Preparation method and application of vanadium pentoxide nanobelt with adjustable interlayer distance
The method for preparing vanadium pentoxide nanoribbons solves the problem of producing high-performance vanadium pentoxide nanoribbons in the existing technology, realizes simple and low-cost industrial production, and improves battery performance.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- HOHAI UNIV
- Filing Date
- 2023-11-07
- Publication Date
- 2026-07-10
AI Technical Summary
Existing technologies make it difficult to mass-produce high-performance vanadium pentoxide nanoribbons using simple methods, and the hydrothermal method has safety issues.
Vanadium pentoxide nanoribbons were prepared by mixing a metal ion solution with vanadium oxide, adding an electret, reacting with ultrasound, filtering, drying, and grinding. The interlayer spacing was controlled by adjusting the metal ion concentration and ultrasound parameters.
Vanadium pentoxide nanoribbons were developed with a simple process, low cost, and suitability for industrial production, which improved battery performance, especially the specific capacitance and cycle life of zinc-ion batteries.
Smart Images
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Abstract
Description
Technical Field
[0001] This invention relates to a method for preparing vanadium pentoxide nanoribbons with adjustable interlayer spacing, belonging to the field of nanomaterials. Background Technology
[0002] Environmental pollution, climate change, and resource scarcity have severely hampered technological progress and social development. Finding new, low-pollution, high-performance energy sources has become an urgent issue for humanity. Against this backdrop, wind power and photovoltaic power generation have developed rapidly. However, wind and photovoltaic power generation are characterized by instability and intermittency, necessitating the vigorous development of supporting energy storage systems.
[0003] Energy storage, a crucial component of the power system, primarily refers to the storage of energy, specifically the storage of electrical energy in various forms, which can be released when needed, achieving energy transfer over time. Among these, pumped hydro storage and electrochemical energy storage are the most widely commercially available technologies. Electrochemical energy storage, in particular, refers to various secondary battery energy storage systems, such as lithium-ion batteries, sodium-ion batteries, and aqueous zinc-ion batteries. These systems offer large capacity, fast response, and the greatest development potential. With the rapid decline in costs and the gradual maturation of commercial applications in recent years, the advantages of electrochemical energy storage have become increasingly apparent, gradually becoming the mainstream for new energy storage installations, and there is still significant room for further cost reductions in the future.
[0004] Whether it's lithium-ion, sodium-ion, or zinc-ion battery energy storage systems, their performance, including conversion efficiency, energy / power density, service life, safety, and stability, is all limited by key electrode materials. Therefore, innovative research on electrode materials is crucial.
[0005] Vanadium pentoxide (VPO) cathode is an important battery material with advantages such as high energy density, long cycle life, and high safety, making it widely used in various batteries including lithium-ion and sodium-ion batteries. In lithium-ion batteries, VPO reacts with lithium ions to form LiV₂O₅, releasing electrons and ions to generate current. In sodium-ion batteries, VPO reacts with sodium ions to form NaV₂O₅, also generating current. VPO has a high energy density, meaning it can store more energy, extending battery life. It also boasts a long cycle life, capable of withstanding thousands of charge-discharge cycles, further extending battery life. Furthermore, VPO is highly safe, less prone to overheating or combustion, making batteries safer and more reliable.
[0006] The preparation of layered vanadium-based materials has undoubtedly become a research hotspot in the cathode materials of secondary batteries. Over the past few decades, researchers have explored the application of layered vanadium-based electrode materials with different hydrated metal ion intercalation types in aqueous zinc-ion battery cathode materials. The choice of intercalating metal ions has a significant impact on their electrochemical zinc storage performance. Ionic or molecular pre-intercalation strategies can effectively solve problems such as insufficient lattice space and low electronic conductivity in cathode materials, thereby further improving battery performance. Currently published research structures are basically synthesized using hydrothermal methods to synthesize hydrated ion-intercalated V₂O₅ nanostructures. However, hydrothermal methods require sophisticated equipment, are technically challenging, and have poor safety performance, making large-scale industrial production impossible. Summary of the Invention
[0007] Purpose of the invention: The purpose of this invention is to provide a method for preparing vanadium pentoxide nanoribbons with adjustable interlayer spacing.
[0008] Technical solution: Prepare a metal salt solution with a metal ion concentration of 0.1M to 5M; add vanadium oxide powder, with a molar ratio of metal ion to vanadium of 10:1 to 500:1; mix thoroughly to form a suspension, add electret, react under ultrasonic conditions, and after the reaction is completed, filter, dry, and grind to obtain vanadium pentoxide nanoribbons.
[0009] In this application, a metal salt is added during the preparation process. The metal ions in this salt are intercalated into the vanadium oxide layer, which plays a role in regulating the interlayer spacing of vanadium pentoxide. The resulting co-intercalated structure of water molecules and metal ions shows that as the concentration of metal ions increases, the number of water molecules intercalated into the interlayer decreases, while the number of metal ions increases, leading to a continuous reduction in the interlayer spacing.
[0010] Furthermore, the metal ion is Li + Na + K + Mg 2+ Ca 2+ Cu 2+ Fe 3+ Co 3+ Ni 3+ Mn 3+ Al 3+ Bi 2+ Cd 2+ Cr 2 / 3+ Ag + Sn 4+ and Zn 2+ One or more of them.
[0011] Furthermore, the metal salt includes one or more of the following: metal chloride / hypochlorite, metal sulfate, metal nitrate, metal carbonate, or metal acetate.
[0012] Furthermore, the vanadium oxide is one or more of V2O5, V2O4, V2O3, VO, or vanadates.
[0013] Furthermore, the electret includes organic material electrets and non-polar material electrets.
[0014] Furthermore, the organic electret material includes one or more of the following: polymethyl methacrylate, polycarbonate, polypropylene, polytetrafluoroethylene, tetrafluoroethylene-perfluoropropylene copolymer, paraffin wax, hard rubber, hydrocarbons, solid acids, or general biopolymers.
[0015] Furthermore, the general biological macromolecules include one or more of polypeptides, polynucleotides, or polysaccharides.
[0016] Furthermore, the electrodeless electret material includes one or more of silicon dioxide, barium titanate, lead zirconate titanate, zinc oxide, tantalum oxide, aluminum oxide, titanium oxide, and silicon nitride.
[0017] Furthermore, the ultrasonic conditions are: ultrasonic frequency of 20KHz to 200KHz; ultrasonic temperature of 40 to 100 degrees Celsius.
[0018] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages: The preparation method of vanadium pentoxide nanoribbons provided by the present invention is simple, low-cost, and suitable for industrial production. This preparation method can control the morphology, crystallinity, and interlayer spacing of vanadium pentoxide nanoribbons by controlling parameters such as the concentration of the intercalating metal ion solution, ultrasonic temperature, and ultrasonic time. Attached Figure Description
[0019] Figure 1 V2O5 nanoribbons with co-intercalation of water molecules and zinc ions and their electrochemical properties.
[0020] Figure 2 Electrochemical properties of V2O5 nanoribbons with co-intercalation of water molecules and sodium ions.
[0021] Figure 3 Electrochemical properties of V2O5 nanoribbons with co-intercalation of water molecules and magnesium ions.
[0022] Figure 4 Electrochemical performance of V2O5 nanoribbons with co-intercalation of water molecules and lithium ions. Detailed Implementation
[0023] The technical solution of the present invention will be further described below with reference to the accompanying drawings.
[0024] Example 1
[0025] Prepare 300 ml of a zinc chloride aqueous solution with a zinc ion concentration of 0.5 mol / L using anhydrous zinc chloride and deionized water. Add 1 g of vanadium pentoxide and shake thoroughly to ensure that the vanadium pentoxide is fully suspended in the aqueous solution. Place a 5*20 cm [structure / component] into the prepared solution. 2 The solution is a polytetrafluoroethylene (PTFE) film; then the solution is placed in an ultrasonic instrument, the water temperature in the ultrasonic instrument is kept at 60℃, and it is ultrasonically vibrated at a frequency of 80000Hz for 5 hours. The solution is a brick-red gel-like liquid; the brick-red gel-like liquid after ultrasonication is filtered to filter out the brick-red sample, the sample is dried, and after grinding, vanadium pentoxide cathode material can be obtained.
[0026] The results are as follows Figure 1 As shown, Figure 1 Photo 'a' shows the appearance of the product, which appears as a brick-red colloidal substance. Figure 1 b is the XRD spectrum of the product, with its first diffraction peak located at 7.22, corresponding to a lattice spacing of 12.23 Å. Figure 1 c is the SEM image of the product, which shows that the product has a nanoribbon-like structure. Figure 1 d and 1e represent the electrochemical performance of the aqueous zinc-ion battery assembled from them. The rate performance of the battery ( Figure 1 d) indicates that the material operates at a current density of 0.1 Ag. -1 0.2Ag -1 0.5Ag -1 0.8Ag -1 1.0Ag -1 2.0Ag -1 The following shows 232mAh g -1 162mAh g -1 123mAh g -1 105mAh g -1 100mAh g -1 52mAh g -1 Specific capacitance. At 1Ag -1 In the following 1000 long-cycle tests ( Figure 1 e) Performance degrades to 90% of reversible capacity.
[0027] Example 2
[0028] Prepare 300ml sodium chloride aqueous solutions with sodium ion concentrations of 0.2mol / L, 1.0mol / L, and 5.0mol / L using sodium chloride and deionized water, respectively. Add 1g of vanadium pentoxide to each solution and shake thoroughly to ensure that the vanadium pentoxide is fully suspended in the aqueous solution. Place a 5*5cm [substrate name missing] in the prepared solution. 2The solution was then placed in an ultrasonic instrument, and the water temperature in the ultrasonic instrument was kept at 70°C. The solution was ultrasonically vibrated at a frequency of 80,000 Hz for 5 hours, and the solution was a brick-red gel-like liquid. The brick-red gel-like liquid after ultrasonication was filtered to obtain a brick-red sample. The sample was dried and ground to obtain vanadium pentoxide cathode material.
[0029] The results are as follows Figure 2 As shown, Figure 2 a is the XRD spectrum of the product. The position of its first diffraction peak shifts significantly with the increase of the concentration of metal ions in the solution. This indicates that the interlayer spacing of V2O5 nanoribbons can be controlled by the concentration of metal ions in the solution. Figure 2 b shows the electrochemical performance of the aqueous zinc-ion battery assembled from it. The synthesized V₂O₅ nanoribbons exhibited the best specific capacity at a NaCl concentration of 2 M / L, with a current density of 0.1 Ag. -1 0.2Ag -1 0.3Ag -1 0.5Ag -1 0.8Ag -1 1.0Ag -1 The following shows 252mAh g -1 173mAh g -1 161mAh g -1 149mAh g -1 145mAh g -1 141mAh g -1 Specific capacitance.
[0030] Example 3
[0031] Prepare 300 ml of magnesium chloride aqueous solution with a magnesium ion concentration of 0.1 mol / L using anhydrous magnesium chloride and deionized water. Add 1.5 g of vanadium pentoxide and shake thoroughly to ensure that the vanadium pentoxide is fully suspended in the aqueous solution. Place a 5*5 cm [material / container] into the prepared solution. 2 The polycarbonate film was then prepared; the solution was placed in an ultrasonic instrument, and the water temperature in the ultrasonic instrument was kept at 80°C. The solution was ultrasonically vibrated at a frequency of 80,000 Hz for 10 hours, and the solution was a brick-red gel-like liquid. The brick-red gel-like liquid after ultrasonication was filtered to obtain a brick-red sample. The sample was dried and ground to obtain vanadium pentoxide cathode material.
[0032] Figure 3 a represents the XRD pattern of the product, with its first diffraction peak located at 6.91 Å, corresponding to a lattice spacing of 12.77 Å. Figure 3 b represents the electrochemical performance of the aqueous zinc-ion battery assembled from it. It operates at a current density of 0.1 Ag. -1 0.3Ag-1 0.5Ag -1 0.7Ag -1 0.9Ag -1 1.0Ag -1 The following shows 363mAh g -1 293mAh g -1 268mAh g -1 245mAh g -1 237mAh g -1 229mAh g -1 Specific capacitance.
[0033] Example 4
[0034] Prepare 300 ml of a lithium chloride aqueous solution with a lithium ion concentration of 0.1 mol / L using anhydrous lithium chloride and deionized water. Add 1.5 g of vanadium pentoxide and shake thoroughly to ensure that the vanadium pentoxide is fully suspended in the aqueous solution. Place a 5*5 cm [material / container] into the prepared solution. 2 The polycarbonate film was then prepared; the solution was placed in an ultrasonic instrument, the water temperature in the ultrasonic instrument was kept at 70°C, and it was ultrasonically vibrated at a frequency of 40000Hz for 5 hours, and the solution was a brick-red gel-like liquid; the brick-red gel-like liquid after ultrasonication was filtered to obtain a brick-red sample, the sample was dried, and after grinding, vanadium pentoxide cathode material was obtained.
[0035] Figure 4 a represents the XRD pattern of the product, with its first diffraction peak at 6.95 Å, corresponding to a lattice spacing of 12.71 Å. Figure 3 b represents the electrochemical performance of the aqueous zinc-ion battery assembled from it. It operates at a current density of 0.1 Ag. -1 0.2Ag -1 0.5Ag -1 0.8Ag -1 1.0Ag -1 2.0Ag -1 The following shows 349mAh g -1 288mAh g -1 231mAh g -1 202mAh g -1 181mAh g -1 136mAh g -1 Specific capacitance.
Claims
1. A method for preparing vanadium pentoxide nanoribbons with adjustable interlayer spacing, characterized in that, Includes the following steps: Prepare a metal salt solution with a metal ion concentration of 0.1M to 5M; add vanadium pentoxide powder, with a molar ratio of metal ions to vanadium of 10:1 to 500:1; mix thoroughly to form a suspension, add electret, react under ultrasonic conditions, and after the reaction is completed, filter, dry, and grind to obtain vanadium pentoxide nanoribbons. The electret includes organic material electrets and non-polar material electrets; The organic electret material includes one or more of the following: polymethyl methacrylate, polycarbonate, polypropylene, polytetrafluoroethylene, tetrafluoroethylene-perfluoropropylene copolymer, paraffin wax, hard rubber, solid acid, or general biopolymer. The electrodeless electret material includes one or more of silicon dioxide, barium titanate, lead zirconate titanate, zinc oxide, tantalum oxide, aluminum oxide, titanium oxide, and silicon nitride.
2. The method for preparing vanadium pentoxide nanoribbons with adjustable interlayer spacing according to claim 1, characterized in that, The metal ion is Li + Na + K + Mg 2+ Ca 2+ Cu 2+ Fe 3+ Co 3+ Ni 3+ Mn 3+ Al 3+ Bi 2+ Cd 2+ Cr 3+ Ag + Sn 4+ or Zn 2+ One or more of them.
3. The method for preparing vanadium pentoxide nanoribbons with adjustable interlayer spacing according to claim 1, characterized in that, The metal salt includes one or more of the following: metal chloride / hypochlorite, metal sulfate, metal nitrate, metal carbonate, or metal acetate.
4. The method for preparing vanadium pentoxide nanoribbons with adjustable interlayer spacing according to claim 1, characterized in that, The general biological macromolecules include one or more of polypeptides, polynucleotides, or polysaccharides.
5. The method for preparing vanadium pentoxide nanoribbons with adjustable interlayer spacing according to claim 1, characterized in that, The ultrasonic conditions are: ultrasonic frequency 20KHz~200KHz; ultrasonic temperature 40~100 degrees Celsius.