AU2020101299A4 - Vanadium tetrasulfide-nitrogen-doped carbon tube composite and preparation method and use thereof - Google Patents
Vanadium tetrasulfide-nitrogen-doped carbon tube composite and preparation method and use thereof Download PDFInfo
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Abstract
The present invention provides a vanadium tetrasulfide-nitrogen-doped carbon tube composite
5 and a preparation method and use thereof, and belongs to the preparation technology field of
electrode materials for sodium ion batteries. The preparation method of a vanadium
tetrasulfide-nitrogen-doped carbon tube composite provided in the present invention includes the
following steps: mixing pyrrole, an initiator, and a methyl orange aqueous solution, and
conducting a polymerization reaction to obtain polypyrrole; calcining the polypyrrole to obtain
10 nitrogen-doped carbon tubes; and mixing the nitrogen-doped carbon tubes, a vanadium source, a
sulfur source, and a reaction solvent, and conducting a solvothermal reaction to obtain a vanadium
tetrasulfide-nitrogen-doped carbon tube composite. The vanadium tetrasulfide-nitrogen-doped
carbon tube composite prepared in the present invention has uniform particle distribution,
relatively high reversible specific capacity, and good electrochemical cycle performance and rate
15 performance. The preparation method in the present invention is simple and has a short process
and low production costs.
1/1
FIG. 1
-800
600
Current density=1iAg g0
e400
Ua
er5 -40
0 200 400 600
Cycle Number
FIG. 2
Description
1/1
Ua
er5 FIG. 1 -40
-800
600 Current density=1iAgg0
e400
0 200 400 600
Cycle Number FIG. 2
VANADIUM TETRASULFIDE-NITROGEN-DOPED CARBON TUBE COMPOSITE AND PREPARATION METHOD AND USE THEREOF TECHNICAL FIELD The present invention relates to the preparation technology field of electrode materials for sodium ion batteries, and in particular, to a vanadium tetrasulfide-nitrogen-doped carbon tube composite and a preparation method and use thereof. BACKGROUND As people's demands for sustainable, renewable, and clean energy storage systems are increasing, lithium ion batteries have been widely applied in the energy storage field in recent years due to their advantages of high energy density, long cycle life, environmental protection, etc. However, due to the shortage of lithium resources, the application of lithium batteries in large-scale commercialization is limited. Sodium resources are rich and have properties similar to those of lithium. Therefore, a sodium ion battery is considered to be the most likely potential alternative to a lithium ion battery. Vanadium tetrasulfide has a unique linear chain structure and is connected by weak van der Waals force between chains. An interchain spacing is 0.583 nm, which is much larger than a diameter (0.196 nm) of a sodium ion. A large interchain spacing facilitates intercalation and deintercalation of sodium ions. In addition, due to the high sulfur content of vanadium tetrasulfide, more sodium ions can participate in an electrochemical reaction, so that vanadium tetrasulfide has a larger theoretical specific capacity, and is considered to be a promising anode material for sodium ion batteries. Pang et al. (Q. Pang, Y. Zhao, Y. Yu, X. Bian, X. Wang, Y. Wei, Y. Gao, G. Chen, VS 4 Nanoparticles Anchored on Graphene Sheets as a High-Rate and Stable Electrode Material for Sodium Ion Batteries, ChemSusChem. 11 (2018) 735-742.) prepared a VS 4/GS-2 composite, where a reversible specific capacity of the VS 4/GS-2 composite is 349 mAh/g after 100 cycles when current density is 0.1 A/g. A reversible specific capacity of VS 4 reported by Sun et al. (R. Sun, Q. Wei, Q. Li, W. Luo, Q. An, J. Sheng, D. Wang, W. Chen, L. Mai, Vanadium Sulfide on Reduced Graphene Oxide Layer as a Promising Anode for Sodium Ion Battery, ACS Appl Mater Interfaces. 7 (2015) 20902-8.) is approximately 320 mAh/g after 50 cycles when current density is 0.1 A/g. A reversible specific capacity of self-assembled vanadium tetrasulfide microspheres reported by Li et al. (W. Li, J. Huang, L. Cao, L. Feng, C. Yao, Controlled construction of 3D self-assembled VS 4 nanoarchitectures as high-performance anodes for sodium-ion batteries, Electrochim. Acta, 274 (2018) 334-342.) is 225 mAh/g after 200 cycles when current density is 0.5 A/g. However, due to the irreversible transformation in a desulfurization process, an actual capacity of vanadium tetrasulfide is much smaller than a theoretical capacity thereof. Therefore, the design and preparation of a high-capacity, long-cycle, and stable vanadium tetrasulfide sodium ion anode material is still a problem that researchers urgently need to resolve. SUMMARY An objective of the present invention is to provide a vanadium tetrasulfide-nitrogen-doped carbon tube composite and a preparation method and use thereof. The prepared vanadium tetrasulfide-nitrogen-doped carbon tube composite has high capacity and good cycle stability. To achieve the above objective of the present invention, the present invention provides the following technical solutions: The present invention provides a preparation method of a vanadium tetrasulfide-nitrogen-doped carbon tube composite, including the following steps: mixing pyrrole, an initiator, and a methyl orange aqueous solution, and conducting a polymerization reaction to obtain polypyrrole; calcining the polypyrrole to obtain nitrogen-doped carbon tubes; and mixing the nitrogen-doped carbon tubes, a vanadium source, a sulfur source, and a reaction solvent, and conducting a solvothermal reaction to obtain a vanadium tetrasulfide-nitrogen-doped carbon tube composite. Preferably, during the preparation of the methyl orange aqueous solution, a dosage ratio of methyl orange to water is (0.05-0.5) g:(50-500) mL. Preferably, the initiator is at least one of ammonium persulfate, potassium persulfate, and ferric chloride, and a dosage ratio of the initiator to the methyl orange in the methyl orange aqueous solution is (5-50) mmol:(0.05-0.5) g. Preferably, a dosage ratio of the pyrrole to methyl orange in the methyl orange aqueous solution is (0.2-2) mL:(0.05-0.5) g. Preferably, the polymerization reaction is conducted at room temperature for 18-30 h. Preferably, the calcination is conducted at 600-900°C for 1-5 h. Preferably, the vanadium source is at least one of vanadium acetylacetonate, vanadium pentoxide, ammonium metavanadate, sodium metavanadate, and sodium orthovanadate; the sulfur source is at least one of sulfur powder, thiourea, thioacetamide, and L-cysteine; and a molar ratio of the vanadium source to the sulfur source is 1:(5-9). Preferably, the solvothermal reaction temperature is 120-220°C, and the heat preservation time is 15-25 h. The present invention provides a vanadium tetrasulfide-nitrogen-doped carbon tube composite prepared by using the preparation method in the foregoing technical solution, where vanadium tetrasulfide is coated on the nitrogen-doped carbon tubes. The present invention provides use of the vanadium tetrasulfide-nitrogen-doped carbon tube composite in the foregoing technical solution as an anode material in a sodium ion battery.
The present invention provides a preparation method of a vanadium tetrasulfide-nitrogen-doped carbon tube composite, including the following steps: mixing pyrrole, an initiator, and a methyl orange aqueous solution, and conducting a polymerization reaction to obtain polypyrrole; calcining the polypyrrole to obtain nitrogen-doped carbon tubes; and mixing the nitrogen-doped carbon tubes, a vanadium source, a sulfur source, and a reaction solvent, and conducting a solvothermal reaction to obtain a vanadium tetrasulfide-nitrogen-doped carbon tube composite. In the present invention, methyl orange is used as a soft template to conduct the polymerization reaction to form hollow tubular polypyrrole; after calcination, the nitrogen-doped carbon tubes are obtained; the nitrogen-doped carbon tubes are subjected to the solvothermal reaction process with the sulfur source and the vanadium source, vanadium tetrasulfide is attached to the nitrogen-doped carbon tubes and grows along a certain crystal plane to form short rod-like vanadium tetrasulfide; and the short rod-like vanadium tetrasulfide is uniformly coated on the surface of the nitrogen-doped carbon tubes to form a three-dimensional structure, thereby increasing a surface area of the composite. The increase in the surface area leads to an increase in active sites, to facilitate the wetting of electrolytes and electrons and the diffusion of Na ions in a solid phase, thereby improving the electronic and ionic conductivity of the vanadium tetrasulfide composite. The prepared vanadium tetrasulfide-nitrogen-doped carbon tube composite has uniform particle distribution, a relatively high reversible specific capacity, and good electrochemical cycle performance and rate performance. The preparation method in the present invention is simple and has a short process and low production costs. BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is an SEM image of a vanadium tetrasulfide-nitrogen-doped carbon tube composite prepared in Example 1; and FIG. 2 is a cycle performance diagram of the vanadium tetrasulfide-nitrogen-doped carbon tube composite prepared in Example 1. DETAILED DESCRIPTION The present invention provides a preparation method of a vanadium tetrasulfide-nitrogen-doped carbon tube composite, including the following steps: mixing pyrrole, an initiator, and a methyl orange aqueous solution, and conducting a polymerization reaction to obtain polypyrrole; calcining the polypyrrole to obtain nitrogen-doped carbon tubes; and mixing the nitrogen-doped carbon tubes, a vanadium source, a sulfur source, and a reaction solvent, and conducting a solvothermal reaction to obtain a vanadium tetrasulfide-nitrogen-doped carbon tube composite.
In the present invention, the required preparation raw materials are all commercially available products well known to a person skilled in the art unless otherwise specified. In the present invention, the pyrrole, the initiator, and the methyl orange aqueous solution are mixed, and are subject to the polymerization reaction to obtain the polypyrrole. In the present invention, during the preparation of the methyl orange aqueous solution, a dosage ratio of methyl orange to water is preferably (0.05-0.5) g:(50-500) mL, more preferably (0.1-0.4) g:(100-400) mL, and further preferably (0.2-0.3) g:(200-300) mL. The water is preferably deionized water. In the present invention, there is no special limitation on the preparation process of the methyl orange aqueous solution, provided that the preparation process can be conducted according to an operation well known in the art. Specifically, the methyl orange may be dispersed in the deionized water to form the methyl orange aqueous solution. In the present invention, the methyl orange is used as a dopant. The methyl orange is a water-soluble azo material. Because it has certain surface activity, it can form fibrous micelle with the initiator. In the polymerization process, pyrrole monomers are continuously polymerized by using the micelle as a template, and the template is eventually consumed in the polymerization process, thereby synthesizing hollow-structured polypyrrolenanotubes. In the present invention, the initiator is preferably at least one of ammonium persulfate, potassium persulfate, and ferric chloride. When the initiator is several types of the foregoing initiators, there is no special limitation on a dosage ratio of different types of initiators in the present invention, and any ratio can be used. In the present invention, a dosage ratio of the initiator to the methyl orange in the methyl orange aqueous solution is preferably (5-50) mmol:(0.05-0.5) g, more preferably (10-40) mmol:(0.1-0.4) g, and further preferably (20-30) mmol:(0.2-0.3) g. In the present invention, the initiator is used to gradually initiate the polymerization of the pyrrole monomers in the micelle template. In the present invention, a dosage ratio of the pyrrole to the methyl orange in the methyl orange aqueous solution is preferably (0.2-2) mL:(0.05-0.5) g, more preferably (0.5-1.5) mL:(0.1-0.4) g, and further preferably (0.8-1.2) mL:(0.2-0.3) g. In the present invention, the process of mixing the pyrrole, the initiator, and the methyl orange aqueous solution is preferably adding the pyrrole and the initiator to the methyl orange aqueous solution. In the present invention, the polymerization reaction is conducted at preferably room temperature for preferably 18-30 h, more preferably 20-28 h, and further preferably 23-25 h; and the polymerization reaction is preferably conducted under stirring. In the present invention, there is no special limitation on a rotational speed of the stirring, and a rotational speed well known in the art that can ensure that the reaction proceeds smoothly can be used. In the polymerization reaction process, the fibrous micelle formed by the methyl orange and the initiator acts as a template, and an electrically neutral pyrrole monomer molecule is oxidized under the action of the initiator to lose an electron and become a cation radical; and then two cation radicals collide in the system to form dicationic dipyrrole containing two cation radicals. The dicationic dipyrrole produced at this time is disproportionated in the system to produce electrically neutral dipyrrole; the electrically neutral dipyrrole will be combined with the cation radicals in the system to form cation radicals of tripyrrole. The cation radicals are disproportionated to produce polypyrrole in a form of a tripolymer. This process is repeated to eventually form polypyrrole of a hollow tubular structure. In the present invention, after the polymerization reaction is completed, the obtained polymerization product is successively centrifugated and washed, and dried at 45-65°C for 10-15 h to obtain polypyrrole. In the present invention, the polypyrrole is of a hollow tubular structure. In the present invention, after the polypyrrole is obtained, the polypyrrole is calcined to obtain the nitrogen-doped carbon tubes. In the present invention, the calcination is conducted at preferably 600-900°C, more preferably 650-850°C, and further preferably 700-800°C; and the calcination time is preferably 1-5 h, more preferably 2-4 h, and further preferably 2.5-3.5 h. In the present invention, the calcination is preferably conducted under the protection of an inert gas atmosphere. In the present invention, there is no special limitation on inert gas, and inert gas well known in the art can be used. In the present invention, impurities and moisture in the polypyrrole product are removed by calcination, so that the product has higher crystallinity, and the polypyrrole is carbonized, and all the polypyrrole is converted into nitrogen-doped carbon tubes. In the present invention, after the nitrogen-doped carbon tubes are obtained, the nitrogen-doped carbon tubes, the vanadium source, the sulfur source, and the reaction solvent are mixed to conduct the solvothermal reaction to obtain the vanadium tetrasulfide-nitrogen-doped carbon tube composite. In the present invention, the vanadium source is preferably at least one of vanadium acetylacetonate, vanadium pentoxide, ammonium metavanadate, sodium metavanadate, and sodium orthovanadate; the sulfur source is preferably at least one of sulfur powder, thiourea, thioacetamide, and L-cysteine; and when the vanadium source or the sulfur source is several of the foregoing substances, there is no special limitation on a dosage ratio of different types of vanadium sources or sulfur sources in the present invention, and any ratio can be used. In the present invention, the reaction solvent is preferably a methanol solution, and the methanol solution is preferably an 99.5 wt.% analytically pure methanol solution. In the present invention, a molar ratio of the vanadium source to the sulfur source is preferably 1:(5-9), and more preferably 1:(6-8); a dosage ratio of the reaction solvent to the nitrogen-doped carbon tubes is preferably (25-35) mL:(10-50) mg; and a molar ratio of the reaction solvent to the vanadium source is preferably 1:1. In the present invention, the process of mixing the nitrogen-doped carbon tubes, the vanadium source, the sulfur source, and the reaction solvent is preferably first dissolving the nitrogen-doped carbon tubes in the reaction solvent, conducting stirring for 20-60 min, and then adding the vanadium source and the sulfur source to the solution and conducting stirring for 1-3 h. In the present invention, there is no special limitation on the stirring process, provided that a uniform solution can be obtained. In the present invention, the solvothermal reaction is preferably conducted in a stainless steel reactor; the solvothermal reaction temperature is preferably 120-220°C, more preferably 150-200°C, and further preferably 180-200°C; and the heat preservation time is preferably 15-25 h, and more preferably 18-22 h. In the present invention, after the solvothermal reaction is completed, an obtained product is preferably centrifugated and washed, and dried at 45-65°C for 10-15 h to obtain the vanadium tetrasulfide-nitrogen-doped carbon tube composite. In the solvothermal reaction process, vanadium tetrasulfide is produced from the vanadium source and the sulfur source, and the vanadium tetrasulfide is coated on the nitrogen-doped carbon tubes according to a certain crystal plane direction to form the vanadium tetrasulfide-nitrogen-doped carbon tube composite. The present invention provides a vanadium tetrasulfide-nitrogen-doped carbon tube composite prepared by using the preparation method in the foregoing technical solution, where vanadium tetrasulfide is coated on the nitrogen-doped carbon tubes. In the present invention, the methyl orange is used as a soft template to conduct the polymerization reaction under stirring to form circular tubular polypyrrole; after calcination, the nitrogen-doped carbon tubes are obtained; the nitrogen-doped carbon tubes are subjected to the solvothermal reaction process with the sulfur source and the vanadium source, vanadium tetrasulfide is attached to the nitrogen-doped carbon tubes. In addition, there are a large number of active sites on the nitrogen-doped carbon tubes. The vanadium tetrasulfide is attached to the tube and grows along a certain crystal plane to form short rod-like vanadium tetrasulfide; and the short rod-like vanadium tetrasulfide is uniformly coated on the surface of the nitrogen-doped carbon tubes to form a three-dimensional structure, thereby increasing a surface area and active sites of the composite, and further facilitating the wetting of electrolytes and electrons. Moreover, based on the interaction between lattices, the uniformly coated short rod-like nanostructure can help improve charge/electron transfer between short nanorods. In addition, the nitrogen-doped carbon tubes have good conductivity and stability, and electrons and ions can be quickly transferred in the tube, thereby enhancing the electrochemical performance of the composite. The present invention provides use of the vanadium tetrasulfide-nitrogen-doped carbon tube composite in the foregoing technical solution as an anode material in a sodium ion battery. In the present invention, there is no special limitation on a method for the use, provided that the vanadium tetrasulfide-nitrogen-doped carbon tube composite is used in a sodium-ion battery as an anode material according to a process well known in the art. The technical solutions in the present invention will be clearly and completely described below with reference to the examples of the present invention. Apparently, the described examples are merely some rather than all of the examples of the present invention. All other examples obtained by a person of ordinary skill in the art based on the examples of the present invention without creative efforts shall fall within the protection scope of the present invention. Example 1 0.1 g of methyl orange was dissolved in 100 mL of deionized water, 0.4 mL of pyrrole monomers and 10 mmol of ferric chloride were added and stirred for 20 h for a polymerization reaction, and an obtained polymerization product was centrifugated and washed for multiple times and dried at 50°C for 14 h to obtain polypyrrole; the polypyrrole was calcined in an argon gas atmosphere at 700°C for 3 h to obtain nitrogen-doped carbon tubes; 30 mg of the nitrogen-doped carbon tubes were solved in 28 mL of a methanol solution (a 99.5 wt.% analytically pure methanol solution) and stirred for 40 min, 0.16 g of ammonium metavanadate and 0.54 g of thioacetamide were added and stirred for 2 h, and an obtained mixture was poured into a 40 mL reactor and held at 180°C for 22 h for a solvothermal reaction; and an obtained product was centrifugated and washed for multiple times and dried at 50°C for 14 h to obtain a vanadium tetrasulfide-nitrogen-doped carbon tube composite. Performance Test: (1) The vanadium tetrasulfide-nitrogen-doped carbon tube composite prepared in Example 1 was characterized by SEM. A result is shown in FIG. 1. It can be seen from FIG. 1 that vanadium tetrasulfide is attached to the nitrogen-doped carbon tubes, and grows along a certain crystal plane to form short rod-like vanadium tetrasulfide. (2) A BET test was conducted on the nitrogen-doped carbon tubes and the vanadium tetrasulfide-nitrogen-doped carbon tube composite prepared in Example 1. Results show that a specific surface area of the prepared nitrogen-doped carbon tubes is 15.4 m2/g; and a specific surface area of the prepared vanadium tetrasulfide-nitrogen-doped carbon tube composite is 30.2 m2 m2/g. (3) The vanadium tetrasulfide-nitrogen-doped carbon tube composite prepared in this example was used as an anode material for a lithium-sulfur battery, and the lithium-sulfur battery was assembled, and then a cycle performance test was conducted in a Neware test system. A charge and discharge voltage range is 0.3-3.0 V, and the result is shown in FIG. 2. It can be seen from FIG.
2 that, a reversible specific capacity of the vanadium tetrasulfide-nitrogen-doped carbon tube composite prepared in this example is approximately 440 mAh/g after 600 cycles when current density is 1 A/g. Example 2 0.15 g of methyl orange was dissolved in 150 mL of deionized water, 0.6 mL of pyrrole monomers and 15 mmol of ferric chloride were added and stirred for 24 h for a polymerization reaction, and an obtained polymerization product was centrifugated and washed for multiple times and dried at 55°C for 12 h to obtain polypyrrole; the polypyrrole was calcined in an argon gas atmosphere at 600°C for 4 h to obtain nitrogen-doped carbon tubes; 10 mg of the nitrogen-doped carbon tubes were solved in 30 mL of a methanol solution (a 99.5 wt.% analytically pure methanol solution) and stirred for 20 min, 0.17 g of vanadium pentoxide and 0.28 g of thiourea were added and stirred for 1 h, and an obtained mixture was poured into a 40 mL reactor and held at 190 °C for 20 h for a solvothermal reaction; and an obtained product was centrifugated and washed for multiple times and dried at 55°C for 12 h to obtain a vanadium tetrasulfide-nitrogen-doped carbon tube composite. Performance Test: (1) A BET test was conducted on the nitrogen-doped carbon tubes and the vanadium tetrasulfide-nitrogen-doped carbon tube composite prepared in Example 2. Results show that a specific surface area of the prepared nitrogen-doped carbon tubes is 14.8 m2/g; and a specific surface area of the prepared vanadium tetrasulfide-nitrogen-doped carbon tube composite is 28.7 m2 m2/g. (2) According to the method in Example 1, a cycle performance test was conducted on the vanadium tetrasulfide-nitrogen-doped carbon tube composite prepared in this example. A result shows that a reversible specific capacity of the vanadium tetrasulfide-nitrogen-doped carbon tube composite prepared in this example is approximately 400 mAh/g after 400 cycles when current density is 1 A/g. Example 3 0.5 g of methyl orange was dissolved in 500 mL of deionized water, 2 mL of pyrrole monomers and 50 mmol of ferric chloride were added and stirred for 30 h for a polymerization reaction, and an obtained polymerization product was centrifugated and washed for multiple times and dried at 65°C for 10 h to obtain polypyrrole; the polypyrrole was calcined in an argon gas atmosphere at 800°C for 2.5 h to obtain nitrogen-doped carbon tubes; 20 mg of the nitrogen-doped carbon tubes were solved in 32 mL of a methanol solution (a 99.5 wt.% analytically pure methanol solution) and stirred for 30 min, 0.13 g of sodium metavanadate and 0.65 g of thioacetamide were added and stirred for 1.5 h, and an obtained mixture was poured into a 40 mL reactor and held at
200°C for 18 h for a solvothermal reaction; and an obtained product was centrifugated and washed for multiple times and dried at 65°C for 10 h to obtain a vanadium tetrasulfide-nitrogen-doped carbon tube composite. Performance Test: (1) A BET test was conducted on the nitrogen-doped carbon tubes and the vanadium tetrasulfide-nitrogen-doped carbon tube composite prepared in Example 3. Results show that a specific surface area of the prepared nitrogen-doped carbon tubes is 16.4 m2/g; and a specific surface area of the prepared vanadium tetrasulfide-nitrogen-doped carbon tube composite is 31.6 m2 m2/g. (2) According to the method in Example 1, a cycle performance test was conducted on the vanadium tetrasulfide-nitrogen-doped carbon tube composite prepared in this example. A result shows that a reversible specific capacity of the vanadium tetrasulfide-nitrogen-doped carbon tube composite prepared in this example is approximately 480 mAh/g after 200 cycles when current density is 1 A/g. The above descriptions are merely preferred implementations of the present invention. It should be noted that a person of ordinary skill in the art may further make several improvements and modifications without departing from the principle of the present invention, but such improvements and modifications should be deemed as falling within the protection scope of the present invention.
Claims (5)
- What is claimed is: 1. A preparation method of a vanadium tetrasulfide-nitrogen-doped carbon tube composite, comprising the following steps: mixing pyrrole, an initiator, and a methyl orange aqueous solution, and conducting a polymerization reaction to obtain polypyrrole; calcining the polypyrrole to obtain nitrogen-doped carbon tubes; and mixing the nitrogen-doped carbon tubes, a vanadium source, a sulfur source, and a reaction solvent, and conducting a solvothermal reaction to obtain a vanadium tetrasulfide-nitrogen-doped carbon tube composite.
- 2. The preparation method according to claim 1, wherein during the preparation of the methyl orange aqueous solution, a dosage ratio of methyl orange to water is (0.05-0.5) g:(50-500) mL.
- 3. The preparation method according to claim 1 or 2, wherein the initiator is at least one of ammonium persulfate, potassium persulfate, and ferric chloride, and a dosage ratio of the initiator to the methyl orange in the methyl orange aqueous solution is (5-50) mmol:(0.05- 0.5) g.
- 4. The preparation method according to claim 1, wherein a dosage ratio of the pyrrole to methyl orange in the methyl orange aqueous solution is (0.2-2) mL:(0.05-0.5) g; wherein the polymerization reaction is conducted at room temperature for 18-30 h; wherein the calcination is conducted at 600-900°C for 1-5 h; wherein the vanadium source is at least one of vanadium acetylacetonate, vanadium pentoxide, ammonium metavanadate, sodium metavanadate, and sodium orthovanadate; the sulfur source is at least one of sulfur powder, thiourea, thioacetamide, and L-cysteine; and a molar ratio of the vanadium source to the sulfur source is 1:(5-9); wherein the solvothermal reaction temperature is 120-220°C, and the heat preservation time is 15-25 h.
- 5. A vanadium tetrasulfide-nitrogen-doped carbon tube composite prepared by using the preparation method according to any one of claims 1 to 4, wherein vanadium tetrasulfide is coated on the nitrogen-doped carbon tubes.
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