CN114229903A - MnO (MnO)2Electrode material and preparation method and application thereof - Google Patents

MnO (MnO)2Electrode material and preparation method and application thereof Download PDF

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CN114229903A
CN114229903A CN202111395962.8A CN202111395962A CN114229903A CN 114229903 A CN114229903 A CN 114229903A CN 202111395962 A CN202111395962 A CN 202111395962A CN 114229903 A CN114229903 A CN 114229903A
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mno
electrode material
ion battery
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CN114229903B (en
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王浩
秦晨晨
万厚钊
吕琳
马国坤
汪汉斌
张军
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Hubei University
Hubei Jiangcheng Laboratory
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    • 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
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    • 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
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses MnO2An electrode material and a preparation method and application thereof, belonging to the technical field of energy storage materials. MnO of the invention2The preparation method of the electrode material comprises the following steps: (1) dripping polyethylene glycol into potassium permanganate aqueous solution, and uniformly stirring; (2) putting the prepared solution into a high-pressure reaction kettle for hydrothermal reaction; (3) filtering and drying the solution after reaction; (4) collecting the dried sample and annealing in air to obtain the MnO2An electrode material. MnO prepared by the invention2The electrode material has high surface active sites and MnO2A C film is formed on the surface so that MnO is2The electrode material has good conductivity and higher specific capacity. After the lithium ion battery is charged and discharged for 2000 circles under the current density of 5A/g, the specific capacity is reduced from 143.0mAh/g to 98.6mAh/g, and the specific capacity retention rate is close to 70%.

Description

MnO (MnO)2Electrode material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of energy storage materials, particularly relates to an electrode material, and more particularly relates to MnO2An electrode material, a preparation method and application thereof.
Background
With the rapid development of world economy in recent years, the energy crisis is becoming more serious, and people pay attention to the research and development of high-efficiency energy storage devices. Currently, lithium ion batteries are widely used in the battery market due to their high specific energy. However, the lithium resources on the earth are few, so that the lithium-containing material is expensive, and most importantly, the lithium ion battery has potential safety hazards, and a fire caused by explosion of the lithium ion battery sometimes occurs, so that a high-safety energy storage device needs to be searched. The zinc ion secondary battery of the water-based electrolyte is the first to come, and is considered to be one of the most promising candidates for replacing the lithium ion battery because there is no danger of explosion.
The water system zinc ion secondary battery has the advantages of large specific capacity, high safety, low cost, environmental friendliness and the like, and has wide application prospect. However, water-based zinc ion batteries still have a series of challenges, and the development of high-performance cathode materials is one of the focuses of people.
The cathode material of the water-based zinc ion battery mainly comprises manganese-based oxide, vanadium-based oxide, Prussian blue analogue and organic compound. The manganese-based oxide has been widely studied because of its abundant storage capacity on earth, no pollution and high discharge voltage. MnO2Has a rich and abundant nutritionRich and varied crystal structures, e.g. alpha-MnO2、β-MnO2、γ-MnO2、δ-MnO2. But MnO made by different methods2The performances are very different, and therefore, a new method needs to be developed to improve the electrochemical performance of the water-based zinc ion battery.
For the above reasons, the present application has been made.
Disclosure of Invention
In view of the problems or disadvantages of the prior art, it is an object of the present invention to provide a MnO2The electrode material, the preparation method and the application thereof solve or at least partially solve the technical defects in the prior art.
The invention develops MnO2The preparation method of the electrode material comprises the following steps:
(1) dripping polyethylene glycol into potassium permanganate aqueous solution, and uniformly stirring;
(2) putting the prepared solution into a high-pressure reaction kettle for hydrothermal reaction;
(3) filtering and drying the solution after reaction;
(4) collecting the dried sample and annealing in air to obtain the MnO2An electrode material.
Further, in the step (1), a certain amount of potassium permanganate is added into deionized water, polyethylene glycol is dropped into the solution by using a liquid-transferring gun, the solution is placed on a magnetic stirrer to be stirred and completely dissolved, the obtained solution is poured into a polytetrafluoroethylene inner container, wherein the amount of the potassium permanganate is 1-100 mmol, the amount of the polyethylene glycol is 1-300 ml, and the amount of the deionized water is 10-6000 ml.
Furthermore, in the above technical scheme, the usage ratio of the potassium permanganate, the polyethylene glycol and the deionized water in the step (1) is 1 mmol: 3 ml: 60 ml.
As a preferred embodiment of the present invention, the solution in step (1) in the above technical solution is prepared by the following method:
(a) weighing 0.15g of potassium permanganate at room temperature by using weighing paper and lightly putting the potassium permanganate into a clean beaker;
(b) weighing 60ml of deionized water by using a measuring cylinder at room temperature, and pouring the deionized water into the beaker in the step (a) to form a solution A;
(c) taking 3ml of polyethylene glycol by using a liquid transfer gun at room temperature, dripping the polyethylene glycol into the solution A, and stirring the solution A on a magnetic stirrer to completely dissolve the polyethylene glycol to form a solution B;
(d) and pouring the solution B into a polytetrafluoroethylene inner container at room temperature for later use.
Further, in the above technical scheme, the hydrothermal reaction in the step (2) is to place the polytetrafluoroethylene inner container in the step (1) into a stainless steel reaction kettle lined with teflon, and then place the reaction kettle into a drying oven for reaction. Wherein the temperature of the drying oven is set to be 100-300 ℃, and the reaction time is set to be 1-30 h.
Furthermore, according to the technical scheme, the temperature of the drying oven is set to be 160 ℃, and the reaction time is set to be 5 h.
Further, the filtering in the step (3) is to take the polytetrafluoroethylene inner container out of the stainless steel reaction kettle, pour the solution into a suction filtration device, clean and filter the solution by using deionized water and ethanol or acetone, collect a filtered powder sample by using filter paper, and place the filtered powder sample into a drying box for drying.
Further, the annealing in the step (4) is to put the dried sample into a high-temperature sintering furnace to react in a gas atmosphere. Wherein the annealing temperature is set to be 100-800 ℃, and the annealing time is set to be 0.5-12 h. Through characterization tests such as XRD and thermal gravimetric differential thermal map (DTA), it can be seen that as the set reaction temperature increases, the generated sample oxygen vacancies increase, so that the sample surface has higher active sites. However, as the temperature rises to about 550 ℃, the sample will move from MnO2Phase change to Mn2O3The specific capacity of the product after cycling is also reduced along with the phase change.
Preferably, the annealing step is carried out in an air atmosphere, the annealing temperature is preferably 400 ℃, and the annealing time is preferably 2 hours.
The second object of the present invention is to provide MnO prepared by the above-mentioned method2An electrode material.
The third purpose of the invention is to provide MnO prepared by the method2An electrode material is applied to an aqueous zinc ion battery.
The water system zinc ion battery positive electrode material comprises a positive electrode active material, a conductive agent and a binder, wherein the positive electrode active material is MnO prepared by the method2An electrode material.
The positive electrode comprises a current collector and a positive electrode material coated and/or filled on the current collector, wherein the positive electrode material is the positive electrode material of the water system zinc ion battery.
Further, according to the technical scheme, the preparation method of the water-based zinc ion battery positive electrode specifically comprises the following steps:
MnO is added to the mixture2Taking an electrode material as an active substance, taking Polytetrafluoroethylene (PTFE) or polyvinylidene fluoride (PVDF) as an adhesive, taking acetylene black as a conductive agent, uniformly grinding, then dripping N-methyl pyrrolidone (NMP), grinding again to obtain electrode slurry, taking a stainless steel mesh as a current collector, coating the prepared electrode slurry on the stainless steel mesh, drying, and tabletting to obtain the anode of the water-based zinc ion battery.
Preferably, in the above technical solution, the MnO2The adding amount ratio of the electrode material, Polytetrafluoroethylene (PTFE) or polyvinylidene fluoride (PVDF), acetylene black and N-methylpyrrolidone (NMP) is 70mg:10mg:20mg:1 ml.
Preferably, in the above technical solution, the electrode slurry is uniformly coated on a stainless steel mesh with a size of 3cm (width) × 6cm (length).
Preferably, the drying temperature is 65 ℃, and the drying time is more than 8 hours, preferably 12 hours.
Preferably, the pressure during tabletting is 10MPa and the time is 30 s.
A water system zinc ion battery comprises an anode, a cathode, a diaphragm arranged between the anode and the cathode, electrolyte and a shell, wherein the anode is the anode of the water system zinc ion battery, and the cathode is a zinc-based material.
The reaction mechanism of the present invention is as follows:
according to the invention, potassium permanganate and polyethylene glycol are subjected to oxidation-reduction reaction in the hydrothermal reaction, and the potassium permanganate is reduced to generate MnOOH. Putting the generated MnOOH in a high-temperature sintering furnace, annealing at different temperatures in air atmosphere, oxidizing trivalent manganese into tetravalent manganese under the action of oxygen in the annealing process, forming oxygen vacancies, improving the specific surface area of a sample due to the existence of the oxygen vacancies, and leaving a part of C element on the surface of the MnOOH after decomposition of polyethylene glycol in hydrothermal reaction, thereby improving the purity of MnO2The specific capacity of (A).
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention prepares MnO by hydrothermal synthesis method2The electrode material has very simple process flow, greatly simplifies the experimental procedures, is convenient for industrial implementation and application, and has wide market prospect. Obtained MnO2The electrode material contains oxygen vacancy, improves the specific surface area of the sample, enables the sample to have higher surface active sites, and has MnO2A C film is formed on the surface so that MnO is2The electrode material has good conductivity and higher specific capacity. After the lithium ion battery is charged and discharged for 2000 circles under the current density of 5A/g, the specific capacity is reduced from 143.0mAh/g to 98.6mAh/g, and the specific capacity retention rate is close to 70%.
Drawings
In FIG. 1, (a), (b), (c), (d), (e) and (f) are sequentially MnO prepared in examples 1 to 6 of the present invention2Scanning Electron Microscope (SEM) images of the electrode material at different magnifications; (g) for Mn prepared in example 72O3Scanning Electron Microscope (SEM) images of the electrode material;
FIG. 2 shows MnO prepared in examples 1 to 7 of the present invention2MnO is obtained by annealing the precursor (MnOOH) in a high-temperature sintering furnace at 280 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃ and 550 DEG C2Corresponding XRD curve contrast diagram;
in FIG. 3, (a) and (b) are MnO prepared in example 4 of the present invention, respectively2CV images of the zinc ion battery assembled by the electrode material at the scanning speed of 1mv/s and different scanning speeds;
FIG. 4 is a thermal gravimetric difference chart (DTA) of a precursor MnOOH in air for all examples of the present invention;
FIG. 5 shows MnO prepared in examples 1-5 of the present invention2Electron Paramagnetic Resonance (EPR) contrast maps of electrode materials;
FIG. 6 shows MnO prepared in example 4 of the present invention2A raman image of the electrode material;
FIG. 7 is MnO obtained in examples 1 to 5 of the present invention2Electrode material and Mn obtained in example 72O3A cycle performance comparison diagram of the water system zinc ion battery assembled by the electrode material under the current density of 5A/g;
FIG. 8 is MnO prepared in example 4 of the present invention2And (3) a rate performance graph of the zinc ion battery assembled by the electrode material under different current densities.
Detailed Description
The present invention will be described in further detail below with reference to examples. The present invention is implemented on the premise of the technology of the present invention, and the detailed embodiments and specific procedures are given to illustrate the inventive aspects of the present invention, but the scope of the present invention is not limited to the following embodiments.
Various modifications to the precise description of the invention will be readily apparent to those skilled in the art from the information contained herein without departing from the spirit and scope of the appended claims. It is to be understood that the scope of the invention is not limited to the procedures, properties, or components defined, as these embodiments, as well as others described, are intended to be merely illustrative of particular aspects of the invention. Indeed, various modifications of the embodiments of the invention which are obvious to those skilled in the art or related fields are intended to be covered by the scope of the appended claims.
For a better understanding of the invention, and not as a limitation on the scope thereof, all numbers expressing quantities, percentages, and other numerical values used in this application are to be understood as being modified in all instances by the term "about". At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
The test methods used in the following examples are all conventional methods unless otherwise specified; the raw materials and reagents used are, unless otherwise specified, those commercially available from ordinary commercial sources.
Electrochemical performance testing in the following examples is based on packaging into button cells: positive electrode (containing MnO)2Electrode material or Mn2O3Positive electrode of electrode material), hydrophilic fiber separator, negative electrode of commercial zinc sheet, and (2M ZnSO)4+0.2M MnSO4) And (3) an electrolyte.
Example 1
MnO of this embodiment2The preparation method of the electrode material comprises the following steps:
(1) solution preparation:
(a) weighing 0.15g of potassium permanganate at room temperature by using weighing paper and lightly putting the potassium permanganate into a clean beaker;
(b) weighing 60ml of deionized water by using a measuring cylinder at room temperature, and pouring the deionized water into the beaker in the step (a) to form a solution A;
(c) dripping 3ml of polyethylene glycol (PEG400) into the solution A by using a liquid transfer gun at room temperature, and stirring on a magnetic stirrer to completely dissolve the polyethylene glycol to form a solution B;
(d) and pouring the solution B into a polytetrafluoroethylene inner container at room temperature for later use.
(2) Hydrothermal reaction: and (2) at room temperature, putting the polytetrafluoroethylene inner container in the step (1) into a stainless steel reaction kettle lined with teflon, and then putting the stainless steel reaction kettle into a drying box for reaction. Wherein the temperature of the drying oven is set to 160 ℃ and the reaction time is set to 5 h.
(3) And (3) suction filtration: and (3) at room temperature, after the reaction in the step (2) is finished, taking the polytetrafluoroethylene inner container out of the stainless reaction kettle, pouring the solution into a suction filtration device, washing with deionized water for 3 times and ethanol for 2 times, and collecting a filtered powder sample with filter paper after filtration.
(4) And (3) drying: putting the powder sample collected in the step (3) into a drying oven at room temperature, setting the temperature to be 60 ℃ for drying, and drying the powder sample after 8 hoursCollecting the product to obtain MnO2Precursor (MnOOH).
(5) Annealing: and (4) putting the precursor MnOOH obtained in the step (4) into a high-temperature sintering furnace to react in an air gas atmosphere. Wherein the temperature is raised at 2 ℃/min, the temperature is raised to 280 ℃ and the constant temperature is kept, and the annealing time is set to 2 h. Collecting a powder sample after the reaction is finished to obtain the MnO2An electrode material.
And (3) electrochemical performance testing:
firstly, preparing an electrode: MnO collected in the above step (5) of this example2Grinding an electrode material sample as an active substance, Polytetrafluoroethylene (PTFE) as an adhesive and acetylene black as a conductive agent uniformly according to a ratio, dripping N-methylpyrrolidone (NMP), and grinding again to obtain electrode slurry; wherein: MnO2The electrode material was mixed with PTFE powder, acetylene black and NMP in a ratio of 70mg:10mg:20mg:1 ml. Using a stainless steel mesh as a current collector, uniformly coating the prepared electrode slurry on a stainless steel mesh with the size of 3cm multiplied by 6cm (the specific mass of active substances per square centimeter on the stainless steel mesh is about 1.3mg), and drying in a drying oven for 8h to obtain the electrode slurry containing MnO2A positive electrode of an electrode material.
Assembling an aqueous zinc ion battery: MnO containing according to the above2Positive electrode and diaphragm of electrode material (dripping 2M ZnSO)4+0.2M MnSO4An aqueous electrolyte of a composite salt), a zinc sheet, a gasket, an elastic sheet and a negative electrode shell.
The cell obtained in this example was subjected to Cyclic Voltammetry (CV) testing using a Chenghua electrochemical workstation (CHI760E) under conditions of a potential sweep rate of 1mV/s and a potential window of 1-1.85V; then, performing an alternating current impedance (EIS) test, wherein the frequency of the test condition is set to be 0.01Hz-1000000Hz, and the voltage is set to be an open-circuit voltage; and the battery obtained in example 1 above was subjected to constant current charging and discharging at a current density of 5A/g using a novice eight-channel battery test apparatus (NEWARE) and a voltage was set to 1-1.85V. The test results show that MnO prepared in this example2When the electrode material is used as an active material to assemble the water-based zinc ion battery, the specific capacity is changed from 40.2mAh/g to 2000 cycles41.6 mAh/g. (specific capacity was calculated by the formula
Figure BDA0003369902090000061
Wherein I represents a discharge current, Deltat represents a discharge time, and m represents a positive electrode MnO2Mass of active substance).
Example 2
MnO of this embodiment2A method of preparing an electrode material, which is substantially the same as in example 1 except that: in step (5) of this example, the annealing temperature was set to 300 ℃.
The electrochemical performance of the electrode material prepared in this example was tested using the same battery assembly method and electrochemical test method as in example 1. The test results show that MnO prepared in this example2The specific capacity of an aqueous zinc ion battery assembled by using an electrode material as an active material is changed from 44.4mAh/g to 65.3mAh/g when the current density is 5A/g and the cycle is 2000 circles.
Example 3
MnO of this embodiment2A method of preparing an electrode material, which is substantially the same as in example 1 except that: in step (5) of this example, the annealing temperature was set to 350 ℃.
The electrochemical performance of the electrode material prepared in this example was tested using the same battery assembly method and electrochemical test method as in example 1. The test results show that MnO prepared in this example2The specific capacity of the water-based zinc ion battery assembled by using the electrode material as an active material is reduced from 77.8mAh/g to 59.7mAh/g when the current density is 5A/g and the cycle is 2000 circles.
Example 4
MnO of this embodiment2A method of preparing an electrode material, which is substantially the same as in example 1 except that: in step (5) of this example, the annealing temperature was set to 400 ℃.
The electrochemical performance of the electrode material prepared in this example was tested using the same battery assembly method and electrochemical test method as in example 1. The test results show that MnO prepared in this example2Electrode for electrochemical cellThe specific capacity of the water-based zinc ion battery assembled by using the material as an active substance is 98.6mAh/g from 143.0mAh/g when the current density is 5A/g and the cycle is 2000 circles.
Example 5
MnO of this embodiment2A method of preparing an electrode material, which is substantially the same as in example 1 except that: in step (5) of this example, the annealing temperature was set to 450 ℃.
The electrochemical performance of the electrode material prepared in this example was tested using the same battery assembly method and electrochemical test method as in example 1. The test results show that MnO prepared in this example2The specific capacity of the water-based zinc ion battery assembled by using the electrode material as an active material is reduced from 83.3mAh/g to 59.7mAh/g when the current density is 5A/g and the cycle is 2000 circles.
Example 6
MnO of this embodiment2A method of preparing an electrode material, which is substantially the same as in example 1 except that: in step (5) of this example, the annealing temperature was set to 500 ℃.
Example 7
A Mn of this example2O3A method of preparing an electrode material, which is substantially the same as in example 1 except that: in step (5) of this example, the annealing temperature was set to 550 ℃.
The electrochemical performance of the electrode material prepared in this example was tested using the same battery assembly method and electrochemical test method as in example 1. The results of the tests show that Mn is produced in this example2O3The specific capacity of the aqueous zinc ion battery assembled by using the electrode material as an active material is changed from 16.6mAh/g to 22.2mAh/g when the current density is 5A/g and the cycle is 2000 circles.
In FIG. 1, (a), (b), (c), (d), (e) and (f) are sequentially MnO prepared in examples 1 to 6 of the present invention2Scanning Electron Microscope (SEM) images of the electrode material at different magnifications; (g) for Mn prepared in example 72O3Scanning Electron Microscope (SEM) images of the electrode material; as can be seen from the figures, MnO obtained in examples 1 to 62The electrode materials are all of nanorod-shaped structures with different diameters and lengths, the diameters are about 0.5-3 nm, the lengths are about 1-5 um, the electrode materials are uniformly distributed in the space, and the appearance does not change along with the change of the temperature. Mn obtained in example 72O3The electrode materials are all of nanometer rod-shaped structures with different diameters and lengths, the diameters are about 50-300 nm, the lengths are about 0.2-5 um, and the nanometer rod-shaped structures are uniformly distributed in the space.
FIG. 2 shows MnO obtained by annealing the precursor (MnOOH) prepared in examples 1-7 of the present invention in a high temperature sintering furnace at 280 deg.C, 300 deg.C, 350 deg.C, 400 deg.C, 450 deg.C, 500 deg.C, 550 deg.C2Or Mn2O3Corresponding XRD image shows that the MnOOH precursor is annealed in air at 280 deg.C, 300 deg.C, 350 deg.C, 400 deg.C, 450 deg.C and 500 deg.C to obtain beta-phase MnO2Annealing at 550 deg.C in air to obtain Mn2O3。
In FIG. 3, (a) and (b) are MnO prepared in example 4 of the present invention, respectively2The electrode material is assembled into CV images of the zinc ion battery at the scanning speed of 1mv/s (left image) and different scanning speeds (right image), and as can be seen from the images, the coincidence of the first circle and the third circle is relatively high at the scanning speed of 1mv/s, and MnO can be obtained2The zinc ion battery assembled by the material has high reversibility.
Fig. 4 is a thermal gravimetric differential thermal Diagram (DTA) of a precursor MnOOH in air in all embodiments of the present invention, in which a sample to be measured and a reference substance (thermal inert substance) are placed in a furnace under the same condition, and are heated or cooled at a constant speed according to a given program, and when the sample is heated to generate a change in physical and chemical properties (such as phase change, crystal structure change, crystallization, boiling, sublimation, gasification, melting, dehydration, decomposition, oxidation, reduction … … and other reactions) at different temperatures, the temperature of the sample itself is lower or higher than that of the reference substance along with heat absorption or heat release, i.e., a temperature difference is generated between the two. The magnitude and polarity of the temperature difference (the temperature difference between the temperature before and after the reaction is zero) are detected by a thermocouple, converted into electric energy, amplified by an amplifier and input into a recorder, and the recorded curve is the differential thermal curve. Wherein the heating furnace adopts 1kW Fe-Cr-Al wire for bidirectional winding, thereby eliminatingThe furnace wire generates the influence of a magnetic field on the test result of the sample and has a longer heating constant-temperature zone. It can be seen from fig. 4 that the precursor MnOOH has three weight losses with the increase of temperature in air, the first weight loss (weight loss 15.3%) is attributed to the removal of nanorod adsorbed water, and the second weight loss is dehydroxylated with gamma-MnOOH, Mn3+Oxidation to Mn4+Formation of MnO2In connection with this, the weight loss of the corresponding fraction was 1.7%, close to the theoretical value of 1.1%. The third weight loss (8.1%) can be attributed to MnO2Conversion to Mn2O3The theoretical value is 9.1%. On the DTA curve, the endothermic peak at 577 ℃ corresponds to MnO2To Mn2O3The transition point of (c).
FIG. 5 shows MnO prepared in examples 1-5 of the present invention2Electron Paramagnetic Resonance (EPR) contrast maps of electrode materials; the electron paramagnetic resonance is a magnetic resonance technology originated from the magnetic moment of unpaired electrons, and can be used for qualitatively and quantitatively detecting the unpaired electrons contained in substance atoms or molecules and exploring the structural characteristics of the surrounding environment. From image analysis, the precursor gamma-MnOOH generates oxygen defects by air annealing at different temperatures, and the oxygen defects increase along with the increase of the temperature.
FIG. 6 shows MnO prepared in example 4 of the present invention2Raman images of the electrode material. The Raman spectrum analysis technology expands a simple single-point analysis mode to comprehensively analyze a sample in a certain range, utilizes the obtained intensity change of the Raman frequency with the characteristic of different components to construct a spatial distribution map of the components on the sample, and displays information such as chemical component distribution, surface physical and chemical properties and the like of the sample in an image mode. The Raman image obtained by the invention is obtained by adopting a 532-ray source and selecting ten percent of power, the peak height of the image shows that the chemical bond of the material has about 4 vibration modes, and the chemical bond is beta-phase MnO through comparison with related documents2A raman image of (a).
FIG. 7 is MnO obtained in examples 1 to 5 of the present invention2Electrode material and Mn obtained in example 72O3A cycle performance contrast diagram of the water system zinc ion battery assembled by the electrode material under the current density of 5A/g,from the figure, the MnO prepared in example 4 can be seen2The battery assembled by the electrode material has higher specific capacity and stability under the current density of 5A/g.
FIG. 8 is MnO prepared in example 4 of the present invention2And (3) a rate performance graph of the zinc ion battery assembled by the electrode material under different current densities. The image shows that the battery can still keep relatively high specific capacity and stably run under different current densities, and the specific capacity is up to 499mAh/g under the current density of 0.1A/g.

Claims (10)

1. MnO (MnO)2The preparation method of the electrode material is characterized by comprising the following steps: the method comprises the following steps:
(1) dripping polyethylene glycol into potassium permanganate aqueous solution, and uniformly stirring;
(2) putting the prepared solution into a high-pressure reaction kettle for hydrothermal reaction;
(3) filtering and drying the solution after reaction;
(4) collecting the dried sample and annealing in air to obtain the MnO2An electrode material.
2. The MnO of claim 12The preparation method of the electrode material is characterized by comprising the following steps: and (2) preparing the solution in the step (1), namely adding a certain amount of potassium permanganate into deionized water, then dripping polyethylene glycol into the deionized water by using a liquid-transferring gun, stirring the mixture on a magnetic stirrer to completely dissolve the polyethylene glycol, and pouring the obtained solution into a polytetrafluoroethylene liner, wherein the amount of the potassium permanganate is 1-100 mmol, the amount of the polyethylene glycol is 1-300 ml, and the amount of the deionized water is 10-6000 ml.
3. The MnO of claim 12The preparation method of the electrode material is characterized by comprising the following steps: and (3) setting the temperature of the hydrothermal reaction in the step (2) to be 100-300 ℃ and setting the reaction time to be 1-30 h.
4. The MnO of claim 12Preparation method of electrode materialThe method is characterized in that: and (4) setting the annealing temperature to be 100-800 ℃ and the annealing time to be 0.5-12 h.
5. The MnO of claim 42The preparation method of the electrode material is characterized by comprising the following steps: the annealing temperature is 400 ℃, and the annealing time is 2 h.
6. The MnO of any one of claims 1 to 52MnO prepared by preparation method of electrode material2An electrode material.
7. MnO obtainable by the process according to any one of claims 1 to 52An electrode material is applied to an aqueous zinc ion battery.
8. A positive electrode material of a water system zinc ion battery comprises a positive electrode active material, a conductive agent and a binder, and is characterized in that: the positive active material is MnO prepared by the method of any one of claims 1 to 52An electrode material.
9. The utility model provides a positive pole of water system zinc ion battery, this positive pole includes the mass flow body and coats and/or fills the positive pole material on the mass flow body, its characterized in that: the positive electrode material is the aqueous zinc-ion battery positive electrode material according to claim 8.
10. An aqueous zinc-ion battery characterized in that: the water-based zinc ion battery comprises a positive electrode, a negative electrode, a diaphragm arranged between the positive electrode and the negative electrode, electrolyte and a shell, wherein the positive electrode is the positive electrode of the water-based zinc ion battery according to claim 9.
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