CN103613093B - A kind of hydrogen reducing prepares the method for Graphene - Google Patents
A kind of hydrogen reducing prepares the method for Graphene Download PDFInfo
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Abstract
The present invention relates to the method preparing Graphene with hydrogen reducing.The method is mixed with SODIUMNITRATE by natural flake graphite, adds sulfuric acid, potassium permanganate, deionized water and hydrogen peroxide successively, vacuum filtration under stirring, filters, and with dilute hydrochloric acid washing until PH is 7, dries, obtain graphene oxide; Under the protection of rare gas element; graphene oxide is put into the reactor of anaerobic; reach the temperature of hydrogen reducing graphene oxide in the temperature of inside reactor after, then pass into reducing gas hydrogen in above-mentioned reactor, prepare the Graphene that purity is very high thus.The present invention prepares the method for Graphene, easy to operate, and simple and feasible can be used for industrial mass production.
Description
Technical field
The present invention relates to the preparation method of Graphene, particularly a kind of hydrogen reducing prepares the method for Graphene.
Background technology
Graphene is the graphite of individual layer atomic thickness, has bi-dimensional cellular mesh network structure.Due to the existence of track towering 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 structurally has ductility, and its electricity, optics and acoustic characteristics significantly can 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, exceedes silicon more than 100 times.This advantage makes Graphene probably replace silicon, and becomes the base mateiral of ultra high frequency transistor of future generation, is applied in high performance integrated circuit and novel nano electron device.Thus, shortly there will be the full carbon circuit of full Graphene formation and be widely used in daily life.
At present, the method 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 prepared by the method; Chemical Vapor deposition process technique is simple, be easy to patterning, but efficiency is low, poor controllability.Oxidation reduction process is mainly through introducing oxygen-containing functional group, reduce the Interaction between layers of graphite on the one hand, increase interlamellar spacing, change its hybridization state, improve its water-wet behavior on the other hand, make it be easy to expand in aqueous, and then realize the cleavage layer by layer of graphite by methods such as heating, supersound process, obtaining the grapheme material of functionalization, is a kind of effective ways being expected to realize the loud and clear preparation of Graphene low cost.But the product prepared by oxidation reduction process adopted at present mostly is the mixture of individual layer, bilayer and multi-layer graphene, the number of plies is difficult to control.In addition, be oxidized in oxidation reduction process, expand and the use of the technique such as ultrasonic causes the defect of prepared Graphene more, second-rate.
Summary of the invention
The object of the present invention is to provide a kind of method preparing high-quality graphene with hydrogen reducing that technique is simple, easy to operate, controllability is good.
Hydrogen reducing of the present invention prepares the method for Graphene, comprises the following steps:
(1) under the condition of temperature of reaction 5-20 DEG C, by 0.1-2g natural flake graphite and the mixing of 0.1-2g SODIUMNITRATE, join in the sulfuric acid of 50-100ml mass concentration 98%, stir, gradation adds 2-20g potassium permanganate again, the amount at every turn added is 0.4-4g, every minor tick 10-20min, after stirring 2-4h, add 150-500ml deionized water, and heat to 80-95 DEG C, add the hydrogen peroxide that 10-100ml mass concentration is 20%-35%, continue to stir 10-30min, ultrasonic 20-60min, vacuum filtration, successively with 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 DEG C of 10-40h drying, 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, after being warming up to 300-800 DEG C, 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, after naturally cooling to 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 obtains is high, and defect is few.Preparation technology is simple, easy to operate, controllability is good, can be used for industrialization scale operation.
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
Illustrate the present invention further below in conjunction with example, but the present invention is not limited to example.
Embodiment 1
In ice-water bath, assemble three mouthfuls of reaction flasks of 1000mL, add the vitriol oil of 100mL mass concentration 98%, under stirring (rotating speed is 200r/min), add the solids mixing of 2.0g natural flake graphite and 2.0g SODIUMNITRATE, stir 60min, start point to add 20 g potassium permanganate for 5 times, add once every 10min, the amount at every turn added is respectively 4.0, 4.0, 4.0, 4.0, 4.0, temperature of reaction is 10 DEG C, after continuing to stir 4h, add 500mL deionized water again, heating there-necked flask is until temperature is raised to 95 DEG C, add the hydrogen peroxide of 100mL mass concentration 35% simultaneously, continue to stir 30min, then ultrasonic 60min, vacuum filtration, hydrochloric acid and the deionized water of priority 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 DEG C, obtain sheet graphene oxide 3.20g.
Take the above-mentioned obtained graphene oxide of 2.0g, be laid in quartz boat, quartz boat is put into tube furnace, start heating, pass into nitrogen, rise to 800 DEG C at quartz tube type furnace temperature, 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 obtained 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 there is 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 close-packed configuration, and D peak and G peak intensity are than less, and the defect struchures of Graphene is fewer.The Raman spectrum result of Fig. 1 illustrates, the Graphene purity obtained through hydrogen reducing is high, and defect struchures is less.
Embodiment 2
In ice-water bath, assemble three mouthfuls of reaction flasks of 500mL, add the sulfuric acid of 50mL mass concentration 98%, under stirring (rotating speed is 100r/min), add the solids mixing of 0.1g natural flake graphite and 0.1g SODIUMNITRATE, stir 10min, start point to add 2g potassium permanganate 5 times, add once every 10min, the amount at every turn added is respectively 0.40g, 0.40g, 0.40g, 0.40g, 0.40g, temperature of reaction is 5 DEG C, after continuing to stir 2h, add 150mL deionized water again, heating there-necked flask is until temperature is raised to 80 DEG C, add the hydrogen peroxide of 10mL mass concentration 20% simultaneously, continue to stir 10min, then ultrasonic 20min, vacuum filtration, hydrochloric acid and the deionized water of priority 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 DEG C, obtain sheet graphene oxide 0.23g.
Take the above-mentioned obtained graphene oxide of 0.10g, be laid in quartz boat, quartz boat is put into tube furnace, start heating, pass into nitrogen, rise to 300 DEG C at quartz tube type furnace temperature, 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, after naturally cooling to 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, it can thus be appreciated that the Graphene purity that example 2 obtains is high, and defect struchures is less.
Embodiment 3
In ice-water bath, assemble three mouthfuls of reaction flasks of 500mL, add the vitriol oil of 80mL mass concentration 98%, under stirring (rotating speed is 150r/min), add the solids mixing of 1.0g natural flake graphite and 1.0g SODIUMNITRATE, stir 30min, start point to add 10g potassium permanganate 5 times, add once every 10min, the amount at every turn added is respectively 2.0g, 2.0g, 2.0g, 2.0g, 2.0g, temperature of reaction is 7 DEG C, after continuing to stir 3h, add 300mL deionized water again, heating there-necked flask is until temperature is raised to 90 DEG C, add the hydrogen peroxide of 40mL mass concentration 30% simultaneously, continue to stir 20min, then ultrasonic 30min, vacuum filtration, hydrochloric acid and the deionized water of priority 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 DEG C, obtain sheet graphene oxide 2.23g.
Take the above-mentioned obtained graphene oxide of 1.0g, be laid in quartz boat, quartz boat is put into tube furnace, start heating, pass into nitrogen, rise to 500 DEG C at quartz tube type furnace temperature, 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, after naturally cooling to 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%, under stirring (rotating speed is 120r/min), add the solids mixing of 1.0g natural flake graphite and 1.0g SODIUMNITRATE, stir 30min, start point to add 10g potassium permanganate 5 times, add once every 10min, the amount at every turn added is respectively 2.0g, 2.0g, 2.0g, 2.0g, 2.0g, temperature of reaction is 15 DEG C, after continuing to stir 3h, add 300mL deionized water again, heating there-necked flask is until temperature is raised to 90 DEG C, add the hydrogen peroxide of 40mL mass concentration 30% simultaneously, continue to stir 20min, then ultrasonic 30min, vacuum filtration, hydrochloric acid and the deionized water of priority 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 DEG C, obtain sheet graphene oxide 2.23g.
Take the above-mentioned obtained graphene oxide of 1.0g, be laid in quartz boat, quartz boat is put into tube furnace, start heating, pass into argon gas, rise to 450 DEG C at quartz tube type furnace temperature, 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, after naturally cooling to 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%, under stirring (rotating speed is 180r/min), add the solids mixing of 0.1g natural flake graphite and 0.1g SODIUMNITRATE, stir 10min, start point to add 2g potassium permanganate 2 times, add once every 10min, the amount at every turn added is respectively 1.0g, 1.0g, temperature of reaction is 12 DEG C, after continuing to stir 2h, add 150mL deionized water again, heating there-necked flask is until temperature is raised to 80 DEG C, add the hydrogen peroxide of 10mL mass concentration 20% simultaneously, continue to stir 10min, then ultrasonic 20min, vacuum filtration, hydrochloric acid and the deionized water of priority 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 DEG C, obtain sheet graphene oxide 0.22g.
Take the above-mentioned obtained graphene oxide of 0.10g, be laid in quartz boat, quartz boat is put into tube furnace, start heating, pass into nitrogen, rise to 650 DEG C at quartz tube type furnace temperature, 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, after naturally cooling to room temperature, take out and weigh, obtain 0.013g Graphene powder.
Claims (2)
1. prepare a method for Graphene with hydrogen reducing, comprise the following steps:
(1) under the condition of temperature of reaction 5-20 DEG C, by 0.1-2g natural flake graphite and the mixing of 0.1-2g SODIUMNITRATE, join in the sulfuric acid of 50-100ml mass concentration 98%, stir, gradation adds 2-20g potassium permanganate again, the amount at every turn added is 0.4-4g, every minor tick 10-20min, after stirring 2-4h, add 150-500ml deionized water, and heat to 80-95 DEG C, add the hydrogen peroxide that 10-100ml mass concentration is 20%-35%, continue to stir 10-30min, ultrasonic 20-60min, vacuum filtration, successively with 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 DEG C of 10-40h drying, 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, after being warming up to 300-800 DEG C, 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, after naturally cooling to room temperature, obtain Graphene powder.
2. hydrogen reducing according to claim 1 prepares the method for Graphene, it is characterized in that described rare gas element is one or both in argon gas and nitrogen.
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| CN105936504A (en) * | 2016-06-15 | 2016-09-14 | 台州嘉洋新能源科技有限公司 | Production method of graphene |
| 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 |
| CN107902641A (en) * | 2017-09-19 | 2018-04-13 | 太原理工大学 | A kind of preparation method of functionalization reduced graphene |
| CN107986267A (en) * | 2017-11-14 | 2018-05-04 | 中国电子科技集团公司第三十三研究所 | The method and its heating furnace that a kind of redox graphene powder upgrading is modified |
| CN110054176B (en) * | 2018-01-18 | 2021-01-19 | 国家纳米科学中心 | High-conductivity graphene, preparation method and application thereof |
| CN113912050B (en) * | 2020-07-09 | 2023-11-14 | Tcl科技集团股份有限公司 | Graphene quantum dot and processing method thereof |
| CN113058645B (en) * | 2021-03-25 | 2022-04-12 | 福州大学 | Graphene aromatic polyamide composite functional filter material prepared by conjugation method |
| CN113620283B (en) * | 2021-09-03 | 2023-01-31 | 陕西六元碳晶股份有限公司 | Graphene and processing method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101602504A (en) * | 2009-07-16 | 2009-12-16 | 上海交通大学 | Graphene preparation method based on xitix |
| CN101997120A (en) * | 2010-10-09 | 2011-03-30 | 深圳市贝特瑞纳米科技有限公司 | Lithium ion battery conductive additive and preparation method thereof |
| CN102259851A (en) * | 2011-06-20 | 2011-11-30 | 清华大学 | Method for preparing graphene by low-temperature chemical reduction method |
| CN102306757A (en) * | 2011-08-26 | 2012-01-04 | 上海交通大学 | Silicon graphene composite anode material of lithium ion battery and preparation method of silicon graphene composite anode material |
| CN102583343A (en) * | 2012-02-08 | 2012-07-18 | 中国科学院福建物质结构研究所 | Method for preparing graphene on large scale |
| CN103331159A (en) * | 2013-07-10 | 2013-10-02 | 中南大学 | Cu2O-TiO2/reduced graphene oxide ternary complex, and preparation method and applications thereof |
-
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- 2013-11-25 CN CN201310598597.XA patent/CN103613093B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101602504A (en) * | 2009-07-16 | 2009-12-16 | 上海交通大学 | Graphene preparation method based on xitix |
| CN101997120A (en) * | 2010-10-09 | 2011-03-30 | 深圳市贝特瑞纳米科技有限公司 | Lithium ion battery conductive additive and preparation method thereof |
| CN102259851A (en) * | 2011-06-20 | 2011-11-30 | 清华大学 | Method for preparing graphene by low-temperature chemical reduction method |
| CN102306757A (en) * | 2011-08-26 | 2012-01-04 | 上海交通大学 | Silicon graphene composite anode material of lithium ion battery and preparation method of silicon graphene composite anode material |
| CN102583343A (en) * | 2012-02-08 | 2012-07-18 | 中国科学院福建物质结构研究所 | Method for preparing graphene on large scale |
| CN103331159A (en) * | 2013-07-10 | 2013-10-02 | 中南大学 | Cu2O-TiO2/reduced graphene oxide ternary complex, and preparation method and applications thereof |
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