CN114899385B - 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
- Publication number
- CN114899385B CN114899385B CN202210663693.7A CN202210663693A CN114899385B CN 114899385 B CN114899385 B CN 114899385B CN 202210663693 A CN202210663693 A CN 202210663693A CN 114899385 B CN114899385 B CN 114899385B
- Authority
- CN
- China
- Prior art keywords
- carbon
- manganese dioxide
- composite material
- manganese
- zinc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
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 performing ultrasonic treatment to obtain a suspension; separating and purifying to obtain a 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 have the advantages that the two-dimensional carbon material is used for providing larger specific surface area and excellent film forming performance, and in addition, the two-dimensional composite material is easy to realize the assembly of electrode materials with larger bulk density, so that the specific capacity of the electrode materials is improved; meanwhile, potassium ions are intercalated in the manganese dioxide nano-sheet, so that the manganese dioxide nano-sheet has excellent electrochemical activity; the preparation method realizes intercalation of manganese dioxide nano-sheets and 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 and a preparation method and application thereof.
Background
The increasing environmental pollution, sustained energy consumption and the tremendous development of green energy economy have prompted the evolutionary development of large-scale renewable energy harvesting and storage systems. Compared with a lithium ion battery, the water-based zinc ion battery is concerned by vast scientific researchers due to the advantages of high energy density, low cost, low toxicity, environmental friendliness and the like, and particularly a high-performance zinc-manganese battery.
Much research effort is currently devoted to how to achieve high reversibility and stability of zinc negative electrodes, while little research is done on the electrochemical activity of manganese-based positive electrode materials.
Although manganese dioxide positive electrode materials of different structural types (e.g., alpha, beta, gamma, and delta) are currently being developed to achieve high performance zinc-manganese batteries, the poor conductivity of manganese dioxide itself can result in slow ion/electron transport, decreasing its structural stability and electrochemical activity, and thus limiting further improvements in the electrochemical performance of zinc-manganese batteries.
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 performing ultrasonic treatment to obtain a suspension;
2) Separating and purifying the suspension from the suspension to obtain a carbon/manganese dioxide composite material;
wherein the surface of the two-dimensional carbon material has a plurality of defects.
In a second aspect, the invention also provides a carbon/manganese dioxide composite material prepared by the preparation method, which comprises a matrix carbon skeleton and a plurality of manganese dioxide nano-sheets loaded on the surface of the matrix carbon skeleton;
the matrix carbon skeleton is formed by a two-dimensional carbon material with a plurality of defects on the surface;
the manganese dioxide nano-sheets are intercalated by potassium ions.
In a third aspect, the invention also provides a preparation method of the zinc-manganese battery anode slurry, which comprises the following steps:
providing the carbon/manganese dioxide composite material;
and dispersing the carbon/manganese dioxide composite material in the carbon nano tube slurry to obtain the zinc-manganese battery anode slurry.
In a fourth aspect, the invention also provides the zinc-manganese battery anode slurry prepared by the preparation method.
In a fifth aspect, 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 film forming treatment of 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:
according to the carbon/manganese dioxide composite material and the preparation method thereof, the two-dimensional carbon material is used for providing larger specific surface area for the manganese dioxide nano-sheet, the prepared carbon/manganese dioxide composite material has excellent film forming performance, and in addition, the two-dimensional composite material is easy to realize the assembly of electrode materials with larger bulk density, so that the specific capacity of the electrode materials is improved; meanwhile, potassium ions are intercalated in the manganese dioxide nano-sheet, so that the manganese dioxide nano-sheet has excellent electrochemical activity, and the electrochemical performance of the zinc-manganese battery is improved; the preparation method provided by the invention utilizes ultrasonic hydrothermal radiation to realize intercalation of manganese dioxide nano-sheets and in-situ deposition of the manganese dioxide nano-sheets on the surface of the two-dimensional carbon material in one step, has low complexity, is simple and convenient to operate, has mild reaction conditions, and is beneficial to large-scale preparation.
The above 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 means of the present application, the present invention may be implemented according to the content of the specification, the following description is given of the preferred embodiments of the present invention with reference to the accompanying drawings.
Drawings
FIG. 1 is a low magnification surface topography electron micrograph of a carbon microchip/manganese dioxide composite provided in accordance with an exemplary embodiment of the present invention;
FIG. 2 is a high-magnification surface topography electron micrograph of a carbon microchip/manganese dioxide composite material provided by an exemplary embodiment of the present invention;
FIG. 3 is an electron micrograph of the surface morphology of an electrode formed from a carbon microchip/manganese dioxide composite material according to an exemplary embodiment of the present invention;
FIG. 4 is an XPS test chart of a carbon microchip/manganese dioxide composite material according to an exemplary embodiment of the present invention;
FIG. 5 is an XRD pattern for a carbon microchip/manganese dioxide composite provided by an exemplary embodiment of the present invention;
FIG. 6 is a schematic diagram of a zinc-manganese cell at 0.1mV s according to an exemplary embodiment of the present invention -1 Cyclic voltammogram for multiple scans at scan rate;
FIG. 7 is a graph of cyclic voltammograms of a zinc-manganese cell at different scan rates in accordance with an exemplary embodiment of the present invention;
fig. 8 is a graph showing constant current charge and discharge at different current densities for a zinc-manganese cell according to an exemplary embodiment of the present invention.
Detailed Description
In view of the shortcomings in the prior art, the inventor of the present invention has long studied and practiced in a large number of ways to propose the technical scheme of the present invention. The technical scheme, the implementation process, the principle and the like are 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 described herein, and therefore the scope of the present invention is not limited to 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) The two-dimensional carbon material is contacted with a potassium permanganate solution and sonicated to obtain a suspension.
2) And separating and purifying the suspension from the suspension to obtain the carbon/manganese dioxide composite material.
Wherein the two-dimensional carbon material has a rich pore structure and a very high specific surface area.
In the embodiment of the invention, the two-dimensional carbon material refers to a nano-scale or micro-scale two-dimensional sheet-like carbon material, and the defect refers to a structure with a plurality of holes.
The two-dimensional carbon material has the characteristics of high specific surface area, excellent conductivity and low cost, becomes an ideal deposition carrier for manganese dioxide, particularly adopts a two-dimensional active carbon microchip, not only can provide high specific surface area for manganese dioxide deposition, but also can be easily combined and assembled with a small amount of nano carbon (such as graphene and carbon nano tube) with higher conductivity to form a flexible film electrode, and further can be used as the anode of a zinc-manganese battery.
In the preparation process, the ultrasonic wave promotes the decomposition of potassium permanganate to generate manganese dioxide and potassium ions, the free manganese dioxide is further deposited on the surface of the two-dimensional carbon material under the action of the ultrasonic wave to form manganese dioxide nano sheets, and simultaneously, the potassium ions are intercalated in the manganese dioxide nano sheets in the formation process under the action of the ultrasonic wave, so that the carbon/manganese dioxide composite material with a special structure is obtained after separation and purification.
Based on the above embodiments, as some typical application examples, the preparation of the above carbon/manganese dioxide composite material may specifically be performed by the following steps:
preparing potassium permanganate solutions with different concentrations.
And dispersing the carbon microchip in the potassium permanganate solution by ultrasonic.
In the ultrasonic dispersion process, the potassium ion intercalated manganese dioxide nano-sheets are deposited on the surfaces of the carbon micro-sheets in situ.
And (5) cleaning and drying to obtain the final carbon microchip/manganese dioxide composite material.
In some embodiments, in step 1), the two-dimensional carbon material comprises any one or a combination of both of porous activated carbon and redox graphene.
In some embodiments, the porous activated carbon comprises carbon microplates. Further, the carbon microchip is preferably prepared by using wood cotton as an original carbon source through activation and high-temperature carbonization of diammonium hydrogen phosphate, and of course, other commercially available carbon microchip can be used as the two-dimensional carbon material of the invention.
In some embodiments, the carbon micro-plate has a diameter of 2-20 μm and a thickness of 200-800nm.
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 potassium permanganate solution has a concentration of 5-50mg/mL.
In some embodiments, the ultrasonic power of the ultrasonic treatment is 300-1000W, the temperature is 5-80 ℃, and the time is 1-4 hours.
In some embodiments, in step 2), the separation and purification comprises precipitation, washing, and drying.
In some embodiments, the cleaning fluid used for the cleaning includes water and absolute ethanol.
In some embodiments, the temperature of the drying is 60-100 ℃ for a period of 5-24 hours.
Based on the above embodiments, as some typical application examples, two-dimensional carbon microplates can be made as the deposited carbon skeleton of manganese dioxide; the manganese dioxide intercalated by potassium ions is deposited uniformly on the two-dimensional carbon microchip.
Specifically, the application instance may include the following steps:
a. preparing a potassium permanganate solution with a certain concentration, wherein the concentration of the solution is 5-40mg mL -1 。
b. C, in-situ ultrasonic dispersing the carbon microchip with a certain mass into the potassium permanganate solution prepared in the step a by adopting a cell pulverizer to obtain a carbon microchip/manganese dioxide composite material suspension.
c. And b, repeatedly filtering and cleaning the carbon microchip/manganese dioxide composite material suspension prepared in the step b through precipitation, deionized water and sewage ethanol, and drying at 60-100 ℃ for 5-24 hours to finally obtain the carbon microchip/manganese dioxide composite material.
The example of the invention also provides a carbon/manganese dioxide composite material prepared by the preparation method of any embodiment, which comprises a matrix carbon skeleton and a plurality of manganese dioxide nano-sheets loaded on the surface of the matrix carbon skeleton; the matrix carbon skeleton is formed by a two-dimensional carbon material with a plurality of defects on the surface; the manganese dioxide nano-sheets are intercalated by potassium ions.
In some embodiments, the manganese dioxide nanoplatelets have a diameter of 10 to 20nm and a thickness of 0.5 to 5nm.
In some embodiments, the mass fraction of manganese dioxide nanoplatelets in the carbon/manganese dioxide composite is from 30 to 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 carbon microplates not only provides a larger deposition area for the manganese dioxide nanoplates, but also greatly improves the electrochemical activity of the manganese dioxide nanoplates 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 potassium ion intercalated manganese dioxide nano-sheet with higher activity on the carbon microchip, thereby greatly improving the electrochemical activity of the manganese dioxide nano-sheet 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:
a carbon/manganese dioxide composite material in the above embodiments is provided.
And dispersing the carbon/manganese dioxide composite material in the carbon nano tube slurry to obtain the zinc-manganese battery anode slurry.
In some embodiments, the concentration of the carbon/manganese dioxide composite material 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 modifying agent comprises any one or a combination of two or more of sodium carboxymethyl cellulose, polyvinyl alcohol, polyacrylic acid, polyacrylamide, and sodium naphthalene sulfonate.
In some embodiments, the mass fraction of surface modifier in the carbon nanotube slurry is 0.1-0.5%.
In some embodiments, the solvent comprises water.
In some embodiments, the mass ratio of the carbon/manganese dioxide composite to carbon nanotubes is from 6:1 to 95:5.
In some embodiments, the preparation method of the zinc-manganese battery positive electrode slurry 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 solidifying the positive electrode slurry of the zinc-manganese battery.
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 And has excellent rate performance and cycle stability.
The technical scheme of the invention is further described in detail below through a plurality of embodiments and with reference to the accompanying drawings. However, the examples are chosen to illustrate the invention only and are not intended to limit the scope of the invention.
Example 1
The embodiment firstly illustrates a preparation process of the carbon microchip/manganese dioxide composite material, which specifically comprises the following steps:
1) Preparing a potassium permanganate solution with a certain concentration, wherein the concentration of the solution is 30mg mL -1 ；
2) Adopting a cell pulverizer to ultrasonically disperse a certain mass of kapok-based activated carbon micro-sheets in situ in the potassium permanganate solution prepared in the step 1) to obtain carbon micro-sheets/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 3 hours.
3) And (3) carrying out repeated filtration and cleaning on the carbon microchip/manganese dioxide composite material suspension prepared in the step (2) through precipitation, deionized water and absolute ethyl alcohol, and drying at 80 ℃ for 12 hours to finally obtain the carbon microchip/manganese dioxide composite material.
The surface morphology 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 the manganese dioxide nano-sheets are uniformly attached to a matrix carbon skeleton formed by the carbon microchip.
The XPS test result is shown in fig. 4, the XRD test result is shown in fig. 5, the deposition of manganese dioxide intercalated by potassium ions can be clarified according to the sharp spectra of manganese element, oxygen element and potassium element obvious in fig. 4, potassium ions are uniformly intercalated in manganese dioxide nano-sheets, and the deposition of manganese dioxide can be clarified according to the obvious 006,119 diffraction peaks of fig. 5.
The application of the carbon microchip/manganese dioxide composite material in preparing zinc-manganese batteries is also exemplified in the embodiment, and the application is specifically shown as follows:
and carrying out ultrasonic dispersion and mixing on the carbon microchip/manganese dioxide composite material prepared in the steps and CMC modified carbon nano tube slurry for 30min (the carbon nano tube slurry contains 0.2wt% of carbon nano tubes and 0.1wt% of CMC, the mass ratio of the carbon nano tubes to the carbon microchip/manganese dioxide composite material is 1:9), wherein the power is 600W during ultrasonic dispersion and mixing, the temperature of the dispersion liquid is kept at 10 ℃, so as to obtain composite zinc-manganese battery anode slurry, and then, carrying out suction filtration and drying to obtain a composite film electrode, and then, cutting the composite film electrode into pieces to serve as an anode, and assembling the composite film electrode and a zinc electrode serving as a cathode 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 wrapped on the carbon microchip, especially the manganese dioxide nanosheets on the surface of the carbon microchip have excellent contact area, and the conductive network formed by the carbon nanotubes remarkably improves the conductivity and electrochemical activity of the electrode.
The zinc-manganese battery exhibits excellent electrochemical performance (0.1A g) -1 The specific capacity is up to 330mAh g -1 ) Rate capability (1A g) -1 The specific capacity retention at this time was 60%), and the electrochemical performance test results thereof are shown in fig. 6 to 7.
Example 2
This example illustrates a process for preparing a carbon microchip/manganese dioxide composite material, which is substantially identical to example 1, except that:
in 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 4 hours;
in the step 3), the temperature of drying is 60 ℃ and the time is 24 hours.
The prepared carbon microchip/manganese dioxide composite material has similar surface morphology as in example 1, and similar specific capacity, rate capability and cycle stability can be obtained when the carbon microchip/manganese dioxide composite material is applied to a zinc-manganese battery.
Example 3
This example illustrates a process for preparing a carbon microchip/manganese dioxide composite material, which is substantially identical to example 1, except that:
in 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 temperature of drying is 100 ℃ and the time is 5 hours.
The prepared carbon microchip/manganese dioxide composite material has similar surface morphology as in example 1, and similar specific capacity, rate capability and cycle stability can be obtained when the carbon microchip/manganese dioxide composite material is applied to a zinc-manganese battery.
Example 4
This example illustrates the use of the carbon microchip/manganese dioxide composite material prepared in example 1 in the preparation of a zinc-manganese battery, which is substantially identical to the zinc-manganese battery preparation 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 0.1 weight percent, the CMC content is 0.5 weight percent, and the mass ratio of the carbon nano tube to the carbon microchip/manganese dioxide composite material is 5:95.
The zinc-manganese battery thus obtained had a specific capacity, rate performance and cycle stability similar to those of example 1.
Example 5
This example illustrates the use of the carbon microchip/manganese dioxide composite material prepared in example 1 in the preparation of a zinc-manganese battery, which is substantially identical to the zinc-manganese battery preparation 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 0.5 weight percent, and the mass ratio of the carbon nano tube to the carbon microchip/manganese dioxide composite material is 1:6.
The zinc-manganese battery thus obtained had a specific capacity, rate performance and cycle stability similar to those of example 1.
Example 6
This example illustrates the use of the carbon microchip/manganese dioxide composite material prepared in example 1 in the preparation of a zinc-manganese battery, which is substantially identical to the zinc-manganese battery preparation in example 1, except that:
when the composite film electrode material is prepared, the conductive nano carbon nano tube is replaced by graphene slurry, wherein the graphene content in the graphene slurry is 0.5wt%, the CMC content is 0.5wt%, and the mass ratio of the graphene to the carbon microchip/manganese dioxide composite material is 1:9.
Comparative example 1
This comparative example a carbon/manganese dioxide composite was prepared substantially similar to example 1, except that:
the deposition of potassium intercalated manganese dioxide can also be achieved by ultrasonic deposition methods using spherical or granular activated carbon. The difference is that the prepared carbon/manganese dioxide composite material needs to be mixed with carbon tubes in a larger proportion to obtain the flexible self-supporting composite electrode. Compared with the traditional granular active carbon, the two-dimensional carbon microchip has excellent film forming property.
Comparative example 2
This example illustrates the use of the carbon microchip/manganese dioxide composite material prepared in example 1 in the preparation of a zinc-manganese battery, which is substantially identical to the zinc-manganese battery preparation in example 1, except that:
when the thin film electrode is prepared, no carbon nano tube is added. If the carbon tube is not added, the carbon microchip/manganese dioxide composite material is powder and cannot be directly used as an electrode.
Based on the above examples and comparative examples, it is clear that the carbon/manganese dioxide composite material and the preparation method thereof provided by the invention provide larger specific surface area for manganese dioxide nanosheets by using the two-dimensional carbon material, and the prepared carbon/manganese dioxide composite material has excellent film forming performance, 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-sheet, so that the manganese dioxide nano-sheet has excellent electrochemical activity, and the electrochemical performance of the zinc-manganese battery is improved; the preparation method provided by the invention utilizes ultrasonic hydrothermal radiation to realize intercalation of manganese dioxide nano-sheets and in-situ deposition of the manganese dioxide nano-sheets on the surface of the two-dimensional carbon material in one step, has low complexity, is simple and convenient to operate, has mild reaction conditions, and is beneficial to large-scale preparation.
It should be understood that the above embodiments are merely for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and implement the same according to the present invention without limiting the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
Claims (10)
1. The preparation method of the zinc-manganese battery anode slurry is characterized by comprising the following steps:
providing a carbon/manganese dioxide composite material, wherein the carbon/manganese dioxide composite material is prepared by the following method:
1) Mixing a two-dimensional carbon material with a potassium permanganate solution, performing ultrasonic treatment to obtain a suspension, performing ultrasonic promotion on the decomposition of potassium permanganate to generate manganese dioxide and potassium ions, depositing free manganese dioxide on the surface of the two-dimensional carbon material under the action of ultrasonic waves to form manganese dioxide nano sheets, and simultaneously, inserting potassium ions into the manganese dioxide nano sheets in the formation process of the manganese dioxide nano sheets under the action of ultrasonic waves;
2) Separating and purifying the suspension from the suspension to obtain a carbon/manganese dioxide composite material;
the surface of the two-dimensional carbon material is provided with a plurality of defects, wherein the defects are of a plurality of pore structures; the two-dimensional carbon material is selected from carbon microplates; the diameter of the carbon microchip is 2-20 mu m, and the thickness is 200-800 nm; the mass ratio of the two-dimensional carbon material to the potassium permanganate is 1:8-2:1, a step of; the concentration of the potassium permanganate solution is 5-50 mg/mL; the ultrasonic power of the ultrasonic treatment is 300-1000W, the temperature is 5-80 ℃ and the time is 1-4 h;
dispersing the carbon/manganese dioxide composite material in carbon nano tube slurry to obtain zinc-manganese battery anode slurry; the concentration of the carbon/manganese dioxide composite material in the zinc-manganese battery positive electrode slurry is 1-10 mg-mL -1 。
2. The method according to claim 1, wherein in step 2), the separation and purification comprises precipitation, washing and drying.
3. The method according to claim 2, wherein the cleaning liquid used for the cleaning comprises water and absolute ethanol.
4. The method according to claim 2, wherein the temperature of the drying is 60-100 ℃ for 5-24h.
5. The method of claim 1, wherein the carbon nanotube slurry comprises carbon nanotubes, a surface modifier, and a solvent;
the surface modifier comprises any one or more than two of sodium carboxymethyl cellulose, polyvinyl alcohol, polyacrylic acid, polyacrylamide and sodium naphthalene sulfonate;
the mass fraction of the surface modifier in the carbon nano tube slurry is 0.1-0.5%, and the mass fraction of the carbon nano tube is 0.1-0.5%.
6. The method of claim 5, wherein the solvent comprises water.
7. The method of claim 5, wherein the mass ratio of the carbon/manganese dioxide composite material to the carbon nanotubes is 6:1-95:5.
8. the preparation method according to claim 7, characterized in that it comprises in particular:
dispersing the carbon/manganese dioxide composite material in carbon nano tube slurry by adopting an ultrasonic dispersion method;
the power of the ultrasonic dispersion is 400-800W, the temperature is 0-10 ℃, and the time is 10-120min.
9. A zinc-manganese battery positive electrode slurry produced by the production method according to any one of claims 1 to 8.
10. A zinc-manganese battery, which is characterized by comprising a positive electrode, a negative electrode and electrolyte, wherein the positive electrode is at least obtained by film forming treatment of the positive electrode slurry of the zinc-manganese battery according to claim 9;
the film forming treatment comprises suction filtration, film coating, drying and rolling;
the specific capacity of the zinc-manganese battery is 250-450 mAh.g -1 。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210663693.7A CN114899385B (en) | 2022-06-10 | 2022-06-10 | Carbon/manganese dioxide composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210663693.7A CN114899385B (en) | 2022-06-10 | 2022-06-10 | Carbon/manganese dioxide composite material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114899385A CN114899385A (en) | 2022-08-12 |
| CN114899385B true CN114899385B (en) | 2023-05-09 |
Family
ID=82728691
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210663693.7A Active CN114899385B (en) | 2022-06-10 | 2022-06-10 | Carbon/manganese dioxide composite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114899385B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108417793A (en) * | 2018-02-01 | 2018-08-17 | 复旦大学 | The laminated film and its preparation method and application of carbon-based frame load manganese dioxide nano-plates |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101923960B (en) * | 2010-08-18 | 2012-05-23 | 东华大学 | Preparation method of composite electrode material using flap-like manganese dioxide nanocrystal to coat carbon nanotubes |
| CN102275903B (en) * | 2011-05-24 | 2015-08-12 | 东华大学 | Preparation method of graphene and manganese dioxide nanocomposite |
| CN102915844B (en) * | 2012-11-09 | 2015-10-28 | 华东理工大学 | A kind of method and application thereof preparing the hierarchical composite material of carbon plate/manganese dioxide nano-plates |
| CN103077835B (en) * | 2013-01-15 | 2015-08-12 | 上海大学 | A kind of graphene-supported flower-shaped manganese dioxide composite material and ultrasonic synthetic method thereof |
| CN106207100A (en) * | 2015-05-04 | 2016-12-07 | 深圳市寒暑科技新能源有限公司 | A kind of carbon fibre fabric electrode and high-capacity battery based on it |
| CN105914049B (en) * | 2016-05-19 | 2018-03-30 | 青岛大学 | A kind of MnO2The preparation method of/carbon fiber pipe combination electrode material |
| CN106783203B (en) * | 2016-12-21 | 2019-07-09 | 浙江大学 | A kind of preparation method, product and the application of manganese dioxide/ultramicropore flexibility carbon cloth |
| CN107978463A (en) * | 2017-12-08 | 2018-05-01 | 天津工业大学 | A kind of preparation method of the ultracapacitor compound porous nanofiber of carbon@manganese dioxide |
| CN108550871B (en) * | 2018-05-11 | 2021-01-19 | 广东工业大学 | Manganese dioxide/carbon black composite material and preparation method and application thereof |
| CN110148716B (en) * | 2019-04-24 | 2021-02-05 | 浙江浙能中科储能科技有限公司 | Structure and preparation method of multi-sphere stacked carbon-coated manganese dioxide composite material |
-
2022
- 2022-06-10 CN CN202210663693.7A patent/CN114899385B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108417793A (en) * | 2018-02-01 | 2018-08-17 | 复旦大学 | The laminated film and its preparation method and application of carbon-based frame load manganese dioxide nano-plates |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114899385A (en) | 2022-08-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhu et al. | Pine needle-derived microporous nitrogen-doped carbon frameworks exhibit high performances in electrocatalytic hydrogen evolution reaction and supercapacitors | |
| CN109037704B (en) | Nitrogen-doped 3D porous carbon material and preparation method and application thereof | |
| Wang et al. | A simple and universal method for preparing N, S co-doped biomass derived carbon with superior performance in supercapacitors | |
| Jiang et al. | Recent advances in carbon-based electrocatalysts for vanadium redox flow battery: Mechanisms, properties, and perspectives | |
| He et al. | Novel 2D porous carbon nanosheet derived from biomass: Ultrahigh porosity and excellent performances toward V2+/V3+ redox reaction for vanadium redox flow battery | |
| WO2022142155A1 (en) | Preparation method for nitrogen-phosphorus doped porous carbon for wide-ph range oxygen reduction electrocatalysis | |
| He et al. | Biomass juncus derived nitrogen-doped porous carbon materials for supercapacitor and oxygen reduction reaction | |
| CN112886134B (en) | Preparation method of modified diaphragm for lithium-sulfur battery | |
| CN108899530B (en) | Silicon-carbon composite material and preparation method and application thereof | |
| CN105152170A (en) | Preparation method for cicada slough based porous carbon material used for electrochemical capacitor | |
| CN111302402A (en) | Hydroxyl ferric oxide/two-dimensional carbide crystal MXene negative electrode material and preparation method and application thereof | |
| Xu et al. | Hierarchical nitrogen-doped porous carbon microspheres as anode for high performance sodium ion batteries | |
| Zhu et al. | Yeast-derived active carbon as sustainable high-performance electrodes for lithium–oxygen batteries | |
| CN110223850B (en) | Rapid in-situ preparation method of high-performance nickel hydroxide electrode material | |
| Shen et al. | Hierarchical porous carbon material regenerated from natural bamboo-leaf: How to improve the performance of lead-carbon batteries? | |
| Zhang et al. | Applications of nanocarbons in redox flow batteries | |
| Yan et al. | Hierarchical MnO2@ NiCo2O4@ Ti3SiC2/carbon cloth core-shell structure with superior electrochemical performance for all solid-state supercapacitors | |
| CN113725444B (en) | Ruthenium/carbon nano tube flexible positive electrode material and preparation method and application thereof | |
| Sun et al. | Facile electrodeposition of Ni3 (BO3) 2 nanospheres on Ti mesh for high-performance asymmetric supercapacitors | |
| Zhai et al. | Biomass-derived carbon materials for vanadium redox flow battery: from structure to property | |
| CN106024403A (en) | Supercapacitor carbon pipe/molybdenum carbide combination electrode material and preparation method thereof | |
| Zhang et al. | Application of Sn-MOF-derived SnO2 and SnO2/CNTs composites in separator modification for lithium-sulfur batteries | |
| Hu et al. | Cu-modified biomass-derived activated carbons for high performance supercapacitors | |
| CN113809286A (en) | Metal Organic Framework (MOF) catalyzed growth carbon nanotube coated nickel-tin alloy electrode material and preparation method and application thereof | |
| CN114899385B (en) | Carbon/manganese dioxide composite material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |