CN110350152B - Graphite alkyne/manganese dioxide nanosheet array material and preparation method and application thereof - Google Patents
Graphite alkyne/manganese dioxide nanosheet array material and preparation method and application thereof Download PDFInfo
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- H01M10/00—Secondary cells; Manufacture thereof
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- 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
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Abstract
The invention provides a graphite alkyne/manganese dioxide nano array material, a preparation method thereof and a zinc ion secondary battery, wherein the method for preparing the graphite alkyne/manganese dioxide nano array material comprises the following steps: (1) preparing a manganese dioxide nanosheet array; (2) the preparation method comprises the steps of taking a manganese dioxide nanosheet array as a first substrate, and preparing the graphite alkyne/manganese dioxide nanosheet array material in situ in a reaction liquid, wherein the reaction liquid comprises hexaethynylbenzene, cuprous iodide, tetramethylethylenediamine and tetrahydrofuran. According to the preparation method provided by the invention, the graphite alkyne can be formed on the surface of the manganese dioxide nanosheet array by an in-situ preparation method, the preparation method is mild in condition, simple to operate and suitable for large-scale preparation, and the prepared graphite alkyne/manganese dioxide nanosheet array material can be used as a zinc ion anode material, so that the specific capacity, the rate capability, the cycle performance and the like of a zinc ion secondary battery can be obviously improved.
Description
Technical Field
The invention relates to the technical field of nano materials and preparation, in particular to a graphite alkyne/manganese dioxide nano array material and a preparation method and application thereof. More particularly, the invention relates to a graphite alkyne/manganese dioxide nano array material, a preparation method thereof and a zinc ion secondary battery.
Background
Currently, energy storage devices have an indispensable position in the development of human society, supporting the operation of the whole world. An ideal energy storage device should have the following characteristics: high specific capacity, rapid charge and discharge, safety, environmental protection and low cost. However, the existing energy storage devices (lithium batteries, super capacitors, etc.) obviously do not have the above characteristics, and the demand of people for energy is not met. Therefore, it is particularly important to seek new energy storage systems.
In 1860, alkaline zinc/manganese dioxide primary cells were invented and were dominant in the commercial primary cell field, with annual values of about $ 100 billion. However, the problems of small energy of primary batteries, waste of resources and the like are not negligible. Therefore, scientists are continuously exploring to develop a secondary battery with high specific capacity, rapid charge and discharge, safety and environmental protection. Zinc has higher specific volumetric capacity (5851mAh/mL) and specific mass capacity (820mAh/g), and is widely concerned by scientific researchers. In recent years, a series of zinc ion batteries have been reported, for example: zinc/manganese dioxide (Xu, C.; Li, B.; Du, H.; Kang, F. Energetic Zinc chemistry: the Rechargeable Zinc base, Angew. chem., int. Ed.2012,51,933-5.Pan, H.; Shao, Y.; Yan, P.; Cheng, Y.; Han, K.S.; Nie, Z.; Wang, C.; Yang, J.; Li, X.; Bhattacharya, P.; Mueller, K.T.; Liu, J.Reversa Zinc/mangenergylene conversion reaction, Nat. Energy 2016,1,16039. Zinc/Prussian (Zk. L.; Zygen. S.; Zygen. K.; Zygen. S.; Zygen. S.S.; Zygen. K.; Zygen. K.S.; you. J.S. J. conversion reaction, N.2016, N.S.2016, 1, K.9, K.S. K. K.; Zinc/S. K.S. K.S.; Zinc oxide, S. K.S. K.S.; Zinc/S. K, n; cheng, f.; liu, y.; zhao, q.; lei, k.; chen, c.; liu, x.; chen, J.Caption-Deficient coil ZnMn2O4 Cathodode in Zn (CF3SO3)2 electric for rechargeable aquouos Zn-ion battery J.Am.chem.Soc.2016,138,12894-12901.), and the like.
However, these positive electrode materials still face the problems of low specific capacity, poor cycling stability, low discharge plateau and the like, so that it is still necessary to develop new positive electrode materials for zinc ion batteries.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art.
The present invention has been completed based on the following findings of the inventors:
aiming at the problems of low specific capacity, poor cycle stability, low discharge platform and the like of the anode material of the zinc ion battery at the present stage, the inventor finds that the graphite alkyne is a conjugated structure formed by connecting benzene rings through diyne bonds and has better conductivity and porosity in the research process. Therefore, the graphite alkyne/manganese dioxide anode material is obtained by the in-situ preparation method, the problem of self pulverization and dissolution of manganese dioxide can be solved, and the specific capacity, the rate capability, the cycling stability and the like of the zinc ion battery can be obviously improved.
In view of the above, an object of the present invention is to provide a method for preparing a graphyne/manganese dioxide nanoarray material, which is simple and easy for mass production.
In a first aspect of the invention, the invention provides a method for preparing a graphite alkyne/manganese dioxide nanosheet array material.
According to an embodiment of the invention, the method comprises: (1) preparing a manganese dioxide nanosheet array; (2) and taking the manganese dioxide nanosheet array as a first substrate, and preparing the graphite alkyne/manganese dioxide nanosheet array material in situ in a reaction liquid, wherein the reaction liquid comprises hexaethynylbenzene, cuprous iodide, tetramethylethylenediamine and tetrahydrofuran.
The inventor finds that by adopting the preparation method of the embodiment of the invention, the graphite alkyne can be formed on the surface of the manganese dioxide nanosheet array by an in-situ preparation method, the preparation method is mild in condition, simple to operate and suitable for large-scale preparation, and the prepared graphite alkyne/manganese dioxide nanosheet array material can be used as a zinc ion positive electrode material, so that the specific capacity, the rate capability, the cycle performance and the like of a zinc ion secondary battery can be obviously improved.
In addition, the preparation method according to the above embodiment of the present invention may further have the following additional technical features:
according to an embodiment of the present invention, the step (1) further comprises: (1-1) carrying out hydrothermal reaction on a potassium permanganate aqueous solution with a second substrate; (1-2) washing the second substrate after the hydrothermal reaction by using water and ethanol in sequence, and drying to obtain the manganese dioxide nanosheet array.
According to an embodiment of the invention, the second substrate is a titanium sheet, a titanium mesh, a stainless steel sheet, a stainless steel mesh, a carbon fiber paper or a carbon cloth.
According to the embodiment of the invention, the temperature of the hydrothermal reaction is 120-200 ℃ and the time is 1-5 hours.
According to the embodiment of the invention, the temperature of the hydrothermal reaction is 180 ℃ and the time is 3 hours.
According to an embodiment of the invention, the in situ preparation is performed at room temperature.
According to the embodiment of the invention, the in-situ preparation time is 2-4 days.
According to an embodiment of the invention, the time for the in situ preparation is 3 days.
According to an embodiment of the present invention, in the reaction liquid, a weight ratio of hexaethynylbenzene, cuprous iodide, tetramethylethylenediamine, and tetrahydrofuran is 5: (17.8-35.6): (0.2-0.5): (1.54-3.08).
In a second aspect of the invention, the invention provides a graphite alkyne/manganese dioxide nanosheet array material.
According to an embodiment of the invention, the graphite alkyne/manganese dioxide nanosheet array material is prepared by the method described above.
The inventor finds that the graphite alkyne/manganese dioxide nanosheet array material provided by the embodiment of the invention can be used as a zinc ion positive electrode material, so that the specific capacity, the rate capability, the cycle performance and the like of a zinc ion secondary battery can be remarkably improved. It will be understood by those skilled in the art that the features and advantages described above with respect to the method for preparing a graphdine/manganese dioxide nanosheet array material are still applicable to the graphdine/manganese dioxide nanosheet array material and will not be described herein in any detail.
In a third aspect of the invention, a zinc ion secondary battery is presented.
According to an embodiment of the present invention, the zinc-ion secondary battery includes a positive electrode, and the positive electrode is formed of the above-described graphdine/manganese dioxide nanosheet array material.
The inventor finds that the positive electrode of the zinc ion secondary battery provided by the embodiment of the invention is formed by a graphite alkyne/manganese dioxide nanosheet array material, so that the specific capacity, the rate capability, the cycle performance and the like of the zinc ion secondary battery are remarkably improved. It will be understood by those skilled in the art that the features and advantages described above for the graphdine/manganese dioxide nanosheet array material are still applicable to the zinc ion secondary battery and will not be described in detail herein.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
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The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a flow diagram of a method of preparing a graphdine/manganese dioxide nanosheet array material according to one embodiment of the present invention;
fig. 2 is a PXRD pattern of an array of manganese dioxide nanoplates according to an embodiment of the present invention;
fig. 3 is an SEM photograph of an array of manganese dioxide nanoplates according to an embodiment of the present invention;
fig. 4 is a TEM photograph of an array of manganese dioxide nanoplates according to an embodiment of the present invention;
fig. 5 is an SEM photograph of a graphdine/manganese dioxide nanosheet array material according to one embodiment of the present invention;
fig. 6 is a TEM photograph of a graphdine/manganese dioxide nanosheet array material according to one embodiment of the present invention;
fig. 7 is a Raman spectrum of a graphdine/manganese dioxide nanosheet array material according to one embodiment of the present invention;
FIG. 8 is a battery rate capability test chart of a comparative example of the present invention;
FIG. 9 is a battery rate capability test chart of one embodiment of the present invention;
FIG. 10 is a battery cycle performance test chart of a comparative example of the present invention;
FIG. 11 is a battery cycle performance test chart of one embodiment of the present invention;
fig. 12 is a cyclic voltammogram of a battery of one comparative example and example of the invention.
Detailed Description
The following examples of the present invention are described in detail, and it will be understood by those skilled in the art that the following examples are intended to illustrate the present invention, but should not be construed as limiting the present invention. Unless otherwise indicated, specific techniques or conditions are not explicitly described in the following examples, and those skilled in the art may follow techniques or conditions commonly employed in the art or in accordance with the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available on the market.
In one aspect of the invention, the invention provides a method for preparing a graphite alkyne/manganese dioxide nanosheet array material. The production method of the present invention is described in detail with reference to fig. 1.
According to an embodiment of the present invention, referring to fig. 1, the preparation method includes:
s100: and preparing a manganese dioxide nanosheet array.
In this step, a manganese dioxide nanosheet array is first prepared. According to the embodiment of the present invention, the specific method of preparing the manganese dioxide nanosheet array is not particularly limited. In some embodiments of the present invention, step S100 may further include:
s110: and carrying out hydrothermal reaction on the potassium permanganate aqueous solution with the second substrate.
In the step, potassium permanganate is firstly dissolved in deionized water, and is transferred to a reaction kettle with a second substrate, and then hydrothermal reaction is carried out, so that a manganese dioxide nanosheet array can be obtained.
According to an embodiment of the present invention, in the aqueous potassium permanganate solution, the specific weight ratio of potassium permanganate to deionized water may be 100: (10-40), and thus, by adopting the potassium permanganate aqueous solution with the concentration range, the manganese dioxide nanosheet array with high quality can be obtained through hydrothermal reaction. According to the embodiment of the invention, the second substrate can be a titanium sheet, a titanium net, a stainless steel sheet, a stainless steel net, carbon fiber paper or carbon cloth, so that the manganese dioxide nanosheet array growing on the surface of the second substrate can be more regular by adopting the second substrate of the kind.
According to the embodiment of the present invention, the specific conditions of the hydrothermal reaction are not particularly limited, and those skilled in the art can adjust the conditions according to the specific concentration of potassium permanganate in the aqueous potassium permanganate solution. In some embodiments of the present invention, the temperature is 120-200 ℃ and the time is 1-5 hours. Thus, the quality, regularity and preparation efficiency of the manganese dioxide nanosheet array prepared under the hydrothermal conditions are high; moreover, the inventor finds that the surface regularity of the formed manganese dioxide nanosheet array is reduced if the hydrothermal temperature is higher than 200 ℃, and the yield of manganese dioxide is low if the hydrothermal temperature is lower than 120 ℃; if the hydrothermal reaction time is longer than 5 hours, the yield of manganese dioxide is not increased, and if the hydrothermal reaction time is shorter than 1 hour, the conversion rate of manganese dioxide is still low. In some specific examples, the temperature of the hydrothermal reaction is 180 degrees celsius, and the time is 3 hours, so that the manganese dioxide nanosheet array with high conversion rate can be further efficiently obtained.
S120: and washing the second substrate after the hydrothermal reaction by using water and ethanol in sequence, and drying to obtain the manganese dioxide nanosheet array.
In the step, the second substrate obtained in the step S110 after the hydrothermal reaction is subjected to a post-treatment mode of washing with water and ethanol and drying, so that a manganese dioxide nanosheet array with higher purity and better surface performance can be obtained.
S200: taking a manganese dioxide nanosheet array as a first substrate, and preparing the graphite alkyne/manganese dioxide nanosheet array material in situ in a reaction solution.
In the step, a manganese dioxide nanosheet array is used as a first substrate, and the graphite alkyne/manganese dioxide nanosheet array material is prepared in situ in a reaction liquid, wherein the reaction liquid comprises hexaethynylbenzene, cuprous iodide, tetramethylethylenediamine and tetrahydrofuran.
According to an embodiment of the present invention, the weight ratio of hexaethynylbenzene, cuprous iodide, tetramethylethylenediamine, and tetrahydrofuran in the reaction solution may be 5: (17.8-35.6): (0.2-0.5): (1.54-3.08), so that the reaction solution formed by adopting the proportion is subjected to in-situ preparation to form the graphite alkyne/manganese dioxide nanosheet array material with better electrical properties.
According to the embodiment of the present invention, the specific conditions of in-situ preparation are not particularly limited, and those skilled in the art can adjust accordingly according to the specific electrical property result of the prepared graphite alkyne/manganese dioxide nanosheet array material. In some embodiments of the invention, the in situ preparation may be performed at room temperature. The term "room temperature" herein specifically means 20 to 35 ℃. Therefore, the condition for preparing the graphite alkyne/manganese dioxide nanosheet array material in situ at the room temperature of 20-35 ℃ is milder, the energy consumption is lower, and the prepared graphite alkyne/manganese dioxide nanosheet array material has better electrical property.
In some embodiments of the invention, the in-situ preparation time can be 2-4 days, so that the graphite alkyne/manganese dioxide nanosheet array material prepared in situ within the time range is more regular; moreover, the inventor also finds that if the in-situ preparation time is less than 2 days, the conversion rate of the graphyne is still low, and if the in-situ preparation time is more than 4 days, the electrical property of the graphyne/manganese dioxide nanosheet array material is not increased any more. In some specific examples, the in-situ preparation time can be 3 days, so that the high-quality graphite alkyne/manganese dioxide nanosheet array material can be prepared in situ more efficiently.
In summary, according to the embodiments of the present invention, the preparation method is provided, the graphdine can be formed on the surface of the manganese dioxide nanosheet array by the in-situ preparation method, the preparation method is mild in condition, simple in operation and suitable for large-scale preparation, and the prepared graphdine/manganese dioxide nanosheet array material can be used as a zinc ion positive electrode material, so that the specific capacity, the rate capability, the cycle performance and the like of the zinc ion secondary battery can be significantly improved.
In another aspect of the invention, the invention provides a graphite alkyne/manganese dioxide nanosheet array material. According to an embodiment of the invention, the graphdine/manganese dioxide nanosheet array material is prepared by the method described above.
In summary, according to the embodiments of the present invention, the invention provides a graphite alkyne/manganese dioxide nanosheet array material, which is used as a zinc ion positive electrode material, and can significantly improve the specific capacity, rate capability, cycle performance and the like of a zinc ion secondary battery. It will be understood by those skilled in the art that the features and advantages described above with respect to the method for preparing a graphdine/manganese dioxide nanosheet array material are still applicable to the graphdine/manganese dioxide nanosheet array material and will not be described herein in any detail.
In another aspect of the present invention, a zinc ion secondary battery is provided.
According to an embodiment of the invention, the zinc ion secondary battery comprises a positive electrode, and the positive electrode is formed by the graphite alkyne/manganese dioxide nanosheet array material.
In summary, according to the embodiments of the present invention, the present invention provides a zinc ion secondary battery, wherein the positive electrode is formed by a graphite alkyne/manganese dioxide nanosheet array material, so that the specific capacity, the rate capability, the cycle performance, and the like of the zinc ion secondary battery can be significantly improved. It will be understood by those skilled in the art that the features and advantages described above for the graphdine/manganese dioxide nanosheet array material are still applicable to the zinc ion secondary battery and will not be described in detail herein.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way. The experimental procedures used in the following examples are all conventional procedures unless otherwise specified. Materials, reagents and the like used in the following examples are commercially available unless otherwise specified. The hexaethynylbenzene used in the following examples can be synthesized by reference to the following references: g.x.li, y.l.li, h.b.liu, y.b.guo, y.j.li, d.b.zhu, chem.commun.2010,46, 3256-propan 3258.
Example 1
In this example, a graphdine/manganese dioxide nanosheet array material was prepared. The specific method comprises the following steps:
(1) dissolving 300mg of potassium permanganate in 40mL of deionized water, transferring the solution to a 50mL reaction kettle containing titanium sheets, carrying out hydrothermal reaction at 180 ℃ for 3h, and naturally cooling the solution to room temperature to obtain a manganese dioxide nanosheet array; washing with water and ethanol in sequence, putting the titanium sheet with the manganese dioxide nanosheet array in a drying oven, and drying at 60 ℃ for 3 h;
(2) dissolving 5mg of hexaethynylbenzene in 30mL of tetrahydrofuran, adding 0.3mg of cuprous iodide and 3mL of tetramethylethylenediamine, then placing the titanium plate with the manganese dioxide nanosheet array in the reaction solution, and reacting at room temperature for 3 days to obtain the graphite alkyne/manganese dioxide nanosheet array.
Example 2
In this example, a graphdine/manganese dioxide nanosheet array material was prepared following essentially the same methods and conditions as in example 1. The difference is that in this embodiment, the second substrate employs carbon fibers instead of titanium sheets.
Then, the manganese dioxide nanosheet array of this example was subjected to powder X-ray diffraction (PXRD), Scanning Electron Microscope (SEM), Transmission Electron Microscope (TEM), and Raman test (Raman), and then subjected to SEM, TEM, and Raman on the graphdine/manganese dioxide nanosheet array material.
Wherein, the PXRD picture, the SEM picture and the TEM picture of the manganese dioxide nanosheet array of the embodiment are respectively shown in fig. 2 to 4, and the SEM picture, the TEM picture and the Raman picture of the graphdine/manganese dioxide nanosheet array material are respectively shown in fig. 5 to 7. The test results show that the preparation method successfully prepares the graphite alkyne/manganese dioxide nanosheet array.
Example 3
In this example, the graphite prepared in example 2 was usedPressing the alkyne/manganese dioxide nanosheet array material into a positive electrode. Then zinc sheet is taken as a negative electrode, a graphite alkyne/manganese dioxide nanosheet array is taken as a positive electrode, a polytetrafluoroethylene film is taken as a diaphragm, and 1MZnSO4Aqueous solution with 0.2M MnSO4Aqueous solution is used as electrolyte to assemble 2032 type button cell
Comparative example 1
In the comparative example, a 2032 type button cell was assembled with a zinc sheet as the negative electrode, a manganese dioxide nanosheet array as the positive electrode, a polytetrafluoroethylene film as the separator, and a 1M ZnSO4 aqueous solution and a 0.2M MnSO4 aqueous solution as the electrolytes.
Example 4
In this example, electrochemical performance tests were performed on the button cell of example 3 and the button cell of comparative example 1, respectively. The method specifically comprises the steps of carrying out a multiplying power performance test under different current densities, and carrying out a cyclic performance test and a cyclic voltammetry test under a current density of 550 mA/g. The above test results show that:
referring to fig. 8, the specific capacities of the batteries of comparative example 1 at current densities of 55, 110, 275, 550, 1100, 1650, 550mA/g were 434, 299, 185, 129, 66, 38, 134mAh/g, respectively, indicating that the rate performance was general and yet to be further improved; referring to fig. 9, the specific capacity of the battery of example 3 is 507, 457, 351, 234, 170, 121, and 223mAh/g at current densities of 55, 110, 275, 550, 1100, 1650, and 550mA/g, respectively, and the rate capability is significantly improved.
Referring to fig. 10 and 11, the specific capacities of the assembled batteries of comparative example 1 and example 3 were 100mAh/g and 164mAh/g, respectively, after the assembled batteries were cycled for 200 cycles at a current density of 550mA/g, and although the specific capacities of the batteries of example 3 both tended to decay, the specific capacity of the battery of example 3 was improved by 64% relative to the battery of comparative example 1.
The assembled cell of comparative example 1 and example 3 was again subjected to cyclic voltammetry at a sweep rate of 0.05mV/s, referring to FIG. 12, which illustrates that the introduction of the graphoyne film did not change the redox reaction potential of the electrode material.
After comprehensive analysis of the electrochemical performance test results of the embodiment, it is fully demonstrated that the graphite alkyne/manganese dioxide nanosheet array is used as the positive electrode of the zinc ion secondary battery, so that the specific capacity, the rate capability, the cycle performance and the like of the battery are greatly improved.
Summary of the invention
By integrating the embodiments 1-4 and the comparative example 1, the preparation method provided by the invention can form the graphyne on the surface of the manganese dioxide nanosheet array through an in-situ preparation method, the preparation method is mild in condition, simple to operate and suitable for large-scale preparation, and the prepared graphyne/manganese dioxide nanosheet array material can be used as a zinc ion positive electrode material, so that the specific capacity of a zinc ion secondary battery can be improved by 64%, the rate capability can be effectively improved, and the cycle can be carried out for more than 200 circles.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (15)
1. A method for preparing a graphite alkyne/manganese dioxide nanosheet array material is characterized by comprising the following steps:
(1) preparing a manganese dioxide nanosheet array;
(2) and taking the manganese dioxide nanosheet array as a first substrate, and preparing the graphite alkyne/manganese dioxide nanosheet array material in situ in a reaction liquid, wherein the reaction liquid comprises hexaethynylbenzene, cuprous iodide, tetramethylethylenediamine and tetrahydrofuran.
2. The method of claim 1, wherein step (1) further comprises:
(1-1) carrying out hydrothermal reaction on a potassium permanganate aqueous solution with a second substrate;
(1-2) washing the second substrate after the hydrothermal reaction by using water and ethanol in sequence, and drying to obtain the manganese dioxide nanosheet array.
3. The method of claim 2, wherein the second substrate is a titanium sheet, a titanium mesh, a stainless steel sheet, a stainless steel mesh, a carbon fiber paper, or a carbon cloth.
4. The method according to claim 2, wherein the hydrothermal reaction is carried out at a temperature of 120 to 200 ℃ for 1 to 5 hours.
5. The method of claim 2, wherein the temperature of the hydrothermal reaction is 180 degrees celsius.
6. The method of claim 2, wherein the hydrothermal reaction is carried out for a period of 3 hours.
7. The method according to claim 2, wherein the drying is performed at 50 to 80 ℃ for 1 to 5 hours.
8. The method of claim 2, wherein the drying temperature is 60 degrees celsius.
9. The method of claim 2, wherein the drying time is 3 hours.
10. The method of claim 1, wherein the in situ preparation is performed at room temperature.
11. The method of claim 1, wherein the in situ preparation is performed for 2 to 4 days.
12. The method of claim 1, wherein the in situ preparation is performed for a period of 3 days.
13. The method according to claim 1, wherein the weight ratio of hexaethynylbenzene, cuprous iodide, tetramethylethylenediamine, and tetrahydrofuran in the reaction solution is 5: (17.8-35.6): (0.2-0.5): (1.54-3.08).
14. A graphdine/manganese dioxide nanosheet array material, prepared by the method of any one of claims 1 to 13.
15. A zinc-ion secondary battery comprising a positive electrode, and the positive electrode is formed of the graphite alkyne/manganese dioxide nanosheet array material of claim 14.
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