Solution preparation method of amorphous organic hybrid vanadium oxide working electrode and application thereof in aqueous zinc ion battery

Abstract

The application belongs to the technical field of aqueous zinc ion batteries, and particularly relates to a solution preparation method of amorphous organic hybrid vanadium oxide working electrode and application of the amorphous organic hybrid vanadium oxide working electrode in aqueous zinc ion batteries. The application dissolves the crystalline organic hybrid vanadium oxide in an organic solvent to form an organic hybrid vanadium oxide solution, and adds a conductive agent and a binder into the solution to prepare the amorphous organic hybrid vanadium oxide working electrode through concentration and drying. The amorphous hybrid vanadium oxide working electrode prepared by the application exhibits high specific capacity, good rate performance and excellent cycle stability as an energy storage electrode of aqueous zinc ion batteries.

Description

Technical Field

[0001] This invention relates to the field of zinc-ion battery technology, and in particular to a solution-based preparation method for an amorphous organic hybrid vanadium oxyoxide working electrode and its application in aqueous zinc-ion batteries. Background Technology

[0002] Aqueous zinc-ion batteries (ZIBs) are considered a strong alternative to lithium-ion batteries due to their high theoretical capacity and good safety. To date, a wide range of materials have been used as electrode materials for ZIBs, among which vanadium oxide (VO₂O₃) is particularly important. x Vanadium exhibits great potential. On the one hand, the abundant oxidation states of vanadium enable VO... x It can provide multiple electron transfers during electrochemical reactions. On the other hand, the relatively low cost and multiple open structures also endow VO with… x Strong competitiveness. Despite VO x While significant progress has been made in the development of electrode materials, many problems and challenges remain to be addressed: their poor conductivity, easy solubility, and structural deformation and collapse inevitably interrupt charge transport pathways, leading to rapid capacity decay after cycling.

[0003] To address this issue, high energy density and extended cycle life can be achieved through morphology control and pre-insertion of guest materials. Constructing nano-VO x Materials can help shorten and improve electron / ion transport paths, while pre-inserted cations / water molecules / organic molecules as guest materials can broaden VO2 max. x Interlayer spacing of the host material. Furthermore, organic molecules can also act as ligands to chelate in VOCs. x Further structural improvements to Zn 2+ Diffusion kinetics. Taking ethylene glycol (EG) as an example, thermodynamically stable ethylene glycol vanadium oxy (VEG) can be synthesized via a solvothermal reaction of EG using vanadium-oxygen precursor materials. During the synthesis process, due to the high reactivity between the VO and OCO bonds, the vanadium-oxygen precursor can combine with EG ligands to form a chain-like VEG structure. In practical energy storage applications of VEG, the electrochemical performance of VEG is often further improved by controlling the synthesis size, inserting metal ions, and compositing with a conductive layer.

[0004] However, most of the reported modification strategies are based on adjusting the crystalline structure, and the synthesized VO xMaterials are all composed of crystalline frameworks, and the influence of the ordered nature of crystalline structures is often overlooked: they cannot provide abundant reaction sites, nor can they adequately accommodate mechanical strain. Compared to crystalline materials, the disordered, open framework structure of amorphous materials exposes more active sites and provides ample pathways for rapid internal diffusion. Furthermore, the lower Gibbs free energy gives amorphous structures excellent stability, contributing to improved cycle life. Currently, most research related to the construction of amorphous structures is based on inorganic vanadium oxyoxide materials, with very little research on amorphous organic-inorganic hybrid vanadium oxyoxide materials. Summary of the Invention

[0005] The purpose of this invention is to provide a solution-based preparation method for an amorphous organic-inorganic hybrid vanadium oxyoxide working electrode and its application in aqueous zinc-ion batteries. The solution-based preparation method for the amorphous organic-inorganic hybrid vanadium oxyoxide working electrode provided by this invention utilizes the principle of "like dissolves like," constructing an amorphous structure by controlling the dissolution and re-precipitation of organic-inorganic hybrid vanadium oxyoxide with a crystalline framework in an organic solvent. When applied to aqueous zinc-ion batteries, this method enables the organic-inorganic hybrid vanadium oxyoxide material to exhibit superior electrochemical performance, significantly improving specific capacity, rate capability, reversibility, and cycle stability.

[0006] To achieve the above objectives, the present invention provides the following technical solution:

[0007] This invention provides a solution-based preparation method for an amorphous organic hybrid vanadium oxyoxide working electrode, comprising the following steps:

[0008] (1) The organic hybrid vanadium oxide and organic solvent are stirred thoroughly under heating conditions to form a solution;

[0009] (2) The obtained solution is heated to evaporate the organic solvent, and amorphous organic hybrid vanadium oxide is obtained.

[0010] Preferably, the organic solvent in step (1) is one of dimethyl sulfoxide (DMSO), n-methyl-2-pyrrolidone (NMP), and N,N-dimethylformamide (DMF);

[0011] Preferably, in step (1), the mass ratio of the organic hybrid vanadium oxide to the volume ratio of the organic solvent is <5 g / L;

[0012] Preferably, the dissolution temperature of the organic hybrid vanadium oxide in the organic solvent in step (1) is 60~100 °C;

[0013] Preferably, the solvent evaporation temperature in step (2) should be controlled at 60~100 ℃.

[0014] This invention provides a solution obtained by the solution preparation method described above and a precipitated amorphous organic hybrid vanadium oxide. The solution is a stable and homogeneous solution, and the precipitated amorphous organic hybrid vanadium oxide material is an amorphous material. The precipitated amorphous organic hybrid vanadium oxide contains vanadium, oxygen, carbon and hydrogen elements.

[0015] This invention also provides the application of the solution preparation method described above in aqueous zinc-ion batteries, comprising the following steps:

[0016] 1) The organic hybrid vanadium oxide and organic solvent are thoroughly stirred under heating conditions to form a solution;

[0017] 2) The solution obtained in step 1) is mixed with carbon black and polyvinylidene fluoride powder and concentrated to obtain an amorphous organic hybrid vanadium oxide working electrode.

[0018] Preferably, in step 2), the mass of the organic hybrid vanadium oxide is 40% to 80% of the total mass of the organic hybrid vanadium oxide, carbon black, and polyvinylidene fluoride powder; the mass of the carbon black is 10% to 30% of the total mass of the organic hybrid vanadium oxide, carbon black, and polyvinylidene fluoride powder; and the mass of the polyvinylidene fluoride is 10% to 30% of the total mass of the organic hybrid vanadium oxide, carbon black, and polyvinylidene fluoride powder.

[0019] The present invention also provides an amorphous organic hybrid vanadium oxyoxide working electrode prepared by the solution-based preparation method of the amorphous organic hybrid vanadium oxyoxide working electrode described in the above technical solution.

[0020] The present invention also provides the application of the amorphous organic hybrid vanadium oxyoxide electrode described above in an aqueous zinc-ion battery.

[0021] This invention provides a solution-based preparation method for an amorphous organic-inorganic hybrid vanadium oxyoxide working electrode, comprising the following steps: thoroughly stirring organic-inorganic hybrid vanadium oxyoxide with an organic solvent under heating conditions to form a solution; and thoroughly heating the solution to evaporate the organic solvent, thereby obtaining the amorphous organic-inorganic hybrid vanadium oxyoxide. The solution-based preparation method provided by this invention utilizes the principle of "like dissolves like," employing DMSO, NMP, and DMF as solvents. By controlling the dissolution and re-precipitation process of the organic-inorganic hybrid vanadium oxyoxide with a crystalline framework in the organic solvent, an amorphous structure is constructed, successfully achieving the transformation from a crystalline to an amorphous state. The amorphous organic-inorganic hybrid vanadium oxyoxide prepared by this invention is an amorphous material. Compared to crystalline organic-inorganic hybrid vanadium oxyoxide, the amorphous organic-inorganic hybrid vanadium oxyoxide material prepared by this invention has more isotropic ion diffusion pathways, which is beneficial for rapid ion diffusion. Simultaneously, the structural change during ion diffusion is less than that of the crystalline structure, contributing to rate performance and cycle stability. The solution-based preparation method provided by this invention preserves the organic ligands chelated on the surface of the organic hybrid vanadium oxide matrix. The organic hybrid structure reduces the electrostatic interaction between metal ions and the vanadium-based framework while further promoting the movement of metal ions within the disordered VO4 matrix. x Diffusion in the bulk phase. Unlike current research that constructs amorphous structures during the material synthesis stage, the solution-based preparation method of the amorphous organic hybrid vanadium oxyoxide working electrode provided by this invention achieves the transformation from crystalline to amorphous state after the crystalline material synthesis stage.

[0022] This invention provides the application of the solution-based preparation method of the aforementioned amorphous organic hybrid vanadium oxide working electrode in aqueous zinc-ion batteries. The amorphous organic hybrid vanadium oxide working electrode prepared by this invention is obtained by directly mixing, concentrating, and drying a solution of organic hybrid vanadium oxide with a conductive agent and a binder, thus avoiding the problem of uneven mixing inherent in traditional dry grinding methods for powder electrodes. In summary, the amorphous organic hybrid vanadium oxide working electrode prepared by this invention, as the positive electrode of an aqueous zinc-ion battery energy storage device, possesses a stable, open vanadium oxide framework, exhibiting higher specific capacity, superior rate performance, and long-term cycle stability compared to crystalline organic hybrid vanadium oxide. The preparation method of the amorphous organic hybrid vanadium oxide working electrode provided by this invention is simple and has low environmental impact. Attached Figure Description

[0023] Figure 1 Optical photographs of the homogeneous solutions formed by dissolving ethylene glycol vanadium oxide in DMSO (a), NMP (b), and DMF (c) solvents in Examples 1-3;

[0024] Figure 2 An optical photograph of the amorphous organic hybrid vanadium oxygen VEG-D solid powder obtained in Example 3;

[0025] Figure 3This is a scanning electron microscope image of the amorphous organic hybrid vanadium oxide VEG-D solid powder obtained in Example 3;

[0026] Figure 4 The image shows the XRD pattern of the amorphous organic hybrid vanadium oxide VEG-D solid powder obtained in Example 3.

[0027] Figure 5 The FT-IR spectrum of the VEG-DMF solution obtained in Example 3;

[0028] Figure 6 The FT-IR spectrum of the amorphous organic hybrid vanadium oxide VEG-D solid powder obtained in Example 3;

[0029] Figure 7 Thermogravimetric analysis spectrum of the amorphous organic hybrid vanadium oxide VEG-D solid powder obtained in Example 3;

[0030] Figure 8 The electrochemical properties of the working electrode of crystalline organic hybrid vanadium oxide powder prepared in Comparative Example 1 using crystalline ethylene glycol as the active material and the mass ratio of active material, carbon black, and polyvinylidene fluoride powder being 7:2:1 are shown in the figure.

[0031] Figure 9 The electrochemical properties of the amorphous organic hybrid vanadium oxide working electrode prepared in Application Example 1 using ethylene glycol vanadium oxide as the solute and with a mass ratio of active material, carbon black, and polyvinylidene fluoride powder of 7:2:1 are shown in Figure 1.

[0032] Figure 10 Comparison of rate performance of amorphous organic hybrid vanadium oxyoxide electrodes prepared in Examples 1-5;

[0033] Figure 11 The image shows the long-cycle properties of the amorphous organic hybrid vanadium oxide electrode prepared in Application Example 2 using ethylene glycol vanadium oxide as the solute and with a mass ratio of active material, carbon black, and polyvinylidene fluoride powder of 6:2:2. Detailed Implementation Plan

[0034] This invention provides a solution preparation method for converting crystalline organic hybrid vanadium oxide into amorphous organic hybrid vanadium oxide, comprising the following steps:

[0035] (1) The organic hybrid vanadium oxide and organic solvent are stirred thoroughly under heating conditions to form a solution;

[0036] (2) The obtained solution is heated to evaporate the organic solvent, and amorphous organic hybrid vanadium oxide is obtained.

[0037] In this invention, the organic solvent is one of dimethyl sulfoxide (DMSO), n-methyl-2-pyrrolidone (NMP), and N,N-dimethylformamide (DMF); wherein, the lower boiling point and higher ignition temperature of DMF significantly reduce the energy consumption required for electrode drying, while improving the safety of the production process. Therefore, in a specific application example of this invention, the organic solvent is more preferably DMF.

[0038] In this invention, the mass ratio of the organic hybrid vanadium oxide to the volume ratio of the organic solvent is <5 g / L.

[0039] In this invention, the dissolution temperature of the organic hybrid vanadium oxide in an organic solvent is preferably 60~100 °C, more preferably 80 °C.

[0040] In this invention, the solvent evaporation temperature of the organic hybrid vanadium oxide solution is preferably 60~100 ℃, more preferably 80 ℃.

[0041] This invention provides an organic hybrid vanadium oxyoxide solution and an amorphous organic hybrid vanadium oxyoxide solid powder obtained by the solution preparation method described above. The organic hybrid vanadium oxyoxide solution is a stable and homogeneous solution, and the precipitated amorphous organic hybrid vanadium oxyoxide material is an amorphous material containing vanadium, oxygen, carbon and hydrogen elements.

[0042] The amorphous organic hybrid vanadium oxide provided by this invention has a dense, bulk structure.

[0043] The amorphous organic hybrid vanadium oxyoxide provided by this invention is an amorphous material. Compared with crystalline organic hybrid vanadium oxyoxide, the amorphous organic hybrid vanadium oxyoxide material prepared by this invention has more isotropic ion diffusion pathways, which is conducive to the rapid diffusion of ions. At the same time, it can effectively avoid the structural damage and irreversible phase generation caused by the insertion / extraction of metal ions in the crystal framework during the ion diffusion process, which is helpful for rate performance and cycle stability.

[0044] The amorphous organic hybrid vanadium oxide provided by this invention retains the organic hybrid structure. This structure reduces the electrostatic interaction between metal ions and the vanadium-based framework while further promoting the movement of metal ions in disordered VO4. x Diffusion in the bulk phase.

[0045] This invention also provides a technical solution for preparing an amorphous organic hybrid vanadium oxyoxide working electrode using the solution preparation method described above, and the application of the obtained amorphous organic hybrid vanadium oxyoxide electrode in an aqueous zinc-ion battery.

[0046] This invention provides an amorphous organic-inorganic hybrid vanadium oxide working electrode, prepared from the organic-inorganic hybrid vanadium oxide solution described in the above-mentioned technical solution, carbon black, and polyvinylidene fluoride. The process includes the following steps:

[0047] 1) The organic hybrid vanadium oxide and organic solvent are thoroughly stirred under heating conditions to form a solution;

[0048] 2) The solution obtained in step 1) is mixed with carbon black and polyvinylidene fluoride powder, concentrated and dried to obtain an amorphous organic hybrid vanadium oxide working electrode;

[0049] In the application of this invention, the preferred mass of the organic hybrid vanadium oxide in the solution is 40% to 80% of the total mass of the organic hybrid vanadium oxide, carbon black, and polyvinylidene fluoride powder, more preferably 60% to 70%; the preferred mass of the carbon black is 10% to 30% of the total mass of the organic hybrid vanadium oxide, carbon black, and polyvinylidene fluoride powder, more preferably 10% to 20%; and the preferred mass of the polyvinylidene fluoride is 10% to 30% of the total mass of the organic hybrid vanadium oxide, carbon black, and polyvinylidene fluoride powder, more preferably 10% to 20%.

[0050] To further illustrate the present invention, the technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0051] Example 1

[0052] Add 20 mg of ethylene glycol vanadium oxide to 10 ml of DMSO solvent and stir at 80 °C for 3 h to completely dissolve the ethylene glycol vanadium oxide, thus obtaining a VEG-DMSO solution.

[0053] Example 2

[0054] 20 mg of ethylene glycol vanadium oxide was added to 10 ml of NMP solvent and stirred at 80 °C for 3 h to completely dissolve the ethylene glycol vanadium oxide, thus obtaining a VEG-NMP solution.

[0055] Example 3

[0056] (1) Add 20 mg of ethylene glycol vanadium oxide to 10 ml of DMF solvent and stir for 3 h under heating at 80 °C to completely dissolve the ethylene glycol vanadium oxide and obtain VEG-DMF solution.

[0057] (2) Stir the ethylene glycol solution at 80 °C to allow the solvent to evaporate naturally, and obtain the precipitated solid, which is denoted as VEG-D.

[0058] Figure 1 In the image, 'a' is an optical photograph of the VEG-DMSO solution obtained in Example 1; Figure 1 b in the image is an optical photograph of the VEG-NMP solution obtained in Example 2; Figure 1 c in the image is an optical photograph of the VEG-DMF solution obtained in Example 3; from Figure 1 It can be seen that the obtained organic hybrid vanadium oxide solutions are all stable and homogeneous solutions.

[0059] Figure 2 An optical photograph of the amorphous organic hybrid vanadium oxide VEG-D solid powder obtained in Example 3. Figure 2 It can be seen that the amorphous organic hybrid vanadium oxide VEG-D obtained in Example 3 is a black solid powder.

[0060] Figure 3 This is a scanning electron microscope (SEM) image of the amorphous organic hybrid vanadium oxide (VEG-D) solid powder obtained in Example 3. Figure 3 It can be seen that the amorphous organic hybrid vanadium oxygenate VEG-D obtained in Example 3 is a dense, irregular bulk.

[0061] Figure 4 The image shows the XRD pattern of the amorphous organic hybrid vanadium oxide VEG-D solid powder obtained in Example 3. Figure 3 It can be seen that the amorphous organic hybrid vanadium oxide VEG-D obtained in Example 3 is an amorphous product.

[0062] Figure 5 The FT-IR spectrum of the VEG-DMF solution obtained in Example 3; Figure 6 The FT-IR spectrum of the amorphous organic hybrid vanadium oxide VEG-D solid powder obtained in Example 3; by Figure 5 and 6 The comparison shows that the chemical bond vibrations associated with chelating ligands have always existed and have not shifted significantly. Figure 6 The presence of DMF-related chemical bond vibrations indicates that DMF molecules are embedded into the framework structure of VEG during the transformation from crystalline organic hybrid vanadium oxygen to amorphous state.

[0063] Figure 7 The thermogravimetric analysis (TGA) spectrum of the amorphous organic hybrid vanadium oxide (VEG-D) solid powder obtained in Example 3 is shown below. Figure 7 It can be seen that the loss of functional groups in amorphous organic hybrid vanadium oxygen VEG-D is relatively slow, exhibiting multiple small-scale weight loss events. The weight loss peaks are relatively flat and the weight loss temperature range is wide, which is consistent with amorphous products.

[0064] Application Example 1

[0065] (1) Add 20 mg of ethylene glycol vanadium oxide to 10 ml of DMF solvent and stir for 3 h under heating at 80 °C to completely dissolve the ethylene glycol vanadium oxide and obtain an ethylene glycol vanadium oxide solution.

[0066] (2) Add 5.7 mg (approximately 20% of the total mass of active material, conductive agent, and binder) of carbon black and 2.85 mg (approximately 10% of the total mass of active material, conductive agent, and binder) of polyvinylidene fluoride to the obtained ethylene glycol vanadium oxide solution. Stir thoroughly at 80 °C to evaporate the solvent, concentrate to obtain a slurry, and uniformly coat the slurry onto titanium foil as the positive electrode, denoted as 7-2-1-V. Use glass fiber as the separator, 3M Zn(CF3SO3)2 as the electrolyte, zinc foil as the negative electrode, and encapsulate with a battery case of model CR2032 to make an aqueous zinc-ion battery.

[0067] Application Example 2

[0068] (1) Add 20 mg of ethylene glycol vanadium oxide to 10 ml of DMF solvent and stir for 3 h under heating at 80 °C to completely dissolve the ethylene glycol vanadium oxide and obtain an ethylene glycol vanadium oxide solution.

[0069] (2) Add 2.5 mg (approximately 10% of the total mass of active material, conductive agent, and binder) of carbon black and 2.5 mg (approximately 10% of the total mass of active material, conductive agent, and binder) of polyvinylidene fluoride to the obtained ethylene glycol vanadium oxide solution. Stir thoroughly under heating conditions of 80 °C to evaporate the solvent, concentrate to obtain a slurry, and uniformly coat the slurry onto titanium foil as the positive electrode, denoted as 8-1-1-V. Use glass fiber as the separator, 3M Zn(CF3SO3)2 as the electrolyte, zinc foil as the negative electrode, and encapsulate with a battery case of model CR2032 to make an aqueous zinc-ion battery.

[0070] Application Example 3

[0071] (1) Add 20 mg of ethylene glycol vanadium oxide to 10 ml of DMF solvent and stir for 3 h under heating at 80 °C to completely dissolve the ethylene glycol vanadium oxide and obtain an ethylene glycol vanadium oxide solution.

[0072] (2) Add 6.67 mg (approximately 20% of the total mass of active material, conductive agent, and binder) of carbon black and 6.67 mg (approximately 20% of the total mass of active material, conductive agent, and binder) of polyvinylidene fluoride to the obtained ethylene glycol vanadium oxide solution. Stir thoroughly at 80 °C to evaporate the solvent, concentrate to obtain a slurry, and uniformly coat the slurry onto titanium foil as the positive electrode, denoted as 6-2-2-V. Use glass fiber as the separator, 3M Zn(CF3SO3)2 as the electrolyte, zinc foil as the negative electrode, and encapsulate with a battery case of model CR2032 to make an aqueous zinc-ion battery.

[0073] Application Example 4

[0074] (1) Add 20 mg of ethylene glycol vanadium oxide to 10 ml of DMF solvent and stir for 3 h under heating at 80 °C to completely dissolve the ethylene glycol vanadium oxide and obtain an ethylene glycol vanadium oxide solution.

[0075] (2) Add 12 mg (about 30% of the total mass of active material, conductive agent and binder) of carbon black and 8 mg (about 20% of the total mass of active material, conductive agent and binder) of polyvinylidene fluoride to the obtained ethylene glycol vanadium oxide solution. Stir thoroughly under heating at 80 °C to evaporate the solvent, concentrate to obtain slurry, and coat the slurry evenly on titanium foil as the positive electrode, denoted as 5-3-2-V. Use glass fiber as the separator, 3M Zn(CF3SO3)2 as the electrolyte, zinc foil as the negative electrode, and encapsulate with a battery case of model CR2032 to make an aqueous zinc-ion battery.

[0076] Application Example 5

[0077] (1) Add 20 mg of ethylene glycol vanadium oxide to 10 ml of DMF solvent and stir for 3 h under heating at 80 °C to completely dissolve the ethylene glycol vanadium oxide and obtain an ethylene glycol vanadium oxide solution.

[0078] (2) Add 15 mg (approximately 30% of the total mass of active material, conductive agent, and binder) of carbon black and 15 mg (approximately 30% of the total mass of active material, conductive agent, and binder) of polyvinylidene fluoride to the obtained ethylene glycol vanadium oxide solution. Stir thoroughly under heating conditions of 80 °C to evaporate the solvent, concentrate to obtain a slurry, and uniformly coat the slurry onto titanium foil as the positive electrode, denoted as 4-3-3-V. Use glass fiber as the separator, 3M Zn(CF3SO3)2 as the electrolyte, zinc foil as the negative electrode, and encapsulate with a battery case of model CR2032 to make an aqueous zinc-ion battery.

[0079] Comparative Example 1

[0080] A water-based zinc-ion battery was fabricated using a powder working electrode (active material: conductive agent: binder ratio of 7:2:1) with crystalline vanadium glycol oxide as the active material as the positive electrode, 3M Zn(CF3SO3)2 as the electrolyte, zinc foil as the negative electrode, and encapsulated in a battery case of model CR2032.

[0081] Electrochemical tests were conducted on the water-based zinc-ion batteries packaged for use cases 1-5 and comparative example 1, respectively. Figure 8 The image shows the electrochemical properties of the powder working electrode in Comparative Example 1, which uses crystalline ethylene glycol vanadium oxide as the active material. Figure 8 The 'a' in Comparative Example 1 indicates that the working electrode of crystalline vanadium oxyethylene glycol powder has general rate capability. Figure 8 The value of b indicates that the reversibility of the crystalline vanadium glycol oxygen powder electrode used in Comparative Example 1 is poor.

[0082] Figure 9 The electrochemical properties of the amorphous organic vanadium oxide working electrode prepared in Application Example 1 with a mass ratio of active material: conductive agent: binder of 7:2:1 are shown in the figure. Figure 9 The a in the figure indicates that the amorphous organic hybrid vanadium oxyoxide working electrode prepared by Example 1 has the advantages of higher specific capacity and higher rate capability compared with the crystalline vanadium oxyoxide powder working electrode; Figure 9 In the figure, b is the charge-discharge curve of the amorphous organic hybrid vanadium oxyoxide working electrode prepared in Example 1, which shows that it has good reversibility; Figure 9 c in the figure is a long-cycle characterization diagram of the amorphous organic hybrid vanadium oxyoxide working electrode prepared in Example 1, which shows that it has good stability during long-term cycling of more than 500 cycles. Figure 9 In the figure, d represents the cyclic voltammetry curve of the amorphous organic hybrid vanadium oxyoxide working electrode prepared in Example 1. The curve did not undergo significant deformation at a high scan rate, indicating that V undergoes a conversion from +3 to +5 valence during its charge and discharge process, and has good reversibility.

[0083] Figure 10 The graph shows a comparison of the rate performance of aqueous zinc-ion batteries packaged using Examples 1-5. As can be seen from the graph, the amorphous organic hybrid vanadium oxide working electrode with the ratio of active material mass: conductive agent mass: binder mass of 6:2:2 exhibits the best rate performance. Adding too much conductive carbon black is detrimental to the improvement of electrode capacity, while adding too little results in poor electrode conductivity. Adding too much polyvinylidene fluoride will block ion channels and affect conductivity, while adding too little will result in insufficient adhesion between the active material, conductive agent, and current collector.

[0084] Figure 10 The long-cycle characterization diagram of the amorphous organic hybrid vanadium oxide working electrode prepared in Application Example 3 with an active material mass: conductive agent mass: binder mass ratio of 6:2:2 shows its performance at 5 A g. -1 Under the test conditions, the capacity retention rate was the best compared to other application examples during more than 500 long-term cycles.

[0085] As can be seen from the application examples, the amorphous organic hybrid vanadium oxyoxide working electrode prepared by the solution preparation method of the present invention exhibits high capacity, good rate performance and good cycle stability.

[0086] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, and not all embodiments. Other embodiments can be obtained based on these embodiments without creative intent, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A solution-based preparation method for an amorphous organic hybrid vanadium oxyoxide working electrode, comprising the following steps: (1) The organic hybrid vanadium oxide and organic solvent are stirred thoroughly under heating conditions to form a solution; (2) The obtained solution is heated to evaporate the organic solvent, and amorphous organic hybrid vanadium oxide is obtained.

2. The solution treatment method for organic hybrid vanadium oxide according to claim 1, characterized in that, The organic solvent in step (1) is one of dimethyl sulfoxide (DMSO), n-methyl-2-pyrrolidone (NMP), and N,N-dimethylformamide (DMF).

3. The solution treatment method for organic hybrid vanadium oxide according to claim 1, characterized in that, In step (1), the mass ratio of the organic hybrid vanadium oxide to the volume of the organic solvent is <5 g / L.

4. The solution treatment method for organic hybrid vanadium oxide according to claim 1, characterized in that, The dissolution temperature of the organic hybrid vanadium oxide in the organic solvent in step (1) is 60~100 ℃.

5. The solution treatment method for organic hybrid vanadium oxide according to claim 1, characterized in that, The solvent evaporation temperature in step (2) should be controlled at 60~100 ℃.

6. The solution-based preparation method of the amorphous organic hybrid vanadium oxyoxide working electrode, when applied to an aqueous zinc-ion battery, includes the following steps: 1) The organic hybrid vanadium oxide and organic solvent are thoroughly stirred under heating conditions to form a solution; 2) The solution obtained in step 1) is mixed with carbon black and polyvinylidene fluoride powder and concentrated to obtain an amorphous organic hybrid vanadium oxide working electrode.

7. The application of the solution-based preparation of the amorphous organic hybrid vanadium oxide working electrode according to claim 6 in an aqueous zinc-ion battery, characterized in that, In step 2), the mass of the organic hybrid vanadium oxide is 40% to 80% of the total mass of the organic hybrid vanadium oxide, carbon black, and polyvinylidene fluoride powder; the mass of the carbon black is 10% to 30% of the total mass of the organic hybrid vanadium oxide, carbon black, and polyvinylidene fluoride powder; and the mass of the polyvinylidene fluoride is 10% to 30% of the total mass of the organic hybrid vanadium oxide, carbon black, and polyvinylidene fluoride powder.

8. The amorphous organic hybrid vanadium oxide obtained by the solution preparation method of the amorphous organic hybrid vanadium oxide working electrode according to any one of claims 1 to 5, characterized in that, The amorphous organic hybrid vanadium oxide is an amorphous material containing vanadium, oxygen, carbon, and hydrogen.

9. The application of the amorphous organic hybrid vanadium oxyoxide working electrode obtained by the preparation method according to any one of claims 6 to 7 in an aqueous zinc-ion battery.

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