CN104916459B - A kind of preparation method of the highly oriented graphene film of ultracapacitor - Google Patents
A kind of preparation method of the highly oriented graphene film of ultracapacitor Download PDFInfo
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- CN104916459B CN104916459B CN201510366344.9A CN201510366344A CN104916459B CN 104916459 B CN104916459 B CN 104916459B CN 201510366344 A CN201510366344 A CN 201510366344A CN 104916459 B CN104916459 B CN 104916459B
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Abstract
A kind of preparation method the present invention relates to ultracapacitor with highly oriented graphene film, including：Graphite oxide is washed, then added in deionized water, suspension is obtained, ultrasound, centrifuge washing, then by supernatant rotary evaporation, obtains graphite oxide slurry；Graphite oxide slurry is scratched in copper foil surface, graphite oxide film is made, is then irradiated reduction treatment, produces.The present invention uses knife coating film forming, and reduction process uses photoreduction, and process is simple, is easy to industrialized production；The highly oriented graphene film of ultracapacitor prepared by the present invention has preferable pliability, and specific capacitance is high, has wide application in the flexible energy storage field such as flexible super capacitor, lithium ion battery.
Description
Technical field
The invention belongs to the preparation field of ultracapacitor thin-film material, more particularly to a kind of ultracapacitor is taken with height
To the preparation method of graphene film.
Background technology
2004, Geim of Manchester universities of Britain et al. was found that by carbon atom with Sp2Hydridization connects what is formed
Monoatomic layer two dimensional crystal-graphene (Graphene), graphene be after fullerene and CNT by it is found that
Another new carbon structural form, it is one of current optimal two-dimension nano materials.The discovery of graphene, make people to carbon
The diversity of element has more deep understanding, forms the fullerene from zero dimension, one-dimensional CNT, the graphene of two dimension
To the diamond and the complete carbon family system of graphite of three-dimensional.As a kind of two-dimentional quantum regime being stabilized at room temperature, graphite
The discovery of alkene has broken that traditional Condensed Matter Physics is theoretical, before having overthrown it has been recognized that strict two dimensional crystal can not have
Existing prophesy at a temperature of limit, to the theoretical development of Condensed Matter Physics, there may be great influence.Graphene is a kind of tight
The two dimensional crystal material of lattice, because it has unique structure and performance, the focus of international field of new materials research is rapidly become.
M.D.Stoller et al. reports for ultracapacitor first in Nano Letter 8 (2008) 3498-3452
The graphene powder of electrode material, grapheme material prepared by this method specific capacitance in aqueous electrolyte have reached 135F/
g.But graphene prepared by this chemical method is still that powder needs that super electricity can just be made with binding agent and the compound of conductive agent
Container electrode.X.F.Duan et al. is in ACS Nano DOI:Report to prepare using hydro-thermal method on 10.1021/nn4000836 and have
There is the graphene film electrode of super capacitor of three-dimensional structure, and this Graphene electrodes have shown outstanding volume ratio electricity
Hold and quality specific capacitance.
However, typically now be used for prepare graphene film method include chemical vapour deposition technique, filter membrane formation process and
Hydro-thermal method etc., preparation process is complicated, and equipment requirement is high, yields poorly and is all unfavorable for mass producing.
The application of this right uses knife coating film forming, and uses photoreduction, and preparation process reduction process is all simple and easy.Mesh
It is preceding there is not yet preparing the report of highly oriented graphene membrane electrode material using photoreduction method.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of preparation of ultracapacitor with highly oriented graphene film
Method, this method technique is simple, is easy to industrialized production, the highly oriented graphene film of prepared ultracapacitor have compared with
Good pliability, specific capacitance is high, has wide application in the flexible energy storage field such as flexible super capacitor, lithium ion battery.
A kind of preparation method of the highly oriented graphene film of ultracapacitor of the present invention, including：
(1) graphite oxide is washed, then added in deionized water, obtain suspension, ultrasound, centrifuge washing remove
Unstripped graphite composite powder, then by supernatant rotary evaporation, obtain graphite oxide slurry；
(2) graphite oxide slurry is scratched in copper foil surface, graphite oxide film is made, be then irradiated also original place
Reason, produces highly oriented graphene film.
Washing is washed 2-4 times for deionized water in the step (1).
The concentration of suspension is 0.5~6mg/mL in the step (1).
Ultrasonic time is 1-3h in the step (1).
Centrifuge washing is in the step (1)：10~40min is centrifuged under the conditions of 2500~3500r/min.
Rotary evaporation is rotary evaporation under the conditions of 40~55 DEG C in the step (1).
Graphite oxide slurry blade coating is specially in copper foil surface in the step (2)：The good copper foil of surface clean is adsorbed
In doctor knife coater surface, by blade coating cutter setting thickness, start doctor knife coater and scratch graphite oxide slurry in copper foil surface.
The blade coating cutter sets thickness as 50~200 μm.
Reduction treatment is irradiated in the step (2) is：Irradiation reduction 3-12h at 10~20cm is placed under xenon lamp.
Graphite oxide is prepared into the slurry that can be scratched by the present invention, scratches on conductive substrates surface, is prepared into large area
Graphite oxide film, and simple photoreduction method is used, graphite oxide film is reduced into highly oriented graphene film.Tool
There is height-oriented graphene film interlayer charge transmission resistance low, be advantageous to the collector that electric charge is importing directly into conduction
Surface.
For the ultracapacitor prepared using this method with highly oriented graphene film, preparation technology is simple, is easy to industrialize
Production, the highly oriented graphene film of prepared ultracapacitor have preferable pliability, and specific capacitance is high, in flexible super electricity
There is wide application in the flexible energy storage field such as container, lithium ion battery.
Beneficial effect
(1) this method preparation technology is simple, and film forming procedure uses photoreduction without conductive agent, binding agent, reduction process,
Without chemical reagent and heating process；
(2) graphene film for supercapacitor prepared by this method has preferable pliability, and specific capacitance is high, in flexible super
There is wide application in the flexible energy storage field such as capacitor, lithium ion battery.
Brief description of the drawings
Fig. 1 is that the X of highly oriented graphene film in embodiment 1, graphene powder, graphite oxide powder and original graphite is penetrated
Ray diffraction diagram is composed；
Fig. 2 is the digital photograph of various samples prepared by embodiment 1：(A) graphite oxide film；(B) figure is after reducing
Highly oriented graphene film；(C) figure is the highly oriented graphene film of self-supporting.
Fig. 3 is the impedance spectrum of the electrode test of highly oriented graphene film three prepared by embodiment 1, and illustration is high-frequency region
Collection of illustrative plates；
Fig. 4 be embodiment 1 prepare the electrode test of highly oriented graphene film three in 1M sodium sulphate electrolyte difference sweep
Retouch the cyclic voltammetry curve under speed；
Fig. 5 be embodiment 1 prepare the electrode test structure of graphene film three in 1M sodium sulphate electrolyte different electric currents
Constant current charge-discharge curve first under density.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
Embodiment 1
Graphite oxide is washed with deionized to the deionized water suspension for being configured to that concentration is 0.5mg/mL after 2 times, surpassed
Sound 1h, 2500r/min centrifugation 40min washings remove unstripped graphite composite powder, by supernatant in 40 DEG C of rotary evaporations to forming oxygen
Graphite slurry.The good copper foil of surface clean is adsorbed in doctor knife coater surface, blade coating cutter is set as 50 μm, starts doctor knife coater
Graphite oxide slurry is scratched in copper foil surface, graphite oxide film is made, graphite oxide film is placed under xenon lamp at 10cm
Irradiation reduction 3h is produced.
Fig. 1 is the X-ray diffractogram of highly oriented graphene film, graphene powder, graphite oxide powder and original graphite
Spectrum.The position of the diffraction maximum of original graphite is located at 2 θ=26.5 ° in figure, and is the very high spike of intensity, and interplanar distance is allusion quotation
The interplanar distance 0.334nm of type graphite, the position that the peak position that graphite oxide occurs is set to graphite oxide typical peaks is 2 θ=11 °,
Graphene powder is uneven because of being arranged between lamella, is to occur steamed bun peak in 2 θ=25.14 °, highly oriented graphene film is then
There is curve in regularly arranged due to graphene sheet layer, and diffraction maximum also shows as stronger spike, but compared with original graphite
Then significantly broadened, interplanar distance is then changed into 0.342nm.
Fig. 2 is the digital photograph of the various samples of product：(A) graphite oxide film；(B) figure is highly oriented after reducing
Graphene film；(C) figure is the highly oriented graphene film of self-supporting.By digital photograph it can be seen that being in graphite oxide film
Reveal typical orange-yellow, be then changed into black after reduction, film forming uniformly and has certain gloss.
Fig. 3 is the impedance spectrum of the electrode test of product three, and illustration is high-frequency region collection of illustrative plates, and gained impedance curve is intended
Conjunction obtains the contact resistance R of graphene filmsFor 3.57 Ω, electric charge transmission resistance RctFor 4.52 Ω.
Fig. 4 is that cyclic voltammetric of the product in two electrode test structures in 1M sodium sulphate electrolyte under different scanning rates is bent
Line, the maximum specific capacitance for being computed highly oriented graphene film reach 302F/g, and maximum energy density is 26.8Wh/kg, maximum
Power density be 23.4kW/kg.
Fig. 5 is product constant current charge and discharge first under different current densities in 1M sodium sulphate electrolyte in two electrode test structures
Electric curve.Show that product all has preferable charge-discharge characteristic under different charging and discharging currents density.
Embodiment 2
Graphite oxide is washed with deionized to the deionized water suspension for being configured to that concentration is 6mg/mL after 4 times, ultrasound
3h, 3500r/min centrifugation 10min washings remove unstripped graphite composite powder, by supernatant in 55 DEG C of rotary evaporations to forming oxidation
Graphite slurry.The good copper foil of surface clean is adsorbed in doctor knife coater surface, blade coating cutter is set as 200 μm, starts doctor knife coater
Graphite oxide slurry is scratched in copper foil surface, graphite oxide film is made, graphite oxide film is placed under xenon lamp at 20cm
Irradiation reduction 12h is produced.
X-ray diffraction analysis, which are shown to be, is prepared highly oriented graphene film, and impedance analysis shows contact resistance, electric charge
It is relatively low to transmit resistance, cyclic voltammetry curve analysis has higher specific capacitance, energy density and power density, constant current charge-discharge point
Analysis has preferable charge-discharge performance.
Embodiment 3
Graphite oxide is washed with deionized to the deionized water suspension for being configured to that concentration is 3mg/mL after 3 times, ultrasound
1h, 3000r/min centrifugation 20min washings remove unstripped graphite composite powder, by supernatant in 45 DEG C of rotary evaporations to forming oxidation
Graphite slurry.The good copper foil of surface clean is adsorbed in doctor knife coater surface, blade coating cutter is set as 100 μm, starts doctor knife coater
Graphite oxide slurry is scratched in copper foil surface, graphite oxide film is made, graphite oxide film is placed under xenon lamp at 15cm
Irradiation reduction 6h is produced.
X-ray diffraction analysis, which are shown to be, is prepared highly oriented graphene film, and impedance analysis shows contact resistance, electric charge
It is relatively low to transmit resistance, cyclic voltammetry curve analysis has higher specific capacitance, energy density and power density, constant current charge-discharge point
Analysis has preferable charge-discharge performance.
Embodiment 4
Graphite oxide is washed with deionized to the deionized water suspension for being configured to that concentration is 2mg/mL after 2 times, ultrasound
1h, 3000r/min centrifugation 30min washings remove unstripped graphite composite powder, by supernatant in 45 DEG C of rotary evaporations to forming oxidation
Graphite slurry.The good copper foil of surface clean is adsorbed in doctor knife coater surface, blade coating cutter is set as 100 μm, starts doctor knife coater
Graphite oxide slurry is scratched in copper foil surface, graphite oxide film is made, graphite oxide film is placed under xenon lamp at 15cm
Irradiation reduction 9h is produced.
X-ray diffraction analysis, which are shown to be, is prepared highly oriented graphene film, and impedance analysis shows contact resistance, electric charge
It is relatively low to transmit resistance, cyclic voltammetry curve analysis has higher specific capacitance, energy density and power density, constant current charge-discharge point
Analysis has preferable charge-discharge performance.
Claims (7)
1. a kind of ultracapacitor preparation method of highly oriented graphene film, including：
(1) graphite oxide is washed, then added in deionized water, obtain suspension, ultrasound, centrifugation, then by supernatant
Liquid rotary evaporation, obtain graphite oxide slurry；
(2) graphite oxide slurry is scratched in copper foil surface, graphite oxide film is made, is then irradiated reduction treatment, i.e.,
Obtain highly oriented graphene film；Wherein graphite oxide slurry blade coating is specially in copper foil surface：The good copper foil of surface clean is inhaled
Doctor knife coater surface is invested, by blade coating cutter setting thickness, starts doctor knife coater and scratches graphite oxide slurry in copper foil surface；Irradiation
Reduction treatment is：Irradiation reduction 3-12h at 10~20cm is placed under xenon lamp.
2. a kind of preparation method of the highly oriented graphene film of ultracapacitor according to claim 1, its feature exist
In：Washing is washed 2-4 times for deionized water in the step (1).
3. a kind of preparation method of the highly oriented graphene film of ultracapacitor according to claim 1, its feature exist
In：The concentration of suspension is 0.5~6mg/mL in the step (1).
4. a kind of preparation method of the highly oriented graphene film of ultracapacitor according to claim 1, its feature exist
In：Ultrasonic time is 1-3h in the step (1).
5. a kind of preparation method of the highly oriented graphene film of ultracapacitor according to claim 1, its feature exist
In：Centrifuged in the step (1) and be：10~40min is centrifuged under the conditions of 2500~3500r/min.
6. a kind of preparation method of the highly oriented graphene film of ultracapacitor according to claim 1, its feature exist
In：Rotary evaporation is rotary evaporation under the conditions of 40~55 DEG C in the step (1).
7. a kind of preparation method of the highly oriented graphene film of ultracapacitor according to claim 1, its feature exist
In：Blade coating cutter sets thickness as 50~200 μm in the step (2).
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| CN107195707B (en) * | 2017-06-02 | 2020-01-14 | 东华大学 | Quantum dot/graphene film light detection material based on photoresponse and preparation and application thereof |
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| CN102531063A (en) * | 2011-11-20 | 2012-07-04 | 湖南理工学院 | Graphene load tungsten trioxide (WO3) nanowire composite material and preparation method thereof |
| CN102983012A (en) * | 2012-12-12 | 2013-03-20 | 东华大学 | Preparation method of graphene film for supercapacitor |
| CN103854880A (en) * | 2012-11-30 | 2014-06-11 | 海洋王照明科技股份有限公司 | Graphene electrode sheet and preparation method and application thereof |
| CN104609404A (en) * | 2015-01-08 | 2015-05-13 | 北京理工大学 | Method for preparing graphene and composite material through sunlight reduction or laser reduction |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102531063A (en) * | 2011-11-20 | 2012-07-04 | 湖南理工学院 | Graphene load tungsten trioxide (WO3) nanowire composite material and preparation method thereof |
| CN103854880A (en) * | 2012-11-30 | 2014-06-11 | 海洋王照明科技股份有限公司 | Graphene electrode sheet and preparation method and application thereof |
| CN102983012A (en) * | 2012-12-12 | 2013-03-20 | 东华大学 | Preparation method of graphene film for supercapacitor |
| CN104609404A (en) * | 2015-01-08 | 2015-05-13 | 北京理工大学 | Method for preparing graphene and composite material through sunlight reduction or laser reduction |
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