Preparation and application of mixed molecular embedded near-layered organic hybrid vanadium oxide materials

Abstract

The present invention relates to the preparation and application of a near-layered organic hybrid vanadium oxymaterial embedded with mixed molecules. The process comprises the following steps: 1) thoroughly stirring an aqueous solution and an organic polyol mixed solvent at a volume ratio of 11 mL:6 mL, adding a vanadium oxy precursor material to the resulting solution, and then further stirring to obtain a mixed solution; 2) conducting a solvothermal reaction of the mixed solution in a stainless steel reactor; and 3) after the solvothermal reaction is completed and naturally cooled, centrifuging to remove impurities, followed by drying in an oven to obtain the near-layered organic hybrid vanadium oxymaterial embedded with mixed molecules. As an electrode material for energy storage devices, the material exhibits an ordered-disordered hybrid structure with a high number of exposed active sites, demonstrating high specific capacity, good rate capability, and long-term cycling stability.

Description

Technical Field

[0001] The invention relates to the preparation and application of a mixed molecule embedded near-layered organic hybrid vanadium oxide material, belonging to the technical field of zinc ion battery electrode materials. Background Art

[0002] Electrochemical energy storage systems, due to their green and efficient characteristics, are considered a crucial component in achieving dual carbon emissions. However, the widespread use of lithium-ion batteries is limited in large-scale production due to the increasing scarcity of lithium resources and the safety risks associated with their organic electrolytes. Consequently, green, safe, and highly conductive aqueous metal-ion batteries (such as sodium, manganese, aluminum, and zinc) are gaining increasing attention.

[0003] Among various electrode materials, vanadium oxides, the materials used in vanadium-based positive electrodes, hold great promise for battery applications due to their structural stability and high theoretical capacity. Vanadium, a highly active element with a wide range of valence states, is inexpensive and abundant. Its compounds exhibit strong metal ion storage capacity, possess high theoretical specific capacity and discharge voltage platforms, and possess diverse crystal structures, making vanadium-based oxides the most promising electrode materials.

[0004] Traditional layered materials possess weak van der Waals interactions between layers, while possessing strong in-plane chemical bonds that promote in-plane extension. This provides unobstructed pathways for accommodating foreign ions, particularly multivalent metal ions or hydrated ions with large radii. However, the strong electrostatic interaction of metal ions in vanadium oxide materials limits their cyclability, leading to dissolution of the electrode material during charge and discharge, and long-term accumulation leading to phase transitions.

[0005] Currently reported optimization strategies for vanadium oxide materials include metal ion doping and water intercalation strategies. In addition, vanadium oxide is compounded with organic molecules such as polyaniline, ethylene glycol, and ethylenediamine to improve the electrochemical performance of electrode materials. However, it still faces the problem of irreversible phase transition during the cycle of metal ion embedding and extraction in its framework. Summary of the Invention

[0006] The present invention aims to provide the preparation and application of a mixed molecule embedded near-layered organic hybrid vanadium oxide material. The method utilizes a mixed solvent of ethylene glycol and propylene glycol to co-intercalate a vanadium oxide precursor to construct a stable mixed molecule embedded near-layered organic hybrid vanadium oxide material. The mixed molecule embedded near-layered organic hybrid vanadium oxide material, as a positive electrode material for an energy storage device (such as an aqueous zinc ion battery), has excellent electrochemical properties, specifically exhibiting excellent rate performance, high specific capacity, good reversibility, and long-term cycle stability.

[0007] To achieve the above-mentioned purpose, the technical solution of the present invention is achieved as follows: the preparation of a near-layered organic hybrid vanadium oxide material embedded with mixed molecules is characterized in that it comprises the following steps: 1) adding a vanadium oxide precursor material to a solution obtained by fully stirring an aqueous solution and an organic polyol mixed solvent in a volume ratio of 11 mL: 6 mL, and then fully stirring again. The stirring temperature is room temperature and the time is 12 h to 48 h, preferably 12 h, to obtain a mixed solution; 2) performing a solvent thermal reaction of the mixed solution in a stainless steel reactor, the inner lining of the stainless steel reactor is preferably a polytetrafluoroethylene material, the solvent thermal reaction temperature is 180 ℃ to 210 ℃, preferably 205 ℃; the holding time is 24 h to 48 h, preferably 36 h; 3) after the solvent thermal reaction is completed and naturally cooled, taking out the reaction liquid, repeatedly washing the precipitate obtained by centrifugation with ethanol until impurities are removed, and drying in an oven at a drying temperature of 60 ℃ to 100 ℃, preferably 80 ℃; and the time is 12 h to 48 h, preferably 24 h, obtaining a near-layered organic hybrid vanadium oxide material embedded with the mixed molecules.

[0008] The organic polyol mixed solvent includes one or both of ethylene glycol and glycerol.

[0009] The vanadium oxide precursor material is vanadium oxide or vanadate, wherein the vanadium oxide includes commercial V2O5, and the vanadate includes NH4VO3.

[0010] The volume ratio of the organic polyol mixed solvent, ethylene glycol to glycerol, is 1-4:2.

[0011] The molar mass ratio of the vanadium oxy precursor material in the mixed solution is 0.1176 mol / L.

[0012] The near-layered organic hybrid vanadium-oxygen material embedded with the mixed molecules contains vanadium, oxygen, carbon and hydrogen.

[0013] The near-layered organic hybrid vanadium oxide material in which the mixed molecules are embedded is a spherical structure of nanosheet stacking.

[0014] The application of the mixed molecule embedded near-layered organic hybrid vanadium oxide material in electrode materials of energy storage devices.

[0015] The energy storage device is preferably an aqueous zinc ion battery, and the electrode material is preferably a positive electrode material.

[0016] The electrode material of the energy storage device includes a near-layered organic hybrid vanadium oxide material embedded with mixed molecules, a conductive agent and a binder; the mass ratio of the near-layered organic hybrid vanadium oxide material embedded with mixed molecules, the conductive agent and the binder is 7:2:1; the conductive agent is carbon black Super-p, and the binder is polyvinylidene fluoride (PVDF).

[0017] The positive effect of the present invention is that a solvent thermal reaction is carried out under aqueous solution conditions using an organic polyol mixed solvent and a vanadium oxide precursor material as raw materials, and a near-layered organic hybrid vanadium oxide material with mixed molecules embedded is successfully prepared under the condition that the volume ratio of the aqueous solution to the organic alcohol mixed solvent is 11 mL:6 mL; the near-layered organic hybrid vanadium oxide material with mixed molecules embedded is used as an electrode material for an energy storage device, and has an ordered-disordered hybrid structure, which not only retains the ordered layered structure, but also exposes more active sites due to the disordered structure, thereby achieving faster ion diffusion. In addition, the organic hybridization can reduce the electrostatic force between the metal ions and the framework, and can also effectively expand the interlayer distance, thereby constructing a more stable structure. In terms of electrochemical performance, it exhibits a high specific capacity, good rate capability and long-term cycle stability.

[0018] Comparison of specific capacity, rate capability and cycle stability with several other typical vanadium-based cathode materials:

[0019] . BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 This is a scanning electron microscope image of a near-layered organic hybrid vanadium oxide material embedded with mixed molecules prepared in Example 1 using a mixed solvent of ethylene glycol and glycerol in a volume ratio of 2:1 as the raw material.

[0021] Figure 2 Scanning electron microscope images of the mixed molecular embedded near-layered organic hybrid vanadium oxide material prepared in Example 1 using a mixed solvent of ethylene glycol and glycerol with a volume ratio of 6:0, 1:1, 1:2, and 0:6 as the raw material.

[0022] Figure 3 XRD patterns of the mixed molecular embedded near-layered organic hybrid vanadium oxide material prepared in Example 1 using a mixed solvent of ethylene glycol and glycerol with a volume ratio of 6:0, 2:1, 1:1, 1:2, and 0:6 as the raw material.

[0023] Figure 4 FT-IR spectra of the mixed molecular embedded near-layered organic hybrid vanadium oxide material prepared in Example 1 using a mixed solvent of ethylene glycol and glycerol with a volume ratio of 6:0, 2:1, 1:1, 1:2, and 0:6 as the raw material.

[0024] Figure 5 This is a transmission electron micrograph of the near-layered organic hybrid vanadium oxide material embedded with mixed molecules obtained when the solvothermal time was 36 h in Example 2.

[0025] Figure 6This is a high-resolution transmission electron microscopy image of the near-layered organic hybrid vanadium oxide material embedded with mixed molecules obtained when the solvothermal time was 36 h in Example 2.

[0026] Figure 7 The XRD patterns of the near-layered organic hybrid vanadium oxide material with mixed molecules embedded therein obtained when the solvent thermal time was 24 h, 36 h, and 48 h in Example 2.

[0027] Figure 8 FT-IR spectra of the near-layered organic hybrid vanadium oxide material with mixed molecules embedded therein obtained when the solvent thermal time was 24 h, 36 h, and 48 h in Example 2.

[0028] Figure 9 This is a graph showing the charge and discharge rate properties of a mixed molecule embedded near-layered organic hybrid vanadium oxide material prepared in Example 1 using a mixed solvent of ethylene glycol and glycerol with a volume ratio of 2:1 and a solvothermal time of 36 h as the raw material.

[0029] Figure 10 This is a constant current charge-discharge curve of the mixed molecule embedded near-layered organic hybrid vanadium oxide material prepared as raw material using a mixed solvent of ethylene glycol and glycerol with a volume ratio of 2:1 and a solvothermal time of 36 h in Example 1.

[0030] Figure 11 This is a long-cycle property diagram of the mixed molecule embedded near-layered organic hybrid vanadium oxide material prepared as raw material using a mixed solvent of ethylene glycol and glycerol with a volume ratio of 2:1 and a solvothermal time of 36 h in Example 1.

[0031] Figure 12 The cyclic voltammetry curve of the mixed molecular embedded near-layered organic hybrid vanadium oxide material prepared in Example 1 using a mixed solvent of ethylene glycol and glycerol with a volume ratio of 2:1 and a solvothermal time of 36 h as the raw material. DETAILED DESCRIPTION

[0032] The present invention will be further described below with reference to the accompanying drawings and embodiments: Figure 1-12As shown, the preparation of a near-layered organic hybrid vanadium oxide material embedded with mixed molecules is characterized by comprising the following steps: 1) adding a vanadium oxide precursor material to a solution obtained by fully stirring an aqueous solution and an organic polyol mixed solvent in a volume ratio of 11 mL:6 mL, and mixing the solution, and then fully stirring again. The stirring temperature is room temperature and the time is 12 h to 48 h, preferably 12 h, to obtain a mixed solution; 2) conducting a solvothermal reaction of the mixed solution in a stainless steel reactor, the inner lining of the stainless steel reactor is preferably a polytetrafluoroethylene material, the solvothermal reaction temperature is 180 ℃ to 210 ℃, preferably 205 ℃; the holding time is 24 h to 48 h, preferably 36 h; 3) after the solvothermal reaction is completed and naturally cooled, removing the reaction liquid, and repeatedly washing the precipitate obtained by centrifugation with ethanol until impurities are removed, and drying in an oven at a drying temperature of 60 ℃ to 100 ℃, preferably 80 ℃; for 12 h to 48 h, preferably 24 h, to obtain the near-layered organic hybrid vanadium oxide material embedded with the mixed molecules.

[0033] The organic polyol mixed solvent includes one or both of ethylene glycol and glycerol.

[0034] The vanadium oxides include commercial V2O 5， Vanadates include NH4VO3.

[0035] The volume ratio of ethylene glycol to glycerol in the organic polyol mixed solvent is 1 to 4:2; preferably 2:1, 1:1, and 1:2.

[0036] The molar mass ratio of the vanadium oxy precursor material in the mixed solution is 0.1176 mol / L.

[0037] The near-layered organic hybrid vanadium-oxygen material embedded with the mixed molecules contains vanadium, oxygen, carbon and hydrogen.

[0038] The near-layered organic hybrid vanadium oxide material in which the mixed molecules are embedded is a spherical structure of nanosheet stacking.

[0039] The application of the mixed molecule embedded near-layered organic hybrid vanadium oxide material in electrode materials of energy storage devices.

[0040] The energy storage device is preferably an aqueous zinc ion battery, and the electrode material is preferably a positive electrode material.

[0041] The electrode material of the energy storage device includes a near-layered organic hybrid vanadium oxide material embedded with mixed molecules, a conductive agent and a binder; the mass ratio of the near-layered organic hybrid vanadium oxide material embedded with mixed molecules, the conductive agent and the binder is 7:2:1; the conductive agent is carbon black Super-p, and the binder is polyvinylidene fluoride (PVDF).

[0042] Hybrid molecularly embedded near-layered organic hybrid vanadium oxide materials, used as electrode materials for energy storage devices, exhibit an ordered-disordered hybrid structure. This structure retains the ordered layered structure while exposing more active sites due to the disordered structure, enabling faster ion diffusion. Furthermore, the organic hybridization of the present invention reduces the electrostatic forces between metal ions and the framework and effectively expands the interlayer spacing, thereby creating a more stable structure. The electrochemical performance exhibits high specific capacity, good rate capability, and long-term cycling stability.

[0043] In order to further illustrate the present invention, the technical solution provided by the present invention is described in detail below in conjunction with embodiments. Example 1

[0044] Mix 6 mL of ethylene glycol and glycerol mixed solvent with 0 mL, 4 mL with 2 mL, 3 mL with 3 mL, 2 mL with 4 mL, and 0 mL with 6 mL with 11 mL of aqueous solution.

[0045] Add 0.234 g of NH4VO3 to the 5 mixed solutions in step (1) and stir until completely mixed to form a uniform solution.

[0046] The five mixed solutions obtained in step (2) were added to the polytetrafluoroethylene liner of a 17 mL stainless steel reactor, which was sealed and placed in an oven at a reaction temperature of 205 °C for 24 h to carry out a solvothermal reaction.

[0047] After the solvent thermal reaction was completed and cooled naturally, the reaction liquid was taken out, and the obtained precipitate was repeatedly washed with ethanol until the impurities were removed, and then dried in an oven at 80 °C for 24 h.

[0048] Figure 1 This is a scanning electron microscope image of a near-layered organic hybrid vanadium oxide material embedded with mixed molecules prepared in Example 1 using a mixed solvent of ethylene glycol and glycerol at a volume ratio of 2:1 as a raw material. Figure 2 Figures a, b, c, and d are scanning electron micrographs of the mixed molecular embedded near-layered organic hybrid vanadium oxide material prepared in Example 1 using a mixed solvent of ethylene glycol and glycerol at a volume ratio of 6:0, 1:1, 1:2, and 0:6 as raw materials. Figure 1 and Figure 2 From a, b, c, and d, it can be seen that the mixed molecular embedded near-layered organic hybrid vanadium oxide material prepared in Example 1 using a mixed solvent of ethylene glycol and glycerol with a volume ratio of 6:0, 2:1, 1:1, 1:2, and 0:6 as the raw material has a spherical structure with lamellar stacking.

[0049] Figure 3The XRD patterns of the mixed molecular embedded near-layered organic hybrid vanadium oxide material prepared in Example 1 using a mixed solvent of ethylene glycol and glycerol with a volume ratio of 6:0, 2:1, 1:1, 1:2, and 0:6 as raw materials. Figure 3 It can be seen that the organic hybrid vanadium oxide material prepared in Example 1 using a mixed solvent of ethylene glycol and glycerol with a volume ratio of 6:0 as the raw material is in a crystalline state, and the organic hybrid vanadium oxide material prepared in Example 1 using a mixed solvent of ethylene glycol and glycerol with a volume ratio of 2:1, 1:1, 1:2, and 0:6 as the raw material has an ordered-disordered mixed structure.

[0050] Figure 4 The FT-IR spectra of the mixed molecular embedded near-layered organic hybrid vanadium oxide material prepared in Example 1 using a mixed solvent of ethylene glycol and glycerol with a volume ratio of 6:0, 2:1, 1:1, 1:2, and 0:6 as the raw material. Figure 4 It can be seen that the VOV bond strength of the mixed alcohol solvent is enhanced, and a more stable VO5 structure is constructed. At the same time, with the addition of propylene glycol into the mixed alcohol solvent, the change in the strength of the CH bond and the OH bond proves that both ethylene glycol and propylene glycol are indeed embedded between the sample layers, which is a near-layered organic hybrid vanadium oxide material embedded with mixed molecules. Example 2

[0051] Mix 4 mL and 2 mL of a mixed solvent of ethylene glycol and glycerol with 11 mL of the aqueous solution.

[0052] (2) Add 0.234 g of NH4VO3 to the mixed solution in step (1) and stir until completely mixed to form a homogeneous solution.

[0053] (3) The mixed solution obtained in step (2) was added to the polytetrafluoroethylene liner of a 17 mL stainless steel reactor, which was sealed and placed in an oven at a reaction temperature of 205 °C for 36 h to carry out a solvothermal reaction.

[0054] (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 ethanol until the impurities are removed, and then dried in an oven at 80 °C for 24 h.

[0055] Figure 5 This is a transmission electron micrograph of the near-layered organic hybrid vanadium oxide material embedded with mixed molecules obtained when the solvothermal time is 36 hours in Example 2; Figure 6 This is a high-resolution transmission electron microscopy image of the near-layered organic hybrid vanadium oxide material embedded with mixed molecules obtained when the solvent thermal time is 36 h in Example 2; Figure 5 and Figure 6It can be concluded that the nearly layered organic hybrid vanadium oxide material embedded in the mixed molecules obtained when the solvothermal time is 36 h has a lamellar stacking structure. Example 3

[0056] (1) Mix 4 mL and 2 mL of a mixed solvent of ethylene glycol and propylene glycol with 11 mL of an aqueous solution.

[0057] (2) Add 0.234 g of NH4VO3 to the mixed solution in step (1) and stir until completely mixed to form a homogeneous solution.

[0058] (3) The mixed solution obtained in step (2) was added to the polytetrafluoroethylene lining of a 17 mL stainless steel reactor, which was sealed and placed in an oven. The reaction temperature was maintained at 205 °C for 24 h, 36 h, and 48 h to carry out a solvothermal reaction. Figure 7 As shown in the figure, the organic hybrid vanadium oxide materials obtained with solvothermal times of 24 h, 36 h, and 48 h all have an ordered-disordered mixed structure. Among them, the near-layered organic hybrid vanadium oxide material with mixed molecules embedded in the solvothermal time of 36 h has a stronger signal on the (111) crystal plane, proving that this sample is more likely to grow along the c-axis and form a thinner layer structure.

[0059] (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 ethanol until the impurities are removed, and then dried in an oven at 80 °C for 24 h.

[0060] Figure 8 The FT-IR spectra of the near-layered organic hybrid vanadium oxide material embedded with mixed molecules obtained in Example 2 using solvent thermal time of 24 h, 36 h, and 48 h; Figure 8 As shown, with increasing solvothermal time, the peak associated with the V-O bond red-shifts, and the signals of organic functional groups (C-H and O-H bonds) increase. This phenomenon is particularly pronounced at a solvothermal time of 36 hours. Furthermore, the organic ligand-related vibrations are still present in the near-layered organic hybrid vanadium oxymaterials obtained with mixed molecular embedding at solvothermal times of 24, 36, and 48 hours, demonstrating that the material prepared by this invention is a near-layered organic hybrid vanadium oxymaterial embedded with mixed molecules. Example 4

[0061] (1) Add the vanadium precursor material to the solution obtained by fully stirring the aqueous solution and the organic polyol mixed solvent in a volume ratio of 11 mL:6 mL, and then fully stir again at room temperature for 12 h to obtain a mixed solution;

[0062] (2) The mixed solution is subjected to a solvothermal reaction in a stainless steel reactor. The inner lining of the stainless steel reactor is preferably made of polytetrafluoroethylene. The solvothermal reaction temperature is 180 °C and the holding time is 24 h.

[0063] (3) After the solvent thermal reaction is completed and cooled naturally, the reaction liquid is taken out, and the precipitate obtained by centrifugal separation is repeatedly washed with ethanol until the impurities are removed, and then dried in an oven at a drying temperature of 60 ° C for 12 h to obtain a near-layered organic hybrid vanadium oxide material embedded with the mixed molecules. Example 5

[0064] (1) A solution of aqueous solution and organic polyol mixed solvent was stirred in a volume ratio of 11 mL:6 mL, and the vanadium precursor material was added to the solution, and the mixture was stirred again at room temperature for 48 h to obtain a mixed solution;

[0065] (2) The solvent thermal reaction of the mixed solution is carried out in a stainless steel reactor. The inner lining of the stainless steel reactor is preferably made of polytetrafluoroethylene. The temperature of the solvent thermal reaction is 210 °C and the holding time is 48 h.

[0066] (3) After the solvent thermal reaction is completed and cooled naturally, the reaction liquid is taken out, and the precipitate obtained by centrifugal separation is repeatedly washed with ethanol until the impurities are removed, and then dried in an oven at a drying temperature of 100 °C for 48 h to obtain the near-layered organic hybrid vanadium oxide material embedded with the mixed molecules.

[0067] Application Example 1

[0068] 4 mL and 2 mL of a mixed solvent of ethylene glycol and glycerol were mixed evenly with 11 mL of aqueous solution. 0.234 g of NH₄VO₃ was added to the mixed solution and stirred until completely mixed. The resulting homogeneous solution was added to the polytetrafluoroethylene-lined 17 mL stainless steel reactor, which was sealed and placed in an oven for a solvothermal reaction at 205°C for 36 h. After the solvothermal reaction was completed and naturally cooled, the reaction solution was removed and the resulting precipitate was repeatedly washed with ethanol until impurities were removed, and then dried in an oven at 80°C for 24 h.

[0069] The mixed molecule embedded near-layered organic hybrid vanadium oxide material, carbon black and polyvinylidene fluoride (PVDF) prepared by taking the above-mentioned ethylene glycol-propylene glycol mixed solvent with a volume ratio of 2:1 as raw materials are mixed evenly in N-methylpyrrolidone (NMP) in a mass ratio of 7:2:1 to form a slurry. The slurry is then evenly coated on a titanium mesh as the battery positive electrode, glass fiber is used as a separator, 3M Zn(CF3SO3)2 is used as the electrolyte, and the battery is encapsulated in a battery shell with model CR2032 to prepare an aqueous zinc ion battery.

[0070] The electrochemical performance of the aqueous zinc ion battery prepared by the package was tested, such as Figure 9 The constant current charge-discharge properties of the mixed molecule embedded near-layered organic hybrid vanadium oxide material prepared by using a mixed solvent of ethylene glycol and glycerol with a volume ratio of 2:1 as the raw material solvent and heating for 36 hours are shown in FIG. Figure 9 The mixed molecule embedded near-layered organic hybrid vanadium oxide material has the characteristics of high specific capacity and high rate performance; Figure 10 As shown in FIG, the constant current charge-discharge curve of the mixed molecule embedded near-layered organic hybrid vanadium oxide material prepared by using a mixed solvent of ethylene glycol and glycerol with a volume ratio of 2:1 and a solvent thermal time of 36 h as the raw material, as shown in FIG. Figure 10 Shows high reversibility during charge and discharge; e.g. Figure 11 The long cycle properties of the mixed molecular embedded near-layered organic hybrid vanadium oxide material prepared using a mixed solvent of ethylene glycol and glycerol with a volume ratio of 2:1 and a solvothermal time of 36 h as the raw material are shown in FIG. Figure 11 Figure a in the middle shows that the material is -1 After 1000 cycles at a current density of 100, the capacity retention rate is 94.9%. Figure 11 Figure b shows that the material is -1 At a high current density, the capacity retention rate is 82.4% during 5000 cycles, and both Figures a and b show good stability. Figure 12 The cyclic voltammetry curve of the mixed molecular embedded near-layered organic hybrid vanadium oxide material prepared by using ethylene glycol glycerol mixed solvent with a volume ratio of 2: 1 and a solvothermal time of 36 h as the raw material is shown. Figure 12 There are two pairs of redox peaks in the cyclic voltammetry curve of Zn 2+ The insertion and extraction behavior of the material is very good, and the peak spacing of the redox peaks is very small, indicating that the material has high reversibility and small polarization.

Claims

1. Preparation of a near-layered organic hybrid vanadium oxide material embedded with mixed molecules, characterized by: The following steps are involved: 1) The aqueous solution and the organic polyol mixed solvent are fully stirred in a volume ratio of 11 mL:6 mL, the vanadium oxide precursor material is added to the obtained solution, the mixture is mixed, and the mixture is fully stirred again at room temperature for 12 h to 48 h to obtain a mixed solution; 2) The mixed solution is subjected to a solvothermal reaction in a stainless steel reactor lined with polytetrafluoroethylene material, the solvothermal reaction temperature is 180°C to 210°C, and the holding time is 24 h to 48 h; 3) After the solvothermal reaction is completed and naturally cooled, the reaction liquid is removed, and the precipitate obtained by centrifugation is repeatedly washed with ethanol until impurities are removed, and dried in an oven at a drying temperature of 60°C to 100°C for 12 h to 48 h to obtain the mixed molecule embedded near-layered organic hybrid vanadium oxide material having an ordered-disordered mixed structure; the organic polyol mixed solvent includes ethylene glycol and glycerol, wherein the volume ratio of ethylene glycol to glycerol is 2:

1.

2. The preparation of the mixed molecular embedded near-layered organic hybrid vanadium oxide material according to claim 1, characterized in that The vanadium oxide precursor material is vanadium oxide or vanadate, wherein the vanadium oxide includes commercial V2O5, and the vanadate includes NH4VO3.

3. The preparation of the mixed molecular embedded near-layered organic hybrid vanadium oxide material according to claim 1, characterized in that The molar mass ratio of the vanadium oxy precursor material in the mixed solution is 0.1176 mol / L.

4. The preparation of the mixed molecular embedded near-layered organic hybrid vanadium oxide material according to claim 1, characterized in that The near-layered organic hybrid vanadium-oxygen material embedded with the mixed molecules contains vanadium, oxygen, carbon and hydrogen.

5. The preparation of the mixed molecular embedded near-layered organic hybrid vanadium oxide material according to claim 4, characterized in that The near-layered organic hybrid vanadium oxide material in which the mixed molecules are embedded is a spherical structure of nanosheet stacking.

6. Use of the mixed molecular embedded near-layered organic hybrid vanadium oxide material according to claim 1 in an electrode material for an energy storage device.

7. Use of the mixed molecular embedded near-layered organic hybrid vanadium oxide material in an electrode material for an energy storage device according to claim 6, characterized in that The energy storage device is an aqueous zinc ion battery.

8. Use of the mixed molecular embedded near-layered organic hybrid vanadium oxide material in an electrode material for an energy storage device according to claim 7, characterized in that The electrode material of the energy storage device includes a near-layered organic hybrid vanadium oxide material embedded with mixed molecules, a conductive agent and a binder; the mass ratio of the near-layered organic hybrid vanadium oxide material embedded with mixed molecules, the conductive agent and the binder is 7:2:1; the conductive agent is carbon black Super-p, and the binder is polyvinylidene fluoride (PVDF).

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