CN108847358A - The preparation method and application of three-dimensional porous manganese dioxide/graphene composite material - Google Patents
The preparation method and application of three-dimensional porous manganese dioxide/graphene composite 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
- H01G11/84—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
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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 present invention relates to a kind of preparation method and applications of three-dimensional porous manganese dioxide/graphene composite material, specific steps：By graphene oxide powder and deionized water ultrasonic disperse, mixed oxidization graphene dispersing solution is formed；Graphene oxide is deposited on foam nickel surface by electrophoretic deposition；It is heat-treated, obtains the Graphene electrodes with three-dimensional porous structure；Manganese dioxide is deposited by electrochemical deposition method, obtains manganese dioxide/graphene composite material with three-dimensional porous structure.Compared with prior art, the present invention passes through electrophoretic deposition and thermal reduction preparation Graphene electrodes, combination electrode is obtained by electrochemical deposition manganese dioxide again, the deficiency for needing binder at present is solved, obtains high specific capacitance and cyclical stability and containing the manganese dioxide/graphene combination electrode for not having binder.
Description
Technical field
The present invention relates to the preparations of super capacitor composite electrode, and in particular to a kind of three-dimensional porous manganese dioxide/graphite
The preparation method and application of alkene composite material.
Background technique
Energy shortage is to face most one of stern challenge 21st century, in face of the exhausted of fossil fuel resource and increasingly
Serious environmental problem, not requiring nothing more than people will accelerate to clean the exploitation of lasting renewable energy, reinforce to carbon dioxide isothermal
Effective control of room gas discharge, and people is required to develop more advanced energy storage and control device, to meet generation
Energy demand within the scope of boundary.Supercapacitor is a kind of novel energy-storing device between traditional capacitor and secondary cell
Part shows huge application in Green Chemistry battery power field by advantages such as high power density, good cycle lives
Prospect, it is likely that become next-generation most important energy storage device.
Electrode material is one of the key factor for restricting supercapacitor development.Therefore exploitation has height ratio capacity, can be into
Row high current charge-discharge and the high electrode material of cost performance are of great practical significance.In recent years, it has developed
A variety of electrode material for super capacitor mainly have carbon material, conducting polymer and metal oxide.Metal oxide is in charge and discharge
Redox reaction can occur when electric, reaction can generate very big pseudo capacitance, therefore metal oxide is caused and ground
Study carefully the extensive concern of personnel.In numerous metal oxides, manganese dioxide is with price is low, yield is big, nontoxic and pollution-free, current potential
The features such as window is wider and superelevation theory specific capacitance value (1370F/g) becomes the electrode material most favored at present by researcher
One of material.However, its theoretical specific capacitance is also much not achieved as the actual specific capacitance of electrode material in manganese dioxide, and it is recycled
Stability is not high.In recent years, researcher proposes that many methods solve the above problems, and compound with carbon material is most simply and effectively
One of method.
In numerous carbon materials, graphene is as a kind of novel carbon material, by high conductivity, high theoretical specific surface
The features such as long-pending, excellent mechanical performance, shows excellent electrochemical properties in supercapacitor applications.Manganese dioxide and stone
Black alkene is compound, can play the high specific capacitance of manganese dioxide and show graphene high conductivity, high-specific surface area characteristic.But
It is that most research is all that manganese dioxide and graphene are prepared into powder sample at present, needs to add additional binder,
Further it is made into electrode.These binders not only increase the weight of active material, and reduce the conductivity of active material,
These reasons cause its specific capacitance to decline, and cyclical stability is deteriorated.So being badly in need of preparing one kind at present without binder, gather around
There is manganese dioxide/graphene combination electrode material of high specific capacitance and cyclical stability.
Summary of the invention
Technical problem to be solved by the present invention lies in existing when the binder of tradition addition at present being overcome to prepare electrode
Defect, and effective integration manganese dioxide and the advantages of two kinds of electrode materials of graphene, propose a kind of operation is simple, thickness is controllable,
The preparation method and applications of improved three-dimensional porous manganese dioxide/graphene composite material without binder.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of three-dimensional porous manganese dioxide/graphene composite material, includes the following steps：
(1) by graphene oxide powder and deionized water ultrasonic disperse, uniform mixed oxidization graphene dispersing solution is formed；
(2) graphene oxide is deposited on by foam nickel surface by electrophoretic deposition；
(3) nickel foam that step (2) obtains is heat-treated, obtains the Graphene electrodes with three-dimensional porous structure；
(4) manganese dioxide is deposited by electrochemical deposition method in Graphene electrodes, obtained with three-dimensional porous structure
Manganese dioxide/graphene composite material.
Further, graphene oxide powder quality and deionized water volume ratio are 0.5g/L, ultrasonic disperse in step (1)
1-2h。
Further, step (2) is by the specific method of electrophoretic deposition graphene oxide in foam nickel surface：With cleaning
Clean nickel foam is placed in the two sides of nickel foam as cathode, by graphite oxide as anode, the graphite flake of two pieces of same sizes
Alkene dispersion liquid, which injects in electrolytic cell, carries out electrophoretic deposition as electrophoresis liquid, and the sample prepared dries in the shade at room temperature later.
Further, when cleaning nickel foam, nickel foam is immersed in the hydrochloric acid of 1mol/L and is cleaned by ultrasonic, is then successively existed
Deionized water, acetone are cleaned by ultrasonic in dehydrated alcohol, and graphite flake is apart from nickel foam 1-1.5cm.
Further, when electrophoretic deposition, voltage 50-70V, sedimentation time 1-3min.
Further, it is carried out in inert atmosphere when step (3) heat-treats in Muffle furnace, temperature is 280-320 DEG C, reduction
Time is 1.5-2.5h.
Further, step (4) deposits the specific method of manganese dioxide in Graphene electrodes and is：With the manganese acetate of 0.5M
Solution is as deposition liquid, and using Graphene electrodes as working electrode, the graphite flake of same size is saturated calomel as auxiliary electrode
Electrode deposits manganese dioxide as reference electrode in three-electrode system.
Further, deposition voltage is 0.5-0.7V, sedimentation time 25-35s in three-electrode system.
Three-dimensional porous manganese dioxide/the graphene composite material being prepared can be used for making supercapacitor.
The present invention is found by electrophoretic deposition and thermal reduction preparation Graphene electrodes by improving electrophoretic deposition process parameter
Suitable deposition voltage and sedimentation time, find suitable thermal reduction temperature, and further electrochemical deposition manganese dioxide obtains most
The combination electrode of good process combination solves the deficiency for needing binder at present, obtains high specific capacitance and cyclical stability and containing not
There is manganese dioxide/graphene combination electrode of binder.
Compared with prior art, the present invention has the following advantages and beneficial effects：
1, the electrode obtained has the characteristics that process conditions are controllable, sedimentary is uniform, method is simple, green non-pollution, and
Substantially increase the repeatability and its capacitive property of electrode preparation.The present invention uses electrophoretic deposition deposited oxide graphene, no
Using any binder, deposit thickness can not only be accurately controlled, moreover it is possible to graphene oxide be made to combine closely with nickel foam.Oxygen
Graphite alkene is reduced to graphene through Overheating Treatment, further deposits manganese dioxide on this basis, manganese dioxide is in electrification
It learns and is uniformly deposited on graphene in deposition process, this preparation method is voluntarily to study to obtain based on practical experience, both at home and abroad
Research had not been reported the preparation method of the combination electrode.
2, manganese dioxide and graphene is compound prepares electrode, thinner manganese dioxide nano particle is mutually handed over graphene
Connection forms higher specific surface area, increases electric conductivity, provides good conductive path for electric charge transfer, and establish multiple
Electroactive site, the utilization rate for improving manganese dioxide increase specific capacitance.In addition, graphene sheet layer serves as cushion, it can
Volume change of the manganese dioxide nano particle in charge and discharge process is accommodated, and discharges the internal stress of this process generation, prevents from living
Property substance falls off, and improves the cyclical stability of electrode.
3, the manganese dioxide/graphene combination electrode prepared possesses higher specific capacitance, high rate performance and stable circulation
Property.In constant current charge-discharge test, when current density is 1A/g, the specific capacitance of combination electrode is up to 432F/g；Work as electric current
When density increases to 10A/g from 1A/g, the specific capacitance of combination electrode still retains 59%.In cyclic voltammetry, combination electrode
When sweep speed is 0.05V/s, after circulation 500 times, specific capacitance only reduces 2.5%.
4, the present invention is no uses any binder, keeps the thickness of graphene oxide sedimentary controllable and even compact,
The graphene sedimentary being had excellent performance after heat treatment, has higher specific surface area and specific capacitance.On this basis into one
One-step electrochemistry deposits manganese dioxide, obtains high performance three-dimensional porous manganese dioxide/graphene composite material, is able to solve dioxy
Change the disadvantages of manganese poorly conductive, volume change cause to fall off, graphene specific capacity is low and binder reduces specific capacitance, to realize two
The mass production of manganese oxide/graphene combination electrode provides may.
Detailed description of the invention
Fig. 1 is the digital photograph of prepared combination electrode preparation process in embodiment 1；
Fig. 2 is the variation diagram of prepared graphene oxygen-containing functional group after heat-treating in embodiment 1；
Fig. 3 is the SEM photograph of prepared Graphene electrodes and combination electrode in embodiment 1；
Fig. 4 is the TEM photo of prepared combination electrode in embodiment 1；
Fig. 5 is the cyclic voltammetry figure of prepared Graphene electrodes and combination electrode in embodiment 1；
Fig. 6 is prepared Graphene electrodes and the constant current charge-discharge test chart of combination electrode in embodiment 1；
Fig. 7 is the high rate performance figure of prepared combination electrode in embodiment 1；
Fig. 8 is the cycle performance figure of prepared combination electrode in embodiment 1.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
A method of three-dimensional porous manganese dioxide/graphene hybrid supercapacitor electrode material is efficiently prepared, including
Following steps：
(1) dispersion is fullyd shake into graphene oxide powder and deionized water, forms uniform mixed oxidization graphene point
Dispersion liquid；
(2) graphene oxide is deposited on by foam nickel surface by the method for electrophoretic deposition, specially：
(2.1) large stretch of nickel foam is taken, the rectangle of 2cm × 2.5cm is cut into, is immersed in the hydrochloric acid of 1mol/L ultrasonic
Cleaning 20 minutes, is then successively cleaned by ultrasonic 10 minutes in deionized water, acetone, dehydrated alcohol.
(2.2) using nickel foam as anode, the graphite flake of two pieces of same sizes is placed in nickel foam two sides as cathode, distance
About 1cm.Electrophoretic deposition will be carried out as electrophoresis liquid in the obtained graphene oxide dispersion injection electrolytic cell of step (1),
Deposition voltage is 60V, and sedimentation time is 2 minutes.
(2.3) the above-mentioned sample room temperature prepared is dried in the shade 12 hours.
(3) above-mentioned sample is heat-treated, thermal reduction method is：Under an argon atmosphere, 2 hours are kept the temperature at 300 DEG C, obtained
To the High-performance graphene electrode with three-dimensional porous structure；
(4) manganese dioxide is deposited by the method for electrochemical deposition in Graphene electrodes, obtains binder free with three
High-performance manganese dioxide/graphene combination electrode of porous structure is tieed up, specific method is：
(4.1) tetra- water manganese acetate of 61.3g is mixed with deionized water, the manganese acetate of 0.5M is prepared in 500mL volumetric flask
Solution is as deposition liquid.
(4.2) Graphene electrodes through above method preparation are as working electrode, and the graphite flake of same size is as auxiliary
Electrode, saturated calomel electrode is as reference electrode.Carry out deposition manganese dioxide in three-electrode system, deposition voltage 0.6V,
Sedimentation time is 30s.
Fig. 1 is the digital photograph of prepared combination electrode preparation process in embodiment 1, is cleaning foam by ultrasonic activation
Electrophoresis deposited oxide graphene on nickel, heat-treats by 300 DEG C, and the color of deposition film becomes black, graphene oxide from yellow
On oxygen-containing functional group be removed.Graphene deposition film is tightly coated on foam nickel surface, does not find crackle and peeling phenomenon.
Manganese dioxide is further deposited on the surface of graphene, and electrode surface gives out metallic luster.
Fig. 2 is prepared graphene oxide and the infrared transformation light of redox graphene Fourier through 300 DEG C of heat treatment
Compose comparison diagram.Five peaks of oxygen-containing functional group on graphene oxide can be clearly identified before thermal reduction.These features
Peak is substantially reduced after 300 DEG C of heat treatment, and the peak strength at these three peaks of especially 1,3 and 4 reduces to become apparent from, peak 3
Vanish from sight with the even almost all of peak 4.These situations show that oxygen-containing functional group can be removed effectively by thermal reduction.
Fig. 3 is the prepared typical microscopic appearance surface sweeping of Graphene electrodes and manganese dioxide/graphene combination electrode
Electron microscopic picture.As shown in Fig. 3 (a), it can be seen that preparing in Graphene electrodes has many fold styles, this is because electrophoresis is heavy
Caused by edge effect when product, the more prominent current density in nickel foam skeleton edges position is correspondinglyd increase, the oxidation stone of deposition
Black alkene accordingly increases to form fold.On the other hand, it is deposited on the graphene oxide of nickel foam skeleton edges under gravity
Slowly flowing, to form this and consistent fold style of gravity direction, these folds increase the specific surface area of electrode.Such as
Fig. 3 (b), (c) are inherited with shown in (d) by manganese dioxide/graphene combination electrode of constant potential electrochemical deposition well
This fold style, manganese dioxide are completely covered on above the fold style of graphene, increase its specific surface area.Moreover, big
Most manganese dioxide nano particles are independently distributed on the surface of graphene, remaining is interconnected to form irregular striated or flower
The bulky grain of shape further improves its specific surface area so that honeycomb is presented in entire combination electrode.
Fig. 4 is prepared manganese dioxide/graphene combination electrode transmission electron microscope photo, as can be seen from the figure largely
Manganese dioxide nano particle be attached to oxidation graphene film surface.Identical as surface sweeping Electronic Speculum result, transmission electron microscope shines
It is about 5-50nm that piece, which also shows manganese dioxide nano particle size, and is dispersed on oxidation graphene film.Such as Fig. 4
(d) shown in, the distance of the spacing of lattice of interplanar is about that 0.48nm corresponds to α-manganese dioxide in (200) crystal face, interplanar distance
For corresponding (211) crystal face of 0.24nm.White ovals shape curve can see many graphene sheet layer accumulations, lamella edge in figure
The skid wire generated when looking like metal forming.A large amount of lamella forms this ladder-like style, and ladder is spaced about
0.34nm, corresponding graphene (002) crystal face.
Cyclic voltammetric survey is carried out to Graphene electrodes and manganese dioxide/graphene combination electrode prepared in embodiment
Examination, as shown in figure 5, the cyclic voltammetry curve of combination electrode deviates rectangle, this is because with addition of manganese dioxide, and oxygen occurs
Faraday pseudo-capacitance can be generated by changing reduction reaction.Compound electric of the cyclic voltammetry curve of Graphene electrodes than being added to manganese dioxide
Extremely closer to perfect rectangle, illustrate it closer to ideal electric double layer capacitance.But the cyclic voltammetry of Graphene electrodes is wrapped
The area enclosed will be far smaller than the area that combination electrode is surrounded.It is calculated by correlation formula, when sweep speed is 0.005V/s
When, the specific capacitance of Graphene electrodes is 139F/g in cyclic voltammetry, and manganese dioxide/graphene combination electrode ratio electricity
Hold and is up to 360F/g.
Constant current charge and discharge is carried out to Graphene electrodes and manganese dioxide/graphene combination electrode prepared in embodiment
Electrical testing, as shown in fig. 6, Graphene electrodes complete charge and discharge time much smaller than combination electrode complete charge-discharge test when
Between.It is calculated according to correlation formula, when current density is 1A/g, the specific capacitance of Graphene electrodes in constant current charge-discharge test
For 151F/g, and manganese dioxide/graphene combination electrode specific capacitance is up to 432F/g.
High rate performance test is carried out to manganese dioxide prepared in embodiment/graphene combination electrode, is illustrated in figure 7
High rate performance of the combination electrode under different scanning rates and current density.In cyclic voltammetry when sweep speed from
When 0.005V/s increases to 0.3V/s, the specific capacitance of combination electrode still remains 38% when 0.005V/s.It is filled in constant current
In discharge test when current density increases to 10A/g from 1A/g, the specific capacitance of redox graphene still remains 1A/g
When 59%.It can be seen that combination electrode has excellent high rate performance.
Cycle performance test is carried out to manganese dioxide prepared in embodiment/graphene combination electrode, is illustrated in figure 8
Combination electrode carries out the cycle life figure of the cyclic voltammetry in 500 periods at 0.05V/s.Compare its first time and
500 cyclic voltammetry curves, it can be seen that figure is closely similar, and the area surrounded is also not much different, and illustrates its specific capacitance
It is lost in 500 cyclic voltammetries little.It is recycled by 500 times, electrode still has about 97.5% specific capacitance to be retained
Get off, shows good stable circulation performance.
Embodiment 2
A kind of preparation method of three-dimensional porous manganese dioxide/graphene composite material, includes the following steps：
(1) by graphene oxide powder and deionized water ultrasonic disperse, uniform mixed oxidization graphene dispersing solution is formed；
(2) graphene oxide is deposited on by foam nickel surface by electrophoretic deposition, when electrophoretic deposition, voltage 50V sinks
The product time is 3min；
(3) nickel foam that step (2) obtains is heat-treated, obtains the Graphene electrodes with three-dimensional porous structure,
It is carried out in inert atmosphere when thermal reduction in Muffle furnace, temperature is 280 DEG C, recovery time 2.5h；
(4) manganese dioxide is deposited by electrochemical deposition method in Graphene electrodes, obtained with three-dimensional porous structure
Manganese dioxide/graphene composite material, deposition voltage 0.5V, sedimentation time 35s.
Remaining is same as Example 1.
Embodiment 3
A kind of preparation method of three-dimensional porous manganese dioxide/graphene composite material, includes the following steps：
(1) by graphene oxide powder and deionized water ultrasonic disperse, uniform mixed oxidization graphene dispersing solution is formed；
(2) graphene oxide is deposited on by foam nickel surface by electrophoretic deposition, when electrophoretic deposition, voltage 70V sinks
The product time is 1min；
(3) nickel foam that step (2) obtains is heat-treated, obtains the Graphene electrodes with three-dimensional porous structure,
It is carried out in inert atmosphere when thermal reduction in Muffle furnace, temperature is 320 DEG C, recovery time 1.5h；
(4) manganese dioxide is deposited by electrochemical deposition method in Graphene electrodes, obtained with three-dimensional porous structure
Manganese dioxide/graphene composite material, deposition voltage 0.7V, sedimentation time 25s.
Remaining is same as Example 1.
The preparation method that the present invention is combined by a kind of electrophoretic deposition and thermal reduction obtains thickness and controllably, uniformly causes
It is close, be tightly combined, the higher three-dimensional porous Graphene electrodes of specific capacitance, and then by electrochemical deposition manganese dioxide obtain thickness
Controllably, Load Balanced, specific capacitance be higher, stable cycle performance, additive-free and repeated high combination electrode.The present invention can be with
The characteristic of the high Faraday pseudo-capacitance of manganese dioxide is efficiently used, and organic with the high-specific surface area of graphene, high conductivity
Ground combines, and solves that Graphene electrodes specific capacity is not high and manganese dioxide conductivity is poor, volume change causes the disadvantages of falling off, and makes two
Manganese oxide/graphene combination electrode has the possibility that can be mass-produced.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (9)
1. a kind of preparation method of three-dimensional porous manganese dioxide/graphene composite material, which is characterized in that include the following steps：
(1) by graphene oxide powder and deionized water ultrasonic disperse, uniform mixed oxidization graphene dispersing solution is formed；
(2) graphene oxide is deposited on by foam nickel surface by electrophoretic deposition；
(3) nickel foam that step (2) obtains is heat-treated, obtains the Graphene electrodes with three-dimensional porous structure；
(4) manganese dioxide is deposited by electrochemical deposition method in Graphene electrodes, obtains two with three-dimensional porous structure
Manganese oxide/graphene composite material.
2. a kind of preparation method of three-dimensional porous manganese dioxide/graphene composite material according to claim 1, feature
It is, graphene oxide powder quality and deionized water volume ratio are 0.5g/L, ultrasonic disperse 1-2h in step (1).
3. a kind of preparation method of three-dimensional porous manganese dioxide/graphene composite material according to claim 1, feature
It is, step (2) is by the specific method of electrophoretic deposition graphene oxide in foam nickel surface：With the nickel foam cleaned up
As anode, the graphite flake of two pieces of same sizes is placed in the two sides of nickel foam as cathode, and graphene oxide dispersion is injected
Electrophoretic deposition is carried out as electrophoresis liquid in electrolytic cell, the sample prepared dries in the shade at room temperature later.
4. a kind of preparation method of three-dimensional porous manganese dioxide/graphene composite material according to claim 3, feature
It is, when cleaning nickel foam, nickel foam is immersed in the hydrochloric acid of 1mol/L and is cleaned by ultrasonic, then successively in deionized water, third
It is cleaned by ultrasonic in ketone, dehydrated alcohol, graphite flake is apart from nickel foam 1-1.5cm.
5. a kind of preparation method of three-dimensional porous manganese dioxide/graphene composite material according to claim 3, feature
It is, when electrophoretic deposition, voltage 50-70V, sedimentation time 1-3min.
6. a kind of preparation method of three-dimensional porous manganese dioxide/graphene composite material according to claim 1, feature
It is, step (3) carries out in inert atmosphere when heat-treating in Muffle furnace, and temperature is 280-320 DEG C, recovery time 1.5-
2.5h。
7. a kind of preparation method of three-dimensional porous manganese dioxide/graphene composite material according to claim 1, feature
It is, the specific method that step (4) deposits manganese dioxide in Graphene electrodes is：Using the acetic acid manganese solution of 0.5M as deposition
Liquid, using Graphene electrodes as working electrode, the graphite flake of same size is as auxiliary electrode, and saturated calomel electrode is as reference
Electrode deposits manganese dioxide in three-electrode system.
8. a kind of preparation method of three-dimensional porous manganese dioxide/graphene composite material according to claim 7, feature
It is, deposition voltage is 0.5-0.7V, sedimentation time 25-35s in three-electrode system.
9. a kind of three-dimensional porous manganese dioxide/graphene composite wood being prepared using preparation method as described in claim 1
The application of material, which is characterized in that be used for production supercapacitor.
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| CN111542945A (en) * | 2018-12-06 | 2020-08-14 | 巴登-符腾堡州太阳能和氢能公益基金研究中心 | Reversible manganese dioxide electrode, method for producing same, use thereof and rechargeable alkaline manganese battery comprising said electrode |
| CN110148528A (en) * | 2019-05-28 | 2019-08-20 | 吉林师范大学 | MnOx/CoNi-LDH/CFP composite electrode material for super capacitor and preparation method thereof |
| CN111403184A (en) * | 2020-04-21 | 2020-07-10 | 南昌航空大学 | Nano carbon doped MnO2Preparation method of heterojunction flexible electrode |
| CN114717624A (en) * | 2022-04-08 | 2022-07-08 | 广东工业大学 | Vertically oriented graphene and preparation method and application thereof |
| CN114717624B (en) * | 2022-04-08 | 2023-08-22 | 广东工业大学 | Vertically oriented graphene and preparation method and application thereof |
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