CN104140096A - Method for manufacturing graphene roll - Google Patents
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- CN104140096A CN104140096A CN201410359512.7A CN201410359512A CN104140096A CN 104140096 A CN104140096 A CN 104140096A CN 201410359512 A CN201410359512 A CN 201410359512A CN 104140096 A CN104140096 A CN 104140096A
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Abstract
The invention relates to a method for manufacturing a graphene roll. The method includes the steps that graphene oxide serves as a precursor and is reduced under the electrochemical effect, a structure with curly wrinkles is formed at the moment, then ultrasonic processing is conducted, and the graphene roll is manufactured. Compared with the prior art, the electrochemical principle and the ultrasonic principle are effectively combined, and the method has the advantages of being easy and convenient to operate, low in cost, safe, free of pollution and the like.
Description
Technical field
The invention belongs to graphene nano material technology field, be specifically related to a kind of preparation method of Graphene volume.
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, excellent performance, has a wide range of applications in a lot of fields in addition.And Graphene volume is as a kind of novel carbon nanomaterial, a kind of by the curling web-like nano material that is similar to carbon nanotube between a peacekeeping two dimension forming of Graphene, the non-closure in two ends and edge, footpath spacing easily regulates and controls, and has higher specific surface area.The special topological framework of Graphene volume self has some excellent performances, for example, high carrier mobility and optical property, it can be for fields such as ultracapacitor, sensor nano electron devices.Because Graphene volume 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 the Graphene of nano-grade size, makes Graphene volume have excellent catalytic performance, and therefore, Graphene twists in the technical fields such as ultracapacitor, catalyzer and is also with a wide range of applications.
At present, people mainly concentrate on Theoretical Calculation aspect for the research of Graphene volume, yet, fewer about preparation method and the performance study of Graphene volume, therefore to prepare high-quality Graphene volume, still face now many difficulties.Current, the common method of preparing Graphene volume mainly contains graphite arc discharge method, high-energy ball milling method and chemical method.The Graphene volume of preparing due to arc discharge method and high-energy ball milling method is blended in graphite and decolorizing carbon conventionally, and this is just difficult to Graphene volume to separate from complicated mixture.Therefore, above-mentioned two kinds of methods can not be prepared the highly purified Graphene volume of high quality.Chemical method is mainly that graphite intercalation is first separated into thin layer, then carries out supersound process, and the graphite that part is peeled off is curled into spool.Although adopt chemical method to prepare Graphene volume, there is higher productive rate, the Graphene volume of preparation, the number of plies of the volume of form heterogeneity, and uncontrollable Graphene conventionally.In addition, in the Graphene volume of being prepared, toward contact meeting, have defect by chemical method, this may affect the partial materialization character of Graphene volume.Meanwhile, the common more complicated of chemical method preparation process, reaction is violent, exists and pollutes, and is difficult for carrying out scale operation.In recent years, also useful micromechanics stripping method is prepared the Graphene volume 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 in order to overcome the defect that above-mentioned prior art exists, provide a kind of green, simple, can stablize on a large scale and prepare the method that Graphene is rolled up.
Object of the present invention can be achieved through the following technical solutions:
A preparation method for Graphene volume, the method is to take graphene oxide as presoma, by electrochemical action, graphene oxide is reduced, form the structure with curling fold simultaneously, carry out again supersound process, prepare Graphene volume, 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 step (1) being made joins in electrochemical reaction appts, opening power, selection voltage is 10～30V, carry out positive pole absorption, after anodal absorption finishes, changing voltage direction, selection voltage is 60～80V, carry out negative pole reduction reaction, obtain product solution;
(3) in the product solution making to step (2), add acid solution, for removing the impurity of product solution, more repeatedly clean with deionized water;
(4) the product solution after step (3) cleaning is carried out after supersound process, dry, prepare Graphene volume.
The described graphite oxide of step (1) is bought 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.
The described electrochemical reaction appts of step (2) comprises D.C. regulated power supply, two electrodes, wire and reactive tank, two described electrodes are arranged in reactive tank, and by wire, being connected to D.C. regulated power supply respectively, the distance between two described electrodes is 0.5～2cm.
The time of the positive pole absorption that step (2) is described is 0.5～1h, and the time of described negative pole reduction reaction is 0.5～4h.
The described acid solution of 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 that step (4) is described 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.
The present invention reduces graphene oxide by electrochemical action, forms simultaneously and has the structure of curling fold, then by ultrasonication, be curled into Graphene and roll up.Wherein, electrochemical action process is mainly divided into anodal absorption and two processes of negative pole reduction reaction, its principle is: graphene oxide particle is electronegative due to chemical group ionization in the aqueous solution, now, by D.C. regulated power supply, apply certain external electrical field, 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 anodal surface, form graphene oxide film, this process is anodal adsorption process; After anodal absorption finishes, by D.C. regulated power supply, change the direction of former electric field, now, surface deposition has the electrode of graphene oxide film to become negative pole, electronics in external circuit is passed to graphene oxide film by negative pole, in negative terminal surface, graphene oxide film obtains electronics and reduction reaction occurs, and former graphene oxide film has been realized reduction from inside to outside, generates reduced graphene.In this process, reduced graphene still can be with part 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 original membrane structure of 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 volume.
Compared with prior art, the present invention has following characteristics:
1. environmental protection, does not relate to poisonous chemical reagent, and safety is pollution-free;
2. the Graphene volume quality of preparing gained is good, and productive rate is high, without purification, can be used for amplifying and produces;
3. reaction unit is simple, and facility investment is few, and raw material is easy to get, with low cost, processing ease, and favorable reproducibility, suitability is strong.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope diagram of Graphene spectrum after electrochemical action in embodiment 1;
Fig. 2 is the transmission electron microscope collection of illustrative plates that embodiment 1 prepares gained Graphene volume;
Fig. 3 is Fourier's Infrared Characterization collection of illustrative plates of graphene oxide and Graphene volume 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 volume in embodiment 1;
Fig. 6 is the scanning electron microscope diagram spectrum of Graphene volume in embodiment 2;
Fig. 7 is Fourier's Infrared Characterization collection of illustrative plates of graphene oxide and Graphene volume 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 volume, the method is to take graphene oxide as presoma, by electrochemical action, graphene oxide is reduced, then carries out supersound process, prepares Graphene volume, specifically comprises the following steps:
(1) will take the 5um graphite oxide of 0.2g, be dissolved in 100ml deionized water, stir 30min, supersound process 3h, being mixed with mass concentration is the graphene oxide suspension of 2mg/ml;
(2) graphene oxide suspension step (1) being made joins 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 by wire, be connected to D.C. regulated power supply respectively, and the distance between two electrodes is 2cm, described reactive tank adopts methacrylate sheet to be processed into; Opening power, selection voltage is 30V, carries out positive pole absorption, adsorption time is 0.5h, after anodal absorption finishes, changing voltage direction, selection voltage is 60V, carries out negative pole reduction reaction, the reaction times is 4h, obtains product solution;
(3) in the product solution making to step (2), adding massfraction is rare HCl solution of 3%, for removing the impurity of product solution, more repeatedly cleans with deionized water;
(4) the product solution after step (3) cleaning is put in ultrasonic cleaning instrument, ultrasonic frequency is 30KHz, processes 2h, prepares Graphene volume.
In the present embodiment, the described graphite oxide Shi Cong Changzhou No.6 Element Material Technology Co., Ltd. of step (1) buys gained.
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 pattern homogeneity is good, without the obvious stacking phenomenon of fragment.
Fig. 2 is the transmission electron microscope collection of illustrative plates that the present embodiment is prepared gained Graphene volume, as can be seen from the figure, Graphene has curled into nano level Graphene volume, the Graphene volume making is elongated cylindrical, good dispersity, also verified thus under ultrasonication, the Graphene of loose fold can curl into Graphene volume.
Fig. 3 is Fourier's Infrared Characterization collection of illustrative plates of graphene oxide and Graphene volume in the present embodiment, and the absorption peak that can find out graphene oxide from collection of illustrative plates is OH (～3400cm
-1), C=O (～1720cm
-1), C=C (～1620cm
-1), C-H (～1300cm
-1) and C-O-C (～1050cm
-1), and oxygen-containing functional group peak in product Graphene volume obviously weakens by force, and explanation thus, after electrochemical action, graphene oxide is reduced into Graphene.
Fig. 4 and Fig. 5 are respectively the x-ray photoelectron power spectrum phenograms of graphene oxide and Graphene volume in the present embodiment, by above-mentioned two phenograms, can be found out, 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, the C of Graphene volume: O is 5.9: 1, and this absolutely proves that graphene oxide has obtained good reduction.
Embodiment 2:
A preparation method for Graphene volume, the method is to take graphene oxide as presoma, by electrochemical action, graphene oxide is reduced, then carries out supersound process, prepares Graphene volume, specifically comprises the following steps:
(1) will take the 5um graphite oxide of 0.24g, be dissolved in 240ml deionized water, stir 30min, supersound process 3h, being mixed with mass concentration is the graphene oxide suspension of 1mg/ml;
(2) graphene oxide suspension step (1) being made joins 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 by wire, be connected to D.C. regulated power supply respectively, and the distance between two electrodes is 2cm, described reactive tank adopts methacrylate sheet to be processed into; Opening power, selection voltage is 30V, carries out positive pole absorption, adsorption time is 0.5h, after anodal absorption finishes, changing voltage direction, selection voltage is 60V, carries out negative pole reduction reaction, the reaction times is 3h, obtains product solution;
(3) in the product solution making to step (2), adding massfraction is rare HCl solution of 3%, for removing the impurity of product solution, more repeatedly cleans with deionized water;
(4) the product solution after step (3) cleaning is put in ultrasonic cleaning instrument, ultrasonic frequency is 30KHz, processes 0.5h, prepares Graphene volume.
In the present embodiment, the described graphite oxide Shi Cong Changzhou No.6 Element Material Technology Co., Ltd. of step (1) buys gained.
Fig. 6 is the scanning electron microscope diagram spectrum that the present embodiment is prepared Graphene volume, as can be seen from the figure, what the present embodiment was prepared gained is micron-sized Graphene volume, than the experiment condition of embodiment 1, the time of step in the present embodiment (4) supersound process is shorter, only processes 0.5h, this just makes a large amount of Graphenes form after volume, be deposited in an orderly manner together, in figure, the pattern homogeneity of Graphene volume is good, is cylindrical web-like.
Fig. 7 is Fourier's Infrared Characterization collection of illustrative plates of graphene oxide and Graphene volume in the present embodiment, and the absorption peak that can find out graphene oxide from collection of illustrative plates is OH (～3400cm
-1), C=O (～1720cm
-1), C=C (～1620cm
-1), C-H (～1300cm
-1) and C-O-C (～1050cm
-1), and oxygen-containing functional group peak in product Graphene volume obviously weakens by force, illustrates by electrochemical action, graphene oxide is reduced into Graphene.
Embodiment 3:
A preparation method for Graphene volume, the method is to take graphene oxide as presoma, by electrochemical action, graphene oxide is reduced, then carries out supersound process, prepares Graphene volume, specifically comprises the following steps:
(1) will take the 5um graphite oxide of 0.2g, be dissolved in 2000ml deionized water, stir 30min, supersound process 1h, being mixed with mass concentration is the graphene oxide suspension of 0.1mg/ml;
(2) graphene oxide suspension step (1) being made joins 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 by wire, be connected to D.C. regulated power supply respectively, and the distance between two electrodes is 0.5cm, described reactive tank adopts methacrylate sheet to be processed into; Opening power, selection voltage is 10V, carries out positive pole absorption, adsorption time is 1h, after anodal absorption finishes, changing voltage direction, selection voltage is 80V, carries out negative pole reduction reaction, the reaction times is 0.5h, obtains product solution;
(3) in the product solution making to step (2), adding massfraction is rare HCl solution of 3%, for removing the impurity of product solution, more repeatedly cleans with deionized water;
(4) the product solution after step (3) cleaning is put in ultrasonic cleaning instrument, ultrasonic frequency is 30KHz, processes 0.5h, prepares Graphene volume.
In the present embodiment, the described graphite oxide Shi Cong Changzhou No.6 Element Material Technology Co., Ltd. of step (1) buys gained.
Embodiment 4:
A preparation method for Graphene volume, the method is to take graphene oxide as presoma, by electrochemical action, graphene oxide is reduced, then carries out supersound process, prepares Graphene volume, specifically comprises the following steps:
(1) will take the 5um graphite oxide of 0.2g, be dissolved in 50ml deionized water, stir 60min, supersound process 4h, being mixed with mass concentration is the graphene oxide suspension of 4mg/ml;
(2) graphene oxide suspension step (1) being made joins 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 by wire, be connected to D.C. regulated power supply respectively, and the distance between two electrodes is 1cm, described reactive tank adopts methacrylate sheet to be processed into; Opening power, selection voltage is 30V, carries out positive pole absorption, adsorption time is 0.5h, after anodal absorption finishes, changing voltage direction, selection voltage is 60V, carries out negative pole reduction reaction, the reaction times is 4h, obtains product solution;
(3) in the product solution making to step (2), adding massfraction is rare HCl solution of 5%, for removing the impurity of product solution, more repeatedly cleans with deionized water;
(4) the product solution after step (3) cleaning is put in ultrasonic cleaning instrument, ultrasonic frequency is 50KHz, processes 2h, prepares Graphene volume.
In the present embodiment, the described graphite oxide Shi Cong Changzhou No.6 Element Material Technology Co., Ltd. of step (1) buys gained.
Claims (7)
1. a preparation method for Graphene volume, is characterized in that, the method is to take graphene oxide as presoma, by electrochemical action, graphene oxide is reduced, form and there is the structure of curling fold simultaneously, then carry out supersound process, prepare Graphene volume, 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 step (1) being made joins in electrochemical reaction appts, and selection voltage is 10～30V, carries out positive pole absorption, after anodal absorption finishes, changing voltage direction, selection voltage is 60～80V, carry out negative pole reduction reaction, obtain product solution;
(3) in the product solution making to step (2), add acid solution, for removing the impurity of product solution, more repeatedly clean with deionized water;
(4) the product solution after step (3) cleaning is carried out after supersound process, dry, prepare Graphene volume.
2. the preparation method of a kind of Graphene volume according to claim 1, is characterized in that, in the described graphene oxide suspension of step (1), the mass concentration of graphene oxide is 0.1～4mg/ml.
3. the preparation method that a kind of Graphene according to claim 1 is rolled up, it is characterized in that, the described electrochemical reaction appts of step (2) comprises D.C. regulated power supply, two electrodes, wire and reactive tank, two described electrodes are arranged in reactive tank, and by wire, being connected to D.C. regulated power supply respectively, the distance between two described electrodes is 0.5～2cm.
4. the preparation method of a kind of Graphene volume according to claim 1, is characterized in that, the time of the positive pole absorption that step (2) is described is 0.5～1h, and the time of described negative pole reduction reaction is 0.5～4h.
5. the preparation method of a kind of Graphene volume according to claim 1, is characterized in that, the described acid solution of step (3) is rare HCl solution, and in this rare HCl solution, the massfraction of HCl is 3～5%.
6. the preparation method of a kind of Graphene volume according to claim 1, is characterized in that, the condition of the supersound process that step (4) is described: ultrasonic frequency is 30～50KHz, and the treatment time is 0.5～2h.
7. the preparation method of a kind of Graphene volume according to claim 3, 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 |
| CN106189297A (en) * | 2016-08-17 | 2016-12-07 | 河南师范大学 | A kind of conductive asphalt and preparation method thereof |
| CN106185904A (en) * | 2016-07-15 | 2016-12-07 | 浙江大学 | A kind of high fold graphene paper |
| CN106277072A (en) * | 2016-08-24 | 2017-01-04 | 合肥学院 | A kind of graphene/nickel cobalt aluminum layered double-hydroxide composite and preparation method thereof |
| CN106698403A (en) * | 2017-01-06 | 2017-05-24 | 南京工业大学 | Method of preparing graphene roll in large area |
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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 |
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| CN106277072A (en) * | 2016-08-24 | 2017-01-04 | 合肥学院 | A kind of graphene/nickel cobalt aluminum layered double-hydroxide composite and preparation method thereof |
| CN106698403A (en) * | 2017-01-06 | 2017-05-24 | 南京工业大学 | Method of preparing graphene roll in large area |
| 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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