CN111048324A - Manganese dioxide-porous carbon composite material and preparation method and application thereof - Google Patents
Manganese dioxide-porous carbon composite material and preparation method and application thereof Download PDFInfo
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- CN111048324A CN111048324A CN201811193309.1A CN201811193309A CN111048324A CN 111048324 A CN111048324 A CN 111048324A CN 201811193309 A CN201811193309 A CN 201811193309A CN 111048324 A CN111048324 A CN 111048324A
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- porous carbon
- manganese dioxide
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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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
- H01G11/46—Metal oxides
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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
The invention discloses a manganese dioxide-porous carbon composite material, a preparation method and application thereof, wherein the porous carbon is used for reducing KMnO4And obtains uniform MnO on the surface of the porous carbon2Nanoparticles to further improve MnO2Reducing structural damage during electrochemical cycling. At 0.5Ag‑1The capacity of the capacitor can be stabilized at 215F g‑1. The method effectively improves the traditional superElectrode material MnO of stage capacitor2And its chalking and flaking phenomenon caused by stress generated during redox cycling. Thus, MnO2The porous carbon composite material has wide application prospect in the aspects of improving the conductivity and stability of the electrode material of the super capacitor.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to manganese dioxide (MnO)2) Porous carbon composite material and preparation method and application thereof.
Background
Global energy shortage was a serious problem in the 21 st century. Some green energy sources, such as solar, wind, hydro, etc., are replacing fossil fuels. Electrochemical energy has become a focus of attention because of its advantages of high energy density and energy conversion efficiency, random assembly and movement, no noise pollution, etc. The super capacitor is a novel green energy storage device, has higher power density than a lithium ion battery, has wide application range, is safe and easy to maintain, and the like, and thus has wide attention in the field of new energy. At present, MnO as an electrode material for supercapacitors2The theoretical capacity is up to 1232m Ah/g, and the method has the characteristics of rich natural yield, environmental friendliness, low cost and the like, and has wide application and research in the fields of catalysts, sensors, electrochemical devices, supercapacitor electrode materials and the like. But its application is limited due to its low conductivity and its disadvantages of powdering, peeling and flaking caused by stress generated during redox cycling.
There are many limiting factors affecting the use of supercapacitor materials in industrial processes, where environmental reasons and cost are the first factors to consider. The ideal electrode material needs to have higher specific capacity and good stability, and the carbon material becomes the most concerned electrode material in the industrial process and is also the most deeply researched material. Porous carbon has received much attention due to its high specific surface area and excellent electrical conductivity. Enhancing MnO with porous carbon2The conductivity of the electrode material is reduced in electrochemistryStructural failure during cycling. Thus, MnO2The porous carbon composite material has wide application prospect in the aspects of improving the conductivity and stability of the electrode material of the super capacitor, can be applied to energy storage equipment such as the super capacitor and the like, and is hopefully applied to the fields of sensors and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a manganese dioxide-porous carbon composite material, a preparation method and application thereof, namely, the invention provides a method for reducing KMnO by using porous carbon4And uniform MnO is obtained on the surface of the porous carbon2Nanoparticles to further improve MnO2The electric conductivity of the composite material reduces the structural damage of the composite material in the electrochemical cycle process, and effectively improves the MnO of the traditional super capacitor electrode material2And its chalking and flaking phenomenon caused by stress generated during redox cycling.
The technical purpose of the invention is realized by the following technical scheme.
Manganese dioxide nanoparticles are obtained by reducing potassium permanganate with porous carbon and are uniformly distributed on the surface of the porous carbon, and the preparation method comprises the following steps:
uniformly dispersing porous carbon in water to form a suspension of the porous carbon, and adding KMnO into the suspension4And Na2SO4Dispersing the KMnO in porous carbon to reduce KMnO under stirring4And uniform MnO is obtained on the surface of the porous carbon2Nanoparticles, KMnO4And carbon in a molar ratio of (1.5-2.5): and 1, taking sodium sulfate as a template agent, and controlling the appearance of manganese dioxide obtained by reduction, wherein the concentration is 0.1-0.5 mol/L.
In the technical scheme, ultrasonic stirring or mechanical stirring is selected, and the speed is 200-500 revolutions per minute.
In the technical scheme, after the reaction is finished, the obtained product is washed by distilled water and is dried in vacuum at the temperature of 120-150 ℃.
In the above technical scheme, the concentration of the porous carbon is 0.005-0.02g/ml，KMnO4The concentration of (A) is 0.1-0.5mol/L, Na2SO4The concentration of (B) is 0.1-0.5 mol/L.
In the technical scheme, porous carbon is selected to be ultrasonically dispersed in water for 30-120 minutes to form suspension.
In the above technical scheme, the reaction temperature is 20-25 ℃ and the reaction is carried out for 1-24 hours, preferably 10-20 hours under the condition of stirring.
In the technical scheme, the KMnO is reduced by using porous carbon4And sodium sulfate is used as a template agent to control the appearance of the manganese dioxide obtained by reduction, and the obtained manganese dioxide is spherical nano-particles with the diameter of 20-30 nm.
Compared with other materials, MnO prepared by the invention2The porous carbon composite material has uniform coating, simple experimental method and easily-reached experimental conditions, and effectively improves MnO2The electrode material is electrically conductive and reduces structural failure during electrochemical cycling. When the dispersion concentration of the porous carbon in water is 0.001g/ml, KMnO4And Na2SO4At a concentration of 0.2mol/L, it is 0.5A · g-1The capacity of the capacitor can be stabilized at 215 F.g-1Is MnO of2Provides a new method as an electrode material of a super capacitor.
Drawings
FIG. 1 shows MnO prepared in example 12Scanning electron microscope photograph of porous carbon composite material sample.
FIG. 2 shows MnO prepared in example 12Electrochemical performance test chart (namely constant current charge and discharge chart) of the porous carbon composite material.
FIG. 3 shows MnO prepared in example 22X-ray diffraction pattern of porous carbon composite sample.
FIG. 4 shows MnO prepared in example 32Scanning electron microscope photograph of porous carbon composite material sample.
Detailed Description
The technical scheme of the invention is further explained by combining specific examples. The raw materials used in the embodiment of the invention are all commercial products, and the purity is divided intoAnd (5) purifying. The morphology of the nanoparticles prepared by the invention is displayed by a Scanning Electron Microscope (SEM), and a Japanese Hitachi S4800 type scanning electron microscope is adopted; MnO2The crystal form is shown by an X-ray diffractometer (XRD), and a German Bruker D8Advanced X-ray diffractometer is adopted; preparing a slurry from the prepared active substance (the manganese dioxide-porous carbon composite material of the invention), acetylene black and a PVDF solution according to a mass ratio of 8:1:1, coating the slurry on treated nickel foam, drying the nickel foam in vacuum at 110 ℃ for 12 hours, tabletting the dried sample, and carrying out electrochemical test on the sample by adopting a three-electrode test system in 1mol/L sodium sulfate electrolyte, wherein a platinum electrode is selected as a counter electrode, a reference electrode is an Ag/AgCl standard electrode, and the prepared electrode slice is a working electrode; the porous carbon is prepared by referring to Chinese patent 2018106219631.
Example 1
Taking 0.03g of porous carbon, ultrasonically dispersing the porous carbon in 30ml of water for 30 minutes, and mixing KMnO4And Na2SO4Adding into porous carbon suspension at concentration of 0.2mol/L, stirring strongly for 16 hr, filtering, washing the obtained product with distilled water, and vacuum drying at 150 deg.C.
The appearance of the prepared product sample is observed by using a scanning electron microscope, and MnO can be seen from the attached figure 1 of the specification2Is a 30nm spherical structure attached to the porous carbon surface. The product is applied to an electrode material of a super capacitor for electrochemical characterization, and can be seen from the attached figure 2, the product is 0.5A-g-1The capacity of the capacitor can be stabilized at 215 F.g-1。
Example 2
Taking 0.03g of porous carbon, ultrasonically dispersing the porous carbon in 30ml of water for 30 minutes, and mixing KMnO4And Na2SO4Adding into porous carbon suspension at concentration of 0.3mol/L, stirring strongly for 8 hr, filtering, washing the obtained product with distilled water, and vacuum drying at 150 deg.C.
The appearance of the prepared product sample is observed by using a scanning electron microscope, and MnO can be seen2Is a spherical structure attached to the porous carbon surface. FIG. 3 is an X-ray diffraction pattern thereof wherein 2 θ is 12.7 °, 18.1 °, X,Diffraction peaks corresponding to 28.7 degrees, 37.5 degrees, 41.8 degrees, 49.8 degrees, 60.1 degrees and 69.5 degrees are consistent with those of standard card JCPDS00-044-0141 and respectively correspond to crystal planes of (110), (200), (310), (211), (301), (411), (521) and (541), so that the composite material structure of porous carbon and manganese dioxide is proved. The product is applied to a super capacitor electrode material for electrochemical characterization, and the electrochemical characterization is carried out, wherein the electrochemical characterization is carried out at 0.5 A.g-1The capacity of the capacitor can be stabilized at 192F g-1。
Example 3
Taking 0.03g of porous carbon, ultrasonically dispersing the porous carbon in 30ml of water for 30 minutes, and mixing KMnO4And Na2SO4Adding into porous carbon suspension at concentration of 0.1mol/L, stirring vigorously for 3 hr, filtering, washing the obtained product with distilled water, and vacuum drying at 150 deg.C.
The appearance of the prepared product sample is observed by using a scanning electron microscope, and MnO can be seen from the attached figure 4 of the specification2Is a spherical structure attached to the porous carbon surface. The product is applied to a super capacitor electrode material for electrochemical characterization, and the electrochemical characterization is carried out on the product at 0.5Ag-1The capacity of the capacitor can be stabilized at 181F g-1。
As can be seen from the above three examples, KMnO4And Na2SO4Is critical. When KMnO is used4And Na2SO4Too low a concentration of reduced MnO2The particle size of the particles is too small, and the capacity of the assembled super capacitor is lower. When KMnO is used4And Na2SO4When the concentration of (A) is too high, reduced MnO2Large particle size, its conductivity and MnO2The stability of (2) is lowered. When KMnO is used4And Na2SO4When the concentration of the component (A) is proper, the obtained product nano particles have proper particle size and uniform dispersion, and can improve MnO2The conductivity of (2) reduces the structural damage of the electrochemical cycle process, and improves the stability of the electrochemical cycle process, and the preferred concentrations of the three are as follows: the porous carbon has a concentration of 0.005-0.02g/ml and KMnO4The concentration of (A) is 0.1-0.5mol/L, Na2SO4The concentration of (B) is 0.1-0.5 mol/L.
Working according to the inventionThe adjustment of the process parameters can realize the preparation of the manganese dioxide-porous carbon composite material and show the basically consistent performance of the invention, namely the application of the manganese dioxide-porous carbon composite material in the preparation of the electrode material of the super capacitor in 0.5Ag-1The capacity can be stabilized at 180-220F g-1. The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (10)
1. A manganese dioxide-porous carbon composite material is characterized in that porous carbon is used for reducing potassium permanganate to obtain manganese dioxide nanoparticles which are uniformly distributed on the surface of the porous carbon, and the manganese dioxide is spherical nanoparticles with the diameter of 20-30 nm; the method comprises the following steps:
uniformly dispersing porous carbon in water to form a suspension of the porous carbon, and adding KMnO into the suspension4And Na2SO4Dispersing the KMnO in porous carbon to reduce KMnO under stirring4And uniform MnO is obtained on the surface of the porous carbon2Nanoparticles, KMnO4And carbon in a molar ratio of (1.5-2.5): 1; and the sodium sulfate is used as a template agent to control the appearance of the manganese dioxide obtained by reduction.
2. The manganese dioxide-porous carbon composite material according to claim 1, wherein ultrasonic agitation or mechanical agitation is selected at a speed of 200 to 500 rpm.
3. The manganese dioxide-porous carbon composite material according to claim 1, wherein the porous carbon is selected for ultrasonic dispersion in water for 30-120 minutes to form a suspension.
4. The manganese dioxide-porous carbon composite material according to claim 1, wherein the porous carbon composite material is porousThe carbon concentration is 0.005-0.02g/ml, KMnO4The concentration of (A) is 0.1-0.5mol/L, Na2SO4The concentration of (B) is 0.1-0.5 mol/L.
5. A manganese dioxide-porous carbon composite according to claim 1, characterized in that the reaction temperature is 20-25 ℃ at room temperature, and the reaction is carried out with stirring for 1-24 hours, preferably 10-20 hours.
6. A preparation method of manganese dioxide-porous carbon composite material is characterized in that porous carbon is used for reducing potassium permanganate to obtain manganese dioxide nanoparticles which are uniformly distributed on the surface of the porous carbon, and the manganese dioxide is spherical nanoparticles with the diameter of 20-30 nm; the method comprises the following steps:
uniformly dispersing porous carbon in water to form a suspension of the porous carbon, and adding KMnO into the suspension4And Na2SO4Dispersing the KMnO in porous carbon to reduce KMnO under stirring4And uniform MnO is obtained on the surface of the porous carbon2Nanoparticles, KMnO4And carbon in a molar ratio of (1.5-2.5): 1; and the sodium sulfate is used as a template agent to control the appearance of the manganese dioxide obtained by reduction.
7. The method for preparing manganese dioxide-porous carbon composite material according to claim 6, wherein ultrasonic stirring or mechanical stirring is selected at a speed of 200-500 rpm; porous carbon is selected to be ultrasonically dispersed in water for 30-120 minutes to form a suspension.
8. The method of claim 6, wherein the porous carbon has a concentration of 0.005-0.02g/ml KMnO4The concentration of (A) is 0.1-0.5mol/L, Na2SO4The concentration of (B) is 0.1-0.5 mol/L.
9. The method of claim 6, wherein the reaction temperature is 20-25 ℃ and the reaction is performed with stirring for 1-24 hours, preferably 10-20 hours.
10. Use of manganese dioxide-porous carbon composite material according to one of claims 1 to 5 for the preparation of supercapacitor electrode material in the presence of 0.5Ag-1The capacity can be stabilized at 180-220F g-1。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111646514A (en) * | 2020-06-17 | 2020-09-11 | 郑州轻工业大学 | MnO of sandwich structure2@rGO@MnO2Composite nanosheet material and preparation method thereof |
| CN112375545A (en) * | 2020-11-16 | 2021-02-19 | 桂林电子科技大学 | Manganese dioxide-melamine formaldehyde resin double-shell composite phase change material and preparation method thereof |
| CN112820550A (en) * | 2021-01-31 | 2021-05-18 | 福州大学 | Manganese dioxide composite nitrogen-sulfur double-doped porous carbon and preparation method and application thereof |
| WO2024000175A1 (en) * | 2022-06-28 | 2024-01-04 | 皖西学院 | Preparation method for porous carbon and manganese dioxide composite supercapacitor electrode material |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111646514A (en) * | 2020-06-17 | 2020-09-11 | 郑州轻工业大学 | MnO of sandwich structure2@rGO@MnO2Composite nanosheet material and preparation method thereof |
| CN111646514B (en) * | 2020-06-17 | 2024-02-06 | 郑州轻工业大学 | MnO of sandwich structure 2 @rGO@MnO 2 Composite nano sheet material and preparation method thereof |
| CN112375545A (en) * | 2020-11-16 | 2021-02-19 | 桂林电子科技大学 | Manganese dioxide-melamine formaldehyde resin double-shell composite phase change material and preparation method thereof |
| CN112375545B (en) * | 2020-11-16 | 2021-07-02 | 桂林电子科技大学 | Manganese dioxide-melamine formaldehyde resin double-shell composite phase change material and preparation method thereof |
| CN112820550A (en) * | 2021-01-31 | 2021-05-18 | 福州大学 | Manganese dioxide composite nitrogen-sulfur double-doped porous carbon and preparation method and application thereof |
| CN112820550B (en) * | 2021-01-31 | 2022-07-08 | 福州大学 | Manganese dioxide composite nitrogen-sulfur double-doped porous carbon and preparation method and application thereof |
| WO2024000175A1 (en) * | 2022-06-28 | 2024-01-04 | 皖西学院 | Preparation method for porous carbon and manganese dioxide composite supercapacitor electrode material |
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