CN103387228B - Preparation method for graphene scrolls - Google Patents
Preparation method for graphene scrolls Download PDFInfo
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- CN103387228B CN103387228B CN201310309672.6A CN201310309672A CN103387228B CN 103387228 B CN103387228 B CN 103387228B CN 201310309672 A CN201310309672 A CN 201310309672A CN 103387228 B CN103387228 B CN 103387228B
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Abstract
The invention provides a preparation method for graphene scrolls. The method comprises steps of mixing a graphene oxide water solution with a strong alkali to perform a reaction to obtain the graphene scrolls, wherein the molar concentration of the strong alkali in the graphene oxide water solution is n, and the n is not less than 12 mol/L. The preparation method has mild reaction conditions, simple operation and low cost, and is prone to popularization and application. Experiments show that the graphene scrolls prepared by the preparation method have complete structures and good quality.
Description
Technical field
The present invention relates to technical field of graphene, especially relate to a kind of preparation method of graphene roll.
Background technology
Graphene (Graphene) is a kind of novel material of the individual layer sheet structure be made up of carbon atom.It a kind ofly forms with sp2 hybridized orbital the flat film that hexangle type is honeycomb lattice by carbon atom, only has the two-dimensional material of a carbon atom thickness.Graphene is very easily reunited, and people imagine graphene platelet curling, forms a kind of web-like nano-carbon material-graphene roll (graphene scrolls) being similar to carbon nanotube between a peacekeeping two dimension.
Relative to carbon nanotube, graphene roll as a kind of novel grapheme material, edge non-close, footpath spacing easily regulates and controls, and has higher specific surface area; Relative to Graphene, curling the brought limit threshold effect of radial nano-scale of graphene roll can significantly improve the catalytic performance of itself and form the catalytic performance of the system that supports as carrier.Research shows, graphene roll has good electricity and chemical property because of its special topological framework, is with a wide range of applications in fields such as ultracapacitor, hydrogen storage material, catalysis, sensor and nano electron devices.
Prior art discloses the multiple method preparing graphene roll, as Lisa M V(Julia J M, RichardB K.A Chemical Route to Carbon Nanoscrolls [J] .Science, 2003.299 (5611): 1361) etc. a kind of method preparing graphene roll is reported.Under inert conditions, potassium metal is inserted flaky graphite between layers, form lamellar compound KC
8, KC
8further with ethanol synthesis, produce a large amount of heat and micro-molecular gas thus cause peeling off of graphite flake, potassium ion dissolves and effusion with hydrogen can help graphite laminated further, and by sonication, the graphite flake oneself of peeling off is curling, forms graphene roll.But this method is due to KC
8in atmosphere easily and oxygenant and water react and decompose, need carry out under inert conditions, therefore be unfavorable for the preparation of extensive graphene roll.
Zhou Xufeng, Liu Zhao equality discloses a kind of method (CN102976316A) preparing graphene roll.The method is by first mixing the organic solution of aniline with the graphene oxide water solution containing initiator, initiator causes aniline polymerization, graphene oxide reacts at the interface of organic solvent and water and aniline, form the matrix material of graphene oxide/polyaniline, again by graphene oxide/polyaniline dry heat, utilize that composite material surface tension force in dry heat process changes, graphene oxide is reduced to Graphene and curls into graphene roll.But the preparation of this graphene roll needs by completing in the surface reaction of organic solvent and water, therefore productive rate is low and operate more complicated, thus limits it and apply on a large scale.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is the preparation method providing a kind of graphene roll, preparation method's reaction temperature of graphene roll provided by the invention and, simple to operate, cost is lower.
The invention provides a kind of preparation method of graphene roll, comprising:
React after graphene oxide water solution is mixed with highly basic, obtain graphene roll;
The volumetric molar concentration of described highly basic in graphene oxide water solution is n, and described n meets the following conditions: n >=12mol/L.
Preferably, the mass concentration of described graphene oxide water solution is m, and described m meets the following conditions: 0g/L < m≤0.3g/L.
Preferably, described highly basic is lithium hydroxide, sodium hydroxide or potassium hydroxide.
Preferably, described steps A) be specially:
A1) graphene oxide water solution mixed with highly basic and stir, obtaining mixing solutions;
A2) above-mentioned mixing solutions is carried out hydro-thermal reaction in encloses container, obtain graphene roll.
Preferably, the temperature of described hydro-thermal reaction is 80 ~ 200 DEG C.
Preferably, the time of described hydro-thermal reaction is 0.5 ~ 48 hour.
Preferably, described encloses container is closed reactor.
Compared with prior art, the present invention reacts after graphene oxide water solution being mixed with highly basic, obtains graphene roll, the volumetric molar concentration >=12mol/L of described highly basic in graphene oxide water solution.Highly basic or strong alkali aqueous solution mix with graphene oxide water solution and stir by the present invention, be mixed with the graphene aqueous solution that alkali concn is higher, then by hydro-thermal reaction, graphene oxide reduced under high density highly basic existence condition, spontaneous crimp simultaneously, forms graphene roll.Preparation method's reaction conditions of graphene roll provided by the invention is gentle, simple to operate, cost is lower, is easy to be extended and applied.Experimental result shows, graphene roll structural integrity prepared by the present invention, quality is better.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope diagram of the graphene roll prepared in the embodiment of the present invention 1;
Fig. 2 is the scanning electron microscope diagram of the graphene roll prepared in the embodiment of the present invention 2.
Embodiment
The invention provides a kind of preparation method of graphene roll, comprising:
React after graphene oxide water solution is mixed with highly basic, obtain graphene roll;
The volumetric molar concentration of described highly basic in graphene oxide water solution is n, and described n meets the following conditions: n >=12mol/L.
Highly basic or strong alkali aqueous solution mix with graphene oxide water solution and stir by the present invention, be mixed with the graphene aqueous solution that alkali concn is higher, then by hydro-thermal reaction, graphene oxide reduced under high density highly basic existence condition, spontaneous crimp simultaneously, forms graphene roll.
The all raw materials of the present invention, are not particularly limited its source, commercially buy.
First graphene oxide water solution mixes with highly basic and stirs by the present invention, obtains mixing solutions; The volumetric molar concentration of described highly basic in graphene oxide water solution, namely in mixing solutions, the volumetric molar concentration of highly basic is n, and described n preferably meets the following conditions: n >=12mol/L, is more preferably n >=15mol/L; The mass concentration of described graphene oxide water solution is m, and described m preferably meets the following conditions: 0g/L < m≤0.3g/L, is more preferably 0.1g/L < m≤0.2g/L; Described highly basic is preferably lithium hydroxide, sodium hydroxide or potassium hydroxide, is more preferably sodium hydroxide or potassium hydroxide.
The method of the present invention to mixing is not particularly limited, and mixes; The condition of the present invention to mixing is not particularly limited, with mixing condition well known to those skilled in the art; The present invention is not particularly limited the method stirred, with stirring means well known to those skilled in the art; The present invention is not particularly limited agitation condition, with agitation condition well known to those skilled in the art; The present invention is not particularly limited whipping device, with whipping device well known to those skilled in the art.
The present invention is also unrestricted to the preparation method of described graphene oxide, preferably adopts the Hummers method improved to prepare:
Rear for the mixing of 1.5g graphite, 1.5g saltpetre and the 90mL vitriol oil and 9g potassium permanganate are reacted, adds 100mL deionized water and 2mL hydrogen peroxide after reaction terminates, obtain 2g graphene oxide.The present invention is not particularly limited for described hybrid mode, hybrid mode well known to those skilled in the art; Described reaction is preferably reacts under the condition stirred; Described temperature of reaction is preferably room temperature; The described reaction times is preferably 1 ~ 10h; Described add deionized water and hydrogen peroxide after preferably also comprise centrifugal rear cleaning supernatant liquor to pH for neutral.The present invention is also unrestricted for described centrifugation, centrifugation well known to those skilled in the art.
Above-mentioned mixing solutions is placed in encloses container and carries out hydro-thermal reaction by the present invention, obtains graphene roll.First above-mentioned mixing solutions is placed in encloses container and carries out hydro-thermal reaction by the present invention.The temperature of described hydro-thermal reaction is preferably 80 ~ 200 DEG C, is more preferably 100 ~ 180 DEG C; The time of described hydro-thermal reaction is preferably 0.5 ~ 48 hour, is more preferably 2 ~ 45 hours; The present invention is not particularly limited described encloses container, is preferably closed reactor; The present invention's other conditions to hydro-thermal reaction are not particularly limited, with hydrothermal reaction condition well known to those skilled in the art.
Secondly, the present invention is carrying out after hydro-thermal reaction obtains reaction mixture, preferably above-mentioned reaction mixture being cooled to room temperature, then after repeatedly washing and filtering, obtaining graphene roll.The present invention repeatedly washs above-mentioned cooled reaction mixture and filters, to remove the soluble inorganic salt impurity in reaction mixture.The mode of the present invention to cooling is not particularly limited, and is preferably Temperature fall; The medium of the present invention to washing is not particularly limited, and is preferably deionized water; The present invention is not particularly limited the method for filtering, with filter method well known to those skilled in the art; The present invention is not particularly limited filter plant, with filter plant well known to those skilled in the art.
The present invention, after obtaining above-mentioned graphene roll, preferably can prepare graphene roll powder, to strengthen the range of application of graphene roll by oven dry, cryodesiccated method; The present invention is not particularly limited drying condition, with the condition of oven dry graphene roll well known to those skilled in the art; The present invention is not particularly limited drying plant, with drying plant well known to those skilled in the art.
It, after obtaining above-mentioned graphene roll, preferably can also be dispersed in other solvents, obtain graphene roll solution after dispersion, to strengthen the range of application of graphene roll by the present invention again; The present invention is not particularly limited solvent, with well known to those skilled in the art can dispersed graphite alkene volume solvent; The mode of the present invention to dispersion is not particularly limited, and is preferably ultrasonic disperse; The present invention is not particularly limited ultrasonic disperse equipment, with ultrasonic disperse equipment well known to those skilled in the art.
Preparation method's reaction temperature provided by the invention and, simple to operate, cost is lower, be easy to be extended and applied.Experimental result shows the graphene roll structural integrity that the present invention prepares, and quality is better.
In order to further illustrate the present invention, below in conjunction with embodiment, the preparation method to graphene roll provided by the invention is described in detail.
Embodiment 1
First rear for the mixing of 1.5g graphite, 1.5g saltpetre and the 90mL vitriol oil and 9g potassium permanganate are reacted, add 100mL deionized water and 2mL hydrogen peroxide after reaction terminates, obtain 2g graphene oxide.Again above-mentioned graphene oxide and deionized water are mixed with the graphene oxide water solution of 0.3g/L.
Then the graphene oxide water solution being 0.3g/L by 40g sodium hydroxide and the above-mentioned mass concentration prepared of 75ml mixes, and uniform stirring obtains mixing solutions, again above-mentioned mixing solutions is placed in the closed reactor of 100ml, hydro-thermal reaction is carried out at 120 DEG C, react 8 hours, obtain reaction mixture.
Finally above-mentioned reaction mixture is naturally cooled to room temperature, more repeatedly wash with deionized water, filter, other soluble inorganic salt impurity in removing solution, obtains 0.02g graphene roll.
As shown in Figure 1, Fig. 1 is the scanning electron microscope diagram of the graphene roll prepared in the embodiment of the present invention 1 to result, and as shown in Figure 1, the present invention obtains graphene roll, and its structural integrity.
The graphene roll obtained after above-mentioned washing can be prepared graphene roll powder, or is again dispersed in other solvent by the graphene roll after washes clean again by oven dry, cryodesiccated method, is obtained the graphene roll solution of good dispersity by ultrasonic disperse.
Embodiment 2
First rear for the mixing of 1.5g graphite, 1.5g saltpetre and the 90mL vitriol oil and 9g potassium permanganate are reacted, add 100mL deionized water and 2mL hydrogen peroxide after reaction terminates, obtain 2g graphene oxide.Again above-mentioned graphene oxide and deionized water are mixed with the graphene oxide water solution of 0.3g/L.
Then the graphene oxide water solution being 0.2g/L by 60g potassium hydroxide and the above-mentioned mass concentration prepared of 75ml mixes, and uniform stirring obtains mixing solutions, again above-mentioned mixing solutions is placed in the closed reactor of 100ml, hydro-thermal reaction is carried out at 80 DEG C, react 48 hours, obtain reaction mixture.
Finally above-mentioned reaction mixture is naturally cooled to room temperature, more repeatedly wash with deionized water, filter, other soluble inorganic salt impurity in removing solution, obtains 0.01g graphene roll.
As shown in Figure 2, Fig. 2 is the scanning electron microscope diagram of the graphene roll prepared in the embodiment of the present invention 2 to result, and as shown in Figure 2, the present invention obtains graphene roll, and its structural integrity.
The graphene roll obtained after above-mentioned washing can be prepared graphene roll powder, or is again dispersed in other solvent by the graphene roll after washes clean again by oven dry, cryodesiccated method, is obtained the graphene roll solution of good dispersity by ultrasonic disperse.
Embodiment 3
First rear for the mixing of 1.5g graphite, 1.5g saltpetre and the 90mL vitriol oil and 9g potassium permanganate are reacted, add 100mL deionized water and 2mL hydrogen peroxide after reaction terminates, obtain 2g graphene oxide.Again above-mentioned graphene oxide and deionized water are mixed with the graphene oxide water solution of 0.3g/L.
Then the graphene oxide water solution being 0.3g/L by 40g sodium hydroxide and the above-mentioned mass concentration prepared of 25ml mixes, and uniform stirring obtains mixing solutions, again above-mentioned mixing solutions is placed in the closed reactor of 100ml, hydro-thermal reaction is carried out at 180 DEG C, react 12 hours, obtain reaction mixture.
Finally above-mentioned reaction mixture is naturally cooled to room temperature, more repeatedly wash with deionized water, filter, other soluble inorganic salt impurity in removing solution, obtains 0.007g graphene roll.
The graphene roll obtained after above-mentioned washing can be prepared graphene roll powder, or is again dispersed in other solvent by the graphene roll after washes clean again by oven dry, cryodesiccated method, is obtained the graphene roll solution of good dispersity by ultrasonic disperse.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (4)
1. a preparation method for graphene roll, comprises the following steps:
A) react after graphene oxide water solution being mixed with highly basic, obtain graphene roll;
Described reaction is hydro-thermal reaction, and the temperature of described hydro-thermal reaction is 80 ~ 200 DEG C; The time of described hydro-thermal reaction is 0.5 ~ 48 hour;
The volumetric molar concentration of described highly basic in graphene oxide water solution is n, and described n meets the following conditions: n >=12mol/L; Described highly basic is lithium hydroxide, sodium hydroxide or potassium hydroxide.
2. preparation method according to claim 1, is characterized in that, the mass concentration of described graphene oxide water solution is m, and described m meets the following conditions: 0g/L < m≤0.3g/L.
3. preparation method according to claim 1, is characterized in that, described steps A) be specially:
A1) graphene oxide water solution mixed with highly basic and stir, obtaining mixing solutions;
A2) above-mentioned mixing solutions is carried out hydro-thermal reaction in encloses container, obtain graphene roll.
4. preparation method according to claim 3, is characterized in that, described encloses container is closed reactor.
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| CN105948031B (en) * | 2016-07-04 | 2017-09-19 | 西北有色金属研究院 | A kind of preparation method of graphene nano volume |
| CN106698403B (en) * | 2017-01-06 | 2019-01-18 | 南京工业大学 | A kind of method of large area preparation graphene roll |
| CN107055511B (en) * | 2017-04-13 | 2019-04-16 | 常州纳欧新材料科技有限公司 | A kind of three-dimensional cross-linked carbon nanotube and preparation method thereof |
| CN106976869A (en) * | 2017-04-26 | 2017-07-25 | 同济大学 | A kind of three-dimensional sleeve-shaped graphene and preparation method thereof |
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Non-Patent Citations (2)
| Title |
|---|
| Deoxygenation of Exfoliated Graphite Oxide under Alkaline Conditions: A Green Route to Graphene Preparation;Xiaobin Fan et al.;《Advanced Materials》;20081006;第20卷;第4490-4493页 * |
| The Real Graphene Oxide Revealed: Stripping the Oxidative Debris from the Graphene-like Sheets;Jonathan P. Rourke et al.;《Angew. Chem.》;20111231;第123卷;第3231-3235页 * |
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