Zinc-based carbon hollow tube array material loaded on carbon cloth as well as preparation and application of zinc-based carbon hollow tube array material

Abstract

The invention belongs to the technical field of sodium metal batteries, and particularly relates to a zinc-based carbon hollow tube array material loaded on carbon cloth as well as preparation and application of the zinc-based carbon hollow tube array material. The preparation method comprises the following steps: firstly, soaking carbon cloth in a zinc acetate solution, performing soaking and heating treatment for multiple times to obtain carbon cloth of a seed layer, then performing hydrothermal reaction twice to obtain ZnO (at) ZIF-8 (at) CC, and finally performing carbonization treatment to obtain the zinc-based carbon hollow tube array loaded on the carbon cloth. According to the material, zinc-based particles are uniformly distributed on a highly-ordered array structure, so that gradient sodium-philic sites are formed, metal sodium can be regulated and controlled to be preferentially deposited / stripped in a carbon hollow tube due to the characteristic, and the growth of sodium dendrites is inhibited; and the unique carbon hollow tube structure can provide sufficient space for sodium storage, can effectively relieve the volume expansion problem of metal sodium in the charging and discharging process, and remarkably improves the cycle life and stability of the sodium metal battery.

Description

Technical Field

[0001] The present invention belongs to the technical field of sodium metal batteries, and in particular relates to a zinc-based carbon hollow tube array material supported on carbon cloth, and its preparation and application. Background Art

[0002] Sodium metal batteries are considered to be one of the promising candidates for the next generation of energy storage systems due to their high energy density and low cost. -1 Its high theoretical specific capacity and low redox potential of -2.71V make it an ideal choice for high energy density batteries. However, sodium metal anodes face many challenges in practical applications. Due to the high reactivity of metallic sodium, once it comes into contact with the electrolyte, a solid electrolyte interface (SEI film) will form on its surface. The formed SEI film is usually not strong enough to withstand the volume expansion of the sodium metal anode during the deposition / stripping process, which causes the SEI film to continuously undergo fracture and reorganization. The cracks in the SEI film are very likely to induce dendrite formation. The unlimited growth of dendrites and the accumulation of "dead sodium" will eventually pierce the diaphragm, causing serious safety hazards. At the same time, the volume fluctuations of metallic sodium during the cycle will destroy the electrode structure, which will seriously affect the electrochemical performance of the sodium metal battery.

[0003] In order to solve the above problems, the prior art uses a three-dimensional conductive framework as a host material for the sodium metal negative electrode to achieve a more stable electrode structure. Using a three-dimensional conductive framework as a growth substrate for the deposition of metallic sodium can reduce the local current density by homogenizing the sodium ion / electron flux, induce uniform deposition of sodium metal, and thus improve the cycle stability of the battery; and the three-dimensional conductive framework usually has a high specific surface area and mechanical strength, which can better alleviate the volume expansion of sodium metal during the charge and discharge process. However, the sodium affinity of the single three-dimensional conductive framework is insufficient, and usually only a small amount of metallic sodium can be stored in the external space of the framework, and its internal space cannot be fully utilized. During the battery cycle, sodium metal is inevitably deposited on the surface of the framework, and eventually dendrite growth will still be induced. Therefore, it is very necessary to explore a more stable three-dimensional conductive framework to ensure the stability of the sodium metal negative electrode. Summary of the Invention

[0004] To overcome the shortcomings of the aforementioned prior art, the present invention provides a zinc-based carbon hollow tube array material supported on carbon cloth, as well as its preparation and application. The carbon hollow tube structure ensures rapid electron transfer, shortens the sodium ion migration path, and accelerates sodium ion diffusion. Furthermore, the zinc-based particles within the carbon hollow tubes have excellent sodium affinity, providing uniform nucleation sites for metallic sodium, thereby ensuring uniform deposition of metallic sodium within the carbon hollow tubes. This addresses the problem of prior art three-dimensional conductive materials having poor sodium dendrite restriction.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is:

[0006] A first aspect of the present invention provides a method for preparing a zinc-based carbon hollow tube array material supported on a carbon cloth, the method comprising the following steps:

[0007] S1. Preparation of the seed layer (ZnO seed@CC): Soak the carbon cloth (CC) in a zinc acetate solution, then dry the soaked carbon cloth (CC) in a forced air drying oven. Repeat this step multiple times to obtain the carbon cloth (ZnOseed@CC) forming the seed layer.

[0008] S2. Preparation of ZnO@CC precursor: The carbon cloth (ZnO seed@CC) formed with the sublayer in step S1 is immersed in a mixed solution of zinc nitrate hexahydrate and hexamethylenetetramine, and then transferred to a reactor for hydrothermal reaction. After the reaction is completed, the ZnO@CC precursor is obtained after washing and drying;

[0009] S3. Preparation of ZnO@ZIF-8@CC: The ZnO@CC precursor prepared in step S2 is immersed in a solution containing 2-methylimidazole, and then a hydrothermal reaction is carried out in a reactor. After the reaction is completed, ZnO@ZIF-8@CC is obtained after washing and drying;

[0010] S4. Preparation of CHT@CC: The ZnO@ZIF-8@CC prepared in step S3 is calcined under inert atmosphere to obtain a zinc-based modified nitrogen-doped carbon hollow tube array material supported on carbon cloth, namely CHT@CC.

[0011] The present invention first soaks the carbon cloth in a zinc acetate solution, and after multiple soaking and heating treatments, a carbon cloth (ZnO seed@CC) with a seed layer is obtained. The ZnO seed@CC is subjected to two hydrothermal reactions to obtain ZnO@ZIF-8@CC, and the obtained ZnO@ZIF-8@CC is then carbonized to obtain a zinc-based carbon hollow tube array material loaded on the carbon cloth, which is denoted as CHT@CC. The preparation method of the present invention is simple, easy to operate, has low requirements for equipment, is moderate in cost, and is suitable for large-scale production. The uniqueness of the present invention is that the constructed CHT@CC material not only has a hollow tubular structure, which can effectively alleviate the volume change of metallic sodium and provide a confined space for the storage of sodium metal; in addition, the relatively ordered nanoarray structure of the material can also promote the rapid transmission of interface electrons. At the same time, the zinc-based particles uniformly distributed inside it can also react with metallic sodium to generate NaZn in situ through a reversible reaction. 13The alloy's sodium affinity can effectively reduce the nucleation barrier of metallic sodium and alleviate the growth problem of sodium dendrites. Therefore, the CHT@CC material prepared according to the above method can significantly improve the cycle life and stability of sodium metal batteries.

[0012] Preferably, in step S1, the concentration of the zinc acetate solution is 10.05-10.10 g / 100 ml.

[0013] Preferably, in step S1, the drying temperature is 130-170°C.

[0014] Preferably, in step S1, the number of repetitions is 4-5 times.

[0015] Preferably, in step S2, the solid-to-liquid ratio of the zinc nitrate hexahydrate, hexamethylenetetramine and deionized water is 0.56-1.19 g / 80 ml.

[0016] Preferably, in step S2, the hydrothermal reaction is carried out at a temperature of 80-100° C. for 4-5 hours.

[0017] Preferably, in step S3, the mass ratio of ZnO@CC to 2-methylimidazole is 1-1.5:8-9.

[0018] Preferably, in step S3, the hydrothermal reaction is carried out at a temperature of 60-80° C. for 20-24 hours.

[0019] Preferably, in step S4, the calcination process is 5°C·min -1 The temperature is raised to 600-700℃ at a heating rate of 100-200℃, and then carbonization is continued at 600-700℃ for 1-2h. The calcination temperature in step S4 affects the formation of carbon hollow tubes. During the carbonization process, the ZIF-8 layer modified by zinc groups is transformed into a carbon hollow tube structure, and the zinc-based particles existing before carbonization are still retained inside it. Since there are sodium-philic sites modified by zinc-based particles inside the carbon hollow tube, sodium can be preferentially guided to be uniformly deposited inside it; at the same time, the structure of the carbon hollow tube determines that it can uniformly distribute the local current density, effectively alleviating the volume expansion problem of the electrode during the cycle.

[0020] Preferably, the carbon cloth in step S1 is cleaned before use: nitric acid, acetone, anhydrous ethanol and water are used to ultrasonically clean the carbon cloth in sequence, and after washing, the carbon cloth is placed in a blast drying oven for drying.

[0021] More preferably, the nitric acid is pure nitric acid, the cleaning time is 5-10 minutes, and the cleaning time of the acetone, anhydrous ethanol, and deionized water is 10-15 minutes respectively.

[0022] Preferably, the inert atmosphere in step S4 is a nitrogen atmosphere or an argon atmosphere.

[0023] The second aspect of the present invention provides a zinc-based carbon hollow tube array material supported on carbon cloth obtained by the preparation method described in the first aspect.

[0024] The zinc-based carbon hollow tube array loaded on carbon cloth prepared by the method of the present invention has good sodium affinity when used as the host material of the sodium metal negative electrode. Its unique hollow tube structure and the zinc-based particles inside can induce sodium metal to preferentially deposit inside the carbon hollow tube, even at high areal capacity (>5mAh·cm -2 ) can still maintain its structural stability under the condition of high conductivity, effectively alleviating the problem of uncontrolled dendrite growth of sodium metal negative electrode during battery cycling.

[0025] The third aspect of the present invention provides an application of the zinc-based carbon hollow tube array material loaded on carbon cloth described in the second aspect in a sodium metal battery, wherein the zinc-based carbon hollow tube array material loaded on carbon cloth serves as a negative electrode host material or a negative electrode material of a sodium metal battery.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] The present invention's method for preparing a zinc-based carbon hollow tube array material supported on carbon cloth involves first soaking the carbon cloth in a zinc acetate solution. After multiple soaking and drying processes, a seed layer of carbon cloth (ZnO seed@CC) is obtained. The ZnOseed@CC is then subjected to two hydrothermal reactions to obtain ZnO@ZIF-8@CC. The resulting ZnO@ZIF-8@CC is then carbonized to obtain a zinc-based carbon hollow tube array (CHT@CC) supported on carbon cloth. This method is simple to operate, requires low temperatures, requires simple equipment, is moderately cost-effective, and is suitable for large-scale production.

[0028] The zinc-based carbon hollow tube array loaded on carbon cloth prepared by the present invention has many advantages in inhibiting the growth of sodium dendrites, which are specifically reflected in the following aspects:

[0029] (1) This material is loaded on a three-dimensional carbon cloth, which determines that it has a large specific surface area, can reduce the local current density, reduce the polarization effect, and better inhibit the local growth of sodium dendrites;

[0030] (2) The structural characteristics of the carbon hollow tube array can provide more storage space for sodium metal deposition, effectively alleviating the volume expansion problem of sodium metal during the deposition / stripping process;

[0031] (3) It is modified by nitrogen doping and the introduction of zinc-based particles. Since zinc-based particles can react in situ with sodium metal in the deposition / stripping process, the sodium-philic NaZn 13The alloy provides more sodium-philic sites, effectively reduces the nucleation barrier of sodium metal, is conducive to the diffusion and nucleation of sodium ions, and thus induces the uniform deposition of metallic sodium.

[0032] Based on the above advantages, the sodium metal battery assembled using this material has better cycle stability and more excellent rate performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 Schematic diagram of the synthesis process of CHT@CC.

[0034] Figure 2 Scanning electron microscope image of the carbon cloth (ZnO seed@CC) forming the seed layer.

[0035] Figure 3 This is the scanning electron microscope image of the ZnO@CC precursor.

[0036] Figure 4 This is the scanning electron microscope image of ZnO@ZIF-8@CC.

[0037] Figure 5 This is a scanning electron microscope image of CHT@CC.

[0038] Figure 6 X-ray diffraction patterns of carbon cloth (CC), ZnO@CC precursor, ZnO@ZIF-8@CC, and CHT@CC.

[0039] Figure 7 CHT@CC as anode material for sodium metal batteries at 5 mA·cm -2 The current density and 5 mAh·cm -2 Coulombic efficiency of sodium deposition / stripping at areal capacity.

[0040] Figure 8 CHT@CC as a sodium metal symmetric battery material at 5 mA·cm -2 The current density and 5 mAh·cm -2 Long cycle performance diagram under area capacity.

[0041] Figure 9 Figure 2 shows the rate performance of CHT@CC as a negative electrode material for sodium metal full batteries. DETAILED DESCRIPTION

[0042] The following is a further description of specific embodiments of the present invention. It should be noted that the description of these embodiments is intended to facilitate understanding of the present invention and does not constitute a limitation of the present invention. In addition, the technical features involved in the various embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.

[0043] The experimental methods in the following examples are conventional methods unless otherwise specified, and the experimental materials used in the following examples are commercially available unless otherwise specified.

[0044] Example 1: Preparation method of zinc-based carbon hollow tube array material supported on carbon cloth (CHT@CC)

[0045] like Figure 1 As shown, the preparation method of zinc-based carbon hollow tube array material supported on carbon cloth (CHT@CC) includes the following steps:

[0046] (1) Cleaning the carbon cloth: First, soak the carbon cloth in pure nitric acid and clean it under ultrasonic conditions at 600W for 10 minutes. Then, ultrasonically clean it with acetone under the same ultrasonic conditions for 15 minutes. Finally, ultrasonically clean it with anhydrous ethanol and deionized water for 10 minutes each.

[0047] (2) Preparation of carbon cloth (ZnO seed@CC) to form seed layer: 1.098 g zinc acetate dihydrate was dissolved in 100 ml deionized water to form zinc acetate solution. Then, the washed and dried carbon cloth (area 2 × 2 cm 2 ) completely immersed in a zinc acetate solution and allowed to stand for 10 minutes, then the soaked carbon cloth was taken out and placed in a blast drying oven at 150° C. to dry for 10 minutes, and the above steps were repeated four times to obtain a carbon cloth forming a seed layer;

[0048] (3) Preparation of ZnO@CC precursor: 1.19 g of zinc nitrate hexahydrate and 0.56 g of hexamethylenetetramine were dissolved in 80 ml of deionized water to form a mixed solution. The carbon cloth with the seed layer prepared in step (2) was then immersed in the mixed solution and then transferred to a reactor for hydrothermal reaction at 95°C for 4 h. After the reaction was completed, the carbon cloth was taken out and washed alternately with anhydrous ethanol and deionized water for 4 times. The washed carbon cloth was then placed in a blast drying oven for drying. The carbon cloth obtained after drying was recorded as ZnO@CC precursor.

[0049] (4) Preparation of ZnO@ZIF-8@CC: The dried ZnO@CC obtained in step (3) was weighed, and then 8 times the mass of the ZnO@CC was used to weigh the corresponding mass of 2-methylimidazole, that is, the mass ratio of ZnO@CC to 2-methylimidazole was 1:8. 2-methylimidazole was dissolved in 80 ml of N-N dimethylformamide to form a mixed solution. The ZnO@CC obtained in step (3) was immersed in the solution and then transferred to a reactor for hydrothermal reaction at 70°C for 24 h. After the reaction was completed, the carbon cloth was taken out and washed alternately with anhydrous ethanol and deionized water for 4 times. The washed carbon cloth was then placed in a blast drying oven for drying. The carbon cloth obtained after drying was recorded as ZnO@ZIF-8@CC.

[0050] (5) Preparation of CHT@CC: The ZnO@ZIF-8@CC prepared in step (4) was placed in an argon atmosphere and heated at 5°C·min -1 The heating rate is increased to 650℃, and carbonization is continued at 650℃ for 2h. After the reaction is completed and cooled to room temperature, a zinc-based carbon hollow tube array material supported on carbon cloth can be obtained, which is recorded as CHT@CC.

[0051] Figure 2 The carbon cloth (ZnO seed@CC) with a seed layer was morphologically characterized. From the scanning electron microscope image, it can be observed that a uniformly distributed particle morphology was formed on the surface of the carbon cloth. This particle is the expected seed layer, which provides growth sites for the subsequent uniform growth of carbon nanotube-shaped ZnO on the carbon cloth.

[0052] Figure 3 The morphology of ZnO@CC was characterized, and from its scanning electron microscope image, it can be seen that on the carbon cloth (ZnO seed@CC) with a pre-formed seed layer, carbon nanotube-shaped ZnO can grow uniformly on the carbon cloth and be arranged in a highly orderly array structure.

[0053] Figure 4 The morphology of ZnO@ZIF-8@CC was characterized. From the scanning electron microscope image, it can be observed that the outer surface of the pre-formed carbon nanotube-shaped ZnO is evenly and tightly wrapped by ZIF-8, thus forming a core-shell structure.

[0054] Figure 5 The morphology of the CHT@CC formed after carbonization was characterized. From the scanning electron microscope image, it can be observed that after carbonization treatment, the material still maintains the morphology of the carbon nanotube array, and the pre-prepared ZnO@ZIF-8 structure is successfully thermally decomposed into a translucent tubular structure, indicating that a zinc-based carbon hollow tube array is successfully established on the carbon cloth.

[0055] Figure 6The X-ray diffraction patterns of carbon cloth (CC), ZnO@CC precursor, ZnO@ZIF-8@CC, and CHT@CC show that the diffraction peaks of the pre-formed ZnO@CC precursor and ZnO@ZIF-8@CC match well with the standard peaks of ZnO and ZIF-8, indicating that the carbon hollow tube structure is successfully constructed with high purity. The carbonized CHT@CC only shows the diffraction peak of carbon, and there are no characteristic peaks of ZIF-8 or ZnO because the internal zinc-based particles are ultrafine particles and are confined in the ZIF-8-derived carbon fibers, making them difficult to detect.

[0056] Experimental Example 1: Preparation of Sodium Metal Anode Materials and Their Performance Testing

[0057] The zinc-based carbon hollow tube array material CHT@CC loaded on carbon cloth in Example 1 was cut into circular pole pieces with a diameter of 12 mm and placed in a vacuum oven at 60°C for 12 h for electrochemical performance testing as a negative electrode host material for sodium metal batteries.

[0058] In the half-cell, the CHT@CC electrode is directly used as a self-supporting electrode; in the full cell, the CHT@CC electrode is used as a composite negative electrode with sodium metal, in which the CHT@CC electrode is the host material of the sodium metal battery negative electrode.

[0059] 1. Characterization of cycle performance

[0060] (1) Assembly of half-cell: A CHT@CC electrode with a diameter of 12 mm was paired with a metal sodium sheet in a glove box filled with argon and with a water and oxygen content of less than 0.01 ppm to assemble a Na||CHT@CC half-cell. The electrolyte system selected was a 1 mol / L sodium hexafluorophosphate (NaPF6) solution in ethylene glycol dimethyl ether (DME) with a dosage of 50 μL. A commercial polypropylene porous membrane was used as the separator.

[0061] (2) Electrochemical test: Coulombic efficiency (CE) is a key indicator for measuring the reversibility and stability of batteries. First, the Na||CHT@CC half-cell was tested at 0.05 mA·cm -2 The current was cycled between 0.01 and 0.6 V for 5 times, and then at 5 mA cm -2 Repeated deposition / stripping at a current of 5 mAh·cm -2 The coulombic efficiency of sodium metal is as follows Figure 7 As shown in the figure, at 5mA·cm -2 High current density and 5 mAh cm -2Despite the high areal capacity, the half-cell can still maintain an extremely high CE after 150 cycles, further proving that the zinc-based particles in the CHT@CC electrode can effectively reduce the nucleation barrier of metallic sodium, achieve uniform deposition of metallic sodium, and have excellent reversibility.

[0062] 2. Characterization of long cycle performance

[0063] (1) Symmetrical cell assembly: CHT@CC electrode was used as the working electrode and sodium metal sheet was used as the counter electrode. The galvanostatic deposition method was used to generate a symmetrical cell at 0.5 mA cm -2 The current density deposited on the electrode surface is 5 mAh cm -2 The researchers then disassembled the half-cell in a glove box, removed the composite sodium metal anode, and cleaned the residual electrolyte on the anode surface with an excess of dimethylbenzene (DME). Two composite electrodes containing the same sodium metal were then assembled into a symmetrical Na@CHT@CC||Na@CHT@CC cell. The electrolyte system consisted of a 1 mol / L sodium hexafluorophosphate (NaPF6) solution in ethylene glycol dimethyl ether (DME) at a volume of 50 μL. A commercially available porous polypropylene membrane was used as the separator.

[0064] (2) Electrochemical test: Na@CHT@CC||Na@CHT@CC symmetrical battery was tested at 5 mA·cm -2 Repeated deposition / stripping at a current density of 5 mAh·cm -2 The cycle performance obtained is as follows Figure 8 As shown in the figure, it can be seen that the symmetrical battery assembled by Na@CHT@CC can be stably cycled for 500h, and its hysteresis voltage is only 42mV. The battery voltage changes relatively smoothly, and no obvious polarization phenomenon occurs, indicating that the material provides sufficient storage space for the deposition of metallic sodium during long-term cycling and can still maintain good stability during the cycling process.

[0065] 3. Characterization of full battery rate performance

[0066] (1) Assembly of the full cell: A Na|CHT@CC half-cell was assembled using the CHT@CC electrode as the working electrode and the sodium metal sheet as the counter electrode. Constant current deposition was performed through the half-cell at 0.5 mA cm -2 The current density of the CHT@CC electrode deposited a surface capacity of 5 mAh cm -2 The half-cell was disassembled in a glove box and the composite metal sodium negative electrode Na@CHT@CC was taken out. The electrolyte remaining on the surface of the electrode was cleaned with excess DME. The electrode will be used as the negative electrode of the assembled full battery. The positive electrode of the assembled full battery will use an active material loading of about 4.5 mg cm -2The positive and negative electrodes were placed in a glove box to assemble the Na@CHT@CC||NVP full battery. The electrolyte system used was 1 mol·L -1 The electrolyte used was 100 μL of propylene carbonate (PC) / fluoroethylene carbonate (FEC) (v / v=1:1) of sodium hexafluorophosphate (NaPF6) and glass fiber filter paper as the diaphragm.

[0067] (2) Electrochemical test: The rate performance of CHT@CC as a negative electrode material for sodium metal full batteries is shown in the figure below. Figure 9 As shown, the Na@CHT@CC||NVP full cell delivers 114 mAh·g at rates of 0.1C, 0.2C, 0.5C, 1C, 2C, and 5C, respectively. -1 , 107mAh·g -1 , 100mAh·g -1 , 95mAh·g -1 ,89mAh·g -1 and 78mAh·g -1 Even at a rate of 10C, it still maintains 64mAh·g -1 The good cycle stability of the full battery also preliminarily confirmed that the zinc-based carbon hollow tube array material supported on carbon cloth has good practical application potential.

[0068] In summary, the present invention first soaks the carbon cloth in a zinc acetate solution, and after multiple soaking and heating treatments, a carbon cloth with a seed layer (ZnO seed@CC) is obtained. After two hydrothermal reactions of the ZnO seed@CC, ZnO@ZIF-8@CC can be obtained. The obtained ZnO@ZIF-8@CC is then carbonized to obtain a zinc-based carbon hollow tube array material loaded on the carbon cloth, which is denoted as CHT@CC. The present invention constructs a carbon hollow tube array modified by zinc-based nanoparticles on a three-dimensional carbon cloth. Thanks to the highly ordered array structure characteristics of the material, the gradient sodium-affinity sites it possesses can regulate the preferential deposition / stripping of metallic sodium inside the carbon hollow tube, thereby inhibiting the growth of sodium dendrites. Its unique carbon hollow tube structure also provides a confined space for the storage of metallic sodium, and effectively alleviates the volume expansion of metallic sodium during the charge and discharge process, thereby solving the problem of poor restriction of sodium dendrites by the host material in the prior art.

[0069] The embodiments of the present invention are described in detail above, but the present invention is not limited to the described embodiments. It is apparent to those skilled in the art that various changes, modifications, substitutions, and variations of these embodiments may be made without departing from the principles and spirit of the present invention, and the changes still fall within the scope of protection of the present invention.

Claims

1. A method for preparing a zinc-based carbon hollow tube array material supported on carbon cloth, characterized in that: The following steps are involved: S1. Preparation of ZnO seed@CC: soaking the carbon cloth in a zinc acetate solution, then drying the soaked carbon cloth, and repeating this step multiple times to obtain a carbon cloth ZnO seed@CC with a seed layer; S2. Preparation of ZnO@CC precursor: soaking ZnO seed@CC in a mixed solution of zinc nitrate hexahydrate and hexamethylenetetramine, followed by hydrothermal reaction. After the reaction is complete, washing and drying are performed to obtain the ZnO@CC precursor; S3. Preparation of ZnO@ZIF-8@CC: The ZnO@CC precursor was immersed in a solution containing 2-methylimidazole, and then subjected to a hydrothermal reaction. After the reaction was completed, ZnO@ZIF-8@CC was obtained after washing and drying. S4. Preparation of CHT@CC: ZnO@ZIF-8@CC was calcined under inert atmosphere to obtain a zinc-based carbon hollow tube array material supported on carbon cloth, which was denoted as CHT@CC.

2. The method for preparing a zinc-based carbon hollow tube array material supported on carbon cloth according to claim 1, characterized in that: In step S1, the concentration of the zinc acetate solution is 10.05-10.10 g / 100 ml.

3. The method for preparing a zinc-based carbon hollow tube array material supported on carbon cloth according to claim 1, characterized in that: In step S1, the drying temperature is 130-170°C.

4. The method for preparing a zinc-based carbon hollow tube array material supported on carbon cloth according to claim 1, characterized in that: In step S2, the solid-liquid ratio of the mixed solution is 0.56-1.19 g / 80 ml.

5. The method for preparing a zinc-based carbon hollow tube array material supported on carbon cloth according to claim 1, characterized in that: In step S2, the hydrothermal reaction is carried out at a temperature of 80-100° C. for 4-5 hours.

6. The method for preparing a zinc-based carbon hollow tube array material supported on carbon cloth according to claim 1, characterized in that: In step S3, the mass ratio of ZnO@CC to 2-methylimidazole is 1-1.5:8-9.

7. The method for preparing a zinc-based carbon hollow tube array material supported on carbon cloth according to claim 1, characterized in that: In step S3, the hydrothermal reaction is carried out at a temperature of 60-80° C. for 20-24 hours.

8. The method for preparing a zinc-based carbon hollow tube array material supported on carbon cloth according to claim 1, characterized in that: In step S4, the calcination procedure is 5°C·min -1 The temperature is raised to 600-700°C at a heating rate of 100-200°C, and then carbonization is continued at 600-700°C for 1-2h.

9. A zinc-based carbon hollow tube array material supported on carbon cloth, prepared by the preparation method according to any one of claims 1 to 8.

10. Use of the zinc-based carbon hollow tube array material supported on carbon cloth as claimed in claim 9 in a sodium metal battery, characterized in that: The zinc-based carbon hollow tube array supported on the carbon cloth is used as a negative electrode host material or a negative electrode material of a sodium metal battery.

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