Amorphous organic hybrid vanadium oxide material and its preparation method and application

Abstract

The present invention belongs to the technical field of electrode materials for energy storage devices, and specifically relates to an amorphous organic hybrid vanadium oxide material, a preparation method thereof, and an application thereof. The present invention mixes an aqueous solution of hydrogen peroxide, an organic polyol solvent, and a vanadium oxide precursor material, and the obtained mixed solution is subjected to a solvent thermal reaction to obtain an amorphous organic hybrid vanadium oxide material. The amorphous organic hybrid vanadium oxide material prepared by the present invention has a high active site, a low metal ion diffusion energy barrier, and a stable vanadium oxide framework as an electrode material for an energy storage device, and can exhibit a high specific capacity, good rate capability, and long-term cycle stability. Moreover, the preparation method provided by the present invention is simple, has low environmental impact, and is low in cost, and can be industrialized and produced on a large scale.

Description

Technical Field

[0001] The present invention belongs to the technical field of zinc ion battery electrode materials, and in particular relates to an amorphous organic hybrid vanadium oxide material and a preparation method and application thereof. Background Art

[0002] Vanadium oxide (VO x ) materials have high theoretical capacity and high electrochemical stability and have been widely used as electrode materials in electrochemical energy storage devices. x As a battery electrode, it has a rich valence state (multiple valence states from +2 to +5), which means that multiple electron transfer can be achieved, achieving high capacity storage. x Has rich valence states, so VO x There are a large number of members in the family with different compositions, crystal structures and electrochemical properties. x Vanadium oxide nanostructures have diverse structures, chemical compositions, and electrochemical properties, offering tremendous potential for the development of emerging electrochemical energy storage technologies. While many researchers are dedicated to developing various vanadium oxide nanostructured electrode materials for energy storage devices, their inherent poor conductivity, unstable structure, and low ion diffusion coefficient during metal ion insertion / extraction inevitably disrupt charge transport pathways, leading to significant volume changes and rapid capacity decay after cycling.

[0003] The currently reported VO-based x Materials modification strategies consist of doping the crystal framework with metal ions or embedding structural water, which can neither fully accommodate the structural strain during metal ion insertion / extraction nor provide sufficient active sites for efficient charge storage.

[0004] In addition, vanadium oxide can improve the electrochemical performance of electrode materials after being combined with organic molecules such as polyaniline, poly (3,4-ethylenedioxythiophene), polypyrrole, ethylene glycol, and ethylenediamine. However, these composite materials are all based on crystalline VO x The framework still faces the problem that the embedding / de-embedding cycle of metal ions in its framework will lead to the destruction of its own structure and the generation of irreversible phases. Summary of the Invention

[0005] The purpose of the present invention is to provide an amorphous organic hybrid vanadium oxide material and its preparation method and application. The amorphous organic hybrid vanadium oxide material provided by the present invention is used as an electrode material for energy storage devices (such as aqueous zinc ion batteries), and has excellent electrochemical properties, showing high specific capacity, high rate capability, good reversibility and good long-term cycle stability.

[0006] In order to achieve the above object, the present invention provides the following technical solutions:

[0007] The present invention provides a method for preparing an amorphous organic hybrid vanadium oxide material, comprising the following steps:

[0008] An aqueous solution of hydrogen peroxide, an organic polyol solvent, and a vanadium oxide precursor material are mixed, and the resulting mixed solution is subjected to a solvothermal reaction to obtain an amorphous organic hybrid vanadium oxide material; the vanadium oxide precursor material includes vanadium oxide and / or vanadate; and the ratio of the mass of H2O2 in the aqueous solution of hydrogen peroxide to the volume of the organic polyol solvent is ≥0.3g:15mL.

[0009] Preferably, the organic polyol solvent includes one or more of ethylene glycol, glycerol, diethylene glycol and triethylene glycol.

[0010] Preferably, the vanadate comprises NH4VO3.

[0011] Preferably, the mass content of H2O2 in the aqueous hydrogen peroxide solution is 30%; the volume ratio of the aqueous hydrogen peroxide solution to the organic polyol solvent is (1-4):15.

[0012] Preferably, the ratio of the mass of the vanadium oxy precursor material to the volume of the organic polyol solvent is (3-24) g:1 L.

[0013] Preferably, the temperature of the solvent thermal reaction is 100 to 220° C., and the insulation time is 1 to 24 hours.

[0014] Preferably, the solvent thermal reaction obtains a solid product, and further comprises drying the solid product to obtain the amorphous organic hybrid vanadium oxide material; the drying temperature is 50 to 120° C., and the drying time is 6 to 24 hours.

[0015] The present invention provides an amorphous organic hybrid vanadium oxide material prepared by the preparation method described in the above technical solution. The amorphous organic hybrid vanadium oxide material is an amorphous material and contains vanadium, oxygen, carbon and hydrogen.

[0016] Preferably, the amorphous organic hybrid vanadium oxide material has a solid structure or a hollow structure.

[0017] The present invention provides the use of the amorphous organic hybrid vanadium oxide material described in the above technical solution in an electrode material for an energy storage device.

[0018] The present invention provides a method for preparing an amorphous organic hybrid vanadium oxide material, comprising the following steps: mixing an aqueous solution of hydrogen peroxide, an organic polyol solvent, and a vanadium oxide precursor material, and subjecting the obtained mixed solution to a solvothermal reaction to obtain an amorphous organic hybrid vanadium oxide material; the vanadium oxide precursor material comprises vanadium oxide and / or vanadate; and the ratio of the mass of H2O2 in the aqueous solution of hydrogen peroxide to the volume of the organic polyol solvent is ≥0.3g:15mL. The preparation method provided by the present invention uses an organic polyol solvent and a vanadium oxide precursor material as raw materials, conducts a solvothermal reaction in the presence of hydrogen peroxide, and successfully prepares an amorphous organic hybrid vanadium oxide material under the condition that the ratio of the mass of H2O2 in the aqueous solution of hydrogen peroxide to the volume of the organic polyol solvent is ≥0.3g:15mL. The amorphous organic hybrid vanadium oxide material prepared by the present invention is an amorphous material. Compared with the crystalline material, the amorphous material prepared by the present invention has more isotropic ion diffusion paths and a large number of vacancies, which is conducive to the rapid diffusion of ions and provides more ion reaction sites. At the same time, the structural change during the ion diffusion process is smaller than that of the crystal structure, which is conducive to cycle stability. At the same time, the present invention can reduce the interaction between metal ions and VO through organic hybridization. x The electrostatic interaction of the framework (VO) can also play a role in expanding the spacing between VO layers, thereby promoting the metal ions in VO x Diffusion in the bulk phase. In summary, the amorphous organic hybrid vanadium oxide material prepared by the present invention, as an electrode material for an energy storage device, has a high number of active sites, a low metal ion diffusion barrier, and a stable vanadium oxide framework, exhibiting a high specific capacity, good rate capability, and long-term cycle stability. Furthermore, the preparation method provided by the present invention is simple, has low environmental impact, and is low-cost, enabling industrial large-scale production.

[0019] The present invention provides an amorphous organic hybrid vanadium oxide material prepared by the preparation method described in the above technical solution. The amorphous organic hybrid vanadium oxide material is an amorphous material and contains vanadium, oxygen, carbon, and hydrogen. As an electrode material for an energy storage device, the amorphous organic hybrid vanadium oxide material provided by the present invention can provide more exposed ion channels and reduce the interaction between metal ions and the VOx framework, thereby accelerating rapid charge transfer at the electrode / electrolyte interface, promoting rapid ion intercalation, and achieving extremely fast charging performance. It also has a low diffusion energy barrier and excellent chemical stability. The structural changes of the amorphous material during ion diffusion are smaller than those of the crystalline structure, which contributes to cyclic stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 This is an optical photograph of an amorphous organic hybrid vanadium oxide material prepared using 2 mL of a 30% aqueous solution of hydrogen peroxide as a raw material in Example 1;

[0021] Figure 2 This is a scanning electron microscope image of an amorphous organic hybrid vanadium oxide material prepared using 2 mL of a 30% aqueous solution of hydrogen peroxide as a raw material in Example 1;

[0022] Figure 3 This is a transmission electron micrograph of an amorphous organic hybrid vanadium oxide material prepared using 2 mL of a 30% aqueous solution of hydrogen peroxide as a raw material in Example 1;

[0023] Figure 4 This is a high-resolution transmission electron microscopy image of an amorphous organic hybrid vanadium oxide material prepared using 2 mL of a 30% aqueous solution of hydrogen peroxide as a raw material in Example 1;

[0024] Figure 5 The scanning electron microscope images of the vanadium material prepared in Example 1 using 0 mL, 0.25 mL, 0.5 mL, 0.75 mL, 1 mL, and 1.5 mL of a 30% aqueous solution of hydrogen peroxide as a raw material;

[0025] Figure 6 XRD patterns of vanadium oxymaterials prepared using 0 mL, 0.25 mL, 0.5 mL, 0.75 mL, 1 mL, 1.5 mL, and 2 mL of a 30% aqueous solution of hydrogen peroxide as raw materials in Example 1;

[0026] Figure 7 FT-IR spectra of the vanadium oxymaterial prepared using 0 mL, 0.25 mL, 0.5 mL, 0.75 mL, 1 mL, 1.5 mL, and 2 mL of a 30% aqueous solution of hydrogen peroxide as a raw material in Example 1;

[0027] Figure 8 Thermogravimetric analysis of the vanadium material prepared in Example 1 using 0 mL, 0.25 mL, 0.5 mL, 0.75 mL, 1 mL, 1.5 mL, and 2 mL of a 30% aqueous solution of hydrogen peroxide as a raw material;

[0028] Figure 9 The scanning electron micrographs of the amorphous organic hybrid vanadium oxide materials obtained with the solvent thermal reaction times of 3 h, 6 h, 9 h, 12 h, and 15 h in Example 3 are shown;

[0029] Figure 10 The XRD patterns of the amorphous organic hybrid vanadyl materials obtained in Example 3 with solvent thermal reaction times of 3 h, 6 h, 9 h, 12 h, and 15 h, respectively;

[0030] Figure 11 The scanning electron microscope images of the amorphous organic hybrid vanadyl material obtained by the solvothermal reaction at temperatures of 120° C. and 160° C. in Example 2 are shown;

[0031] Figure 12 The XRD patterns of the amorphous organic hybrid vanadyl materials obtained by the solvothermal reaction at temperatures of 120° C. and 160° C. in Example 2 are shown;

[0032] Figure 13 FT-IR spectra of the amorphous organic hybrid vanadyl material obtained by the solvothermal reaction at temperatures of 120° C. and 160° C. in Example 2;

[0033] Figure 14 This is a scanning electron microscope image of a crystalline organic hybrid vanadyl material prepared using propylene glycol, diethylene glycol, and triethylene glycol as solvents in Example 4;

[0034] Figure 15 The XRD pattern of the crystalline organic hybrid vanadyl material prepared using propylene glycol, diethylene glycol and triethylene glycol as solvents in Example 4;

[0035] Figure 16 Scanning electron micrographs of samples prepared in Example 5 using mixed solvents of ethylene glycol:glycerol = 1:1, ethylene glycol:glycerol:diethylene glycol = 1:1:1, and ethylene glycol:glycerol:diethylene glycol:triethylene glycol = 1:1:1:1;

[0036] Figure 17 XRD patterns of samples prepared in Example 5 using mixed solvents of ethylene glycol:glycerol = 1:1, ethylene glycol:glycerol:diethylene glycol = 1:1:1, and ethylene glycol:glycerol:diethylene glycol:triethylene glycol = 1:1:1:1;

[0037] Figure 18 This is a diagram of the electrochemical properties of an amorphous organic hybrid vanadium oxide material prepared as a positive electrode material for an aqueous zinc ion battery using 2 mL of a 30% aqueous hydrogen peroxide solution as a raw material in Example 1. DETAILED DESCRIPTION

[0038] The present invention provides a method for preparing an amorphous organic hybrid vanadium oxide material, comprising the following steps:

[0039] An aqueous solution of hydrogen peroxide, an organic polyol solvent, and a vanadium oxide precursor material are mixed, and the resulting mixed solution is subjected to a solvothermal reaction to obtain an amorphous organic hybrid vanadium oxide material; the vanadium oxide precursor material includes vanadium oxide and / or vanadate; and the ratio of the mass of H2O2 in the aqueous solution of hydrogen peroxide to the volume of the organic polyol solvent is ≥0.3g:15mL.

[0040] In the present invention, unless otherwise specified, all preparation raw materials / components are commercially available products well known to those skilled in the art.

[0041] In the present invention, the mass content of H2O2 in the aqueous hydrogen peroxide solution is preferably 30%.

[0042] In the present invention, the organic polyol solvent preferably includes one or more of ethylene glycol (EG), glycerol (Gly), diethylene glycol (DG), and triethylene glycol (TEG). In a specific embodiment of the present invention, when the organic polyol solvent preferably includes two or more of ethylene glycol, glycerol, diethylene glycol, and triethylene glycol, the present invention preferably adopts an equal volume mixing method to obtain the organic polyol solvent.

[0043] In one or more embodiments of the present invention, the organic polyol solvent is ethylene glycol.

[0044] As one or more embodiments of the present invention, the organic polyol solvent is glycerol.

[0045] In one or more embodiments of the present invention, the organic polyol solvent is diethylene glycol.

[0046] As one or more embodiments of the present invention, the organic polyol solvent is triethylene glycol.

[0047] As one or more embodiments of the present invention, the organic polyol solvent is ethylene glycol and glycerol; the volume ratio of the ethylene glycol to glycerol is 1:1.

[0048] As one or more embodiments of the present invention, the organic polyol solvent is ethylene glycol, glycerol and diethylene glycol; the volume ratio of the ethylene glycol, glycerol and diethylene glycol is 1:1:1.

[0049] As one or more embodiments of the present invention, the organic polyol solvent is ethylene glycol, glycerol, diethylene glycol and triethylene glycol; the volume ratio of ethylene glycol, glycerol, diethylene glycol and triethylene glycol is 1:1:1:1.

[0050] In the present invention, the vanadate preferably includes NH4VO3.

[0051] In the present invention, the ratio of the mass of H2O2 in the aqueous solution of hydrogen peroxide to the volume of the organic polyol solvent is preferably (0.3-1.4) g:15 mL.

[0052] In the present invention, the mass content of H2O2 in the aqueous hydrogen peroxide solution is preferably 30%; the volume ratio of the aqueous hydrogen peroxide solution to the organic polyol solvent is preferably (1-4):15, specifically preferably 1:15, 1.5:15, 2:15, 2.5:15, 3:15, 3.5:15 or 4:15.

[0053] In the present invention, the ratio of the mass of the vanadium oxy precursor material to the volume of the organic polyol solvent is preferably (3-24) g:1 L, more preferably (3.5-23.5) g:1 L, and even more preferably (10-20) g:1 L. In a specific embodiment of the present invention, the vanadium oxy precursor material is preferably NH4VO3, and the ratio of the mass of NH4VO3 to the volume of the organic polyol solvent is preferably 15.6 g:1 L.

[0054] In the present invention, the method for mixing an aqueous hydrogen peroxide solution, an organic polyol solvent, and a vanadyl precursor material preferably includes: first stirring and mixing the aqueous hydrogen peroxide solution and the organic polyol solvent to obtain a first mixed solution; and second stirring and mixing the first mixed solution and the vanadyl precursor material to obtain a mixed solution. The first stirring is preferably performed at room temperature for 1 hour. The second stirring is preferably performed at room temperature for 1 hour.

[0055] In the present invention, the solvothermal reaction is preferably carried out in a stainless steel reactor, the inner lining of which is preferably polytetrafluoroethylene. In the present invention, the solvothermal reaction temperature is preferably 100-220°C, more preferably 120-200°C, and more preferably 120°C, 150°C, 160°C, 180°C, or 200°C; the holding time is preferably 1-20 hours, more preferably 1-15 hours, and more preferably 1 hour, 3 hours, 6 hours, 9 hours, 12 hours, and 15 hours.

[0056] In the present invention, after the solvothermal reaction is completed, a solvothermal reaction liquid is obtained. The present invention preferably performs solid-liquid separation on the solvothermal reaction liquid to obtain a solid product; the solid-liquid separation is preferably performed by filtration. To obtain the solid product, the present invention preferably further comprises drying the solid product to obtain the amorphous organic hybrid vanadyl material; the drying is preferably performed under vacuum; the drying temperature is preferably 50 to 120° C., more preferably 60 to 100° C., and the drying time is preferably 6 to 24 hours, more preferably 10 to 12 hours.

[0057] The amorphous organic hybrid vanadyl material prepared by the above-mentioned preparation method provided by the present invention has a solid structure or a hollow structure. In the present invention, the organic polyol solvent is preferably ethylene glycol, diethylene glycol, or triethylene glycol, and the temperature of the solvothermal reaction is preferably 200°C. The obtained amorphous organic hybrid vanadyl material has a hollow structure.

[0058] In a specific embodiment of the present invention, the mass content of H2O2 in the aqueous hydrogen peroxide solution is preferably 30%, the organic polyol solvent is preferably ethylene glycol, diethylene glycol or triethylene glycol, the volume ratio of the aqueous hydrogen peroxide solution to the organic polyol solvent is preferably 2:15, and the temperature of the solvent thermal reaction is 200°C, and the obtained amorphous organic hybrid vanadium oxide material has a hollow structure.

[0059] The present invention provides an amorphous organic hybrid vanadium oxide material prepared by the preparation method described in the above technical solution. The amorphous organic hybrid vanadium oxide material is an amorphous material and contains vanadium, oxygen, carbon and hydrogen.

[0060] The amorphous organic hybrid vanadium oxide material provided by the present invention is amorphous VO x Products chelated with organic polyol solvent molecules.

[0061] In the present invention, the amorphous organic hybrid vanadium oxide material is a solid structure or a hollow structure, and is a micro-nano sized particle.

[0062] The amorphous organic hybrid vanadium oxide material provided by the present invention can not only provide more exposed ion channels, but also reduce the interaction between metal ions and VO x This synergistic strategy can better accelerate the rapid charge transfer at the electrode / electrolyte interface, jointly promote fast ion intercalation, achieve extremely fast charging performance, and provide superior electrochemical stability.

[0063] The amorphous organic hybrid vanadium oxide material provided by the present invention has greatly improved electrochemical properties such as capacity, rate capability, and cycle stability compared with amorphous vanadium oxide materials (amorphous vanadium oxide materials).

[0064] The amorphous organic hybrid vanadium material provided by the present invention is x Compared with the composite of crystalline materials and organic compounds as the positive electrode material of aqueous zinc-ion batteries, there is no crystalline framework, which can effectively avoid the destruction of the structure and the generation of irreversible phases caused by the insertion / extraction cycle of metal ions in the crystal framework, thereby greatly improving the electrochemical performance such as capacity, rate capability, and cycle stability.

[0065] The present invention provides the use of the amorphous organic hybrid vanadium oxide material described in the above technical solution in an electrode material for an energy storage device.

[0066] In the present invention, the energy storage device includes an ion battery such as a zinc ion battery, a lithium ion battery, a sodium ion battery, a potassium ion battery, a magnesium ion battery, an aluminum ion battery, or a calcium ion battery. The ion battery is preferably an aqueous zinc ion battery. The electrode material of the aqueous zinc ion battery is preferably a positive electrode material.

[0067] The present invention provides an electrode material for an energy storage device, comprising the amorphous organic hybrid vanadium oxide material described in the above technical solution, a conductive agent, and a binder; the mass ratio of the amorphous organic hybrid vanadium oxide material, the conductive agent, and the binder described in the above technical solution is 7:2:1. The conductive agent is preferably carbon black Super-P. The binder is preferably polyvinylidene fluoride (PVDF).

[0068] The present invention has no special requirements on the specific implementation of the application 。

[0069] In order to further illustrate the present invention, the technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0070] Example 1

[0071] (1) Dissolve 0 mL, 0.25 mL, 0.5 mL, 0.75 mL, 1 mL, 1.5 mL, and 2 mL of a 30% hydrogen peroxide solution in 15 mL of ethylene glycol solvent and stir for 1 h until uniformly mixed.

[0072] (2) Add 2 mmol of NH4VO3 to the mixed solution obtained in step (1) and stir at room temperature for 1 h to completely dissolve NH4VO3.

[0073] (3) The mixed solution obtained in step (2) was added to the polytetrafluoroethylene lining of a 25 mL stainless steel reactor, which was sealed and placed in an oven at a reaction temperature of 200° C. for 1 h to perform a solvothermal reaction.

[0074] (4) After the solvent thermal reaction is completed and cooled naturally, the reaction liquid is taken out, and the obtained precipitate is repeatedly washed with water and ethanol until the impurities are removed, and then dried in a vacuum oven at 80°C for 12 hours.

[0075] Figure 1 This is an optical photograph of an amorphous organic hybrid vanadium oxide material prepared using 2 mL of a 30% aqueous solution of hydrogen peroxide as a raw material in Example 1. Figure 1 It can be concluded that the amorphous organic hybrid vanadium oxide material prepared in Example 1 using 2 mL of a 30% aqueous solution of hydrogen peroxide as a raw material is in powder form.

[0076] Figure 2 This is a scanning electron microscope image of an amorphous organic hybrid vanadium oxide material prepared using 2 mL of a 30% aqueous solution of hydrogen peroxide as a raw material in Example 1. Figure 2 As can be seen from the left figure, the amorphous organic hybrid vanadium oxide material prepared by using 2 mL of 30% hydrogen peroxide aqueous solution as a raw material is a micro-nano particle with uniform particle size distribution; Figure 2 As shown in the right figure, the amorphous organic hybrid vanadium oxide material prepared in Example 1 using 2 mL of a 30% hydrogen peroxide aqueous solution and ethylene glycol solvent as raw materials at 200° C. has a hollow structure.

[0077] Figure 3 This is a transmission electron microscope image of an amorphous organic hybrid vanadium oxide material prepared using 2 mL of a 30% aqueous solution of hydrogen peroxide as a raw material in Example 1. Figure 4 This is a high-resolution transmission electron microscope image of the amorphous organic hybrid vanadium oxide material prepared using 2 mL of a 30% aqueous solution of hydrogen peroxide as a raw material in Example 1. Figure 3 and Figure 4 It can also be concluded that the amorphous organic hybrid vanadium oxide material prepared in Example 1 using 2 mL of 30% hydrogen peroxide aqueous solution and ethylene glycol solvent as raw materials at 200° C. has a hollow structure.

[0078] Figure 5 These are scanning electron microscope images of vanadium oxymaterials prepared using 0 mL, 0.25 mL, 0.5 mL, 0.75 mL, 1 mL, and 1.5 mL of a 30% aqueous solution of hydrogen peroxide as a raw material in Example 1. Figure 6 The XRD patterns of the vanadium oxymaterials prepared using 0 mL, 0.25 mL, 0.5 mL, 0.75 mL, 1 mL, 1.5 mL, and 2 mL of a 30% aqueous solution of hydrogen peroxide as raw materials in Example 1 are as follows; Figure 5 and Figure 6 It can be seen that when the amount of the 30% aqueous solution of hydrogen peroxide in Example 1 is 0 mL, 0.25 mL, 0.5 mL, and 0.75 mL, the prepared vanadium oxymaterial product is a crystalline product, and when the amount of the 30% aqueous solution of hydrogen peroxide is 1 mL, 1.5 mL, and 2 mL, the prepared vanadium oxymaterial product is an amorphous product.

[0079] Figure 7 The FT-IR spectra of the vanadium oxymaterial prepared in Example 1 using 0 mL, 0.25 mL, 0.5 mL, 0.75 mL, 1 mL, 1.5 mL, and 2 mL of 30% aqueous hydrogen peroxide solution as raw materials. Figure 7 As the amount of hydrogen peroxide solution increases, the peaks associated with the V-O and V-O-V bonds gradually red-shift and broaden. This phenomenon is particularly pronounced when the amount of hydrogen peroxide solution used is ≥1 mL. Notably, the vanadium oxycarbon material product (AO-HVO sample) obtained when the amount of hydrogen peroxide solution used is ≥1 mL still exhibits vibrations associated with the ethylene glycol organic ligand, confirming that the vanadium oxycarbon material prepared by the present invention is an amorphous organic hybrid vanadium oxide material.

[0080] Figure 8The thermogravimetric analysis spectrum of the vanadium material prepared in Example 1 using 0 mL, 0.25 mL, 0.5 mL, 0.75 mL, 1 mL, 1.5 mL, and 2 mL of 30% hydrogen peroxide aqueous solution as raw materials. Figure 8 Able to verify Figure 6 According to the XRD pattern results, when the amount of the 30% hydrogen peroxide aqueous solution in Example 1 is 0 mL, 0.25 mL, 0.5 mL, and 0.75 mL, the prepared vanadium material product is a crystalline product, and there is a relatively obvious sharp single weight loss peak in the thermogravimetric analysis spectrum, which is consistent with the crystalline product; when the amount of the 30% hydrogen peroxide aqueous solution is 1 mL, 1.5 mL, and 2 mL, the prepared vanadium material product is an amorphous product, and the weight loss peak in the thermogravimetric analysis spectrum is relatively gentle, and the weight loss temperature range is wide, which is consistent with the amorphous product.

[0081] Example 2

[0082] (1) Dissolve 2 mL of 30% hydrogen peroxide aqueous solution in 15 mL of ethylene glycol solvent and stir for 1 h until uniformly mixed.

[0083] (2) Add 2 mmol of NH4VO3 to the mixed solution obtained in step (1) and stir at room temperature for 1 h to completely dissolve NH4VO3.

[0084] (3) The mixed solution obtained in step (2) was added to the polytetrafluoroethylene liner of a 25 mL stainless steel reactor, which was sealed and placed in an oven, and maintained at reaction temperatures of 120° C., 160° C., and 200° C. for 12 h, respectively, to carry out a solvothermal reaction.

[0085] (4) After the solvent thermal reaction is completed and cooled naturally, the reaction liquid is taken out, and the obtained precipitate is repeatedly washed with water and ethanol until the impurities are removed, and then dried in a vacuum oven at 80°C for 12 hours.

[0086] Figure 11 The scanning electron micrographs of the amorphous organic hybrid vanadium oxide material obtained by the solvothermal reaction at temperatures of 120°C (left) and 160°C (right) in Example 2 are shown; Figure 12 The XRD patterns of the amorphous organic hybrid vanadyl materials obtained by the solvothermal reaction at temperatures of 120° C. and 160° C. in Example 2 are shown; Figure 13 FT-IR spectra of the amorphous organic hybrid vanadyl material obtained by the solvent thermal reaction at temperatures of 120°C and 160°C in Example 2; Figures 11-13 It can be seen that the morphology of the product obtained by reacting at 120°C and 160°C in Example 2 is granular and amorphous. The FT-IR spectrum of the product contains absorption peaks of VOV, V=O, COV, CH, CHO and OH, indicating the presence of organic hybridization.

[0087] Example 3

[0088] (1) Dissolve 2 mL of 30% hydrogen peroxide aqueous solution in 15 mL of ethylene glycol solvent and stir for 1 h until uniformly mixed.

[0089] (2) Add 2 mmol of NH4VO3 to the mixed solution obtained in step (1) and stir at room temperature for 1 h to completely dissolve NH4VO3.

[0090] (3) The mixed solution obtained in step (2) was added to the polytetrafluoroethylene liner of a 25 mL stainless steel reactor, which was sealed and placed in an oven, and maintained at a reaction temperature of 200° C. for 1 h, 3 h, 6 h, 9 h, 12 h, and 15 h, respectively, to carry out a solvothermal reaction.

[0091] (4) After the solvent thermal reaction is completed and cooled naturally, the reaction liquid is taken out, and the obtained precipitate is repeatedly washed with water and ethanol until the impurities are removed, and then dried in a vacuum oven at 80°C for 12 hours.

[0092] Figure 9 The solvent thermal reaction time in Example 3 is 3h( Figure 9 (a) in), 6h( Figure 9 (b) in), 9h( Figure 9 (c) in), 12h( Figure 9 (d)), 15h( Figure 9 Scanning electron microscope image of the amorphous organic hybrid vanadium material obtained in (e)); Figure 10 The solvent thermal reaction time in Example 3 is 3h( Figure 9 (a) in), 6h( Figure 9 (b) in), 9h( Figure 9 (c) in), 12h( Figure 9 (d)), 15h( Figure 9 The XRD pattern of the amorphous organic hybrid vanadium material obtained by (e)); Figure 9 and Figure 10 It can be seen that: with the extension of the solvent thermal reaction time, the morphology and XRD characterization structure of the product do not change significantly, that is, after the reaction solvent thermal insulation is carried out for 1 hour, the amorphous organic hybrid vanadium oxide material is generated.

[0093] Example 4

[0094] (1) Dissolve 2 mL of 30% H2O2 aqueous solution in 15 mL of ethylene glycol, 15 mL of glycerol, 15 mL of diethylene glycol, and 15 mL of triethylene glycol, respectively, and stir for 1 h until uniformly mixed.

[0095] (2) Add 2 mmol of NH4VO3 to the mixed solution obtained in step (1) and stir at room temperature for 1 h to completely dissolve NH4VO3.

[0096] (3) The mixed solution obtained in step (2) was added to the polytetrafluoroethylene liner of a 25 mL stainless steel reactor, which was sealed and placed in an oven at a reaction temperature of 200° C. for 12 h to perform a solvothermal reaction.

[0097] (4) After the solvent thermal reaction is completed and cooled naturally, the reaction liquid is taken out, and the obtained precipitate is repeatedly washed with water and ethanol until the impurities are removed, and then dried in a vacuum oven at 80°C for 12 hours.

[0098] Figure 14 For Example 4, glycerol ( Figure 14 (a) in), diethylene glycol ( Figure 14 (b)) and triethylene glycol ( Figure 14 (c)) is a scanning electron microscope image of the product prepared by solvent. Figure 14 It can be seen that: this embodiment uses diethylene glycol ( Figure 14 (b)) and triethylene glycol ( Figure 14 (c)) as the reaction solvent, at 200 ° C, 2 mL of 30% H2O2 hydrogen peroxide aqueous solution under the conditions of solvothermal reaction for 12 hours, the obtained organic hybrid vanadium oxide material product is a hollow structure.

[0099] Figure 15 The XRD pattern of the organic hybrid vanadium oxide material prepared using propylene glycol, diethylene glycol and triethylene glycol as solvents in Example 4 is shown in FIG. Figure 15 It can be seen that the product prepared in this embodiment using propylene glycol, diethylene glycol and triethylene glycol as solvents is mainly in an amorphous state.

[0100] Example 5

[0101] (1) Dissolve 2 mL of 30% aqueous hydrogen peroxide solution in 15 mL of a mixed solvent of ethylene glycol and glycerol (the volume ratio of ethylene glycol and glycerol is 1:1), 15 mL of a mixed solvent of ethylene glycol, glycerol and diethylene glycol (the volume ratio of ethylene glycol, glycerol and diethylene glycol is 1:1:1), and 15 mL of a mixed solvent of ethylene glycol, glycerol, diethylene glycol and triethylene glycol (the volume ratio of ethylene glycol, glycerol, diethylene glycol and triethylene glycol is 1:1:1:1) and stir for 1 h until uniformly mixed.

[0102] (2) Add 2 mmol of NH4VO3 to the mixed solution obtained in step (1) and stir at room temperature for 1 h to completely dissolve NH4VO3.

[0103] (3) The mixed solution obtained in step (2) was added to the polytetrafluoroethylene liner of a 25 mL stainless steel reactor, which was sealed and placed in an oven, and maintained at a reaction temperature of 200° C. for 12 h for a solvothermal reaction.

[0104] (4) After the solvent thermal reaction is completed and cooled naturally, the reaction liquid is taken out, and the obtained precipitate is repeatedly washed with water and ethanol until the impurities are removed, and then dried in a vacuum oven at 80°C for 12 hours.

[0105] Figure 16 The scanning electron microscope images of the samples prepared in Example 5 using mixed solvents of ethylene glycol: glycerol = 1:1, ethylene glycol: glycerol: diethylene glycol = 1:1:1 and ethylene glycol: glycerol: diethylene glycol: triethylene glycol = 1:1:1:1; Figure 16 It can be seen that the product prepared by using the mixed solvent in this embodiment is in granular form. Figure 17 The XRD patterns of the samples prepared in Example 5 using mixed solvents of ethylene glycol: glycerol = 1:1, ethylene glycol: glycerol: diethylene glycol = 1:1:1 and ethylene glycol: glycerol: diethylene glycol: triethylene glycol = 1:1:1:1; Figure 17 It can be seen that the product prepared by using the mixed solvent in this embodiment is amorphous.

[0106] Application Example 1

[0107] The amorphous organic hybrid vanadium oxide material prepared in Example 1 using 2 mL of a 30% aqueous solution of hydrogen peroxide as a raw material, superP and polyvinylidene fluoride (PVDF) were mixed evenly in N-methylpyrrolidone (NMP) in a mass ratio of 7:2:1 to form a slurry. The slurry was then evenly coated on a titanium mesh as a positive electrode, glass fiber was used as a separator, 3M Zn(CF3SO3)2 was used as an electrolyte, and the battery was packaged in a CR2032 battery case to prepare an aqueous zinc ion battery.

[0108] The electrochemical performance test of aqueous zinc ion battery was carried out according to the encapsulated aqueous zinc ion battery of Example 1. Figure 18 This is a diagram of the electrochemical properties of an amorphous organic hybrid vanadium oxide material prepared as a positive electrode material for an aqueous zinc ion battery using 2 mL of a 30% hydrogen peroxide aqueous solution as a raw material in Example 1. Figure 18 a in the figure indicates that the amorphous organic hybrid vanadium oxide material prepared in Example 1 has the advantages of high specific capacity and high rate capability as a positive electrode material for aqueous zinc ion batteries; Figure 18 b is the charge-discharge curve of the amorphous organic hybrid vanadium oxide material prepared in Example 1 as the positive electrode material of the aqueous zinc ion battery, indicating its good reversibility; Figure 18 c in the figure is the long cycle characterization of the amorphous organic hybrid vanadium oxide material prepared in Example 1 as a positive electrode material for aqueous zinc ion batteries, indicating that it has good stability during long-term cycles exceeding 25,000 times; Figure 18 d in the figure is the cyclic voltammetry curve of the amorphous organic hybrid vanadium oxide material prepared in Example 1 as the positive electrode material of the aqueous zinc ion battery, indicating that during the charge and discharge process, V undergoes a valence conversion from +3 to +5, with good reversibility.

[0109] In summary, the preparation method of the amorphous organic hybrid vanadium oxide material provided by the present invention is as follows: adding an aqueous solution of hydrogen peroxide (30% H2O2) to an organic polyol solvent, and then x ) or vanadate is added to the above-mentioned solvent to form a uniform mixed solution, and then the mixed solution is subjected to a solvothermal reaction to obtain an amorphous organic hybrid vanadium oxide nanomaterial. This material is used as an electrode material for an energy storage device, which has high active sites, low metal ion diffusion energy barrier, and a stable vanadium oxide framework. Therefore, the amorphous organic hybrid vanadium oxide nanomaterial as an electrode material exhibits high specific capacity, good rate performance and long-term cycle stability. The preparation method provided by the present invention is simple, has low environmental impact, is low cost, and can be industrialized and produced on a large scale.

[0110] Although the above embodiment provides a detailed description of the present invention, it is only a part of the embodiments of the present invention, not all of the embodiments. Other embodiments can be obtained based on this embodiment without creativity, and these embodiments all fall within the scope of protection of the present invention.

Claims

1. A method for preparing an amorphous organic hybrid vanadyl material, characterized in that: The following steps are involved: An aqueous solution of hydrogen peroxide, an organic polyol solvent, and a vanadyl precursor material are mixed, and the resulting mixed solution is subjected to a solvothermal reaction to obtain an amorphous organic hybrid vanadyl material; the vanadyl precursor material comprises vanadium oxide and / or vanadate; and the ratio of the mass of H2O2 in the aqueous solution of hydrogen peroxide to the volume of the organic polyol solvent is ≥0.3g:15mL; The amorphous organic hybrid vanadium oxide material is amorphous VO x Products chelated with organic polyol solvent molecules; The amorphous organic hybrid vanadium oxide material is a hollow structure and micro-nano sized particles.

2. The preparation method according to claim 1, characterized in that The organic polyol solvent includes one or more of ethylene glycol, glycerol, diethylene glycol and triethylene glycol.

3. The preparation method according to claim 1, characterized in that The vanadate includes NH4VO3.

4. The preparation method according to claim 1 or 2, characterized in that The mass content of H2O2 in the hydrogen peroxide aqueous solution is 30%; the volume ratio of the hydrogen peroxide aqueous solution to the organic polyol solvent is (1-4):

15.

5. The preparation method according to any one of claims 1 to 3, characterized in that The ratio of the mass of the vanadium oxy precursor material to the volume of the organic polyol solvent is (3-24) g:1 L.

6. The preparation method according to claim 1, characterized in that The temperature of the solvent thermal reaction is 100 to 220° C., and the insulation time is 1 to 24 hours.

7. The preparation method according to claim 1 or 6, characterized in that The solvent thermal reaction obtains a solid product, and further comprises drying the solid product to obtain the amorphous organic hybrid vanadium oxide material; the drying temperature is 50 to 120° C., and the drying time is 6 to 24 hours.

8. The amorphous organic hybrid vanadyl material prepared by the preparation method according to any one of claims 1 to 7, characterized in that: The amorphous organic hybrid vanadium oxide material is an amorphous material, and the amorphous organic hybrid vanadium oxide material contains vanadium, oxygen, carbon and hydrogen; The amorphous organic hybrid vanadium oxide material is amorphous VO x Products chelated with organic polyol solvent molecules; The amorphous organic hybrid vanadium oxide material is a hollow structure and micro-nano sized particles.

9. Use of the amorphous organic hybrid vanadium oxide material according to claim 8 in an electrode material for an energy storage device.

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