CN116598467B - Zinc ion battery, positive electrode material thereof and preparation method - Google Patents

Zinc ion battery, positive electrode material thereof and preparation method Download PDF

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CN116598467B
CN116598467B CN202310870859.7A CN202310870859A CN116598467B CN 116598467 B CN116598467 B CN 116598467B CN 202310870859 A CN202310870859 A CN 202310870859A CN 116598467 B CN116598467 B CN 116598467B
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CN116598467A (en
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张宝
徐宝和
程磊
龙祝迪
林可博
邓梦轩
张坤
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Pawa Changsha New Energy Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention belongs to the technical field of zinc ion batteries, and discloses a positive electrode material of a zinc ion battery and a preparation method thereof. The positive electrode material is ZnGe 2 O 4 /ZnMn 2 O 4 Composite coated hollow porous defect type manganese oxide material with chemical general formula of ZnGe 2 O 4 /ZnMn 2 O 4 @Mn 1‑x O 2‑y Wherein x is more than or equal to 0.003 and less than or equal to 0.02, and y is more than or equal to 0.01 and less than or equal to 0.05. The preparation method comprises the following steps: preparing Mn-MOF material; oxidizing and roasting Mn-MOF material to obtain MnO 2 A nanomaterial; calcination of the coated ZnGe 2 O 4 /ZnMn 2 O 4 . The positive electrode material should be used in zinc ion batteries, and the rate performance of the batteries is improved.

Description

Zinc ion battery, positive electrode material thereof and preparation method
Technical Field
The invention belongs to the technical field of zinc ion batteries, and particularly relates to a positive electrode material of a zinc ion battery.
Background
Compared with the traditional organic lithium ion battery, the water system zinc ion battery has the advantages of high safety, low cost, high energy density and the like, is considered as a next-generation renewable and safe energy storage system, and has great application prospect in the fields of wearable equipment, large-scale energy storage and the like. With alpha-MnO 2 The theory of multivalent state transition of (2) suggests that a zinc ion battery system based on a neutral aqueous solution is realized, namely, in a high-concentration neutral zinc ion salt solution, zinc ions are in alpha-MnO 2 Intercalation/deintercalation in the tunnel is accompanied by dissolution/deposition at the zinc anode, where electrons are transferred, constituting the cell. The neutral and water characteristics of the zinc ion battery change the reaction mechanism, greatly prolong the cycle life and have extremely high energy density. alpha-MnO based on intercalation/deintercalation theory of water system zinc ion battery 2 In electrochemical reactions mainly from MnO 2 The phase is finally converted into ZnMn 2 O 4 And (3) phase (C). But in the phase change process, the main body structure is changed to form manganese-based compounds Zn with various different valence states x MnO 4 MnOOH and Mn 2 O 3 The complex phase transition and electrochemical reactions of the intermediate phases also lead to the disputes of the energy storage mechanism of the zinc ion battery.
In order to ensure the reaction reversibility of the manganese dioxide material, a modification method is needed to be explored to ensure the structural stability of the manganese dioxide material, and meanwhile, the formation of excessive intermediate phases can be avoided to a certain extent, so that the purposes of improving the reversibility and structural stability of the material are finally achieved.
Disclosure of Invention
The invention aims to provide ZnGe 2 O 4 /ZnMn 2 O 4 Composite coated hollow porous defect type manganese oxide positive electrode material, and a preparation method and application thereof.
In order to solve the problems of poor cycling stability, poor structural reversibility and the like of manganese dioxide materials and improve the capacity retention rate and structural durability of the materials, the invention provides a positive electrode material of a zinc ion battery, which is ZnGe 2 O 4 /ZnMn 2 O 4 A composite coated hollow porous defect type manganese oxide material,the chemical general formula is ZnGe 2 O 4 /ZnMn 2 O 4 @Mn 1-x O 2-y Wherein x is more than or equal to 0.003 and less than or equal to 0.02, and y is more than or equal to 0.01 and less than or equal to 0.05.
Based on the same inventive concept, the invention provides a preparation method of the positive electrode material, which comprises the following steps:
step S1, dissolving manganese salt in deionized water or an organic solvent I to form a solution A; dissolving an organic complexing agent in deionized water or an organic solvent II to form a solution B; slowly adding the solution A into the solution B, continuously stirring, centrifuging, washing and drying after the reaction is completed to obtain the Mn-MOF material;
step S2, oxidizing and roasting the Mn-MOF material to obtain MnO 2 A nanomaterial;
step S3, continuously introducing nitrogen or inert gas into the calciner to lead MnO to be in a reaction state of 2 Mixing nano material, zinc salt and germanium dioxide, calcining to obtain ZnGe 2 O 4 /ZnMn 2 O 4 Composite coated hollow porous defect type manganese oxide material.
In a further preferred scheme, the manganese salt is one or more of manganese nitrate, manganese acetate and manganese sulfate; the organic solvent I and the organic solvent II are at least one of methanol, ethanol, glycol, acetone, N-Dimethylformamide (DMF), N-Diethylformamide (DEF) and dimethyl sulfoxide (DMSO); the organic complexing agent is at least one of fumaric acid, terephthalic acid, trimesic acid, phthalic acid and 1, 4-naphthalene dicarboxylic acid. The zinc salt is one or two of zinc acetate and zinc nitrate.
In a further preferred embodiment, the concentration of said solution A is 0.5-3mol/L; the concentration of the solution B is 0.3-3mol/L.
In a further preferred embodiment, the molar ratio of manganese salt to organic complexing agent is 1: 10-20.
In a further preferred embodiment, the solution A is slowly added to the solution B at a rate of 1-5mL/min.
In a further preferred scheme, the reaction temperature is 15-25 ℃, and the reaction time is 10-30 hours.
In a further preferred embodiment, the drying temperature is 60-100 ℃.
In a further preferred embodiment, the oxidizing roasting atmosphere is an oxygen or air atmosphere; the temperature of the oxidizing roasting is 700-1000 ℃, and the time of the oxidizing roasting is 8-20 h.
In a further preferred embodiment, in the calciner, mnO 2 The molar ratio of the nano material to the zinc nitrate to the germanium dioxide is 1:0.03 to 0.08:0.05 to 0.16.
In a further preferred scheme, the calcination temperature is 700-900 ℃ and the calcination time is 5-20 h.
In addition, the invention provides an aqueous zinc ion battery comprising ZnGe 2 O 4 /ZnMn 2 O 4 Composite coated hollow porous defect type manganese oxide material.
The invention has the following obvious beneficial effects:
the ZnGe provided by the invention 2 O 4 /ZnMn 2 O 4 Compared with the manganese dioxide material which is not modified in a composite manner, the composite-coated hollow porous defective manganese oxide material has the advantages that the conductivity is greatly improved, and the high rate performance and the reversibility of the material are realized through the structural transformation of the material.
The invention prepares ZnGe 2 O 4 /ZnMn 2 O 4 The method for the composite coated hollow porous defect type manganese oxide material is novel, the modification effect is obvious, and a new idea is provided for researching the water system zinc ion battery anode material.
Drawings
FIG. 1 is a TEM image of the product of example 1;
FIG. 2 is an XPS diagram of the product Mn in example 1;
fig. 3 is a HRTEM image of the product of example 1.
Detailed Description
In order to solve the problems of poor cycling stability, poor structural reversibility and the like of manganese dioxide materials and improve the capacity retention rate and structural durability of the materials, the invention provides a positive electrode of a zinc ion batteryA positive electrode material of ZnGe 2 O 4 /ZnMn 2 O 4 Composite coated hollow porous defect type manganese oxide material with chemical general formula of ZnGe 2 O 4 /ZnMn 2 O 4 @Mn 1-x O 2-y Wherein x is more than or equal to 0.003 and less than or equal to 0.02, and y is more than or equal to 0.01 and less than or equal to 0.05.
Manganese dioxide material mainly generates MnO in electrochemical process 2 The phase is finally converted into ZnMn 2 O 4 While in the long-term deintercalation process, the phase transition will form manganese-based compounds Zn with various different valence states due to the change of the main structure x MnO 4 MnOOH and Mn 2 O 3 The intermediate phases, the phase change and the electrochemical reaction are complex, and the capacity retention rate of the material is affected. But if the surface is coated with ZnMn 2 O 4 The phase will effectively promote ZnMn 2 O 4 The formation of the final phase, which reduces the production of by-products, will effectively increase the capacity retention of the material. Furthermore, znGe 2 O 4 /ZnMn 2 O 4 Has a similar crystal structure and can be used in ZnMn 2 O 4 The phase is used as the main transition phase, and the structural stability and ZnMn of the main material are protected 2 O 4 The stability of the phase eventually improves the structural durability of the manganese oxide material.
The ZnGe powder 2 O 4 /ZnMn 2 O 4 The preparation method of the composite coated hollow porous defect type manganese oxide material comprises the following steps:
step S1, dissolving manganese salt in deionized water or an organic solvent I to form a solution A; dissolving an organic complexing agent in deionized water or an organic solvent II to form a solution B; slowly adding the solution A into the solution B, continuously stirring, centrifuging, washing and drying after the reaction is completed to obtain the Mn-MOF material;
step S2, oxidizing and roasting the Mn-MOF material to obtain MnO 2 A nanomaterial;
step S3, continuously introducing nitrogen or inert gas into the calciner to lead MnO to be in a reaction state of 2 Mixing nano material, zinc salt and germanium dioxide, calcining to obtain ZnGe 2 O 4 /ZnMn 2 O 4 Composite hollow porous defect type manganese oxide material.
1. Preparation of Mn-MOF materials
Mn-MOF material was prepared as a template in step S1.
In the process of preparing the Mn-MOF material, the type of manganese salt is not particularly limited as long as it can be dissolved in water or an organic solvent I. In the specific embodiment of the invention, the manganese salt is one or more of manganese nitrate, manganese acetate and manganese sulfate; the organic solvent I or II is at least one of methanol, ethanol, glycol, acetone, N-Dimethylformamide (DMF), N-Diethylformamide (DEF) and dimethyl sulfoxide (DMSO).
The organic complexing agent is used for forming complex precipitate or floccule, namely the metal organic framework material. Organic complexing agents which can be used as metal organic framework materials can be used as the reaction raw materials of the invention. In a specific embodiment of the present invention, the organic complexing agent is at least one of fumaric acid, terephthalic acid, trimesic acid, phthalic acid, and 1, 4-naphthalene dicarboxylic acid.
In addition, in the specific embodiment of the invention, the concentration of the solution A is selected to be 0.5-3mol/L according to a plurality of experimental data; the concentration of the solution B is 0.3-3mol/L; the molar ratio of the manganese salt to the organic complexing agent is 1: 10-20 parts of a base; the slow adding speed of the solution A and the solution B is 1-5mL/min; the reaction temperature is 15-25 ℃, and the reaction time is 10-30 h; the drying temperature is 60-100 ℃.
2. Oxidizing and roasting to obtain MnO 2 Nanomaterial for the preparation of a nanoparticle
Roasting Mn-MOF template in oxidizing atmosphere to obtain hollow porous MnO 2 The nano material has ultrahigh specific surface area and more pore structures. In a specific embodiment of the present invention, the oxidizing roasting atmosphere is an oxygen or air atmosphere; the temperature of the oxidizing roasting is 700-1000 ℃, and the time of the oxidizing roasting is 8-20 h.
3. Composite coated ZnGe 2 O 4 /ZnMn 2 O 4
MnO is added to 2 Uniformly mixing the nano material, zinc salt and germanium dioxide, and calcining under nitrogen or inert atmosphere to obtain ZnGe 2 O 4 /ZnMn 2 O 4 Composite hollow porous defect type manganese oxide material. During this reaction, a reduction reaction mainly takes place, in which Zn in the zinc salt 2+ With MnO 2 React to form ZnMn 2 O 4 ，Zn 2+ React with germanium dioxide to form ZnGe 2 O 4 . The species that react at high temperatures will eventually form a reduction product by chemical bonding.
Through investigation of the composite clad calcination process, in particular embodiments of the present invention, the following implementation parameters are further preferred: the zinc salt is one or two of zinc acetate and zinc nitrate. In the calciner, mnO 2 The molar ratio of the nano material to the zinc salt to the germanium dioxide is 1:0.03 to 0.08: 0.05-0.16; the calcination temperature is 700-900 ℃, and the calcination time is 5-20 h.
In addition, the invention provides an aqueous zinc ion battery comprising ZnGe 2 O 4 /ZnMn 2 O 4 Composite coated hollow porous defect type manganese oxide material.
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1
0.025mol of manganese nitrate was dissolved in 50ml of deionized water to form solution A. 0.25mol of terephthalic acid was dissolved in 200ml of DMF to form solution B. Slowly adding the solution A into the solution B at a speed of 1mL/min at 15 ℃ and continuously stirring for reaction for 10 hours, and obtaining the Mn-MOF material after centrifugation, washing and drying at 60 ℃.
Sintering Mn-MOF material for 10 hours at a high temperature of 800 ℃ in oxygen atmosphere to obtain hollow porous MnO 2 A nanomaterial.
Hollow porous MnO is treated under nitrogen atmosphere 2 Mixing the nano material, 1mmol zinc nitrate and 1.9mmol germanium dioxide, placing in a calciner, and calcining at 900 ℃ for 8 hours to form a final product ZnGe 2 O 4 /ZnMn 2 O 4 Composite coated defective manganese oxide nano material.
Fig. 1 is a TEM image of the material finally prepared in example 1, from which it can be seen: the product has a hollow porous structure.
FIG. 2 is an XPS plot of Mn for the product of example 1. Table 1 is the data from the fit of fig. 2.
TABLE 1
+4 valence +3 valence +2 valence
Mn valence state ratio 73.2% 19.3% 7.5%
It can be found that MnO 2 The valence state of Mn in the nanomaterial shifts to a lower valence state, indicating that oxygen defects are present in the material. Meanwhile, as can be confirmed from FIG. 3, due to the outer coating and MnO 2 A transition layer is arranged between the two layers, and a small amount of Zn is doped into MnO 2 In the material, the metal electronic structure is changed to generate defects; meanwhile, the surface layer has two lattice distances, which indicates that the coating layer contains 2 phases, and the specific phase composition of the coating layer can be obtained according to the feeding ratio and the reaction process and is ZnGe 2 O 4 /ZnMn 2 O 4 。
Example 2
0.05mol of manganese acetate was dissolved in 50ml of deionized water to form solution A. 0.6mol of trimesic acid was dissolved in 200ml of ethanol to form a solution B. Slowly adding the solution A into the solution B at the speed of 2mL/min at the temperature of 20 ℃ and continuously stirring for reacting for 20 hours, and obtaining the Mn-MOF material with a cube structure after centrifugation, washing and drying at the temperature of 100 ℃.
Sintering Mn-MOF material for 20 hours at 700 ℃ in oxygen atmosphere to obtain MnO 2 A nanomaterial.
Under argon atmosphere, the prepared MnO is prepared 2 After mixing 4mmol zinc nitrate and 2.5mmol germanium dioxide, the final product is formed by calcination at 700 ℃ for 18 h.
Example 3
0.15mol of manganese sulfate was dissolved in 50ml of deionized water to form solution A. 1.5mol of phthalic acid was dissolved in 2000ml of methanol to form solution B. Slowly adding the solution A into the solution B at the speed of 5mL/min at the temperature of 25 ℃ and continuously stirring for reaction for 30 hours, and obtaining the Mn-MOF material with a cube structure after centrifugation, washing and drying at the temperature of 80 ℃.
Sintering for 10h at 1000 ℃ in oxygen atmosphere to obtain MnO 2 A nanomaterial.
Under nitrogen atmosphere, the prepared MnO 2 45mmol of zinc nitrate and 75mmol of germanium dioxide are mixed and calcined at a high temperature of 800 ℃ for 12 hours to form the final product ZnGe2O4/ZnMn2O4 composite coated defective manganese oxide nano material.
Example 4
0.04mol of manganese acetate was dissolved in 50ml of deionized water to form solution A. 0.4mol of fumaric acid was dissolved in 200ml of deionized water to form solution B. Slowly adding the solution A into the solution B at the speed of 3mL/min at 15 ℃ and continuously stirring for reaction for 20 hours, and obtaining the Mn-MOF material with a cubic structure after centrifugation, washing and drying at 60 ℃.
Sintering Mn-MOF material for 15h at 900 ℃ in oxygen atmosphere to obtain MnO 2 A nanomaterial.
Under nitrogen atmosphere, the prepared MnO 2 Mixing 2mmol zinc nitrate and 4mmol germanium dioxide, calcining at 900 deg.C for 8 hr to obtain final product ZnGe 2 O 4 /ZnMn 2 O 4 Composite coated defective manganese oxide nano material.
Example 5
0.05mol of manganese nitrate was dissolved in 50ml of deionized water to form solution A. 1mol of 1, 4-naphthalenedicarboxylic acid was dissolved in 2000ml of ethanol to prepare a solution B. Slowly adding the solution A into the solution B at the speed of 3mL/min at the temperature of 25 ℃ and continuously stirring for reaction for 20 hours, and obtaining the Mn-MOF material with a cube structure after centrifugation, washing and drying at the temperature of 100 ℃.
Sintering Mn-MOF material at 1000 ℃ for 8 hours in oxygen atmosphere to obtain MnO 2 A nanomaterial.
Under argon atmosphere, the prepared MnO is prepared 2 After 2mmol of zinc acetate and 5mmol of germanium dioxide are mixed, the mixture is calcined at 900 ℃ for 8 hours to form the final product ZnGe2O4/ZnMn2O4 composite coated defective manganese oxide nanomaterial.
The final materials prepared in examples 1-5 were MnO as the currently commonly used positive electrode material for aqueous zinc ion batteries 2 (purchased from Jiangsu Xianfeng nano materials science and technology Co., ltd.) as a positive electrode material, and mixing with conductive agent Acetylene Black (AB) and binder polyvinylidene fluoride (PVDF) according to the mass ratio of 7:2:1, taking N-methyl pyrrolidone (NMP) as a solvent, and placing in a small beaker to stir and mix for 2 hours at the rotating speed of 800r/min to obtain slurry. Coating the slurry on a current collector stainless steel foil by using an automatic coating machine, horizontally placing on toughened glass, and turningDrying in a vacuum drying oven at 85deg.C for 4 hr, preparing the punched sheet into 12mm diameter pole piece, and drying in a vacuum drying oven at 105deg.C for 4 hr to obtain CR2032 button cell. The battery takes a pure metal zinc sheet with the diameter of 16mm and the thickness of 0.5mm as a negative electrode, takes a mixed solution of 3M zinc sulfate and 0.05M manganese sulfate as an electrolyte, and takes a glass fiber diaphragm with the model of Whatman GF/D with the diameter of 18mm as a diaphragm.
After the battery is assembled and aged for 12 hours, the charge and discharge tests with different potentials are carried out. The specific discharge capacity results of the cells after 100 cycles at a current density of 500mA/g at a voltage of 0.8-1.9V are shown in Table 2.
TABLE 2
As can be seen from Table 2, with MnO 2 In contrast, via ZnGe 2 O 4 /ZnMn 2 O 4 The composite coated defective manganese oxide nanomaterial has higher capacity retention rate. The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (10)

1. A positive electrode material of a zinc ion battery is characterized in that the positive electrode material is ZnGe 2 O 4 /ZnMn 2 O 4 Composite coated hollow porous defect type manganese oxide material with chemical general formula of ZnGe 2 O 4 /ZnMn 2 O 4 @Mn 1-x O 2-y Wherein x is more than or equal to 0.003 and less than or equal to 0.02, and y is more than or equal to 0.01 and less than or equal to 0.05.
2. The method for preparing a positive electrode material of a zinc-ion battery according to claim 1, comprising the steps of:
step S1, dissolving manganese salt in deionized water or an organic solvent I to form a solution A; dissolving an organic complexing agent in deionized water or an organic solvent II to form a solution B; slowly adding the solution A into the solution B, continuously stirring, centrifuging, washing and drying after the reaction is completed to obtain the Mn-MOF material;
step S2, oxidizing and roasting the Mn-MOF material to obtain MnO 2 A nanomaterial;
step S3, continuously introducing nitrogen or inert gas into the calciner to lead MnO to be in a reaction state of 2 Mixing nano material, zinc salt and germanium dioxide, calcining to obtain ZnGe 2 O 4 /ZnMn 2 O 4 Composite coated hollow porous defect type manganese oxide material.
3. The preparation method according to claim 2, wherein the manganese salt is one or more of manganese nitrate, manganese acetate and manganese sulfate; the organic solvent I and the organic solvent II are at least one of methanol, ethanol, glycol, acetone, N-Dimethylformamide (DMF), N-Diethylformamide (DEF) and dimethyl sulfoxide (DMSO); the organic complexing agent is at least one of fumaric acid, terephthalic acid, trimesic acid, phthalic acid and 1, 4-naphthalene dicarboxylic acid; the zinc salt is one or two of zinc acetate and zinc nitrate.
4. A process according to claim 2 or 3, wherein the concentration of solution a is 0.5-3mol/L; the concentration of the solution B is 0.3-3mol/L; the molar ratio of the manganese salt to the organic complexing agent is 1: 10-20.
5. The process of claim 4, wherein solution A is slowly added to solution B at a rate of 1-5mL/min.
6. The preparation method according to claim 2, wherein the reaction temperature is 15-25 ℃, and the reaction time is 10-30 hours; the drying temperature is 60-100 ℃.
7. The method according to claim 2, wherein the oxidizing roasting atmosphere is an oxygen or air atmosphere; the temperature of the oxidizing roasting is 700-1000 ℃, and the time of the oxidizing roasting is 8-20 h.
8. The method of claim 2, wherein MnO is in the calciner 2 The molar ratio of the nano material to the zinc nitrate to the germanium dioxide is 1:0.03 to 0.08:0.05 to 0.16.
9. The method according to claim 2 or 8, wherein the calcination temperature is 700 to 900 ℃ and the calcination time is 5 to 20 hours.
10. An aqueous zinc-ion battery comprising the ZnGe of claim 1 2 O 4 /ZnMn 2 O 4 Composite coated hollow porous defective manganese oxide material or ZnGe prepared by the preparation method of any one of claims 2-9 2 O 4 /ZnMn 2 O 4 Composite coated hollow porous defect type manganese oxide material.
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