 °C for 12 h.

[0015] Further, the second hydrothermal reaction in Step 2 is carried out at a temperature of 150 °C for 18 h.

[0016] Further, the molar ratio of metal elements in the nickel source, iron source, cobalt source, zinc source, and manganese source in Step 2 is 5:1:1:1:1.

[0017] Further, the nickel source, iron source, cobalt source, zinc source, and manganese source are nickel acetate, ferric chloride, cobalt acetate, zinc acetate, and manganese acetate, respectively.

[0018] Further, the calcination temperature in Step 3 is 500 °C, the reaction time is 120 min, and the heating rate is 5 °C / min.

[0019] Further, the reaction time in Step 4 is 120 min, the reaction is carried out during stirring, and the stirring speed is 300 - 500 rpm.

[0020] Further, the mass ratio of the quinary high-entropy nanotubes to selenium powder in step 5 is 1:3, the calcination temperature is 500 °C, and the reaction time is 180 min.

[0021] Further, the inert gas in steps 3 and 5 is argon.

[0022] By the above technical solutions, the beneficial effects of the present invention are as follows: (1) For the method for preparing the hexary high-entropy nanotubes of the present invention, a method combining solvothermal (hydrothermal reaction) and selenization is adopted. The raw materials are easily available, and the preparation process is simple to operate. A large number of high-entropy nanotubes with uniform sizes can be synthesized, and the electrochemical performance and stability of the high-entropy materials are ensured.

[0023] (2) The hexary high-entropy nanotubes prepared by the present invention have uniform morphology and size, small particles, a large specific surface area, good electrochemical performance, and great application prospects in the fields of energy storage devices, electrocatalysis and fuel cells.

[0024] (3) The present invention uses selenization to transform the sample from an amorphous state to a crystalline state. The ordered crystal structure provides a clear sodium ion diffusion channel. At the same time, selenization introduces additional active sites, making the material more stable during the cycling of sodium ion batteries and providing a higher pseudocapacitance contribution.

[0025] (4) The present invention uses a carbon coating technology to confine the selenium element within the nanotube framework, preventing the shuttle of the selenium element, better confining the selenium element in the nanomaterial, and better maintaining the stability of the high-entropy material. Description of the Drawings

[0026] Figure 1 It is a scanning electron microscope photograph of the hexary high-entropy nanotube HE-NiSe2@C prepared in Example 1; Figure 2 It is a scanning electron microscope photograph of the hexary high-entropy nanotube HE-NiSe2 prepared in Comparative Example 2; Figure 3 It is a scanning electron microscope photograph of the quinary high-entropy nanotube HE-Ni prepared in Comparative Example 1; Figure 4 It is an XRD characterization diagram of the hexary high-entropy nanotube HE-NiSe2@C prepared in Example 1; Figure 5 It is an XRD characterization diagram of the hexary high-entropy nanotube HE-NiSe2 prepared in Comparative Example 2; Figure 6 It is an XRD characterization diagram of the quinary high-entropy nanotube HE-Ni prepared in Comparative Example 1; Figure 7Raman spectrum of the six - element high - entropy nanotube HE - NiSe2@C prepared in Example 1; Figure 8 Raman spectrum of the six - element high - entropy nanotube HE - NiSe2 prepared in Comparative Example 2; Figure 9 Raman characterization diagram of the five - element high - entropy nanotube HE - Ni prepared in Comparative Example 1; Figure 10 CV characterization diagram of the six - element high - entropy nanotube HE - NiSe2@C of Example 1 at 0.2~1.2 mV s -1 (Peak1 is Peak 1; Peak is Peak 2); Figure 11 CV characterization diagram of the six - element high - entropy nanotube HE - NiSe2 prepared in Comparative Example 2 at 0.2~1.2 mV s -1 (Peak1 is Peak 1; Peak is Peak 2); Figure 12 CV characterization diagram of the five - element high - entropy nanotube HE - Ni prepared in Comparative Example 1 at 0.2~1.2 mV s -1 (Peak1 is Peak 1; Peak is Peak 2); Figure 13 Pseudocapacitance contribution of the six - element high - entropy nanotube HE - NiSe2@C of Example 1 (Capacitive is capacitance; Diffusion is diffusion); Figure 14 Pseudocapacitance contribution of the six - element high - entropy nanotube HE - NiSe2 prepared in Comparative Example 2; Figure 15 Pseudocapacitance contribution of the five - element high - entropy nanotube HE - Ni prepared in Comparative Example 1; Figure 16 Rate performance test diagram of the six - element high - entropy nanotube HE - NiSe2@C of Example 1; Figure 17 Rate performance test diagrams of the six - element high - entropy nanotube HE - NiSe2 prepared in Comparative Example 2 and the five - element high - entropy nanotube HE - Ni prepared in Comparative Example 1; Figure 18 Cycling diagram of the six - element high - entropy nanotube HE - NiSe2@C of Example 1 at 0.1 A g -1 (charge: charging; discharge: discharging); Figure 19 Cycling diagrams of the six - element high - entropy nanotube HE - NiSe2 prepared in Comparative Example 2 and the five - element high - entropy nanotube HE - Ni prepared in Comparative Example 1 at 0.1 A g -1 Cycling diagram. Detailed implementation manners

[0027] To make the objectives, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below in conjunction with specific embodiments. Obviously, the described embodiments are some, but not all, of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the scope of protection of the present invention.

[0028] It should be understood that the terms described in the present invention are only for describing specific embodiments and are not used to limit the present invention. In addition, for the numerical ranges in the present invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Each intermediate value within any stated value or stated range, as well as each smaller range between any other stated value or intermediate value within the stated range, is also included in the present invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0029] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention pertains. Although the present invention only describes preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials related to the documents. In case of conflict with any incorporated document, the content of this specification shall prevail.

[0030] The present invention will be described in detail below with specific embodiments. For those not specified in the following embodiments, they are all carried out according to conventional conditions or conditions recommended by the manufacturer. The raw materials and reagents used without indicating the manufacturer are all conventional products that can be obtained through commercial purchase.

[0031] Comparative Example 1: Five-component high-entropy nanotube NiCoFeMnZn (denoted as five-component high-entropy nanotube HE-Ni) The preparation method of the five-component high-entropy nanotube HE-Ni includes the following steps: Step 1: Add 0.227 g of melamine, 0.252 g of trimesic acid, 0.111 g of boric acid, and 1.2 mmol of phosphoric acid to 35 mL of methanol solution, and mix them evenly by ultrasonic method to obtain a precursor solution; then put the precursor solution into an oven for the first hydrothermal reaction to obtain a mixture containing one-dimensional HOF nanowires; the ultrasonic power is 900 W, and the ultrasonic time is 1 h; the first hydrothermal reaction is carried out at a temperature of 150 °C for 12 h.

[0032] Step 2: Add 0.249 g of nickel acetate, 0.039 g of iron chloride, 0.035 g of cobalt acetate, 0.044 g of zinc acetate, and 0.049 g of manganese acetate to the mixed solution containing one-dimensional HOF nanowires obtained in Step 1. Then, under the condition of a rotation speed of 300 rpm, stir for 20 min, and then place it in an oven for the second hydrothermal reaction; after the reaction is completed, wash the reaction product with anhydrous ethanol solvent, and then dry it at 60 °C to obtain NiCoFeMnZn-MOF; the second hydrothermal reaction is carried out at a temperature of 150 °C for 18 h.

[0033] Step 3: Place the NiCoFeMnZn-MOF obtained in Step 2 into a tubular furnace, introduce argon, and react at a temperature of 500 °C for 120 min to obtain a five-element high-entropy nanotube. Denote it as five-element high-entropy nanotube HE-Ni.

[0034] Comparative Example 2: Six-element high-entropy nanotube NiCoFeMnZnSe (denoted as six-element high-entropy nanotube HE-NiSe2) Preparation method of six-element high-entropy nanotube HE-NiSe2, comprising the following steps: Step 1: Add 0.227 g of melamine, 0.252 g of trimesic acid, 0.111 g of boric acid, and 1.2 mmol of phosphoric acid to 35 mL of methanol solution, and mix evenly by ultrasonic method to obtain a precursor solution; then place the precursor solution in an oven for the first hydrothermal reaction to obtain a mixed solution containing one-dimensional HOF nanowires; the ultrasonic power is 900 W, and the ultrasonic time is 1 h; the first hydrothermal reaction is carried out at a temperature of 150 °C for 12 h.

[0035] Step 2: Add 0.249 g of nickel acetate, 0.039 g of iron chloride, 0.035 g of cobalt acetate, 0.044 g of zinc acetate, and 0.049 g of manganese acetate to the mixed solution containing one-dimensional HOF nanowires obtained in Step 1. Then, under the condition of a rotation speed of 300 rpm, stir for 20 min, and then place it in an oven for the second hydrothermal reaction; after the reaction is completed, wash the reaction product with anhydrous ethanol solvent, and then dry it at 60 °C to obtain NiCoFeMnZn-MOF; the second hydrothermal reaction is carried out at a temperature of 150 °C for 18 h.

[0036] Step 3: Place the NiCoFeMnZn-MOF obtained in Step 2 into a tubular furnace, introduce argon, and react at a temperature of 500 °C for 120 min to obtain a five-element high-entropy nanotube.

[0037] Step 4: Put the quinary high-entropy nanotubes obtained in Step 3 and selenium powder into a tube furnace at a mass ratio of 1:3, introduce argon gas, and react at a temperature of 500 °C for 180 min to obtain hexary high-entropy nanotubes. Denote as hexary high-entropy nanotubes HE-NiSe2.

[0038] Example 1: Carbon-coated hexary high-entropy nanotubes NiCoFeMnZnSe@C (denoted as hexary high-entropy nanotubes HE-NiSe2@C) Preparation method of hexary high-entropy nanotubes HE-NiSe2@C, comprising the following steps: Step 1: Add 0.227 g of melamine, 0.252 g of trimesic acid, 0.111 g of boric acid, and 1.2 mmol of phosphoric acid to 35 mL of methanol solution, and mix evenly by ultrasonic method to obtain a precursor solution; then put the precursor solution into an oven for the first hydrothermal reaction to obtain a mixture containing one-dimensional HOF nanowires; the ultrasonic power is 900 W, and the ultrasonic time is 1 h; the first hydrothermal reaction is carried out at a temperature of 150 °C for 12 h.

[0039] Step 2: Add 0.249 g of nickel acetate, 0.039 g of ferric chloride, 0.035 g of cobalt acetate, 0.044 g of zinc acetate, and 0.049 g of manganese acetate to the mixture containing one-dimensional HOF nanowires obtained in Step 1, then stir at a rotation speed of 300 rpm for 20 min, and then put it into an oven for the second hydrothermal reaction; after the reaction is completed, wash the reaction product with anhydrous ethanol solvent, and then dry it at 60 °C to obtain NiCoFeMnZn-MOF; the second hydrothermal reaction is carried out at a temperature of 150 °C for 18 h. Step 3: Put the NiCoFeMnZn-MOF obtained in Step 2 into a tube furnace, introduce argon gas, and react at a temperature of 500 °C for 120 min to obtain quinary high-entropy nanotubes; Step 4: Weigh 100 mg of the quinary high-entropy nanotubes obtained in Step 3, 242 mg of tris(hydroxymethyl)aminomethane, and 150 mg of dopamine hydrochloride, add these three substances to 200 ml of deionized water, then stir at a rotation speed of 300 rpm for 120 min, and then centrifuge the reaction product (rotation speed of 300 rpm) to obtain carbon-coated quinary high-entropy nanotubes, and then dry them at 60 °C for standby; Step 5: Put the carbon-coated quinary high-entropy nanotubes obtained in Step 4 and selenium powder into a tube furnace at a mass ratio of 1:3, introduce argon gas, and react at a temperature of 500 °C for 180 min to obtain hexary high-entropy nanotubes. Denote as hexary high-entropy nanotubes HE-NiSe2@C (the font of 2 should be in lowercase).

[0040] The high-entropy nanotubes prepared in Comparative Examples 1-2 and Example 1 were characterized and measured. The results are as follows: Figure 1 The microscopic detailed structure of the six-component high-entropy nanotube HE-NiSe2@C prepared in Example 1 is shown. At this magnification, it can be clearly observed that the surface of the six-component high-entropy nanotube is covered by a carbon layer, and the carbon layer confines the selenium element inside the nanotube; when the six-component high-entropy nanotube HE-NiSe2@C is used as the anode of a sodium-ion battery, the carbon layer confines the selenium element inside the nanotube, preventing the shuttle of the selenium element and effectively enhancing the stability of the material. In contrast Figures 2 - 3 , this design is significantly different from the porous structures shown by the six-component high-entropy nanotube HE-NiSe2 sample prepared in Comparative Example 2 and the five-component high-entropy nanotube HE-Ni sample prepared in Comparative Example 1.

[0041] Figures 4 - 6 The XRD characterization diagrams of the high-entropy nanotubes prepared in Example 1 and Comparative Examples 1 and 2 are shown. From Figure 4 it can be seen that the sample of the six-component high-entropy nanotube HE-NiSe2@C prepared in Example 1 has a crystal structure, and the presence of the carbon bulge proves the successful carbon coating; from Figure 5 it can be seen that peaks appear in the six-component high-entropy nanotube NHE-NiSe2 sample prepared in Comparative Example 2, indicating that the selenization has transformed the material from an amorphous state to a crystalline state. From Figure 6 it can be seen that no crystallization appears in the unselenized five-component high-entropy nanotube HE-Ni sample prepared in Comparative Example 1.

[0042] Figure 7 The Raman peaks of the HE-NiSe2@C sample prepared in Example 1 in Figure 8 are not obvious, which may be due to the carbon layer coverage; Figure 9 the Raman peaks in the six-component high-entropy nanotube HE-NiSe2 sample prepared in Comparative Example 2 are Figure 10 shifted relative to the Raman peaks of the five-component high-entropy nanotube HE-Ni sample prepared in Comparative Example 1 in Figure 11 、 12 ), and the combined effect of carbon coating and selenization adopted in Example 1 makes the redox peaks of the six-component high-entropy nanotube HE-NiSe2@C sample more obvious. This advantage is due on the one hand to the transformation of the material from a non-static state to a crystalline state by selenization, and on the other hand to the fact that the carbon layer also provides certain conductivity.

[0043] Figure 13 shows that for the six - element high - entropy nanotube HE - NiSe2@C of Example 1, the capacitance contribution accounts for 63% at a current density of 0.2 mV s⁻¹, which is higher than that of the six - element high - entropy nanotube HE - NiSe2 (43%) of Comparative Example 2 in Figure 14 and the five - element high - entropy nanotube HE - Ni (26%) of Comparative Example 1 in Figure 15. From the above comparison, it can be seen that selenization increases the crystallinity of the six - element high - entropy material by increasing the types of elements in the material, improves the stability of the material, thereby increasing the proportion of pseudocapacitance contribution of the material. And carbon coating further improves the stability of the material by confining selenium elements in the nanotubes, thus increasing the pseudocapacitance contribution of the six - element high - entropy nanotube HE - NiSe2@C electrode.

[0044] Figure 16 For the rate performance test of the six - element high - entropy nanotube HE - NiSe2@C prepared in Example 1 at a current density of 0.1 A g -1 , the average discharge specific capacity is 552.5 mAh g -1 , and even at a large current density of 5 A g -1 , the average discharge specific capacity still reaches 288.2 mAh g -1 , which is significantly better than Figure 17 the 83.7 mAh g of the six - element high - entropy nanotube HE - NiSe2 prepared in Comparative Example 2 -1 and the 30.7 mAh g of the five - element high - entropy nanotube HE - Ni prepared in Comparative Example 1. -1

[0045] Figure 18 For the six - element high - entropy nanotube HE - NiSe2@C prepared in Example 1 after cycling 100 times at a current density of 0.1 A g -1 , the discharge specific capacity is 330.2 mAh g -1 , showing excellent stability, which is higher than Figure 19 the 175.3 mAh g of the six - element high - entropy nanotube HE - NiSe2 prepared in Comparative Example 2 -1 and the 156.4 mAh g of the five - element high - entropy nanotube HE - Ni prepared in Comparative Example 1. -1

[0046] The above - mentioned embodiments are only preferred embodiments of the present invention, which are only used to explain the present invention and do not limit the scope of implementation of the present invention. For those skilled in the art of this technology, of course, other implementation manners can be easily made according to the technical content disclosed in this specification by means of substitution or change. Therefore, all changes and improvements made on the principle of the present invention should be included within the scope of the patent application of the present invention.

Claims

1. A preparation method of a six - element high - entropy nanotube for a sodium - ion battery anode material, characterized in that, It includes the following steps: Step 1: Add melamine, trimesic acid, boric acid, and phosphoric acid into an organic solvent, mix them evenly to obtain a precursor solution; Then carry out the first hydrothermal reaction on the precursor solution; after the first hydrothermal reaction is completed, a mixed solution containing one-dimensional HOF nanowires is obtained; Step 2: Add a nickel source, an iron source, a cobalt source, a zinc source, and a manganese source into the mixed solution containing one-dimensional HOF nanowires obtained in Step 1, mix them evenly, and then carry out the second hydrothermal reaction; after the reaction ends, wash and dry the reaction product to obtain NiCoFeMnZn-MOF; Step 3: Calcinate the NiCoFeMnZn-MOF obtained in Step 2 in an inert gas atmosphere to obtain a five-component high-entropy nanotube; Step 4: Add the five-component high-entropy nanotube, tris(hydroxymethyl)aminomethane, and dopamine hydrochloride obtained in Step 3 into deionized water and react to obtain a carbon-coated five-component high-entropy nanotube; Step 5: Mix the carbon-coated five-component high-entropy nanotube obtained in Step 4 with selenium powder evenly and then calcinate it in an inert gas atmosphere to obtain a six-component high-entropy nanotube.

2. The preparation method of a six-component high-entropy nanotube for a sodium-ion battery anode material according to claim 1, wherein The organic solvent described in Step 1 is methanol, and the molar ratio of melamine, trimesic acid, boric acid, and phosphoric acid is 3:2:2:

3.

3. The preparation method of a six-component high-entropy nanotube for a sodium-ion battery anode material according to claim 1, wherein, When adding melamine, trimesic acid, boric acid, and phosphoric acid into the organic solvent in Step 1, mix them evenly by ultrasonic method, with an ultrasonic power of 900 W and a time of 1 h; The first hydrothermal reaction described in Step 1 is carried out at a temperature of 150 °C for 12 h.

4. The preparation method of a six-component high-entropy nanotube for a sodium-ion battery anode material according to claim 1, characterized in that, The second hydrothermal reaction described in Step 2 is carried out at a temperature of 150 °C for 18 h.

5. The preparation method of a six-component high-entropy nanotube for the negative electrode material of a sodium-ion battery according to claim 1, wherein The molar ratio of metal elements in the nickel source, iron source, cobalt source, zinc source, and manganese source described in Step 2 is 5:1:1:1:

1.

6. The preparation method of a six - element high - entropy nanotube for the negative electrode material of a sodium - ion battery according to claim 1, characterized in that, The nickel source, iron source, cobalt source, zinc source, and manganese source are nickel acetate, iron chloride, cobalt acetate, zinc acetate, and manganese acetate respectively.

7. The preparation method of a six-component high-entropy nanotube for the negative electrode material of a sodium-ion battery according to claim 1, characterized in that, The calcination temperature described in Step 3 is 500 °C, the reaction time is 120 min, and the heating rate is 5 °C / min.

8. The preparation method of a six-component high-entropy nanotube for the negative electrode material of a sodium-ion battery according to claim 1, wherein, The reaction time in Step 4 is 120 min, the reaction is carried out during stirring, and the stirring speed is 300 - 500 rpm.

9. The preparation method of a six-component high-entropy nanotube for a sodium-ion battery anode material according to claim 1, characterized in that, The mass ratio of the five-component high-entropy nanotube to selenium powder described in Step 5 is 1:3, the calcination temperature is 500 °C, and the reaction time is 180 min.

10. The preparation method of a six - element high - entropy nanotube for a sodium - ion battery anode material according to claim 1, characterized in that, The inert gas described in Steps 3 and 5 is argon.

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