CN104140096B - A kind of preparation method of graphene roll - Google Patents
A kind of preparation method of graphene roll Download PDFInfo
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- CN104140096B CN104140096B CN201410359512.7A CN201410359512A CN104140096B CN 104140096 B CN104140096 B CN 104140096B CN 201410359512 A CN201410359512 A CN 201410359512A CN 104140096 B CN104140096 B CN 104140096B
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Abstract
The present invention relates to a kind of preparation method of graphene roll, the method is presoma with graphene oxide, reduced by graphene oxide by electrochemical action, forms the structure with curling fold simultaneously, then carry out supersound process, namely prepare graphene roll.Compared with prior art, electrochemical principle and ultrasonic principle combine by the present invention effectively, have the advantages such as easy and simple to handle, with low cost, safety non-pollution.
Description
Technical field
The invention belongs to graphene nano field of material technology, be specifically related to a kind of preparation method of graphene roll.
Background technology
In recent years, carbon nanomaterial is as carbon nanotube and Graphene, and because it has desirable one-dimentional structure and two-dirnentional structure, in addition excellent performance, has a wide range of applications in a lot of fields.And graphene roll is as a kind of novel carbon nanomaterial, a kind of web-like nano material of being similar to carbon nanotube between a peacekeeping two dimension between curling by Graphene, two ends and edge non-closed, footpath spacing easily regulates and controls, and has higher specific surface area.The special topological framework of graphene roll self has the performance of some excellences, and such as, high carrier mobility and optical property, it may be used for the field such as ultracapacitor, sensor nano electron device.Because graphene roll has hollow structure, and specific surface area is large, and it also can be used for Chu Qing field.In addition, curling the had limit threshold effect of Graphene of nano-grade size, make graphene roll have excellent catalytic performance, therefore, graphene roll is also with a wide range of applications in the technical field such as ultracapacitor, catalyzer.
At present, people mainly concentrate on Theoretical Calculation aspect for the research of graphene roll, but, about the preparation method of graphene roll and performance study then fewer, therefore to prepare high-quality graphene roll, still face many difficulties now.Current, the common method of preparation graphene roll mainly contains graphite arc discharge method, high-energy ball milling method and chemical method.The graphene roll prepared due to arc discharge method and high-energy ball milling method is blended in graphite and decolorizing carbon usually, and this is just difficult to graphene roll to separate from the mixture of complexity.Therefore, above-mentioned two kinds of methods can not prepare the highly purified graphene roll of high quality.Graphite intercalation is mainly first separated into thin layer by chemical method, then carries out supersound process, and the graphite that part is peeled off is curled into spool.Although adopt chemical method to prepare graphene roll have higher productive rate, the graphene roll of preparation, usual form heterogeneity, and the number of plies of uncontrollable graphene roll.In addition, in the graphene roll prepared by chemical method, toward contact meeting existing defects, this may affect the partial materialization character of graphene roll.Meanwhile, the usual more complicated of chemical method preparation process, reaction is violent, exists and pollutes, not easily carry out scale operation.In recent years, also useful micromechanics stripping method prepares the graphene roll of individual layer and few layer, but the productive rate of the method is lower, can not apply.
Summary of the invention
Object of the present invention be exactly provide to overcome defect that above-mentioned prior art exists a kind of green, simple, the method preparing graphene roll can be stablized on a large scale.
Object of the present invention can be achieved through the following technical solutions:
A preparation method for graphene roll, the method take graphene oxide as presoma, reduced by graphene oxide by electrochemical action, form the structure with curling fold simultaneously, carry out supersound process again, namely prepare graphene roll, specifically comprise the following steps:
(1) graphite oxide is soluble in water, stir 30 ~ 60min, supersound process 1 ~ 4h, is mixed with graphene oxide suspension;
(2) graphene oxide suspension that step (1) is obtained is joined in electrochemical reaction appts, opening power, selection voltage is 10 ~ 30V, carry out positive pole absorption, after positive pole absorption terminates, changing voltage direction, selection voltage is 60 ~ 80V, carry out cathodic reduction reaction, obtain reaction mixture;
(3) in the obtained reaction mixture of step (2), adding acid solution, for removing the impurity in reaction mixture, more repeatedly cleaning with deionized water;
(4) after the reaction mixture after step (3) being cleaned carries out supersound process, dry, namely prepare graphene roll.
Graphite oxide described in step (1) buys gained from Changzhou No.6 Element Material Technology Co., Ltd., and in described graphene oxide suspension, the mass concentration of graphene oxide is 0.1 ~ 4mg/ml.
Electrochemical reaction appts described in step (2) comprises D.C. regulated power supply, two electrodes, wire and reactive tank, two described electrodes are arranged in reactive tank, and being connected to D.C. regulated power supply respectively by wire, the distance between two described electrodes is 0.5 ~ 2cm.
The time of the positive pole absorption described in step (2) is 0.5 ~ 1h, and the time of described cathodic reduction reaction is 0.5 ~ 4h.
Acid solution described in step (3) is rare HCl solution, and in this rare HCl solution, the massfraction of HCl is 3 ~ 5%.
The condition of the supersound process described in step (4) is: ultrasonic frequency is 30 ~ 50KHz, and the treatment time is 0.5 ~ 2h.
Two described electrodes are ganoid copper sheet, and described reactive tank is that methacrylate sheet is processed into.
Graphene oxide is reduced by electrochemical action by the present invention, forms the structure with curling fold simultaneously, then is curled into graphene roll by ultrasonication.Wherein, electrochemical action process is mainly divided into positive pole to adsorb and cathodic reduction reacts two processes, its principle is: graphene oxide particle is electronegative due to chemical group ionization in aqueous, now, certain external electrical field is applied by D.C. regulated power supply, graphene oxide particle electronegative in solution can move to positive pole under the effect of electrical forces, and when arriving positive pole, be deposited on layer by layer on positive electrode surface, form graphene oxide membrane, this process is positive pole adsorption process; After positive pole absorption terminates, the direction of former electric field is changed by D.C. regulated power supply, now, surface deposition has the electrode of graphene oxide membrane to become negative pole, electronics in external circuit is passed to graphene oxide membrane by negative pole, in negative terminal surface, graphene oxide membrane obtains electronics and reduction reaction occurs, and former graphene oxide membrane achieves reduction from inside to outside, generates reduced graphene.In the process, reduced graphene still can with partial negative charge, in the effect of electrical forces, reduced graphene can outwards move towards positive extreme direction, now, Graphene is transformed into the coiled structure of loose fold gradually by the membrane structure of originally piling up layer by layer, and splits away off from electrode.The coiled structure of this loose fold, under hyperacoustic effect, is transformed into curling Graphene, i.e. graphene roll.
Compared with prior art, the present invention has following characteristics:
1. environmental protection, does not relate to poisonous chemical reagent, safety, pollution-free;
2. the graphene roll quality preparing gained is good, and productive rate is high, without the need to purifying, can be used for amplifying and producing;
3. reaction unit is simple, and facility investment is few, and raw material is easy to get, with low cost, processing ease, favorable reproducibility, and suitability is strong.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope diagram spectrum of Graphene after electrochemical action in embodiment 1;
Fig. 2 is the transmission electron microscope collection of illustrative plates that embodiment 1 prepares gained graphene roll;
Fig. 3 is Fourier's Infrared Characterization collection of illustrative plates of graphene oxide and graphene roll in embodiment 1;
Fig. 4 is the x-ray photoelectron power spectrum phenogram of graphene oxide in embodiment 1;
Fig. 5 is the x-ray photoelectron power spectrum phenogram of graphene roll in embodiment 1;
Fig. 6 is the scanning electron microscope diagram spectrum of graphene roll in embodiment 2;
Fig. 7 is Fourier's Infrared Characterization collection of illustrative plates of graphene oxide and graphene roll in embodiment 2.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1:
A preparation method for graphene roll, the method take graphene oxide as presoma, reduced by graphene oxide by electrochemical action, then carry out supersound process, namely prepares graphene roll, specifically comprise the following steps:
(1) will the 5um graphite oxide of 0.2g be taken, be dissolved in 100ml deionized water, and stir 30min, supersound process 3h, be mixed with the graphene oxide suspension that mass concentration is 2mg/ml;
(2) graphene oxide suspension that step (1) is obtained is joined in electrochemical reaction appts, described electrochemical reaction appts comprises D.C. regulated power supply, two electrodes, wire and reactive tank, two electrodes are that (wide be 15cm to ganoid copper sheet, long is 15cm), all be arranged in reactive tank, and being connected to D.C. regulated power supply respectively by wire, the distance between two electrodes is 2cm, and described reactive tank adopts methacrylate sheet to be processed into; Opening power, selection voltage is 30V, carries out positive pole absorption, and adsorption time is 0.5h, after positive pole absorption terminates, changing voltage direction, selection voltage is 60V, carries out cathodic reduction reaction, and the reaction times is 4h, obtains reaction mixture;
(3) in the obtained reaction mixture of step (2), adding rare HCl solution that massfraction is 3%, for removing the impurity in reaction mixture, more repeatedly cleaning with deionized water;
(4) reaction mixture after step (3) being cleaned is put in ultrasonic cleaning instrument, and ultrasonic frequency is 30KHz, and process 2h, namely prepares graphene roll.
In the present embodiment, the graphite oxide described in step (1) buys gained from Changzhou No.6 Element Material Technology Co., Ltd..
Fig. 1 is the scanning electron microscope diagram spectrum of Graphene after the present embodiment electrochemical action, and as can be seen from the figure, after electrochemical action, Graphene forms the short texture of many folds, and topography uniformity is good, without the stacking phenomenon of obvious fragment.
Fig. 2 is the transmission electron microscope collection of illustrative plates that the present embodiment prepares gained graphene roll, as can be seen from the figure, Graphene has curled into nano level graphene roll, obtained graphene roll is elongated cylindrical, good dispersity, also demonstrate thus under ultrasonication, the Graphene of loose fold can curl into graphene roll.
Fig. 3 is Fourier's Infrared Characterization collection of illustrative plates of graphene oxide and graphene roll in the present embodiment, can find out that the absorption peak of graphene oxide is OH (~ 3400cm from collection of illustrative plates
-1), C=O (~ 1720cm
-1), C=C (~ 1620cm
-1), C-H (~ 1300cm
-1) and C-O-C (~ 1050cm
-1), and the oxygen-containing functional group peak in product graphene roll obviously weakens by force, illustrates thus, after electrochemical action, graphene oxide is reduced into Graphene.
Fig. 4 and Fig. 5 is the x-ray photoelectron power spectrum phenogram of graphene oxide and graphene roll in the present embodiment respectively, as can be seen from above-mentioned two phenograms, the main peak of graphene oxide is-COOH (289.0eV), C=O (287.8eV), C-O (286.3eV) and C=C (284.6eV); After electrochemical reducting reaction, the peak intensity of C=O and C-O obviously reduces, and C: the O of graphene roll is 5.9: 1, and this absolutely proves that graphene oxide obtains good reduction.
Embodiment 2:
A preparation method for graphene roll, the method take graphene oxide as presoma, reduced by graphene oxide by electrochemical action, then carry out supersound process, namely prepares graphene roll, specifically comprise the following steps:
(1) will the 5um graphite oxide of 0.24g be taken, be dissolved in 240ml deionized water, and stir 30min, supersound process 3h, be mixed with the graphene oxide suspension that mass concentration is 1mg/ml;
(2) graphene oxide suspension that step (1) is obtained is joined in electrochemical reaction appts, described electrochemical reaction appts comprises D.C. regulated power supply, two electrodes, wire and reactive tank, two electrodes are that (wide be 25cm to ganoid copper sheet, long is 25cm), all be arranged in reactive tank, and being connected to D.C. regulated power supply respectively by wire, the distance between two electrodes is 2cm, and described reactive tank adopts methacrylate sheet to be processed into; Opening power, selection voltage is 30V, carries out positive pole absorption, and adsorption time is 0.5h, after positive pole absorption terminates, changing voltage direction, selection voltage is 60V, carries out cathodic reduction reaction, and the reaction times is 3h, obtains reaction mixture;
(3) in the obtained reaction mixture of step (2), adding rare HCl solution that massfraction is 3%, for removing the impurity in reaction mixture, more repeatedly cleaning with deionized water;
(4) reaction mixture after step (3) being cleaned is put in ultrasonic cleaning instrument, and ultrasonic frequency is 30KHz, and process 0.5h, namely prepares graphene roll.
In the present embodiment, the graphite oxide described in step (1) buys gained from Changzhou No.6 Element Material Technology Co., Ltd..
Fig. 6 is the scanning electron microscope diagram spectrum that the present embodiment prepares graphene roll, as can be seen from the figure, what the present embodiment prepared gained is micron-sized graphene roll, compared to the experiment condition of embodiment 1, in the present embodiment, the time of step (4) supersound process is shorter, only processes 0.5h, after this just makes a large amount of Graphene form volume, be deposited in together in an orderly manner, in figure, the topography uniformity of graphene roll is good, is cylindrical web-like.
Fig. 7 is Fourier's Infrared Characterization collection of illustrative plates of graphene oxide and graphene roll in the present embodiment, can find out that the absorption peak of graphene oxide is OH (~ 3400cm from collection of illustrative plates
-1), C=O (~ 1720cm
-1), C=C (~ 1620cm
-1), C-H (~ 1300cm
-1) and C-O-C (~ 1050cm
-1), and the oxygen-containing functional group peak in product graphene roll obviously weakens by force, illustrates that, by electrochemical action, graphene oxide is reduced into Graphene.
Embodiment 3:
A preparation method for graphene roll, the method take graphene oxide as presoma, reduced by graphene oxide by electrochemical action, then carry out supersound process, namely prepares graphene roll, specifically comprise the following steps:
(1) will the 5um graphite oxide of 0.2g be taken, be dissolved in 2000ml deionized water, and stir 30min, supersound process 1h, be mixed with the graphene oxide suspension that mass concentration is 0.1mg/ml;
(2) graphene oxide suspension that step (1) is obtained is joined in electrochemical reaction appts, described electrochemical reaction appts comprises D.C. regulated power supply, two electrodes, wire and reactive tank, two electrodes are that (wide be 25cm to ganoid copper sheet, long is 25cm), all be arranged in reactive tank, and being connected to D.C. regulated power supply respectively by wire, the distance between two electrodes is 0.5cm, and described reactive tank adopts methacrylate sheet to be processed into; Opening power, selection voltage is 10V, carries out positive pole absorption, and adsorption time is 1h, after positive pole absorption terminates, changing voltage direction, selection voltage is 80V, carries out cathodic reduction reaction, and the reaction times is 0.5h, obtains reaction mixture;
(3) in the obtained reaction mixture of step (2), adding rare HCl solution that massfraction is 3%, for removing the impurity in reaction mixture, more repeatedly cleaning with deionized water;
(4) reaction mixture after step (3) being cleaned is put in ultrasonic cleaning instrument, and ultrasonic frequency is 30KHz, and process 0.5h, namely prepares graphene roll.
In the present embodiment, the graphite oxide described in step (1) buys gained from Changzhou No.6 Element Material Technology Co., Ltd..
Embodiment 4:
A preparation method for graphene roll, the method take graphene oxide as presoma, reduced by graphene oxide by electrochemical action, then carry out supersound process, namely prepares graphene roll, specifically comprise the following steps:
(1) will the 5um graphite oxide of 0.2g be taken, be dissolved in 50ml deionized water, and stir 60min, supersound process 4h, be mixed with the graphene oxide suspension that mass concentration is 4mg/ml;
(2) graphene oxide suspension that step (1) is obtained is joined in electrochemical reaction appts, described electrochemical reaction appts comprises D.C. regulated power supply, two electrodes, wire and reactive tank, two electrodes are that (wide be 15cm to ganoid copper sheet, long is 15cm), all be arranged in reactive tank, and being connected to D.C. regulated power supply respectively by wire, the distance between two electrodes is 1cm, and described reactive tank adopts methacrylate sheet to be processed into; Opening power, selection voltage is 30V, carries out positive pole absorption, and adsorption time is 0.5h, after positive pole absorption terminates, changing voltage direction, selection voltage is 60V, carries out cathodic reduction reaction, and the reaction times is 4h, obtains reaction mixture;
(3) in the obtained reaction mixture of step (2), adding rare HCl solution that massfraction is 5%, for removing the impurity in reaction mixture, more repeatedly cleaning with deionized water;
(4) reaction mixture after step (3) being cleaned is put in ultrasonic cleaning instrument, and ultrasonic frequency is 50KHz, and process 2h, namely prepares graphene roll.
In the present embodiment, the graphite oxide described in step (1) buys gained from Changzhou No.6 Element Material Technology Co., Ltd..
Claims (5)
1. a preparation method for graphene roll, is characterized in that, the method take graphene oxide as presoma, by electrochemical action, graphene oxide is reduced, form the structure with curling fold simultaneously, then carry out supersound process, namely prepare graphene roll, specifically comprise the following steps:
(1) graphite oxide is soluble in water, stir 30 ~ 60min, supersound process 1 ~ 4h, is mixed with graphene oxide suspension;
(2) graphene oxide suspension that step (1) is obtained is joined in electrochemical reaction appts, selection voltage is 10 ~ 30V, carry out positive pole absorption, after positive pole absorption terminates, changing voltage direction, selection voltage is 60 ~ 80V, carries out cathodic reduction reaction, obtains reaction mixture;
(3) in the obtained reaction mixture of step (2), adding acid solution, for removing the impurity in reaction mixture, more repeatedly cleaning with deionized water;
(4) after the reaction mixture after step (3) being cleaned carries out supersound process, dry, namely prepare graphene roll;
Wherein, described electrochemical reaction appts comprises D.C. regulated power supply, two electrodes, wire and reactive tank, and two described electrodes are arranged in reactive tank, and are connected to D.C. regulated power supply respectively by wire, and the distance between two described electrodes is 0.5 ~ 2cm;
The time of the positive pole absorption described in step (2) is 0.5 ~ 1h, and the time of described cathodic reduction reaction is 0.5 ~ 4h.
2. the preparation method of a kind of graphene roll according to claim 1, is characterized in that, in the graphene oxide suspension described in step (1), the mass concentration of graphene oxide is 0.1 ~ 4mg/ml.
3. the preparation method of a kind of graphene roll according to claim 1, is characterized in that, the acid solution described in step (3) is rare HCl solution, and in this rare HCl solution, the massfraction of HCl is 3 ~ 5%.
4. the preparation method of a kind of graphene roll according to claim 1, is characterized in that, the condition of the supersound process described in step (4): ultrasonic frequency is 30 ~ 50KHz, and the treatment time is 0.5 ~ 2h.
5. the preparation method of a kind of graphene roll according to claim 1, is characterized in that, two described electrodes are ganoid copper sheet, and described reactive tank is that methacrylate sheet is processed into.
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| CN104576083A (en) * | 2015-01-07 | 2015-04-29 | 浙江碳谷上希材料科技有限公司 | Preparation method for supercapacitor made of graphene nanoscrolls |
| CN106185904B (en) * | 2016-07-15 | 2018-02-09 | 浙江大学 | A kind of high fold graphene paper |
| CN106189297B (en) * | 2016-08-17 | 2018-10-19 | 河南师范大学 | A kind of conductive asphalt and preparation method thereof |
| CN106277072B (en) * | 2016-08-24 | 2018-01-30 | 合肥学院 | A kind of graphene/nickel cobalt aluminium layered double-hydroxide composite and preparation method thereof |
| CN106698403B (en) * | 2017-01-06 | 2019-01-18 | 南京工业大学 | A kind of method of large area preparation graphene roll |
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