CN104362001A - Method for preparing manganese dioxide/graphene/porous carbon (MnO2/rGO/C) composite material and application of MnO2/rGO/C composite material to supercapacitor as electrode material - Google Patents
Method for preparing manganese dioxide/graphene/porous carbon (MnO2/rGO/C) composite material and application of MnO2/rGO/C composite material to supercapacitor as 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
- H01G11/46—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
- H01G11/22—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
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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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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- 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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention provides a hexagonal flake manganese dioxide/graphene/porous carbon (MnO2/rGO/C) composite material used in electrodes of a supercapacitor, and belongs to the technical field of composite materials. Graphite oxide, potato starch and potassium permanganate are used as raw materials, and the MnO2/rGO/C composite material is obtained through a hydrothermal reaction. Electrochemical property tests show that the prepared MnO2/rGO/C composite material not only has a synergistic effect of two properties but also has an excellent property which cannot be achieved by a single electrode, high electrochemical capacitance behaviors are revealed, the good doubled dissolution rate and the good cycling stability are achieved, and therefore the MnO2/rGO/C composite material can be used as an electrode material of the supercapacitor. In addition, the raw material has the advantages of being low in price, easy to obtain, low in weight, recyclable, free of pollution and the like. The preparing process is simple, the technology is stable, operation is easy, quality is reliable, and the MnO2/rGO/C composite material can meet the basic commercialized requirements when being used as the electrode material of the supercapacitor.
Description
Technical field
The invention belongs to technical field of composite materials, relate to a kind of sheet hexagon manganese dioxide/Graphene/porous carbon (MnO
2/ rGO/C) preparation of composite material; The present invention also relates to this MnO simultaneously
2/ rGO/C composite material is as the application of electrode material in ultracapacitor.
Technical background
Along with the development and utilization of clean energy resource, aobvious particularly important of the deposit of the energy, develops a kind of novel energy storage equipment extremely urgent.Ultracapacitor is a kind of novel energy storage/reforming unit, its energy density high (10kw/kg), charge and discharge time is short, have extended cycle life and the advantage such as pollution-free is widely used in portable type electronic product, mixed power electric car and large industry equipment etc.And the selection of electrode material is the main cause affecting ultracapacitor, mainly comprise metal oxide, conducting polymer and carbon-based material.
MnO
2because it is abundant, inexpensive, environmental friendliness, active redox active and high theoretical ratio capacitance (1232 Fg
-1) and receive numerous concerns.Graphene by one deck intensive be wrapped in the two dimensional crystal material with carbon element that the carbon atom in honeycomb crystal lattice forms, the fullerene of zero dimension can be warped into, be rolled into the carbon nano-tube of one dimension or be stacked to three-dimensional graphite, therefore Graphene is the elementary cell forming other graphite materials.Compared with carbon nano-tube, Graphene has more excellent character, such as, and good conductivity (10
3~ 10
4s/m), specific area (2630 m of super large
2/ g), stable chemical nature and machinability etc., this makes it become to transform and the electrode material stored than the better electrochemistry new forms of energy of carbon nano-tube.But in actual applications, because the effect of Van der Waals force makes it easily reunite or stacking and cause the result that actual specific electric capacity is not high again.Graphene-based composite material then effectively overcomes this difficult problem of Graphene, because positive synergy makes other composition in composite material effectively prevent the reunion of Graphene, thus make the electric double layer capacitance of Graphene be able to good displaying, effectively raise the ratio capacitance of whole material.Therefore, materials different with Graphene two kinds for the sheet hexagon manganese dioxide of subsidiary porous carbon is carried out compound, and expect to obtain the more excellent composite material of performance, composite material is as electrode material for super capacitor, obtain the premium properties having unitary electrode and do not possess, application prospect is extensive.
Summary of the invention
The object of the present invention is to provide a kind of sheet hexagon manganese dioxide/Graphene/porous carbon (MnO
2/ rGO/C) preparation method of composite material.
More free-revving engine of the present invention is to provide a kind of sheet hexagon manganese dioxide/Graphene/porous carbon (MnO
2/ rGO/C) composite material is as the application of electrode material for super capacitor.
one, the preparation of sheet hexagon manganese dioxide/Graphene/porous carbon composite
The preparation method of sheet hexagon manganese dioxide/Graphene/porous carbon composite of the present invention, comprises following processing step:
(1) preparation of graphite oxide dispersion: by graphite oxide ultrasonic disperse in distilled water, forming concentration is the graphite oxide dispersion of 1.0 ~ 1.5mg/mL;
(2) preparation of sheet hexagon manganese dioxide: potassium permanganate is dissolved in distilled water, forming concentration is the potassium permanganate solution of 0.05 ~ 0.1g/L; Add farina again, stir and make it fully dissolve, obtain mixed solution; After reconciling mixed solution pH value to 9 ~ 10, hydro-thermal reaction 12 ~ 24h at 160 ~ 180 DEG C; Be cooled to room temperature, suction filtration, with absolute ethyl alcohol, distilled water washing to neutral, dry, obtain sheet hexagon manganese dioxide; The mass ratio of potassium permanganate and farina is 1:1 ~ 2:1;
(3) preparation of sheet hexagon manganese dioxide/Graphene/porous carbon composite: add sheet hexagon manganese dioxide in graphite oxide dispersion, then makes solution system hydro-thermal reaction 12 ~ 24h at 160 ~ 180 DEG C; Be cooled to room temperature, suction filtration, with absolute ethyl alcohol, distilled water washing to neutral, dry, obtain, obtain manganese dioxide/Graphene/porous carbon (MnO
2/ rGO/C) composite material.The mass ratio of graphite oxide and sheet hexagon manganese dioxide is 1:3 ~ 1:5.In order to change the polarity of solution system, making reactant reach the dispersion of height, in graphite oxide dispersion, add the n-hexane and absolute ethyl alcohol that add minute quantity after sheet hexagon manganese dioxide mixes again and stir, then carrying out hydro-thermal reaction.In mixed dispersion liquid, the percentage by volume of n-hexane is 2.5 ~ 5%, and the percentage by volume of absolute ethyl alcohol is 1.5 ~ 5%.
two, the structural characterization of manganese dioxide/Graphene/porous carbon composite
Below by manganese dioxide/Graphene/porous carbon (MnO that field emission scanning electron microscope (FE-SEM), thermal analyzer (TG), infrared spectrum (FTIR) and X-ray diffraction (XRD) are prepared the present invention
2/ rGO/C) structure of composite material characterizes.
1, ESEM (SEM) is analyzed
Fig. 1 is manganese dioxide/Graphene/porous carbon (MnO prepared by the present invention
2/ rGO/C) the field emission scanning electron microscope figure (SEM) of composite material.Wherein a, b are the MnO of different amplification
2sEM.C, d are the MnO of different amplification
2the SEM figure of/rGO/C composite material.A large amount of uniform hexagon manganese dioxide nano-plates can be seen from figure a, b; From figure c, d can see that thinner graphene film is coated with hexagon manganese dioxide nano-plates uniformly, and hexagon manganese dioxide nano-plates can intercept the reunion between graphene nanometer sheet, the carbon structure forming 3D solid is more conducive to the infiltration of electrolyte, be conducive to graphene nanometer sheet and produce higher electric double layer capacitance, be more conducive to manganese dioxide and produce higher fake capacitance.
2, elementary analysis (EDS)
Fig. 2 is the present invention (MnO
2/ rGO/C) the elementary analysis figure (EDS) of composite material.As seen from Figure 2, compound is made up of C, O, Mn tri-kinds of elements, and carbon derives from the starch be carbonized, and exists with the form of porous carbon; The compound of manganese and oxygen element composition manganese and oxygen.
3, X diffraction spectrogram (XRD) is analyzed
Fig. 3 is pure MnO
2and MnO prepared by the present invention
2the X diffraction spectrogram (XRD) of/rGO/C composite material.MnO
2it is consistent with (JCPDS 42-1169) standard diagram that all diffraction maximums go out peak position.The diffraction maximum of compound and pure MnO
2compare with rGO, go out peak position and be positioned between the two, be occur more wide in range diffraction maximum near 25 ° at 2 θ, illustrate that rGO is MnO
2carry out good coated.
4, thermogravimetric spectrogram (TG) is analyzed
Fig. 4 is MnO prepared by the present invention
2, rGO and MnO
2the thermogravimetric spectrogram (TG) of/rGO/C compound.As seen from Figure 4, near 100 DEG C, TG curve has occurred slight mass loss, this loses surface physics adsorbed water by sample and causes.Composite sample has obvious weightlessness after 350 DEG C, and this is caused by the decomposition of rGO in compound.After 500 DEG C, TG curve tends towards stability substantially, illustrates that rGO decomposes completely.Draw through estimation, MnO in compound
23% and 97% is about with the mass ratio of rGO.
5, infrared spectrogram (FT-IR) is analyzed
Fig. 5 is MnO prepared by the present invention
2the infrared spectrogram (FT-IR) of/rGO/C composite material.As can be seen from Figure 5, MnO
2there is stronger characteristic absorption peak, for MnO
2the infrared spectrogram of/rGO composite material, absworption peak go out peak position and pure MnO
2, that rGO goes out peak position is consistent, thus proves MnO
2coated by rGO institute.
Three, the chemical property of manganese dioxide/Graphene/porous carbon composite
Below by the MnO that electrochemical workstation CHI660B is prepared the present invention
2the Electrochemical Characterization of/rGO/C composite material is tested.
1, the preparation of electrode of super capacitor: by MnO
2hybrid solid powder totally 5.88 mg(MnO of/rGO/C composite material and acetylene black
2the mass percent difference 85%, 15% of/rGO/C composite material and acetylene black) be dispersed in 1ml Nafion solution, after ultrasonic 30min, measure 5ul mixed solution with liquid-transfering gun and drop on the glass-carbon electrode that diameter is 5mm, naturally dry, obtain test electrode.
2, electrochemical property test
Fig. 6 is the H of electrode material for super capacitor at 1mol/L of above-mentioned preparation
2sO
4in electrolyte solution, electromotive force window ranges is-0.2-1.1V, the cyclic voltammetry curve (CV) under different scanning rates.Result shows, the CV curve of all sweep speeds all can see a pair redox peak, is the symbol producing faraday's electric capacity.And along with the increase of sweep speed, the shape of CV curve remains unchanged substantially, illustrate that times capacity rate of compound is better, compound has the potential doing capacitor electrode material.
Fig. 7 is the H of electrode material for super capacitor at 1mol/L of above-mentioned preparation
2sO
4in solution, electromotive force window ranges is-0.2-1.1V, the constant current charge-discharge curve chart under different current density.As shown in Figure 7, when current density is 0.5A/g, the ratio capacitance of electrode can reach 760F/g; When current density is 1A/g, the ratio capacitance of electrode can reach 399F/g, and illustrate that compound has higher ratio capacitance, have the potential doing capacitor electrode material, this is consistent with cyclic voltammetry curve test result.
Fig. 8 is respectively with MnO
2, rGO and MnO
2/ rGO/C compound as electrode material for super capacitor, at the H of 1mol/L
2sO
4in electrolyte solution, electromotive force window ranges is-0.2-1.1V, and sweep speed is the cyclic voltammetry curve (CV) of 30mv/s.Result shows, at MnO
2and MnO
2the CV curve of/rGO/C compound all can see a pair redox peak, is the symbol producing faraday's electric capacity; The CV class of a curve of rGO is similar to rectangle, has typical two electrical measurement electric capacity.And, MnO
2the area of the CV curve of/rGO/C compound is maximum, illustrates that compound has higher ratio capacitance.
Fig. 9 is respectively with MnO
2, rGO and MnO
2/ rGO/C is as the H of electrode material for super capacitor at 1mol/L
2sO
4in solution, electromotive force window ranges is-0.2-1.1V, and current density is the constant current charge-discharge curve chart of 1A/g.As shown in Figure 9, MnO is described
2/ rGO/C has the ratio capacitance higher than monomer, and this is consistent with cyclic voltammetry curve test result.
Figure 10 is respectively with MnO
2, rGO and MnO
2/ rGO/C electrode material is 0.1 ~ 100kHz in frequency range, AC impedance figure when bias voltage is 0.4V.As shown in Figure 10, MnO
2the charge migration resistance of/rGO/C composite material is minimum.This mainly can make electrolyte to penetrate into fast in electrode material due to structure that composite material is special and can greatly improve solid-liquid reaction interface, thus significantly reduces the charge migration resistance of composite material.The slope of the linear segment of low frequency range represents the diffusion resistance of electrolyte in electrode duct.Can also find from figure, MnO
2the slope of/rGO/C electrode is higher than rGO and MnO
2electrode, illustrates relative to rGO and MnO
2electrode, MnO
2/ rGO/C ion diffuse resistance is in the electrolytic solution less and electron transfer speed is faster.
Figure 11 is MnO of the present invention
2the ratio capacitance figure of/rGO/C electrode material under different current density.As shown in Figure 11, be respectively 0.5 in current density, 1,2,3,5,7,10, corresponding ratio capacitance is respectively 760,399,295,286,234,218,208,197 F/g under 20A/g.When current density changes to 20A/g from 1A/g, MnO
2/ rGO/C composite material ratio capacitance conservation rate can reach 50%.This improves power density to ultracapacitor under high energy density is very important.
Figure 12 is that the present invention prepares MnO
2the cycle life figure of/rGO/C combination electrode material when 3A/g.Known by Figure 12, in front 200 cyclic processes, electroactive material is constantly activated, and ratio capacitance improves gradually, reaches peak 290 F/g.Although ratio capacitance decreases to a certain extent thereafter, after 5000 circulations, its ratio capacitance is still 96% of initial value, therefore MnO
2/ rGO/C material has very high electrochemical stability.
Experiment shows, when preparing electrode of super capacitor, the mass ratio of manganese dioxide nanowire material and acetylene black is 5.8:1 ~ 6.3:1, the mass concentration being scattered in manganese dioxide nanowire material in Nafion solution and acetylene black is 5.5 ~ 6.0mg/mL, and the amount being coated on mixed liquor on glass-carbon electrode is 23.5 ~ 26.5uL/cm
2time, as electrode material for super capacitor, all there is excellent chemical property.
In sum, the MnO for preparing of the present invention
2/ rGO/C composite material, can not only realize the cooperative effect of both performances, and has the premium properties that unitary electrode do not possess, demonstrate higher electrochemical capacitor performance, excellent times capacity rate, good cyclical stability, therefore can as electrode material for super capacitor.
The present invention relatively now technology has the following advantages:
1, the present invention with graphite oxide, farina and potassium permanganate for raw material, all have with low cost, wide material sources, quality is light, renewable, the feature such as pollution-free, and preparation process is simple, process stabilizing, be easy to operation, reliable in quality, with low cost, meets business-like basic demand as electrode material for super capacitor;
2, Graphene of the present invention derives from the reduction of graphite oxide, makes Graphene effectively recover its structure by high-temperature water thermal reduction, ensure that the quick transmission of its electric charge in electrochemical process;
3, the present invention is by being loaded with manganese dioxide and the Graphene compound of porous carbon, effectively reduce the reunion of Graphene, showing of the infiltration of more favourable electrolyte and Graphene electric double layer capacitance and manganese dioxide fake capacitance, and then improve the chemical property of composite material.
Accompanying drawing explanation
Fig. 1 is MnO of the present invention
2and MnO
2the field emission scanning electron microscope figure (SEM) of/rGO/C.
Fig. 2 is MnO of the present invention
2the field elementary analysis figure (EDS) of/rGO/C composite material.
Fig. 3 is MnO of the present invention
2the X diffraction spectrogram figure (XRD) of/rGO/C composite material.
Fig. 4 is MnO of the present invention
2the thermal analysis curue (TG) of/rGO/C composite material.
Fig. 5 is MnO of the present invention
2/ rGO/C composite material infrared spectrum figure (FT-IR).
Fig. 6 is MnO of the present invention
2/ rGO/C composite electrode is at the H of 1mol/L
2sO
4cyclic voltammetry curve figure in electrolyte during different scanning rates.
Fig. 7 is MnO of the present invention
2/ rGO/C composite electrode is at the H of 1mol/L
2sO
4constant current charge-discharge discharge curve in electrolyte under different current density.
Fig. 8 is MnO
2, rGO and MnO
2/ rGO/C composite material is as the H of electrode of super capacitor at 1mol/L
2sO
4cyclic voltammetry curve figure when sweep speed is 30mv/s in electrolyte.
Fig. 9 is MnO
2, rGO and MnO
2/ rGO/C composite material is as the H of electrode of super capacitor at 1mol/L
2sO
4in electrolyte than electric current be 1A/g discharge discharge curve.
Figure 10 is MnO
2, rGO and MnO
2/ rGO/C composite material is as the H of electrode of super capacitor at 1mol/L
2sO
4ac impedance spectroscopy in electrolyte.
Figure 11 is MnO prepared by the present invention
2/ rGO/C composite material is as the H of electrode of super capacitor at 1mol/L
2sO
4ratio capacitance curve chart in electrolyte under different current density.
Figure 12 is MnO prepared by the present invention
2/ rGO/C composite material is as the H of electrode of super capacitor at 1mol/L
2sO
4be 3A/g cycle life curve chart than electric current in electrolyte.
Embodiment
Below by specific embodiment to MnO of the present invention
2the preparation of/rGO/C composite material and the preparation of electrode material thereof and chemical property are described in further detail.
The instrument used and reagent: CHI660B electrochemical workstation (Shanghai Chen Hua instrument company) is for electrochemical property test; Blue electricity (LAND) series battery test macro (Wuhan Lan electricity Electronics Co., Ltd.) is tested for the cycle life of electrode; Electronic balance (Beijing Sai Duolisi Instrument Ltd.) is for weighing medicine; JSM-6701F cold field emission type ESEM (Jeol Ltd.) is for the morphology characterization of material; Perkin-Elmer TG/DTA-6300 type thermal analyzer is used for thermal analyses; FTS3000 type Fourier infrared spectrograph (DIGILAB company of the U.S.) is used for analyzing composition.Sulfuric acid (silver West silver ring chemical reagent factory), farina (Dingxi, Gansu), Pintsch process graphite powder, acetylene black (Guiyang, Hunan Province Tan Sha graphite factory), potassium permanganate (Ke Miou chemical reagent development centre, Tianjin), absolute ethyl alcohol (Anhui An Te biochemistry corporation,Ltd.), potassium hydroxide (Chemical Reagent Co., Ltd., Sinopharm Group).Glass-carbon electrode (the many reform Materials Co., Ltd in Shanghai).The water used in experimentation is first water, test reagent used be analyze pure.
Embodiment 1
(1) sheet hexagon manganese dioxide/Graphene/porous carbon (MnO
2/ rGO/C) preparation of composite material
The preparation of graphite oxide dispersion: take 100mg graphite oxide ultrasonic disperse in 100ml distilled water, forms graphite oxide dispersion;
The preparation of sheet hexagon manganese dioxide: be dissolved in 100ml distilled water by high 1.264g potassium manganate, forms potassium permanganate solution; Again 1g farina is dispersed in 100ml potassium permanganate solution, magnetic agitation 5h, obtains mixed solution.Then by KOH solution, the pH value of mixed solution is transferred to 9 ~ 10, moves in autoclave, hydro-thermal 24h at 180 DEG C; After being cooled to room temperature, suction filtration, with absolute ethyl alcohol, distilled water cyclic washing to neutral, 60 DEG C of vacuumize 12h, obtain sheet hexagon manganese dioxide;
Sheet hexagon manganese dioxide/Graphene/porous carbon (MnO
2/ rGO/C) preparation of composite material: in above-mentioned graphite oxide dispersion, first add sheet hexagon manganese dioxide, the mass ratio making graphite oxide and sheet hexagon manganese dioxide is 1:3; Add 10mL n-hexane under strong agitation again and without 5mL water-ethanol, after mixing, reactant is moved in autoclave, hydro-thermal 12h at 180 DEG C; After being cooled to room temperature, suction filtration, with absolute ethyl alcohol, distilled water cyclic washing, 60 DEG C of vacuumize 12h, obtain manganese dioxide/Graphene/porous carbon (MnO
2/ rGO/C) composite material.
(2) preparation of electrode
By the MnO of above-mentioned preparation
2/ rGO/C composite material is at agate mortar pulverize, getting after 5mg and 0.88mg acetylene black mixes is scattered in 1ml Nafion solution, after ultrasonic 50min, getting 5ul mixed solution respectively by liquid-transfering gun amount drops on two glass-carbon electrodes that diameter is 5mm respectively, naturally dry, obtain test electrode.
(3) test of chemical property
With the electrode of above-mentioned preparation for work electrode, be to electrode with platinum guaze, with Ag/AgCl electrode for reference electrode composition three-electrode system carries out electrochemical property test, electrolyte is the H of 1mol/L
2sO
4solution, potential window scope is-0.2-1.1V.Adopt the mapping of origin 8.0 software.Test result shows: when current density is 0.5A/g, and the ratio capacitance of composite electrode can reach 760F/g; When current density is 1A/g, the ratio capacitance of composite electrode can reach 399F/g, illustrates that compound has higher ratio capacitance, has the potential doing capacitor electrode material.
Embodiment 2
(1) sheet hexagon manganese dioxide/Graphene/porous carbon (MnO
2/ rGO/C) preparation of composite material
The preparation of graphite oxide dispersion: take 100g graphite oxide ultrasonic disperse in 80ml distilled water, forms graphite oxide dispersion;
The preparation of sheet hexagon manganese dioxide: be dissolved in 100ml distilled water by high 1.3g potassium manganate, forms potassium permanganate solution; Again 0.8g farina is dispersed in 100ml potassium permanganate solution, magnetic agitation 5h, obtains mixed solution.Then by KOH solution, the pH value of mixed solution is transferred to 9 ~ 10, moves in autoclave, hydro-thermal 24h at 180 DEG C; After being cooled to room temperature, suction filtration, with absolute ethyl alcohol, distilled water cyclic washing to neutral, 60 DEG C of vacuumize 12h, obtain sheet hexagon manganese dioxide;
Sheet hexagon manganese dioxide/Graphene/porous carbon (MnO
2/ rGO/C) preparation of composite material: in above-mentioned graphite oxide dispersion, first add sheet hexagon manganese dioxide, the mass ratio making graphite oxide and sheet hexagon manganese dioxide is 1:3; Add 10ml n-hexane under strong agitation again and without 3ml water-ethanol, after mixing, reactant is moved in autoclave, hydro-thermal 12h at 180 DEG C; After being cooled to room temperature, suction filtration, with absolute ethyl alcohol, distilled water cyclic washing, 60 DEG C of vacuumize 12h, obtain manganese dioxide/Graphene/porous carbon (MnO
2/ rGO/C) composite material.
(2) preparation of electrode
By the MnO of above-mentioned preparation
2/ rGO/C composite material is at agate mortar pulverize, getting after 5mg and 0.88mg acetylene black mixes is scattered in 1ml Nafion solution, after ultrasonic 30min, getting 5ul mixed solution respectively by liquid-transfering gun amount drops on two glass-carbon electrodes that diameter is 5mm respectively, naturally dry, obtain test electrode.
(3) test of chemical property
With the electrode of above-mentioned preparation for work electrode, be to electrode with platinum guaze, with Ag/AgCl electrode for reference electrode composition three-electrode system carries out electrochemical property test, electrolyte is the H of 1mol/L
2sO
4solution, potential window scope is-0.2-1.1V.When current density is 0.5A/g, the ratio capacitance of composite electrode can reach 750F/g.
Embodiment 3
(1) sheet hexagon manganese dioxide/Graphene/porous carbon (MnO
2/ rGO/C) preparation of composite material
The preparation of graphite oxide dispersion: take 100g graphite oxide ultrasonic disperse in 120ml distilled water, forms graphite oxide dispersion;
The preparation of sheet hexagon manganese dioxide: be dissolved in 100ml distilled water by high 1.1g potassium manganate, forms potassium permanganate solution; Again 0.7g farina is dispersed in 100ml potassium permanganate solution, magnetic agitation 5h, obtains mixed solution.Then by KOH solution, the pH value of mixed solution is transferred to 9 ~ 10, moves in autoclave, hydro-thermal 24h at 180 DEG C; After being cooled to room temperature, suction filtration, with absolute ethyl alcohol, distilled water cyclic washing to neutral, 60 DEG C of vacuumize 12h, obtain sheet hexagon manganese dioxide;
Sheet hexagon manganese dioxide/Graphene/porous carbon (MnO
2/ rGO/C) preparation of composite material: in above-mentioned graphite oxide dispersion, first add sheet hexagon manganese dioxide, the mass ratio making graphite oxide and sheet hexagon manganese dioxide is 1:3; Add 5ml n-hexane under strong agitation again and without 100ml water-ethanol, after mixing, reactant is moved in autoclave, hydro-thermal 12h at 180 DEG C; After being cooled to room temperature, suction filtration, with absolute ethyl alcohol, distilled water cyclic washing, 60 DEG C of vacuumize 12h, obtain manganese dioxide/Graphene/porous carbon (MnO
2/ rGO/C) composite material.
(2) preparation of electrode
By the MnO of above-mentioned preparation
2/ rGO/C composite material is at agate mortar pulverize, getting after 5mg and 0.88mg acetylene black mixes is scattered in 1ml Nafion solution, after ultrasonic 30min, getting 5ul mixed solution respectively by liquid-transfering gun amount drops on two glass-carbon electrodes that diameter is 5mm respectively, naturally dry, obtain test electrode.
(3) test of chemical property
With the electrode of above-mentioned preparation for work electrode, be to electrode with platinum guaze, with Ag/AgCl electrode for reference electrode composition three-electrode system carries out electrochemical property test, electrolyte is the H of 1mol/L
2sO
4solution, potential window scope is-0.2-1.1V.When current density is 1A/g, the ratio capacitance of composite electrode can reach 365F/g, illustrates that compound has higher ratio capacitance, has the potential doing capacitor electrode material.
Embodiment 4
(1) sheet hexagon manganese dioxide/Graphene/porous carbon (MnO
2/ rGO/C) preparation of composite material
The preparation of graphite oxide dispersion: take 80g graphite oxide ultrasonic disperse in 120ml distilled water, forms graphite oxide dispersion;
The preparation of sheet hexagon manganese dioxide: be dissolved in 100ml distilled water by high 1.5g potassium manganate, forms potassium permanganate solution; Again 1.3g farina is dispersed in 100ml potassium permanganate solution, magnetic agitation 5h, obtains mixed solution.Then by KOH solution, the pH value of mixed solution is transferred to 9 ~ 10, moves in autoclave, hydro-thermal 24h at 180 DEG C; After being cooled to room temperature, suction filtration, with absolute ethyl alcohol, distilled water cyclic washing to neutral, 60 DEG C of vacuumize 12h, obtain sheet hexagon manganese dioxide;
Sheet hexagon manganese dioxide/Graphene/porous carbon (MnO
2/ rGO/C) preparation of composite material: in above-mentioned graphite oxide dispersion, first add sheet hexagon manganese dioxide, the mass ratio making graphite oxide and sheet hexagon manganese dioxide is 1:3; Add 3ml n-hexane under strong agitation again and without 10ml water-ethanol, after mixing, reactant is moved in autoclave, hydro-thermal 12h at 180 DEG C; After being cooled to room temperature, suction filtration, with absolute ethyl alcohol, distilled water cyclic washing, 60 DEG C of vacuumize 12h, obtain manganese dioxide/Graphene/porous carbon (MnO
2/ rGO/C) composite material.
(2) preparation of electrode
By the MnO of above-mentioned preparation
2/ rGO/C composite material is at agate mortar pulverize, getting after 5mg and 0.88mg acetylene black mixes is scattered in 1ml Nafion solution, after ultrasonic 40min, getting 6ul mixed solution respectively by liquid-transfering gun amount drops on two glass-carbon electrodes that diameter is 5mm respectively, naturally dry, obtain test electrode.
(3) test of chemical property
With the electrode of above-mentioned preparation for work electrode, be to electrode with platinum guaze, with Ag/AgCl electrode for reference electrode composition three-electrode system carries out electrochemical property test, electrolyte is the H of 1mol/L
2sO
4solution, potential window scope is-0.2-1.1V.Test result shows: when current density is 2A/g, and the ratio capacitance of composite electrode can reach 286F/g, illustrates that compound has higher ratio capacitance, has the potential doing capacitor electrode material.
Claims (10)
1. the preparation method of sheet hexagon manganese dioxide/Graphene/porous carbon composite, comprises following processing step:
(1) preparation of graphite oxide dispersion: by graphite oxide ultrasonic disperse in distilled water, forming concentration is the graphite oxide dispersion of 1 ~ 1.5mg/mL;
(2) preparation of sheet hexagon manganese dioxide: potassium permanganate is dissolved in distilled water, forming concentration is the potassium permanganate solution of 0.05 ~ 0.1g/L; Add farina again, stir and make it fully dissolve, obtain mixed solution; After reconciling mixed solution pH value to 9 ~ 10, hydro-thermal reaction 12 ~ 24h at 160 ~ 180 DEG C; Be cooled to room temperature, suction filtration, with absolute ethyl alcohol, distilled water washing to neutral, dry, obtain sheet hexagon manganese dioxide;
(3) preparation of sheet hexagon manganese dioxide/Graphene/porous carbon composite: first add sheet hexagon manganese dioxide in graphite oxide dispersion, makes mixed liquor hydro-thermal reaction 12 ~ 24h at 160 ~ 180 DEG C after mixing; Be cooled to room temperature, suction filtration, with absolute ethyl alcohol, distilled water washing to neutral, dry, obtain, obtain manganese dioxide/Graphene/porous carbon (MnO
2/ rGO/C) composite material.
2. the preparation method of sheet hexagon manganese dioxide/Graphene/porous carbon composite as claimed in claim 1, is characterized in that: in the technique of preparation sheet hexagon manganese dioxide, and the mass ratio of potassium permanganate and farina is 1:1 ~ 2:1.
3. the preparation method of sheet hexagon manganese dioxide/Graphene/porous carbon composite as claimed in claim 1, it is characterized in that: in the technique of preparation sheet hexagon manganese dioxide/Graphene/porous carbon composite, the mass ratio of graphite oxide and sheet hexagon manganese dioxide is 1:3 ~ 1:5.
4. the preparation method of sheet hexagon manganese dioxide/Graphene/porous carbon composite as claimed in claim 1, it is characterized in that: in the technique of preparation sheet hexagon manganese dioxide/Graphene/porous carbon composite, add in graphite oxide dispersion and to add n-hexane and absolute ethyl alcohol after sheet hexagon manganese dioxide mixes again and stir, then carry out hydro-thermal reaction; In mixed dispersion liquid, the percentage by volume of n-hexane is 2.5 ~ 5%, and the percentage by volume of absolute ethyl alcohol is 1.5 ~ 5%.
5. the preparation method of sheet hexagon manganese dioxide/Graphene/porous carbon composite as claimed in claim 1, is characterized in that: described drying is vacuumize 6 ~ 12h at 60 ~ 70 DEG C.
6. as claimed in claim 1 sheet hexagon manganese dioxide/Graphene/porous carbon composite of preparing of method as the application of electrode material for super capacitor.
7. as claimed in claim 5 sheet hexagon manganese dioxide/Graphene/porous carbon composite of preparing of method as the application of electrode material for super capacitor, it is characterized in that: be scattered in Nafion solution after sheet hexagon manganese dioxide/Graphene/porous carbon composite and acetylene black are mixed, after ultrasonic 20 ~ 80min, mixed liquor liquid-transfering gun is evenly coated on glass-carbon electrode, naturally dries.
8. sheet hexagon manganese dioxide/Graphene/porous carbon composite of preparing of method, as the application of electrode material for super capacitor, is characterized in that: the mass ratio of sheet hexagon manganese dioxide/Graphene/porous carbon composite and acetylene black is 5.8:1 ~ 6.3:1 as claimed in claim 6.
9. sheet hexagon manganese dioxide/Graphene/porous carbon composite of preparing of method, as the application of electrode material for super capacitor, is characterized in that as claimed in claim 5: the mass concentration being scattered in sheet hexagon manganese dioxide/Graphene/porous carbon composite in Nafion solution and acetylene black is 5.5 ~ 6.0mg/mL.
10. sheet hexagon manganese dioxide/Graphene/porous carbon composite of preparing of method, as the application of electrode material for super capacitor, is characterized in that: the amount being coated on mixed liquor on glass-carbon electrode is 23.5 ~ 26.5uL/cm as claimed in claim 5
2.
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