CN110350126B - Graphite oxide alkyne film material, preparation method thereof and water system secondary battery - Google Patents

Graphite oxide alkyne film material, preparation method thereof and water system secondary battery Download PDF

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CN110350126B
CN110350126B CN201810282517.2A CN201810282517A CN110350126B CN 110350126 B CN110350126 B CN 110350126B CN 201810282517 A CN201810282517 A CN 201810282517A CN 110350126 B CN110350126 B CN 110350126B
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alkyne
graphite
film material
secondary battery
graphite oxide
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CN110350126A (en
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刘辉彪
李玉良
李教富
李勇军
左自成
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Institute of Chemistry CAS
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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
    • 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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention provides a graphite oxide alkyne film material, a preparation method thereof and a water system secondary battery. The method for preparing the graphite oxide alkyne film material comprises the following steps: (1) preparing a reaction solution, wherein the reaction solution comprises graphite alkyne powder, potassium permanganate and water; (2) carrying out hydrothermal reaction on the reaction solution to obtain a graphite oxide alkyne solution; (3) and carrying out post-treatment on the graphite oxide alkyne solution to obtain the graphite oxide alkyne film material. The preparation method provided by the invention has the advantages that the graphite alkyne is oxidized into the graphite alkyne oxide by a low-temperature hydrothermal method, the preparation method is mild in condition, simple to operate and suitable for large-scale preparation, and the prepared graphite alkyne oxide film can be used as a new diaphragm material of a water system secondary battery, so that the specific capacity, the rate capability, the cycle performance and the like of the battery are obviously improved.

Description

Graphite oxide alkyne film material, preparation method thereof and water system secondary battery
Technical Field
The invention relates to the technical field of nano materials and preparation, in particular to a graphite oxide alkyne film material and a preparation method thereof and a water system secondary battery.
Background
At present, lithium ion batteries have high energy density, are widely applied to various electronic devices and energy storage fields, and have a leading position in commercialized batteries. However, lithium ion batteries have disadvantages of high cost, flammability, and lack of lithium resources, and it is very important to find a new secondary battery system.
Wherein the sodium-Ion battery (Zhou, J.; Wang, L.; Yang, M.; Wu, J.; Chen, F.; Huang, W.; Han, N.; Ye, H.; Zhao, F.; Li, Y., Hierarchical VS2Nanosheet Assemblies: A Universal host Material for the Reversible Storage of Alkali metallic ions.adv.Mat.2017.), the magnesium-Ion battery (Li, W.; Li, C.; Zhou, C.; Mahar, H.; Chen J., metallic magnesium/metallic structures: the same type of the battery (Li, W.; N.; N.9452. C.; C. the same type of the battery (C. K, s. carrying out; yang, C.; fan, x.; ma, z.; gao, t.; han, F.; hu, r.; zhu, m.; wang, C., Zn/MnO2Battery Chemistry With H + and Zn2+ Co-insertion.J.Am.chem.Soc.2017; zhang, n.; cheng, f.; liu, y.; zhao, q.; lei, k.; chen, c.; liu, x.; chen, J., chair-defect spin ZnMn2O4 Cathodode in Zn (CF3SO3)2 Electrovariable Zn-IonBatttery.J.Am.chem.Soc.2016, 138(39), 12894-12901; parker, j.f.; chervin, c.n.; pala, i.r.; machler, m.; burz, m.f.; long, j.w.; the Rechargeable batteries have the advantages of high energy density, abundant resources and the like, and have been widely researched.
Meanwhile, compared with an organic system secondary battery, the water system secondary battery has the advantages of low cost, environmental friendliness, high safety and the like, and is favored by researchers. The elements of the water system secondary battery such as the anode and cathode materials, the diaphragm, the electrolyte and the like play a decisive role in the performance of the battery. However, the current separator material generally adopts a polytetrafluoroethylene film, so that the specific capacity of the battery is relatively low.
Therefore, the separator material of the water-based secondary battery at the present stage still remains to be improved.
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:
the inventor discovers in the research process that the graphite alkyne can be oxidized into the oxidized graphite alkyne through a low-temperature hydrothermal method, the preparation method is mild in condition, simple to operate and suitable for large-scale preparation, and the prepared oxidized graphite alkyne film can be used as a new diaphragm material of a water system secondary battery, so that the specific capacity, the rate capability, the cycle performance and the like of the battery can be remarkably improved, the development of the water system secondary battery can be further promoted, and the prepared oxidized graphite alkyne film has potential practical application value.
In view of the above, an object of the present invention is to provide a method for preparing a graphite oxide alkyne thin film material, which is simple and easy for mass production.
In a first aspect of the invention, a method of preparing a graphite oxide alkyne film material is presented.
According to an embodiment of the invention, the method comprises: (1) preparing a reaction solution, wherein the reaction solution comprises graphite alkyne powder, potassium permanganate and water; (2) carrying out hydrothermal reaction on the reaction solution to obtain a graphite oxide alkyne solution; (3) and carrying out post-treatment on the graphite oxide alkyne solution to obtain the graphite oxide alkyne film material.
The inventor finds that the preparation method provided by the embodiment of the invention has mild conditions, is simple to operate and is suitable for large-scale preparation, and the prepared oxidized graphite alkyne film can be used as a diaphragm of a water system secondary battery, so that the specific capacity, the rate capability, the cycle performance and the like of the battery can be remarkably 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, in the reaction liquid, the weight ratio of the graphdiyne powder, the potassium permanganate, and the water is 1: (1-6): (1-3).
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 post-processing comprises: (3-1) adding concentrated hydrochloric acid into the graphite oxide alkyne solution, soaking, and performing suction filtration; (3-2) washing the powder subjected to suction filtration treatment by using secondary water and ethanol in sequence to obtain the graphite oxide alkyne film material.
According to the embodiment of the invention, the added concentrated hydrochloric acid is 5-15 mL, and the soaking treatment time is 24-72 hours.
According to the embodiment of the present invention, the amount of the added concentrated hydrochloric acid was 10mL, and the soaking treatment time was 48 hours.
In a second aspect of the invention, the invention provides a graphite oxide alkyne film material.
According to the embodiment of the invention, the graphite oxide alkyne film material is prepared by the method.
The inventor finds that the graphite oxide alkyne thin film material provided by the embodiment of the invention is used as a new diaphragm material of a water system secondary battery, so that the specific capacity, the rate capability, the cycle performance and the like of the battery can be obviously improved. It will be appreciated by those skilled in the art that the features and advantages described above with respect to the method of preparing the graphite oxide alkyne thin film material, are still applicable to the graphite oxide alkyne thin film material and will not be described in detail herein.
In a third aspect of the present invention, an aqueous secondary battery is provided.
According to an embodiment of the present invention, the aqueous system secondary battery includes a separator, and the separator is formed of the above-described graphite alkyne oxide thin film material.
The inventor finds that the diaphragm of the water system secondary battery provided by the embodiment of the invention is formed by the graphite oxide alkyne film material, so that the specific capacity, the rate capability, the cycle performance and the like of the water system secondary battery can be obviously improved. It will be appreciated by those skilled in the art that the features and advantages described above with respect to the oxidized graphite alkyne thin film material are still applicable to the aqueous secondary battery and will not be described in detail herein.
In addition, the water-based secondary battery 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 water-system secondary battery is one selected from a sodium battery, a magnesium battery, an aluminum battery, and a zinc battery.
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.
Drawings
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 chart of a method of preparing a graphite oxide alkyne thin film material in accordance with one embodiment of the present invention;
FIG. 2 is an SEM photograph of a graphite oxide alkyne thin film material in accordance with one embodiment of the present invention;
FIG. 3 is a TEM image of a oxidized graphite alkyne thin film material in accordance with one embodiment of the present invention;
FIG. 4 is a photoelectron spectroscopy analysis chart of the oxidized graphite alkyne thin film material of one embodiment of the present invention;
FIG. 5 is a photograph of a graphite oxide alkyne film in accordance with one embodiment of the present invention;
FIG. 6 is a battery rate capability test chart of a comparative example of the present invention;
FIG. 7 is a graph showing the cycle performance test of one embodiment of the present invention and a comparative example;
FIG. 8 is a cycle ratio performance test chart for one embodiment of the present invention;
FIG. 9 is a cyclic voltammetry test chart of one example of the present invention and a comparative example.
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, a method of preparing a graphite oxide alkyne film material is provided. 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 reaction solution.
In the step, a reaction solution is prepared, wherein the reaction solution comprises graphite alkyne powder, potassium permanganate and water. According to an embodiment of the present invention, in the reaction liquid, the weight ratio of the graphdiyne powder, the potassium permanganate, and the water may be 1: (1-6): (1-3), so that the oxidized graphite alkyne formed by the reaction solution formed by adopting the proportion through the hydrothermal reaction is more compact. According to the embodiment of the present invention, the specific method for forming the reaction solution is not particularly limited, and for example, the graphite alkyne powder may be ultrasonically dispersed in the aqueous solution, and then potassium permanganate may be added and magnetically stirred, and those skilled in the art may adjust the method according to the dispersion degree of the reaction solution.
According to the embodiment of the present invention, the specific kind of water used in the reaction liquid is not particularly limited. In some embodiments of the invention, secondary water may be used, and as such, the effect of impurities in the water on the hydrothermal reaction may be further reduced, resulting in higher yields of the oxidized graphdine obtained. It should be noted that, as used herein, the term "secondary water" refers to a fraction obtained by distilling tap water and collecting 95 to 100 degrees celsius fractions again.
S200: and carrying out hydrothermal reaction on the reaction solution to obtain a graphite oxide alkyne solution.
In this step, the reaction solution prepared in step S100 is subjected to a hydrothermal reaction to obtain a graphite oxide alkyne solution.
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 specific ratio of the graphdine powder to the potassium permanganate in the reaction solution accordingly.
In some embodiments of the invention, the composition comprises, in a weight ratio of 1: (1-6): and (1) reacting the graphite alkyne powder, the potassium permanganate and the water at 120-200 ℃ for 1-5 hours. Thus, the efficiency and yield of the graphite alkyne oxide prepared by adopting the hydrothermal conditions are higher; moreover, the inventor also finds that the density of the formed graphite alkyne oxide is reduced on the contrary if the hydrothermal temperature is higher than 200 ℃, and the oxidized proportion of the graphite alkyne is lower if the hydrothermal temperature is lower than 120 ℃; if the hydrothermal reaction time is longer than 5 hours, the yield of the oxidized graphdine is not increased any more, and if the hydrothermal reaction time is shorter than 1 hour, the conversion rate of the graphdine is still low. In some specific examples, the hydrothermal reaction may be performed at 180 degrees celsius for 3 hours, such that a high conversion of the graphdine oxide may be efficiently obtained.
S300: and carrying out post-treatment on the graphite oxide alkyne solution to obtain the graphite oxide alkyne film material.
In this step, the graphite alkyne oxide solution obtained in step S200 is subjected to post-treatment to obtain a graphite alkyne oxide thin film material.
In some embodiments of the present invention, step S300 may further include: s310, adding concentrated hydrochloric acid into the graphite oxide alkyne solution, soaking, and performing suction filtration; s320, washing the powder subjected to suction filtration treatment by using secondary water and ethanol in sequence to obtain the graphite oxide alkyne film material. The term "concentrated hydrochloric acid" as used herein specifically means an aqueous hydrochloric acid solution having a mass fraction of more than 20%.
According to the embodiment of the present invention, the specific conditions of the concentrated hydrochloric acid soaking are not particularly limited as long as the residual by-product manganese dioxide in the graphite oxide alkyne solution can be removed by the concentrated hydrochloric acid soaking step. In some embodiments of the present invention, the amount of the added concentrated hydrochloric acid may be 5-15 mL, and the corresponding soaking time may be 24-72 hours, so that the manganese dioxide in the oxidized graphite alkyne solution can be removed well. In some embodiments, the amount of concentrated hydrochloric acid added may be 10mL, and the soaking time may be 48 hours, so that the graphite alkyne oxide can be efficiently purified.
In summary, according to the embodiments of the present invention, the present invention provides a preparation method, in which a low-temperature hydrothermal method is used to oxidize a graphite alkyne into a graphite alkyne oxide, the preparation method has mild conditions, is simple to operate, and is suitable for large-scale preparation, and the prepared graphite alkyne oxide film can be used as a new diaphragm material of a water system secondary battery, so that the specific capacity, rate capability, cycle performance, and the like of the battery can be significantly improved.
In another aspect of the invention, the invention provides a graphite oxide alkyne film material. According to an embodiment of the present invention, the graphite oxide alkyne thin film material is prepared by the method described above.
In summary, according to the embodiments of the present invention, the graphite oxide alkyne thin film material provided by the present invention can be used as a new membrane material of a water system secondary battery, so that the specific capacity, rate capability, cycle performance, etc. of the battery can be significantly improved. It will be appreciated by those skilled in the art that the features and advantages described above with respect to the method of preparing the graphite oxide alkyne thin film material, are still applicable to the graphite oxide alkyne thin film material and will not be described in detail herein.
In another aspect of the present invention, an aqueous secondary battery is provided. According to an embodiment of the present invention, the water-based secondary battery includes a separator, and the separator is formed of the above-described graphite alkyne oxide thin film material.
According to the embodiment of the present invention, the specific type of the water-based secondary battery is not limited, such as a zinc battery, and the like, and those skilled in the art can select the water-based secondary battery according to the specific use requirement of the water-based secondary battery. In some embodiments of the present invention, the aqueous secondary battery may be one selected from a sodium battery, a magnesium battery, an aluminum battery and a zinc battery, and thus, the aqueous secondary battery using the negative electrode of the above material kind has better specific capacity, rate capability and cycle performance due to the selection of graphene oxide as the separator material.
In summary, according to the embodiments of the present invention, the present invention provides a water system secondary battery, wherein a diaphragm of the water system secondary battery is formed by a graphite oxide alkyne thin film material, so that the specific capacity, the rate capability, the cycle performance, and the like of the water system secondary battery can be significantly improved. It will be appreciated by those skilled in the art that the features and advantages described above with respect to the oxidized graphite alkyne thin film material are still applicable to the aqueous 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. Materials, reagents and the like used in the following examples are commercially available unless otherwise specified. The graphdiyne powders used in the following examples can be synthesized with 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 graphite oxide alkyne thin film material was prepared.
Ultrasonically dispersing 10mg of graphite alkyne powder into 30mL of secondary water, then adding 20mg of potassium permanganate (the ratio of the graphite alkyne powder to the secondary water to the potassium permanganate in the reaction solution is 1mg:3mL:2mg), and magnetically stirring for 10 minutes; then transferring the mixture to a 50mL reaction kettle, reacting for 3h at 180 ℃, naturally cooling to room temperature, and centrifuging to obtain brown graphite oxide alkyne solution; then 10mL of concentrated hydrochloric acid is added, the mixture is soaked for 48 hours, the graphite oxide alkyne is filtered to a polytetrafluoroethylene membrane in a suction way, and the graphite oxide alkyne thin film material is washed by secondary water and ethanol in sequence to obtain the uniform graphite oxide alkyne thin film material.
Example 2
In this example, a graphite oxide alkyne thin film material was prepared in substantially the same manner and under substantially the same conditions as in example 1. Except that, in this example, 15mg of graphdine powder was ultrasonically dispersed in 30mL of secondary water, followed by addition of 30mg of potassium permanganate (the ratio of graphdine powder, secondary water, and potassium permanganate was 1mg:2mL:2 mg).
Example 3
In this example, a graphite oxide alkyne thin film material was prepared in substantially the same manner and under substantially the same conditions as in example 1. Except that, in this example, 30mg of graphdiyne powder was ultrasonically dispersed in 30mL of secondary water, followed by addition of 60mg of potassium permanganate (the ratio of graphdiyne powder, secondary water, and potassium permanganate was 1mg:1mL:2 mg).
Then, the graphite oxide alkyne thin film material of this example was subjected to Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), and photoelectron spectroscopy. The SEM photograph, TEM photograph, and energy spectrum analysis of this example are shown in fig. 2 to 4, respectively, indicating that the graphite oxide alkyne thin film material was successfully prepared by this preparation method.
Example 4
In this example, the graphite alkyne oxide thin film material prepared in example 3 was first pressed into a membrane, and the graphite alkyne oxide thin film obtained in this step can be referred to fig. 5. Then, zinc sheet is taken as a negative electrode, manganese dioxide nano sheet is taken as a positive electrode, graphite oxide alkyne film material is taken as a diaphragm, and 1M ZnSO4Aqueous solution with 0.2M MnSO4The aqueous solution is used as electrolyte to assemble a 2032 type button cell.
Comparative example 1
In this comparative example, a zinc plate was used as a negative electrode, a manganese dioxide nanosheet as a positive electrode, a polytetrafluoroethylene film as a separator, and 1M ZnSO4Aqueous solution with 0.2M MnSO4The aqueous solution is used as electrolyte to assemble a 2032 type button cell.
Example 5
In this example, electrochemical performance tests were performed on the button cell of example 4 and the button cell of comparative example 1, respectively. Specifically, the method 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 308 mA/g. The above test results show that:
referring to fig. 6, the specific capacities of the batteries of comparative example 1 at 154, 308, 716, 1540 and 3080mA/g current densities were 210, 190, 160, 100 and 50mAh/g, respectively, and their performances were general and yet to be further improved.
In the results of the cycle performance test at a current density of 308mA/g, referring to fig. 7, the specific capacities of the assembled batteries of comparative example 1(Without GDYOmembrane) and example 4(With GDYO membrane) were 175mAh/g and 300mAh/g, respectively; referring to fig. 8, the specific capacity performance of the assembled battery of example 4 is stable, while the performance of the assembled battery of comparative example 1 tends to decline.
The results of cyclic voltammetry tests performed on the cells assembled in comparative example 1 and example 4, respectively, at a sweep rate of 0.05mV/s, can be seen in fig. 9, where it is evident that the incorporation of the oxidized graphite alkyne membrane does not change the redox reaction potential of the electrode material.
In addition, the battery of example 4 was tested for cycling performance at a high current density of 3080mA/g (10C) alone, the specific capacity of the battery was 100mAh/g, and the cycle was 1950 cycles.
Summary of the invention
The preparation method provided by the invention has the advantages that the graphite alkyne is oxidized into the graphite alkyne oxide by a low-temperature hydrothermal method, the preparation method is mild in condition, simple to operate and suitable for large-scale preparation, and the prepared graphite alkyne oxide film can be used as a diaphragm of a water system secondary battery, so that the specific capacity of the battery can be doubled, the rate capability can be effectively improved to 10 ℃ and the cycle time can be about 2000 circles.
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 (8)

1. A method for preparing a graphite alkyne oxide thin film material for a water system secondary battery diaphragm is characterized by comprising the following steps:
(1) preparing a reaction solution, wherein the reaction solution comprises graphite alkyne powder, potassium permanganate and water;
(2) carrying out hydrothermal reaction on the reaction liquid to obtain a graphite oxide alkyne solution, wherein the temperature of the hydrothermal reaction is 180 ℃ and the time is 3 hours;
(3) post-treating the oxidized graphite alkyne solution, wherein the post-treating comprises:
(3-1) adding concentrated hydrochloric acid into the graphite oxide alkyne solution, soaking, and performing suction filtration on a polytetrafluoroethylene film to obtain the graphite oxide alkyne film material, wherein the mass fraction of hydrochloric acid in the concentrated hydrochloric acid is more than 20%.
2. The method according to claim 1, wherein the weight ratio of the graphdiyne powder, the potassium permanganate and the water in the reaction solution is 1: (1-6): (1-3).
3. The method of claim 1, wherein the post-processing further comprises:
(3-2) washing the graphite oxide alkyne film material subjected to suction filtration treatment by using secondary water and ethanol in sequence.
4. The method according to claim 3, wherein the amount of the added concentrated hydrochloric acid is 5 to 15mL, and the soaking time is 24 to 72 hours.
5. The method according to claim 4, wherein the added concentrated hydrochloric acid is 10mL, and the soaking treatment time is 48 hours.
6. A graphite oxide alkyne thin film material for a water system secondary battery diaphragm is characterized by being prepared by the method of any one of claims 1 to 5.
7. An aqueous secondary battery comprising a separator, wherein the separator is formed of the graphite alkyne oxide thin film material of claim 6.
8. The water-based secondary battery according to claim 7, wherein the water-based secondary battery is one selected from a sodium battery, a magnesium battery, an aluminum battery, and a zinc battery.
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