CN108017052B - Method for preparing graphene in large scale - Google Patents
Method for preparing graphene in large scale Download PDFInfo
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- CN108017052B CN108017052B CN201711190738.9A CN201711190738A CN108017052B CN 108017052 B CN108017052 B CN 108017052B CN 201711190738 A CN201711190738 A CN 201711190738A CN 108017052 B CN108017052 B CN 108017052B
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- C01B2204/00—Structure or properties of graphene
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Abstract
The invention discloses a method for preparing graphene in a large scale, which comprises the following steps: 1) uniformly mixing graphite, potassium permanganate and sulfuric acid, stirring and reacting at 0-100 ℃ for 10-120 min, adding water and a hydrogen peroxide solution, stirring and reacting for 1-15 min, and carrying out solid-liquid separation to obtain intercalated graphite; 2) dispersing intercalated graphite with water, placing the dispersed intercalated graphite in a microwave reactor, introducing protective gas, carrying out microwave reaction for 1-15 min, and carrying out solid-liquid separation to obtain graphene. The method has the advantages of simple process, short flow, mild reaction conditions, low cost and easiness in large-scale production, and the prepared graphene has excellent performance, few structural defects and good quality stability among different batches, and has very wide application prospects in various fields.
Description
Technical Field
The invention relates to a method for preparing graphene in a large scale.
Background
Graphene is a honeycomb-shaped planar thin film formed by carbon atoms in an sp2 hybridization mode, has a unique two-dimensional nano structure, has the advantages of high electron transmission rate, good electrical conductivity, high thermal conductivity and the like, is the thinnest, most rigid and best conductive and heat-conducting nano material at present, and has good application prospects in the fields of physics, materials science, electronic information, computers, aerospace and the like.
At present, the preparation method of graphene mainly comprises: mechanical lift-off, vapor deposition, liquid phase lift-off, redox, and the like. Among them, the redox method is currently recognized as a method by which graphene can be obtained in large quantities at a low cost. The preparation of graphene by a redox method comprises two processes of oxidation and reduction: 1) oxidizing graphite by using strong oxidants such as concentrated sulfuric acid, potassium permanganate and hydrogen peroxide, and obtaining graphene oxide through ultrasonic dispersion or thermal expansion; 2) and reducing the graphene oxide into graphene by a reducing agent or high temperature and the like. However, strong oxidants such as concentrated sulfuric acid, potassium permanganate and hydrogen peroxide can seriously damage the crystal structure of graphene, ultrasonic stripping can also damage graphene sheet layers, and the graphene cannot completely recover the two-dimensional crystal structure in the reduction process, so that the prepared graphene has more structural defects and is not ideal in performance.
The microwave is an electromagnetic wave with extremely high frequency, and has the advantages of uniform heating, rapidness, high efficiency, suitability for large-scale production and the like, so researchers try to apply the microwave technology to graphene preparation, but no satisfactory result is obtained. CN102107870A discloses a method for rapidly preparing graphene by using microwaves, which comprises grinding graphite oxide into fine powder, and performing microwave radiation in a high vacuum state to obtain graphene, but the method has the disadvantages of long preparation process, high requirement on equipment, high equipment preparation cost and the like, and cannot be popularized and used in a large scale; the paper "microwave solid-phase peeling method for preparing functionalized graphene and research on electrochemical capacitance performance thereof (report of inorganic chemistry, 2010, 26 (8): 1375-1381)" also discloses a method for preparing graphene by using microwaves, firstly, graphene oxide is prepared by using a Hummers method, and then, graphene is prepared by heating in a microwave oven.
Disclosure of Invention
The invention aims to provide a method for preparing graphene in a large scale.
The technical scheme adopted by the invention is as follows:
a method for preparing graphene in a large scale comprises the following steps:
1) uniformly mixing graphite, potassium permanganate and sulfuric acid, stirring and reacting at 0-100 ℃ for 10-120 min, adding water and a hydrogen peroxide solution, stirring and reacting for 1-15 min, and carrying out solid-liquid separation to obtain intercalated graphite;
2) dispersing intercalated graphite with water, placing the dispersed intercalated graphite in a microwave reactor, introducing protective gas, carrying out microwave reaction for 1-15 min, and carrying out solid-liquid separation to obtain graphene.
The mass ratio of the graphite, the potassium permanganate and the sulfuric acid in the step 1) is 1: (0.5-1.5): (10-30).
The adding amount ratio of the graphite, the water and the hydrogen peroxide solution in the step 1) is 1 g: (15-25) mL: (1-3) mL.
The mass fraction of the sulfuric acid in the step 1) is 30-99%.
The mass fraction of the hydrogen peroxide solution in the step 1) is 5-30%.
The water content of the intercalated graphite in the step 2) is 75-99% after being dispersed by water.
The protective gas in the step 2) is at least one of nitrogen and argon.
The power of the microwave in the step 2) is 500-3000W.
The invention is based on the following principle: after graphite is intercalated by an intercalating agent, the interlayer distance is increased, the interlayer acting force is reduced, and the edge of the graphite carries oxygen-containing groups, so that the hydrophilicity of the graphite is enhanced, water molecules are diffused into the graphite layers, polar water molecules can vibrate violently after being subjected to microwave radiation, huge acting force is generated between the graphite layers, when the acting force is greater than the van der Waals force between the graphite layers, the layered structure of the graphite collapses, the graphite is stripped to form graphene, meanwhile, the oxygen-containing functional groups on the intercalated graphite are decomposed into gas under the action of the microwave radiation, and the gas can also generate acting force to strip the graphite layers, so that the graphene is obtained.
The invention has the beneficial effects that: the method has the advantages of simple process, short flow, mild reaction conditions, low cost and easiness in large-scale production, and the prepared graphene has excellent performance, few structural defects and good quality stability among different batches, and has very wide application prospects in various fields.
1) The quantity of the intercalation agent and the oxidant used in the invention is little, the oxidation degree of the intercalation graphite is low, the absorption effect on microwave is strong, and the intercalation graphite contains oxygen-containing groups and can be well dispersed in water;
2) according to the invention, the graphene is stripped and reduced into graphene by utilizing the synergistic effect of the polarization effect of water molecules and the thermal effect of the weak graphite oxide sheet layer of microwaves, so that the damage of the graphene sheet layer structure easily caused by using high-power ultrasonic stripping equipment is avoided, and meanwhile, the use of a chemical reducing agent with high toxicity and high pollution is also avoided.
Drawings
Fig. 1 is a TEM image of graphene of example 1.
Detailed Description
A method for preparing graphene in a large scale comprises the following steps:
1) uniformly mixing graphite, potassium permanganate and sulfuric acid, stirring and reacting at 0-100 ℃ for 10-120 min, adding water and a hydrogen peroxide solution, stirring and reacting for 1-15 min, and carrying out solid-liquid separation to obtain intercalated graphite;
2) dispersing intercalated graphite with water, placing the dispersed intercalated graphite in a microwave reactor, introducing protective gas, carrying out microwave reaction for 1-15 min, and carrying out solid-liquid separation to obtain graphene.
Preferably, the method for preparing graphene in a large scale comprises the following steps:
1) uniformly mixing graphite, potassium permanganate and sulfuric acid, stirring and reacting at 25-100 ℃ for 60-120 min, adding water and a hydrogen peroxide solution, stirring and reacting for 4-10 min, and carrying out solid-liquid separation to obtain intercalated graphite;
2) dispersing intercalated graphite with water, placing the dispersed intercalated graphite in a microwave reactor, introducing protective gas, carrying out microwave reaction for 4-10 min, and carrying out solid-liquid separation to obtain graphene.
Preferably, the mass ratio of the graphite to the potassium permanganate to the sulfuric acid in the step 1) is 1: (0.5-1.5): (10-30).
Preferably, the adding amount ratio of the graphite, the water and the hydrogen peroxide solution in the step 1) is 1 g: (15-25) mL: (1-3) mL.
Preferably, the mass fraction of the sulfuric acid in the step 1) is 30-99%.
More preferably, the mass fraction of the sulfuric acid in the step 1) is 50 to 99 percent.
Preferably, the mass fraction of the hydrogen peroxide solution in the step 1) is 5-30%.
Preferably, the water content of the intercalated graphite in the step 2) is 75-99% after the intercalated graphite is dispersed by water.
Preferably, the protective gas in step 2) is at least one of nitrogen and argon.
Preferably, the power of the microwave in the step 2) is 500-3000W.
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
a method for preparing graphene in a large scale comprises the following steps:
1) uniformly mixing 5g of graphite, 5g of potassium permanganate and 100mL of sulfuric acid with the mass fraction of 70%, stirring and reacting at 70 ℃ for 60min, then adding 100mL of deionized water and 10mL of hydrogen peroxide solution with the mass fraction of 10%, stirring and reacting for 5min, and centrifuging at 8000r/min for 5min to obtain intercalated graphite;
2) dispersing the intercalated graphite by using 15mL of deionized water (the water content of the intercalated graphite after being dispersed by using water is 75%), then placing the intercalated graphite in a microwave reactor, introducing nitrogen for protection, radiating by using 800W microwaves for 5min, and filtering to obtain the graphene.
The graphene prepared by the embodiment has the conductivity of 1250S/cm through testing, and a TEM image of the graphene is shown in FIG. 1.
Example 2:
a method for preparing graphene in a large scale comprises the following steps:
1) uniformly mixing 5g of graphite, 5g of potassium permanganate and 80mL of sulfuric acid with the mass fraction of 90%, stirring and reacting at 50 ℃ for 100min, then adding 100mL of deionized water and 10mL of hydrogen peroxide solution with the mass fraction of 10%, stirring and reacting for 5min, and centrifuging at 8000r/min for 5min to obtain intercalated graphite;
2) dispersing the intercalated graphite by using 20mL of deionized water (the water content of the intercalated graphite after being dispersed by using water is 80%), then placing the intercalated graphite in a microwave reactor, introducing nitrogen for protection, radiating by using 1000W microwaves for 5min, and filtering to obtain the graphene.
The graphene prepared by the embodiment has the conductivity of more than 1300S/cm through testing.
Example 3:
a method for preparing graphene in a large scale comprises the following steps:
1) uniformly mixing 5g of graphite, 5g of potassium permanganate and 150mL of sulfuric acid with the mass fraction of 50%, stirring and reacting at 90 ℃ for 120min, then adding 75mL of deionized water and 15mL of hydrogen peroxide solution with the mass fraction of 10%, stirring and reacting for 5min, and centrifuging at 8000r/min for 5min to obtain intercalated graphite;
2) dispersing the intercalated graphite by 30mL of deionized water (the water content of the intercalated graphite after being dispersed by water is 85%), placing the intercalated graphite in a microwave reactor, introducing nitrogen for protection, radiating by 1000W microwaves for 8min, and filtering to obtain the graphene.
Through testing, the electric conductivity of the graphene prepared by the embodiment is more than 1100S/cm.
Example 4:
a method for preparing graphene in a large scale comprises the following steps:
1) uniformly mixing 50g of graphite, 50g of potassium permanganate and 1000mL of sulfuric acid with the mass fraction of 98%, stirring and reacting for 60min at 35 ℃, then adding 1250mL of deionized water and 50mL of hydrogen peroxide solution with the mass fraction of 10%, stirring and reacting for 5min, and centrifuging for 5min at 8000r/min to obtain intercalated graphite;
2) dispersing the intercalated graphite with 150mL of deionized water (the water content of the intercalated graphite is 75% after being dispersed with water), then placing the intercalated graphite in a microwave reactor, introducing nitrogen for protection, radiating the intercalated graphite by 1000W microwaves for 5min, and filtering to obtain the graphene.
The graphene prepared by the embodiment has the conductivity of more than 1200S/cm through testing.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (4)
1. A method for preparing graphene in a large scale is characterized by comprising the following steps: the method comprises the following steps:
1) uniformly mixing graphite, potassium permanganate and sulfuric acid, stirring and reacting at 25-100 ℃ for 60-120 min, adding water and a hydrogen peroxide solution, stirring and reacting for 4-10 min, and carrying out solid-liquid separation to obtain intercalated graphite;
2) dispersing intercalated graphite with water, placing the dispersed intercalated graphite in a microwave reactor, introducing protective gas, carrying out microwave reaction for 4-10 min, and carrying out solid-liquid separation to obtain graphene;
the mass ratio of the graphite, the potassium permanganate and the sulfuric acid in the step 1) is 1: (0.5-1.5): (10-30);
the adding amount ratio of the graphite, the water and the hydrogen peroxide solution in the step 1) is 1 g: (15-25) mL: (1-3) mL;
the mass fraction of the sulfuric acid in the step 1) is 50-99%;
the mass fraction of the hydrogen peroxide solution in the step 1) is 5-30%.
2. The method of claim 1, wherein: the water content of the intercalated graphite in the step 2) is 75-99% after being dispersed by water.
3. The method of claim 1, wherein: the protective gas in the step 2) is at least one of nitrogen and argon.
4. The method of claim 1, wherein: the power of the microwave in the step 2) is 500-3000W.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104022272A (en) * | 2013-02-28 | 2014-09-03 | 王也 | Method based on negative electrode composite material battery |
| CN104556017A (en) * | 2015-01-23 | 2015-04-29 | 青岛科技大学 | Macroscopic quantity preparation method for high-quality graphene |
| CN105948033A (en) * | 2016-07-11 | 2016-09-21 | 黑龙江碳时代石墨烯科技有限公司 | Method of preparing graphene by means of wet microwave stripping |
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| US20130266501A1 (en) * | 2011-07-05 | 2013-10-10 | Rutgers, The State University Of New Jersey | Direct Production of Large and Highly Conductive Low-Oxygen Graphene Sheets and Monodispersed Low-Oxygen Graphene Nanosheets |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104022272A (en) * | 2013-02-28 | 2014-09-03 | 王也 | Method based on negative electrode composite material battery |
| CN104556017A (en) * | 2015-01-23 | 2015-04-29 | 青岛科技大学 | Macroscopic quantity preparation method for high-quality graphene |
| CN105948033A (en) * | 2016-07-11 | 2016-09-21 | 黑龙江碳时代石墨烯科技有限公司 | Method of preparing graphene by means of wet microwave stripping |
Non-Patent Citations (2)
| Title |
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| 微波法制备石墨烯及石墨烯基材料的研究进展;杨蓉等;《化学通报》;20160618;第79卷(第6期);第504-505页 * |
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