CN103613093A - Method for preparing graphene through hydrogen gas reduction - Google Patents
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Abstract
The invention relates to a method for preparing graphene through hydrogen gas reduction. The method comprises the steps of mixing natural flake graphite and sodium nitrate, sequentially adding sulfuric acid, potassium permanganate, deionized water and hydrogen peroxide while stirring, carrying out vacuum suction filtration, filtrating, washing by using dilute hydrochloric acid until the pH value is 7, and baking, so as to obtain graphene oxide; putting graphene oxide in an oxygen-free reactor under the protection of inert gas, and introducing reductive gas, namely hydrogen gas, into the reactor after the inside temperature of the reactor reaches the temperature which is used for reducing graphene oxide by hydrogen gas, thereby preparing graphene with very high purity. The method for preparing graphene, disclosed by the invention, is convenient in operation, is simple, easy and feasible, and can be applied to industrial large-scale production.
Description
Technical field
The present invention relates to the preparation method of Graphene, particularly a kind of method of preparing Graphene with hydrogen reducing.
Background technology
Graphene is the graphite of individual layer atomic thickness, has bi-dimensional cellular mesh network structure.Due to the existence of towering track in graphene film plane, electronics can move freely in crystal, makes Graphene have very excellent electronic transmission performance.Owing to having excellent mechanics, calorifics, electricity and magnetic performance, Graphene is expected to obtain a wide range of applications in fields such as high-performance nanometer electronic device, matrix material, field emmision material, gas sensor, energy storage.Graphene is structurally ductile, and its electricity, optics and acoustic characteristics can significantly be adjusted by stress and deformation, even can change the bandwidth structure of Graphene, and to bending, the research of folding and curling Graphene is also just being accelerated to start.Graphene has impayable high electron mobility, and the mobility of electric charge in Graphene can reach unprecedented 200000cm
2/ vs, surpasses silicon more than 100 times.This advantage makes Graphene probably replace silicon, and becomes the transistorized base mateiral of ultra high frequency of future generation, is applied in high performance integrated circuit and novel nano electron device.Thereby, just there will be soon the full carbon circuit of full Graphene formation and be widely used in daily life.
At present, the method for preparing Graphene mainly contains mechanically peel method, SiC matrix surface epitaxial growth method, chemical Vapor deposition process and oxidation reduction process.Mechanically peel method can only obtain minute quantity graphene film, and efficiency is low, randomness is very large; SiC matrix surface epitaxial growth method cost is high, efficiency is low, poor controllability, and nearest STM research shows, the electronic structure heterogeneity of the Graphene that the method is prepared; Chemical Vapor deposition process technique is simple, is easy to patterning, but efficiency is low, poor controllability.Oxidation reduction process is mainly by introducing oxygen-containing functional group, reduce on the one hand the Interaction between layers of graphite, increase interlamellar spacing, change its hybridization state, improve on the other hand its water-wet behavior, make it be easy to expand in the aqueous solution, and then by methods such as heating, supersound process, realize the cleavage layer by layer of graphite, obtaining the grapheme material of functionalization, is a kind of effective ways that are expected to realize the low-cost loud and clear preparation of Graphene.Yet the prepared product of oxidation reduction process adopting mostly at present is the mixture of individual layer, bilayer and multi-layer graphene, the number of plies is difficult to control.The use of oxidation in oxidation reduction process in addition,, expansion and the technique such as ultrasonic causes the defect of prepared Graphene more, second-rate.
Summary of the invention
What the object of the present invention is to provide that a kind of technique is simple, easy to operate, controllability is good prepares the method for high-quality graphene with hydrogen reducing.
The method of preparing Graphene with hydrogen reducing of the present invention, comprises the following steps:
(1) under the condition of temperature of reaction 5-20 ℃, 0.1-2g natural flake graphite and 0.1-2g SODIUMNITRATE are mixed, join in the sulfuric acid of 50-100ml mass concentration 98%, stir, gradation adds 2-20g potassium permanganate again, the amount at every turn adding is 0.4-4g, every minor tick 10-20min, stir after 2-4h, add 150-500ml deionized water, and heat to 80-95 ℃, adding 10-100ml mass concentration is the hydrogen peroxide of 20%-35%, continue to stir 10-30min, ultrasonic 20-60min, vacuum filtration, successively use hydrochloric acid and the deionized water wash of mass concentration 2-10%, until sulfate radical-free ion in filtrate, the pH value of solution is 7, after 60-120 ℃ of 10-40h is dry, obtain graphene oxide,
(2) take graphene oxide prepared by 0.1-2g step (1), be laid in quartz boat, quartz boat is put into tube furnace,
Pass into rare gas element, be warming up to after 300-800 ℃, close rare gas element, pass into reducing gas hydrogen, the air pressure of hydrogen is 0.01-0.1MPa, and flow is 100-500mL/min, after reduction reaction 1-4h, stop heating, close hydrogen, then after logical rare gas element 1～2h, close rare gas element, naturally cool to after room temperature, obtain Graphene powder.
In the present invention, described rare gas element is one or both in argon gas and nitrogen.
The Graphene purity that the inventive method makes is high, and defect is few.Preparation technology is simple, easy to operate, controllability is good, can be used for large-scale industrialization and produces.
Accompanying drawing explanation
Fig. 1 is the Raman spectrum of the Graphene of embodiment 1 gained.
Fig. 2 is the Raman spectrum of the Graphene of embodiment 2 gained.
Embodiment
Below in conjunction with example, further illustrate the present invention, but the present invention is not limited to example.
In ice-water bath, assemble three mouthfuls of reaction flasks of 1000mL, add the vitriol oil of 100mL mass concentration 98%, stir the solids mixing that adds 2.0g natural flake graphite and 2.0g SODIUMNITRATE under (rotating speed is 200r/min), stir 60min, start minute to add for 5 times 20 g potassium permanganate, every 10min, add once, the amount at every turn adding is respectively 4.0, 4.0, 4.0, 4.0, 4.0, temperature of reaction is 10 ℃, continue to stir after 4h, add again 500mL deionized water, heating there-necked flask is until temperature is raised to 95 ℃, the hydrogen peroxide that simultaneously adds 100mL mass concentration 35%, continue to stir 30min, then ultrasonic 60min, vacuum filtration, successively with hydrochloric acid and the deionized water of mass concentration 10%, fully wash, until sulfate radical-free ion in filtrate, the pH value of solution is 7, precipitation after filtering is moved in culture dish, dry 40h in the baking oven of 100 ℃, obtain sheet graphene oxide 3.20g.
Take the above-mentioned graphene oxide making of 2.0g, be laid in quartz boat, quartz boat is put into tube furnace, start heating, pass into nitrogen, at quartz tube type furnace temperature, rise to 800 ℃, close nitrogen, start logical hydrogen, the air pressure of hydrogen is 0.1MPa, flow is 500mL/min, after reduction reaction 4h, stops the heating of tube furnace, close hydrogen, then after logical nitrogen 2h, close nitrogen, naturally cool to room temperature, take out and weigh, obtain 0.25g Graphene powder.
The Raman spectrum of this Graphene is shown in Fig. 1.As shown in Figure 1, the Graphene obtaining through hydrogen reducing is at 1350cm
-1the D peak intensity at place compares 1580cm
-1the G peak intensity at place is low, and wherein D peak characterizes the randomness of Graphene, shows to exist oxygen-containing functional group, other defect and irregular carbon structure (sp
3key) etc., G peak is carbon sp
2the characteristic peak of structure, shows that carbon atom has six side's solid matter structures, and D peak is with G peak intensity than less, and impurity and the defect of Graphene are fewer.The Raman spectrum presentation of results of Fig. 1, the Graphene purity obtaining through hydrogen reducing is high, and impurity and defect are less.
Embodiment 2
In ice-water bath, assemble three mouthfuls of reaction flasks of 500mL, add the sulfuric acid of 50mL mass concentration 98%, stir the solids mixing that adds 0.1g natural flake graphite and 0.1g SODIUMNITRATE under (rotating speed is 100r/min), stir 10min, start minute to add 2g potassium permanganate 5 times, every 10min, add once, the amount at every turn adding is respectively 0.40g, 0.40g, 0.40g, 0.40g, 0.40g, temperature of reaction is 5 ℃, continue to stir after 2h, add again 150mL deionized water, heating there-necked flask is until temperature is raised to 80 ℃, the hydrogen peroxide that simultaneously adds 10mL mass concentration 20%, continue to stir 10min, then ultrasonic 20min, vacuum filtration, successively with hydrochloric acid and the deionized water of mass concentration 2%, fully wash, until sulfate radical-free ion in filtrate, the pH value of solution is 7, precipitation after filtering is moved in culture dish, dry 10h in the baking oven of 60 ℃, obtain sheet graphene oxide 0.23g.
Take the above-mentioned graphene oxide making of 0.10g, be laid in quartz boat, quartz boat is put into tube furnace, start heating, pass into nitrogen, at quartz tube type furnace temperature, rise to 300 ℃, close nitrogen, start logical hydrogen, the air pressure of hydrogen is 0.01MPa, flow is 100mL/min, after reduction reaction 1h, stops the heating of tube furnace, close hydrogen, then after logical nitrogen 1h, close nitrogen, naturally cool to after room temperature, take out and weigh, obtain 0.013g Graphene powder.
The Raman spectrum of this Graphene is shown in Fig. 2.Fig. 2 Raman spectrum analysis and Fig. 1 Raman spectrum analysis come to the same thing, and hence one can see that, and the Graphene purity that example 2 obtains is high, and impurity and defect are less.
Embodiment 3
In ice-water bath, assemble three mouthfuls of reaction flasks of 500mL, add the vitriol oil of 80mL mass concentration 98%, stir the solids mixing that adds 1.0g natural flake graphite and 1.0g SODIUMNITRATE under (rotating speed is 150r/min), stir 30min, start minute to add 10g potassium permanganate 5 times, every 10min, add once, the amount at every turn adding is respectively 2.0g, 2.0g, 2.0g, 2.0g, 2.0g, temperature of reaction is 7 ℃, continue to stir after 3h, add again 300mL deionized water, heating there-necked flask is until temperature is raised to 90 ℃, the hydrogen peroxide that simultaneously adds 40mL mass concentration 30%, continue to stir 20min, then ultrasonic 30min, vacuum filtration, successively with hydrochloric acid and the deionized water of mass concentration 5%, fully wash, until sulfate radical-free ion in filtrate, the pH value of solution is 7, precipitation after filtering is moved in culture dish, dry 30h in the baking oven of 80 ℃, obtain sheet graphene oxide 2.23g.
Take the above-mentioned graphene oxide making of 1.0g, be laid in quartz boat, quartz boat is put into tube furnace, start heating, pass into nitrogen, at quartz tube type furnace temperature, rise to 500 ℃, close nitrogen, start logical hydrogen, the air pressure of hydrogen is 0.05MPa, flow is 300mL/min, after reduction reaction 2h, stops the heating of tube furnace, close hydrogen, then after logical nitrogen 1.5h, close nitrogen, naturally cool to after room temperature, take out and weigh, obtain 1.23g Graphene powder.
Embodiment 4
In ice-water bath, assemble three mouthfuls of reaction flasks of 500mL, add the sulfuric acid of 80mL mass concentration 98%, stir the solids mixing that adds 1.0g natural flake graphite and 1.0g SODIUMNITRATE under (rotating speed is 120r/min), stir 30min, start minute to add 10g potassium permanganate 5 times, every 10min, add once, the amount at every turn adding is respectively 2.0g, 2.0g, 2.0g, 2.0g, 2.0g, temperature of reaction is 15 ℃, continue to stir after 3h, add again 300mL deionized water, heating there-necked flask is until temperature is raised to 90 ℃, the hydrogen peroxide that simultaneously adds 40mL mass concentration 30%, continue to stir 20min, then ultrasonic 30min, vacuum filtration, successively with hydrochloric acid and the deionized water of mass concentration 5%, fully wash, until sulfate radical-free ion in filtrate, the pH value of solution is 7, precipitation after filtering is moved in culture dish, dry 35h in the baking oven of 120 ℃, obtain sheet graphene oxide 2.23g.
Take the above-mentioned graphene oxide making of 1.0g, be laid in quartz boat, quartz boat is put into tube furnace, start heating, pass into argon gas, at quartz tube type furnace temperature, rise to 450 ℃, close argon gas, start logical hydrogen, the air pressure of hydrogen is 0.05MPa, flow is 300mL/min, after reduction reaction 2h, stops the heating of tube furnace, close hydrogen, then after logical argon gas 1.5h, close argon gas, naturally cool to after room temperature, take out and weigh, obtain 1.22g Graphene powder.
Embodiment 5
In ice-water bath, assemble three mouthfuls of reaction flasks of 500mL, add the sulfuric acid of 50mL mass concentration 98%, stir the solids mixing that adds 0.1g natural flake graphite and 0.1g SODIUMNITRATE under (rotating speed is 180r/min), stir 10min, start minute to add 2g potassium permanganate 2 times, every 10min, add once, the amount at every turn adding is respectively 1.0g, 1.0g, temperature of reaction is 12 ℃, continue to stir after 2h, add again 150mL deionized water, heating there-necked flask is until temperature is raised to 80 ℃, the hydrogen peroxide that simultaneously adds 10mL mass concentration 20%, continue to stir 10min, then ultrasonic 20min, vacuum filtration, successively with hydrochloric acid and the deionized water of mass concentration 2%, fully wash, until sulfate radical-free ion in filtrate, the pH value of solution is 7, precipitation after filtering is moved in culture dish, dry 20h in the baking oven of 90 ℃, obtain sheet graphene oxide 0.22g.
Take the above-mentioned graphene oxide making of 0.10g, be laid in quartz boat, quartz boat is put into tube furnace, start heating, pass into nitrogen, at quartz tube type furnace temperature, rise to 650 ℃, close nitrogen, start logical hydrogen, the air pressure of hydrogen is 0.01MPa, flow is 100mL/min, after reduction reaction 1h, stops the heating of tube furnace, close hydrogen, then after logical nitrogen 1h, close nitrogen, naturally cool to after room temperature, take out and weigh, obtain 0.013g Graphene powder.
Claims (2)
1. with hydrogen reducing, prepare a method for Graphene, comprise the following steps:
(1) under the condition of temperature of reaction 5-20 ℃, 0.1-2g natural flake graphite and 0.1-2g SODIUMNITRATE are mixed, join in the sulfuric acid of 50-100ml mass concentration 98%, stir, gradation adds 2-20g potassium permanganate again, the amount at every turn adding is 0.4-4g, every minor tick 10-20min, stir after 2-4h, add 150-500ml deionized water, and heat to 80-95 ℃, adding 10-100ml mass concentration is the hydrogen peroxide of 20%-35%, continue to stir 10-30min, ultrasonic 20-60min, vacuum filtration, successively use hydrochloric acid and the deionized water wash of mass concentration 2-10%, until sulfate radical-free ion in filtrate, the pH value of solution is 7, after 60-120 ℃ of 10-40h is dry, obtain graphene oxide,
(2) take graphene oxide prepared by 0.1-2g step (1), be laid in quartz boat, quartz boat is put into tube furnace,
Pass into rare gas element, be warming up to after 300-800 ℃, close rare gas element, pass into reducing gas hydrogen, the air pressure of hydrogen is 0.01-0.1MPa, and flow is 100-500mL/min, after reduction reaction 1-4h, stop heating, close hydrogen, then after logical rare gas element 1～2h, close rare gas element, naturally cool to after room temperature, obtain Graphene powder.
2. the method for preparing Graphene with hydrogen reducing according to claim 1, is characterized in that described rare gas element is one or both in argon gas and nitrogen.
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| CN106674904A (en) * | 2016-12-30 | 2017-05-17 | 中国科学院深圳先进技术研究院 | Heat conducting composite material and preparation method thereof |
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