Polyaniline and metal ion co-intercalated vanadium pentoxide nanomaterial, and preparation method and application thereof
By preparing polyaniline and metal ion co-intercalated vanadium pentoxide nanomaterials, the conductivity and structural stability issues of vanadium pentoxide materials in zinc-ion batteries were solved, achieving high specific capacity and good rate performance, making it suitable as a cathode material for zinc-ion batteries.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- BEIFANG UNIV OF NATITIES
- Filing Date
- 2025-11-27
- Publication Date
- 2026-06-05
AI Technical Summary
Existing vanadium pentoxide materials in zinc-ion batteries suffer from poor conductivity, insufficient structural stability, and limited active sites, which affect their rate performance and specific capacity.
A method for preparing vanadium pentoxide nanomaterials by co-intercalation of polyaniline and metal ions was adopted. The petal-shaped nanoribbon structure was formed through solvothermal and heat treatment processes. Combined with secondary hydrothermal intercalation of polyaniline, the conductivity and structural stability of the material were enhanced.
It significantly improves the electrochemical performance of zinc-ion batteries, especially maintaining good specific capacity and cycle stability at high current densities, making it suitable for mass production.
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Figure CN122158502A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of nanomaterials technology, specifically to a polyaniline and metal ion co-intercalated vanadium pentoxide nanomaterial, its preparation method, and its application. Background Technology
[0002] Vanadium pentoxide (V₂O₅) is considered an ideal cathode material for aqueous zinc-ion batteries due to its layered structure and high theoretical specific capacity (589 mAh / g). However, its practical application faces the following key bottlenecks: Poor conductivity: low intrinsic conductivity (<10) -3 The low electron transport efficiency (S / cm) limits the rate performance of the battery.
[0003] Insufficient structural stability: The interlayer spacing is prone to collapse during repeated zinc ion insertion and extraction, leading to rapid capacity decay (e.g., capacity retention rate <60% after 100 cycles).
[0004] Limited active sites: Traditional metal cations (such as Li) + K + While intercalation can improve conductivity, it occupies the active sites of zinc ion reactions, resulting in a significant decrease in specific capacity (reduced by 30%-50%).
[0005] Existing technologies include the preparation of V₂O₅ nanomaterials via polyaniline intercalation to address the aforementioned defects, achieving certain results. For example, CN2020107852559 discloses the in-situ polymerization of polyaniline intercalated with vanadium pentoxide as an electrode material, achieving results at 1 A·g -1 and 5A·g -1 The initial discharge specific capacity at the current density was 330–390 mAh·g. -1 and 120~180mAh·g -1 For example, CN2022115331393 reported that a polyaniline-intercalated vanadium pentoxide composite material, when applied to an aqueous zinc-ion battery at 8.0 A / g and room temperature, maintained a high reversible capacity of 268 mAh / g after 2000 cycles. Furthermore, the specific capacities at current densities of 0.1 A / g, 0.2 A / g, 0.5 A / g, 1.0 A / g, and 2.0 A / g were 490.1 mAh / g, 474.2 mAh / g, 464.1 mAh / g, 448.6 mAh / g, and 422.3 mAh / g, respectively. This demonstrates that polyaniline-intercalated V₂O₅ nanomaterials play a significant role as electrode materials in zinc-ion batteries in improving conductivity and ensuring the stability of battery structure and specific capacity.
[0006] Therefore, this invention further explores the development of polyaniline and metal ion co-intercalated vanadium pentoxide nanomaterials, in order to further broaden the range of electrode materials with high conductivity, high specific capacity, and high rate performance. Summary of the Invention
[0007] The purpose of this invention is to further explore the preparation of polyaniline and metal ion co-intercalated vanadium pentoxide nanomaterials, in order to further improve the conductivity, specific capacity and rate performance of this material in zinc-ion batteries. Therefore, this invention provides a polyaniline and metal ion co-intercalated vanadium pentoxide nanomaterial, its preparation method and application.
[0008] To achieve this technical objective, the technical solution adopted by this invention is as follows: In a first aspect, the present invention provides a polyaniline and metal ion co-intercalated vanadium pentoxide nanomaterial, the nanomaterial comprising nano-vanadium pentoxide, wherein polyaniline and metal ions are co-intercalated in the nano-vanadium pentoxide, and the nano-vanadium pentoxide has a petal-shaped nanoribbon structure; and the ratio of the nano-vanadium pentoxide, the metal ions, and the aniline monomer forming the polyaniline is 1~2 mmol: 0.04~0.4 mmol: 30~150 μL; the metal ions are at least one of divalent manganese ions, sodium ions, and potassium ions.
[0009] Preferably, the ratio of the nano-vanadium pentoxide, the metal ions, and the aniline monomer that forms the polyaniline is 1.5~1.8 mmol: 0.1~0.3 mmol: 30~100 μL.
[0010] Preferably, the nano-vanadium pentoxide has a length of 400-500 nm and a width of 50-100 nm.
[0011] In a second aspect, the present invention provides a method for preparing the polyaniline and metal ion co-intercalated vanadium pentoxide nanomaterials described in the first aspect, comprising the following steps: Step 1: Mix vanadium pentoxide with deionized water, and then add template agent and metal ion-providing components in sequence to obtain a suspension. Step 2: The suspension is subjected to a solvothermal reaction in a closed environment to obtain vanadium pentoxide nanoribbons; Step 3: Heat-treat vanadium pentoxide nanoribbons in air atmosphere to obtain vanadium pentoxide nanorods; Step 4: Prepare an acidic mixture of vanadium pentoxide nanorods and add aniline monomer to the acidic mixture. Through chemical oxidation reaction, polyaniline and metal ion co-intercalated vanadium pentoxide nanomaterials are obtained.
[0012] Preferably, in step 1, the ratio of vanadium pentoxide to deionized water is 1g:30~100mL; and / or, the mixing time of vanadium pentoxide and deionized water is 2~6h.
[0013] Preferably, in step 1, the mixing time for adding the template agent is 4-8 hours; more preferably, the molar ratio of vanadium pentoxide to the template agent is 5.5:0.65-1.8; even more preferably, the template agent is ethylenediamine, propylenediamine, or dodecylamine, more preferably ethylenediamine; and / or, the mixing time for adding the component providing metal ions is 1-2 hours; even more preferably, the component providing metal ions is at least one of water-soluble divalent manganese salt, water-soluble sodium salt, or water-soluble potassium salt.
[0014] Preferably, in step 2, the control conditions for the solvothermal reaction include: reaction temperature of 160~200℃ and reaction time of 18~30h.
[0015] Preferably, in step 3, the heat treatment control conditions include: a reaction temperature of 350~400℃ and a reaction time of 30~90min; more preferably, the rate of heating to the reaction temperature is 2~10℃ / min.
[0016] Preferably, in step 4, the concentration of vanadium pentoxide nanorods in the acidic mixture is 0.3g:30~50ml, and the pH of the acidic mixture is 2~5. More preferably, the acidic medium in the acidic mixture is one of hydrochloric acid, sulfuric acid, and nitric acid; and / or, the controlled conditions for the chemical oxidation reaction include: reaction temperature 110~130℃, and reaction time 18~30h.
[0017] Thirdly, the present invention provides the application of the polyaniline and metal ion co-intercalated vanadium pentoxide nanomaterials described in the first aspect in the preparation of battery cathode materials.
[0018] Fourthly, the present invention provides an aqueous zinc-ion battery, comprising: a cathode material made of polyaniline and vanadium pentoxide nanomaterials co-intercalated with metal ions as described in the first aspect.
[0019] Compared with the prior art, the present invention has the following technical effects: 1) This invention uses vanadium pentoxide as a raw material. In the presence of a template agent and specific metal ions, vanadium pentoxide nanorods are obtained through a combination of solvothermal and heat treatment processes, providing a stable substrate for subsequent intercalation. Then, through secondary hydrothermal intercalation with polyaniline (PANI), the vanadium pentoxide (V₂O₅) nanorods are reconstructed into hierarchical petal-shaped nanoribbons with a high specific surface area. This hierarchical porous structure can significantly increase the contact area between the electrode material and the electrolyte, shortening the contact time between ions (such as Li₂O₅). + Zn 2+ This improves diffusion pathways and enhances reaction kinetics. Furthermore, the petal-like morphology provides more active sites, thus enhancing surface redox reactivity.
[0020] 2) The polyaniline and metal ion co-intercalated vanadium pentoxide nanomaterials obtained in this invention, wherein the metal ions are, for example, Mn 2+ As a 'structural pillar,' PANI stabilizes the interlayer structure and provides additional redox activity to enhance capacity. Its conjugated framework enhances electronic conductivity, while its amino / imine functional groups stabilize the interlayer structure and suppress vanadium dissolution through π-π interactions. This strategy aims to obtain MnVO-PANI composites with large interlayer spacing, providing more ion diffusion channels and active sites, enhancing ion / electron transfer kinetics, and suppressing cathode dissolution, thereby achieving excellent electrochemical performance. The mechanisms for sodium and potassium ions are the same.
[0021] 3) Experimental results confirm that the polyaniline and metal ion co-intercalated vanadium pentoxide nanomaterials obtained in this invention exhibit good rate performance when applied to zinc-ion batteries. Specifically, they demonstrate good specific capacity at different current densities, and at 10Ag... -1 After 2000 cycles at room temperature, it still retains 200~300mAh g. -1 One preferred case also confirms that zinc-ion batteries at current densities of 0.2 Ag... -1 0.5 Ag -1 1 Ag -1 2 Ag -1 5 Ag -1 and 10 Ag -1 The specific capacities at these times reached 473 mAh g⁻¹ and 472 mAh g⁻¹, respectively. -1 452 mAh g -1 419 mAh g -1 and 363 mAh g -1 295 mAhg -1 Moreover, when the current density recovers to 0.2Ag -1 At that time, the discharge specific capacity can recover to 469 mAhg. -1 .
[0022] 4) The process for preparing polyaniline and metal ion co-intercalated vanadium pentoxide nanomaterials is simple and low in cost. By adjusting parameters such as PANI concentration and hydrothermal time, the morphology and intercalation depth of the composite material can be precisely controlled. The entire process uses water as a solvent, which is suitable for large-scale production. Attached Figure Description
[0023] The accompanying drawings, which are included to provide a further understanding of the invention and form part of this invention, illustrate exemplary embodiments of the invention and are used to explain the invention, but do not constitute an undue limitation of the invention. In the drawings: Figure 1 The images show the XRD patterns of vanadium pentoxide nanorods (b) obtained by annealing (heat treatment) in Example 1 of this invention and the petal-shaped nanoribbons (a) of polyaniline and manganese ion co-intercalated vanadium pentoxide.
[0024] Figure 2 These are SEM images of vanadium pentoxide nanoribbons (a) obtained from the first hydrothermal reaction in Example 1 of this invention, vanadium pentoxide nanorods (b) after annealing, and petal-shaped nanoribbons (c) finally obtained with polyaniline and manganese ions co-intercalated with vanadium pentoxide.
[0025] Figure 3 For 10Ag -1 Cyclic performance diagrams of Example 1 (PVO-60), Example 2 (PVO-30), Example 3 (PVO-90), and an aqueous zinc-ion battery assembled using vanadium pentoxide powder as raw material, under room temperature conditions.
[0026] Figure 4 The graph shows the rate performance of Example 1 (PVO-60), Example 2 (PVO-30), Example 3 (PVO-90), and an aqueous zinc-ion battery assembled using vanadium pentoxide powder as raw material, under room temperature conditions.
[0027] Figure 5 The images show SEM images of vanadium pentoxide nanoribbons formed by the solvothermal reaction of the suspension in a closed environment in Example 1 of the present invention at temperatures above 200°C and below 160°C. In the images, A represents vanadium pentoxide nanoribbons formed at temperatures above 200°C, and B represents vanadium pentoxide nanoribbons formed at temperatures below 160°C. Detailed Implementation
[0028] The specific embodiments of this invention disclose a method for preparing petal-shaped nanoribbons formed by co-intercalation of polyaniline and metal ions with vanadium pentoxide nanoribbons, comprising the following steps: Step 1: Add vanadium pentoxide to deionized water and stir at room temperature for 2-6 hours. Then, add template agent and continue stirring for 4-8 hours. Further add metal ions and continue stirring for 1-2 hours to obtain a suspension. The ratio of vanadium pentoxide to deionized water is 1g:30~100ml; the stirring method can be magnetic stirring, mechanical stirring, etc. The molar ratio of vanadium pentoxide to template agent is 5.5:0.65~1.8; the molar ratio of vanadium pentoxide to metal ions is 1~2mmol:0.04~0.4mmol, preferably 1.5~1.8mmol:0.1~0.3mmol, more preferably 1.6~1.8mmol:0.1~0.2mmol.
[0029] The template agent is selected from at least one of ethylenediamine, propylenediamine, and dodecylamine, with ethylenediamine being the most preferred. The role of the template agent is to embed into the atomic layers of vanadium pentoxide, regulate the formation of highly crystalline V2O5 nanoribbons and further form V2O5 nanorods, and provide a stable substrate for subsequent intercalation.
[0030] The metal ion is at least one of divalent manganese ion, sodium ion, and potassium ion. The components providing the metal ion include, but are not limited to: manganese chloride, manganese bromide, manganese iodide, manganese sulfate, manganese nitrate, sodium chloride, sodium nitrate, sodium sulfate, sodium bromide, sodium iodide, potassium chloride, potassium nitrate, potassium sulfate, potassium bromide, and potassium iodide. Hydrothermal doping allows the metal ion to enter the vanadium pentoxide layered structure, thereby improving the stability of the material.
[0031] Step 2: Pour the suspension prepared in Step 1 into a beaker, mix well, and then transfer it into a high-pressure reactor for solvothermal reaction to obtain vanadium pentoxide nanoribbons; The solvothermal reaction conditions are as follows: reaction at 160–200°C for 18–30 hours, using deionized water as the reaction solvent. Excessive temperature will cause the template agent to decompose rapidly, losing its template function for V₂O₅ crystal growth, and will also lead to uneven doping and the formation of impurity phases. Conversely, if the temperature is too low, the V₂O₅ precursor cannot be fully dissolved and recrystallized, leaving unreacted V₂O₅ powder in the product, resulting in poor crystallinity, low doping efficiency, and uneven morphology. The coordination effect of the template agent is also limited, making it difficult to induce the directional growth of layered structures, leading to disordered nanosheets rather than nanoribbons.
[0032] Step 3: Pyrolyze vanadium pentoxide nanoribbons in air atmosphere to obtain vanadium pentoxide nanorods; The pyrolysis treatment, also known as annealing, is performed at 350–400°C for 30–90 minutes, with a heating rate of 2–10°C / min. If the pyrolysis temperature is too high, the precursor structure will collapse, leading to a decrease in the purity of the final product; if the pyrolysis temperature is too low, the precursor will not crystallize sufficiently, and impurities will remain.
[0033] Step 4: Add aniline monomer to an acidic mixture of vanadium pentoxide nanorods, and obtain polyaniline intercalated vanadium pentoxide composite material through chemical oxidation reaction.
[0034] The concentration of vanadium pentoxide nanorods in the acidic mixture is 0.3g: 30~50ml, and the pH of the acidic mixture is 2~5. Hydrochloric acid, sulfuric acid, nitric acid, etc. are preferably used to adjust the pH of the acidic mixture.
[0035] The ratio of vanadium pentoxide nanorods to aniline monomer is 1-2 mmol: 30-150 μL. Preferably, the ratio is 1.5-1.8 mmol: 30-100 μL, and more preferably 1.6-1.8 mmol: 50-70 μL. This is because if there is too much aniline monomer, resulting in an excessively high proportion of polyaniline intercalation, the overall discharge specific capacity of the composite material will decrease due to its low theoretical capacity. Simultaneously, excessive polyaniline is prone to aggregation, hindering zinc ion migration and diffusion, increasing electrode polarization, and thus reducing the electrochemical performance of the material. Conversely, if the proportion of polyaniline is too low, the conductivity and structural stability of the composite material cannot be effectively improved, and its buffering effect on volume expansion is insufficient, resulting in limited improvement in overall electrochemical performance. Therefore, the above ratio range can achieve a balance between capacity contribution and conductivity buffering effect, and the optimal balance is achieved when the ratio of vanadium pentoxide nanorods to aniline monomer is 1.6-1.8 mmol: 50-70 μL.
[0036] The chemical oxidation reaction is carried out at 110–130°C for 18–30 hours, using deionized water as the reaction solvent. Excessive temperature will degrade polyaniline, preventing it from forming an effective intercalation composite structure with V₂O₅, leading to morphology reconstruction failure (inability to form petal-shaped nanoribbons). Insufficient temperature will result in incomplete polyaniline intercalation, insufficient aniline monomer polymerization rate, and excessively short PANI segments that cannot penetrate the V₂O₅ interlayers, leading to insufficient intercalation depth.
[0037] The preparation of the aqueous zinc-ion battery used in the specific embodiments of the present invention includes the following steps: 1) Preparation of the positive electrode: 175 mg of polyaniline and metal ion co-intercalated vanadium pentoxide composite were weighed and added to a mortar. Then, 50 mg of acetylene black and 25 mg of polyvinylidene fluoride (PVDF) were weighed and mixed evenly in an appropriate amount of 1-methyl-2-pyrrolidone (NMP) solvent. The slurry was then evenly coated onto a cut titanium foil and vacuum dried at 80°C for 10 hours to obtain the positive electrode sheet.
[0038] 2) Preparation of electrolyte: Weigh 10.9 g of zinc trifluoromethanesulfonate and add it to a beaker. Then add 10 mL of deionized water and stir for 6 h to obtain a 3 mol / L zinc trifluoromethanesulfonate aqueous solution.
[0039] 3) Preparation of aqueous zinc-ion batteries: The CR2025 battery casing is selected. The battery assembly sequence is as follows: positive electrode casing - positive electrode sheet - glass fiber separator - electrolyte (take 8 to 10 drops of electrolyte and drop them into the middle of the separator) - negative electrode sheet (polished zinc sheet) - negative electrode casing.
[0040] 4) Determination of cycle performance and rate performance of aqueous zinc-ion batteries Electrochemical tests, including cycle performance and rate performance, were performed on the assembled button batteries using a battery testing system (LAND CT 2001A). It should be noted in the description of this invention that, unless specific conditions are specified in the examples, conventional conditions or conditions recommended by the manufacturer were followed. Reagents or instruments whose manufacturers are not specified are all commercially available products.
[0041] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0042] Example 1 1 g of vanadium pentoxide (5.5 mmol) was added to 70 ml of deionized water and stirred magnetically for 6 hours at room temperature. Then, 1.12 mmol of ethylenediamine template agent was added and stirring continued for 6 hours. Subsequently, 0.55 mmol of manganese chloride was added and stirring continued for 1 hour to obtain a suspension. The suspension was poured into a beaker, mixed evenly, and then transferred to a high-pressure reactor for solvothermal reaction at 180 °C for 24 hours. After centrifugation, washing, and drying, vanadium pentoxide nanoribbon powder was obtained. The vanadium pentoxide nanoribbon powder was then pyrolyzed in air at a temperature of 400 °C, a heating rate of 2-10 °C / min, and a reaction time of 30 min to obtain vanadium pentoxide nanorod powder. 0.3 g (1.65 mmol) of vanadium pentoxide nanorod powder was weighed and added to 40 ml of deionized water. Then, dilute hydrochloric acid was added to adjust the pH of the solution to 3.5. Subsequently, 60 μL of aniline monomer was added to a weakly acidic aqueous solution of vanadium pentoxide nanorods and heated at 120 °C for 24 h; centrifugation, washing, and drying were performed to obtain a polyaniline and manganese ion co-intercalated vanadium pentoxide composite material.
[0043] Regarding the step of "pouring the suspension into a beaker, mixing thoroughly, and then transferring it to a high-pressure reactor for a solvothermal reaction at 180°C for 24 hours," this invention, during experimental exploration, also employed first hydrothermal reactions at temperatures above 200°C and below 160°C. The SEM morphology of the obtained vanadium pentoxide nanoribbons is as follows: Figure 5 As shown, experiment A was conducted at 240℃, and experiment B was conducted at 120℃. It is evident that excessively high initial hydrothermal temperatures (above 200℃) weaken the template effect of ethylenediamine, resulting in irregularly aggregated nanoribbons. Conversely, excessively low initial hydrothermal temperatures (below 160℃) limit the coordination effect of ethylenediamine, making it difficult to induce the directional growth of layered structures, leading to the formation of mostly disordered nanosheets rather than nanoribbons.
[0044] Figure 1 The XRD pattern of the polyaniline and manganese ion co-intercalated vanadium pentoxide composite material prepared in this embodiment shows a distinct diffraction peak (001) at 6.2°. Figure 1 In Figure (a), after the V₂O₅ nanorods were transformed into a composite material of polyaniline and manganese ions co-intercalated vanadium pentoxide, the strongest peak shifted from 20.3 ° to 6.2 °, indicating an increase in lattice spacing. The calculated interlayer distance was approximately 1.42 nm, which is much larger than that of the original V₂O₅ nanorods. This confirms that the intercalation of polyaniline and manganese ions into the vanadium pentoxide nanoribbons altered the microstructure of vanadium pentoxide, resulting in petal-shaped vanadium pentoxide nanoribbons.
[0045] Figure 2 The first hydrothermal reaction clearly shows that vanadium pentoxide obtained is a nanoribbon structure ((a) figure), after annealing it becomes a nanorod structure ((b) figure), and finally polyaniline and manganese ion co-intercalated vanadium pentoxide forms a petal-shaped nanoribbon structure ((c) figure).
[0046] Example 2 1 g of vanadium pentoxide was added to 70 ml of deionized water and magnetically stirred for 6 hours at room temperature. Then, 1.12 mmol of ethylenediamine, a template agent, was added and stirring continued for another 6 hours. Subsequently, 0.55 mmol of manganese chloride was added and stirring continued for 1 hour to obtain a suspension. The suspension was poured into a beaker, mixed thoroughly, and then transferred to a high-pressure reactor for solvothermal reaction at 180°C for 24 hours. After centrifugation, washing, and drying, vanadium pentoxide nanoribbon powder was obtained. The vanadium pentoxide nanoribbon powder was then pyrolyzed in air at a temperature of 360°C, a heating rate of 2–10°C / min, and a reaction time of 80 min to obtain vanadium pentoxide nanorod powder. 0.3 g (1.65 mmol) of the vanadium pentoxide nanorod powder was weighed out. 30 μL of vanadium pentoxide nanorod powder (mmol) was added to 40 ml of deionized water, followed by the addition of dilute hydrochloric acid to adjust the pH of the solution to 3.2. Then, 30 μL of aniline monomer was added to the weakly acidic aqueous solution of vanadium pentoxide nanoribbons and heated at 120 degrees Celsius for 24 h. After centrifugation, washing and drying, polyaniline and metal ion co-intercalated vanadium pentoxide composite material was obtained.
[0047] Example 3 1 g of vanadium pentoxide was added to 70 ml of deionized water and magnetically stirred for 6 hours at room temperature. Then, 1.12 mmol of ethylenediamine, a template agent, was added and stirring continued for another 6 hours. Subsequently, 0.55 mmol of manganese chloride was added and stirring continued for 1 hour to obtain a suspension. The suspension was poured into a beaker, mixed thoroughly, and then transferred to a high-pressure reactor for solvothermal reaction at 180°C for 24 hours. After centrifugation, washing, and drying, vanadium pentoxide nanoribbon powder was obtained. The vanadium pentoxide nanoribbon powder was then pyrolyzed in air at a temperature of 350°C, a heating rate of 2–10°C / min, and a reaction time of 90 min to obtain vanadium pentoxide nanorod powder. 0.3 g (1.65 mmol) of the vanadium pentoxide nanorod powder was weighed out. 90 μL of aniline monomer was added to the weakly acidic aqueous solution of vanadium pentoxide nanorods and heated at 120 degrees Celsius for 24 h. After centrifugation, washing and drying, polyaniline and metal ion co-intercalated vanadium pentoxide composite material was obtained.
[0048] Figure 3 For 10Ag -1 Cycling performance diagrams of aqueous zinc-ion batteries in Examples 1, 2, and 3 under room temperature conditions. The results show that the aqueous zinc-ion battery of Example 1 still exhibits a high discharge specific capacity even at high current densities (retaining 295 mAh g⁻¹ after 2000 cycles). -1 The aqueous zinc-ion batteries of Examples 2 and 3 had capacities of 245 and 242 mAh g⁻¹ after 2000 cycles, respectively, indicating that the aqueous zinc-ion battery of Example 1 has a higher discharge specific capacity and better cycle stability.
[0049] Figure 4 The graph shows the rate performance of aqueous zinc-ion batteries in Examples 1, 2, and 3 at room temperature. The results indicate that at current densities of 0.2 Ag... -1 0.5 Ag -1 1 Ag -1 2 Ag -1 5 Ag -1 and 10 Ag -1 At that time, the aqueous zinc-ion battery of Example 1 provided a specific capacity of 473 mAh g. -1 472 mAh g -1 452 mAh g -1 419 mAh g -1 and 363 mAhg -1 295 mAh g -1 Moreover, when the current density recovers to 0.2Ag -1 At that time, the discharge specific capacity can recover to 469 mAhg.-1 This is far superior to Example 2 (at 0.2 Ag). -1 0.5 Ag -1 1 Ag -1 2 Ag -1 5 Ag -1 and 10 Ag -1 At that time, the specific capacity provided by the aqueous zinc-ion battery in Example 2 was 421 mAh g. -1 420 mAh g -1 393mAh g -1 364 mAh g -1 and 305 mAh g -1 248 mAh g -1 Example 3 (at 0.2 Ag) -1 0.5 Ag -1 1 Ag -1 2 Ag -1 5 Ag -1 and 10 Ag -1 At that time, the specific capacity provided by the aqueous zinc-ion battery in Example 3 was 409 mAh g. -1 408 mAh g -1 385mAh g -1 359 mAh g -1 and 305 mAh g -1 247 mAh g -1 The aqueous zinc-ion battery of Example 1 demonstrates that it has better rate performance.
[0050] The results of Examples 1-3 show that different amounts of aniline monomer added result in different amounts of polyaniline intercalated into vanadium pentoxide, which ultimately affects the rate performance of aqueous zinc-ion batteries.
[0051] The present invention further provides the following case studies to demonstrate the impact of different template agent types on the performance of aqueous zinc-ion batteries.
[0052] Example 4 1 g of vanadium pentoxide (5.5 mmol) was added to 70 ml of deionized water and stirred magnetically for 6 hours at room temperature. Then, 1.12 mmol of propylenediamine template agent was added and stirring continued for 6 hours. Subsequently, 0.55 mmol of manganese chloride was added and stirring continued for 1 hour to obtain a suspension. The suspension was poured into a beaker, mixed evenly, and then transferred to a high-pressure reactor for solvothermal reaction at 180 °C for 24 hours. After centrifugation, washing, and drying, vanadium pentoxide nanoribbon powder was obtained. The vanadium pentoxide nanoribbon powder was then pyrolyzed in air at a temperature of 400 °C, a heating rate of 2-10 °C / min, and a reaction time of 30 min to obtain vanadium pentoxide nanorod powder. 0.3 g (1.65 mmol) of vanadium pentoxide nanorod powder was weighed and added to 40 ml of deionized water. Then, dilute hydrochloric acid was added to adjust the pH of the solution to 3.5. Subsequently, 60 μL of aniline monomer was added to a weakly acidic aqueous solution of vanadium pentoxide nanorods, and the mixture was heated at 120 °C for 24 h. After centrifugation, washing, and drying, the polyaniline and manganese ion co-intercalated vanadium pentoxide composite material was obtained. The current density was 0.2 Ag. -1 0.5 Ag -1 1 Ag -1 2 Ag -1 5 Ag -1 and 10 Ag -1 At that time, the specific capacity provided by the aqueous zinc-ion battery in Example 4 was 461 mAh g. -1 457mAh g -1 420mAh g -1 393mAhg -1 and 341mAh g -1 269mAh g -1 .
[0053] Example 5 1 g of vanadium pentoxide (5.5 mmol) was added to 70 ml of deionized water and stirred magnetically for 6 hours at room temperature. Then, 1.12 mmol of the template agent dodecylamine was added and stirring was continued for another 6 hours. Subsequently, 0.55 mmol of manganese chloride was added and stirring was continued for another 1 hour to obtain a suspension. The suspension was poured into a beaker, mixed evenly, and then transferred to a high-pressure reactor for solvothermal reaction at 180 °C for 24 hours. After centrifugation, washing, and drying, vanadium pentoxide nanoribbon powder was obtained. The vanadium pentoxide nanoribbon powder was then pyrolyzed in air at a temperature of 400 °C, a heating rate of 2-10 °C / min, and a reaction time of 30 min to obtain vanadium pentoxide nanorod powder. 0.3 g (1.65 mmol) of vanadium pentoxide nanorod powder was weighed and added to 40 ml of deionized water. Then, dilute hydrochloric acid was added to adjust the pH of the solution to 3.5. Subsequently, 60 μL of aniline monomer was added to a weakly acidic aqueous solution of vanadium pentoxide nanorods, and the mixture was heated at 120 °C for 24 h. After centrifugation, washing, and drying, the polyaniline and manganese ion co-intercalated vanadium pentoxide composite material was obtained. The current density was 0.2 Ag. -1 0.5 Ag -1 1 Ag -1 2 Ag -1 5 Ag -1 and 10 Ag -1 At that time, the aqueous zinc-ion battery of Example 5 provided a specific capacity of 444 mAh g. -1 421mAh g -1 409mAh g -1 381mAhg -1 and 336mAh g -1 268mAh g -1 .
[0054] The results of Examples 1, 4 and 5 show that ethylenediamine, propylenediamine and dodecylamine can all serve as template agents of the present invention, but the results are different. Among them, ethylenediamine as a template agent produces the best rate performance in aqueous zinc-ion batteries.
[0055] The present invention further provides the following case studies to demonstrate the impact of different metal ion types on the performance of aqueous zinc-ion batteries.
[0056] Example 6 1 g of vanadium pentoxide (5.5 mmol) was added to 70 ml of deionized water and stirred magnetically for 6 hours at room temperature. Then, 1.12 mmol of ethylenediamine template agent was added and stirring was continued for another 6 hours. Subsequently, 0.55 mmol of sodium chloride was added and stirring was continued for another 1 hour to obtain a suspension. The suspension was poured into a beaker, mixed evenly, and then transferred to a high-pressure reactor for solvothermal reaction at 180 °C for 24 hours. After centrifugation, washing, and drying, vanadium pentoxide nanoribbon powder was obtained. The vanadium pentoxide nanoribbon powder was then pyrolyzed in air at a temperature of 400 °C, a heating rate of 2-10 °C / min, and a reaction time of 30 min to obtain vanadium pentoxide nanorod powder. 0.3 g (1.65 mmol) of vanadium pentoxide nanorod powder was weighed and added to 40 ml of deionized water. Then, dilute hydrochloric acid was added to adjust the pH of the solution to 3.5. Subsequently, 60 μL of aniline monomer was added to a weakly acidic aqueous solution of vanadium pentoxide nanorods, and the mixture was heated at 120 °C for 24 h. After centrifugation, washing, and drying, the polyaniline and manganese ion co-intercalated vanadium pentoxide composite material was obtained. The current density was 0.2 Ag. -1 0.5 Ag -1 1 Ag -1 2 Ag -1 5 Ag -1 and 10 Ag -1 At that time, the specific capacity provided by the aqueous zinc-ion battery in Example 1 was 432 mAh g. -1 429mAh g -1 401mAh g -1 373mAhg -1 and 326mAh g -1 280mAh g -1 .
[0057] Example 7 1 g of vanadium pentoxide (5.5 mmol) was added to 70 ml of deionized water and stirred magnetically for 6 hours at room temperature. Then, 1.12 mmol of ethylenediamine template agent was added and stirring continued for 6 hours. Subsequently, 0.55 mmol of potassium chloride was added and stirring continued for 1 hour to obtain a suspension. The suspension was poured into a beaker, mixed evenly, and then transferred to a high-pressure reactor for solvothermal reaction at 180 °C for 24 hours. After centrifugation, washing, and drying, vanadium pentoxide nanoribbon powder was obtained. The vanadium pentoxide nanoribbon powder was then pyrolyzed in air at a temperature of 400 °C, a heating rate of 2-10 °C / min, and a reaction time of 30 min to obtain vanadium pentoxide nanorod powder. 0.3 g (1.65 mmol) of vanadium pentoxide nanorod powder was weighed and added to 40 ml of deionized water. Then, dilute hydrochloric acid was added to adjust the pH of the solution to 3.5. Subsequently, 60 μL of aniline monomer was added to a weakly acidic aqueous solution of vanadium pentoxide nanorods, and the mixture was heated at 120 °C for 24 h. After centrifugation, washing, and drying, the polyaniline and manganese ion co-intercalated vanadium pentoxide composite material was obtained. The current density was 0.2 Ag. -1 0.5 Ag -1 1 Ag -1 2 Ag -1 5 Ag -1 and 10 Ag -1 At that time, the aqueous zinc-ion battery of Example 1 provided a specific capacity of 438 mAh g. -1 434mAh g -1 403mAh g -1 377mAhg -1 and 331mAh g -1 282mAh g -1 .
[0058] The results of Examples 1, 6, and 7 show that manganese ions, potassium ions, and sodium ions can all be intercalated into vanadium pentoxide nanostructures, but the aqueous zinc-ion battery formed by manganese ions intercalating into the vanadium pentoxide nanostructures of the present invention exhibits the best rate performance.
[0059] Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents. The embodiments described above merely illustrate several implementations of the invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention. It should be noted that those skilled in the art can make several modifications and improvements without departing from the concept of the invention, and these all fall within the protection scope of the invention. Therefore, the protection scope of this invention should be determined by the appended claims.
Claims
1. A polyaniline and metal ion co-intercalated vanadium pentoxide nanomaterial, characterized in that, The nanomaterial includes nano-vanadium pentoxide, in which polyaniline and metal ions are co-intercalated, and the nano-vanadium pentoxide has a petal-shaped nanoribbon structure; and the ratio of the nano-vanadium pentoxide, the metal ions, and the aniline monomer forming the polyaniline is 1~2 mmol: 0.04~0.4 mmol: 30~150 μL; the metal ions are at least one of divalent manganese ions, sodium ions, and potassium ions.
2. The polyaniline and metal ion co-intercalated vanadium pentoxide nanomaterial according to claim 1, characterized in that, The nano-vanadium pentoxide has a length of 400~500 nm and a width of 50~100 nm.
3. The method for preparing the polyaniline and metal ion co-intercalated vanadium pentoxide nanomaterial according to claim 1 or 2, characterized in that, Includes the following steps: Step 1: Mix vanadium pentoxide with deionized water, and then add template agent and metal ion-providing components in sequence to obtain a suspension. Step 2: The suspension is subjected to a solvothermal reaction in a closed environment to obtain vanadium pentoxide nanoribbons; Step 3: Heat-treat vanadium pentoxide nanoribbons in air atmosphere to obtain vanadium pentoxide nanorods; Step 4: Prepare an acidic mixture of vanadium pentoxide nanorods and add aniline monomer to the acidic mixture. Through chemical oxidation reaction, polyaniline and metal ion co-intercalated vanadium pentoxide nanomaterials are obtained.
4. The method for preparing polyaniline and metal ion co-intercalated vanadium pentoxide nanomaterials according to claim 3, characterized in that, In step 1, the ratio of vanadium pentoxide to deionized water is 1g:30~100mL; and / or, the mixing time of vanadium pentoxide and deionized water is 2~6h.
5. The method for preparing polyaniline and metal ion co-intercalated vanadium pentoxide nanomaterials according to claim 3 or 4, characterized in that, In step 1, the mixing time for adding the template agent is 4-8 hours; preferably, the molar ratio of vanadium pentoxide to the template agent is 5.5:0.65-1.8; more preferably, the template agent is ethylenediamine, propylenediamine, or dodecylamine, more preferably ethylenediamine; and / or, the mixing time for adding the component providing metal ions is 1-2 hours; preferably, the component providing metal ions is at least one of water-soluble divalent manganese salt, water-soluble sodium salt, or water-soluble potassium salt.
6. The method for preparing polyaniline and metal ion co-intercalated vanadium pentoxide nanomaterials according to claim 3, characterized in that, In step 2, the control conditions for the solvothermal reaction include: reaction temperature 160~200℃, reaction time 18~30h.
7. The method for preparing polyaniline and metal ion co-intercalated vanadium pentoxide nanomaterials according to claim 3, characterized in that, In step 3, the heat treatment control conditions include: reaction temperature 350~400℃, reaction time 30~90min; preferably, the rate of heating to the reaction temperature is 2~10℃ / min.
8. The method for preparing polyaniline and metal ion co-intercalated vanadium pentoxide nanomaterials according to claim 3, characterized in that, In step 4, the concentration of vanadium pentoxide nanorods in the acidic mixture is 0.3g:30~50ml, the pH of the acidic mixture is 2~5, and preferably, the acidic medium in the acidic mixture is one of hydrochloric acid, sulfuric acid, and nitric acid. And / or, the controlled conditions for chemical oxidation reactions include: reaction temperature 110~130℃, reaction time 18~30h.
9. The application of the polyaniline and metal ion co-intercalated vanadium pentoxide nanomaterials as described in claim 1 or 2 in the preparation of battery cathode materials.
10. An aqueous zinc-ion battery, characterized in that, include: The cathode material made of polyaniline and metal ion co-intercalated vanadium pentoxide nanomaterials as described in claim 1 or 2.