CN110581028A - Preparation method of manganese dioxide/carbon-based flexible electrode material - Google Patents
Preparation method of manganese dioxide/carbon-based flexible electrode material Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/40—Fibres
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- 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
- Y02E60/13—Energy storage using capacitors
Abstract
A preparation method of a manganese dioxide/carbon-based flexible electrode material comprises the following steps: (1) cleaning and drying the flexible carbon substrate; (2) carrying out immersion acidification treatment on the treated carbon substrate by using mixed acid; the mixed acid is formed by mixing concentrated nitric acid and concentrated sulfuric acid according to the volume ratio of 1: 1-1: 6; (3) preparing 10-1000 mM metal salt aqueous solution, wherein the metal salt is at least one of potassium permanganate, sodium permanganate, lithium permanganate, barium permanganate and zinc permanganate; (4) placing the carbon substrate treated in the step (2) in a metal salt solution for ultrasonic treatment for 20-60 min; (5) heating the mixture subjected to the ultrasonic treatment in the step (4); (6) and naturally cooling the heated product to room temperature, washing and then drying in vacuum to obtain the manganese dioxide/carbon-based flexible electrode material. According to the preparation method, the manganese dioxide is firmly attached to the surface of the flexible carbon substrate, so that the flexible carbon substrate can be used for a flexible super capacitor, and has high specific capacity and good cycling stability.
Description
Technical Field
the invention relates to a preparation method of a novel manganese dioxide/carbon-based flexible electrode material.
Background
As a new energy storage device, the super capacitor has higher power density, shorter charge-discharge time and longer cycle life than a battery, and has good application prospect. With the development of duet and economy, flexible and portable electronic equipment can be seen everywhere in human life in the future, so that the research and development of high-performance mobile power supplies are of great significance. Nowadays, how to further improve the quality and the volume specific capacitance of the mobile power supply and ensure high energy and power output is a main problem facing us. It is not desirable to carry a heavy mobile power supply to meet our demand for energy, so the mass and volume of the mobile power supply can be further miniaturized. Through research and development in recent years, flexible electronic devices have become mature and perfect, but development of corresponding flexible mobile power supplies has lagged behind. The flexibility of the super capacitor needs to be started from the structure, and the electrode material and the ion transmission mechanism of the super capacitor are improved, so that the super capacitor has stable electrochemical performance as the common super capacitor under the flexible and bendable condition. The electrode material is the key for determining the performance of the super capacitor, so the research on the preparation method and the thought of the electrode material has important significance for exploring a composite electrode material with a novel structure.
The metal oxide generates oxidation-reduction reaction at the interface of the electrode solution through valence state change, and can generate Faraday capacitance, so the metal oxide is always a research hotspot of electrode materials. The metal oxide electrode material mainly includes ruthenium oxide, nickel oxide, cobalt oxide, manganese oxide, iron oxide, and the like. Among them, manganese oxide is considered as an electrode material with great research prospects due to its higher theoretical specific capacity, wide resources, low price, environmental friendliness and multiple oxidation states. The manganese oxide which is most studied at present is manganese dioxide electrode material which shows good capacitance characteristics in a neutral electrolyte and has a wide potential window. The energy storage mechanism of manganese dioxide is that the surface and the interior of an electrode in electrolyte generate a Faraday reaction process, the Faraday reaction on the surface is mainly the adsorption of cations, and the Faraday reaction in the electrode is realized by the intercalation and the deintercalation of the cations in the electrolyte.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the preparation method of the manganese dioxide/carbon-based flexible electrode material, which has the advantages of low preparation cost, simple and convenient process, safe and reliable operation, no toxic and harmful chemicals and suitability for large-scale green development.
in order to achieve the purpose, the invention adopts the following technical scheme:
A preparation method of a manganese dioxide/carbon-based flexible electrode material comprises the following steps:
(1) cleaning and drying the flexible carbon substrate;
(2) carrying out immersion acidification treatment on the carbon substrate treated in the step (1) by using mixed acid; the mixed acid is formed by mixing concentrated nitric acid and concentrated sulfuric acid according to the volume ratio of 1: 1-1: 6;
(3) Weighing metal salt, dissolving the metal salt in deionized water, and stirring uniformly to completely dissolve the metal salt to obtain a metal salt solution; the metal salt is at least one of potassium permanganate, sodium permanganate, lithium permanganate, barium permanganate and zinc permanganate, and the concentration of the metal salt in the metal salt solution is 10-1000 mM;
(4) Placing the carbon substrate treated in the step (2) in the metal salt solution obtained in the step (3) for ultrasonic treatment for 20-60min, and controlling the molar amount of the metal salt in the system to be 0.075-7.5mmol/cm based on the area of the carbon substrate2；
(5) Heating the mixture subjected to the ultrasonic treatment in the step (4), wherein the heating temperature is 40-90 ℃, and the treatment time is 0.5-8 h;
(6) And (3) naturally cooling the carbon substrate heated in the step (5) to room temperature, washing, and drying at 40-80 ℃ for 4-12 h in vacuum to obtain the manganese dioxide/carbon-based flexible electrode material.
the core of the preparation method is that manganese dioxide nano-sheets with uniform size and controllable size and thickness are formed on the surfaces of different flexible carbon substrates by changing the types and concentration of metal salts and the temperature and time of heating treatment.
in step (1) of the present invention, the flexible carbon substrate has excellent conductivity, and is preferably a carbon cloth, a carbon felt, a graphite paper, a graphene paper or a carbon nanotube paper, and these flexible carbon substrate materials can be obtained by purchasing commercially available products or preparing them according to the methods disclosed in the prior documents. Preferably, step (1) is carried out as follows: and ultrasonically cleaning the carbon substrate by using acetone, deionized water and ethanol in sequence, wherein the cleaning time is 10-90 min each time, and the drying temperature is 45-90 ℃.
in the step (2), the oxygen-containing functional groups on the surface of the carbon substrate are increased after the mixed acid is acidified, so that the loading capacity of the metal oxide can be increased. The degree of acidification of the carbon substrate is affected by the mixed acid solution in different proportions, preferably in the proportions of concentrated nitric acid: concentrated sulfuric acid is 1: 3. Preferably, the acidification treatment is dipping ultrasound for 20-60min, and more preferably 30 min.
in the step (3) of the invention, the metal salts with different concentrations can influence the size, thickness and loading amount of the manganese dioxide nanosheets. Preferably, the metal salt is potassium permanganate, sodium permanganate, lithium permanganate, barium permanganate or zinc permanganate. The concentration of the metal salt in the mixed solution affects the size of the manganese dioxide nanosheets, with the higher the concentration of the metal salt, the larger the size of the nanosheets, and most preferably the concentration of the metal salt in the mixed solution is 20 mM.
In the step (4) of the invention, the molar amount of the metal salt in the system is controlled to be 0.15mmol/cm based on the area of the carbon substrate2。
In step (4) of the present invention, the ultrasonic treatment time is preferably 30 min.
In the step (5), the size and the crystal form of the manganese dioxide nanosheet can be influenced by the heating treatment temperature, the higher the temperature is, the smaller the size of the nanosheet is, and the most preferable high temperature is 85 ℃; the heating treatment time affects the size and loading of the manganese dioxide nanosheets, with shorter times, smaller nanometer sizes and lower loadings, with a heating time of 3 hours being most preferred.
in step (6) of the present invention, the washing is preferably carried out by sequentially washing with deionized water and ethanol; the vacuum drying temperature is preferably 60 ℃ and the time is preferably 8 h.
The invention particularly preferably relates to a preparation method which comprises the following steps:
(1) Ultrasonically cleaning a flexible carbon substrate by using acetone, deionized water and ethanol in sequence, wherein the cleaning time is 10-90 min each time, and drying at 45-90 ℃;
(2) Placing the flexible carbon substrate treated in the step (1) in concentrated nitric acid: concentrated sulfuric acid is 1:3, soaking and ultrasonic treating for 30 min;
(3) weighing metal salt, dissolving the metal salt in deionized water, and stirring uniformly to dissolve the metal salt completely to obtain a metal salt solution with the concentration of 20 mM;
(4) Placing the flexible carbon substrate treated by the mixed acid in the step (2) into the metal salt solution prepared in the step (3), and controlling the molar usage of the metal salt in the system to be 0.15mmol/cm based on the area of the carbon substrate2carrying out ultrasonic treatment for 30 min;
(5) Heating the mixture obtained in the step (4) to 85 ℃ for treatment for 3 h;
(6) and (4) naturally cooling the carbon substrate heated in the step (5) to room temperature, washing the carbon substrate with deionized water and absolute ethyl alcohol in sequence, and drying the carbon substrate for 8 hours in vacuum at the temperature of 60 ℃ to obtain the manganese dioxide/carbon-based flexible electrode material.
The nano manganese dioxide/carbon-based flexible electrode material prepared by the method can be used for flexible super capacitors.
Compared with the prior art, the invention has the following characteristics and advantages:
(1) the invention relates to a flexible electrode material prepared by using different types of carbon substrates as flexible substrates by utilizing water bath heating which is simple to operate and is safe and controllable. The preparation method firmly attaches the manganese dioxide nano-sheet on the surface of the carbon substrate with excellent conductivity, so that the carbon substrate has good conductivity; the size and the distribution of manganese dioxide can be regulated and controlled, the electrode material has good chemical stability due to the in-situ growth of the nanosheets, the preparation processes such as tabletting and coating are reduced, a binder and a conductive agent are not needed, the preparation cost is low, the process is simple and convenient, the operation is safe and reliable, the use of toxic and harmful chemicals is not involved, and the method is suitable for large-scale green development.
(2) The prepared flexible electrode material improves the conductivity and stability of the manganese dioxide electrode material, the contact area between the nanosheet and an electrolyte is increased due to the lamellar structure of the nanosheet, and the manganese dioxide/carbon cloth composite material in the electrolyte has high specific capacity and good cycling stability.
Drawings
The accompanying drawings, which are included to provide a further understanding of the embodiments of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the principles of the invention.
fig. 1 is a Scanning Electron Microscope (SEM) image of the flexible base carbon cloth of example 1.
FIG. 2 shows MnO prepared in example 12SEM image of/carbon cloth electrode.
FIG. 3 shows MnO prepared in example 12SEM image of/carbon cloth electrode under high magnification.
FIG. 4 shows MnO prepared in example 12X-ray diffraction (XRD) pattern of/carbon cloth electrode.
FIG. 5 shows MnO prepared in example 12Transmission Electron Microscopy (TEM) images of/carbon cloth electrodes.
FIG. 6 shows MnO prepared in example 12Cyclic Voltammetry (CV) plot for carbon cloth electrode.
FIG. 7 shows MnO prepared in example 12Constant current charge and discharge (GCD) diagram of/carbon cloth electrode.
FIG. 8 shows MnO prepared in example 12long cycle performance diagram of carbon cloth electrode.
Fig. 9 is an SEM image of the flexible substrate carbon felt of example 2.
FIG. 10 shows MnO prepared in example 22SEM image of/carbon felt electrode under high magnification.
FIG. 11 is a block diagramMnO prepared in example 22GCD diagram of/carbon felt electrode.
FIG. 12 is MnO prepared in example 32TEM images of graphene paper electrodes.
FIG. 13 shows MnO prepared in example 32GCD diagram of graphene paper electrode.
FIG. 14 shows MnO prepared in example 42GCD diagram of graphite paper electrode.
FIG. 15 shows MnO prepared in example 52GCD diagram of/carbon nanotube paper electrode.
Detailed Description
the technical solution of the present invention is described in detail below with reference to the accompanying drawings and embodiments, but is not limited thereto:
In the embodiment of the invention, CV and GCD tests of the manganese dioxide/carbon-based flexible composite electrode are completed in an electrochemical workstation, a three-electrode system is adopted, an electrolyte is a 1M sodium sulfate solution, a reference electrode is a saturated calomel electrode, and a counter electrode is a platinum electrode.
example 1:
(1) 2X 2cm2Ultrasonically cleaning carbon cloth with acetone, deionized water and ethanol for 30min in sequence, and drying at 35 ℃;
(2) Placing the cleaned carbon cloth in concentrated nitric acid: concentrated sulfuric acid is 1:3, soaking and ultrasonic treating for 30 min;
(3) Weighing potassium permanganate, dissolving the potassium permanganate in 30mL of deionized water to obtain a solution with the concentration of 20mM, placing the solution in a beaker, and stirring for 20min to completely dissolve the solution;
(4) putting the carbon cloth treated by the mixed acid into a beaker, and carrying out ultrasonic treatment for 30 min;
(5) placing the beaker in a water bath kettle, heating to 85 ℃ and treating for 3 h;
(6) Naturally cooling the heated carbon cloth to room temperature, washing with deionized water and anhydrous ethanol in sequence, and vacuum drying at 60 deg.C for 8 hr to obtain load of about 2mg cm-2MnO of2The carbon cloth composite material is an electrode material suitable for a carbon cloth-based flexible supercapacitor.
MnO prepared in example 12The/carbon cloth electrode material takes flexible carbon cloth as a carbon substrate. Drawings1 is an SEM image of the carbon cloth, and it can be seen that the flexible carbon cloth is formed by orderly weaving carbon fibers with the diameter of about several micrometers, and the surface is smooth. FIG. 2 shows MnO2the nano sheets are uniformly and densely distributed on the surface of the carbon fiber, the size is uniform, and the loading capacity is about 2mg cm-2. FIG. 3 is MnO at high magnification2The SEM image of the nano-sheet shows that the thickness of the nano-sheet is several nanometers. FIG. 4 is an XRD pattern of the electrode material prepared in example 1, and it can be seen that MnO is2characteristic peak of (2). FIG. 5 shows MnO2and (4) a nano-sheet TEM image, further showing that the distribution of manganese dioxide on the carbon cloth is uniform. FIGS. 6 and 7 are CV and GCD plots of electrode materials, respectively, from which MnO was derived2The charge-discharge process of the carbon cloth electrode is reversible, and the specific discharge capacity reaches 347F g-1fig. 8 is a long cycle performance diagram of the electrode material, and it is seen that the electrode material still has a high capacity retention rate after 2000 cycles, and its excellent electrochemical performance proves that the flexible electrode prepared by the present invention can be well applied in a flexible supercapacitor.
Example 2:
(1) 2X 2cm2Ultrasonically cleaning the carbon felt for 90min by using acetone, deionized water and ethanol in sequence, and drying at 90 ℃;
(2) Putting the cleaned carbon felt into concentrated nitric acid: concentrated sulfuric acid is 1:1, soaking and ultrasonic treating for 30 min;
(3) Weighing sodium permanganate, dissolving the sodium permanganate in 30mL of deionized water to obtain a solution with the concentration of 1000mM, placing the solution in a beaker, and stirring for 60min to completely dissolve the solution;
(4) Putting the carbon felt treated by the mixed acid into a beaker, and carrying out ultrasonic treatment for 40 min;
(5) Placing the beaker in a water bath kettle, heating to 90 ℃, and treating for 8 hours;
(6) Naturally cooling the heated carbon felt to room temperature, washing with deionized water and absolute ethyl alcohol in sequence, and vacuum drying at 80 ℃ for 12h to obtain the load of about 4.5mg cm-2MnO of2The carbon felt composite material is an electrode material suitable for a carbon felt-based flexible supercapacitor.
MnO prepared in example 22the/carbon felt electrode material takes flexible carbon felt as a carbon substrate. Drawingsfig. 9 is an SEM image of the flexible carbon felt, and it can be seen that the carbon felt is composed of carbon fibers having a diameter of about several micrometers in disorder and has a slightly rough surface. FIG. 10 is MnO2SEM image of/carbon felt with loading of about 4.5mg cm-2. FIG. 11 is a GCD diagram of the electrode material of example 2.
example 3:
(1) 2X 2cm2sequentially ultrasonically cleaning the flexible graphene paper for 10min by using acetone, deionized water and ethanol, and drying at 45 ℃;
(2) Putting the cleaned graphene paper in concentrated nitric acid: concentrated sulfuric acid is 1: 2, dipping and ultrasonic treating for 30 min;
(3) Weighing high lithium manganate, dissolving the high lithium manganate in 30mL of deionized water to obtain a solution with the concentration of 10mM, placing the solution in a beaker, and stirring for 20min to completely dissolve the solution;
(4) putting the graphene paper treated by the mixed acid into a beaker, and carrying out ultrasonic treatment for 20 min;
(5) Placing the beaker in a water bath kettle, heating to 40 ℃, and treating for 0.5 h;
(6) Naturally cooling the heated graphene paper to room temperature, sequentially washing with deionized water and absolute ethyl alcohol, and vacuum drying at 40 ℃ for 4h to obtain the load of about 0.5mg cm-2MnO of2The graphene paper composite material is an electrode material suitable for a graphene paper-based flexible supercapacitor.
MnO prepared in example 32The graphene paper electrode material takes flexible graphene paper as a carbon substrate. The flexible graphene paper is prepared by performing vacuum filtration on graphene through a filter membrane with the aperture of 0.22um, and the disordered stacking surface of graphene sheets has a microporous structure. FIG. 12 is MnO2TEM images loaded on graphene paper. FIG. 13 is a GCD diagram of the electrode material of example 3.
Example 4:
(1) 2X 2cm2Ultrasonically cleaning graphite paper with acetone, deionized water and ethanol for 20min in sequence, and drying at 50 deg.C;
(2) putting the cleaned graphite paper in concentrated nitric acid: concentrated sulfuric acid is 1: 5, soaking and ultrasonic treating for 30 min;
(3) Weighing barium permanganate, dissolving the barium permanganate in 30mL of deionized water to obtain a solution with the concentration of 100mM, placing the solution in a beaker, and stirring for 20min to completely dissolve the solution;
(4) Putting the graphite paper treated by the mixed acid into a beaker, and carrying out ultrasonic treatment for 20 min;
(5) Placing the beaker in a water bath kettle, heating to 50 ℃ and processing for 1 h;
(6) naturally cooling the graphite paper after heating treatment to room temperature, washing with deionized water and absolute ethyl alcohol in sequence, and vacuum drying at 70 ℃ for 6h to obtain the load of about 1.2mg cm-2MnO of2The graphite paper composite material is an electrode material suitable for a graphite paper-based flexible supercapacitor.
MnO prepared in example 42The graphite paper electrode material takes flexible graphite paper as a carbon substrate. Flexible graphite paper was prepared according to the procedure of example 1 of CN 1122787A. FIG. 14 is a GCD diagram of the electrode material of example 4.
example 5:
(1) 2X 2cm2Ultrasonically cleaning carbon nanotube paper with acetone, deionized water and ethanol for 40min in sequence, and drying at 70 deg.C;
(2) Putting the cleaned graphite paper in concentrated nitric acid: concentrated sulfuric acid is 1:6, dipping and ultrasonic treating for 30 min;
(3) Weighing and dissolving the zinc permanganate in 30mL of deionized water to obtain a solution with the concentration of 500mM, placing the solution in a beaker, and stirring for 50min to completely dissolve the solution;
(4) Putting the carbon nano tube paper treated by the mixed acid into a beaker, and carrying out ultrasonic treatment for 20 min;
(5) Placing the beaker in a water bath kettle, heating to 70 ℃, and treating for 5 hours;
(6) Naturally cooling the carbon nano tube paper after the heating treatment to room temperature, sequentially washing the carbon nano tube paper by using deionized water and absolute ethyl alcohol, and drying the carbon nano tube paper for 8 hours in vacuum at the temperature of 60 ℃ to obtain the carbon nano tube paper with the load of about 3mg cm-2MnO of2the carbon nanotube paper composite material is an electrode material suitable for a carbon nanotube paper-based flexible supercapacitor.
MnO prepared in example 52the/carbon nanotube paper electrode material takes flexible carbon nanotube paper as a carbon substrate. The flexible carbon nanotube paper is prepared from multi-wall carbon nanotubesThe filter membrane with the aperture of 0.22um is prepared by vacuum filtration, and the disordered stacking surface of the carbon nano tube has a microporous structure. FIG. 15 is a GCD diagram of the electrode material of example 5.
the embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (10)
1. a preparation method of manganese dioxide/carbon-based flexible electrode material is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) Cleaning and drying the flexible carbon substrate;
(2) Carrying out immersion acidification treatment on the carbon substrate treated in the step (1) by using mixed acid; the mixed acid is formed by mixing concentrated nitric acid and concentrated sulfuric acid according to the volume ratio of 1: 1-1: 6;
(3) Weighing metal salt, dissolving the metal salt in deionized water, and stirring uniformly to completely dissolve the metal salt to obtain a metal salt solution; the metal salt is at least one of potassium permanganate, sodium permanganate, lithium permanganate, barium permanganate and zinc permanganate, and the concentration of the metal salt in the metal salt solution is 10-1000 mM;
(4) Placing the carbon substrate treated in the step (2) in the metal salt solution obtained in the step (3) for ultrasonic treatment for 20-60min, and controlling the molar amount of the metal salt in the system to be 0.075-7.5mmol/cm based on the area of the carbon substrate2；
(5) heating the mixture subjected to the ultrasonic treatment in the step (4), wherein the heating temperature is 40-90 ℃, and the treatment time is 0.5-8 h;
(6) And (3) naturally cooling the carbon substrate heated in the step (5) to room temperature, washing, and drying at 40-80 ℃ for 4-12 h in vacuum to obtain the manganese dioxide/carbon-based flexible electrode material.
2. The method of preparing manganese dioxide/carbon-based flexible electrode material according to claim 1, wherein: in the step (1), the flexible carbon substrate is carbon cloth, carbon felt, graphite paper, graphene paper or carbon nanotube paper.
3. the method of preparing manganese dioxide/carbon-based flexible electrode material according to claim 1, wherein: the step (1) is implemented as follows: and ultrasonically cleaning the flexible carbon substrate by using acetone, deionized water and ethanol in sequence, wherein the cleaning time is 10-90 min each time, and the drying temperature is 45-90 ℃.
4. the method of preparing manganese dioxide/carbon-based flexible electrode material according to claim 1, wherein: in the step (2), the volume ratio of the concentrated nitric acid to the concentrated sulfuric acid in the mixed acid is 1: 3.
5. The method of preparing manganese dioxide/carbon-based flexible electrode material according to claim 1, wherein: in the step (2), the acidification treatment is dipping and ultrasonic treatment for 20-60 min.
6. the method of preparing manganese dioxide/carbon-based flexible electrode material according to claim 1, wherein: in the step (3), the concentration of the metal salt in the mixed solution is 20 mM.
7. The method of preparing manganese dioxide/carbon-based flexible electrode material according to claim 1, wherein: in the step (4), the molar dosage of the metal salt in the system is controlled to be 0.15mmol/cm based on the area of the carbon substrate2。
8. The method of preparing manganese dioxide/carbon-based flexible electrode material according to claim 1, wherein: in the step (5), the temperature is 85 ℃, and the heating time is 3 h.
9. The method of preparing manganese dioxide/carbon-based flexible electrode material according to claim 1, wherein: in the step (6), the washing is sequentially washing with deionized water and ethanol; the vacuum drying temperature is 60 ℃, and the time is 8 h.
10. The method of claim 1, wherein the method comprises the steps of:
(1) ultrasonically cleaning a flexible carbon substrate by using acetone, deionized water and ethanol in sequence, wherein the cleaning time is 10-90 min each time, and drying at 45-90 ℃;
(2) placing the flexible carbon substrate treated in the step (1) in concentrated nitric acid: concentrated sulfuric acid is 1:3, soaking and ultrasonic treating for 30 min;
(3) Weighing metal salt, dissolving the metal salt in deionized water, and stirring uniformly to dissolve the metal salt completely to obtain a metal salt solution with the concentration of 20 mM;
(4) Placing the flexible carbon substrate treated by the mixed acid in the step (2) into the metal salt solution prepared in the step (3), and controlling the molar usage of the metal salt in the system to be 0.15mmol/cm based on the area of the carbon substrate2Carrying out ultrasonic treatment for 30 min;
(5) Heating the mixture obtained in the step (4) to 85 ℃ for treatment for 3 h;
(6) and (4) naturally cooling the carbon substrate heated in the step (5) to room temperature, washing the carbon substrate with deionized water and absolute ethyl alcohol in sequence, and drying the carbon substrate for 8 hours in vacuum at the temperature of 60 ℃ to obtain the manganese dioxide/carbon-based flexible electrode material.
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| CN112701295A (en) * | 2020-12-29 | 2021-04-23 | 蜂巢能源科技有限公司 | Graphite fibrofelt flexible current collector, preparation method thereof and flexible battery |
| CN112908722A (en) * | 2021-01-21 | 2021-06-04 | 南京工业大学 | MnO for preparing high specific capacitance2Method for compounding flexible electrode material with carbon cloth |
| CN113077995A (en) * | 2021-03-05 | 2021-07-06 | 广东轻工职业技术学院 | Flexible solid-state asymmetric supercapacitor device and preparation method and application thereof |
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| CN113394025A (en) * | 2021-05-17 | 2021-09-14 | 太原理工大学 | Flexible self-repairing supercapacitor based on activated carbon cloth/manganese dioxide composite material and preparation method thereof |
| CN113422074A (en) * | 2021-06-24 | 2021-09-21 | 焦作大学 | Pretreatment method of carbon-based electrode material of electrochemical system |
| CN115020113A (en) * | 2022-05-17 | 2022-09-06 | 陇东学院 | MnO (MnO) 2 Flexible supercapacitor electrode material and preparation method thereof |
| CN114974931A (en) * | 2022-05-31 | 2022-08-30 | 南京工业大学 | Preparation of manganese-based high-voltage window electrode material and super capacitor energy storage device |
| CN114974931B (en) * | 2022-05-31 | 2023-09-01 | 南京工业大学 | Manganese-based high-voltage window electrode material and preparation of supercapacitor energy storage device |
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