CN103035409A - Graphene composite electrode and preparation method and application - Google Patents
Graphene composite electrode and preparation method and application Download PDFInfo
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- CN103035409A CN103035409A CN2011103028927A CN201110302892A CN103035409A CN 103035409 A CN103035409 A CN 103035409A CN 2011103028927 A CN2011103028927 A CN 2011103028927A CN 201110302892 A CN201110302892 A CN 201110302892A CN 103035409 A CN103035409 A CN 103035409A
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- 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 graphene composite electrode which comprises a current collector and electrode active materials arranged on the surface of the current collector, wherein the electrode active materials comprise graphene and manganese dioxide. The graphene is in a stratified structure and is arranged on the surface of the current collector, and the manganese dioxide is arranged on the surface of the graphene in the stratified structure. Mass percentage content of the graphene in the electrode active materials is 80%-90%. In addition, the invention further relates to a preparation method and an application of the graphene composite electrode. Oxidized graphene and the manganese dioxide are deposited on the current collector step by step, adhesion agents are not needed, and therefore equivalent series resistance of the whole electrode is reduced effectively, capacity and pseudocapacitance of an electric double-layer of the graphene and the manganese dioxide are developed simultaneously, and stability and conductivity of the electrode are well improved by addition of the graphene. In addition, through the method of electro-deposition, the electrode materials are directly deposited on an electrode plate, a complex coating process is saved, the process is simple, and time is short.
Description
[technical field]
The present invention relates to the electrode material field of battery or capacitor, relate in particular to a kind of graphene combination electrode and its preparation method and application.
[background technology]
Ultracapacitor is with its high-energy-density, high power density, long-life, to advantages such as environment friendlinesses and receive much concern.Have of crucial importance and wide application prospect at aspects such as the Aero-Space such as the stand-by power supply of solar charger, warning device, household electrical appliance, microcomputer, the igniter of aircraft and science and techniques of defence, become the focus of countries in the world research.
In the research and development process of ultracapacitor, the material with carbon element of high-specific surface area is the desirable electrode material of ultracapacitor, such as active carbon, carbon aerogels, carbon nano-tube and carbon fiber etc.Although the material with carbon element ultracapacitor is preliminary commercial applications because its capacity is smaller, thereby its use and also be subject to a certain extent larger restriction, need to seek new jumbo, reliable and stable electrode material for super capacitor.The electrochemical capacitor that the pseudo capacitance that utilizes metal oxide generation redox reaction and produce carries out stored energy has caused the very big interest of researcher.Wherein, ruthenium-oxide is desirable super capacitor material in the middle of the transition metal oxide, but it is expensive, is difficult to industrialization and uses; There are the narrower shortcoming of operating potential window in nickel oxide and cobalt oxide; And the manganese oxide aboundresources, cheap, have the double grading of electric double layer capacitance and fake capacitance, and the manganese oxide material is pollution-free, available transports in large-scale production, is considered to have the electrode material for super capacitor of potentiality, has caused people's extensive concern.But there is the larger problem of resistance in the manganese oxide electrode material of tradition preparation, has limited its further application.
[summary of the invention]
Based on this, be necessary electrode that provides a kind of resistance less and preparation method thereof.
The invention provides a kind of graphene combination electrode, comprise collector and be positioned at the electrode active material of described collection liquid surface, described electrode active material comprises Graphene and manganese dioxide, described Graphene is positioned at described collection liquid surface, the described Graphene of described manganese dioxide surface, wherein, the quality percentage composition of Graphene in described electrode active material is 80-90%.
In preferred embodiment, described collector is nickel foil or aluminium foil.
A kind of preparation method of graphene combination electrode comprises the steps:
Step 1: graphite oxide ultrasonic dispersion in solvent is prepared graphene oxide solution, by electrodeposition process described graphene oxide is deposited into collection liquid surface again, obtain graphene oxide/collector electrode;
Step 2: with described graphene oxide/collector electrode as work electrode, cooperate reference electrode and auxiliary electrode, in the electrolyte that contains the manganese source, deposit manganese dioxide at graphene oxide/collector electrode under the constant current effect, and manganese dioxide is deposited on described graphene oxide surface, obtains manganese dioxide/graphene oxide/collector electrode;
Step 3: reduce described manganese dioxide/graphene oxide/collector electrode, obtain described graphene combination electrode, the quality percentage composition of Graphene in described electrode active material is 80-90%.
In preferred embodiment, graphite oxide described in the step 1 prepares according to following step:
Graphite powder is added in 0 ℃ the concentrated sulfuric acid, add potassium permanganate, the temperature of system remains on below 10 ℃ again, stirs after 2 hours more at room temperature stirring in water bath 24 hours, then in condition of ice bath downhill reaction system, slowly add deionized water, after 15 minutes, add again the deionized water that contains hydrogen peroxide, until the color of the solution becomes glassy yellow, suction filtration while hot, be that 10% hydrochloric acid washs with concentration again, suction filtration, 60 ℃ of vacuumizes namely obtain graphite oxide.
In preferred embodiment, electrodeposition process comprises the steps: at first in the step 1, adds electrolyte in the graphene oxide solution that makes, and ultrasonic dispersion is to obtain uniform solution as electrolyte; Then get collector as electrode, its Parallel Symmetric is placed in the electrolyte, two electrode spacings are 0.5cm; Between two electrodes, pass into again the direct current 5～20 minutes of 40～80V, at described electrode surface deposition graphene oxide, make graphene oxide/collector electrode.
In preferred embodiment, described electrolyte is Mg (NO
3)
26H
2O, Fe (NO
3)
39H
2O or Zn (NO
3)
26H
2O, electrolytical concentration is 0.2～5mg/mL in the electrolyte.
In preferred embodiment, in the step 2, described reference electrode is calomel electrode; Described auxiliary electrode is platinum electrode; The described electrolyte that contains the manganese source is the Mn (CH of concentration 0.25-0.5mol/L
3COO)
2Solution; The current density of constant current is 1.25mA/cm
2
In preferred embodiment, after reduction described manganese dioxide/graphene oxide/collector electrode comprises the steps: the manganese dioxide/graphene oxide of step 2 gained/collector electrode dried naturally in the step 3, vacuum bakeout 1～3 hour, put it into again in the furnace tubing, under atmosphere of inert gases, be warming up to 500 ℃～800 ℃ with the rate of heat addition of 10 ℃/min, kept 2～4 hours, react complete after, cool to room temperature in inert atmosphere obtains described graphene combination electrode.
In preferred embodiment, described collector is nickel foil or aluminium foil.
Said method is by depositing to step by step graphene oxide and manganese dioxide on the collector, again graphene oxide is reduced, do not need to use binding agent in the preparation process, thereby effectively reduce the equivalent series resistance of whole electrode, bring into play simultaneously capacity and the fake capacitance of Graphene and manganese dioxide electric double layer, the adding of Graphene can well improve stability and the conductivity of electrode.In addition, by the method for electro-deposition, the electrode material Direct precipitation can save complicated coating process on electrode slice, and technique is simple and the time short.Graphene combination electrode of the present invention can be widely used in the fields such as high-power lithium ion battery, ultracapacitor.
A kind of ultracapacitor, comprise electrolyte, two electrode slices and place two barrier films between the electrode slice, described electrode slice comprises collector and is positioned at the electrode active material of described collection liquid surface, it is characterized in that, described electrode active material comprises Graphene and manganese dioxide, and described Graphene is positioned at described collection liquid surface, and described manganese dioxide is positioned at described Graphene surface, wherein, the quality percentage composition of Graphene in described electrode active material is 80-90%.
This ultracapacitor uses above-mentioned graphene combination electrode to make electrode slice, good stability, and conductivity is high.In addition, owing to do not use the higher binding agent of resistance in the preparation process of graphene combination electrode, thus the equivalent series resistance of electrode slice is less, and the power density of ultracapacitor is higher.
[description of drawings]
Fig. 1 is the preparation flow figure of the graphene combination electrode of an execution mode;
Fig. 2 is the charging and discharging curve figure of the graphene combination electrode that makes of embodiment.
[embodiment]
The below mainly is described in further detail graphene combination electrode and its preparation method and application in conjunction with the drawings and the specific embodiments.
The graphene combination electrode of one execution mode comprises collector and is positioned at the electrode active material of collection liquid surface.Electrode active material is the composite material of Graphene and manganese dioxide, and wherein, Graphene is positioned at collection liquid surface with layer structure, and manganese dioxide is positioned at the Graphene surface of layer structure, and the quality percentage composition of Graphene in electrode active material is 80-90%.
Collector can be the metal formings such as nickel foil or aluminium foil.
As shown in Figure 1, the preparation method of the graphene combination electrode of present embodiment comprises the steps:
Step S1: graphite oxide ultrasonic dispersion in solvent is prepared graphene oxide solution, by electrodeposition process graphene oxide is deposited into collection liquid surface again, obtain graphene oxide/collector electrode.
Preferably, graphite oxide in this step prepares in accordance with the following steps: graphite powder is added in 0 ℃ the concentrated sulfuric acid, add again potassium permanganate, the temperature of system remains on below 10 ℃, stirred after 2 hours more at room temperature stirring in water bath 24 hours, then in condition of ice bath downhill reaction system, slowly add deionized water, after 15 minutes, add again the deionized water that contains hydrogen peroxide, until the color of the solution becomes glassy yellow, suction filtration while hot is that 10% hydrochloric acid washs with concentration again, suction filtration, 60 ℃ of vacuumizes namely obtain graphite oxide.Further, preferred 100～500 purpose natural flake graphite powder of graphite powder.
After making graphite oxide, it is joined in the alcohols solvent, such as ethanol, isopropyl alcohol, propyl alcohol etc., ultrasonic dispersion obtained homodisperse graphene oxide solution after 0.5～1 hour; Then in graphene oxide solution, add electrolyte, such as Mg (NO
3)
26H
2O, Mg (SO
4)
27H
2O, Fe (NO
3)
39H
2O or Zn (NO
3)
26H
2O etc., ultrasonic dispersion 15～60 minutes is even to solution, and include electrolytical graphene oxide solution and can be used as electrolyte this moment, and electrolytical concentration is 0.2～5mg/mL in the electrolyte; Get collector as electrode, its Parallel Symmetric is placed in the electrolyte, two electrode spacings are 0.5cm; Between two electrodes, pass into again the direct current 5～20 minutes of 40～80V, at electrode surface deposition graphene oxide, make graphene oxide/collector electrode.
Step S2: with graphene oxide/collector electrode as work electrode, cooperate reference electrode and auxiliary electrode, in the electrolyte that contains the manganese source, deposit manganese dioxide at graphene oxide/collector electrode under the constant current effect, and manganese dioxide is deposited on described graphene oxide surface, obtains manganese dioxide/graphene oxide/collector electrode.
The preferred calomel electrode of reference electrode in this step; The preferred platinum electrode of auxiliary electrode; The electrolyte preferred concentration that contains the manganese source is the Mn (CH of 0.25-0.5mol/L
3COO)
2Solution; The current density of constant current is 1.25mA/cm
2
Step S3: manganese dioxide reduction/graphene oxide/collector electrode obtains graphene combination electrode.
Specifically comprise the steps: after manganese dioxide/graphene oxide/the collector electrode dries naturally of step S2 gained, vacuum bakeout 1～3 hour, put it into again in the furnace tubing, under the high-purity atmosphere of inert gases, be warming up to 500 ℃～800 ℃ with the rate of heat addition of 10 ℃/min, kept 2～4 hours, react complete after, cool to room temperature in inert atmosphere obtains manganese dioxide/Graphene/collector electrode, i.e. graphene combination electrode of the present invention.
The present invention is by depositing to step by step graphene oxide and manganese dioxide on the collector, again graphene oxide is reduced, do not need to use binding agent in the preparation process, thereby effectively reduce the equivalent series resistance of whole electrode, bring into play simultaneously capacity and the fake capacitance of Graphene and manganese dioxide electric double layer, the adding of Graphene can well improve stability and the conductivity of electrode.In addition, by the method for electro-deposition, the electrode material Direct precipitation can save complicated coating process on electrode slice, and technique is simple and the time short.Graphene combination electrode of the present invention can be widely used in the fields such as high-power lithium ion battery, ultracapacitor.
Below be the 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: several 100 orders of order.
(2) graphite oxide: the 100 order natural flake graphite powder of 0.5g are joined in 0 ℃, the concentrated sulfuric acid of 11.5mL, add again 1.5g potassium permanganate, the temperature of mixture remains on below 10 ℃, stirred 2 hours, then after room-temperature water bath stirs 24 hours, under condition of ice bath, slowly add the 46mL deionized water.After 15 minutes, add 140mL deionized water (wherein contain 2.5mL concentration be 30% hydrogen peroxide), the mixture color becomes glassy yellow afterwards, suction filtration again, again with 250mL concentration be that 10% hydrochloric acid washs, suction filtration, 60 ℃ of vacuumize 48 hours, namely obtain graphite oxide.
(3) graphene oxide/nickel electrode: the graphene oxide that step (2) is made was added in the 500mL ethanol ultrasonic dispersion 0.5 hour, prepared homodisperse graphene oxide solution; Mg (the NO that adds again 0.5g in the graphene oxide solution
3)
26H
2O, ultrasonic 15 minutes, to obtain uniform solution as electrolyte; , as electrode its Parallel Symmetric is placed in the electrolyte with the nickel foil of 5cm diameter, adds the direct current of 40V at the two ends of electrode, two die openings are 0.5cm, switch on 5 minutes, can get graphene oxide/nickel electrode, with its washing and dry.
(4) manganese dioxide/graphene oxide/nickel electrode: as work electrode, calomel electrode is made reference electrode with graphene oxide/nickel electrode in the step (3), and platinum electrode is made auxiliary electrode, at room temperature with the Mn (CH of 0.25mol/L
3COO)
2Solution is 1.25mA/cm as electrolyte in current density
2The constant current effect under electro-deposition after 5 minutes, use deionized water rinsing, obtain manganese dioxide/graphene oxide/nickel electrode.
(5) manganese dioxide/graphene/nickel electrode: after step (4) gained manganese dioxide/graphene oxide/nickel electrode is dried naturally, vacuum bakeout 1 hour.Put it to again in the furnace tubing and pass to highly purified nitrogen, then stove is warming up to 500 ℃ with the rate of heat addition of 10 ℃/min, kept 2 hours.React complete after, cool to room temperature in inert atmosphere obtains manganese dioxide/graphene/nickel electrode.
The graphene combination electrode of gained is carried out roll extrusion with roller mill, and the pole piece of roll-in breaks into the circular pole piece that diameter is 10mm with card punch, accurately weighs.Then in glove box with pole piece, barrier film and electrolyte are assembled into ultracapacitor according to cell making process, its septation is celgard 2000, electrolyte is the ammonium sulfate of 2mol/L.Leave standstill after assembling is finished and carried out the constant current charge-discharge test in one day, wherein voltage range is 0-1V, and electric current is that 0.15A/g carries out constant current charge-discharge.The result can find out from charging and discharging curve that as shown in Figure 2 the charging and discharging curve shape that the charging and discharging curve of sample under the 0.15A/g current density is near the mark has good charge-discharge performance, and the voltage-drop data from figure is according to formula
Can calculate equivalent series resistance is 0.76 Ω, and resistance is less comparatively speaking, because power density and resistance are inversely proportional to, then power density is higher.
Embodiment 2
Technological process is as follows:
Natural flake graphite → graphite oxide → graphene oxide/aluminium electrode → manganese dioxide/graphene oxide/aluminium electrode → manganese dioxide/graphene/aluminum electrode
(1) natural flake graphite: several 500 orders of order.
(2) graphite oxide: the 500 order natural flake graphite powder of 0.5g are added in 0 ℃, the concentrated sulfuric acid of 11.5mL, add again 1.5g potassium permanganate, the temperature of mixture remains on below 10 ℃, stirred 2 hours, then after room-temperature water bath stirs 24 hours, under condition of ice bath, slowly add the 46mL deionized water.After 15 minutes, add 140mL deionized water (wherein contain 2.5mL concentration be 30% hydrogen peroxide), the mixture color becomes glassy yellow afterwards, suction filtration again, again with 250mL concentration be that 10% hydrochloric acid washs, suction filtration, 60 ℃ of vacuumize 48 hours, namely obtain graphite oxide.
(3) graphene oxide/aluminium electrode: graphene oxide was added in the 2500mL ethanol ultrasonic dispersion 1 hour, obtain homodisperse graphene oxide solution.Fe (the NO that adds again 0.5g in the graphene oxide solution
3)
39H
2O, ultrasonic 60 minutes, to obtain uniform solution as electrolyte,, as electrode its Parallel Symmetric is placed in the electrolyte with the aluminium foil of 10cm diameter, adds the direct current of 80V at the two ends of electrode, two die openings are 0.5cm, switched on 20 minutes, and can get graphene oxide/aluminium electrode, with its washing and dry.
(4) manganese dioxide/graphene oxide/aluminium electrode: with graphene oxide/the aluminium electrode is as work electrode in the step (3), calomel electrode is made reference electrode, and platinum electrode is made auxiliary electrode, at room temperature with the Mn (CH of 0.5mol/L
3COO)
2Solution is 1.25mA/cm as electrolyte in current density
2The constant current effect under electro-deposition after 10 minutes, use deionized water rinsing, obtain manganese dioxide/graphene oxide/aluminium electrode.
(5) manganese dioxide/graphene/aluminum electrode: after step (4) gained manganese dioxide/graphene oxide/the aluminium electrode dries naturally, vacuum bakeout 1 hour.Put it to again in the furnace tubing and pass to highly purified nitrogen, then stove is warming up to 800 ℃ with the rate of heat addition of 10 ℃/min, kept 2 hours.React complete after, cool to room temperature in 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/aluminium electrode → manganese dioxide/graphene/aluminum foil electrode
(1) natural flake graphite: several 500 orders of order.
(2) graphite oxide: the 500 order natural flake graphite powder of 0.5g are added in 0 ℃, the concentrated sulfuric acid of 11.5mL, add again 1.5g potassium permanganate, the temperature of mixture remains on below 10 ℃, stirred 2 hours, then after room-temperature water bath stirs 24 hours, under condition of ice bath, slowly add the 46mL deionized water.After 15 minutes, add 140mL deionized water (wherein contain 2.5mL concentration be 30% hydrogen peroxide), the mixture color becomes glassy yellow afterwards, suction filtration again, again with 250mL concentration be that 10% hydrochloric acid washs, suction filtration, 60 ℃ of vacuumize 48 hours, namely obtain graphite oxide.
(3) graphene oxide/foil electrode: graphene oxide was added in the 100mL ethanol ultrasonic dispersion 1 hour, obtain homodisperse graphene oxide solution.Zn (the NO that adds again 0.5g in the graphene oxide solution
3)
26H
2O, ultrasonic 60 minutes, to obtain uniform solution as electrolyte,, as electrode its Parallel Symmetric is placed in the electrolyte with the aluminium foil of 10cm diameter, adds the direct current of 80V at the two ends of electrode, two die openings are 0.5cm, switched on 20 minutes, and can get graphene oxide/foil electrode, with its washing and dry.
(4) manganese dioxide/graphene oxide/foil electrode: with graphene oxide/the aluminium electrode is as work electrode in the step (3), calomel electrode is made reference electrode, and platinum electrode is made auxiliary electrode, at room temperature with the Mn (CH of 0.5mol/L
3COO)
2Solution is 1.25mA/cm as electrolyte in current density
2The constant current effect under electro-deposition after 10 minutes, use deionized water rinsing, obtain manganese dioxide/graphene oxide/foil electrode.
(5) manganese dioxide/graphene/aluminum foil electrode: after step (4) gained manganese dioxide/graphene oxide/foil electrode dries naturally, vacuum bakeout 3 hours.Put it to again in the furnace tubing and pass to highly purified nitrogen, then stove is warming up to 800 ℃ with the rate of heat addition of 10 ℃/min, kept 4 hours.React complete after, cool to room temperature in inert atmosphere obtains manganese dioxide/graphene/aluminum foil electrode.
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (10)
1. graphene combination electrode, comprise collector and be positioned at the electrode active material of described collection liquid surface, it is characterized in that, described electrode active material comprises Graphene and manganese dioxide, described Graphene is positioned at described collection liquid surface, described manganese dioxide is positioned at described Graphene surface, and wherein, the quality percentage composition of Graphene in described electrode active material is 80-90%.
2. graphene combination electrode as claimed in claim 1 is characterized in that, described collector is nickel foil or aluminium foil.
3. the preparation method of a graphene combination electrode is characterized in that, comprises the steps:
Step 1: graphite oxide ultrasonic dispersion in solvent is prepared graphene oxide solution, by electrodeposition process described graphene oxide is deposited into collection liquid surface again, obtain graphene oxide/collector electrode;
Step 2: with described graphene oxide/collector electrode as work electrode, cooperate reference electrode and auxiliary electrode, in the electrolyte that contains the manganese source, deposit manganese dioxide at graphene oxide/collector electrode under the constant current effect, and manganese dioxide is deposited on described graphene oxide surface, obtains manganese dioxide/graphene oxide/collector electrode;
Step 3: reduce described manganese dioxide/graphene oxide/collector electrode, obtain described graphene combination electrode, wherein, the quality percentage composition of Graphene in described electrode active material is 80-90%.
4. the preparation method of graphene combination electrode as claimed in claim 3 is characterized in that, graphite oxide described in the step 1 prepares according to following step:
Graphite powder is added in 0 ℃ the concentrated sulfuric acid, add potassium permanganate, the temperature of system remains on below 10 ℃ again, stirs after 2 hours at room temperature stirring in water bath 24 hours, then in condition of ice bath downhill reaction system, slowly add deionized water, after 15 minutes, add again the deionized water that contains hydrogen peroxide, until the color of the solution becomes glassy yellow, suction filtration while hot, be that 10% hydrochloric acid washs with concentration again, suction filtration, 60 ℃ of vacuumizes namely obtain graphite oxide.
5. the preparation method of graphene combination electrode as claimed in claim 3, it is characterized in that electrodeposition process comprises the steps: at first in the step 1, in the graphene oxide solution that makes, add electrolyte, ultrasonic dispersion is to obtain uniform solution as electrolyte; Then get collector as electrode, its Parallel Symmetric is placed in the electrolyte, two electrode spacings are 0.5cm; Between two electrodes, pass into again the direct current 5～20 minutes of 40～80V, at described electrode surface deposition graphene oxide, make graphene oxide/collector electrode.
6. the preparation method of graphene combination electrode as claimed in claim 5 is characterized in that, described electrolyte is Mg (NO
3)
26H
2O, Fe (NO
3)
39H
2O or Zn (NO
3)
26H
2O, electrolytical concentration is 0.2～5mg/mL in the electrolyte.
7. the preparation method of graphene combination electrode as claimed in claim 3 is characterized in that, in the step 2, described reference electrode is calomel electrode; Described auxiliary electrode is platinum electrode; The described electrolyte that contains the manganese source is the Mn (CH of concentration 0.25-0.5mol/L
3COO)
2Solution; The current density of constant current is 1.25mA/cm
2
8. the preparation method of graphene combination electrode as claimed in claim 3, it is characterized in that, after reduction described manganese dioxide/graphene oxide/collector electrode comprises the steps: the manganese dioxide/graphene oxide of step 2 gained/collector electrode dried naturally in the step 3, vacuum bakeout 1～3 hour, put it into again in the furnace tubing, under atmosphere of inert gases, the rate of heat addition with 10 ℃/min is warming up to 500 ℃～800 ℃, kept 2～4 hours, react complete after, continuation is cool to room temperature in inert atmosphere, obtains described graphene combination electrode.
9. such as the preparation method of each described graphene combination electrode among the claim 3-8, it is characterized in that described collector is nickel foil or aluminium foil.
10. ultracapacitor, comprise electrolyte, immerse two electrode slices of described electrolyte and place two barrier films between the electrode slice, each electrode slice comprises collector and is positioned at the electrode active material of described collection liquid surface, it is characterized in that, described electrode active material comprises Graphene and manganese dioxide, described Graphene is positioned at described collection liquid surface, described manganese dioxide is positioned at described Graphene surface, wherein, the quality percentage composition of Graphene in described electrode active material is 80-90%.
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