CN103035409B - Graphene combination electrode and its preparation method and application - Google Patents
Graphene combination electrode and its preparation method and application Download PDFInfo
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- CN103035409B CN103035409B CN201110302892.7A CN201110302892A CN103035409B CN 103035409 B CN103035409 B CN 103035409B CN 201110302892 A CN201110302892 A CN 201110302892A CN 103035409 B CN103035409 B CN 103035409B
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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
- Y02E60/10—Energy storage using batteries
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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 kind of graphene combination electrode, including collector and the electrode active material that is positioned at collection liquid surface, wherein, electrode active material includes Graphene and manganese dioxide, Graphene is positioned at collection liquid surface with layer structure, manganese dioxide is positioned at the graphenic surface of layer structure, and Graphene weight/mass percentage composition in electrode active material is 80 90%.Moreover, it relates to the preparation method and applications of a kind of graphene combination electrode.By by graphene oxide and manganese dioxide stepped depositions to collector, need not use binding agent, thus effectively reduce the equivalent series resistance of whole electrode, playing Graphene and the capacity of manganese dioxide electric double layer and fake capacitance, the addition of Graphene can well improve stability and the electrical conductivity of electrode simultaneously.Additionally, by the method for electro-deposition, electrode material is deposited directly on electrode slice, can save the coating process of complexity, technique is simple and the time is short.
Description
[technical field]
The present invention relates to the electrode material field of battery or capacitor, particularly relate to a kind of graphene combination electrode
And its preparation method and application.
[background technology]
Ultracapacitor with its high-energy-density, high power density, the long-life, to advantages such as environment are friendly
Receive much concern.At solar charger, alarm device, household electrical appliance, the stand-by power supply of microcomputer, aircraft
The aspects such as Aero-Space and science and techniques of defence such as igniter have of crucial importance and wide application prospect, become
Focus for countries in the world research.
During the research and development of ultracapacitor, the material with carbon element of high-specific surface area is ultracapacitor reason
The electrode material thought, such as activated carbon, carbon aerogels, CNT and carbon fiber etc..Although material with carbon element is super
The commercial applications that capacitor is the most preliminary, but owing to its capacity is smaller, thus its application is also necessarily
Limited by bigger in degree, need to find new jumbo, reliable and stable electrode of super capacitor
Material.The pseudo capacitance utilizing metal-oxide generation redox reaction and produce carries out energy storage
Electrochemical capacitor cause the great interest of researcher.Wherein, ruthenium-oxide is transiting metal oxidation
Preferable super capacitor material in the middle of thing, but it is expensive, it is difficult to and industrialization uses；Nickel oxide and oxygen
Change cobalt and there is the shortcoming that operating potential window is narrower；And manganese oxide aboundresources, cheap, there is double electricity
Layer capacitance and the double grading of fake capacitance, and manganese oxide material is pollution-free, available transport in large-scale production, quilt
It is considered the electrode material for super capacitor of great potential, causes the extensive concern of people.But tradition preparation
Manganese oxide electrode material there is the problem that resistance is bigger, limit it and apply further.
[summary of the invention]
Based on this, it is necessary to provide relatively small electrode of a kind of resistance and preparation method thereof.
The invention provides a kind of graphene combination electrode, including collector and be positioned at described collection liquid surface
Electrode active material, described electrode active material includes that Graphene and manganese dioxide, described Graphene are positioned at institute
Stating collection liquid surface, graphenic surface described in described manganese dioxide, wherein, Graphene is at described electrode activity
Weight/mass percentage composition in material is 80-90%.
In a preferred embodiment, described collector is nickel foil or aluminium foil.
The preparation method of a kind of graphene combination electrode, comprises the steps:
Step one: graphene oxide solution is prepared by graphite oxide ultrasonic disperse in a solvent, more heavy by electricity
Described graphene oxide is deposited to collection liquid surface by area method, obtains graphene oxide/collector electrode；
Step 2: using described graphene oxide/collector electrode as working electrode, coordinates reference electrode and auxiliary
Help electrode, in the electrolyte containing manganese source, deposit on graphene oxide/collector electrode under constant current effect
Manganese dioxide, and manganese dioxide is deposited on described surface of graphene oxide, obtain manganese dioxide/graphene oxide/
Collector electrode；
Step 3: reduce described manganese dioxide/graphene oxide/collector electrode, obtains described Graphene and is combined
Electrode, Graphene weight/mass percentage composition in described electrode active material is 80-90%.
In a preferred embodiment, described in step one, graphite oxide is prepared as steps described below:
Being added to the concentrated sulphuric acid of 0 DEG C by graphite powder, add potassium permanganate, the temperature of system is maintained at 10 DEG C
Hereinafter, the most at room temperature stirring in water bath 24 hours after stirring 2 hours, then at condition of ice bath downhill reaction body
System is slowly added to deionized water, after 15 minutes, adds the deionized water containing hydrogen peroxide, until solution
Color becomes glassy yellow, while hot sucking filtration, then washs with the hydrochloric acid that concentration is 10%, sucking filtration, and 60 DEG C true
Empty drying to obtain graphite oxide.
In a preferred embodiment, in step one, first electrodeposition process comprises the steps:, to preparing
Graphene oxide solution in add electrolyte, ultrasonic disperse, to obtain uniform solution as electrolyte；
Then taking collector as electrode, placed in the electrolytic solution by its Parallel Symmetric, two electrode spacings are 0.5cm；
Be passed through the most between electrodes 40～80V unidirectional current 5～20 minutes, at described electrode surface deposited oxide stone
Ink alkene, prepares graphene oxide/collector electrode.
In a preferred embodiment, described electrolyte is Mg (NO3)2·6H2O、Fe(NO3)3·9H2O or
Zn(NO3)2·6H2O, in electrolyte, the concentration of electrolyte is 0.2～5mg/mL.
In a preferred embodiment, in step 2, described reference electrode is calomel electrode；Described auxiliary electricity
Extremely platinum electrode；The described electrolyte containing manganese source is the Mn (CH of concentration 0.25-0.5mol/L3COO)2Solution；
The electric current density of constant current is 1.25mA/cm2。
In a preferred embodiment, step 3 reduces described manganese dioxide/graphene oxide/collector electrode
After comprising the steps: naturally to dry the manganese dioxide/graphene oxide/collector electrode of step 2 gained,
Vacuum bakeout 1～3 hours, then put it in furnace tubing, under atmosphere of inert gases, with 10 DEG C/min
The rate of heat addition be warming up to 500 DEG C～800 DEG C, keep 2～4 hours, after completion of the reaction, the coldest
But arrive room temperature, obtain described graphene combination electrode.
In a preferred embodiment, described collector is nickel foil or aluminium foil.
Said method is by by graphene oxide and manganese dioxide stepped depositions to collector, then will aoxidize stone
Ink alkene reduction, need not in preparation process use binding agent, thus effectively reduces the equivalent string of whole electrode
Connection resistance, plays Graphene and the capacity of manganese dioxide electric double layer and fake capacitance simultaneously, and the addition of Graphene can
Well to improve stability and the electrical conductivity of electrode.Additionally, by the method for electro-deposition, electrode material is straight
Connecing and be deposited on electrode slice, can save the coating process of complexity, technique is simple and the time is short.The present invention's
Graphene combination electrode can be widely used in the field such as high-power lithium ion battery, ultracapacitor.
A kind of ultracapacitor, including electrolyte, two electrode slices and be placed in the barrier film between two electrode slices,
Described electrode slice includes collector and is positioned at the electrode active material of described collection liquid surface, it is characterised in that
Described electrode active material includes that Graphene and manganese dioxide, described Graphene are positioned at described collection liquid surface,
Described manganese dioxide is positioned at described graphenic surface, wherein, Graphene matter in described electrode active material
Amount percentage composition is 80-90%.
This ultracapacitor uses above-mentioned graphene combination electrode to make electrode slice, good stability, and electrical conductivity is high.
Further, since the preparation process of graphene combination electrode does not use the binding agent that resistance is higher, thus electric
The equivalent series resistance of pole piece is less, and the power density of ultracapacitor is higher.
[accompanying drawing explanation]
Fig. 1 is the preparation flow figure of the graphene combination electrode of an embodiment；
Fig. 2 is the charging and discharging curve figure of the graphene combination electrode that embodiment prepares.
[detailed description of the invention]
Mainly in combination with drawings and the specific embodiments, graphene combination electrode and its preparation method and application is made below
Further details of explanation.
The graphene combination electrode of one embodiment, including collector and the electrode activity that is positioned at collection liquid surface
Material.Electrode active material is the composite of Graphene and manganese dioxide, and wherein, Graphene is tied with stratiform
Structure is positioned at collection liquid surface, and manganese dioxide is positioned at the graphenic surface of layer structure, and Graphene is at electrode activity
Weight/mass percentage composition in material is 80-90%.
Collector can be the metal forming such as nickel foil or aluminium foil.
As it is shown in figure 1, the preparation method of the graphene combination electrode of present embodiment, comprise the steps:
Step S1: graphene oxide solution is prepared by graphite oxide ultrasonic disperse in a solvent, more heavy by electricity
Graphene oxide is deposited to collection liquid surface by area method, obtains graphene oxide/collector electrode.
Preferably, the graphite oxide in this step is prepared in accordance with the following steps: add graphite powder to 0 DEG C is dense
In sulphuric acid, adding potassium permanganate, the temperature of system is maintained at less than 10 DEG C, again in room after stirring 2 hours
The lower stirring in water bath of temperature 24 hours, is then slowly added to deionized water in condition of ice bath downhill reaction system, and 15
After minute, add the deionized water containing hydrogen peroxide, until the color of solution becomes glassy yellow, sucking filtration while hot,
Washing with the hydrochloric acid that concentration is 10%, sucking filtration, 60 DEG C of vacuum drying i.e. obtain graphite oxide again.Enter one
Step, the natural flake graphite powder of graphite powder preferably 100～500 mesh.
After prepared graphite oxide, add it in alcohols solvent, such as ethanol, isopropanol, propanol etc.,
Ultrasonic disperse 0.5～after 1 hour, obtains homodisperse graphene oxide solution；Then molten to graphene oxide
Liquid adds electrolyte, such as Mg (NO3)2·6H2O、Mg(SO4)2·7H2O、Fe(NO3)3·9H2O or
Zn(NO3)2·6H2O etc., ultrasonic disperse 15～60 minutes to solution are uniform, now include the oxidation of electrolyte
Graphene solution can be as electrolyte, and in electrolyte, the concentration of electrolyte is 0.2～5mg/mL；Take collector to make
For electrode, being placed in the electrolytic solution by its Parallel Symmetric, two electrode spacings are 0.5cm；The most between electrodes
Be passed through 40～80V unidirectional current 5～20 minutes, at electrode surface deposited oxide Graphene, prepare graphite oxide
Alkene/collector electrode.
Step S2: using graphene oxide/collector electrode as working electrode, coordinates reference electrode and auxiliary electricity
Pole, in the electrolyte containing manganese source, deposits dioxy on graphene oxide/collector electrode under constant current effect
Change manganese, and manganese dioxide is deposited on described surface of graphene oxide, obtains manganese dioxide/graphene oxide/afflux
Body electrode.
The preferred calomel electrode of reference electrode in this step；The preferred platinum electrode of auxiliary electrode；Electrolysis containing manganese source
Liquid preferred concentration is the Mn (CH of 0.25-0.5mol/L3COO)2Solution；The electric current density of constant current is
1.25mA/cm2。
Step S3: manganese dioxide reduction/graphene oxide/collector electrode, obtains graphene combination electrode.
Specifically include following steps: by the manganese dioxide/graphene oxide/collector electrode of step S2 gained certainly
After so drying, vacuum bakeout 1～3 hours, then put it in furnace tubing, at high-purity noble gas atmosphere
Under enclosing, it is warming up to 500 DEG C～800 DEG C with the rate of heat addition of 10 DEG C/min, keeps 2～4 hours, react complete
After, it is cooled to room temperature in an inert atmosphere, obtains manganese dioxide/Graphene/collector electrode, the i.e. present invention
Graphene combination electrode.
The present invention is by by graphene oxide and manganese dioxide stepped depositions to collector, then by graphite oxide
Alkene reduces, and need not use binding agent, thus effectively reduce the equivalent series of whole electrode in preparation process
Resistance, plays Graphene and the capacity of manganese dioxide electric double layer and fake capacitance simultaneously, and the addition of Graphene is permissible
Well improve stability and the electrical conductivity of electrode.Additionally, by the method for electro-deposition, electrode material is direct
Being deposited on electrode slice, can save the coating process of complexity, technique is simple and the time is short.The stone of the present invention
Ink alkene combination electrode can be widely used in the field such as high-power lithium ion battery, ultracapacitor.
It is below specific embodiment part:
Embodiment 1
Technological process is as follows:
Natural flake graphite → graphite oxide → graphene oxide/nickel electrode → manganese dioxide/graphene oxide/nickel
Electrode → manganese dioxide/graphene/nickel electrode
(1) natural flake graphite: mesh number 100 mesh.
(2) graphite oxide: the 100 mesh natural flake graphite powder of 0.5g are joined 0 DEG C, 11.5mL
In concentrated sulphuric acid, adding 1.5g potassium permanganate, the temperature of mixture is maintained at less than 10 DEG C, stirs 2 hours,
Then, after room-temperature water bath stirs 24 hours, under condition of ice bath, 46mL deionized water it is slowly added to.15 points
Zhong Hou, adds 140mL deionized water (wherein containing the hydrogen peroxide that 2.5mL concentration is 30%), mixes afterwards
Compound color becomes glassy yellow, sucking filtration, then with the hydrochloric acid that 250mL concentration is 10% carry out washing, sucking filtration,
60 DEG C are vacuum dried 48 hours, i.e. obtain graphite oxide.
(3) graphene oxide/nickel electrode: graphene oxide step (2) prepared adds to 500mL second
Ultrasonic disperse 0.5 hour in alcohol, prepares homodisperse graphene oxide solution；Again to graphene oxide solution
Mg (the NO of middle addition 0.5g3)2·6H2O, ultrasonic 15 minutes, to obtain uniform solution as electrolyte；
Using the nickel foil of 5cm diameter as electrode, its Parallel Symmetric is placed in electrolyte, adds at the two ends of electrode
Entering the unidirectional current of 40V, two die openings are 0.5cm, are energized 5 minutes, can obtain graphene oxide/nickel electrode,
Washed and dried.
(4) manganese dioxide/graphene oxide/nickel electrode: using graphene oxide/nickel electrode in step (3) as work
Making electrode, reference electrode made by calomel electrode, and auxiliary electrode made by platinum electrode, at room temperature with 0.25mol/L's
Mn(CH3COO)2Solution, as electrolyte, is 1.25mA/cm in electric current density2Constant current effect under electricity heavy
After long-pending 5 minutes, with deionized water rinsing, obtain manganese dioxide/graphene oxide/nickel electrode.
(5) manganese dioxide/graphene/nickel electrode: by step (4) gained manganese dioxide/graphene oxide/nickel electrode
Naturally after drying, vacuum bakeout 1 hour.Put it to again in furnace tubing and pass to highly purified nitrogen,
Then stove is warming up to 500 DEG C with the rate of heat addition of 10 DEG C/min, keeps 2 hours.After completion of the reaction,
It is cooled to room temperature in an inert atmosphere, obtains manganese dioxide/graphene/nickel electrode.
Being rolled by the graphene combination electrode roller mill of gained, the pole piece card punch of roll-in breaks into
The circular pole piece of a diameter of 10mm, correct amount.Then by pole piece, barrier film and electrolyte in glove box
Being assembled into ultracapacitor according to cell making process, its septation is celgard 2000, and electrolyte is 2mol/L
Ammonium sulfate.Standing after being completed and within one day, carry out constant current charge-discharge test, wherein voltage range is
0-1V, electric current is that 0.15A/g carries out constant current charge-discharge.Result is as in figure 2 it is shown, can from charging and discharging curve
Go out, the charging and discharging curve shape that sample charging and discharging curve under 0.15A/g electric current density is near the mark, have
Good charge-discharge performance, the voltage-drop data from figure, according to formula
Equivalent string can be calculated
Connection resistance is 0.76 Ω, and resistance is less comparatively speaking, owing to power density is inversely proportional to resistance, then and power density
Higher.
Embodiment 2
Technological process is as follows:
Natural flake graphite → graphite oxide → graphene oxide/aluminum electrode → manganese dioxide/graphene oxide/aluminum
Electrode → manganese dioxide/graphene/aluminum electrode
(1) natural flake graphite: mesh number 500 mesh.
(2) graphite oxide: by 0.5g 500 mesh natural flake graphite powder add 0 DEG C, 11.5mL dense
In sulphuric acid, adding 1.5g potassium permanganate, the temperature of mixture is maintained at less than 10 DEG C, stirs 2 hours,
Then, after room-temperature water bath stirs 24 hours, under condition of ice bath, 46mL deionized water it is slowly added to.15
After minute, add 140mL deionized water (wherein containing the hydrogen peroxide that 2.5mL concentration is 30%), afterwards
Mixture color becomes glassy yellow, sucking filtration, then with the hydrochloric acid that 250mL concentration is 10% carry out washing, sucking filtration,
60 DEG C are vacuum dried 48 hours, i.e. obtain graphite oxide.
(3) graphene oxide/aluminum electrode: add graphene oxide into ultrasonic disperse 1 in 2500mL ethanol little
Time, obtain homodisperse graphene oxide solution.In graphene oxide solution, add 0.5g's again
Fe(NO3)3·9H2O, ultrasonic 60 minutes, to obtain uniform solution as electrolyte, with 10cm diameter
Its Parallel Symmetric, as electrode, is placed in electrolyte by aluminium foil, adds the direct current of 80V at the two ends of electrode
Electricity, two die openings are 0.5cm, are energized 20 minutes, can obtain graphene oxide/aluminum electrode, washed and dry in the air
Dry.
(4) manganese dioxide/graphene oxide/aluminum electrode: using graphene oxide/aluminum electrode in step (3) as work
Making electrode, reference electrode made by calomel electrode, and auxiliary electrode made by platinum electrode, at room temperature with 0.5mol/L's
Mn(CH3COO)2Solution, as electrolyte, is 1.25mA/cm in electric current density2Constant current effect under electricity heavy
After long-pending 10 minutes, with deionized water rinsing, obtain manganese dioxide/graphene oxide/aluminum electrode.
(5) manganese dioxide/graphene/aluminum electrode: by step (4) gained manganese dioxide/graphene oxide/aluminum electrode
Naturally after drying, vacuum bakeout 1 hour.Put it to again in furnace tubing and pass to highly purified nitrogen,
Then stove is warming up to 800 DEG C with the rate of heat addition of 10 DEG C/min, keeps 2 hours.After completion of the reaction,
It is cooled to room temperature in an inert atmosphere, obtains manganese dioxide/graphene/aluminum electrode.
Embodiment 3
Technological process is as follows:
Natural flake graphite → graphite oxide → graphene oxide/foil electrode → manganese dioxide/graphene oxide/
Aluminum electrode → manganese dioxide/graphene/aluminum foil electrode
(1) natural flake graphite: mesh number 500 mesh.
(2) graphite oxide: by 0.5g 500 mesh natural flake graphite powder add 0 DEG C, 11.5mL dense
In sulphuric acid, adding 1.5g potassium permanganate, the temperature of mixture is maintained at less than 10 DEG C, stirs 2 hours,
Then, after room-temperature water bath stirs 24 hours, under condition of ice bath, 46mL deionized water it is slowly added to.15
After minute, add 140mL deionized water (wherein containing the hydrogen peroxide that 2.5mL concentration is 30%), afterwards
Mixture color becomes glassy yellow, sucking filtration, then with the hydrochloric acid that 250mL concentration is 10% carry out washing, sucking filtration,
60 DEG C are vacuum dried 48 hours, i.e. obtain graphite oxide.
(3) graphene oxide/foil electrode: add graphene oxide into ultrasonic disperse 1 in 100mL ethanol
Hour, obtain homodisperse graphene oxide solution.In graphene oxide solution, add 0.5g's again
Zn(NO3)2·6H2O, ultrasonic 60 minutes, to obtain uniform solution as electrolyte, with 10cm diameter
Its Parallel Symmetric, as electrode, is placed in electrolyte by aluminium foil, adds the direct current of 80V at the two ends of electrode
Electricity, two die openings are 0.5cm, are energized 20 minutes, can obtain graphene oxide/foil electrode, be washed also
Dry.
(4) manganese dioxide/graphene oxide/foil electrode: using graphene oxide/aluminum electrode in step (3) as
Working electrode, calomel electrode makees reference electrode, and auxiliary electrode made by platinum electrode, at room temperature with 0.5mol/L's
Mn(CH3COO)2Solution, as electrolyte, is 1.25mA/cm in electric current density2Constant current effect under electricity heavy
After long-pending 10 minutes, with deionized water rinsing, obtain manganese dioxide/graphene oxide/foil electrode.
(5) manganese dioxide/graphene/aluminum foil electrode: by step (4) gained manganese dioxide/graphene oxide/aluminium foil
After electrode dries naturally, vacuum bakeout 3 hours.Put it to again in furnace tubing and pass to highly purified nitrogen
Gas, is then warming up to 800 DEG C to stove with the rate of heat addition of 10 DEG C/min, keeps 4 hours.React complete
After, it is cooled to room temperature in an inert atmosphere, obtains manganese dioxide/graphene/aluminum foil electrode.
Embodiment described above only have expressed the several embodiments of the present invention, and it describes more concrete and detailed,
But therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that, for this area
Those of ordinary skill for, without departing from the inventive concept of the premise, it is also possible to make some deformation and
Improving, these broadly fall into protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be with appended
Claim is as the criterion.
Claims (10)
1. a graphene combination electrode, including collector and the electrode activity that is deposited on described collection liquid surface
Material, it is characterised in that described electrode active material includes Graphene and manganese dioxide, described Graphene sinks
Amassing at described collection liquid surface, described manganese dioxide is deposited on described graphenic surface, and wherein, Graphene exists
Weight/mass percentage composition in described electrode active material is 80-90%.
2. graphene combination electrode as claimed in claim 1, it is characterised in that described collector is nickel foil
Or aluminium foil.
3. the preparation method of a graphene combination electrode, it is characterised in that comprise the steps:
Step one: graphite oxide ultrasonic disperse in a solvent is prepared graphene oxide solution, then passes through electrophoresis
Described graphene oxide is deposited to collection liquid surface by sedimentation, obtains graphene oxide/collector electrode；
Step 2: using described graphene oxide/collector electrode as working electrode, coordinates reference electrode and auxiliary
Help electrode, in the electrolyte containing manganese source, deposit on graphene oxide/collector electrode under constant current effect
Manganese dioxide, and manganese dioxide is deposited on described surface of graphene oxide, obtain manganese dioxide/graphene oxide/
Collector electrode；
Step 3: reduce described manganese dioxide/graphene oxide/collector electrode, obtains described Graphene and is combined
Electrode, wherein, Graphene weight/mass percentage composition in described electrode active material is 80-90%.
4. the preparation method of graphene combination electrode as claimed in claim 3, it is characterised in that step one
Described in graphite oxide prepare as steps described below:
Being added to the concentrated sulphuric acid of 0 DEG C by graphite powder, add potassium permanganate, the temperature of system is maintained at 10 DEG C
Hereinafter, at room temperature stirring in water bath 24 hours after stirring 2 hours, then in condition of ice bath downhill reaction system
In be slowly added to deionized water, after 15 minutes, add the deionized water containing hydrogen peroxide, until the face of solution
Complexion changed is glassy yellow, while hot sucking filtration, then washs with the hydrochloric acid that concentration is 10%, sucking filtration, 60 DEG C of vacuum
Drying to obtain graphite oxide.
5. the preparation method of graphene combination electrode as claimed in claim 3, it is characterised in that step one
First middle electrophoretic deposition process comprises the steps:, adds electrolyte in prepared graphene oxide solution,
Ultrasonic disperse, to obtain uniform solution as electrolyte；Then collector is taken as electrode, it is parallel
Symmetrically placed in the electrolytic solution, two electrode spacings are 0.5cm；Be passed through the most between electrodes 40～80V straight
Stream electricity 5～20 minutes, at described electrode surface deposited oxide Graphene, prepares graphene oxide/collector electrode.
6. the preparation method of graphene combination electrode as claimed in claim 5, it is characterised in that described electricity
Solving matter is Mg (NO3)2·6H2O、Fe(NO3)3·9H2O or Zn (NO3)2·6H2O, electrolyte in electrolyte
Concentration is 0.2～5mg/mL.
7. the preparation method of graphene combination electrode as claimed in claim 3, it is characterised in that step 2
In, described reference electrode is calomel electrode；Described auxiliary electrode is platinum electrode；The described electrolyte containing manganese source
Mn (CH for concentration 0.25-0.5mol/L3COO)2Solution；The electric current density of constant current is 1.25mA/cm2。
8. the preparation method of graphene combination electrode as claimed in claim 3, it is characterised in that step 3
Described manganese dioxide/graphene oxide/collector the electrode of middle reduction comprises the steps: the two of step 2 gained
After manganese oxide/graphene oxide/collector electrode dries naturally, vacuum bakeout 1～3 hours, then put it into and add
In hot boiler tube, under atmosphere of inert gases, it is warming up to 500 DEG C～800 DEG C with the rate of heat addition of 10 DEG C/min,
Keep 2～4 hours, after completion of the reaction, continue to be cooled to room temperature in an inert atmosphere, obtain described Graphene
Combination electrode.
9. the preparation method of the graphene combination electrode as according to any one of claim 3-8, its feature exists
In, described collector is nickel foil or aluminium foil.
10. a ultracapacitor, two electrode slices including electrolyte, immersing described electrolyte and being placed in
Barrier film between two electrode slices, each electrode slice includes collector and is positioned at the electrode of described collection liquid surface
Active material, it is characterised in that described electrode active material includes Graphene and manganese dioxide, described graphite
Alkene is deposited on described collection liquid surface, and described manganese dioxide is deposited on described graphenic surface, wherein, graphite
Alkene weight/mass percentage composition in described electrode active material is 80-90%.
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| CN103643274B (en) * | 2013-11-12 | 2016-08-17 | 天津大学 | A kind of method and application thereof preparing graphene oxide layer by being electrodeposited in titanium surface |
| CN103854877A (en) * | 2013-12-23 | 2014-06-11 | 燕山大学 | Self-supporting grapheme-manganese oxide combined electrode material and manufacturing method thereof |
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