CN114899385A - Carbon/manganese dioxide composite material and preparation method and application thereof - Google Patents
Carbon/manganese dioxide composite material and preparation method and application thereof Download PDFInfo
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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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
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H01M6/00—Primary cells; Manufacture thereof
- H01M6/04—Cells with aqueous electrolyte
- H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
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Abstract
The invention discloses a carbon/manganese dioxide composite material and a preparation method and application thereof. The preparation method comprises the following steps: mixing a two-dimensional carbon material with a potassium permanganate solution, and carrying out ultrasonic treatment to obtain a suspension; separating and purifying to obtain the carbon/manganese dioxide composite material; wherein the surface of the two-dimensional carbon material has a plurality of defects. The carbon/manganese dioxide composite material and the preparation method thereof provided by the invention utilize the two-dimensional carbon material to provide larger specific surface area, and have excellent film forming performance, and in addition, the two-dimensional composite material is easy to realize the assembly of electrode materials with larger stacking density, thereby improving the specific capacity of the electrode materials; meanwhile, potassium ions are intercalated in the manganese dioxide nano-sheets, so that the manganese dioxide nano-sheets have excellent electrochemical activity; the preparation method realizes the intercalation of the manganese dioxide nano-sheets and the in-situ deposition of the manganese dioxide nano-sheets on the surface of the two-dimensional carbon material in one step, has low complexity, simple and convenient operation and mild reaction conditions, and is beneficial to large-scale preparation.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to the technical field of composite electrode materials, and particularly relates to a carbon/manganese dioxide composite material as well as a preparation method and application thereof.
Background
The rapid development of increasingly severe environmental pollution, sustained energy consumption, and green energy economy has prompted the evolutionary development of large-scale renewable energy acquisition and storage systems. Compared with a lithium ion battery, the water system zinc ion battery is concerned by the majority of researchers due to the advantages of high energy density, low cost, low toxicity, environmental friendliness and the like, and particularly is a high-performance zinc-manganese battery.
At present, a great deal of research work is devoted to realizing the high reversibility and stability of the zinc cathode, and the research on the electrochemical activity of the manganese-based cathode material is little.
Although manganese dioxide cathode materials of different structural types (e.g., α -type, β -type, γ -type, and δ -type) are currently developed to realize high-performance zn-mn batteries, poor conductivity of manganese dioxide itself causes slow ion/electron transport, and decreases its structural stability and electrochemical activity, thereby limiting further improvement of electrochemical performance of the zn-mn battery.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a carbon/manganese dioxide composite material and a preparation method and application thereof.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
in a first aspect, the present invention provides a method for preparing a carbon/manganese dioxide composite material, comprising:
1) Contacting a two-dimensional carbon material with a potassium permanganate solution, and carrying out ultrasonic treatment to obtain a suspension;
2) Separating the purified suspension from said suspension to obtain a carbon/manganese dioxide composite;
wherein the surface of the two-dimensional carbon material has a plurality of defects.
In a second aspect, the invention further provides a carbon/manganese dioxide composite material prepared by the preparation method, which comprises a matrix carbon skeleton and a plurality of manganese dioxide nanosheets loaded on the surface of the matrix carbon skeleton;
the matrix carbon skeleton is formed of a two-dimensional carbon material having a plurality of defects on the surface;
the manganese dioxide nanosheets are intercalated by potassium ions.
In a third aspect, the invention further provides a preparation method of the positive electrode slurry of the zinc-manganese battery, which comprises the following steps:
providing the carbon/manganese dioxide composite material;
and dispersing the carbon/manganese dioxide composite material in the carbon nanotube slurry to obtain the zinc-manganese battery anode slurry.
In a fourth aspect, the invention also provides the positive electrode slurry of the zinc-manganese battery prepared by the preparation method.
In a fifth aspect, the invention further provides a zinc-manganese battery, which comprises a positive electrode, a negative electrode and an electrolyte, wherein the positive electrode is formed by performing film forming treatment on at least the positive electrode slurry of the zinc-manganese battery.
Based on the technical scheme, compared with the prior art, the invention has the beneficial effects that at least:
the carbon/manganese dioxide composite material and the preparation method thereof provided by the invention utilize the two-dimensional carbon material to provide larger specific surface area for the manganese dioxide nano-sheets, and the prepared carbon/manganese dioxide composite material has excellent film-forming property, and in addition, the two-dimensional composite material is easy to realize the assembly of electrode materials with larger bulk density, thereby improving the specific capacity of the electrode materials; meanwhile, potassium ions are intercalated in the manganese dioxide nano-sheets, so that the manganese dioxide nano-sheets have excellent electrochemical activity, and the electrochemical performance of the zinc-manganese battery is improved; the preparation method provided by the invention realizes the intercalation of the manganese dioxide nano-sheets and the in-situ deposition of the manganese dioxide nano-sheets on the surface of the two-dimensional carbon material in one step by utilizing ultrasonic hydrothermal radiation, has low complexity, simple and convenient operation and mild reaction conditions, and is beneficial to large-scale preparation.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to enable those skilled in the art to more clearly understand the technical solutions of the present invention and to implement them according to the content of the description, the following description is made with reference to the preferred embodiments of the present invention and the detailed drawings.
Drawings
FIG. 1 is an electron micrograph of a low-power surface morphology of a carbon micro-platelet/manganese dioxide composite provided in an exemplary embodiment of the present invention;
FIG. 2 is an electron micrograph of a high-magnification surface morphology of a carbon micro-platelet/manganese dioxide composite material according to an exemplary embodiment of the present invention;
FIG. 3 is an electron micrograph of the surface of an electrode formed of a carbon micro-platelet/manganese dioxide composite provided in accordance with an exemplary embodiment of the present invention;
FIG. 4 is an XPS test chart of a carbon micro-platelet/manganese dioxide composite material according to an exemplary embodiment of the present invention;
FIG. 5 is an XRD test pattern of a carbon platelet/manganese dioxide composite material provided in accordance with an exemplary embodiment of the present invention;
FIG. 6 shows a zinc-manganese cell at 0.1mV s according to an exemplary embodiment of the present invention -1 Cyclic voltammograms for a plurality of scans at the scan rate;
FIG. 7 is a plot of cyclic voltammetry for a zinc-manganese cell at various scan rates in accordance with an exemplary embodiment of the present invention;
fig. 8 is a constant current charging and discharging curve diagram of a zn-mn battery provided in an exemplary embodiment of the present invention under different current densities.
Detailed Description
In view of the defects in the prior art, the inventor of the present invention has made extensive research and practice to propose the technical solution of the present invention. The technical solution, its implementation and principles, etc. will be further explained as follows.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced otherwise than as specifically described herein, and thus the scope of the present invention is not limited by the specific embodiments disclosed below.
The embodiment of the invention provides a preparation method of a carbon/manganese dioxide composite material, in particular to a method for preparing the carbon/manganese dioxide composite material by an in-situ hydrothermal radiation method, which comprises the following steps:
1) And (3) contacting the two-dimensional carbon material with a potassium permanganate solution, and carrying out ultrasonic treatment to obtain a suspension.
2) Separating the purified suspension from said suspension to obtain the carbon/manganese dioxide composite.
Wherein the two-dimensional carbon material has a rich pore structure and a very high specific surface.
In the embodiment of the present invention, the two-dimensional carbon material refers to a nanoscale or microscale two-dimensional sheet-like carbon material, and the defect refers to a structure having many pores.
The two-dimensional carbon material has the characteristics of high specific surface area, excellent conductivity and low cost, so that the two-dimensional carbon material becomes an ideal deposition carrier of manganese dioxide, particularly, the two-dimensional activated carbon micro-sheet is adopted, so that the high specific surface area can be provided for manganese dioxide deposition, and the prepared sheet manganese dioxide/carbon composite material can be easily compounded with a small amount of nano carbon (such as graphene and carbon nano tubes) with higher conductivity to be assembled into a flexible film electrode, so that the sheet manganese dioxide/carbon composite material can be used as a positive electrode of a zinc-manganese battery.
In the preparation process, potassium permanganate is promoted to decompose by ultrasound to generate manganese dioxide and potassium ions, free manganese dioxide is further deposited on the surface of the two-dimensional carbon material under the action of ultrasound to form manganese dioxide nano-sheets, and meanwhile, the potassium ions are intercalated in the manganese dioxide nano-sheets in the formation process under the action of ultrasound, so that the carbon/manganese dioxide composite material with the special structure is obtained after separation and purification.
Based on the above embodiments, as some typical application examples, the preparation of the carbon/manganese dioxide composite material can be specifically performed by the following steps:
potassium permanganate solutions with different concentrations are prepared.
And ultrasonically dispersing the carbon micro-sheets in the potassium permanganate solution.
In the ultrasonic dispersion process, manganese dioxide nano-sheets intercalated by potassium ions are deposited on the surfaces of the carbon micro-sheets in situ.
And cleaning and drying to obtain the final carbon micro-sheet/manganese dioxide composite material.
In some embodiments, in step 1), the two-dimensional carbon material comprises any one or a combination of two of porous activated carbon and redox graphene.
In some embodiments, the porous activated carbon comprises carbon micro-platelets. Further, the carbon nanoplatelets may be prepared by activating diammonium hydrogen phosphate and carbonizing the activated carbon by using kapok wool as an original carbon source, and of course, other commercially available carbon nanoplatelets may be used as the two-dimensional carbon material of the present invention.
In some embodiments, the carbon micro-platelets have a diameter of 2 to 20 μm and a thickness of 200 to 800nm.
In some embodiments, the mass ratio of the two-dimensional carbon material to potassium permanganate is from 1: 8 to 2: 1.
In some embodiments, the concentration of the potassium permanganate solution is between 5 and 50mg/mL.
In some embodiments, the sonication is performed at a power of 300-1000W, at a temperature of 5-80 ℃ and for a time of 1-4h.
In some embodiments, in step 2), the separation and purification comprises precipitation, washing and drying.
In some embodiments, the cleaning solution used for cleaning comprises water and absolute ethanol.
In some embodiments, the drying is at a temperature of 60-100 ℃ for 5-24 hours.
Based on the above embodiments, as some typical application examples, two-dimensional carbon micro-platelets can be made to serve as a deposited carbon skeleton of manganese dioxide; the manganese dioxide with the potassium ion intercalation is uniformly deposited on the two-dimensional carbon micro-sheets.
Specifically, the application example may include the following steps:
a. preparing potassium permanganate solution with a certain concentration, wherein the concentration of the solution is 5-40mg mL -1 。
b. And (b) ultrasonically dispersing carbon micro-sheets with certain mass in situ in the potassium permanganate solution prepared in the step a by adopting a cell crusher to obtain a carbon micro-sheet/manganese dioxide composite material suspension.
c. And c, repeatedly filtering and cleaning the carbon micro-sheet/manganese dioxide composite material suspension prepared in the step b by using precipitation, deionized water and sewage ethanol, and drying at 60-100 ℃ for 5-24 hours to finally obtain the carbon micro-sheet/manganese dioxide composite material.
The embodiment of the invention also provides a carbon/manganese dioxide composite material prepared by the preparation method of any embodiment, which comprises a matrix carbon framework and a plurality of manganese dioxide nano-sheets loaded on the surface of the matrix carbon framework; the matrix carbon skeleton is formed of a two-dimensional carbon material having a plurality of defects on a surface thereof; the manganese dioxide nanosheets are intercalated by potassium ions.
In some embodiments, the manganese dioxide nanoplates have a diameter of 10-20nm and a thickness of 0.5-5nm.
In some embodiments, the mass fraction of manganese dioxide nanoplates in the carbon/manganese dioxide composite is 30-80%.
The embodiment of the invention provides a carbon/manganese dioxide nano-sheet composite material with a unique structure and a novel preparation method thereof. The two-dimensional carbon material such as the carbon micro-sheet not only provides a larger deposition area for the manganese dioxide nano-sheet, but also greatly improves the electrochemical activity of the manganese dioxide nano-sheet due to the excellent conductivity. In addition, the preparation method adopts a one-step ultrasonic in-situ deposition method, and can realize the deposition of the higher active potassium ion intercalation manganese dioxide nano-plate on the carbon micro-plate, thereby greatly improving the electrochemical activity of the manganese dioxide nano-plate and the structural stability of the whole composite material, and further improving the electrochemical performance of the zinc-manganese battery, such as high specific capacity and high rate performance.
The embodiment of the invention also provides a preparation method of the zinc-manganese battery anode slurry, which comprises the following steps:
the carbon/manganese dioxide composite of the above embodiment is provided.
And dispersing the carbon/manganese dioxide composite material in the carbon nanotube slurry to obtain the zinc-manganese battery anode slurry.
In some embodiments, the concentration of carbon/manganese dioxide composite in the zinc-manganese battery positive electrode slurry is 1-10mg mL -1
In some embodiments, the carbon nanotube slurry includes carbon nanotubes, a surface modifier, and a solvent.
In some embodiments, the surface modifier comprises any one or a combination of two or more of sodium carboxymethylcellulose, polyvinyl alcohol, polyacrylic acid, polyacrylamide, and sodium naphthalenesulfonate.
In some embodiments, the mass fraction of surface modifying agent in the carbon nanotube slurry is 0.1 to 0.5%.
In some embodiments, the solvent comprises water.
In some embodiments, the mass ratio of the carbon/manganese dioxide composite to the carbon nanotubes is from 6: 1 to 95: 5.
In some embodiments, the preparation method of the positive electrode slurry for the zinc-manganese battery specifically comprises the following steps:
and dispersing the carbon/manganese dioxide composite material in the carbon nano tube slurry by adopting an ultrasonic dispersion method.
In some embodiments, the power of the ultrasonic dispersion is 400-800W, the temperature is 0-10 ℃, and the time is 10-120min.
The embodiment of the invention also provides the zinc-manganese battery anode slurry prepared by the preparation method.
The embodiment of the invention also provides a zinc-manganese battery, which comprises a positive electrode, a negative electrode and electrolyte, wherein the positive electrode is formed by at least coating, drying and curing the positive electrode slurry of the zinc-manganese battery.
Preferably, the film forming process comprises suction filtration, film coating, drying and rolling.
Preferably, the specific capacity of the zinc-manganese battery is 250-450 mAh.g -1 And has excellent rate performance and cycle stability.
The technical scheme of the invention is further explained in detail by a plurality of embodiments and the accompanying drawings. However, the examples are chosen only for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention.
Example 1
This example first illustrates a process for preparing a carbon microchip/manganese dioxide composite material, which specifically includes the following steps:
1) Preparing a potassium permanganate solution with a certain concentration, wherein the concentration of the solution is 30mg mL -1 ；
2) In-situ ultrasonic dispersion of a certain mass of kapok-based activated carbon micro-sheets in the potassium permanganate solution prepared in the step 1) is carried out by adopting a cell crusher to obtain a carbon micro-sheet/manganese dioxide composite material suspension; during ultrasonic treatment, the temperature of the dispersion liquid is 10 ℃, the power is 600, and the ultrasonic treatment time is 3h.
3) And (3) repeatedly filtering and cleaning the carbon micro-sheet/manganese dioxide composite material suspension prepared in the step 2) by precipitation, deionized water and absolute ethyl alcohol, and drying at 80 ℃ for 12 hours to finally obtain the carbon micro-sheet/manganese dioxide composite material.
The surface topography of the carbon microchip/manganese dioxide composite material prepared by the steps is shown in figures 1-2, and it can be seen from the figures that manganese dioxide nanosheets are uniformly attached to a matrix carbon skeleton formed by the carbon microchip.
The XPS test result is shown in fig. 4, and the XRD test result is shown in fig. 5, and the peak spectra of manganese element, oxygen element and potassium element apparent in fig. 4 can clearly indicate the deposition of manganese dioxide in which potassium ions are intercalated, the potassium ions are uniformly intercalated in the manganese dioxide nanosheets, and the peaks of 006 and 119 diffraction of fig. 5 can clearly indicate the deposition of manganese dioxide.
This example also illustrates the application of the carbon micro-plate/manganese dioxide composite material in the preparation of a zinc-manganese battery, which is specifically as follows:
the carbon micro-sheet/manganese dioxide composite material prepared in the steps and CMC modified carbon nano-tube slurry are subjected to ultrasonic dispersion and mixing for 30min (in the carbon nano-tube slurry, the content of carbon nano-tubes is 0.2wt%, the content of CMC is 0.1wt%, and the mass ratio of the carbon nano-tubes to the carbon micro-sheet/manganese dioxide composite material is 1: 9), the power during ultrasonic dispersion and mixing is 600W, the temperature of dispersion liquid is kept at 10 ℃, composite zinc-manganese battery anode slurry is obtained, then, the composite film electrode is obtained by suction filtration and drying, and is used as an anode after being subjected to cutting, and the anode and a zinc electrode used as a cathode are assembled into a button battery (namely a zinc-manganese battery).
The surface morphology of the composite film electrode is shown in fig. 3, and it can be seen that the carbon nanotubes are uniformly dispersed and wrap the carbon micro-sheets, and particularly have excellent contact area with the manganese dioxide nano-sheets on the surfaces of the carbon micro-sheets, and the conductivity and electrochemical activity of the electrode are remarkably improved by the conductive network formed by the carbon nanotubes.
The zinc-manganese battery shows excellent electrochemical performance (0.1A g) -1 The specific capacity per hour is as high as 330mAh g -1 ) And rate capability (1 Ag) -1 The specific capacity retention rate at that time is 60%), and the electrochemical performance test results thereof are shown in fig. 6 to 7.
Example 2
This example illustrates the preparation of a carbon micro-platelet/manganese dioxide composite, which is substantially the same as example 1, except that:
in the step 1), the concentration of potassium permanganate is 5mg mL -1 ；
In the step 2), during ultrasonic treatment, the temperature of the dispersion liquid is 80 ℃, the power is 1000W, and the ultrasonic treatment time is 4h;
in the step 3), the drying temperature is 60 ℃ and the drying time is 24h.
The prepared carbon microchip/manganese dioxide composite material has the surface appearance similar to that in the embodiment 1, and when the carbon microchip/manganese dioxide composite material is applied to a zinc-manganese battery, similar specific capacity, rate capability and cycling stability can be obtained.
Example 3
This example illustrates the preparation of a carbon platelet/manganese dioxide composite, substantially the same as in example 1, except that:
in the step 1), the concentration of potassium permanganate is 50mg mL -1 ；
In the step 2), during ultrasonic treatment, the temperature of the dispersion liquid is 5 ℃, the power is 300W, and the ultrasonic treatment time is 1h;
in the step 3), the drying temperature is 100 ℃ and the drying time is 5h.
The prepared carbon microchip/manganese dioxide composite material has the surface appearance similar to that in the embodiment 1, and when the carbon microchip/manganese dioxide composite material is applied to a zinc-manganese battery, similar specific capacity, rate capability and cycling stability can be obtained.
Example 4
This example illustrates the use of a carbon micro-platelet/manganese dioxide composite material prepared in example 1 in the preparation of a zinc-manganese cell, which is substantially the same as the zinc-manganese cell prepared in example 1, except that:
the power of ultrasonic dispersion is 400W, the temperature is 0 ℃, and the time is 120min;
in the carbon nano tube slurry, the content of the carbon nano tube is 0.1wt%, the content of the CMC is 0.5wt%, and the mass ratio of the carbon nano tube to the carbon micro-sheet/manganese dioxide composite material is 5: 95.
The prepared zinc-manganese battery has similar specific capacity, rate capability and cycling stability as those of the zinc-manganese battery in the embodiment 1.
Example 5
This example illustrates the use of a carbon micro-platelet/manganese dioxide composite material prepared in example 1 in the preparation of a zinc-manganese cell, which is substantially the same as the zinc-manganese cell prepared in example 1, except that:
the power of ultrasonic dispersion is 800W, the temperature is 10 ℃, and the time is 10min;
in the carbon nano tube slurry, the content of the carbon nano tube is 0.5wt%, and the mass ratio of the carbon nano tube to the carbon micro-sheet/manganese dioxide composite material is 1: 6.
The prepared zinc-manganese battery has similar specific capacity, rate capability and cycling stability as those of the zinc-manganese battery in the embodiment 1.
Example 6
This example illustrates the use of a carbon platelet/manganese dioxide composite material prepared in example 1 to prepare a zinc-manganese cell, substantially the same as the zinc-manganese cell prepared in example 1, except that:
when the composite film electrode material is prepared, the conductive nano carbon-carbon nano tube is replaced by graphene slurry, wherein the graphene content is 0.5wt%, the CMC content is 0.5wt%, and the mass ratio of graphene to the carbon micro-sheet/manganese dioxide composite material is 1: 9.
Comparative example 1
This comparative example illustrates the preparation of a carbon/manganese dioxide composite, substantially similar to example 1, except that:
the deposition of potassium ion intercalated manganese dioxide can also be achieved by ultrasonic deposition using spherical or granular activated carbon. The difference is that the prepared carbon/manganese dioxide composite material needs to be mixed with a carbon tube in a larger proportion to obtain the flexible self-supporting composite electrode. Compared with the traditional granular activated carbon, the two-dimensional carbon micro-tablet has superior film forming property.
Comparative example 2
This example illustrates the use of a carbon micro-platelet/manganese dioxide composite material prepared in example 1 in the preparation of a zinc-manganese cell, which is substantially the same as the zinc-manganese cell prepared in example 1, except that:
when the film electrode is prepared, the carbon nano tube is not added. If no carbon tube is added, the carbon micro-sheet/manganese dioxide composite material is powder and can not be directly used as an electrode.
Based on the above embodiments and comparative examples, it can be clear that the carbon/manganese dioxide composite material and the preparation method thereof provided by the present invention utilize the two-dimensional carbon material to provide a larger specific surface area for the manganese dioxide nanosheets, and the prepared carbon/manganese dioxide composite material has excellent film forming properties, and in addition, the two-dimensional composite material is easy to realize the assembly of electrode materials with a larger stacking density, so as to improve the specific capacity of the electrode materials; meanwhile, potassium ions are intercalated in the manganese dioxide nanosheets, so that the manganese dioxide nanosheets have excellent electrochemical activity, and the electrochemical performance of the zinc-manganese battery is improved; the preparation method provided by the invention realizes the intercalation of the manganese dioxide nano-sheets and the in-situ deposition of the manganese dioxide nano-sheets on the surface of the two-dimensional carbon material in one step by utilizing ultrasonic hydrothermal radiation, has the advantages of low complexity, simple and convenient operation and mild reaction conditions, and is beneficial to large-scale preparation.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, and are intended to enable those skilled in the art to understand the contents of the present invention and implement the invention, and not to limit the scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered in the protection scope of the present invention.
Claims (10)
1. A preparation method of a carbon/manganese dioxide composite material is characterized by comprising the following steps:
1) Mixing a two-dimensional carbon material with a potassium permanganate solution, and carrying out ultrasonic treatment to obtain a suspension;
2) Separating the purified suspension from said suspension to obtain a carbon/manganese dioxide composite;
wherein the surface of the two-dimensional carbon material has a plurality of defects.
2. The production method according to claim 1, wherein in step 1), the two-dimensional carbon material comprises any one or a combination of two of porous activated carbon and redox graphene;
preferably, the porous activated carbon comprises carbon micro-sheets;
preferably, the diameter of the carbon micro-sheet is 2-20 μm, and the thickness is 200-800nm;
preferably, the mass ratio of the two-dimensional carbon material to the potassium permanganate is 1: 8-2: 1;
preferably, the concentration of the potassium permanganate solution is 5-50mg/mL;
preferably, the ultrasonic power of the ultrasonic treatment is 300-1000W, the temperature is 5-80 ℃, and the time is 1-4h.
3. The preparation method according to claim 1, wherein in the step 2), the separation and purification comprises precipitation, washing and drying;
preferably, the cleaning solution used for cleaning comprises water and absolute ethyl alcohol;
preferably, the drying temperature is 60-100 ℃ and the drying time is 5-24h.
4. The carbon/manganese dioxide composite material prepared by the preparation method according to any one of claims 1 to 3, comprising a base carbon skeleton and a plurality of manganese dioxide nanosheets supported on the surface of the base carbon skeleton;
the matrix carbon skeleton is formed of a two-dimensional carbon material having a plurality of defects on a surface thereof;
the manganese dioxide nanosheets are intercalated by potassium ions.
5. The carbon/manganese dioxide composite material according to claim 4, wherein the manganese dioxide nanoplates have a diameter of 10-20nm and a thickness of 0.5-5nm;
preferably, the mass fraction of the manganese dioxide nano-sheets in the carbon/manganese dioxide composite material is 30-80%.
6. A preparation method of positive electrode slurry of a zinc-manganese battery is characterized by comprising the following steps:
providing a carbon/manganese dioxide composite material according to any one of claims 4 to 5;
dispersing the carbon/manganese dioxide composite material in carbon nanotube slurry to obtain zinc-manganese battery anode slurry;
preferably, the concentration of the carbon/manganese dioxide composite material in the positive electrode slurry of the zinc-manganese battery is 1-10mg mL -1 。
7. The production method according to claim 6, wherein the carbon nanotube slurry comprises carbon nanotubes, a surface modifier, and a solvent;
preferably, the surface modifier comprises one or a combination of more than two of sodium carboxymethylcellulose, polyvinyl alcohol, polyacrylic acid, polyacrylamide and sodium naphthalene sulfonate;
preferably, the mass fraction of the surface modifier in the carbon nanotube slurry is 0.1-0.5%, and the mass fraction of the carbon nanotube is 0.1-0.5%;
preferably, the solvent comprises water;
preferably, the mass ratio of the carbon/manganese dioxide composite material to the carbon nano tube is 6: 1-95: 5.
8. The preparation method according to claim 7, comprising:
dispersing the carbon/manganese dioxide composite material in carbon nanotube slurry by adopting an ultrasonic dispersion method;
preferably, the power of ultrasonic dispersion is 400-800W, the temperature is 0-10 ℃, and the time is 10-120min.
9. The positive electrode slurry of the zinc-manganese battery prepared by the preparation method of claims 6-8.
10. A zinc-manganese battery, characterized by comprising a positive electrode, a negative electrode and an electrolyte, wherein the positive electrode is obtained by performing film forming treatment on at least the positive electrode slurry of the zinc-manganese battery according to claim 9;
preferably, the film forming treatment comprises suction filtration, film coating, drying and rolling;
preferably, the specific capacity of the zinc-manganese battery is 250-450 mAh.g -1 。
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