CN104409225A - Preparation method of manganese dioxide/ carbon microspheres composite material and application of composite material serving as supercapacitor electrode material - Google Patents
Preparation method of manganese dioxide/ carbon microspheres composite material and application of composite material serving as supercapacitor electrode material Download PDFInfo
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- CN104409225A CN104409225A CN201410705232.7A CN201410705232A CN104409225A CN 104409225 A CN104409225 A CN 104409225A CN 201410705232 A CN201410705232 A CN 201410705232A CN 104409225 A CN104409225 A CN 104409225A
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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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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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
- H01G11/42—Powders or particles, e.g. composition thereof
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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
- H01G11/44—Raw materials therefor, e.g. resins or coal
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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/ carbon microspheres (MnO2/CMSs) composite material used as a supercapacitor electrode material, and belongs to the technical field of composite materials. The MnO2/CMSs composite material is obtained by a preparation method including taking glucose as an initial raw material, obtaining the carbon microspheres according to a hydrothermal method and compositing the carbon microspheres with the manganese dioxide according to an in-situ self-assembly method. Electrochemical property tests show that the prepared MnO2/CMSs composite material can achieve a synergistic effect of properties of the carbon microspheres and the manganese dioxide, has excellent properties which a single electrode does not have, and demonstrates high electrochemical capacitor behaviors, excellent rate capability and high cycling stability, thereby being capable of serving as the supercapacitor electrode material. Moreover, the composite material is simple in preparation process, stable in technology, easy to operate, reliable in quality and low in cost, and can meet basic requirements of commercialization when serving as the supercapacitor electrode material.
Description
Technical field
The present invention relates to a kind of preparation of manganese dioxide/carbon microballoon composite material, particularly relate to a kind of manganese dioxide/carbon microballoon (MnO
2/ CMSs) preparation of composite material; The present invention also relates to this manganese dioxide/carbon microballoon (MnO simultaneously
2/ CMSs) composite material applies as electrode material for super capacitor, belongs to field of compound material and electrochemical material field.
Background technology
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.MnO
2not only without the need to just running well in neutral electrolyte in strong acid or strong alkaline electrolytes, but also charging and discharging capabilities and be similar to the behavior of non-faraday's stored energy fast can be shown, this and hydration RuO
2charge storage mechanism similar.Therefore, MnO in the application of ultracapacitor
2be considered to the most promising a kind of RuO
2substitute.But MnO
2the cyclical stability of low ratio capacitance and difference makes it be limited by very large in actual applications, this mainly owing to conductivity of its difference and in iterative cycles process the expansion/contraction of crystal and peeling off of causing, in order to make up these weak points, conductive carbon material carbosphere can be used as backing material and MnO
2form compound.And simple MnO
2poorly conductive, electrochemical utilization rate is low, thus limits it and exceeding the time limit to apply in capacitor.
Carbosphere is typical 2D material with carbon element, it has good conductivity, large specific area, stable chemical nature, mechanical strength is large, tap density is high and machinability, can be widely used in preparing high performance composite material as the carrier of growth activity nano material.By MnO
2carry out combined desired with carbosphere and obtain the more excellent composite material of performance.
Prepare manganese dioxide/carbon microballoon (MnO
2/ CMSs) composite material is as electrode material for super capacitor, and obtain the premium properties having unitary electrode and do not possess, application prospect is extensive.
Summary of the invention
The object of the invention is in conjunction with MnO
2with the characteristic of carbosphere CMSs, provide a kind of manganese dioxide/carbon microballoon (MnO
2/ CMSs) composite material.
The present invention also aims to provide a kind of manganese dioxide/carbon microballoon (MnO
2/ CMSs) preparation method of composite material.
More free-revving engine of the present invention is to provide a kind of manganese dioxide/carbon microballoon (MnO
2/ CMSs) composite material is as the application of electrode material for super capacitor.
One,
manganese dioxide/carbon microballoon(MnO
2/ CMSs)
the preparation of composite material
The preparation of manganese dioxide/carbon microballoon composite material of the present invention, is take glucose as initiation material, first obtains nano-sized carbon microballoon by hydro thermal method, then makes carbosphere and manganese dioxide compound by primary reconstruction and obtain.Concrete preparation technology is as follows:
(1) preparation of nano-sized carbon microballoon: powdered glucose is fully dissolved in deionized water, hydro-thermal reaction 12 ~ 24h at 160 ~ 200 DEG C; After cool to room temperature, suction filtration, product absolute ethyl alcohol and deionized water washing, dry, obtain nano-sized carbon microballoon (CMSs);
(2) preparation of manganese dioxide/carbon microballoon composite material: by nano-sized carbon microballoon and KMnO
4mix in deionized water, add pH=1 ~ 2 that the concentrated sulfuric acid makes reaction system; Then under oil bath, 75 ~ 90 DEG C are heated to, backflow 0.5 ~ 1.5h; After question response system cool to room temperature, suction filtration, product absolute ethyl alcohol and deionized water washing, dry, obtain manganese dioxide/carbon microballoon composite material (MnO
2/ CMSs).Wherein carbosphere and KMnO
4mass ratio control at 1:8 ~ 1:9.
two, the structural characterization of the preparation of manganese dioxide/carbon microballoon composite material
Below by the manganese dioxide (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) structure of nano-bar material is described in detail.
1, ESEM (SEM) is analyzed
Field emission scanning electron microscope (SEM) picture of the carbosphere CMSs material that Fig. 1 (a) is prepared for the present invention.By figure a can see, the size of extensive homogeneous monodispersed carbon microspheres (CMSs) is about about 700nm, this material there is bigger serface with good conductivity and strong mechanical performance.Fig. 1 (b), (c) and (d) are respectively MnO prepared by the present invention
2field emission scanning electron microscope figure (SEM) under/CMSs composite material different amplification.Can be seen by Fig. 1, MnO
2be coated on uniformly on carbon microspheres, form nano flower pattern.MnO
2be carried on uniformly on CMSs, CMSs provides good conductive substrates, is more conducive to MnO
2showing of fake capacitance.The structure of this uniqueness of composite material can not only at MnO
2surface provides sufficient electro-chemical activity site, and greatly can also increase effective liquid-solid contact area, to the embedding of electrolyte ion/deviate to provide fast path, and then the carrying out of impelling faraday to react, and be more conducive to MnO
2produce higher fake capacitance.
2, X diffraction spectrogram (XRD) is analyzed
Fig. 2 is pure CMSs, MnO
2and MnO
2the X diffraction spectrogram (XRD) of/CMSs composite material.Pure CMSs has a broadening diffraction maximum at 22 ° of places, is the characteristic peak of carbon microspheres.MnO
2/ CMSs compound diffraction maximum goes out peak position, corresponds respectively to MnO
2go out peak position, just remitted its fury.The characteristic peak of CMSs is at MnO
2intensity in the XRD spectra of/CMSs is very weak, but or can make a distinction with other diffraction maximum.As can be seen from Figure 2, CMSs and MnO
2carry out good compound.
3, infrared spectrogram (FT-IR) is analyzed
Fig. 3 is MnO prepared by the present invention
2the infrared spectrogram (FT-IR) of/CMSs composite material.As can be seen from Figure 3, CMSs has stronger characteristic absorption peak, for MnO
2the infrared spectrogram of/CMSs composite material, absworption peak go out peak position and pure MnO
2, that CMSs goes out peak position is consistent, thus proves MnO
2good compound has been carried out with CMSs.
4, thermogravimetric analysis
Fig. 4 is MnO prepared by the present invention
2the thermogravimetric analyzer figure (TG) of/CMSs composite material.As can be 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 CMSs in compound.After 500 DEG C, TG curve tends towards stability substantially, illustrates that CMSs decomposes completely.Draw through estimation, MnO in compound
23:1 ~ 2:1 is about with the mass ratio of CMSs.
5, suction-desorption isotherm analysis
Fig. 5 is MnO prepared by the present invention
2suction-the desorption isotherm of/CMSs composite material.Compound MnO
2there is comparatively significantly hysteresis loop in the curve of/CMSs, show that composite material is mesoporous material.BET test result display compound MnO
2the specific area of/CMSs is 71.2m
2/ g.
Fig. 6 is MnO prepared by the present invention
2the pore size distribution curve of/CMSs composite material.As can see from Figure 6, compound MnO
2/ CMSs has two pore-size distributions, and one is the pore-size distribution at about 2.5 nm; Another is the wide distribution within the scope of 10 ~ 30 nm, the MnO of this mainly cross-join
2the macroporous structure that nanometer sheet is formed.This special double-pore structure expands the contact area of electrode material and electrolyte and provides more electro-chemical activity site, thus improves the chemical property of electrode material.
Three, chemical property
Below by the MnO that electrochemical workstation CHI660B is prepared the present invention
2the Electrochemical Characterization of/CMSs composite material is described in detail.
1, the preparation of electrode of super capacitor: by MnO
2hybrid solid powder totally 5.88 mg(MnO of/CMSs composite material and acetylene black
2the mass percent difference 85%, 15% of/CMSs composite material and acetylene black)) be dispersed in 1ml Nafion solution, after ultrasonic 30min, measure 5ul mixed solution with liquid-transfering gun to drop on the glass-carbon electrode that diameter is 5mm, naturally dry, obtain test electrode.
2, electrochemical property test
Fig. 7 is MnO prepared by the present invention
2/ CMSs composite material is as the Na of electrode material for super capacitor at 1mol/L
2sO
4in electrolyte solution, be-1.3-1.4V in electromotive force window ranges, difference sweeps the cyclic voltammetry curve (CV) under speed.Result shows, the CV curve of all samples all can see two pairs of redox peaks, 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 composite material is better, composite material has the potential doing electrode material for super capacitor.
Fig. 8 is MnO prepared by the present invention
2/ CMSs composite material is as the Na of electrode material for super capacitor at 1mol/L
2sO
4in electrolyte, electromotive force window ranges is-1.3-1.4V, the constant current charge-discharge curve chart under different current density.As shown in Figure 6, when current density is 0.5 A/g, the ratio capacitance of electrode material can reach 151F/g, and illustrative material has higher ratio capacitance under wide potential window, have the potential doing electrode material for super capacitor, this is consistent with cyclic voltammetry curve test result.
Fig. 9 is MnO prepared by the present invention
2/ CMSs composite material is 0.1 ~ 100kHz in frequency range, AC impedance figure when bias voltage is 0.8V.As shown in Figure 7, the charge migration resistance of composite material is less, 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.
Experiment shows, when preparing electrode of super capacitor, and MnO
2the mass ratio of/CMSs composite material and acetylene black is 6.0:1 ~ 6.5:1, is scattered in the MnO in Nafion solution
2the mass concentration of/CMSs composite material 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/ CMSs 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, and good cyclical stability, therefore can as electrode material for super capacitor.In addition, the preparation process of composite material of the present invention 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.
Accompanying drawing explanation
Fig. 1 is carbosphere CMSs and MnO prepared by the present invention
2the field emission scanning electron microscope figure (SEM) of/CMSs composite material.
Fig. 2 is pure CMSs, MnO
2and MnO
2the X diffraction spectrogram (XRD) of/CMSs composite material.
Fig. 3 is MnO prepared by the present invention
2the infrared spectrogram (FT-IR) of/CMSs composite material.
Fig. 4 is MnO prepared by the present invention
2the thermogravimetric analyzer figure (TG) of/CMSs composite material.
Fig. 5 is MnO prepared by the present invention
2suction-the desorption isotherm of/CMSs composite material.
Fig. 6 is MnO prepared by the present invention
2the pore size distribution curve of/CMSs composite material.
Fig. 7 is MnO prepared by the present invention
2/ CMSs composite material is as the Na of electrode material for super capacitor at 1mol/L
2sO
4the different cyclic voltammetry curve (CV) swept under speed in electrolyte solution.
Fig. 8 is MnO prepared by the present invention
2/ CMSs composite material is as the Na of electrode material for super capacitor at 1mol/L
2sO
4constant current charge-discharge curve chart in electrolyte under different current density.
Fig. 9 is MnO prepared by the present invention
2/ CMSs composite material is 0.1 ~ 100kHz in frequency range, AC impedance figure when bias voltage is 0.8V.
Embodiment
Below by specific embodiment to MnO of the present invention
2the preparation of/CMSs 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; 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; Specific area and pore-size distribution test are completed by physics automatic absorbing instrument (ASAP 2020).Sulfuric acid (silver West silver ring chemical reagent factory), (Yantai City is Chemical Co., Ltd. in pairs for glucose, analyze pure), 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.), sodium sulphate (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) manganese dioxide/carbon microballoon (MnO
2/ CMSs) preparation of composite material
6 g glucose powder are added in the beaker that 100mL deionized water is housed, stir 1h, then mixed solution is placed in autoclave, hydro-thermal reaction 24h at 180 DEG C, after autoclave cool to room temperature, by product suction filtration, wash for several times with absolute ethyl alcohol and deionized water, vacuumize 12h at 60 DEG C, obtains carbosphere (CMSs).Then by 0.86g KMnO
4join in 100mL deionized water with 0.15g CMSs and constantly stir, mixture the adds 1mL concentrated sulfuric acid after stirring 5min makes the pH of reaction system be 1 ~ 2, stirred at ambient temperature 30 min, adopts the method for oil bath heating that mixture is heated to 80 DEG C immediately, backflow 1h; After question response system cool to room temperature, suction filtration, product absolute ethyl alcohol and deionized water washing for several times, are dried 12h at 60 DEG C, are obtained product MnO
2/ CMSs composite material.
(2) preparation of electrode material for super capacitor
By manganese dioxide/carbon microballoon (MnO
2/ CMSs) composite material 5 mg, acetylene black the mass percent respectively 85%, 15% of hybrid solid powder both totally 0.88 mg() be dispersed in 1ml Nafion solution, after ultrasonic 30min, measuring 5uL mixed solution with liquid-transfering gun drops on the glass-carbon electrode that diameter is 5mm, naturally dry, obtain test electrode.
(3) electrochemical property test: with the electrode material of above-mentioned preparation for work electrode, be to electrode with platinum guaze, carry out electrochemical property test with Ag/AgCl electrode for reference electrode forms three-electrode system, electrolyte is the Na of 1mol/L
2sO
4solution, potential window scope is-1.3-1.4V.Adopt the mapping of origin 8.0 software.Test result display is when current density is 0.5A/g, and the ratio capacitance of electrode material can reach 151 F/g, and illustrative material has higher ratio capacitance under wide potential window, has the potential doing electrode material for super capacitor.
Embodiment 2
1) manganese dioxide/carbon microballoon (MnO
2/ CMSs) preparation of composite material
5.5 glucose powder are added in the beaker that 100mL deionized water is housed, stir 1h, then mixed solution is placed in autoclave, hydro-thermal reaction 12h at 185 DEG C, after autoclave cool to room temperature, by product suction filtration, wash for several times with absolute ethyl alcohol and deionized water, vacuumize 12h at 60 DEG C, obtains carbosphere (CMSs).Then by 0.9g KMnO
4join in 100mL deionized water with 0.15g CMSs and constantly stir, mixture the adds 1mL concentrated sulfuric acid after stirring 5min makes the pH of reaction system be 1 ~ 2, stirred at ambient temperature 50 min, adopts the method for oil bath heating that mixture is heated to 80 DEG C immediately, backflow 1h; After question response system cool to room temperature, suction filtration, product absolute ethyl alcohol and deionized water washing for several times, are dried 12h at 60 DEG C, are obtained product MnO
2/ CMSs composite material.
(2) preparation of electrode material for super capacitor
By manganese dioxide/carbon microballoon (MnO
2/ CMSs) composite material 5.1 mg, acetylene black the mass percent respectively 85%, 15% of hybrid solid powder both totally 0.88 mg() be dispersed in 1ml Nafion solution, after ultrasonic 30min, measuring 5uL mixed solution with liquid-transfering gun drops on the glass-carbon electrode that diameter is 5mm, naturally dry, obtain test electrode.
(3) electrochemical property test: with the electrode material of above-mentioned preparation for work electrode, be to electrode with platinum guaze, carry out electrochemical property test with Ag/AgCl electrode for reference electrode forms three-electrode system, electrolyte is the Na of 1mol/L
2sO
4solution, potential window scope is-1.3-1.4V.Test result shows: in cyclic voltammetry, along with the increase of sweep speed, the shape of CV curve remains unchanged substantially, and illustrate that times capacity rate of composite material is better, composite material has the potential doing electrode material for super capacitor.
Embodiment 3
1) manganese dioxide/carbon microballoon (MnO
2/ CMSs) preparation of composite material
6 g glucose powder are added in the beaker that 100mL deionized water is housed, stir 2h, then mixed solution is placed in autoclave, hydro-thermal reaction 24h at 180 DEG C, after autoclave cool to room temperature, by product suction filtration, wash for several times with absolute ethyl alcohol and deionized water, vacuumize 12h at 60 DEG C, obtains carbosphere (CMSs).Then by 0.8g KMnO
4join in 100mL deionized water with 0.16g CMSs and constantly stir, mixture the adds 1mL concentrated sulfuric acid after stirring 5min makes the pH of reaction system be 1 ~ 2, stirred at ambient temperature 30 min, adopts the method for oil bath heating that mixture is heated to 80 DEG C immediately, backflow 1h; After question response system cool to room temperature, suction filtration, product absolute ethyl alcohol and deionized water washing for several times, are dried 12h at 60 DEG C, are obtained product MnO
2/ CMSs composite material.
(2) preparation of electrode material for super capacitor
By manganese dioxide/carbon microballoon (MnO
2/ CMSs) composite material 5.1 mg, acetylene black the mass percent respectively 85%, 15% of hybrid solid powder both totally 0.88 mg() be dispersed in 1ml Nafion solution, after ultrasonic 40min, measuring 5uL mixed solution with liquid-transfering gun drops on the glass-carbon electrode that diameter is 5mm, naturally dry, obtain test electrode.
(3) electrochemical property test: with the electrode material of above-mentioned preparation for work electrode, be to electrode with platinum guaze, carry out electrochemical property test with Ag/AgCl electrode for reference electrode forms three-electrode system, electrolyte is the Na of 1mol/L
2sO
4solution, potential window scope is-1.3-1.4V.Test result shows: when current density is 0.5A/g, the ratio capacitance of electrode material can reach 155F/g.
Embodiment 4
1) manganese dioxide/carbon microballoon (MnO
2/ CMSs) preparation of composite material
6 g glucose powder are added in the beaker that 150mL deionized water is housed, stir 3h, then mixed solution is placed in autoclave, hydro-thermal reaction 16h at 180 DEG C, after autoclave cool to room temperature, by product suction filtration, wash for several times with absolute ethyl alcohol and deionized water, vacuumize 24h at 60 DEG C, obtains carbosphere (CMSs).Then by 1.0g KMnO
4join in 100mL deionized water with 0.12g CMSs and constantly stir, mixture the adds 1mL concentrated sulfuric acid after stirring 5min makes the pH of reaction system be 1 ~ 2, stirred at ambient temperature 30 min, adopts the method for oil bath heating that mixture is heated to 80 DEG C immediately, backflow 1h; After question response system cool to room temperature, suction filtration, product absolute ethyl alcohol and deionized water washing for several times, are dried 12h at 60 DEG C, are obtained product MnO
2/ CMSs composite material.
(2) preparation of electrode material for super capacitor
By manganese dioxide/carbon microballoon (MnO
2/ CMSs) composite material 4.9mg, acetylene black the mass percent respectively 85%, 15% of hybrid solid powder both totally 0.88 mg() be dispersed in 1ml Nafion solution, after ultrasonic 30min, measuring 5.2uL mixed solution with liquid-transfering gun drops on the glass-carbon electrode that diameter is 5mm, naturally dry, obtain test electrode.
(3) electrochemical property test: with the electrode material of above-mentioned preparation for work electrode, be to electrode with platinum guaze, carry out electrochemical property test with Ag/AgCl electrode for reference electrode forms three-electrode system, electrolyte is the Na of 1mol/L
2sO
4solution, potential window scope is-1.3-1.2V.Test result shows: when current density is 0.5A/g, the ratio capacitance of electrode material can reach 165F/g.
Claims (9)
1. a preparation method for manganese dioxide/carbon microballoon composite material, is take glucose as initiation material, first obtains nano-sized carbon microballoon by hydro thermal method, then makes carbosphere and manganese dioxide compound by primary reconstruction method and obtain.
2. the preparation method of manganese dioxide/carbon microballoon composite material as claimed in claim 1, is characterized in that: comprise following processing step:
(1) preparation of nano-sized carbon microballoon: powdered glucose is fully dissolved in deionized water, hydro-thermal reaction 12 ~ 24h at 160 ~ 200 DEG C; After cool to room temperature, suction filtration, product absolute ethyl alcohol and deionized water washing, dry, obtain nano-sized carbon microballoon;
(2) preparation of manganese dioxide/carbon microballoon composite material: by nano-sized carbon microballoon and KMnO
4mix in deionized water, add pH=1 ~ 2 that the concentrated sulfuric acid makes reaction system; Then under oil bath, 75 ~ 90 DEG C are heated to, backflow 0.5 ~ 1.5h; After question response system cool to room temperature, suction filtration, product absolute ethyl alcohol and deionized water washing, dry, obtain manganese dioxide/carbon microballoon composite material.
3. the preparation method of manganese dioxide/carbon microballoon composite material as claimed in claim 1 or 2, is characterized in that: carbosphere and KMnO
4mass ratio be 1:8 ~ 1:9.
4. the preparation method of manganese dioxide/carbon microballoon composite material as claimed in claim 1 or 2, is characterized in that: described oven dry is vacuumize 8 ~ 12h at 60 ~ 70 DEG C.
5. as claimed in claim 1 the manganese dioxide/carbon microballoon composite material prepared of method as the application of electrode material for super capacitor.
6. as claimed in claim 5 manganese dioxide/carbon microballoon composite material as the application of electrode material for super capacitor, it is characterized in that: be scattered in after manganese dioxide/carbon microballoon composite material and acetylene black are mixed in Nafion solution, after ultrasonic 20 ~ 50min, mixed liquor is evenly coated on glass-carbon electrode, naturally dries.
7. manganese dioxide/carbon microballoon composite material, as the application of electrode material for super capacitor, is characterized in that as claimed in claim 5: the mass ratio of manganese dioxide/carbon microballoon composite material and acetylene black is 6.0:1 ~ 6.5:1.
8. manganese dioxide/carbon microballoon composite material, as the application of electrode material for super capacitor, is characterized in that as claimed in claim 5: the mass concentration being scattered in manganese dioxide/carbon microballoon composite material in Nafion solution and acetylene black is 5.5 ~ 6.0mg/mL.
9. manganese dioxide/carbon microballoon composite material, as the application of electrode material for super capacitor, is characterized in that as claimed in claim 5: the amount being coated on mixed liquor on glass-carbon electrode is 23.5 ~ 26.5uL/cm
2.
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| CN104741051A (en) * | 2015-03-27 | 2015-07-01 | 安徽农业大学 | Method for preparing sugar-based carbon microsphere at low temperature |
| CN104979551A (en) * | 2015-07-17 | 2015-10-14 | 武汉大学 | Carbon nano-sphere/NiCo2O4 composite material as well as preparation method and application thereof |
| CN105118962A (en) * | 2015-07-20 | 2015-12-02 | 上海交通大学 | Carbon sphere/ferroferric oxide composite material, preparation and application method thereof |
| CN105304355A (en) * | 2015-11-05 | 2016-02-03 | 上海应用技术学院 | Method for preparing manganese dioxide/carbon microsphere electrode by organic matter electrolytic process |
| CN105289583A (en) * | 2015-10-30 | 2016-02-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of carbon nanosphere supported manganese oxide based catalyst |
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| CN105869922A (en) * | 2016-04-11 | 2016-08-17 | 太原理工大学 | Rapid preparation method of manganese oxide/carbon sphere composite material for three-dimensional (3D) printing |
| CN106449147A (en) * | 2016-11-16 | 2017-02-22 | 广州大学 | CMS/MnO2/PPY (carbon microsphere/manganese dioxide/polypyrrole) composite electrode material, as well as preparation method and application thereof |
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| CN106952746A (en) * | 2017-03-23 | 2017-07-14 | 潍坊正远粉体工程设备有限公司 | Active carbon electrode material preparation method and manganese oxide/activated carbon composite electrode material preparation method |
| WO2017182891A1 (en) * | 2016-04-20 | 2017-10-26 | The Hong Kong Polytechnic University | An improved method for preparing aqueous mno2 ink and capacitive energy storage |
| CN108155023A (en) * | 2017-12-25 | 2018-06-12 | 温州大学新材料与产业技术研究院 | A kind of preparation method of nitrogen-phosphor codoping biological carbon/manganese compound composite material |
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| CN110164702A (en) * | 2018-01-23 | 2019-08-23 | 泰顺永庆电力技术有限公司 | A kind of lithium battery carbon/manganese dioxide composite material and its application |
| CN112337432A (en) * | 2020-11-03 | 2021-02-09 | 广州大学 | Transition metal doped carbon microsphere and preparation method and application thereof |
| CN112794308A (en) * | 2020-12-31 | 2021-05-14 | 西安理工大学 | Preparation method of carbon microspheres with columnar hierarchical structure |
| CN112958087A (en) * | 2021-01-31 | 2021-06-15 | 福建工程学院 | MnO distributed on surface of symmetrical carbon microsphere2Preparation method of Pt-supported double-catalyst micro-nano motor |
| CN114823167A (en) * | 2022-03-18 | 2022-07-29 | 电子科技大学 | Rapid preparation C @ MnO 2 Method and application of nanoparticles |
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| CN106952746A (en) * | 2017-03-23 | 2017-07-14 | 潍坊正远粉体工程设备有限公司 | Active carbon electrode material preparation method and manganese oxide/activated carbon composite electrode material preparation method |
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| CN108155023A (en) * | 2017-12-25 | 2018-06-12 | 温州大学新材料与产业技术研究院 | A kind of preparation method of nitrogen-phosphor codoping biological carbon/manganese compound composite material |
| CN110164702A (en) * | 2018-01-23 | 2019-08-23 | 泰顺永庆电力技术有限公司 | A kind of lithium battery carbon/manganese dioxide composite material and its application |
| CN108538612A (en) * | 2018-03-30 | 2018-09-14 | 徐州工业职业技术学院 | A kind of preparation method of the N doping carbon/manganese dioxide composite electrode material of porous intercommunication network |
| CN112337432A (en) * | 2020-11-03 | 2021-02-09 | 广州大学 | Transition metal doped carbon microsphere and preparation method and application thereof |
| CN112794308A (en) * | 2020-12-31 | 2021-05-14 | 西安理工大学 | Preparation method of carbon microspheres with columnar hierarchical structure |
| CN112794308B (en) * | 2020-12-31 | 2022-05-17 | 西安理工大学 | Preparation method of carbon microspheres with columnar hierarchical structure |
| CN112958087A (en) * | 2021-01-31 | 2021-06-15 | 福建工程学院 | MnO distributed on surface of symmetrical carbon microsphere2Preparation method of Pt-supported double-catalyst micro-nano motor |
| CN114823167A (en) * | 2022-03-18 | 2022-07-29 | 电子科技大学 | Rapid preparation C @ MnO 2 Method and application of nanoparticles |
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