One-dimensional tubular selenide and carbon composite material assembled by hollow particles and preparation method and application thereof

Abstract

The invention discloses a one-dimensional tubular selenide-carbon composite material assembled by hollow particles and a preparation method and application thereof.The preparation method comprises the following steps that ZnCo-ZIF nanotubes and 2, 5-dihydroxyterephthalic acid are mixed, N, N-dimethylformamide is added, a reaction is conducted, after the reaction is completed, a product is subjected to centrifugal separation, and the one-dimensional tubular selenide-carbon composite material assembled by the hollow particles is obtained. And washing and drying to obtain the one-dimensional tubular MOF material assembled by the hollow particles. And annealing the MOF material in an argon atmosphere to obtain the one-dimensional porous carbon nanotube material assembled by the hollow particles. And then uniformly mixing with selenium powder, and annealing under argon protection to obtain the one-dimensional tubular selenide-carbon composite material assembled by hollow particles. The method is simple to operate and controllable in process, and the prepared product is widely applied to the fields of energy storage, catalysis, environmental governance, biomedicine and the like.

Description

Technical Field

[0001] The present invention belongs to the technical field of functional nanomaterial synthesis, and in particular relates to a one-dimensional tubular selenide@carbon composite material assembled from hollow particles, and a preparation method and application thereof. Background Art

[0002] Since their commercialization in 1991, lithium-ion batteries (LIBs) have become a core technology for modern energy storage, thanks to their high energy density, long cycle life, and mature industrial chain. However, lithium reserves are limited and unevenly distributed, while sodium resources are abundant (2.8% of the Earth's crust) and cost only one-tenth as much, making them suitable for large-scale energy storage. Consequently, research on sodium-ion batteries (SIBs) is gaining increasing attention. Metal-organic framework (MOF)-derived carbon or composite materials store sodium ions through adsorption, intercalation, or alloying reactions. Their structure is flexibly tunable, with the pore size, specific surface area, and active sites modulated by selecting metal nodes (Fe, Co, Zn, etc.) and organic ligands (imidazole, carboxylic acids). The rich, hierarchical pore structure provides channels for rapid ion transport. Furthermore, high-temperature carbonization of MOFs allows the one-step preparation of porous carbon composites that combine electrical conductivity with high specific capacity.

[0003] Currently, most ZnCo-BTC precursors are synthesized using DMF and ethanol as solvents in a reactor under high temperature and pressure, requiring very long reaction times. Furthermore, in the step of converting solid materials into hollow materials, traditional methods such as templates, chemical etching, and vapor deposition are also too expensive and require high processes. Therefore, finding a simpler and more cost-effective method is highly desirable. Summary of the Invention

[0004] The purpose of the present invention is to provide a one-dimensional tubular selenide@carbon composite material assembled from hollow particles, and its preparation method and application. The process of converting solid material into hollow material is simple and has broad application prospects.

[0005] In one aspect of the present invention, the present invention provides a method for preparing a one-dimensional tubular MOF material assembled from hollow particles. According to an embodiment of the present invention, the method comprises the following steps:

[0006] (1) Preparation of ZnCo-BTC nanowires: 1,3,5-benzenetricarboxylic acid was dissolved in deionized water to form solution A, zinc acetate dihydrate and cobalt acetate tetrahydrate were dissolved in deionized water to form solution B, solution A was preheated to 90-100°C in an oil bath, solution B was added to solution A, and the mixture was stirred at a constant temperature for 15-20 minutes. The product was centrifuged, washed, and dried to obtain ZnCo-BTC nanowire powder;

[0007] (2) Preparation of ZnCo-ZIF nanotubes: ZnCo-BTC nanowire powder was dispersed in an ethanol aqueous solution to form a uniform suspension C, 2-methylimidazole and triethylamine were dissolved in the ethanol aqueous solution to form a solution D, solution D was preheated to the reaction temperature, suspension C was added to solution D, the reaction was stirred at a constant temperature, the product was centrifuged, and then washed and dried to obtain ZnCo-ZIF nanotube powder;

[0008] (3) Preparation of MOF nanotubes assembled from hollow particles: ZnCo-ZIF nanotube powder was mixed with 2,5-dihydroxyterephthalic acid, and N,N-dimethylformamide was added to react. After the reaction was completed, the product was centrifuged and then washed and dried to obtain a one-dimensional tubular MOF material assembled from hollow particles.

[0009] In addition, the method for preparing a one-dimensional tubular MOF material assembled from hollow particles according to the above embodiment of the present invention may also have the following additional technical features:

[0010] In some embodiments of the present invention, in step (1), the concentration of 1,3,5-benzenetricarboxylic acid in solution A is 0.020-0.024 mol / L; the concentration of cobalt acetate tetrahydrate in solution B is 0.12-0.16 mol / L, and the concentration of zinc acetate dihydrate is 0.04-0.08 mol / L; the volume ratio of solution A to solution B is 10:1-8:1; the washing is carried out with ethanol; the drying temperature is 75-85°C, and the drying time is 10-15 h.

[0011] In some embodiments of the present invention, in step (2): the concentration of ZnCo-BTC nanowire powder in the suspension C is 5-9 g / L; the concentration of 2-methylimidazole in the solution D is 60-70 g / L, the amount of triethylamine added is 14-15 mL per liter of ethanol aqueous solution, and the volume ratio of water to ethanol in the ethanol aqueous solution is 1:9-3:7; the volume ratio of the suspension C to the solution D is 1:4-1:3; the preheating temperature is 60-80°C, and the reaction time is 28-32 min; the washing is carried out with ethanol, and the number of ethanol washings is 2-4 times; the drying temperature is 75-85°C, and the drying time is 10-15 h.

[0012] In some embodiments of the present invention, in step (3), the mass ratio of the ZnCo-ZIF nanotube powder to 2,5-dihydroxyterephthalic acid is 1:1.2 to 1:2; the amount of N,N-dimethylformamide added is 0.9 to 1.1 L per gram of ZnCo-ZIF nanotube powder; the reaction temperature is 65 to 75°C, and the reaction time is 700 to 800 min; the washing is carried out with ethanol, and the number of ethanol washings is 2 to 4 times; the drying temperature is 75 to 85°C, and the drying time is 10 to 15 h.

[0013] In another aspect of the present invention, the present invention provides a method for preparing a one-dimensional tubular MOF material assembled from hollow particles, thereby obtaining a one-dimensional tubular MOF material assembled from hollow particles.

[0014] In another aspect of the present invention, a method for preparing a one-dimensional tubular selenide@carbon composite material assembled from hollow particles is provided. According to an embodiment of the present invention, the method comprises the following steps:

[0015] (1) placing the one-dimensional tubular MOF material assembled by hollow particles in a tube furnace and annealing under argon protection to obtain a one-dimensional porous carbon nanotube material assembled by hollow particles;

[0016] (2) The one-dimensional porous carbon nanotube material assembled by hollow particles is mixed evenly with selenium powder and then annealed under argon protection to obtain a one-dimensional tubular selenide@carbon composite material assembled by hollow particles.

[0017] In addition, the method for preparing a one-dimensional tubular selenide@carbon composite material assembled from hollow particles according to the above embodiment of the present invention may also have the following additional technical features:

[0018] In some embodiments of the present invention, in step (1), the annealing temperature is 600-800° C., and the holding time is 1.5-2.5 h.

[0019] In some embodiments of the present invention, in step (2), the mass ratio of the one-dimensional porous carbon nanotube material assembled by hollow particles to selenium powder is 1:1.5 to 1:2.5; the annealing temperature is 300 to 500° C., and the holding time is 1.5 to 2.5 hours.

[0020] In another aspect of the present invention, the present invention provides a method for preparing a one-dimensional tubular selenide@carbon composite material assembled from hollow particles, to obtain a one-dimensional tubular selenide@carbon composite material assembled from hollow particles.

[0021] In another aspect of the present invention, the present invention proposes a one-dimensional tubular selenide@carbon composite material assembled from hollow particles for preparing a negative electrode for a sodium ion battery.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] 1. The ZnCo-ZIF nanotube material prepared by the present invention has a stable one-dimensional tubular structure. The one-dimensional tubular MOF has an extremely high specific surface area and an adjustable pore structure, which provides abundant active sites for charge storage and can significantly improve the energy storage capacity. On this basis, the particles constituting the nanotubes are further converted into hollow structures to prepare a one-dimensional tubular selenide@carbon composite material assembled by hollow particles, which further increases the specific surface area of the material. Its porous structure can effectively increase the electrode-electrolyte contact area and optimize the charge storage capacity. The tubular structure can provide a one-dimensional ion channel, shorten the sodium ion diffusion path, and promote the rapid migration of sodium ions inside the material. The combination of hollow particles and tubular structures forms a hierarchical pore network, the internal cavity of which can buffer Na + Volume expansion during intercalation / deintercalation.

[0024] 2. The one-dimensional tubular selenide@carbon composite material assembled from hollow particles prepared by the present invention adopts a composite structure of selenide and carbon coating, and has a high theoretical capacity. The porous carbon skeleton formed after MOF carbonization has high conductivity, which can effectively alleviate the intrinsic low conductivity problem of selenide. The theoretical capacity of selenide is significantly higher than that of traditional carbon-based materials, but its volume expansion problem limits its practical application. The present invention controls the size of selenide particles to be smaller through nanostructure design and carbon coating strategy, and uses the elasticity of the carbon matrix to buffer its volume change, which can enhance the cyclic stability of SIBs.

[0025] 3. During the synthesis of the ZnCo-BTC nanowires prepared by the present invention, only water is used as a solvent, the reaction conditions are simple and mild, and the reaction time is relatively fast. In the subsequent conversion into ZnCo-ZIF nanotubes and one-dimensional tubular MOF materials assembled from hollow particles, a solvent-assisted ligand exchange method is used, the reaction conditions are mild, and the solvent cost used is also very low.

[0026] 4. The preparation method adopted by the present invention has the advantages of low time cost, low process threshold, and controllable safety risks. It has extremely high application value in sodium-ion batteries and can be applied to other fields such as catalysis, environmental governance, and biomedicine. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 This is an SEM image of ZnCo-BTC nanowires prepared in Example 1 of the present invention;

[0028] Figure 2 This is an SEM image of the ZnCo-ZIF nanotubes prepared in Example 2 of the present invention;

[0029] Figure 3SEM (a) and TEM (b) images of MOF nanotubes assembled from hollow particles prepared in Example 3 of the present invention;

[0030] Figure 4 This is a SEM image of MOF nanotubes assembled from hollow particles prepared in Example 4 of the present invention;

[0031] Figure 5 This is an SEM image of a one-dimensional porous carbon nanotube material assembled from hollow particles prepared in Example 5 of the present invention;

[0032] Figure 6 This is an SEM image of a one-dimensional porous carbon nanotube material assembled from hollow particles prepared in Example 6 of the present invention;

[0033] Figure 7 This is an SEM image of a one-dimensional tubular selenide@carbon composite material assembled from hollow particles prepared in Example 6 of the present invention;

[0034] Figure 8 This is the XRD pattern of the one-dimensional porous carbon nanotube material assembled from hollow particles prepared in Example 6 of the present invention;

[0035] Figure 9 This is the XRD pattern of the one-dimensional tubular selenide@carbon composite material assembled from hollow particles prepared in Example 6 of the present invention;

[0036] Figure 10 This is a rate performance diagram of the CR2032 button battery prepared in Example 7 of the present invention;

[0037] Figure 11 This is a cycle performance diagram of the CR2032 button battery prepared in Example 7 of the present invention. DETAILED DESCRIPTION

[0038] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without making any creative efforts shall fall within the scope of protection of the present invention.

[0039] Example 1

[0040] The preparation method of ZnCo-BTC nanowire material comprises the following steps:

[0041] (1) Dissolve 420 mg of 1,3,5-benzenetricarboxylic acid in 90 mL of deionized water to form solution A. Dissolve 131.7 mg of zinc acetate dihydrate and 348.7 mg of cobalt acetate tetrahydrate in 10 mL of deionized water to form solution B. Preheat solution A to 100°C in an oil bath, then add solution B to solution A and stir at constant temperature for 17 minutes.

[0042] (2) The product was centrifuged, washed with ethanol three times, and then dried in an oven at 80°C for 12 h to obtain ZnCo-BTC nanowire powder.

[0043] Figure 1 This is an SEM image of the ZnCo-BTC nanowire material prepared in this example. It can be seen that it presents a one-dimensional nanowire morphology with a smooth surface.

[0044] Example 2

[0045] The preparation method of ZnCo-ZIF nanotube material comprises the following steps:

[0046] (1) 50 mg of the ZnCo-BTC nanowire powder prepared in Example 1 was dispersed in 10 mL of an ethanol aqueous solution (V ethanol:V water = 9:1) to form a uniform suspension C. 2 g of 2-methylimidazole and 0.425 mL of triethylamine were dissolved in 30 mL of an ethanol aqueous solution (V ethanol:V water = 9:1) to form a solution D. After preheating the solution D to 60°C in a water bath, the suspension C was added to the solution D and the mixture was stirred at a constant temperature for 30 min.

[0047] (2) The product was centrifuged, washed with ethanol three times, and dried in an oven at 80°C for 12 h to obtain ZnCo-ZIF nanotube powder.

[0048] Figure 2 The SEM image of the ZnCo-ZIF nanotube material prepared in this example shows that the solid nanowires are transformed into hollow nanotubes with rough particles on the surface.

[0049] Example 3

[0050] The preparation method of MOF nanotube material assembled from hollow particles comprises the following steps:

[0051] (1) 30 mg of the ZnCo-ZIF nanotube powder prepared in Example 2 was mixed with 45 mg of 2,5-dihydroxyterephthalic acid and placed in a reaction kettle. 40 mL of N,N-dimethylformamide was added and the mixture was placed in an oven at 70°C for 750 min.

[0052] (2) After the reaction was completed, the product was centrifuged and washed with ethanol three times, thereby obtaining a one-dimensional tubular MOF material assembled by hollow particles after drying in an oven at 80°C for 12 h.

[0053] Figure 3 The SEM (a) and TEM (b) images of the MOF nanotube material assembled from hollow particles prepared in this example show that the rough particles on the surface of the ZIF nanotube have been transformed into a hollow structure.

[0054] Example 4

[0055] The preparation method of MOF nanotube material assembled from hollow particles comprises the following steps:

[0056] (1) 30 mg of the ZnCo-ZIF nanotube powder prepared in Example 2 was mixed with 36 mg of 2,5-dihydroxyterephthalic acid and placed in a reaction kettle. 40 mL of N,N-dimethylformamide was added and the mixture was placed in an oven at 70°C for 800 min.

[0057] (2) After the reaction is completed, the product is centrifuged, washed with ethanol three times, and dried in an oven at 80°C for 12 h to obtain a one-dimensional tubular MOF material assembled from hollow particles.

[0058] Figure 4 This is an SEM image of the MOF nanotube material assembled from hollow particles prepared in this example. It can be seen that the particles on the surface of the ZIF nanotube have been transformed into a hollow structure.

[0059] Example 5

[0060] A method for preparing a one-dimensional tubular selenide@carbon composite material assembled from hollow particles comprises the following steps:

[0061] (1) The one-dimensional tubular MOF material assembled from hollow particles prepared in Example 3 was placed in a tube furnace and annealed under argon protection at a heating rate of 2°C / min and an annealing temperature of 600°C for 2 h to obtain a one-dimensional porous carbon nanotube material assembled from hollow particles;

[0062] (2) The one-dimensional porous carbon nanotube material assembled by hollow particles was evenly mixed with selenium powder (mass ratio of 1:2) and then annealed under argon protection. The heating rate of the tubular furnace was 2℃ / min, the annealing temperature was 400℃, and the temperature was kept for 2h to obtain a one-dimensional tubular selenide@carbon composite material assembled by hollow particles.

[0063] Figure 5 : is an SEM image of the porous carbon nanotube material assembled from hollow particles prepared in this example, indicating that the hollow structure of the one-dimensional porous carbon nanotube material assembled from hollow particles is well maintained after carbonization.

[0064] Example 6

[0065] A method for preparing a one-dimensional tubular selenide@carbon composite material assembled from hollow particles comprises the following steps:

[0066] (1) The one-dimensional tubular MOF material assembled from hollow particles prepared in Example 3 was placed in a tube furnace and annealed under argon protection at a heating rate of 2°C / min and an annealing temperature of 700°C for 2 h to obtain a one-dimensional porous carbon nanotube material assembled from hollow particles;

[0067] (2) The one-dimensional porous carbon nanotube material assembled by hollow particles was evenly mixed with selenium powder (mass ratio of 1:2) and then annealed under argon protection. The heating rate of the tubular furnace was 2℃ / min, the annealing temperature was 400℃, and the temperature was kept for 2h to obtain a one-dimensional tubular selenide@carbon composite material assembled by hollow particles.

[0068] Figure 6 This is an SEM image of the porous carbon nanotube material assembled from hollow particles prepared in this example, which shows that the morphology of the one-dimensional porous carbon nanotube material assembled from hollow particles is well maintained after carbonization without collapse.

[0069] Figure 7 This is an SEM image of the one-dimensional tubular selenide@carbon composite material assembled from hollow particles prepared in this example. It can be seen that the morphology after carbonization is basically retained after selenization, with some selenide particles on the surface.

[0070] Figure 8 This is the XRD pattern of the one-dimensional porous carbon nanotube material assembled from hollow particles prepared in this example. It can be seen that the phases of the material after carbonization are carbon and reduced Co.

[0071] Figure 9 This is the XRD pattern of the one-dimensional tubular selenide@carbon composite material assembled from hollow particles prepared in this example. It can be seen that the material is completely transformed into carbon and CoSe2.

[0072] Example 7

[0073] A method for preparing a sodium ion battery comprises the following steps:

[0074] (1) Preparation of a working electrode: The one-dimensional tubular selenide@carbon composite material assembled from hollow particles prepared in Example 4 was uniformly mixed with conductive carbon black and PVDF in a mass ratio of 8:1:1 and dissolved in 1-methyl-2-pyrrolidone (NMP) to prepare a slurry. The slurry was then uniformly coated on a copper foil current collector with a thickness of approximately 50 μm. The slurry was dried in a vacuum drying oven at 80°C for 24 h and then sliced to prepare a working electrode.

[0075] (2) Battery assembly: Using sodium sheet as the positive electrode material, glass fiber as the separator, and NaPF6 electrolyte (solvent: DME), CR2032 button cells were assembled in an argon-filled glove box.

[0076] Performance test: 0.1V~3V vs Na + / Na, the rate performance of the battery was tested twice at current densities of 0.1A / g, 0.2A / g, 0.5A / g, 1A / g, 2A / g, 5A / g, and 10A / g. + / Na, and the cycling performance of the battery was tested at a current density of 2 A / g.

[0077] Figure 10 This example shows the electrochemical rate performance test of a CR2032 button cell. It can be seen that the one-dimensional tubular selenide@carbon composite material assembled from hollow particles has good specific capacity at different current densities, especially at high current densities.

[0078] Figure 11 This is the electrochemical performance cycle performance test performed on the CR2032 button battery in this embodiment. It can be seen that the battery has excellent capacity retention rate even after 2500 cycles.

[0079] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in similar ways. As long as they do not deviate from the structure of the present invention or exceed the scope defined by the claims, they shall fall within the scope of protection of the present invention.

Claims

1. A method for preparing a one-dimensional tubular MOF material assembled from hollow particles, comprising the following steps: (1) Preparation of ZnCo-BTC nanowires: 1,3,5-benzenetricarboxylic acid was dissolved in deionized water to form solution A, zinc acetate dihydrate and cobalt acetate tetrahydrate were dissolved in deionized water to form solution B, solution A was preheated to 90-100°C in an oil bath, solution B was added to solution A, and the mixture was stirred at a constant temperature for 15-20 minutes. The product was centrifuged, washed, and dried to obtain ZnCo-BTC nanowire powder; (2) Preparation of ZnCo-ZIF nanotubes: ZnCo-BTC nanowire powder was dispersed in an ethanol aqueous solution to form a uniform suspension C, 2-methylimidazole and triethylamine were dissolved in the ethanol aqueous solution to form a solution D, solution D was preheated to the reaction temperature, suspension C was added to solution D, the reaction was stirred at a constant temperature, the product was centrifuged, and then washed and dried to obtain ZnCo-ZIF nanotube powder; (3) Preparation of MOF nanotubes assembled from hollow particles: ZnCo-ZIF nanotube powder was mixed with 2,5-dihydroxyterephthalic acid, and N,N-dimethylformamide was added to react. After the reaction was completed, the product was centrifuged and then washed and dried to obtain a one-dimensional tubular MOF material assembled from hollow particles.

2. The method for preparing a one-dimensional tubular MOF material assembled from hollow particles according to claim 1, characterized in that: In step (1), the concentration of 1,3,5-benzenetricarboxylic acid in solution A is 0.020-0.024 mol / L; the concentration of cobalt acetate tetrahydrate in solution B is 0.12-0.16 mol / L, and the concentration of zinc acetate dihydrate is 0.04-0.08 mol / L; the volume ratio of solution A to solution B is 10:1-8:1; the washing is carried out with ethanol; the drying temperature is 75-85° C., and the drying time is 10-15 h.

3. The method for preparing a one-dimensional tubular MOF material assembled from hollow particles according to claim 1, characterized in that: In step (2): The concentration of the ZnCo-BTC nanowire powder in the suspension C is 5 to 9 g / L; the concentration of 2-methylimidazole in the solution D is 60 to 70 g / L; the amount of triethylamine added is 14 to 15 mL per liter of ethanol aqueous solution; and the volume ratio of water to ethanol in the ethanol aqueous solution is 1:9 to 3:7; The volume ratio of the suspension C to the solution D is 1:4 to 1:3; the preheating temperature is 60 to 80° C., and the reaction time is 28 to 32 minutes; the washing is performed with ethanol, and the number of ethanol washings is 2 to 4 times; the drying temperature is 75 to 85° C., and the drying time is 10 to 15 hours.

4. The method for preparing a one-dimensional tubular MOF material assembled from hollow particles according to claim 1, characterized in that: In step (3), the mass ratio of the ZnCo-ZIF nanotube powder to 2,5-dihydroxyterephthalic acid is 1:1.2 to 1:2; the amount of N,N-dimethylformamide added is 0.9 to 1.1 L per gram of ZnCo-ZIF nanotube powder; the reaction temperature is 65 to 75°C, and the reaction time is 700 to 800 min; the washing is carried out with ethanol, and the number of ethanol washings is 2 to 4 times; the drying temperature is 75 to 85°C, and the drying time is 10 to 15 h. 5 . A one-dimensional tubular MOF material assembled from hollow particles prepared by the method for preparing a one-dimensional tubular MOF material assembled from hollow particles according to any one of claims 1 to 4 .

6. A method for preparing a one-dimensional tubular selenide@carbon composite material assembled from hollow particles, comprising the following steps: (1) placing the one-dimensional tubular MOF material assembled by hollow particles as claimed in claim 5 in a tube furnace and annealing under argon protection to obtain a one-dimensional porous carbon nanotube material assembled by hollow particles; (2) The one-dimensional porous carbon nanotube material assembled by hollow particles is mixed evenly with selenium powder and then annealed under argon protection to obtain a one-dimensional tubular selenide@carbon composite material assembled by hollow particles.

7. The method for preparing a one-dimensional tubular selenide@carbon composite material assembled from hollow particles according to claim 6, characterized in that: In step (1), the annealing temperature is 600-800° C., and the holding time is 1.5-2.5 hours.

8. The method for preparing a one-dimensional tubular selenide@carbon composite material assembled from hollow particles according to claim 6, wherein: In step (2), the mass ratio of the one-dimensional porous carbon nanotube material assembled from hollow particles to selenium powder is 1:1.5 to 1:2.5; the annealing temperature is 300 to 500° C., and the holding time is 1.5 to 2.5 hours.

9. A one-dimensional tubular selenide@carbon composite material assembled from hollow particles, prepared by the method for preparing a one-dimensional tubular selenide@carbon composite material assembled from hollow particles according to claim 6.

10. The one-dimensional tubular selenide@carbon composite material assembled from hollow particles according to claim 9 is used to prepare a negative electrode for a sodium ion battery.

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