CN113880079B - Graphene nano roll and preparation method thereof - Google Patents
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Abstract
The invention provides a graphene nano roll and a preparation method thereof, belonging to the technical field of new material preparation. The preparation method of the graphene nano roll provided by the invention comprises the following steps: preparing a graphite oxide mixed solution containing graphite oxide, hydrogen ions and sulfate ions by using a modified Hummers method, performing ultrasonic treatment on the graphite oxide mixed solution, adding an appropriate amount of alkaline solution to adjust the pH of the solution, adding an organic alcohol solution into the solution, separating to obtain a graphene oxide mixed material, performing heat preservation treatment on the obtained graphene oxide mixed material, adding deionized water while the material is hot, fully stirring, repeatedly washing and drying a reaction product, placing the dried product in a tubular furnace, heating in a protective atmosphere, and collecting a product, namely the graphene nano roll. The method has the advantages of simple process, short preparation period, low cost, no pollution, high quality of the prepared graphene nano roll and convenience for large-scale preparation, popularization and application.
Description
Technical Field
The invention belongs to the technical field of new material preparation, and particularly relates to a graphene nano roll and a preparation method thereof.
Background
The graphene nanocolloid is one of graphene material derivatives, can be regarded as a one-dimensional roller formed by curling a two-dimensional graphene sheet by a special method, and has a special one-dimensional tubular topological structure. Therefore, the graphene nano roll not only has excellent physical and chemical properties of graphene, such as electrical conductivity, mechanical property, optical property, heat conductivity and the like. In addition, the tubular topological structure enables the graphene to be free from interference of an external atmosphere and a substrate when transporting electrons, and the performance of the graphene device is greatly influenced by the same interference.
Both ends and one side of the graphene nanoribbon are open. Therefore, the graphene nano coil can encapsulate various external particles in the inner cavity of the graphene nano coil and inhibit the radial expansion of ions, and due to the fact that pi electrons between the concentric shaft layers of the graphene nano coil are continuous, the graphene nano coil can be under the action of pi-pi electrons of the inner layer and the outer layer when transporting electrons, and due to the unique properties, the graphene nano coil has wide application prospects in the fields of electronic devices, catalysis, adsorption, biosensors, environmental protection, composite materials, energy storage and the like.
At present, the preparation method of the graphene nano roll mainly comprises a freeze drying method, a template method, an ion induction method, an ultrasonic method, a high-energy ball milling method, an arc discharge method, a photoetching technology and the like, but the preparation method has high requirement on conditions, complicated preparation steps, high preparation difficulty and a large number of byproducts, and also faces the challenges of cost benefit and scale-up production. Therefore, there is an urgent need to develop a method for producing graphene nanocoils in a simple and convenient manner with low requirements for preparation conditions and in a large scale.
Disclosure of Invention
The invention aims to provide a graphene nano roll and a preparation method thereof, and solves the problems that the method for preparing the graphene nano roll in the prior art is high in requirement on conditions, complicated in preparation steps, high in preparation difficulty, high in byproduct, high in cost, incapable of realizing mass production and the like.
The technical scheme of the invention is as follows:
a preparation method of graphene nano-volume comprises the following steps:
(1) Preparing a graphite oxide mixed solution containing graphite oxide, hydrogen ions and sulfate ions by adopting a modified Hummers method, carrying out ultrasonic treatment on the prepared graphite oxide mixed solution, and adding a proper amount of alkaline solution into the mixed solution to adjust the pH value of the solution to 5-8 after the ultrasonic treatment is finished;
(2) Adding an organic alcohol solution into the solution obtained in the step (1), and filtering and separating to obtain a graphene oxide mixed material;
(3) Placing the graphene oxide mixed material obtained in the step (2) at the temperature of 130-200 ℃, and preserving heat for 2-4h;
(4) Adding the graphene oxide mixed material into deionized water while the graphene oxide mixed material is hot after heat preservation is finished, and fully stirring;
(5) Repeatedly washing the solid product obtained in the step (4) by using deionized water, and then placing the solid product in a drying box for drying;
(6) And (5) placing the product obtained in the step (5) in a tube furnace, heating to 300-800 ℃ in a protective atmosphere, preserving heat for 1-4h, and collecting the product after the tube furnace is cooled to room temperature, namely the graphene nano roll.
Further, the concentration of the graphite oxide in the graphite oxide mixed solution in the step (1) is as follows: 0.5-5g/L, the ultrasonic treatment power is 500-1000W, and the ultrasonic treatment time is 1-5h.
Further, the alkaline solution in the step (1) is KOH, naOH and NH 4 One or more of OH.
Further, the organic alcohol solution in step (2) includes one or more of ethanol, ethylene glycol and polyethylene glycol.
Further, the volume ratio of the organic alcohol solution to the graphite oxide mixed solution in the step (2) is 0.5-5.
Further, the temperature of the deionized water in the step (4) is 25-90 ℃, and the stirring time is 5-10min.
Further, the number of repeated washing in the step (5) is 3 to 4.
Further, the protective atmosphere in the step (6) is any one of nitrogen, argon or argon-hydrogen mixed gas.
Furthermore, the drying temperature in the step (5) is 60-80 ℃, and the drying time is 4-6h.
The invention also aims to provide the graphene nano coil prepared by adopting the method.
The invention has the beneficial effects that:
1. according to the invention, the modified Hummers method is adopted to prepare the graphite oxide mixed solution containing graphite oxide, hydrogen ions and sulfate ions without separation and purification steps, the alkaline solution is added into the graphite oxide mixed solution to adjust the pH value of the graphite oxide mixed solution, and the organic alcohol solution is added, so that sulfate is separated out from sulfate ions and cations in the alkaline solution in the anti-solvent reaction process initiated after the organic alcohol is added, and the sulfate is loaded on the surface of graphene oxide to obtain the graphene oxide mixed material, thereby effectively avoiding the problems of agglomeration and stacking of the graphene oxide;
2. according to the method, the surface stress generated by the rapid dissolution and removal process of sulfate in the graphene oxide mixed material in water on the graphene oxide is fully utilized, the two-dimensional graphene oxide is induced and driven to curl, and the spontaneous winding of the graphene is realized;
3. according to the invention, the graphene oxide mixed material is placed at a proper heat preservation temperature, so that a part of oxygen-containing functional groups of the graphene oxide are removed, and the occurrence of curling is facilitated. Meanwhile, the higher heat preservation temperature (130-200 ℃) can ensure that the sulfate in the graphene oxide mixed material can be dissolved and removed in water when the graphene oxide mixed material is hot, and larger surface driving stress is generated on the graphene oxide, thereby being beneficial to the driving and winding process;
4. according to the invention, the temperature in the tubular furnace is set within a proper temperature range, so that the graphene oxide is fully reduced;
5. the method provided by the invention can be used for preparing a large number of graphene nano rolls with high winding compactness;
6. the method has the advantages of simple process, easy operation, no need of special harsh devices, low requirement on preparation conditions, low cost and easy large-scale production.
Drawings
Fig. 1 is a scanning electron microscope image of a graphene nanocolloid prepared in example 1 of the present invention;
FIG. 2 is a scanning electron micrograph of graphene nanocoils prepared in example 2 of the present invention;
FIG. 3 is a scanning electron micrograph of graphene nanocoils prepared in example 3 of the present invention;
FIG. 4 is a transmission electron micrograph of graphene nanocoils prepared in example 3 of the present invention;
FIG. 5 is a scanning electron micrograph of graphene nanocoils prepared in example 4 of the present invention;
FIG. 6 is a transmission electron micrograph of graphene nanocoils prepared in example 4 of the present invention;
FIG. 7 is a scanning electron micrograph of graphene nanocoils prepared in example 5 of the present invention;
fig. 8 is a scanning electron micrograph of a graphene nanocoil prepared in example 6 of the present invention;
FIG. 9 is a scanning electron micrograph of graphene nanocoils prepared in example 7 of the present invention;
Detailed Description
The present invention is described in detail below by way of examples, it should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and those skilled in the art can make some insubstantial modifications and adaptations of the present invention based on the above-described disclosure. In the following examples, reagents and equipment not specifically described are commercially available, and experimental procedures not specifically described are carried out according to manufacturer's specifications or conventional techniques in the art, unless otherwise defined, and all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the practice of the present invention.
The embodiment of the invention provides a preparation method of a graphene nano roll, which comprises the following steps:
(1) Preparing a graphite oxide mixed solution containing graphite oxide, hydrogen ions and sulfate ions by adopting a modified Hummers method, carrying out ultrasonic treatment on the prepared graphite oxide mixed solution, and adding a proper amount of alkaline solution into the mixed solution to adjust the pH value of the solution to 5-8 after the ultrasonic treatment is finished;
(2) Adding an organic alcohol solution into the solution obtained in the step (1), and filtering and separating to obtain a graphene oxide mixed material;
(3) Placing the graphene oxide mixed material obtained in the step (2) at the temperature of 130-200 ℃, and preserving heat for 2-4h;
(4) Adding the graphene oxide mixed material into deionized water while the graphene oxide mixed material is hot after the heat preservation is finished, and fully stirring;
(5) Repeatedly washing the solid product obtained in the step (4) by using deionized water, and then placing the solid product in a drying box for drying;
(6) And (5) placing the product obtained in the step (5) in a tube furnace, heating to 300-800 ℃ in a protective atmosphere, preserving heat for 1-4h, and collecting the product after the tube furnace is cooled to room temperature, namely the graphene nano roll.
According to the preparation method of the graphene nanocolloid provided by the embodiment of the invention, the modified Hummers method is adopted to prepare the graphite oxide mixed solution containing graphite oxide, hydrogen ions and sulfate ions without separation and purification steps, the alkaline solution is added into the graphite oxide mixed solution to adjust the pH value of the graphite oxide mixed solution, and the organic alcohol solution is added, so that sulfate is separated out from sulfate ions and cations in the alkaline solution in the anti-solvent reaction process initiated after the organic alcohol is added, and the sulfate is loaded on the surface of graphene oxide to obtain the graphene oxide mixed material, thereby effectively avoiding the problems of agglomeration and stacking of graphene oxide; and the graphene oxide mixed material is placed at a proper heat preservation temperature of 130-200 ℃ for heat preservation, so that part of oxygen-containing functional groups of the graphene oxide are removed, and the occurrence of curling is facilitated; the surface stress generated by the graphene oxide in the process of quickly dissolving and removing sulfate in the graphene oxide mixed material in water is fully utilized to induce and drive the two-dimensional graphene oxide to curl, so that the spontaneous winding of the graphene is realized; and finally, placing the graphene oxide tube in a tube type with a proper temperature for heating, and ensuring that the graphene oxide is fully reduced to form the graphene nano coil.
It should be noted that: the invention adopts the modified Hummers method to prepare the graphite oxide mixed solution containing graphite oxide, hydrogen ions and sulfate ions, which is the prior art, namely the required graphite oxide mixed solution is obtained by adopting the prior modified Hummers method without final separation and purification steps.
In some preferred embodiments of the present invention, the temperature of the graphene oxide mixed material in the step (3) may also be 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃; the heat preservation time can also be selected from 2h, 2.5h, 3h and 3.5h.
In some preferred embodiments of the present invention, the heating temperature in step (6) may be selected from 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃; the heating time can also be selected from 1.5h, 2h, 2.5h, 3h and 3.5h.
In some preferred embodiments of the present invention, the concentration of graphite oxide in the graphite oxide mixed solution in step (1) is: 0.5-5g/L, the ultrasonic treatment power is 500-1000W, and the ultrasonic treatment time is 1-5h. The concentration of the graphite oxide can also be selected from 1g/L, 1.5g/L, 2g/L, 2.5g/L, 3g/L, 3.5g/L, 4g/L and 4.5g/L; the ultrasonic treatment power can be 600W, 700W, 800W and 900W, and the ultrasonic treatment time can be 2h, 2.5h, 3h, 3.5h, 4h and 4.5h.
In some preferred embodiments of the present invention, the alkaline solution in step (1) is KOH, naOH, or NH 4 One or more of OH.
In some preferred embodiments of the present invention, the organic alcohol solution in step (2) comprises one or more of ethanol, ethylene glycol and polyethylene glycol.
In some preferred embodiments of the present invention, the volume ratio of the organic alcohol solution to the graphite oxide mixed solution in step (2) is 0.5-5, and 1.
In some preferred embodiments of the present invention, the temperature of the deionized water in the step (4) is 25-90 ℃ and the stirring time is 5-10min. The deionized water temperature can be selected from 30 deg.C, 35 deg.C, 40 deg.C, 45 deg.C, 50 deg.C, 55 deg.C, 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C, 80 deg.C, and 85 deg.C; the stirring time can be selected from 6min, 7min, 8min and 9min.
In some preferred embodiments of the present invention, the number of washing repetitions in step (5) is 3 to 4.
In some preferred embodiments of the present invention, the protective atmosphere in step (6) is any one of nitrogen, argon or argon-hydrogen mixed gas.
In some preferred embodiments of the present invention, the drying temperature in step (5) is 60-80 ℃ and the drying time is 4-6h. The drying temperature can also be 65 deg.C, 70 deg.C, 75 deg.C; the drying time can also be selected from 4.5h, 5h and 5.5h.
The graphene nano roll is prepared by the preparation method of the graphene nano roll, and has high winding compactness.
The following are specific examples:
example 1
A preparation method of graphene nano-volume comprises the following steps:
(1) Preparing a graphite oxide mixed solution containing graphite oxide, hydrogen ions and sulfate ions by adopting a modified Hummers method, carrying out ultrasonic treatment on 150ml of 1g/L graphite oxide mixed solution for 2 hours under the ultrasonic power of 800W, and adding a certain amount of 1mol -1 The final pH value of the solution is 5-8;
(2) Adding 200mL of ethanol solution into the solution obtained in the step (1), and filtering and separating to obtain a graphene oxide mixed material;
(3) Placing the graphene oxide mixed material obtained in the step (2) at 130 ℃, and preserving heat for 4h;
(4) Adding the graphene oxide mixed material after the heat preservation into deionized water at 45 ℃ while the material is hot, and stirring for reaction for 5min;
(5) Repeatedly washing the solid product obtained in the step (4) for 3 times by using deionized water, and then drying the solid product in a drying oven at 60 ℃ for 6 hours;
(6) And (4) heating the product obtained in the step (5) in a tube furnace filled with argon and at the temperature of 500 ℃ for 3 hours, and collecting the product after the tube furnace is cooled to the room temperature.
Observing the product prepared in the embodiment by using a scanning electron microscope, as shown in fig. 1, it can be seen that the two-dimensional sheet graphene is curled, and the graphene nanocolloid is obtained.
Example 2
A preparation method of a graphene nano roll comprises the following steps:
(1) Preparing a graphite oxide mixed solution containing graphite oxide, hydrogen ions and sulfate ions by adopting a modified Hummers method, carrying out ultrasonic treatment on 150ml of 1g/L graphite oxide mixed solution for 2 hours under the ultrasonic power of 800W, and adding a certain amount of 1mol -1 In the presence of a NaOH solution of (2),so that the final pH value of the solution is 5-8;
(2) Adding 200mL of ethanol solution into the solution obtained in the step (1), and filtering and separating to obtain a graphene oxide mixed material;
(3) Placing the graphene oxide mixed material obtained in the step (2) at a temperature of 140 ℃, and preserving heat for 4 hours;
(4) Adding the graphene oxide mixed material after the heat preservation into deionized water at 45 ℃ while the material is hot, and stirring for reaction for 5min;
(5) Repeatedly washing the solid product obtained in the step (4) for 3 times by using deionized water, and then drying the solid product in a drying oven at 60 ℃ for 6 hours;
(6) And (4) heating the product obtained in the step (5) in a tube furnace filled with argon and at the temperature of 500 ℃ for 3 hours, and collecting the product after the tube furnace is cooled to the room temperature.
Observing the product prepared by the embodiment by using a scanning electron microscope, as shown in fig. 2, it can be seen that the two-dimensional sheet graphene is curled to obtain a graphene nano roll, and the surface morphology of the graphene nano roll can be obviously observed.
Example 3
A preparation method of a graphene nano roll comprises the following steps:
(1) Preparing a graphite oxide mixed solution containing graphite oxide, hydrogen ions and sulfate ions by adopting a modified Hummers method, carrying out ultrasonic treatment on 150ml of 1g/L graphite oxide mixed solution for 2 hours under the ultrasonic power of 800W, and adding a certain amount of 1mol -1 The final pH value of the solution is 5-8;
(2) Adding 200mL of ethanol solution into the solution obtained in the step (1), and filtering and separating to obtain a graphene oxide mixed material;
(3) Placing the graphene oxide mixed material obtained in the step (2) at the temperature of 150 ℃, and preserving heat for 4 hours;
(4) Adding the graphene oxide mixed material after the heat preservation into deionized water at 45 ℃ while the mixed material is hot, and stirring for reaction for 5min;
(5) Repeatedly washing the solid product obtained in the step (4) with deionized water for 3 times, and then drying in a drying oven at 60 ℃ for 6 hours;
(6) And (4) heating the product obtained in the step (5) in a tube furnace filled with argon and at the temperature of 500 ℃ for 3h, and collecting the product after the tube furnace is cooled to room temperature.
When the product prepared in this example is observed by using a scanning electron microscope, as shown in fig. 3, it can be seen that the two-dimensional graphene sheet is curled to form a graphene nano roll with a winding structure, and the diameter of the graphene nano roll is less than 100nm.
The graphene nano-roll prepared in this example is characterized by TEM, and as shown in fig. 4, it can be seen that the diameter of the graphene nano-roll prepared under the conditions of this example is about 60nm.
Example 4
A preparation method of a graphene nano roll comprises the following steps:
(1) Preparing a graphite oxide mixed solution containing graphite oxide, hydrogen ions and sulfate ions by adopting a modified Hummers method, carrying out ultrasonic treatment on 150ml of 1g/L graphite oxide mixed solution for 2 hours under the ultrasonic power of 800W, and adding a certain amount of 1mol -1 The final pH value of the solution is 5-8;
(2) Adding 200mL of ethanol solution into the solution obtained in the step (1), and filtering and separating to obtain a graphene oxide mixed material;
(3) Placing the graphene oxide mixed material obtained in the step (2) at a temperature of 180 ℃, and preserving heat for 4 hours;
(4) Adding the graphene oxide mixed material after the heat preservation into deionized water at 45 ℃ while the mixed material is hot, and stirring for reaction for 5min;
(5) Repeatedly washing the solid product obtained in the step (4) for 3 times by using deionized water, and then drying the solid product in a drying oven at 60 ℃ for 6 hours;
(6) And (4) heating the product obtained in the step (5) in a tube furnace filled with argon and at the temperature of 500 ℃ for 3h, and collecting the product after the tube furnace is cooled to room temperature.
When the product prepared in this embodiment is observed by using a scanning electron microscope, as shown in fig. 5, it can be seen that the two-dimensional graphene sheet is curled to form a graphene nano-roll with high winding compactness.
The graphene nano-roll prepared in this example is characterized by TEM, and as shown in fig. 6, it can be seen that the diameter of the graphene nano-roll prepared under the conditions of this example is about 40 nm.
Example 5
A preparation method of a graphene nano roll comprises the following steps:
(1) Preparing a graphite oxide mixed solution containing graphite oxide, hydrogen ions and sulfate ions by adopting a modified Hummers method, carrying out ultrasonic treatment on 150ml of 1g/L graphite oxide mixed solution for 2 hours under the ultrasonic power of 800W, and adding a certain amount of 1mol -1 So that the final pH value of the solution is 7;
(2) Adding 200mL of ethanol solution into the solution obtained in the step (1), and filtering and separating to obtain a graphene oxide mixed material;
(3) Placing the graphene oxide mixed material obtained in the step (2) at the temperature of 200 ℃, and preserving heat for 4 hours;
(4) Adding the graphene oxide mixed material after the heat preservation into deionized water at 45 ℃ while the material is hot, and stirring for reaction for 5min;
(5) Repeatedly washing the solid product obtained in the step (4) with deionized water for 3 times, and then drying in a drying oven at 60 ℃ for 6 hours;
(6) And (4) heating the product obtained in the step (5) in a tube furnace filled with argon and at the temperature of 500 ℃ for 3h, and collecting the product after the tube furnace is cooled to room temperature.
When the product prepared in this embodiment is observed by using a scanning electron microscope, as shown in fig. 7, it is seen that the two-dimensional graphene sheet is curled to form a graphene nano roll with high winding compactness, but a part of the surface of the graphene nano roll has pores because of a slight reduction reaction between graphene and sodium sulfate.
Example 6
A preparation method of a graphene nano roll comprises the following steps:
(1) MiningPreparing a graphite oxide mixed solution containing graphite oxide, hydrogen ions and sulfate ions by a modified Hummers method, carrying out ultrasonic treatment on 150ml of 1g/L graphite oxide mixed solution for 5h under the ultrasonic power of 500W, and adding a certain amount of 1mol -1 The final pH value of the solution is 5-8;
(2) Adding 200mL of ethanol solution into the solution obtained in the step (1), and filtering and separating to obtain a graphene oxide mixed material;
(3) Placing the graphene oxide mixed material obtained in the step (2) at the temperature of 180 ℃, and preserving heat for 2 hours;
(4) Adding the graphene oxide mixed material after the heat preservation into deionized water at 25 ℃ while the mixed material is hot, and stirring for reaction for 10min;
(5) Repeatedly washing the solid product obtained in the step (4) with deionized water for 3 times, and then drying in a drying oven at 70 ℃ for 5 hours;
(6) And (4) heating the product obtained in the step (5) in a tube furnace filled with argon and at the temperature of 300 ℃ for 4 hours, and collecting the product after the tube furnace is cooled to the room temperature.
When the product prepared in this example is observed by using a scanning electron microscope, as shown in fig. 8, it can be seen that the two-dimensional sheet graphene is curled to form a graphene nano roll with high winding compactness, and the diameter of the graphene nano roll is about 50nm.
Example 7
A preparation method of graphene nano-volume comprises the following steps:
(1) Preparing a graphite oxide mixed solution containing graphite oxide, hydrogen ions and sulfate ions by adopting a modified Hummers method, carrying out ultrasonic treatment on 150ml of 1g/L graphite oxide mixed solution for 1h under the ultrasonic power of 1000W, and adding a certain amount of 1mol after the ultrasonic treatment is finished -1 The final pH value of the solution is 5-8;
(2) Adding 200mL of ethanol solution into the solution obtained in the step (1), and filtering and separating to obtain a graphene oxide mixed material;
(3) Placing the graphene oxide mixed material obtained in the step (2) at a temperature of 180 ℃, and preserving heat for 3 hours;
(4) Adding the graphene oxide mixed material after the heat preservation into deionized water at 90 ℃ while the material is hot, and stirring for reaction for 5min;
(5) Repeatedly washing the solid product obtained in the step (4) for 3 times by using deionized water, and then drying the solid product in a drying oven at the temperature of 80 ℃ for 4 hours;
(6) And (4) heating the product obtained in the step (5) in a tube furnace filled with argon and at the temperature of 800 ℃ for 1h, and collecting the product after the tube furnace is cooled to room temperature.
When the product prepared in this embodiment is observed by using a scanning electron microscope, as shown in fig. 9, it can be seen that the two-dimensional graphene sheet is curled to form a graphene nano roll with high winding compactness, and the diameter of the graphene nano roll is about 40-50nm.
In summary, it should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited too much, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that the technical solutions described in the foregoing embodiments can be easily deduced, replaced, or substituted for some technical features without departing from the spirit of the present invention, and any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of graphene nano-volume is characterized by comprising the following steps: the method comprises the following steps:
(1) Preparing a graphite oxide mixed solution containing graphite oxide, hydrogen ions and sulfate ions by adopting a modified Hummers method, carrying out ultrasonic treatment on the prepared graphite oxide mixed solution, and adding a proper amount of alkaline solution into the mixed solution to adjust the pH value of the solution to 5-8 after the ultrasonic treatment is finished;
(2) Adding an organic alcohol solution into the solution obtained in the step (1), and filtering and separating to obtain a graphene oxide mixed material;
(3) Placing the graphene oxide mixed material obtained in the step (2) at the temperature of 130-200 ℃, and preserving heat for 2-4h;
(4) Adding the graphene oxide mixed material into deionized water while the graphene oxide mixed material is hot after heat preservation is finished, and fully stirring;
(5) Repeatedly washing the solid product obtained in the step (4) by using deionized water, and then placing the solid product in a drying box for drying;
(6) And (6) placing the product obtained in the step (5) in a tube furnace, heating to 300-800 ℃ in a protective atmosphere, preserving heat for 1-4h, and collecting the product after the tube furnace is cooled to room temperature, namely the graphene nano roll.
2. The method for preparing graphene nano-coil according to claim 1, wherein the method comprises the following steps: the concentration of the graphite oxide in the graphite oxide mixed solution in the step (1) is as follows: 0.5-5g/L, the ultrasonic treatment power is 500-1000W, and the ultrasonic treatment time is 1-5h.
3. The method for preparing graphene nano-coil according to claim 1, wherein the method comprises the following steps: the alkaline solution in the step (1) is KOH, naOH and NH 4 One or more of OH.
4. The method for preparing graphene nano-scrolls according to claim 1, wherein: the organic alcohol solution in the step (2) comprises one or more of ethanol, ethylene glycol and polyethylene glycol.
5. The method for preparing graphene nano-coil according to claim 1, wherein the method comprises the following steps: the volume ratio of the organic alcohol solution to the graphite oxide mixed solution in the step (2) is 0.5-5.
6. The method for preparing graphene nano-coil according to claim 1, wherein the method comprises the following steps: the temperature of the deionized water in the step (4) is 25-90 ℃, and the stirring time is 5-10min.
7. The method for preparing graphene nano-coil according to claim 1, wherein the method comprises the following steps: the number of repeated washing in the step (5) is 3-4.
8. The method for preparing graphene nano-scrolls according to claim 1, wherein: the protective atmosphere in the step (6) is any one of nitrogen, argon or argon-hydrogen mixed gas.
9. The method for preparing graphene nano-coil according to claim 1, wherein the method comprises the following steps: the drying temperature of the step (5) is 60-80 ℃, and the drying time is 4-6h.
10. A graphene nanovolume, comprising: the graphene nano-volume is prepared by the method of any one of claims 1 to 9.
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| CN108178149A (en) * | 2018-02-07 | 2018-06-19 | 南京信息工程大学 | A kind of preparation method of graphene nano volume |
| US20190312261A1 (en) * | 2018-04-09 | 2019-10-10 | Nanotek Instruments, Inc. | Production process for a graphene foam-protected selenium cathode and an alkali metal-selenium secondary battery containing same |
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