A high-performance zinc ion battery cathode material based on EDTA-MnO2 organic / inorganic dual storage interface and its preparation method

Abstract

The present invention provides a high-performance zinc ion battery positive electrode material based on EDTA-MnO2 organic / inorganic dual storage interface and a preparation method thereof, comprising the steps of: dissolving a manganese salt and an ammonium-containing compound in deionized water, performing a hydrothermal reaction with a porous carbon material as a substrate to obtain a MnO2 / C precursor; mixing an EDTA solution with the MnO2 / C precursor to perform a chelating reaction, and finally drying to obtain an EDTA-MnO2 / C composite material; after cooling to room temperature, taking out and drying, annealing, to obtain an EDTA-MnO2 / C composite material with a nanoarray structure, i.e., a high-performance zinc ion battery positive electrode material. The positive electrode material of the present invention constructs an EDTA-MnO2 organic / inorganic hybrid positive electrode material by introducing EDTA as an organic guest molecule, significantly improving the electrochemical performance of the zinc ion battery.

Description

Technical Field

[0001] The present invention belongs to the technical field of zinc ion battery positive electrode materials, and in particular relates to a high-performance zinc ion battery positive electrode material based on an EDTA-MnO2 organic / inorganic dual storage interface and a preparation method thereof. Background Art

[0002] Globally, energy and environmental issues have always been the focus of human attention. Traditional energy is non-renewable and its excessive consumption has led to serious environmental pollution problems. Therefore, it is of great significance to develop a new energy system that is low-carbon, environmentally friendly, clean and pollution-free. However, clean energy such as wind power, hydropower, and solar energy have problems such as storage and transportation difficulties and unstable energy output due to limited conditions. Therefore, the development of large-scale energy storage equipment has become the key to solving these problems. Aqueous zinc-manganese batteries have shown broad application prospects in the fields of large-scale energy storage and portable electronic devices due to their low cost, high safety, and environmental friendliness. As the core positive electrode material, manganese-based compounds (such as MnO2) have high theoretical capacity (about 308 mAh·g -1 ), rich resource reserves and a voltage platform that matches the zinc negative electrode have become research hotspots.

[0003] However, existing manganese-based cathode materials have 2+ During the intercalation / deintercalation process, Mn 3+ The Jahn-Teller distortion of Zn leads to lattice stress accumulation, resulting in material structure collapse and active material stripping, which significantly reduces the cycle life. In addition, manganese-based materials are prone to dissolution in acidic electrolytes, further exacerbating capacity decay. 2+ In the hydrated state (such as Zn(H2O)6 2+ ) need to overcome the high desolvation energy barrier (usually >15 eV), resulting in slow interface reaction kinetics. At the same time, the compact layered structure of MnO2 (interlayer spacing <0.3 nm) limits the Zn 2+ The rapid diffusion of ions causes a sharp drop in capacity, especially at high-rate charge and discharge. + 、Na + ) or introduce structural defects to expand the interlayer spacing, but such methods often sacrifice the proportion of active materials or introduce instability. Traditional modification strategies (such as heteroatom doping and surface coating) can partially improve cycle stability, but often at the expense of specific capacity. Therefore, there is an urgent need to develop a new type of manganese-based cathode material that, through interface coupling and structural collaborative design, can achieve a combination of high ion diffusion rate, low desolvation energy barrier, and excellent structural stability to promote the practical application of aqueous zinc-manganese batteries. Summary of the Invention

[0004] In view of this, the present invention aims to overcome the defects in the prior art and proposes a high-performance zinc ion battery positive electrode material based on EDTA-MnO2 organic / inorganic dual storage interface and a preparation method thereof.

[0005] To achieve the above object, the technical solution of the present invention is achieved as follows:

[0006] In a first aspect, the present invention provides a method for preparing a high-performance zinc ion battery positive electrode material based on an EDTA-MnO2 organic / inorganic dual storage interface, comprising the following steps:

[0007] Step 1: dissolving a manganese salt and an ammonium-containing compound in deionized water and performing a hydrothermal reaction on a porous carbon material substrate to obtain a MnO2 / C precursor;

[0008] Step 2: Mixing the EDTA solution with the MnO2 / C precursor to carry out a chelating reaction, and finally drying to obtain an EDTA-MnO2 / C composite material;

[0009] Step 3: After cooling to room temperature, the mixture is taken out, dried, and annealed to obtain an EDTA-MnO2 / C composite material having a nano-array structure, i.e., a high-performance zinc ion battery positive electrode material;

[0010] Preferably, in step 1, the concentration of the manganese salt is 5-15 mmol / L, and the concentration of the ammonium compound is 3-5 mmol / L.

[0011] Preferably, the manganese salt is selected from manganese salts that can be hydrothermally decomposed into MnO2, specifically permanganate, selected from one or a mixture of potassium permanganate, sodium permanganate, lithium permanganate, and ammonium permanganate.

[0012] Preferably, the ammonium-containing compound is selected from one or a mixture of (NH4)2SO4, NH4Cl, NH4NO3, NH4HCO3, and urea.

[0013] Preferably, the porous carbon material is selected from one or a mixture of carbonized cotton fiber, carbon fiber, carbon nanotube, carbon nanofiber, and biomass-derived carbon.

[0014] Preferably, the concentration of the EDTA solution in step 2 is 0.5-1.5 mmol / L.

[0015] Preferably, in step 2, the molar ratio of EDTA to MnO2 is controlled to be 0.05-0.15.

[0016] Preferably, the hydrothermal reaction temperature in step 1 is 120-140° C., and the reaction time is 1-3 hours.

[0017] Preferably, the reaction temperature of the chelating reaction in step 2 is 60-80° C., and the reaction time is 6-12 hours.

[0018] Preferably, in step 3, the annealing temperature is 270-350° C., and the annealing time is 1-3 hours.

[0019] In a second aspect, the present invention provides a high-performance zinc ion battery positive electrode material prepared by the above preparation method.

[0020] In a third aspect, the present invention provides the use of the above-mentioned high-performance zinc ion battery positive electrode material in the preparation of a zinc ion battery.

[0021] In a fourth aspect, the present invention provides a zinc ion battery comprising a positive electrode, a negative electrode, a separator and an electrolyte, wherein the positive electrode material used in the positive electrode is the above-mentioned high-performance zinc ion battery positive electrode material.

[0022] Preferably, the negative electrode is a metal zinc sheet, the separator is Whatman GF / D glass fiber filter paper, and the electrolyte is a mixed aqueous solution of ZnSO4 with a concentration of 1-3 mol / L and MnSO4 with a concentration of 0.1-0.3 mol / L.

[0023] The positive electrode material of the present invention is composed of ethylenediaminetetraacetic acid (EDTA) and manganese dioxide (MnO2) to form an organic / inorganic hybrid structure, wherein the polar group of EDTA can destroy the solvation shell of zinc ions and enhance the Zn 2+ It has a strong adsorption capacity and forms a stable interaction with the MnO2 framework, thereby improving the structural stability of the material.

[0024] The positive electrode material of the present invention has a nanometer array structure, and the EDTA molecules are embedded in the MnO2 interlayer through chelation.

[0025] The EDTA-MnO2 / C composite material prepared by the present invention has a self-supporting property and can be directly cut into pieces for use when used as a positive electrode of ZIBs without using a current collector, a binder and a conductive additive.

[0026] Compared with the prior art, the present invention has the following advantages:

[0027] (1) The cathode material of the present invention introduces EDTA as an organic guest molecule to construct an EDTA-MnO2 organic / inorganic hybrid cathode material, which significantly improves the electrochemical performance of zinc ion batteries;

[0028] (2) The cathode material of the present invention not only accelerates the desolvation process of zinc ions, but also improves the structural stability and capacity retention of the material by constructing a dual storage interface, providing a new direction for the development of high-performance zinc-ion batteries. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 is a SEM image of EDTA0.05-MnO2 obtained in Example 1;

[0030] Figure 2 is a SEM image of EDTA0.1-MnO2 obtained in Example 2;

[0031] Figure 3 is a SEM image of EDTA0.15-MnO2 obtained in Example 3;

[0032] Figure 4 1 is an electrochemical short cycle performance diagram of the composite materials obtained in Examples 1 to 3 and Comparative Examples 1 to 4;

[0033] Figure 5 It is a desolvation energy test graph of the composite materials obtained in Examples 1 to 3 and Comparative Examples 1 to 4. DETAILED DESCRIPTION

[0034] The embodiments of the present invention are described in detail below. The embodiments described below are exemplary and are only used to explain the present invention, and should not be understood as limiting the present invention.

[0035] Unless defined otherwise herein, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.

[0036] Where values are described herein as ranges, it should be understood that such disclosure includes disclosure of all possible sub-ranges within that range, as well as specific values falling within that range, regardless of whether a specific value or sub-range is explicitly stated.

[0037] In this document, "a plurality of" and the like, unless otherwise specified, refer to a number greater than or equal to 2. For example, "one or more" means one or more than or equal to two.

[0038] In this document, the terms “preferably” and “more preferably” are only used to describe implementation methods or examples with better effects. It should be understood that they do not limit the scope of protection of the present invention.

[0039] In this document, the word "further" and the like are used for descriptive purposes to indicate differences in content, but should not be construed as limiting the scope of protection of the present invention.

[0040] In this article, the term "and / or" is used to describe the association relationship between objects, indicating that three relationships can exist. For example, A and / or B means: A or B, or A and B.

[0041] As used herein, the term "about" means + / - 10%, preferably + / - 5%, more preferably + / - 1% of the specified value.

[0042] In this document, the terms “include,” “including,” “have,” “contain,” etc. are open-ended terms, meaning including but not limited to.

[0043] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention pertains. Although preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention.

[0044] The present invention will be described in detail below with reference to the embodiments.

[0045] Example 1

[0046] The first step is to prepare MnO2 / CCF precursor;

[0047] 10 mmol / L KMnO₄ and 4 mmol / L (NH₄)₂SO₄ were dissolved in deionized water and subjected to a hydrothermal reaction at 140°C for 2 hours on a carbonized cotton fiber (CCF) substrate to produce MnO₂ / CCF nanosheets. After cooling to room temperature, the sample was removed, washed three times with distilled water, and dried in a 60°C forced air drying oven for 24 hours to obtain the MnO₂ / CCF precursor.

[0048] Step 2: Prepare EDTA0.05-MnO2 / CCF composite material;

[0049] The MnO2 / CCF precursor was immersed in a 0.5 mmol / L EDTA solution, the molar ratio of EDTA to MnO2 was controlled to 0.05, and the mixture was stirred and reacted at 70 °C for 10 h to obtain the EDTA0.05-MnO2 / CCF composite material.

[0050] The third step is to prepare EDTA0.05-MnO2 / CCF composite materials with nano-array structure;

[0051] After the EDTA0.05-MnO2 / CCF composite material prepared in the second step is cooled to room temperature, it is taken out, washed three times with distilled water, and then placed in a 60 ℃ forced air drying oven for 24 h. After it is completely dried, it is annealed in an air atmosphere for 1 h at an annealing temperature of 270 ℃ to obtain an EDTA0.05-MnO2 / CCF composite material. Its SEM image is shown in FIG. Figure 1 shown.

[0052] Step 4: Assemble the button battery;

[0053] The EDTA0.05-MnO2 / CCF composite material prepared in the third step was directly cut into pieces and used as the positive electrode. The negative electrode was a metal zinc sheet, the separator was Whatman GF / D glass fiber filter paper, and the electrolyte was a mixed aqueous solution of 2 mol / L ZnSO4 and 0.2 mol / L MnSO4. They were assembled into CR2032 batteries in an air atmosphere.

[0054] Electrochemical performance test;

[0055] The assembled CR2032 battery was subjected to electrochemical performance test. Figure 4 As shown, at 100mA•g -1 The capacity after 100 cycles is 221.3 mA g -1 .

[0056] Desolvation energy test;

[0057] The assembled CR2032 battery was subjected to desolvation energy test using the Arrhenius equation. For the specific test process, please refer to the literature (CHENG X, XIANG Z, YANG C, et al. Polar Organic MoleculesInserted in Vanadium Oxide with Enhanced Reaction Kinetics for PromotingAqueous Zinc-Ion Storage [J]. Advanced Functional Materials, 2024, 34(9):2311412.). The test results are as follows Figure 5 As shown, the desolvation energy is 23.27 KJ·mol -1 .

[0058] Example 2

[0059] The first step is to prepare MnO2 / CCF precursor;

[0060] Same as the first step in Example 1.

[0061] The second step is to prepare EDTA0.1-MnO2 composite material;

[0062] The same as Example 1, except that the MnO2 / CCF precursor was immersed in a 1 mmol / L EDTA solution, the molar ratio of EDTA to MnO2 was controlled to be 0.1, and the reaction was stirred at 70°C for 10 hours.

[0063] The third step is to prepare EDTA0.1-MnO2 / CCF composite materials with nano-array structure;

[0064] The SEM image of the EDTA0.1-MnO2 / CCF composite material obtained in the third step of Example 1 is as follows: Figure 2 shown.

[0065] Step 4: Assemble the button battery;

[0066] Same as the fourth step in Example 1.

[0067] Electrochemical performance test;

[0068] The assembled CR2032 battery was subjected to electrochemical performance test. The test results are as follows Figure 4 As shown, at 100 mA•g -1 The capacity after 100 cycles is 283.6 mAh·g -1 .

[0069] Desolvation energy test;

[0070] The assembled CR2032 battery was subjected to desolvation energy test. The test results are as follows Figure 5 As shown, the desolvation energy is 20.86 KJ·mol -1 .

[0071] Example 3

[0072] The first step is to prepare MnO2 / CCF precursor;

[0073] Same as the first step in Example 1.

[0074] Step 2: prepare EDTA0.15-MnO2 composite material;

[0075] The same as Example 1, except that the MnO2 / CCF precursor was immersed in a 1.5 mmol / L EDTA solution, the molar ratio of EDTA to MnO2 was controlled to be 0.15, and the reaction was stirred at 70°C for 10 hours.

[0076] The third step is to prepare EDTA0.15-MnO2 / CCF composite materials with nano-array structure;

[0077] The same third step as in Example 1, the SEM image of the prepared EDTA0.15-MnO2 / CCF composite material is as follows Figure 3 shown.

[0078] Step 4: Assemble the button battery;

[0079] Same as the fourth step in Example 1.

[0080] Electrochemical performance test;

[0081] The assembled CR2032 battery was subjected to electrochemical performance test. The test results are as follows Figure 4 As shown, at 100 mA•g -1 After 100 cycles, the capacity is 197.5 mAh·g -1 .

[0082] Desolvation energy test;

[0083] The assembled CR2032 battery was subjected to desolvation energy test. The test results are as follows Figure 5 As shown, the desolvation energy is 23.22 KJ·mol -1 .

[0084] Example 4

[0085] The first step is to prepare MnO2 / CCF precursor;

[0086] The difference from the first step in Example 1 is that the manganese salt is sodium permanganate with a concentration of 5 mmol / L, the ammonium-containing compound is NH4Cl with a concentration of 3 mmol / L, and the porous carbon fibers are carbon nanotubes.

[0087] Step 2: prepare EDTA0.15-MnO2 composite material;

[0088] Same as the second step in Example 1.

[0089] The third step is to prepare EDTA0.1-MnO2 / CCF composite materials with nano-array structure;

[0090] Same as the third step in Example 1.

[0091] Step 4: Assemble the button battery;

[0092] Same as the fourth step in Example 1.

[0093] Example 5

[0094] The first step is to prepare MnO2 / CCF precursor;

[0095] The difference from the first step in Example 1 is that the manganese salt is lithium permanganate with a concentration of 15 mmol / L, the ammonium-containing compound is NH4NO3 with a concentration of 5 mmol / L, and the porous carbon fiber is carbon nanofiber.

[0096] Step 2: prepare EDTA0.15-MnO2 composite material;

[0097] Same as the second step in Example 1.

[0098] The third step is to prepare EDTA0.1-MnO2 / CCF composite materials with nano-array structure;

[0099] Same as the third step in Example 1.

[0100] Step 4: Assemble the button battery;

[0101] Same as the fourth step in Example 1.

[0102] Example 6

[0103] The first step is to prepare MnO2 / CCF precursor;

[0104] The difference from the first step in Example 1 is that the manganese salt is ammonium permanganate with a concentration of 12 mmol / L, the ammonium-containing compound is NH4HCO3 with a concentration of 4 mmol / L, and the porous carbon fiber is biomass-derived carbon.

[0105] Step 2: prepare EDTA0.15-MnO2 composite material;

[0106] Same as the second step in Example 1.

[0107] The third step is to prepare EDTA0.1-MnO2 / CCF composite materials with nano-array structure;

[0108] Same as the third step in Example 1.

[0109] Step 4: Assemble the button battery;

[0110] Same as the fourth step in Example 1.

[0111] Comparative Example 1

[0112] The first step is to prepare MnO2 / CCF precursor;

[0113] Same as the first step in Example 1.

[0114] Step 2: Prepare MnO2 / CCF composite material;

[0115] The dried MnO2 / CCF precursor obtained in the first step was annealed in air atmosphere for 1 h at an annealing temperature of 270°C to obtain a MnO2 / CCF composite cathode material.

[0116] Step 3: Assemble the button battery;

[0117] The MnO2 / CCF composite material prepared in the second step was directly cut into pieces and used as the positive electrode. The negative electrode was a metal zinc sheet, the separator was Whatman GF / D glass fiber filter paper, and the electrolyte was a mixed aqueous solution of 2 mol / L ZnSO4 and 0.2 mol / L MnSO4. They were assembled into CR2032 batteries in an air atmosphere.

[0118] Electrochemical performance test;

[0119] The assembled CR2032 battery was subjected to electrochemical performance test. The test results are as follows Figure 4 As shown, at 100 mA•g -1 After 100 cycles, the capacity is 99.6 mAh·g -1 .

[0120] Desolvation energy test;

[0121] The assembled CR2032 battery was subjected to desolvation energy test. The test results are as follows Figure 5 As shown, the desolvation energy is 36.49 KJ·mol -1 .

[0122] Comparative Example 2

[0123] The first step is to prepare MnO2 / CCF precursor;

[0124] Same as Example 1.

[0125] Step 2: Prepare NTA0.1-MnO2 / CCF composite material;

[0126] The MnO2 / CCF precursor was immersed in 1 mmol / L NTA solution (nitrilotriacetic acid aqueous solution), the molar ratio of NTA to MnO2 was controlled to 0.1, and the reaction was stirred at 70°C for 10 hours to obtain the NTA0.1-MnO2 / CCF composite material.

[0127] The third step is to prepare NTA0.1-MnO2 / CCF composite materials;

[0128] After the NTA0.1-MnO2 / CCF composite material prepared in the second step is cooled to room temperature, it is taken out, washed three times with distilled water, and then placed in a 60°C forced air drying oven for 24 hours. After it is completely dried, it is annealed in an air atmosphere for 1 hour at an annealing temperature of 270°C.

[0129] Step 4: Assemble the button battery;

[0130] The NTA0.1-MnO2 / CCF composite material prepared in the third step was directly cut into pieces and used as the positive electrode. The negative electrode was a metal zinc sheet, the separator was Whatman GF / D glass fiber filter paper, and the electrolyte was a mixed aqueous solution of 2 mol / L ZnSO4 and 0.2 mol / L MnSO4. They were assembled into CR2032 batteries in an air atmosphere.

[0131] Electrochemical performance test;

[0132] The assembled CR2032 battery was subjected to electrochemical performance test. The test results are as follows Figure 4 As shown, at 100 mA•g -1 The capacity after 100 cycles is 121.1 mAh·g -1 .

[0133] Desolvation energy test;

[0134] The assembled CR2032 battery was subjected to desolvation energy test. The test results are as follows Figure 5 As shown, the desolvation energy is 24.96 KJ·mol -1 .

[0135] Comparative Example 3

[0136] The first step is to prepare MnO2 / CCF precursor;

[0137] Same as the first step in Example 1.

[0138] The second step is to prepare EDTA0.02-MnO2 composite material;

[0139] The same as Example 1, except that the MnO2 / CCF precursor was immersed in a 0.2 mmol / L EDTA solution, the molar ratio of EDTA to MnO2 was controlled to be 0.02, and the reaction was stirred at 70°C for 10 hours.

[0140] The third step is to prepare EDTA0.02-MnO2 / CCF composite materials with nano-array structure;

[0141] Same as the third step in Example 1.

[0142] Step 4: Assemble the button battery;

[0143] Same as the fourth step in Example 1.

[0144] Electrochemical performance test;

[0145] The assembled CR2032 battery was subjected to electrochemical performance test. The test results are as follows Figure 4 As shown, at 100 mA•g -1The capacity after 100 cycles is 139.8 mAh·g -1 .

[0146] Desolvation energy test;

[0147] The assembled CR2032 battery was subjected to desolvation energy test. The test results are as follows Figure 5 As shown, the desolvation energy is 34.08 KJ·mol -1 .

[0148] Comparative Example 4

[0149] The first step is to prepare MnO2 / CCF precursor;

[0150] Same as the first step in Example 1.

[0151] Step 2: prepare EDTA0.2-MnO2 composite material;

[0152] The same as Example 1, except that the molar ratio of EDTA to MnO2 was controlled differently. The MnO2 / CCF precursor was immersed in a 2 mmol / L EDTA solution with a molar ratio of EDTA to MnO2 of 0.2, and stirred at 70°C for 10 hours.

[0153] The third step is to prepare EDTA0.2-MnO2 / CCF composite materials with nano-array structure;

[0154] Same as the third step in Example 1.

[0155] Step 4: Assemble the button battery;

[0156] Same as the fourth step in Example 1.

[0157] Electrochemical performance test;

[0158] The assembled CR2032 battery was subjected to electrochemical performance test. The test results are as follows Figure 4 As shown, at 100 mA•g -1 After 100 cycles, the capacity is 179.5 mAh·g -1 .

[0159] Desolvation energy test;

[0160] The assembled CR2032 battery was subjected to desolvation energy test. The test results are as follows Figure 5 As shown, the desolvation energy is 27.18 KJ·mol -1 .

[0161] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing a high-performance zinc ion battery positive electrode material based on an EDTA-MnO2 organic / inorganic dual storage interface, characterized in that: The steps include: Step 1: dissolving a manganese salt and an ammonium-containing compound in deionized water and performing a hydrothermal reaction on a porous carbon material as a substrate to obtain a MnO2 / C precursor; Step 2: Mixing the EDTA solution with the MnO2 / C precursor to carry out a chelating reaction, and finally drying to obtain an EDTA-MnO2 / C composite material; Step 3: After cooling to room temperature, the mixture is taken out and dried and annealed to obtain an EDTA-MnO2 / C composite material with a nano-array structure, i.e., a high-performance zinc ion battery positive electrode material.

2. The method for preparing a high-performance zinc ion battery positive electrode material based on EDTA-MnO2 organic / inorganic dual storage interface according to claim 1, characterized in that: In the step 1, the concentration of the manganese salt is 5-15 mmol / L, and the concentration of the ammonium compound is 3-5 mmol / L.

3. The method for preparing a high-performance zinc ion battery positive electrode material based on EDTA-MnO2 organic / inorganic dual storage interface according to claim 1, characterized in that: The manganese salt is permanganate, selected from one or a mixture of potassium permanganate, sodium permanganate, lithium permanganate, and ammonium permanganate; The ammonium-containing compound is selected from one or a mixture of (NH4)2SO4, NH4Cl, NH4NO3, NH4HCO3, and urea; The porous carbon material is selected from one or a mixture of carbonized cotton fiber, carbon fiber, carbon nanotube, carbon nanofiber, and biomass-derived carbon.

4. The method for preparing a high-performance zinc ion battery positive electrode material based on EDTA-MnO2 organic / inorganic dual storage interface according to claim 1, characterized in that: The concentration of the EDTA solution in step 2 is 0.5-1.5 mmol / L.

5. The method for preparing a high-performance zinc ion battery positive electrode material based on EDTA-MnO2 organic / inorganic dual storage interface according to claim 1, characterized in that: In the step 2, the molar ratio of EDTA to MnO2 is controlled to be 0.05-0.

15.

6. The method for preparing a high-performance zinc ion battery positive electrode material based on EDTA-MnO2 organic / inorganic dual storage interface according to claim 1, characterized in that: The hydrothermal reaction temperature in step 1 is 140° C. and the reaction time is 2 hours; the reaction temperature of the chelating reaction in step 2 is 70° C. and the reaction time is 10 hours; the annealing temperature in step 3 is 270° C. and the annealing time is 1 hour.

7. A high-performance zinc ion battery positive electrode material prepared by the preparation method according to any one of claims 1 to 6.

8. Use of the high performance zinc ion battery cathode material according to claim 7 in the preparation of zinc ion batteries.

9. A zinc ion battery, characterized in that: The invention comprises a positive electrode, a negative electrode, a separator and an electrolyte, wherein the positive electrode material used in the positive electrode is the high-performance zinc ion battery positive electrode material according to claim 7.

10. The zinc ion battery according to claim 9, wherein: The negative electrode is a metal zinc sheet, the separator is Whatman GF / D glass fiber filter paper, and the electrolyte is a mixed aqueous solution of ZnSO4 with a concentration of 1-3 mol / L and MnSO4 with a concentration of 0.1-0.3 mol / L.

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