CN103632853A - Preparation method of graphene composite electrode and capacitor - Google Patents
Preparation method of graphene composite electrode and capacitor Download PDFInfo
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- CN103632853A CN103632853A CN201210305502.6A CN201210305502A CN103632853A CN 103632853 A CN103632853 A CN 103632853A CN 201210305502 A CN201210305502 A CN 201210305502A CN 103632853 A CN103632853 A CN 103632853A
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Abstract
The invention provides a preparation method of a graphene composite electrode. The method comprises the steps that a current collector is placed in a reaction chamber of a chemical vapor deposition device; the current collector is heated to 500 DEG C to 1300 DEG C; a gaseous carbon source is put into the reaction chamber; reaction is carried out for 1 minute to 300 minutes, and then cooling is carried out; the dried current collector is used as a working electrode, wherein a graphene layer is formed on the surface of the current collector; the current collector is placed into an electrolyte with a manganese source and electrolytes; electrolysis is carried out for 30S to 90S, and the is stopped for 1 minute to 2 minutes; repeated electrolysis is carried out for 20 to 30 times; a manganese dioxide-graphene composite material layer is formed on the surface of the current collector; the current collector is heated to 600 DEG C to 800 DEG C, and the heating keeps for 1 hour to 4 hours, wherein the manganese dioxide-graphene composite material layer is formed on the surface of the current collector; and after cooling, the graphene composite electrode is acquired. According to the preparation method of the graphene composite electrode, the cycle performance of a capacitor which uses the graphene composite electrode is improved. The invention further provides a preparation method of the capacitor.
Description
Technical field
The present invention relates to a kind of preparation method of graphene combination electrode and the preparation method of capacitor.
Background technology
Electrochemical capacitor, as a kind of novel energy-storing device, due to advantages such as its charge-discharge velocity are fast, power density is high, have extended cycle life, is the another energy storage device that has application potential and exploitation value after lithium ion battery.Yet energy density is lower, be a key factor of the development of restriction ultracapacitor and application, the energy density how exploration improves ultracapacitor is the emphasis of current this area research.
Manganese dioxide is as a kind of electrode material of electrochemical capacitor, due to it have excellent chemical property be employed with capacitor in.The more little energy storage efficiency that is more conducive to improve it of manganese dioxide size, therefore nanoscale manganese dioxide is the focus of studying at present, but because nano effect causes manganese dioxide particle, be very easy to reunite, cause using manganese dioxide as electrode material, to make the cycle performance variation of the capacitor of graphene combination electrode.
Summary of the invention
Based on this, be necessary to provide a kind of preparation method of graphene combination electrode and the preparation method of capacitor to improve the cycle performance of the capacitor that uses this graphene combination electrode.
A kind of preparation method of graphene combination electrode, comprise the steps: collector to be positioned over the reative cell of chemical vapor depsotition equipment, under protective gas atmosphere, described collector is heated to 500 ℃ ~ 1300 ℃, then in described reative cell, pass into gaseous carbon source and protective gas, react cooling after 1 minute ~ 300 minutes, on the surface of described collector, form graphene layer;
The collector that described surface is formed with to graphene layer soaks after 2 hours washing to neutral and dry in acid solution;
The collector that dried described surface is formed with to graphene layer is as work electrode, with to electrode, reference electrode composition three-electrode system is placed in and contains manganese source and electrolyte solution, controlling described work electrode is-0.35V ~-0.25V with respect to the electrode potential of described reference electrode, after electrolysis 30S ~ 90S, stop 1 minute ~ 2 minutes, repeat electrolysis 20 times ~ 30 times, at described collection liquid surface, form manganese dioxide-graphene composite material layer; And
Under protective gas atmosphere, the collector that described surface is formed with to manganese dioxide-graphene composite material layer is warming up to 600 ℃ ~ 800 ℃, and keeps 1 hour ~ 4 hours, obtains graphene combination electrode after cooling.
In an embodiment, described gaseous carbon source is selected from least one in methane, ethane, ethene and acetylene therein.
In an embodiment, described collector is Copper Foil or nickel foil therein.
In an embodiment, described protective gas is at least one being selected from nitrogen and argon gas therein.
In an embodiment, described acid solution is sulfuric acid solution or salpeter solution therein.
In an embodiment, described manganese source is selected from least one in manganese acetate and manganese carbonate therein, and in described electrolyte, the concentration in manganese source is 0.05mol/L ~ 0.1mol/L.
In an embodiment, described electrolyte is selected from least one in sodium sulphate and potassium sulfate therein, and in described electrolyte, electrolytical concentration is 0.1mol/L ~ 0.2mol/L.
Therein in an embodiment, the collector that described surface is formed with to manganese dioxide-graphene composite material layer is warming up to 600 ℃ ~ 800 ℃ with the heating rate of 15 ℃/min ~ 50 ℃/min.
A preparation method for capacitor, comprises the following steps:
Graphene combination electrode is provided, and described graphene combination electrode is prepared by the preparation method of the graphene combination electrode described in claim 1 to 8 any one;
Described graphene combination electrode is carried out roll-in, is dried and cuts processing and make electrode slice; And
By being soaked in electrolyte after described electrode slice and barrier film assembling, obtain capacitor.
In an embodiment, described electrolyte is that concentration is the sulfuric acid of 1mol/L ~ 2mol/L therein.
The preparation method of above-mentioned graphene combination electrode and the preparation method of capacitor, by preparing graphene through chemical vapor deposition layer, and prepare manganese dioxide-graphene composite material layer by electrochemical method, can reduce the internal resistance that contacts between manganese dioxide-graphene composite material and collector, by high-temperature process, make the crystal formation of the manganese dioxide in manganese dioxide-graphene composite material can be converted into β type from γ type, thereby make to use the capacitor of this graphene combination electrode to there is excellent cycle performance.
Accompanying drawing explanation
Fig. 1 is preparation method's the flow chart of the graphene combination electrode of an execution mode;
Fig. 2 is preparation method's the flow chart of the capacitor of an execution mode.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.A lot of details have been set forth in the following description so that fully understand the present invention.But the present invention can implement to be much different from alternate manner described here, and those skilled in the art can do similar improvement without prejudice to intension of the present invention in the situation that, so the present invention is not subject to the restriction of following public concrete enforcement.
Refer to Fig. 1, the preparation method of the graphene combination electrode of an execution mode, comprises the steps:
Step S110, collector is positioned over to the reative cell of chemical vapor depsotition equipment; under protective gas atmosphere; it is 500 ℃ ~ 1300 ℃ that heating collector makes the temperature of collector; then in reative cell, pass into gaseous carbon source and protective gas; react cooling after 1 minute ~ 300 minutes, on the surface of collector, form graphene layer.
Preferably, collector is Copper Foil or nickel foil.
Preferably, collector was first used successively deionized water, ethanol and acetone ultrasonic cleaning post-drying before being positioned over the reative cell of chemical vapor depsotition equipment.
Preferably, chemical vapor depsotition equipment is that hot-filament chemical vapor deposition equipment, radio frequency plasma strengthen chemical vapor depsotition equipment, microwave plasma enhanced chemical vapor depsotition equipment, laser chemical vapor deposition equipment, low pressure chemical vapor deposition equipment or aumospheric pressure cvd equipment.
Preferably, collector is positioned over after reative cell, in reative cell, passes into protective gas, adopt mechanical pump, lobe pump and molecular pump are evacuated to 10 by reative cell step by step
-3below Pa, and keep 1 ~ 30 minute, stop afterwards logical protective gas, closure molecule pump, starts collector to heat.
Preferably, protective gas is selected from least one in nitrogen and argon gas.
Preferably, gaseous carbon source is selected from least one in methane, ethane, ethene and acetylene.
Preferably, the flow of gaseous carbon source is 50ml/min ~ 100ml/min, and the flow of protective gas is 100ml/min ~ 200ml/min.
Step S120, the collector that surface is formed with to graphene layer soak after 2 hours washing to neutral and dry in acid solution.
Preferably, acid solution is sulfuric acid solution or salpeter solution.
Preferably, the concentration of acid solution is 1mol/L ~ 3mol/L.
Preferably, be dried in the vacuum drying oven of 60 ℃ and carry out, the dry time is 10 hours.
Step S130, the collector that dried surface is formed with to graphene layer form three-electrode system as work electrode and are placed in and contain manganese source and electrolyte solution, control work electrode with respect to the electrode potential of reference electrode is-0.35V ~-0.25V, after electrolysis 30S ~ 90S, stop 1 minute ~ 2 minutes, repeat electrolysis 20 times ~ 30 times, at collection liquid surface, form manganese dioxide-graphene composite material layer.
Preferably, in three-electrode system is platinum to electrode, and reference electrode is Ag/AgCl.
Preferably, manganese source is at least one being selected from manganese acetate and manganese carbonate, and in electrolyte, the concentration in manganese source is 0.05mol/L ~ 0.1mol/L.
Preferably, electrolyte is selected from least one in sodium sulphate and potassium sulfate, and in electrolyte, electrolytical concentration is 0.1mol/L ~ 0.2mol/L.
Step S140, under protective gas atmosphere, the collector that surface is formed with to manganese dioxide-graphene composite material layer is warming up to 600 ℃ ~ 800 ℃, and keeps 1 hour ~ 4 hours, obtains graphene combination electrode after cooling.
Preferably, the atmosphere that the collector that first surface is formed with to manganese dioxide-graphene composite material layer is positioned over protective gas is warming up to 600 ℃ ~ 800 ℃ again after lower 30 minutes.
Preferably, protective gas is selected from least one in nitrogen and argon gas.
Preferably, the flow velocity of protective gas is 400ml/min.
Preferably, the collector that surface is formed with to manganese dioxide-graphene composite material layer is warming up to 600 ℃ ~ 800 ℃ with the heating rate of 15 ℃/min ~ 50 ℃/min.
Preferably, under protective gas atmosphere, naturally cool to room temperature.
The preparation method of above-mentioned manganese dioxide-graphene composite material, technique is comparatively simple, simple to operate; By preparing graphene through chemical vapor deposition layer, and prepare manganese dioxide-graphene composite material layer by electrochemical method, can reduce the internal resistance that contacts between manganese dioxide-graphene composite material and collector, by high-temperature process, make the crystal formation of the manganese dioxide in manganese dioxide-graphene composite material can be converted into β type from γ type, thereby the capacitor of this graphene combination electrode of use making have excellent stored energy capacitance and cycle performance.
Refer to Fig. 2, the preparation method of the capacitor of an execution mode, comprises the steps:
Step S210, provide graphene combination electrode.
Graphene combination electrode is prepared by the preparation method of above-mentioned graphene combination electrode.
Step S220, graphene combination electrode is carried out to roll-in, dry and cut to process and make electrode slice.
Step S230, by being soaked in electrolyte after the assembling of electrode slice and barrier film, obtain capacitor.
In present embodiment, electrolyte is that concentration is the sulfuric acid of 1mol/L ~ 2mol/L.
In present embodiment, diaphragm clip is held in stacked composition battery core between two electrode slices, then uses capacitor casing sealed electrical core, finally by the liquid injection port being arranged in capacitor casing, injects electrolyte, and sealing liquid injection port can obtain capacitor.
The preparation method of above-mentioned capacitor is comparatively simple, by preparing graphene through chemical vapor deposition layer, and prepare manganese dioxide-graphene composite material layer by electrochemical method, can reduce the internal resistance that contacts between manganese dioxide-graphene composite material and collector, by high-temperature process, make the crystal formation of the manganese dioxide in manganese dioxide-graphene composite material can be converted into β type from γ type, thereby the capacitor of this graphene combination electrode of use making have excellent stored energy capacitance and cycle performance.
Below in conjunction with specific embodiment, further illustrate.
Embodiment 1
(1), by deionized water, ethanol, acetone ultrasonic cleaning post-drying for collector;
(2), collector is put into reative cell, is filled with nitrogen, and adopts mechanical pump, lobe pump and molecular pump are evacuated to 10 by reative cell step by step
-3below Pa, and keep, after 30 minutes, stopping filling nitrogen, air to close closes molecular pump, starts heating;
(3), when collector temperature reaches 900 ℃, start to reative cell be filled with methane (flow: 100ml/min) and nitrogen (flow: mist 200ml/min), keep temperature-resistant, start to generate Graphene;
(4), the Graphene with collector obtaining in (3) be placed in to 1mol/L salpeter solution soak 2 hours, with deionized water graphite water alkene, to neutral, be placed in 60 ℃ of vacuum drying ovens dry 10 hours; And then using this with the low Graphene of lining as work electrode, be placed in the aqueous electrolyte of 0.05mol/L manganese acetate and 0.1mol/L sodium sulphate, platinum is as to electrode, Ag/AgCl is as reference electrode, apply-0.3V voltage, continues 60 seconds, stops 2 minutes; Apply again-0.3V voltage, continues 60 seconds, stops 2 minutes, and circulation continuous 20 times, finally obtains manganese dioxide-graphene composite material at collection liquid surface.
(5), the manganese dioxide-graphene composite material with collector obtaining in (4) is placed in to argon gas (flow velocity: 400ml/min) under atmosphere; after 30 minutes; with the heating rates of 50 ℃/min by manganese dioxide/temperature of graphene composite material rises to 700 ℃; and keep 1 hour; finally at argon gas (flow velocity: be naturally down to room temperature under protection 400ml/min), obtain graphene combination electrode.
Embodiment 2
(1), by deionized water, ethanol, acetone ultrasonic cleaning post-drying for collector;
(2), collector is put into reative cell, is filled with nitrogen, and adopts mechanical pump, lobe pump and molecular pump are evacuated to 10 by reative cell step by step
-3below Pa, and keep, after 30 minutes, stopping filling nitrogen, air to close closes molecular pump, starts heating;
(3), when collector temperature reaches 1000 ℃, start to reative cell be filled with acetylene (flow: 100ml/min) and nitrogen (flow: mist 150ml/min), keep temperature-resistant, start to generate Graphene;
(4), the Graphene with collector obtaining in (3) be placed in to 1mol/L sulfuric acid solution soak 2 hours, with deionized water graphite water alkene, to neutral, be placed in 60 ℃ of vacuum drying ovens dry 10 hours; And then using this Graphene with collector as work electrode, and being placed in the aqueous electrolyte of 0.1mol/L manganese acetate and 0.2mol/L sodium sulphate, platinum is as to electrode, Ag/AgCl is as reference electrode, apply-0.35V voltage, continues 30 seconds, stops 1 minute; Apply again-0.35V voltage, continues 30 seconds, stops 1 minute, and circulation continuous 20 times finally obtains manganese dioxide-graphene composite material on collector.
(5), the manganese dioxide-graphene composite material with collector obtaining in (4) is placed in to argon gas (flow velocity: 400ml/min) under atmosphere; after 30 minutes; with the heating rates of 40 ℃/min by manganese dioxide/temperature of graphene composite material rises to 800 ℃; and keep 1 hour; finally at argon gas (flow velocity: be naturally down to room temperature under protection 400ml/min), obtain graphene combination electrode.
Embodiment 3
(1), by deionized water, ethanol, acetone ultrasonic cleaning post-drying for collector;
(2), collector is put into reative cell, is filled with nitrogen, and adopts mechanical pump, lobe pump and molecular pump are evacuated to 10 by reative cell step by step
-3below Pa, and keep, after 20 minutes, stopping filling nitrogen, air to close closes molecular pump, starts heating;
(3), when collector temperature reaches 800 ℃, start to reative cell be filled with ethene (flow: 50ml/min) and nitrogen (flow: mist 150ml/min), keep temperature-resistant, start to generate Graphene;
(4), the Graphene with collector obtaining in (3) be placed in to 1mol/L salpeter solution soak 2 hours, with deionized water graphite water alkene, to neutral, be placed in 60 ℃ of vacuum drying ovens dry 10 hours; And then using this Graphene with collector as work electrode, and being placed in the aqueous electrolyte of 0.05mol/L manganese acetate and 0.15mol/L sodium sulphate, platinum is as to electrode, Ag/AgCl is as reference electrode, apply-0.25V voltage, continues 90 seconds, stops 2 minutes; Apply again-0.25V voltage, continues 90 seconds, stops 2 minutes, and circulation continuous 20 times finally obtains manganese dioxide-graphene composite material on collector.
(5), the manganese dioxide-graphene composite material with collector obtaining in (4) is placed in to argon gas (flow velocity: 400ml/min) under atmosphere; after 30 minutes; with the heating rates of 20 ℃/min by manganese dioxide/temperature of graphene composite material rises to 750 ℃; and keep 1 hour; finally at argon gas (flow velocity: be naturally down to room temperature under protection 400ml/min), obtain graphene combination electrode.
Embodiment 4
(1), by deionized water, ethanol, acetone ultrasonic cleaning post-drying for collector;
(2), collector is put into reative cell, is filled with nitrogen, and adopts mechanical pump, lobe pump and molecular pump are evacuated to 10 by reative cell step by step
-3below Pa, and keep, after 30 minutes, stopping filling nitrogen, air to close closes molecular pump, starts heating;
(3), when collector temperature reaches 900 ℃, start to reative cell be filled with methane (flow: 100ml/min) and nitrogen (flow: mist 100ml/min), keep temperature-resistant, start to generate Graphene;
(4), the Graphene with collector obtaining in (3) be placed in to 1mol/L sulfuric acid solution soak 2 hours, with deionized water graphite water alkene, to neutral, be placed in 60 ℃ of vacuum drying ovens dry 10 hours; And then using this Graphene with collector as work electrode, and being placed in the aqueous electrolyte of 0.05mol/L manganese acetate and 0.1mol/L sodium sulphate, platinum is as to electrode, Ag/AgCl is as reference electrode, apply-0.35V voltage, continues 30 seconds, stops 2 minutes; Apply again-0.35V voltage, continues 30 seconds, stops 2 minutes, and circulation continuous 30 times finally obtains manganese dioxide-graphene composite material on collector.
(5), the manganese dioxide-graphene composite material with collector obtaining in (4) is placed in to argon gas (flow velocity: 400ml/min) under atmosphere; after 30 minutes; with the heating rates of 15 ℃/min by manganese dioxide/temperature of graphene composite material rises to 600 ℃; and keep 1 hour; finally at argon gas (flow velocity: be naturally down to room temperature under protection 400ml/min), obtain graphene combination electrode.
Embodiment 5
(1), the graphene combination electrode of embodiment 1 preparation is carried out to roll-in, is dried and cuts processing and make electrode slice.
(2) electrode slice that the electrode slice, (1) being obtained, barrier film, (1) obtain in order stack of laminations is dressed up battery core, use again battery housing seal battery core, toward being arranged on liquid injection port on battery container toward the sulfuric acid that injects 2mol/L in battery container, sealing liquid injection port, obtains capacitor subsequently.
Embodiment 6
(1), the graphene combination electrode of embodiment 2 preparations is carried out to roll-in, is dried and cuts processing and make electrode slice.
(2) electrode slice that the electrode slice, (1) being obtained, barrier film, (1) obtain in order stack of laminations is dressed up battery core, use again battery housing seal battery core, toward being arranged on liquid injection port on battery container toward the sulfuric acid that injects 2mol/L in battery container, sealing liquid injection port, obtains capacitor subsequently.
Embodiment 7
(1), the graphene combination electrode of embodiment 3 preparations is carried out to roll-in, is dried and cuts processing and make electrode slice.
(2) electrode slice that the electrode slice, (1) being obtained, barrier film, (1) obtain in order stack of laminations is dressed up battery core, use again battery housing seal battery core, toward being arranged on liquid injection port on battery container toward the sulfuric acid that injects 2mol/L in battery container, sealing liquid injection port, obtains capacitor subsequently.
Embodiment 8
(1), the graphene combination electrode of embodiment 4 preparations is carried out to roll-in, is dried and cuts processing and make electrode slice.
(2) electrode slice that the electrode slice, (1) being obtained, barrier film, (1) obtain in order stack of laminations is dressed up battery core, use again battery housing seal battery core, toward being arranged on liquid injection port on battery container toward the sulfuric acid that injects 2mol/L in battery container, sealing liquid injection port, obtains capacitor subsequently.
Refer to table 1, the capacitor that table 1 is depicted as embodiment 5 ~ 8 preparations is the equivalent resistance that under 0.8V, test obtains at voltage window.Packaged capacitor is carried out to ac impedance measurement with IM6e electrochemical workstation, and frequency range is 10KHZ-10mHZ, and direct voltage is 0V, and direct current is 1mA, and interchange response excursion is 5mv.
Table 1
| Equivalent resistance (milliohm) | |
| Embodiment 5 | 1.2 |
| Embodiment 6 | 0.8 |
| Embodiment 7 | 1.1 |
| Embodiment 8 | 1.2 |
As can be seen from Table 1, use the equivalent internal resistance of capacitor of graphene combination electrode prepared by method provided by the invention lower.
Refer to table 2, the capacitor that table 2 is depicted as embodiment 5 ~ 8 preparations discharges and recharges the test data of the specific capacity obtaining under the current density of 0.5A/g.
Table 2
As can be seen from Table 2, graphene combination electrode prepared by the present invention specific capacity under the current density of 0.5A/g is up to 578F/g, and the conservation rate of the specific capacity after 1000 times of circulating is more than 90%, is up to 94%.
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 the scope of the claims of the present invention.It 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. a preparation method for graphene combination electrode, is characterized in that, comprises the steps:
Collector is positioned over to the reative cell of chemical vapor depsotition equipment, under protective gas atmosphere, described collector is heated to 500 ℃ ~ 1300 ℃, then in described reative cell, pass into gaseous carbon source and protective gas, react cooling after 1 minute ~ 300 minutes, on the surface of described collector, form graphene layer;
The collector that described surface is formed with to graphene layer soaks after 2 hours washing to neutral and dry in acid solution;
The collector that dried described surface is formed with to graphene layer is as work electrode, with to electrode, reference electrode composition three-electrode system is placed in and contains manganese source and electrolyte solution, controlling described work electrode is-0.35V ~-0.25V with respect to the electrode potential of described reference electrode, after electrolysis 30S ~ 90S, stop 1 minute ~ 2 minutes, repeat electrolysis 20 times ~ 30 times, at described collection liquid surface, form manganese dioxide-graphene composite material layer; And
Under protective gas atmosphere, the collector that described surface is formed with to manganese dioxide-graphene composite material layer is warming up to 600 ℃ ~ 800 ℃, and keeps 1 hour ~ 4 hours, obtains graphene combination electrode after cooling.
2. the preparation method of graphene combination electrode according to claim 1, is characterized in that, described gaseous carbon source is selected from least one in methane, ethane, ethene and acetylene.
3. the preparation method of graphene combination electrode according to claim 1, is characterized in that, described collector is Copper Foil or nickel foil.
4. the preparation method of graphene combination electrode according to claim 1, is characterized in that, described protective gas is at least one being selected from nitrogen and argon gas.
5. the preparation method of graphene combination electrode according to claim 1, is characterized in that, described acid solution is sulfuric acid solution or salpeter solution.
6. the preparation method of graphene combination electrode according to claim 1, is characterized in that, described manganese source is selected from least one in manganese acetate and manganese carbonate, and in described electrolyte, the concentration in manganese source is 0.05mol/L ~ 0.1mol/L.
7. the preparation method of graphene combination electrode according to claim 1, is characterized in that, described electrolyte is selected from least one in sodium sulphate and potassium sulfate, and in described electrolyte, electrolytical concentration is 0.1mol/L ~ 0.2mol/L.
8. the preparation method of graphene combination electrode according to claim 1, is characterized in that, the collector that described surface is formed with to manganese dioxide-graphene composite material layer is warming up to 600 ℃ ~ 800 ℃ with the heating rate of 15 ℃/min ~ 50 ℃/min.
9. a preparation method for capacitor, is characterized in that, comprises the following steps:
Graphene combination electrode is provided, and described graphene combination electrode is prepared by the preparation method of the graphene combination electrode described in claim 1 to 8 any one;
Described graphene combination electrode is carried out roll-in, is dried and cuts processing and make electrode slice; And
By being soaked in electrolyte after described electrode slice and barrier film assembling, obtain capacitor.
10. the preparation method of capacitor according to claim 9, is characterized in that, described electrolyte is that concentration is the sulfuric acid of 1mol/L ~ 2mol/L.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105070524A (en) * | 2015-09-08 | 2015-11-18 | 哈尔滨工业大学 | Preparation method of flocculent manganese dioxide/graphene composite electrode material |
| CN105448531A (en) * | 2015-11-13 | 2016-03-30 | 哈尔滨工业大学 | Method for preparing needle-like manganese dioxide/graphene composite electrode material |
| CN105719852A (en) * | 2016-02-04 | 2016-06-29 | 天津大学 | Preparation method for three-dimensional nano-porous graphene/manganese dioxide composite electrode material |
| CN107742746A (en) * | 2017-09-18 | 2018-02-27 | 深圳市烯谷能源控股有限公司 | A kind of manufacture method of composite graphite alkene lithium ion battery and composite graphite alkene electrode |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105070524A (en) * | 2015-09-08 | 2015-11-18 | 哈尔滨工业大学 | Preparation method of flocculent manganese dioxide/graphene composite electrode material |
| CN105448531A (en) * | 2015-11-13 | 2016-03-30 | 哈尔滨工业大学 | Method for preparing needle-like manganese dioxide/graphene composite electrode material |
| CN105719852A (en) * | 2016-02-04 | 2016-06-29 | 天津大学 | Preparation method for three-dimensional nano-porous graphene/manganese dioxide composite electrode material |
| CN107742746A (en) * | 2017-09-18 | 2018-02-27 | 深圳市烯谷能源控股有限公司 | A kind of manufacture method of composite graphite alkene lithium ion battery and composite graphite alkene electrode |
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