CN104362001B - 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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- CN104362001B CN104362001B CN201410706384.9A CN201410706384A CN104362001B CN 104362001 B CN104362001 B CN 104362001B CN 201410706384 A CN201410706384 A CN 201410706384A CN 104362001 B CN104362001 B CN 104362001B
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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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- 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 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, it is related to a kind of lamellar hexagon manganese dioxide/Graphene/porous carbon
(MnO2/ rGO/C) composite preparation；The present invention also relates to this MnO2/ rGO/C composite exists as electrode material
Application in ultracapacitor.
Technical background
With the development and utilization of clean energy resource, a kind of aobvious particularly important, the new energy storage of exploitation of the deposit of the energy
Deposit equipment extremely urgent.Ultracapacitor is a kind of new energy storage/reforming unit, and its energy density is high（10kw/kg）、
The charge and discharge time is short, have extended cycle life and be widely used in portable type electronic product, mixed power electric car the advantages of pollution-free
With large industry equipment etc..And the selection of electrode material is the main cause of impact ultracapacitor, the main metal that includes aoxidizes
Thing, conducting polymer and carbon-based material.
MnO2Because it is abundant, inexpensive, environmental friendliness, active redox active and high theory compare electric capacity
（1232 F·g-1）And receive numerous concerns.Graphene is former by one layer of intensive carbon being wrapped in Nidus Vespae crystal lattice
Molecular two dimensional crystal material with carbon element, can be warped into the fullerene of zero dimension, be rolled into one-dimensional CNT or be stacked to three
The graphite of dimension, therefore Graphene are the elementary cells constituting other graphite materials.Compared with CNT, Graphene has more
Excellent property, for example, good electric conductivity（103~104S/m）, the specific surface area of super large（2630 m2/g）, chemical property
Stable and machinability etc., this makes it become the electrode of more preferable electrochemistry new forms of energy conversion and storage than CNT
Material.But in actual applications, due to the effect of Van der Waals force makes it easily reunite or again stacking and cause actual than electric capacity not
High result.Graphene-based composite then effectively overcomes this difficult problem of Graphene, because positive synergism makes
Other compositions in composite effectively prevent the reunion of Graphene, so that the electric double layer capacitance of Graphene is able to very
Good displaying, effectively raises the ratio electric capacity of whole material.Therefore, by the lamellar hexagon manganese dioxide of subsidiary porous carbon and
Two kinds of different materials of Graphene are combined it is desirable to be obtained the more excellent composite of performance, composite is as super capacitor
Device electrode material, has obtained thering is the premium properties that unitary electrode does not possess, application prospect is extensive.
Content of the invention
It is an object of the invention to provide a kind of lamellar hexagon manganese dioxide/Graphene/porous carbon (MnO2/rGO/C)
The preparation method of composite.
The more free-revving engine of the present invention is to provide a kind of lamellar hexagon manganese dioxide/Graphene/porous carbon (MnO2/
RGO/C) composite is as the application of electrode material for super capacitor.
First, the preparation of lamellar hexagon manganese dioxide/Graphene/porous carbon composite
The preparation method of lamellar hexagon manganese dioxide/Graphene/porous carbon composite of the present invention, including following technique
Step：
（1）The preparation of graphite oxide dispersion：By graphite oxide ultrasonic disperse in distilled water, formed concentration be 1.0 ~
The graphite oxide dispersion of 1.5mg/mL；
（2）The preparation of lamellar hexagon manganese dioxide：Potassium permanganate is dissolved in distilled water, formed concentration be 0.05 ~
The potassium permanganate solution of 0.1g/L；Add potato starch, stirring makes it fully dissolve, and obtains mixed solution；Reconcile mixed
Close solution ph to after 9 ~ 10, hydro-thermal reaction 12 ~ 24h at 160 ~ 180 DEG C；It is cooled to room temperature, sucking filtration, with dehydrated alcohol, steaming
Distilled water is washed to neutrality, is dried, obtains lamellar hexagon manganese dioxide；Potassium permanganate is 1 with the mass ratio of potato starch:1~
2:1；
（3）The preparation of lamellar hexagon manganese dioxide/Graphene/porous carbon composite：In graphite oxide dispersion
Add lamellar hexagon manganese dioxide, then make solution system hydro-thermal reaction 12 ~ 24h at 160 ~ 180 DEG C；It is cooled to room temperature,
Sucking filtration, with dehydrated alcohol, distilled water wash to neutral, is dried, obtains, obtain manganese dioxide/Graphene/porous carbon (MnO2/
RGO/C) composite.Graphite oxide is 1 with the mass ratio of lamellar hexagon manganese dioxide:3~1:5.In order to change solution system
Polarity, make reactant reach the dispersion of height, graphite oxide dispersion add the mixing of lamellar hexagon manganese dioxide all
Add minimal amount of normal hexane and dehydrated alcohol after even and stir, then carry out hydro-thermal reaction.In mixed dispersion liquid just
The percentage by volume of hexane is 2.5 ~ 5%, and the percentage by volume of dehydrated alcohol is 1.5 ~ 5%.
2nd, the structural characterization of manganese dioxide/Graphene/porous carbon composite
Below by field emission scanning electron microscope (FE-SEM), thermal analyzer (TG), infrared spectrum (FTIR) and X-ray diffraction
(XRD) manganese dioxide/Graphene/porous carbon (MnO to present invention preparation2/ rGO/C) structure of composite characterized.
1st, scanning electron microscope（SEM）Analysis
Manganese dioxide/Graphene/porous carbon (MnO that Fig. 1 is prepared for the present invention2/ rGO/C) Flied emission of composite sweeps
Retouch electron microscope（SEM）.Wherein a, b are the MnO of different amplification2SEM.C, d are the MnO of different amplification2/ rGO/C is multiple
The SEM figure of condensation material.From figure a, b can see uniform hexagon manganese dioxide nano-plates in a large number；From figure c, d can see relatively
Thin graphene film is uniformly coated with hexagon manganese dioxide nano-plates, and hexagon manganese dioxide nano-plates can intercept graphite
Reunion between alkene nanometer sheet, forms the infiltration that the three-dimensional carbon structure of 3D is more beneficial for electrolyte, is conducive to graphene nanometer sheet
Produce higher electric double layer capacitance, be more beneficial for manganese dioxide and produce higher fake capacitance.
2nd, elementary analysiss（EDS）
Fig. 2 is the present invention (MnO2/ rGO/C) composite elementary analysiss figure（EDS）.From Figure 2 it can be seen that complex is by C,
Tri- kinds of O, Mn is elementary composition, and carbon derives from the starch being carbonized, presented in porous carbon；Manganese and oxygen element composition manganese
Compound with oxygen.
3rd, X diffraction spectrogram（XRD）Analysis
Fig. 3 is pure MnO2And the MnO of present invention preparation2The X diffraction spectrogram of/rGO/C composite（XRD）.MnO2All of
Diffraction maximum go out peak position with（JCPDS 42-1169）Standard diagram is consistent.The diffraction maximum of complex and pure MnO2With rGO phase
Relatively, go out peak position to be located between the two, be, near 25 °, more wide in range diffraction maximum occurs in 2 θ, illustrate rGO MnO2Carry out
Good cladding.
4th, thermogravimetric spectrogram（TG）Analysis
The MnO that Fig. 4 is prepared for the present invention2, rGO and MnO2The thermogravimetric spectrogram of/rGO/C complex（TG）.From fig. 4, it can be seen that
Near 100 DEG C, TG curve occurs in that slight mass loss, this loses surface physics absorption water by sample and causes.Multiple
Compound sample has obvious weightlessness after 350 DEG C, and this is caused by the decomposition of rGO in complex.At 500 DEG C afterwards, TG
Curve tends towards stability substantially, illustrates that rGO decomposes completely.Estimated draw, MnO in complex2It is about 3% with the mass ratio of rGO
With 97%.
5th, infrared spectrogram（FT-IR）Analysis
The MnO that Fig. 5 is prepared for the present invention2The infrared spectrogram of/rGO/C composite（FT-IR）.From fig. 5, it can be seen that
MnO2There is stronger characteristic absorption peak, for MnO2The infrared spectrogram of/rGO composite, absworption peak go out peak position and pure
MnO2, rGO appearance position consistency, thus proving MnO2Coated by rGO.
3rd, the chemical property of manganese dioxide/Graphene/porous carbon composite
The MnO below by electrochemical workstation CHI660B being prepared by the present invention2The electrochemistry of/rGO/C composite
Can characterize and be tested.
1st, the preparation of electrode of super capacitor：By MnO2The hybrid solid powder of/rGO/C composite and acetylene black is altogether
5.88 mg（MnO2The mass percent difference 85%, 15% of/rGO/C composite and acetylene black）It is dispersed in 1ml
In Nafion solution, after ultrasonic 30min, measure 5ul mixed solution with liquid-transfering gun and drop on the glass-carbon electrode of a diameter of 5mm, from
So dry, obtain final product test electrode.
2nd, electrochemical property test
Fig. 6 is the H in 1mol/L for the electrode material for super capacitor of above-mentioned preparation2SO4Potential window model in electrolyte solution
Enclose for the cyclic voltammetry curve under -0.2-1.1V, different scanning rates（CV）.Result shows, bent in the CV of all sweep speeds
A pair of redox peaks all can be seen on line, be the symbol producing faraday's electric capacity.And, with the increasing of sweep speed
Greatly, the shape of CV curve is held essentially constant, and times capacity rate of complex is described preferably, and complex has and does capacitor electrode material
Potential.
Fig. 7 is the H in 1mol/L for the electrode material for super capacitor of above-mentioned preparation2SO4In solution, potential window scope be-
0.2-1.1V, the constant current charge-discharge curve chart under different electric current densities.As shown in Figure 7, when electric current density is for 0.5A/g, electricity
The ratio electric capacity of pole can reach 760F/g；When electric current density is for 1A/g, the ratio electric capacity of electrode can reach 399F/g, illustrates multiple
Compound has higher ratio electric capacity, has the potential doing capacitor electrode material, this and cyclic voltammetry curve test result phase one
Cause.
Fig. 8 is respectively with MnO2, rGO and MnO2/ rGO/C complex as electrode material for super capacitor, 1mol/L's
H2SO4In electrolyte solution, potential window scope is -0.2-1.1V, and sweep speed is the cyclic voltammetry curve of 30mv/s（CV）.
Result shows, in MnO2And MnO2All a pair of redox peaks can be seen on the CV curve of/rGO/C complex, be generation method
Draw the symbol of electric capacity；The CV curve of rGO, similar to rectangle, has typically double electrical measurement electric capacity.And, MnO2/ rGO/C is multiple
The area of the CV curve of compound is maximum, illustrates that complex has higher ratio electric capacity.
Fig. 9 is respectively with MnO2, rGO and MnO2/ rGO/C as electrode material for super capacitor 1mol/L H2SO4Molten
In liquid, potential window scope is -0.2-1.1V, and electric current density is the constant current charge-discharge curve chart of 1A/g.As shown in Figure 9, say
Bright MnO2/ rGO/C has the ratio electric capacity higher than monomer, and this is consistent with cyclic voltammetry curve test result.
Figure 10 is respectively with MnO2, rGO and MnO2/ rGO/C electrode material is 0.1 ~ 100kHz in frequency range, biased electrical
Press as AC impedance figure during 0.4V.As shown in Figure 10, MnO2The charge migration resistance of/rGO/C composite is minimum.This is main
It is due to the special structure of composite so that electrolyte quickly penetrates in electrode material and can greatly improve
Solid-liquid reaction interface, thus significantly reduce the charge migration resistance of composite.The slope generation of the linear segment of low frequency range
Table diffusion resistance in electrode duct for the electrolyte.From in figure it is also found that MnO2The slope of/rGO/C electrode is higher than
RGO and MnO2Electrode, illustrates with respect to rGO and MnO2Electrode, MnO2/ rGO/C ion diffusion resistance in the electrolytic solution less with
And electron transfer speed is faster.
Figure 11 is MnO of the present invention2Ratio capacitance map under the different electric current densities for/rGO/C electrode material.As shown in Figure 11,
Be respectively 0.5 in electric current density, 1,2,3,5,7,10, corresponding ratio electric capacity under 20A/g be respectively 760,399,295,286,
234、218、208、197 F/g.When electric current density changes to 20A/g from 1A/g, MnO2/ rGO/C composite is protected than electric capacity
Holdup can reach 50%.This improves power density to ultracapacitor under high energy density is highly important.
Figure 12 prepares MnO for the present invention2The cycle life figure in the 3A/g for/rGO/C combination electrode material.Known by Figure 12
Road, in front 200 cyclic processes, electroactive material is constantly activated, and gradually steps up than electric capacity, reaches peak 290 F/g.
Although decreasing to a certain extent than electric capacity thereafter, after 5000 circulations, it remains as initial value than electric capacity
96%, therefore MnO2/ rGO/C material has very high electrochemical stability.
Experiment shows, when preparing electrode of super capacitor, manganese dioxide nanowire material with the mass ratio of 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, the amount being coated on mixed liquor on glass-carbon electrode is 23.5 ~ 26.5uL/cm2When, as electrode of super capacitor material
Material, is respectively provided with excellent chemical property.
In sum, the MnO of present invention preparation2/ rGO/C composite, can not only realize the collaborative effect of both performances
Should, and there is the premium properties that unitary electrode does not possess, show higher electrochemical capacitor performance, excellent times capacity rate,
Preferably cyclical stability, therefore can be used as electrode material for super capacitor.
The relatively present technology of the present invention has advantages below：
1st, the present invention, with graphite oxide, potato starch and potassium permanganate as raw material, all has with low cost, wide material sources,
Light weight, renewable, the features such as pollution-free, and preparation process is simple, process stabilizing, easily operated, reliable in quality, low cost
Honest and clean, meet business-like basic demand as electrode material for super capacitor；
2nd, the Graphene of the present invention derives from the reduction of graphite oxide, makes Graphene effective by high temperature hydrothermal reduction
Recover its structure it is ensured that the quick transmission of its electric charge in electrochemical process；
3rd, the present invention is combined by the manganese dioxide and Graphene being loaded with porous carbon, effectively reduces the group of Graphene
Poly-, the infiltration of more favourable electrolyte and Graphene electric double layer capacitance are shown with manganese dioxide fake capacitance, and then improve compound
The chemical property of material.
Brief description
Fig. 1 is the MnO of the present invention2And MnO2The field emission scanning electron microscope figure of/rGO/C（SEM）.
Fig. 2 is the MnO of the present invention2The field elementary analysiss figure of/rGO/C composite（EDS）.
Fig. 3 is MnO of the present invention2The X diffraction spectrogram figure of/rGO/C composite（XRD）.
Fig. 4 is MnO of the present invention2The thermal analysis curue of/rGO/C composite（TG）.
Fig. 5 is MnO of the present invention2/ rGO/C composite infrared spectrum figure (FT-IR).
Fig. 6 is the MnO of the present invention2/ rGO/C composite electrode is in the H of 1mol/L2SO4Different scanning rates in electrolyte
When cyclic voltammetry curve figure.
Fig. 7 is the MnO of the present invention2/ rGO/C composite electrode is in the H of 1mol/L2SO4Different electric current densities in electrolyte
Under constant current charge-discharge discharge curve.
Fig. 8 is MnO2, rGO and MnO2/ rGO/C composite as electrode of super capacitor 1mol/L H2SO4Electrolysis
In liquid, sweep speed is cyclic voltammetry curve figure during 30mv/s.
Fig. 9 is MnO2, rGO and MnO2/ rGO/C composite as electrode of super capacitor 1mol/L H2SO4Electrolysis
In liquid than electric current be 1A/g electric discharge discharge curve.
Figure 10 is MnO2, rGO and MnO2/ rGO/C composite as electrode of super capacitor 1mol/L H2SO4Electricity
Ac impedance spectroscopy in solution liquid.
The MnO that Figure 11 is prepared for the present invention2/ rGO/C composite as electrode of super capacitor 1mol/L H2SO4
Ratio capacitance curve figure under different electric current densities in electrolyte.
The MnO that Figure 12 is prepared for the present invention2/ rGO/C composite as electrode of super capacitor 1mol/L H2SO4
It is 3A/g cycle life curve chart than electric current in electrolyte.
Specific embodiment
Below by specific embodiment to MnO of the present invention2The preparation of/rGO/C composite and its preparation of electrode material
It is described in further detail with chemical property.
The instrument using and reagent：CHI660B electrochemical workstation (Shanghai Chen Hua instrument company) is used for electrochemistry
Can test；Blue electricity（LAND）Series battery test system（Wuhan Lan electricity Electronics Co., Ltd.）Cycle life for electrode is surveyed
Examination；Electronic balance (Beijing Sai Duolisi Instrument Ltd.) is used for weighing medicine；JSM-6701F cold field emission type scans
Electronic Speculum (Jeol Ltd.) is used for the morphology characterization of material；Perkin-Elmer TG/DTA-6300 type heat analysis
Instrument is used for heat analysis；FTS3000 type Fourier infrared spectrograph（DIGILAB company of the U.S.）It is used for analyzing composition.Sulphuric acid（Silver
West silver ring chemical reagent factory）, potato starch（Dingxi, Gansu）, Pintsch process graphite powder, acetylene black（Hunan Province Guiyang Tan Sha
Graphite factory）, potassium permanganate（Tianjin Ke Miou chemical reagent development centre）, dehydrated alcohol（Anhui An Te biochemistry is limited
Company）, potassium hydroxide（Chemical Reagent Co., Ltd., Sinopharm Group）.Glass-carbon electrode（Shanghai crowd reform Materials Co., Ltd）.Real
Test water used in process and be first water, it is pure that experiment reagent used is analysis.
Embodiment 1
（1）Lamellar hexagon manganese dioxide/Graphene/porous carbon (MnO2/ rGO/C) composite preparation
The preparation of graphite oxide dispersion：Weigh 100mg graphite oxide ultrasonic disperse in 100ml distilled water, form oxygen
Graphite dispersion liquid；
The preparation of lamellar hexagon manganese dioxide：High 1.264g potassium manganate is dissolved in 100ml distilled water, forms Gao Meng
Sour aqueous solutions of potassium；Again 1g potato starch is dispersed in 100ml potassium permanganate solution, magnetic agitation 5h, obtains mixing molten
Liquid.Then with KOH solution, the pH value of mixed solution is transferred to 9 ~ 10, moves in autoclave, hydro-thermal 24h at 180 DEG C；Cold
But to room temperature, sucking filtration, with dehydrated alcohol, distilled water cyclic washing to neutral, 60 DEG C of vacuum drying 12h, obtain lamellar six side
Shape manganese dioxide；
Lamellar hexagon manganese dioxide/Graphene/porous carbon (MnO2/ rGO/C) composite preparation：In above-mentioned oxidation
It is initially charged lamellar hexagon manganese dioxide in graphite dispersing solution, make the graphite oxide with the mass ratio of lamellar hexagon manganese dioxide be
1:3；Add 10mL normal hexane and no 5mL water-ethanol under strong agitation, after mix homogeneously, reactant is moved to autoclave
In, hydro-thermal 12h at 180 DEG C；After being cooled to room temperature, sucking filtration, with dehydrated alcohol, distilled water cyclic washing, 60 DEG C of vacuum drying
12h, obtains manganese dioxide/Graphene/porous carbon (MnO2/ rGO/C) composite.
（2）The preparation of electrode
MnO by above-mentioned preparation2/ rGO/C composite is ground into powder in agate mortar, takes 5mg and 0.88mg acetylene black
It is scattered in after mix homogeneously in 1ml Nafion solution, after ultrasonic 50min, take 5ul mixed solution respectively respectively with liquid-transfering gun amount
Drop on two glass-carbon electrodes of a diameter of 5mm, naturally dry, obtain final product test electrode.
（3）The test of chemical property
With the electrode of above-mentioned preparation as working electrode, it is to electrode with platinum guaze, is formed for reference electrode with Ag/AgCl electrode
Three-electrode system carries out electrochemical property test, and electrolyte is the H of 1mol/L2SO4Solution, potential window scope is -0.2-
1.1V.Using the mapping of origin 8.0 software.Test result shows：When electric current density is for 0.5A/g, the ratio of composite electrode
Electric capacity can reach 760F/g；When electric current density is for 1A/g, the ratio electric capacity of composite electrode can reach 399F/g, illustrates multiple
Compound has higher ratio electric capacity, has the potential doing capacitor electrode material.
Embodiment 2
（1）Lamellar hexagon manganese dioxide/Graphene/porous carbon (MnO2/ rGO/C) composite preparation
The preparation of graphite oxide dispersion：Weigh 100g graphite oxide ultrasonic disperse in 80ml distilled water, form oxidation
Graphite dispersing solution；
The preparation of lamellar hexagon manganese dioxide：High 1.3g potassium manganate is dissolved in 100ml distilled water, forms permanganic acid
Aqueous solutions of potassium；Again 0.8g potato starch is dispersed in 100ml potassium permanganate solution, magnetic agitation 5h, obtains mixing molten
Liquid.Then with KOH solution, the pH value of mixed solution is transferred to 9 ~ 10, moves in autoclave, hydro-thermal 24h at 180 DEG C；Cold
But to room temperature, sucking filtration, with dehydrated alcohol, distilled water cyclic washing to neutral, 60 DEG C of vacuum drying 12h, obtain lamellar six side
Shape manganese dioxide；
Lamellar hexagon manganese dioxide/Graphene/porous carbon (MnO2/ rGO/C) composite preparation：In above-mentioned oxidation
It is initially charged lamellar hexagon manganese dioxide in graphite dispersing solution, make the graphite oxide with the mass ratio of lamellar hexagon manganese dioxide be
1:3；Add 10ml normal hexane and no 3ml water-ethanol under strong agitation, after mix homogeneously, reactant is moved to autoclave
In, hydro-thermal 12h at 180 DEG C；After being cooled to room temperature, sucking filtration, with dehydrated alcohol, distilled water cyclic washing, 60 DEG C of vacuum drying
12h, obtains manganese dioxide/Graphene/porous carbon (MnO2/ rGO/C) composite.
（2）The preparation of electrode
MnO by above-mentioned preparation2/ rGO/C composite is ground into powder in agate mortar, takes 5mg and 0.88mg acetylene black
It is scattered in after mix homogeneously in 1ml Nafion solution, after ultrasonic 30min, take 5ul mixed solution respectively respectively with liquid-transfering gun amount
Drop on two glass-carbon electrodes of a diameter of 5mm, naturally dry, obtain final product test electrode.
（3）The test of chemical property
With the electrode of above-mentioned preparation as working electrode, it is to electrode with platinum guaze, is formed for reference electrode with Ag/AgCl electrode
Three-electrode system carries out electrochemical property test, and electrolyte is the H of 1mol/L2SO4Solution, potential window scope is -0.2-
1.1V.When electric current density is for 0.5A/g, the ratio electric capacity of composite electrode can reach 750F/g.
Embodiment 3
（1）Lamellar hexagon manganese dioxide/Graphene/porous carbon (MnO2/ rGO/C) composite preparation
The preparation of graphite oxide dispersion：Weigh 100g graphite oxide ultrasonic disperse in 120ml distilled water, form oxidation
Graphite dispersing solution；
The preparation of lamellar hexagon manganese dioxide：High 1.1g potassium manganate is dissolved in 100ml distilled water, forms permanganic acid
Aqueous solutions of potassium；Again 0.7g potato starch is dispersed in 100ml potassium permanganate solution, magnetic agitation 5h, obtains mixing molten
Liquid.Then with KOH solution, the pH value of mixed solution is transferred to 9 ~ 10, moves in autoclave, hydro-thermal 24h at 180 DEG C；Cold
But to room temperature, sucking filtration, with dehydrated alcohol, distilled water cyclic washing to neutral, 60 DEG C of vacuum drying 12h, obtain lamellar six side
Shape manganese dioxide；
Lamellar hexagon manganese dioxide/Graphene/porous carbon (MnO2/ rGO/C) composite preparation：In above-mentioned oxidation
It is initially charged lamellar hexagon manganese dioxide in graphite dispersing solution, make the graphite oxide with the mass ratio of lamellar hexagon manganese dioxide be
1:3；Add 5ml normal hexane and no 100ml water-ethanol under strong agitation, after mix homogeneously, reactant is moved to autoclave
In, hydro-thermal 12h at 180 DEG C；After being cooled to room temperature, sucking filtration, with dehydrated alcohol, distilled water cyclic washing, 60 DEG C of vacuum drying
12h, obtains manganese dioxide/Graphene/porous carbon (MnO2/ rGO/C) composite.
（2）The preparation of electrode
MnO by above-mentioned preparation2/ rGO/C composite is ground into powder in agate mortar, takes 5mg and 0.88mg acetylene black
It is scattered in after mix homogeneously in 1ml Nafion solution, after ultrasonic 30min, take 5ul mixed solution respectively respectively with liquid-transfering gun amount
Drop on two glass-carbon electrodes of a diameter of 5mm, naturally dry, obtain final product test electrode.
（3）The test of chemical property
With the electrode of above-mentioned preparation as working electrode, it is to electrode with platinum guaze, is formed for reference electrode with Ag/AgCl electrode
Three-electrode system carries out electrochemical property test, and electrolyte is the H of 1mol/L2SO4Solution, potential window scope is -0.2-
1.1V.When electric current density is for 1A/g, the ratio electric capacity of composite electrode can reach 365F/g, illustrates that complex has higher
Ratio electric capacity, has the potential doing capacitor electrode material.
Embodiment 4
（1）Lamellar hexagon manganese dioxide/Graphene/porous carbon (MnO2/ rGO/C) composite preparation
The preparation of graphite oxide dispersion：Weigh 80g graphite oxide ultrasonic disperse in 120ml distilled water, form oxidation
Graphite dispersing solution；
The preparation of lamellar hexagon manganese dioxide：High 1.5g potassium manganate is dissolved in 100ml distilled water, forms permanganic acid
Aqueous solutions of potassium；Again 1.3g potato starch is dispersed in 100ml potassium permanganate solution, magnetic agitation 5h, obtains mixing molten
Liquid.Then with KOH solution, the pH value of mixed solution is transferred to 9 ~ 10, moves in autoclave, hydro-thermal 24h at 180 DEG C；Cold
But to room temperature, sucking filtration, with dehydrated alcohol, distilled water cyclic washing to neutral, 60 DEG C of vacuum drying 12h, obtain lamellar six side
Shape manganese dioxide；
Lamellar hexagon manganese dioxide/Graphene/porous carbon (MnO2/ rGO/C) composite preparation：In above-mentioned oxidation
It is initially charged lamellar hexagon manganese dioxide in graphite dispersing solution, make the graphite oxide with the mass ratio of lamellar hexagon manganese dioxide be
1:3；Add 3ml normal hexane and no 10ml water-ethanol under strong agitation, after mix homogeneously, reactant is moved to autoclave
In, hydro-thermal 12h at 180 DEG C；After being cooled to room temperature, sucking filtration, with dehydrated alcohol, distilled water cyclic washing, 60 DEG C of vacuum drying
12h, obtains manganese dioxide/Graphene/porous carbon (MnO2/ rGO/C) composite.
（2）The preparation of electrode
MnO by above-mentioned preparation2/ rGO/C composite is ground into powder in agate mortar, takes 5mg and 0.88mg acetylene black
It is scattered in after mix homogeneously in 1ml Nafion solution, after ultrasonic 40min, take 6ul mixed solution respectively respectively with liquid-transfering gun amount
Drop on two glass-carbon electrodes of a diameter of 5mm, naturally dry, obtain final product test electrode.
（3）The test of chemical property
With the electrode of above-mentioned preparation as working electrode, it is to electrode with platinum guaze, is formed for reference electrode with Ag/AgCl electrode
Three-electrode system carries out electrochemical property test, and electrolyte is the H of 1mol/L2SO4Solution, potential window scope is -0.2-
1.1V.Test result shows：When electric current density is for 2A/g, the ratio electric capacity of composite electrode can reach 286F/g, illustrates multiple
Compound has higher ratio electric capacity, has the potential doing capacitor electrode material.
Claims (10)
1. the preparation method of lamellar hexagon manganese dioxide/Graphene/porous carbon composite, comprises the following steps that：
（1）The preparation of graphite oxide dispersion：By graphite oxide ultrasonic disperse in distilled water, forming concentration is 1 ~ 1.5mg/mL
Graphite oxide dispersion；
（2）The preparation of lamellar hexagon manganese dioxide：Potassium permanganate is dissolved in distilled water, forming concentration is 0.05 ~ 0.1g/
The potassium permanganate solution of L；Add potato starch, stirring makes it fully dissolve, and obtains mixed solution；Reconcile mixed solution
PH value to after 9 ~ 10, hydro-thermal reaction 12 ~ 24h at 160 ~ 180 DEG C；It is cooled to room temperature, sucking filtration, with dehydrated alcohol, distillation washing
Wash to neutrality, be dried, obtain lamellar hexagon manganese dioxide；
（3）The preparation of lamellar hexagon manganese dioxide/Graphene/porous carbon composite：Graphite oxide dispersion first adds
Enter lamellar hexagon manganese dioxide, after mix homogeneously, make mixed liquor hydro-thermal reaction 12 ~ 24h at 160 ~ 180 DEG C；It is cooled to room
Temperature, sucking filtration, with dehydrated alcohol, distilled water wash to neutral, it is dried, obtains, obtain manganese dioxide/Graphene/porous carbon
(MnO2/ rGO/C) composite.
2. the preparation method of lamellar hexagon manganese dioxide/Graphene/porous carbon composite as claimed in claim 1, it is special
Levy and be：In the technique of preparation lamellar hexagon manganese dioxide, potassium permanganate is 1 with the mass ratio of potato starch:1~2:
1.
3. the preparation method of lamellar hexagon manganese dioxide/Graphene/porous carbon composite as claimed in claim 1, it is special
Levy and be：In the technique of preparation lamellar hexagon manganese dioxide/Graphene/porous carbon composite, graphite oxide and lamellar
The mass ratio of hexagon manganese dioxide is 1:3~1:5.
4. the preparation method of lamellar hexagon manganese dioxide/Graphene/porous carbon composite as claimed in claim 1, it is special
Levy and be：In the technique of preparation lamellar hexagon manganese dioxide/Graphene/porous carbon composite, in graphite oxide dispersion
Add normal hexane and dehydrated alcohol after adding lamellar hexagon manganese dioxide mix homogeneously in liquid and stir, then carry out
Hydro-thermal reaction；In mixed dispersion liquid, the percentage by volume of normal hexane is 2.5 ~ 5%, and the percentage by volume of dehydrated alcohol is 1.5 ~ 5%.
5. the preparation method of lamellar hexagon manganese dioxide/Graphene/porous carbon composite as claimed in claim 1, it is special
Levy and be：Described drying is vacuum drying 6 ~ 12h at 60 ~ 70 DEG C.
6. the lamellar hexagon manganese dioxide/Graphene/porous carbon composite of method preparation as claimed in claim 1 is as super
The application of level capacitor electrode material.
7. the lamellar hexagon manganese dioxide/Graphene/porous carbon composite of method preparation as claimed in claim 6 is as super
Level capacitor electrode material application it is characterised in that：By lamellar hexagon manganese dioxide/Graphene/porous carbon composite
It is scattered in Nafion solution with after acetylene black mix homogeneously, after ultrasonic 20 ~ 80min, mixed liquor liquid-transfering gun is evenly applied to
On glass-carbon electrode, naturally dry.
8. the lamellar hexagon manganese dioxide/Graphene/porous carbon composite of method preparation as claimed in claim 7 is as super
Level capacitor electrode material application it is characterised in that：Lamellar hexagon manganese dioxide/Graphene/porous carbon composite with
The mass ratio of acetylene black is 5.8:1~6.3:1.
9. the lamellar hexagon manganese dioxide/Graphene/porous carbon composite of method preparation as claimed in claim 7 is as super
Level capacitor electrode material application it is characterised in that：It is scattered in the lamellar hexagon manganese dioxide/graphite in Nafion solution
The mass concentration of alkene/porous carbon composite and acetylene black is 5.5 ~ 6.0mg/mL.
10. the lamellar hexagon manganese dioxide/Graphene/porous carbon composite conduct of method preparation as claimed in claim 7
The application of electrode material for super capacitor it is characterised in that：The amount being coated on mixed liquor on glass-carbon electrode is 23.5 ~ 26.5uL/
cm2.
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| CN106207100A (en) * | 2015-05-04 | 2016-12-07 | 深圳市寒暑科技新能源有限公司 | A kind of carbon fibre fabric electrode and high-capacity battery based on it |
| CN105977053A (en) * | 2016-04-07 | 2016-09-28 | 铜陵泰力电子有限公司 | Graphene/manganese dioxide composite material mixed-type electrode material with enhanced specific capacity and preparation method thereof |
| CN105914048B (en) * | 2016-07-07 | 2018-08-28 | 西华大学 | A kind of porous carbon-Graphene-metal oxide composite material and its preparation method and application |
| TWI668718B (en) * | 2016-10-14 | 2019-08-11 | 國立臺北科技大學 | A method for producing an ws2/rgo hybrid |
| CN106601496B (en) * | 2016-12-28 | 2018-10-30 | 西北师范大学 | The synthetic method of class popped rice spherical manganese dioxide composite electrode material for super capacitor |
| CN108417793B (en) * | 2018-02-01 | 2021-02-26 | 复旦大学 | Composite film of carbon-based frame loaded with manganese dioxide nanosheets and preparation method and application thereof |
| CN108335920B (en) * | 2018-04-13 | 2020-03-24 | 上海海事大学 | Nano linear MnO for super capacitor2Material, method for the production thereof and use thereof |
| CN108767210A (en) * | 2018-04-27 | 2018-11-06 | 西安理工大学 | A kind of electrochemical preparation method of self-supporting graphene/sulphur positive plate |
| CN109671576B (en) * | 2018-12-12 | 2021-01-26 | 福建翔丰华新能源材料有限公司 | Carbon nano tube-MXene composite three-dimensional porous carbon 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 |
| CN112266497B (en) * | 2020-11-04 | 2021-09-14 | 北京航空航天大学 | Shell-like light high-strength composite material and preparation method thereof |
| CN112481652B (en) * | 2020-11-20 | 2022-01-21 | 河南大学 | Graphene modified CoOOH/Fe2O3Composite electrode material and preparation method thereof |
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