Micron-sized tetramolybdenum undecanoate / molybdenum dioxide ternary heterojunction capable of being used for positive electrode of aqueous zinc ion battery and preparation method of micron-sized tetramolybdenum undecanoate / molybdenum dioxide ternary heterojunction

Abstract

The invention discloses a micron-sized tetramolybdenum undecanoate / molybdenum dioxide ternary heterojunction capable of being used for an aqueous zinc ion battery positive electrode and a preparation method of the micron-sized tetramolybdenum undecanoate / molybdenum dioxide ternary heterojunction, and belongs to the technical field of material preparation. Firstly, ammonium molybdate tetrahydrate is dissolved in water, nitric acid is added to obtain a mixed solution, then the mixed solution is put into a reaction kettle to be subjected to a hydrothermal reaction to obtain MoO3, then the MoO3 and molybdenum powder are mixed and ground, and finally the powder is calcined to form the heterostructure material. The micron-sized molybdenum trioxide is synthesized through a simple solvothermal method, and the micron-sized molybdenum trioxide is used as a precursor for preparing the micron-sized ternary heterojunction Mo4O11 / MoO2 (at) Mo, so that structure inheritance and conversion and formation of a stable heterojunction surface are facilitated; the structural stability and the energy storage efficiency of the material can be greatly improved; the ternary heterostructure effectively relieves volume expansion and structural collapse of the material in the charging and discharging process, the micron-sized material is not prone to side reaction, the cycle life of the battery is prolonged, and the material has high specific capacity and excellent cycle performance when serving as the water-based zinc ion battery positive electrode material.

Description

Technical Field

[0001] The present invention belongs to the technical field of material preparation and relates to a 11-oxo-tetramolybdenum / molybdenum dioxide@molybdenum (Mo4O 11 / MoO2@Mo) heterostructure material and its preparation method. Background Art

[0002] With the rise of new energy, a variety of energy storage systems have been developed and utilized. Batteries, as rechargeable energy storage devices, will become an indispensable component of new energy vehicles, electronic devices, and other applications. Currently, lithium-ion batteries dominate due to their high energy density and mature industrial system. However, issues such as high cost, uneven distribution of lithium resources, and safety hazards of flammable electrolytes are becoming increasingly prominent. With the continuous development of the times and technological innovation, the development of new energy storage technologies that combine low cost, high safety, and environmental friendliness is urgent. Aqueous zinc-ion batteries completely avoid the flammable and explosive risks of organic electrolytes and are an important candidate for next-generation energy storage systems. Aqueous zinc-ion batteries (AZIBs) have attracted widespread attention in recent years due to their advantages, such as the high theoretical capacity of the zinc anode (820 mAh / g), low redox potential (-0.76 V vs. SHE), abundant reserves (the content in the Earth's crust is 1000 times that of lithium), and the ability to be processed directly in air. The performance of AZIBs is highly dependent on the ion storage capacity, structural stability, and reaction kinetics of the cathode material. Molybdenum dioxide (MoO2) has emerged as a new material in transition metals due to its unique physical and chemical properties. MoO2 has a high conductivity (about 10 4 S / cm) and a monoclinic one-dimensional tunnel structure allow for rapid ion transport, providing an ideal platform for the rapid insertion and extraction of zinc ions and exhibiting a high theoretical capacity (838 mAh / g). Designing heterostructures by combining different materials can not only enhance structural stability and suppress volume expansion and phase collapse, but also accelerate reaction kinetics, reduce the energy barrier for ion migration, and optimize electron / ion transfer efficiency. Furthermore, the synergistic effect of the heterostructure's multiple components can provide abundant redox active sites. For example, Xun et al. prepared MoO2 / Mo2N heterostructured nanoribbons via electrochemical activation and found that the in situ generated MoO2 particles within the Mo2N nanoribbon matrix not only accommodated the intercalated zinc ions, resulting in a significant increase in capacity, but also provided high electronic conductivity, thereby improving rate capability. They delivered 89 mAh / g after 1000 cycles at 1 A / g (Energy Storage Materials 15 (2018) 374–379).

[0003] Among the many methods for preparing heterostructure materials, most are heterojunctions formed by binary components, which have poor conductivity. Ternary heterojunctions have greatly improved the energy storage efficiency of materials through bandgap engineering, interface optimization and high-quality epitaxial growth in batteries, and have also emerged in zinc-ion batteries. This heterostructure effectively alleviates the volume expansion and structural collapse of the material during the charge and discharge process, thereby extending the cycle life. In addition, due to its small specific surface area, the side reactions of micron-sized materials with the electrolyte during the charge and discharge process are significantly reduced, thereby improving the coulombic efficiency and cycle stability of the battery. Therefore, the oxidizing property of molybdenum trioxide and the reducibility of molybdenum are innovatively utilized to prepare micron-sized undecanoic tetramolybdenum / molybdenum dioxide@molybdenum (Mo4O 11 / MoO2@Mo) ternary heterostructure materials are of great significance and greatly improve the performance of molybdenum-based zinc-ion batteries. Summary of the Invention

[0004] In view of the problems existing in the prior art, the present invention provides a micron-sized undecanoate tetramolybdenum / molybdenum dioxide@molybdenum ternary heterojunction that can be used for the positive electrode of aqueous zinc ion batteries and its preparation method. In the preparation process of the present invention, micron-sized molybdenum trioxide is synthesized by a simple solvent thermal method. Micron-sized molybdenum trioxide is used as the catalyst for the preparation of micron-sized ternary heterojunction Mo4O 11 / MoO2@Mo precursor is conducive to structural inheritance and transformation as well as the formation of a stable heterojunction surface. Molybdenum trioxide and molybdenum powder are fully mixed by grinding, and then the product is calcined in an argon atmosphere in a tube furnace to generate Mo4O with a ternary heterostructure. 11 / MoO2@Mo significantly improves the material's structural stability and energy storage efficiency. The ternary heterostructure effectively mitigates volume expansion and structural collapse during charge and discharge. Furthermore, the micron-sized material is less susceptible to side reactions, which helps extend the battery's cycle life. As a cathode material for aqueous zinc-ion batteries, it exhibits high specific capacity and excellent cycling performance.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is:

[0006] A novel undecanoate tetramolybdenum / molybdenum dioxide@molybdenum (Mo4O 11 / MoO2@Mo) heterostructure material and preparation method thereof, firstly, ammonium molybdate tetrahydrate is dissolved in water, nitric acid is added to obtain a mixed solution, which is then placed in a reactor for hydrothermal reaction to obtain molybdenum trioxide MoO3, then the molybdenum trioxide is mixed with molybdenum powder and ground, and finally the completely mixed powder is calcined in a tube furnace under argon atmosphere to form (Mo4O 11 / MoO2@Mo) heterostructure material, the specific steps are as follows:

[0007] The first step is to prepare MoO3 in strip form;

[0008] Ammonium molybdate tetrahydrate (NH4)6Mo7O 24 4H2O is dissolved in water under magnetic stirring to form a uniform solution. After stirring for 0.5-1 hour, concentrated nitric acid is slowly added and stirred continuously to obtain a mixed solution. The mixed solution is then transferred to an autoclave for a hydrothermal reaction at 180-200°C for 12-24 hours. Finally, the resulting precipitate is rinsed with deionized water and dried to obtain the micron-sized, ribbon-shaped MoO3 precursor.

[0009] Furthermore, in the first step, 1.4-2.8 g of ammonium molybdate tetrahydrate is dissolved in every 70 mL of water, and the stirring time is 0.5-1 hour.

[0010] Furthermore, in the first step, the volume ratio of concentrated nitric acid to water is 1:5-1:10, and the stirring time is continued for 0.5-1 hour.

[0011] Furthermore, in the first step, the drying temperature is 60-80° C., and the drying time is 12-24 hours.

[0012] The second step is to prepare Mo4O 11 / MoO2@Mo heterojunction;

[0013] The MoO3 obtained in the first step is mixed with molybdenum powder and then put into a planetary ball mill for grinding to obtain a powder uniformly mixed with MoO3 and molybdenum powder; the powder is calcined in a tube furnace under an argon atmosphere at a high temperature to obtain Mo4O 11 / MoO2@Mo heterojunction.

[0014] Furthermore, in the second step, the molar ratio of MoO3 to molybdenum powder is 1:2-2:1.

[0015] Furthermore, in the second step, the grinding speed is 600-800 r / min, and the grinding time is 6-12 hours.

[0016] Furthermore, in the second step, the temperature is raised to the calcination temperature at a rate of 5°C / min.

[0017] Furthermore, in the second step, the calcination temperature is 600-700° C., and the calcination time is 2-12 hours.

[0018] A novel undecanoate tetramolybdenum / molybdenum dioxide@molybdenum (Mo4O 11 / MoO2@Mo) heterostructure material was prepared by the above preparation method.

[0019] The ternary heterostructure material prepared by the present invention can be used as a positive electrode material for aqueous zinc ion batteries, greatly improving the performance of aqueous molybdenum-based zinc ion batteries.

[0020] The beneficial effects of the present invention are:

[0021] 1) In this preparation process, micron-sized molybdenum trioxide with uniform diameter is synthesized via a simple solvothermal method and used as a precursor for the micron-sized ternary heterojunction. The similar particle size facilitates structural inheritance and transformation, as well as the formation of a stable heterojunction interface. Furthermore, micron-sized materials offer better reaction controllability, facilitating the regulation of the material's density and pore structure.

[0022] 2) In the preparation process of the present invention, micron-sized molybdenum trioxide is used as a precursor and mixed with molybdenum powder. The redox properties of the molybdenum-based material are utilized to partially reduce the molybdenum trioxide through high-temperature calcination to generate micron-sized Mo4O3 with a ternary heterogeneous structure. 11 / MoO2@Mo, greatly improving the structural stability and energy storage efficiency of the material. The ternary heterostructure effectively alleviates the volume expansion and structural collapse of the material during the charge and discharge process. In addition, the micron-scale material is not prone to side reactions, which helps to improve the cycle life of the battery.

[0023] 3) During the preparation process of the present invention, the micron-scale ternary heterostructure Mo4O 11 / MoO2@Mo as the positive electrode material of aqueous zinc-ion batteries has high specific capacity and excellent cycle performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 This is the SEM photograph of the MoO3 sample of Example 1.

[0025] Figure 2 The sample Mo4O in Example 1 11 XRD photograph of / MoO2@Mo ternary heterojunction.

[0026] Figure 3 The sample Mo4O in Example 1 11 SEM photo of / MoO2@Mo ternary heterojunction.

[0027] Figure 4 This is the cycle performance diagram of the sample in Example 1.

[0028] Figure 5 This is the cycle performance diagram of the sample in Example 2.

[0029] Figure 6 This is the cycle performance diagram of the sample in Example 3. DETAILED DESCRIPTION

[0030] The following non-limiting examples may enable those skilled in the art to more fully understand the present invention, but are not intended to limit the present invention in any way.

[0031] Example 1

[0032] 2.8 g (NH4)6Mo7O 24 4H2O was dissolved in 70 mL of water under magnetic stirring to form a uniform solution. After stirring for 1 hour, concentrated nitric acid and water were slowly added at a ratio of (1:5 = v / v) and stirred for 0.5 hours. The mixed solution was then transferred to a 100 mL autoclave and kept at 180 ° C for 24 hours. The resulting precipitate was then rinsed three times with deionized water. Subsequently, the product was dried at 60 ° C for 12 hours to obtain MoO3. The SEM image of MoO3 is shown in FIG. Figure 1 As shown, from Figure 1 It can be seen that the prepared MoO3 morphology exists in the form of micron-sized and ribbon-like structures.

[0033] 0.025 mol of the prepared MoO3 was mixed with molybdenum powder in a ratio of (1:1 = mol / mol) in a planetary ball mill and ground at 700 r / min for 12 hours to obtain a powder in which MoO3 and molybdenum powder were evenly mixed. The powder in which MoO3 and molybdenum powder were evenly mixed was calcined in a tube furnace under argon atmosphere at a rate of 5 ℃ / min to 600 ℃ for 2 hours to obtain Mo4O 11 / MoO2@Mo heterojunction.

[0034] When used as the positive electrode material for aqueous zinc-ion batteries, the discharge capacity reaches 291 mAh / g after ten cycles at 0.5 A / g, and 145 mAh / g after ten cycles at 3 A / g. After 1500 cycles at 3 A / g, the capacity decays from 145 mAh / g to 110 mAh / g, and the capacity retention rate reaches 75.86%. Figure 2 As shown, from Figure 2 It can be seen that the peaks are molybdenum peak, tetramolybdenum undodecanoate peak and molybdenum dioxide peak, proving the formation of ternary heterojunction. Figure 3 As shown, it presents a micron-sized particle structure. The cycle performance diagram is shown in Figure 4 shown.

[0035] Example 2

[0036] 1.4 g (NH4)6Mo7O 244H2O was dissolved in 70 mL of water under magnetic stirring to form a homogeneous solution. After stirring for 0.5 hours, concentrated nitric acid and water were slowly added at a ratio of 1:10 (v / v) and stirred for 0.5 hours. The mixed solution was then transferred to a 100 mL autoclave and maintained at 200°C for 12 hours. The resulting precipitate was then rinsed three times with deionized water. Subsequently, the product was dried at 60°C for 12 hours to obtain micron-sized, ribbon-like MoO3.

[0037] 0.025 mol of the prepared MoO3 was mixed with molybdenum powder in a ratio of (1:2 = mol / mol) in a planetary ball mill and ground at 700 r / min for 24 hours to obtain a powder in which MoO3 and molybdenum powder were evenly mixed. The powder in which MoO3 and molybdenum powder were evenly mixed was calcined at 600 °C in a tube furnace under argon atmosphere at a rate of 5 °C / min for 12 hours to obtain Mo4O 11 / MoO2@Mo heterojunction.

[0038] When used as the positive electrode material for aqueous zinc-ion batteries, the discharge capacity reaches 278 mAh / g after ten cycles at 0.5 A / g, and 146 mAh / g after ten cycles at 3 A / g. After 1500 cycles at 3 A / g, the capacity decays from 146 mAh / g to 110 mAh / g, and the capacity retention rate reaches 74.34%. The cycle performance diagram is shown in the figure below. Figure 5 shown.

[0039] Example 3

[0040] 2.8 g (NH4)6Mo7O 24 4H2O was dissolved in 70 mL of water under magnetic stirring to form a homogeneous solution. After stirring for 0.5 hours, concentrated nitric acid and water were slowly added at a ratio of 1:7.5 (v / v) and stirred for 0.5 hours. The mixed solution was then transferred to a 100 mL autoclave and maintained at 180°C for 18 hours. The resulting precipitate was then rinsed three times with deionized water. Subsequently, the product was dried at 60°C for 12 hours to obtain micron-sized, ribbon-like MoO3.

[0041] 0.025 mol of the prepared MoO3 was mixed with molybdenum powder in a ratio of (2:1 = mol / mol) in a planetary ball mill and ground at 600 r / min for 12 hours to obtain a powder in which MoO3 and molybdenum powder were evenly mixed. The powder in which MoO3 and molybdenum powder were evenly mixed was calcined in a tube furnace under argon atmosphere at a rate of 5 ℃ / min to 700 ℃ for 6 hours to obtain Mo4O 11 / MoO2@Mo heterojunction.

[0042] When used as the positive electrode material for aqueous zinc-ion batteries, the discharge capacity reaches 284 mAh / g after ten cycles at 0.5 A / g, and 139 mAh / g after ten cycles at 3 A / g. After 1500 cycles at 3 A / g, the capacity decays from 139 mAh / g to 107 mAh / g, and the capacity retention rate reaches 76.97%. The cycle performance diagram is shown in the figure below. Figure 6 shown.

[0043] Example 4

[0044] 1.4 g (NH4)6Mo7O 24 4H2O was dissolved in 70 mL of water under magnetic stirring to form a homogeneous solution. After stirring for 0.5 hours, concentrated nitric acid and water were slowly added at a ratio of 1:10 (v / v) and stirred for 0.5 hours. The mixed solution was then transferred to a 100 mL autoclave and maintained at 190°C for 20 hours. The resulting precipitate was then rinsed five times with deionized water. Subsequently, the product was dried at 60°C for 12 hours to obtain micron-sized, ribbon-like MoO3.

[0045] 0.025 mol of the prepared MoO3 was taken and mixed with molybdenum powder in a ratio of (1:2 = mol / mol) in a planetary ball mill and ground at 800 r / min for 6 hours to obtain a powder in which MoO3 and molybdenum powder were evenly mixed. The powder in which MoO3 and molybdenum powder were evenly mixed was calcined in a tube furnace under argon atmosphere at a rate of 5 ℃ / min to 650 ℃ for 6 hours to obtain Mo4O 11 / MoO2@Mo heterojunction.

[0046] When used as the positive electrode material for aqueous zinc-ion batteries, the discharge specific capacity reaches 288 mAh / g after ten cycles at 0.5 A / g, and the discharge specific capacity reaches 142 mAh / g after ten cycles at 3 A / g. After 1500 cycles at 3 A / g, the specific capacity decays from 142 mAh / g to 104 mAh / g, and the capacity retention rate reaches 73.24%.

[0047] Example 5

[0048] 1.4 g (NH4)6Mo7O 24 4H2O was dissolved in 70 mL of water under magnetic stirring to form a homogeneous solution. After stirring for 0.75 hours, concentrated nitric acid and water were slowly added at a ratio of 1:5 (v / v) and stirred for 0.5 hours. The mixed solution was then transferred to a 100 mL autoclave and maintained at 200°C for 24 hours. The resulting precipitate was then rinsed three times with deionized water. Subsequently, the product was dried at 60°C for 12 hours to obtain micron-sized, ribbon-like MoO3.

[0049] 0.025 mol of the prepared MoO3 was mixed with molybdenum powder in a ratio of (1:2 = mol / mol) in a planetary ball mill and ground at 750 r / min for 9 hours to obtain a powder in which MoO3 and molybdenum powder were evenly mixed. The powder in which MoO3 and molybdenum powder were evenly mixed was calcined at 680 °C at a rate of 5 °C / min in a tube furnace under argon atmosphere for 10 hours to obtain Mo4O 11 / MoO2@Mo heterojunction.

[0050] When used as the positive electrode material for aqueous zinc-ion batteries, the discharge specific capacity reaches 277 mAh / g after ten cycles at 0.5 A / g, and the discharge specific capacity reaches 138 mAh / g after ten cycles at 3 A / g. After 1500 cycles at 3 A / g, the specific capacity decays from 138 mAh / g to 100 mAh / g, and the capacity retention rate reaches 72.46%.

[0051] Example 6

[0052] 2.8 g (NH4)6Mo7O 24 4H2O was dissolved in 70 mL of water under magnetic stirring to form a homogeneous solution. After stirring for 0.5 hours, concentrated nitric acid and water were slowly added at a ratio of 1:10 (v / v) and stirred for 0.5 hours. The mixed solution was then transferred to a 100 mL autoclave and maintained at 180°C for 24 hours. The resulting precipitate was then rinsed three times with deionized water. Subsequently, the product was dried at 60°C for 12 hours to obtain micron-sized, ribbon-like MoO3.

[0053] 0.025 mol of the prepared MoO3 was mixed with molybdenum powder in a ratio of (2:1 = mol / mol) in a planetary ball mill and ground at 700 r / min for 12 hours to obtain a powder in which MoO3 and molybdenum powder were evenly mixed. The powder in which MoO3 and molybdenum powder were evenly mixed was calcined in a tube furnace under argon atmosphere at a rate of 5 ℃ / min to 600 ℃ for 10 hours to obtain Mo4O 11 / MoO2@Mo heterojunction.

[0054] When used as the positive electrode material for aqueous zinc-ion batteries, the discharge specific capacity reaches 273 mAh / g after ten cycles at 0.5 A / g, and the discharge specific capacity reaches 132 mAh / g after ten cycles at 3 A / g. After 1500 cycles at 3 A / g, the specific capacity decays from 132 mAh / g to 94 mAh / g, and the capacity retention rate reaches 71.21%.

[0055] Example 7

[0056] 2.8 g (NH4)6Mo7O 244H2O was dissolved in 70 mL of water under magnetic stirring to form a homogeneous solution. After stirring for 0.5 hours, concentrated nitric acid and water were slowly added at a ratio of 1:5 (v / v) and stirred for 0.5 hours. The mixed solution was then transferred to a 100 mL autoclave and maintained at 200°C for 24 hours. The resulting precipitate was then rinsed three times with deionized water. Subsequently, the product was dried at 60°C for 12 hours to obtain micron-sized, ribbon-like MoO3.

[0057] 0.025 mol of the prepared MoO3 was mixed with molybdenum powder in a ratio of (1:1 = mol / mol) in a planetary ball mill and ground at 700 r / min for 12 hours to obtain a powder in which MoO3 and molybdenum powder were evenly mixed. The powder in which MoO3 and molybdenum powder were evenly mixed was calcined in a tube furnace under argon atmosphere at a rate of 5 ℃ / min to 700 ℃ for 4 hours to obtain Mo4O 11 / MoO2@Mo heterojunction.

[0058] When used as the positive electrode material for aqueous zinc-ion batteries, the discharge specific capacity reaches 257 mAh / g after ten cycles at 0.5 A / g, and the discharge specific capacity reaches 126 mAh / g after ten cycles at 3 A / g. After 1500 cycles at 3 A / g, the specific capacity decays from 126 mAh / g to 89 mAh / g, and the capacity retention rate reaches 70.63%.

[0059] The above-described embodiments merely express the implementation methods of the present invention, but should not be understood as limiting the scope of the patent of the present invention. It should be pointed out that for those skilled in the art, several variations and improvements can be made without departing from the concept of the present invention, and these all fall within the scope of protection of the present invention.

Claims

1. A micron-sized undecanoate tetramolybdenum / molybdenum dioxide@molybdenum ternary heterojunction for use in aqueous zinc ion battery cathodes and a method for preparing the same, characterized in that: The preparation method first dissolves ammonium molybdate tetrahydrate in water, adds nitric acid to obtain a mixed solution, then puts the mixed solution into a reactor for hydrothermal reaction to obtain molybdenum trioxide MoO3, then mixes the molybdenum trioxide with molybdenum powder and grinds them, and finally calcines the completely mixed powder in an argon atmosphere in a tube furnace to form a heterogeneous structure material Mo4O 11 / MoO2@Mo.

2. A micron-sized undecanoic acid tetramolybdenum / molybdenum dioxide@molybdenum ternary heterojunction for use in aqueous zinc ion battery positive electrodes and a preparation method thereof according to claim 1, characterized in that: The following steps are involved: The first step is to prepare MoO3 in strip form; Ammonium molybdate tetrahydrate (NH4)6Mo7O 24 4H2O is dissolved in water to form a uniform solution, and concentrated nitric acid is slowly added with stirring to obtain a mixed solution. The mixed solution is subjected to a hydrothermal reaction at a temperature of 180-200°C for 12-24 hours. The resulting precipitate is rinsed with deionized water and dried to obtain a micron-sized, ribbon-shaped MoO3 precursor. The second step is to prepare Mo4O 11 / MoO2@Mo heterojunction; The MoO3 obtained in the first step is mixed with molybdenum powder and then ground to obtain a uniformly mixed powder; the powder is calcined in an argon atmosphere in a tube furnace to obtain Mo4O 11 / MoO2@Mo heterojunction.

3. The micron-sized undecanoate tetramolybdenum / molybdenum dioxide@molybdenum ternary heterojunction for use in aqueous zinc ion battery positive electrodes and a preparation method thereof according to claim 1, characterized in that: In the first step, 1.4-2.8 g of ammonium molybdate tetrahydrate is dissolved in 70 mL of water, and the stirring time is 0.5-1 hour.

4. The micron-sized undecanoate tetramolybdenum / molybdenum dioxide@molybdenum ternary heterojunction for use in aqueous zinc ion battery positive electrodes and a preparation method thereof according to claim 1, characterized in that: In the first step, the volume ratio of concentrated nitric acid to water is 1:5-1:10, and the stirring time is continued for 0.5-1 hour.

5. The micron-sized undecanoate tetramolybdenum / molybdenum dioxide@molybdenum ternary heterojunction for use in aqueous zinc ion battery positive electrodes and a preparation method thereof according to claim 1, characterized in that: In the first step, the drying temperature is 60-80° C., and the drying time is 12-24 hours.

6. The micron-sized undecanoate tetramolybdenum / molybdenum dioxide@molybdenum ternary heterojunction for use in aqueous zinc ion battery positive electrodes and a preparation method thereof according to claim 1, characterized in that: In the second step, the molar ratio of MoO3 to molybdenum powder is 1:2-2:

1.

7. The micron-sized undecanoate tetramolybdenum / molybdenum dioxide@molybdenum ternary heterojunction for use in aqueous zinc ion battery positive electrodes and a preparation method thereof according to claim 1, characterized in that: In the second step, the grinding speed is 600-800 r / min, and the grinding time is 6-12 hours.

8. The micron-sized undecanoate tetramolybdenum / molybdenum dioxide@molybdenum ternary heterojunction for use in aqueous zinc ion battery positive electrodes and a preparation method thereof according to claim 1, characterized in that: In the second step, the calcination temperature is 600-700° C., and the calcination time is 2-12 hours.

9. A 11-Oxytetramolybdenum / Molybdenum Dioxide@Molybdenum (Mo4O 11 / MoO2@Mo) heterostructure material, characterized by The method is prepared by any one of claims 1 to 8.

10. The undecanoic acid tetramolybdenum / molybdenum dioxide@molybdenum (Mo4O 11 / MoO2@Mo) heterostructure materials, characterized by The ternary heterostructure material can be used as a positive electrode material for aqueous zinc ion batteries.

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