High-performance zinc ion battery positive electrode material based on EDTA-MnO2 organic / inorganic dual-storage interface and preparation method of high-performance zinc ion battery positive electrode material

Abstract

The invention provides a high-performance zinc ion battery positive electrode material based on EDTA-MnO2 organic / inorganic double storage interfaces and a preparation method thereof, and the preparation method comprises the following steps: dissolving a manganese salt and an ammonium-containing compound in deionized water, and carrying out a hydrothermal reaction by taking a porous carbon material as a substrate to obtain a MnO2 / C precursor; mixing an EDTA (Ethylene Diamine Tetraacetic Acid) solution with the MnO2 / C precursor to carry out chelation reaction, and finally drying to obtain an EDTA-MnO2 / C composite material; and after cooling to room temperature, taking out, drying and annealing to obtain an EDTA-MnO2 / C composite material with a nano array structure, namely the high-performance zinc ion battery positive electrode material. According to the positive electrode material, EDTA is introduced as an organic guest molecule, an EDTA-MnO2 organic / inorganic hybrid positive electrode material is constructed, and the electrochemical performance of the zinc ion battery is remarkably improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of cathode materials for zinc-ion batteries, and particularly relates to a high-performance cathode material for zinc-ion batteries based on an organic / inorganic dual storage interface of EDTA-MnO2 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 excessive consumption has led to serious environmental pollution problems. Therefore, it is of great significance to develop a new energy system with low carbon, environmental protection, and clean and pollution-free characteristics. However, clean energies such as wind power, hydropower, and solar energy have problems such as difficult storage and transportation and unstable energy output due to conditions. Therefore, the development of large-scale energy storage devices 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 cathode material, manganese-based compounds (such as MnO2) have become a research hotspot due to their high theoretical capacity (about 308 mAh·g -1 )), rich resource reserves, and voltage platform matching the zinc anode.

[0003] However, in the existing manganese-based cathode materials during the Zn 2+ insertion / extraction process, the Jahn-Teller distortion of Mn 3+ causes lattice stress accumulation, leading to material structure collapse and active material stripping, significantly reducing the cycle life. In addition, manganese-based materials are prone to dissolution in acidic electrolytes, further exacerbating capacity decay. Zn 2+ in the hydrated state (such as Zn(H2O)6 2+ ) needs to overcome a high desolvation energy barrier (usually > 15 eV), resulting in slow interfacial reaction kinetics. At the same time, the close layered structure of MnO2 (layer spacing < 0.3 nm) limits the rapid diffusion of Zn 2+ , especially the capacity drops sharply during high-rate charge and discharge. Existing technologies mostly pre-insert metal ions (such as K + , Na + ) or introduce structural defects to expand the layer spacing, but such methods often sacrifice the proportion of active substances or introduce instability factors. Traditional modification strategies (such as heteroatom doping, surface coating) can partially improve the cycle stability, but often at the cost of sacrificing specific capacity. Therefore, there is an urgent need to develop a new type of manganese-based cathode material to achieve the unity of high ion diffusion rate, low desolvation energy barrier, and excellent structural stability through interface coupling and structural co-design, and 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 deficiencies in the prior art and proposes a high-performance cathode material for zinc-ion batteries based on an 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 realized as follows: In a first aspect, the present invention provides a preparation method of a high-performance cathode material for zinc-ion batteries based on an EDTA-MnO2 organic / inorganic dual storage interface, comprising the following steps: Step 1: Dissolve a manganese salt and an ammonium-containing compound in deionized water, and perform a hydrothermal reaction using a porous carbon material substrate to obtain a MnO2 / C precursor; Step 2: Mix an EDTA solution with the MnO2 / C precursor for a chelation reaction, and finally dry to obtain an EDTA-MnO2 / C composite material; Step 3: After cooling to room temperature, take it out, dry, and anneal to obtain an EDTA-MnO2 / C composite material with a nanoarray structure, that is, a high-performance cathode material for zinc-ion batteries; Preferably, in Step 1, the concentration of the manganese salt is 5-15 mmol / L, and the concentration of the ammonium-containing compound is 3-5 mmol / L.

[0006] Preferably, the manganese salt is selected from manganese salts that can be hydrothermally decomposed into MnO2, specifically permanganates, and is selected from one or a mixture of several of potassium permanganate, sodium permanganate, lithium permanganate, and ammonium permanganate.

[0007] Preferably, the ammonium-containing compound is selected from one or a mixture of several of (NH4)2SO4, NH4Cl, NH4NO3, NH4HCO3, and urea.

[0008] Preferably, the porous carbon material is selected from one or a mixture of several of carbonized cotton fibers, carbon fibers, carbon nanotubes, carbon nanofibers, and biomass-derived carbon.

[0009] Preferably, in Step 2, the concentration of the EDTA solution is 0.5-1.5 mmol / L.

[0010] Preferably, in Step 2, the molar ratio of EDTA to MnO2 is controlled to be 0.05-0.15.

[0011] Preferably, in Step 1, the hydrothermal reaction temperature is 120-140 °C, and the reaction time is 1-3 hours.

[0012] Preferably, in Step 2, the reaction temperature of the chelation reaction is 60-80 °C, and the reaction time is 6-12 hours.

[0013] Preferably, in the third step, the annealing temperature is 270~350 °C and the annealing time is 1~3 hours.

[0014] In a second aspect, the present invention provides a high-performance cathode material for zinc ion batteries prepared by the above preparation method.

[0015] In a third aspect, the present invention provides the use of the above high-performance cathode material for zinc ion batteries in the preparation of zinc ion batteries.

[0016] 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 for the positive electrode is the above high-performance cathode material for zinc ion batteries.

[0017] 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.

[0018] The cathode material of the present invention is composed of ethylenediaminetetraacetic acid (EDTA) and manganese dioxide (MnO2), forming an organic / inorganic hybrid structure. The polar groups of EDTA can destroy the solvation shell of zinc ions and enhance the adsorption capacity for Zn 2+ , while forming a stable interaction with the MnO2 framework to improve the structural stability of the material.

[0019] The cathode material of the present invention has a nanoarray structure, and the EDTA molecules are embedded between the MnO2 layers through chelation.

[0020] The EDTA-MnO2 / C composite material prepared by the present invention has self-supporting characteristics. When used as the cathode of ZIBs, it does not require the use of current collectors, binders and conductive additives and can be directly cut into pieces for use.

[0021] Compared with the prior art, the present invention has the following advantages: (1) By introducing EDTA as an organic guest molecule, the present invention constructs an EDTA-MnO2 organic / inorganic hybrid cathode material, significantly improving the electrochemical performance of zinc ion batteries; (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 rate of the material by constructing a dual storage interface, providing a new direction for the development of high-performance zinc ion batteries. Description of the Drawings

[0022] Figure 1 is the SEM image of EDTA0.05-MnO2 obtained in Example 1; Figure 2It is the SEM image of EDTA 0.1-MnO2 obtained in Example 2; Figure 3 It is the SEM image of EDTA 0.15-MnO2 obtained in Example 3; Figure 4 It is the electrochemical short-cycle performance graph of the composite materials obtained in Examples 1 to 3 and Comparative Examples 1 to 4; Figure 5 It is the desolvation energy test graph of the composite materials obtained in Examples 1 to 3 and Comparative Examples 1 to 4. Detailed Embodiments

[0023] 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 construed as a limitation to the present invention.

[0024] In this article, unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field to which this application belongs.

[0025] In this article, when a value is described as a range, it should be understood that such disclosure includes the disclosure of all possible sub-ranges within that range, as well as specific numerical values falling within that range, regardless of whether specific numerical values or specific sub-ranges are explicitly indicated.

[0026] In this article, when referring to "multiple", etc., unless otherwise specified, it means greater than 2 or equal to 2 in quantity. For example, "one or more" means one or greater than or equal to two.

[0027] In this article, when referring to "preferred", "more preferred", it is only for describing embodiments or examples with better effects. It should be understood that it does not constitute a limitation to the protection scope of the present invention.

[0028] In this article, when referring to "further", etc., it is used for descriptive purposes and indicates differences in content, but should not be construed as a limitation to the protection scope of the present invention.

[0029] In this article, the term "and / or" is a description of the association relationship of an object, indicating that there can be three relationships. For example, A and / or B means: A or B, or the three relationships of A and B.

[0030] In this article, the term "about" means + / - 10% of the specified value, preferably + / - 5%, more preferably + / - 1%.

[0031] In this article, the terms "comprising", "including", "having", "containing", etc. are all open-ended terms, that is, they are intended to include but not be limited to.

[0032] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which this invention pertains. Although this invention only describes preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of this invention.

[0033] The present invention will be described in detail below in conjunction with examples.

[0034] Example 1 First step, prepare the MnO2 / CCF precursor; Dissolve 10 mmol / L KMnO4 and 4 mmol / L (NH4)2SO4 in deionized water. Using carbonized cotton fiber (CCF) as the substrate, perform a hydrothermal reaction at 140 °C for 2 hours to obtain MnO2 / CCF nanosheets. After cooling to room temperature, take out the sample, wash it three times with distilled water, and then place it in a 60 °C forced-air drying oven for 24 h to obtain the MnO2 / CCF precursor.

[0035] Second step, prepare the EDTA0.05-MnO2 / CCF composite material; Immerse the MnO2 / CCF precursor in a 0.5 mmol / L EDTA solution, control the molar ratio of EDTA to MnO2 to be 0.05, and stir and react at 70 °C for 10 hours to obtain the EDTA0.05-MnO2 / CCF composite material.

[0036] Third step, prepare the EDTA0.05-MnO2 / CCF composite material with a nanoarray structure; After the EDTA0.05-MnO2 / CCF composite material prepared in the second step is cooled to room temperature, take it out, wash it three times with distilled water, and then place it in a 60 °C forced-air drying oven for 24 h. After complete drying, perform an annealing treatment. Anneal for 1 h in an air atmosphere, and the annealing temperature is 270 °C to obtain the EDTA0.05-MnO2 / CCF composite material, and its SEM image is as Figure 1 shown.

[0037] Fourth step, assemble a button battery; Directly cut the EDTA0.05-MnO2 / CCF composite material prepared in the third step and use it as the positive electrode, 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 2 mol / L ZnSO4 and 0.2 mol / L MnSO4. Assemble it into a CR2032 type battery in an air atmosphere.

[0038] Electrochemical performance test; Perform an electrochemical performance test on the assembled CR2032 type battery. AsFigure 4 As shown, the capacity after 100 cycles at 100 mA•g -1 is 221.3 mA•g -1 .

[0039] Desolvation energy test; The assembled CR2032 battery was tested for desolvation energy through the Arrhenius equation. The specific test process can be found in the reference (CHENG X, XIANG Z, YANG C, et al. Polar Organic Molecules Inserted in Vanadium Oxide with Enhanced Reaction Kinetics for Promoting Aqueous Zinc-Ion Storage [J]. Advanced Functional Materials, 2024, 34(9): 2311412.). The test results are as Figure 5 shown, and the desolvation energy is 23.27 KJ•mol -1 .

[0040] Example 2 First step: Prepare the MnO2 / CCF precursor; Same as the first step in Example 1.

[0041] Second step: Prepare the EDTA0.1-MnO2 composite material; Same as Example 1, except that the MnO2 / CCF precursor was immersed in a 1 mmol / L EDTA solution, and the molar ratio of EDTA to MnO2 was controlled to be 0.1, and stirred and reacted at 70 °C for 10 hours.

[0042] Third step: Prepare the EDTA0.1-MnO2 / CCF composite material with a nanoarray structure; Same as the third step in Example 1. The SEM image of the prepared EDTA0.1-MnO2 / CCF composite material is as Figure 2 shown.

[0043] Fourth step: Assemble the button battery; Same as the fourth step in Example 1.

[0044] Electrochemical performance test; The assembled CR2032 battery was tested for electrochemical performance. The test results are as Figure 4 shown, and the capacity after 100 cycles at 100 mA•g -1 is 283.6 mAh•g -1。

[0045] Desolvation energy test; The assembled CR2032 battery was subjected to desolvation energy test. The test results are as Figure 5 shown, the desolvation energy is 20.86 KJ•mol -1 。

[0046] Example 3 First step, prepare the MnO2 / CCF precursor; Same as the first step in Example 1.

[0047] Second step, prepare the EDTA0.15-MnO2 composite material; Same as Example 1, except that: the MnO2 / CCF precursor was immersed in a 1.5 mmol / L EDTA solution, controlling the molar ratio of EDTA to MnO2 to be 0.15, and stirring and reacting at 70 °C for 10 hours.

[0048] Third step, prepare the EDTA0.15-MnO2 / CCF composite material with a nanoarray structure; Same as the third step in Example 1, and the SEM image of the prepared EDTA0.15-MnO2 / CCF composite material is as Figure 3 shown.

[0049] Fourth step, assemble the button battery; Same as the fourth step in Example 1.

[0050] Electrochemical performance test; The assembled CR2032 battery was subjected to electrochemical performance test. The test results are as Figure 4 shown, at 100 mA•g -1 after 100 cycles, the capacity is 197.5 mAh•g -1 。

[0051] Desolvation energy test; The assembled CR2032 battery was subjected to desolvation energy test. The test results are as Figure 5 shown, the desolvation energy is 23.22 KJ•mol -1 。

[0052] Example 4 First step, prepare the MnO2 / CCF precursor; 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 fiber is carbon nanotube.

[0053] Step 2: Prepare the EDTA0.15-MnO2 composite material; Same as the second step in Example 1.

[0054] Step 3: Prepare the EDTA0.1-MnO2 / CCF composite material with a nanoarray structure; Same as the third step in Example 1.

[0055] Step 4: Assemble a button battery; Same as the fourth step in Example 1.

[0056] Example 5 Step 1: Prepare the MnO2 / CCF precursor; 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.

[0057] Step 2: Prepare the EDTA0.15-MnO2 composite material; Same as the second step in Example 1.

[0058] Step 3: Prepare the EDTA0.1-MnO2 / CCF composite material with a nanoarray structure; Same as the third step in Example 1.

[0059] Step 4: Assemble a button battery; Same as the fourth step in Example 1.

[0060] Example 6 Step 1: Prepare the MnO2 / CCF precursor; 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.

[0061] Step 2: Prepare the EDTA0.15-MnO2 composite material; Same as the second step in Example 1.

[0062] Step 3: Prepare the EDTA0.1-MnO2 / CCF composite material with a nanoarray structure; Same as the third step in Example 1.

[0063] Step 4: Assemble a button battery; Same as the fourth step in Example 1.

[0064] Comparative Example 1 Step 1: Prepare the MnO2 / CCF precursor; Same as the first step in Example 1.

[0065] Step 2: Prepare the MnO2 / CCF composite material; Anneal the dried MnO2 / CCF precursor obtained in the first step in an air atmosphere for 1 h at an annealing temperature of 270 °C to obtain the MnO2 / CCF composite cathode material.

[0066] Step 3: Assemble the coin cell; Cut the MnO2 / CCF composite material prepared in the second step directly into pieces and use it as the positive electrode, 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 2 mol / L ZnSO4 and 0.2 mol / L MnSO4. Assemble a CR2032 type battery in an air atmosphere.

[0067] Electrochemical performance test; Conduct an electrochemical performance test on the assembled CR2032 type battery. The test results are as Figure 4 shown. The capacity after 100 cycles at 100 mA•g -1 is 99.6 mAh•g -1 .

[0068] Desolvation energy test; Conduct a desolvation energy test on the assembled CR2032 type battery. The test results are as Figure 5 shown. The desolvation energy is 36.49 KJ•mol -1 .

[0069] Comparative Example 2 Step 1: Prepare the MnO2 / CCF precursor; Same as Example 1.

[0070] Step 2: Prepare the NTA0.1-MnO2 / CCF composite material; Immerse the MnO2 / CCF precursor in a 1 mmol / L NTA solution (nitrilotriacetic acid aqueous solution), control the molar ratio of NTA to MnO2 to be 0.1, and stir and react at 70 °C for 10 hours to obtain the NTA0.1-MnO2 / CCF composite material.

[0071] Step 3: Prepare the NTA0.1-MnO2 / CCF composite material; 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 blast drying oven at 60 °C for 24 h. After complete drying, annealing treatment is carried out, annealing for 1 h in an air atmosphere, and the annealing temperature is 270 °C.

[0072] Step 4: Assemble a button battery; The NTA0.1-MnO2 / CCF composite material prepared in the third step is directly cut into pieces and used as the positive electrode, 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 2 mol / L ZnSO4 and 0.2 mol / L MnSO4. A CR2032 type battery is assembled in an air atmosphere.

[0073] Electrochemical performance test; The assembled CR2032 type battery is subjected to an electrochemical performance test. The test results are as Figure 4 shown. The capacity after 100 cycles at 100 mA•g -1 is 121.1 mAh•g -1 .

[0074] Desolvation energy test; The assembled CR2032 type battery is subjected to a desolvation energy test. The test results are as Figure 5 shown. The desolvation energy is 24.96 KJ•mol -1 .

[0075] Comparative Example 3 Step 1: Prepare the MnO2 / CCF precursor; Same as the first step in Example 1.

[0076] Step 2: Prepare the EDTA0.02-MnO2 composite material; Same as Example 1, except that: the MnO2 / CCF precursor is immersed in a 0.2 mmol / L EDTA solution, controlling the molar ratio of EDTA to MnO2 to be 0.02, and stirring and reacting at 70 °C for 10 hours.

[0077] Step 3: Prepare the EDTA0.02-MnO2 / CCF composite material with a nanoarray structure; Same as the third step in Example 1.

[0078] Step 4: Assemble a button battery; Same as the fourth step in Example 1.

[0079] Electrochemical performance test; The assembled CR2032 battery was subjected to electrochemical performance testing. The test results are as Figure 4 shown. At 100 mA•g -1 , the capacity after 100 cycles was 139.8 mAh•g -1 .

[0080] Desolvation energy test; The assembled CR2032 battery was subjected to desolvation energy testing. The test results are as Figure 5 shown. The desolvation energy was 34.08 KJ•mol -1 .

[0081] Comparative Example 4 First step: Prepare the MnO2 / CCF precursor; Same as the first step in Example 1.

[0082] Second step: Prepare the EDTA0.2-MnO2 composite material; 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, and the molar ratio of EDTA to MnO2 was controlled to be 0.2. Stirring reaction was carried out at 70 °C for 10 hours.

[0083] Third step: Prepare the EDTA0.2-MnO2 / CCF composite material with a nanoarray structure; Same as the third step in Example 1.

[0084] Fourth step: Assemble the button battery; Same as the fourth step in Example 1.

[0085] Electrochemical performance test; The assembled CR2032 battery was subjected to electrochemical performance testing. The test results are as Figure 4 shown. At 100 mA•g -1 , the capacity after 100 cycles was 179.5 mAh•g -1 .

[0086] Desolvation energy test; The assembled CR2032 battery was subjected to desolvation energy testing. The test results are as Figure 5 shown. The desolvation energy was 27.18 KJ•mol -1 .

[0087] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims

1. A preparation method of a high-performance cathode material for zinc-ion batteries based on an EDTA-MnO2 organic / inorganic dual storage interface, characterized in that: It includes the following steps: Step 1: Dissolve manganese salt and ammonium-containing compound in deionized water, and carry out hydrothermal reaction using porous carbon material as the substrate to obtain the MnO2 / C precursor; Step 2: Mix the EDTA solution with the MnO2 / C precursor for chelation reaction, and finally dry to obtain the EDTA-MnO2 / C composite material; Step 3: After cooling to room temperature, take it out, dry and anneal to obtain the EDTA-MnO2 / C composite material with a nanoarray structure, that is, the positive electrode material for high-performance zinc ion batteries.

2. The preparation method of the high-performance zinc ion battery cathode material based on the EDTA-MnO2 organic / inorganic dual storage interface according to claim 1, wherein: In the above Step 1, the concentration of the manganese salt is 5-15 mmol / L, and the concentration of the ammonium-containing compound is 3-5 mmol / L.

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

4. The preparation method of the high-performance zinc ion battery cathode material based on the EDTA-MnO2 organic / inorganic dual storage interface according to claim 1, characterized in that: In the above Step 2, the concentration of the EDTA solution is 0.5-1.5 mmol / L.

5. The preparation method of the high-performance zinc ion battery cathode material based on the EDTA-MnO2 organic / inorganic dual storage interface according to claim 1, characterized in that: In the above Step 2, control the molar ratio of EDTA to MnO2 to be 0.05-0.

15.

6. The preparation method of the high-performance cathode material for zinc-ion batteries based on the EDTA-MnO2 organic / inorganic dual storage interface according to claim 1, characterized in that: In the above Step 1, the hydrothermal reaction temperature is 140 °C and the reaction time is 2 hours; in the above Step 2, the reaction temperature of the chelation reaction is 70 °C and the reaction time is 10 hours; in the above Step 3, the annealing temperature is 270 °C and the annealing time is 1 hour.

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

8. Use of the positive electrode material for high-performance zinc ion batteries according to claim 7 in the preparation of zinc ion batteries.

9. A zinc-ion battery, characterized in that: It includes a positive electrode, a negative electrode, a separator and an electrolyte. Among them, the positive electrode material used for the positive electrode is the positive electrode material for high-performance zinc ion batteries according to claim 7.

10. The zinc ion battery according to claim 9, characterized in that: The negative electrode is a metal zinc sheet, the separator is Whatman GF / D glass fiber filter paper, and the electrolyte is an aqueous mixed 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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