CN103387224A - Preparation method of graphite - Google Patents
Preparation method of graphite Download PDFInfo
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- CN103387224A CN103387224A CN2012101375602A CN201210137560A CN103387224A CN 103387224 A CN103387224 A CN 103387224A CN 2012101375602 A CN2012101375602 A CN 2012101375602A CN 201210137560 A CN201210137560 A CN 201210137560A CN 103387224 A CN103387224 A CN 103387224A
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Abstract
The invention provides a preparation method of graphite. The method comprises the following steps of: placing intercalation graphite in a reactor; sealing the reactor and vacuumizing to a vacuum degree of 10<-3>-100 Pa; heating to 280-400 DEG C to thermal decompose gas out of an insert substance through heating, wherein the insert substance between the layers of the intercalation graphite comprises one or any combination of the followings: formic acid, acetate, propionic acid, sulfuric acid, nitric acid and nitromethane; then stopping heating and vacuumizing; and cooling and collecting a solid product namely the graphite. The method utilizes negative pressure low temperature pyrolysis on the insert substance between the layers of the intercalation graphite to realize peeling of the intercalation graphite, thereby preparing the graphite. Compared with graphite prepared by a common redox method, the graphite prepared by the preparation method has advantages of little defect and complete crystal structure; meanwhile the preparation method has advantages of low reaction temperature, short reaction time, simple equipment, simple and feasible operations and easiness to realize automation and industrialized production.
Description
Technical field
The present invention relates to the synthetic field of material, particularly relate to a kind of method for preparing Graphene.
Background technology
Graphene is a kind of Two-dimensional Carbon atomic crystal that the strong K of the peace moral of Univ Manchester UK in 2004 sea nurse (Andre K.Geim) etc. is found, is the carbon material as thin as a wafer of single or multiple lift.Single-layer graphene has good conduction, heat conductivility and low thermal expansivity, and its theoretical specific surface area is up to 2630m
2/ g (A Peigney, Ch Laurent, et al.Carbon, 2001,39,507), can be used for effect transistor, electrode materials, matrix material, liquid crystal display material, sensor.
The method for preparing at present Graphene mainly contain graphite breakaway (et al.Science 2004,306,666 for Novoselov K S, Geim A K), chemistry redox method [D A Dikin, et al.Nature 2007,448,457; Sasha Stankovich, Dmitriy A Dikin, Richard D Piner, et al.Carbon 2007,45,1558], ultrasonic stripping method (Guohua Chen, Wengui Weng, Dajun Wu, et al.Carbon.2004,42,753), chemical Vapor deposition process (Alexander N, Obraztsov.Nature nanotechnology.2009,4,212) etc.The place that these methods come with some shortcomings at present, as can not meet simultaneously the Graphene performance that makes high, be easy to the preparation and to the simple requirement of equipment requirements.
Summary of the invention
For addressing the above problem, the present invention aims to provide a kind of method for preparing Graphene, and the method is take intercalated graphite alkene as raw material, by the pyrogenically prepared well behaved Graphene of low-temp low-pressure, and the method equipment is simple, and the operation simple and feasible, easily be automated and suitability for industrialized production.
A kind of method for preparing Graphene provided by the invention comprises the following steps:
Getting intercalated graphite and be placed in reactor, is 10 with being evacuated to vacuum tightness after the reactor sealing
-3～100Pa, being heated to 280 ~ 400 ℃ makes the insertion material decomposes of intercalated graphite interlayer go out gas, the insertion material of described intercalated graphite interlayer is a kind of or arbitrary combination in formic acid, acetic acid, propionic acid, sulfuric acid, nitric acid and Nitromethane 99Min., stopped heating and stop vacuumizing subsequently, cooling, collect solid product, described solid product is Graphene.
In the present invention, but the insertion material decomposes of intercalated graphite interlayer goes out gas.This intercalated graphite can adopt common chemical method or electrochemical process to make.
Preferably, the material of reactor is stainless steel.
Preferably, ratio adds intercalated graphite in reactor volume, being 5 ~ 10g/L.
Vacuumize after sealing, subsequently reactor is heated.At this moment, under negative pressure, the insertion material low temperature of intercalated graphite interlayer is heated and can decomposites a large amount of gases, and the generation of a large amount of gases and diffusion couple intercalated graphite produce reactive force, peels off after making intercalated graphite stressed, obtains solid graphite alkene.The Graphene defect that makes in this preparation method is few, and crystalline structure is complete.
, for giving the reactive force that provides stronger of peeling off of intercalated graphite, preferably, described reactor was heated to 280 ~ 400 ℃ in 3 ~ 5 minutes.And preferably, kept 5 ~ 10 minutes after described reactor is heated to 280 ~ 400 ℃, stopped heating and stop vacuumizing, cooling subsequently.
The operation of collecting solid graphite alkene is specially, and after the question response device is cooling, first opens the venting hole of reactor, the gas of inside reactor is discharged, then open reactor, the collecting reaction product Graphene.
The method for preparing Graphene provided by the invention, be to realize that by the insertion material that utilizes negative pressure low temperature pyrogenation intercalated graphite interlayer intercalated graphite peels off, thereby make the method for Graphene.The Graphene that makes by this preparation method is compared the advantages such as to have defect few, and crystalline structure is complete with the Graphene of common oxidation reduction process preparation, simultaneously, this preparation method's temperature of reaction is low, the reaction times is short, equipment is simple, and the operation simple and feasible, easily be automated and suitability for industrialized production.
Description of drawings
Fig. 1 is the prepared Graphene SEM figure of the embodiment of the present invention one.
Embodiment
A kind of method for preparing Graphene provided by the invention comprises the following steps:
Getting intercalated graphite and be placed in reactor, is 10 with being evacuated to vacuum tightness after the reactor sealing
-3～100Pa, being heated to 280 ~ 400 ℃ makes the insertion material decomposes of intercalated graphite interlayer go out gas, the insertion material of described intercalated graphite interlayer is a kind of or arbitrary combination in formic acid, acetic acid, propionic acid, sulfuric acid, nitric acid and Nitromethane 99Min., stopped heating and stop vacuumizing subsequently, cooling, collect solid product, described solid product is Graphene.
In the present invention, but the insertion material decomposes of intercalated graphite interlayer goes out gas.This intercalated graphite can adopt common chemical method or electrochemical process to make.
The operating process of chemical method is: with insertion material, iron(ic) chloride and the chromium trioxide of natural flake graphite, interlayer, be 1 ︰ 3～4 ︰ 0.8～1.2 ︰ 0.4～0.5 according to mass ratio, add successively the there-necked flask that reflux condensate device and agitator are housed under constantly stirring in, put into the water bath with thermostatic control of 30～60 ℃, after stirring and reacting 60～120min, wash colourless to solution and pH value for neutral, suction filtration and in 50 ℃ of vacuum drying ovens dry 12 ~ 24 hours, obtain intercalated graphite.In chemical method, the insertion material of intercalated graphite interlayer is not limit, and can be electrolyte compound, can be the nonelectrolyte compound yet.
The operating process of electrochemical process is: adopt stainless steel substrates as collector, natural scale graphite is pressed into graphite flake as working electrode, use stereotype as to electrode, Hg/Hg
2SO
4As reference electrode, use the insertion substance solution of interlayer as electrolytic solution, three electrodes are put into electrolyzer and are fully immersed in electrolytic solution, under room temperature, at 5 ~ 20mA/cm
2Current density under, reacted 10 ~ 24 hours, can obtain intercalated graphite.The insertion material that electrochemical process is only applicable to interlayer is the situation of electrolyte compound.
The material of reactor is stainless steel.
Ratio adds intercalated graphite in reactor volume, being 5 ~ 10g/L.
Vacuumize after sealing, carry out subsequently reactor is heated.At this moment, under negative pressure, the insertion material low temperature of intercalated graphite interlayer is heated and can decomposites a large amount of gases, and the generation of a large amount of gases and diffusion couple intercalated graphite produce reactive force, peels off after making intercalated graphite stressed, obtains solid graphite alkene.The Graphene defect that makes in this preparation method is few, and crystalline structure is complete.
For giving the reactive force that provides stronger of peeling off of intercalated graphite, described reactor was heated to 280 ~ 400 ℃ in 3 ~ 5 minutes.
After described reactor is heated to 280 ~ 400 ℃, kept 5 ~ 10 minutes, stopped heating and stop vacuumizing, cooling subsequently.
The operation of collecting solid graphite alkene is specially, and after the question response device is cooling, first opens the venting hole of reactor, the gas of inside reactor is discharged, then open reactor, the collecting reaction product Graphene.
The method for preparing Graphene provided by the invention, be to realize that by the insertion material that utilizes negative pressure low temperature pyrogenation intercalated graphite interlayer intercalated graphite peels off, thereby make the method for Graphene.The Graphene that makes by this preparation method is compared the advantages such as to have defect few, and crystalline structure is complete with the Graphene of common oxidation reduction process preparation, simultaneously, this preparation method's temperature of reaction is low, the reaction times is short, equipment is simple, and the operation simple and feasible, easily be automated and suitability for industrialized production.
The following stated is the preferred embodiment of the present invention; 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 are considered as protection scope of the present invention.
Embodiment one
A kind of method for preparing Graphene comprises the following steps:
Adopt chemical method to prepare the formic acid intercalated graphite, namely the insertion material of intercalated graphite interlayer is formic acid.Operating process is: with natural flake graphite, formic acid, iron(ic) chloride and chromium trioxide, be 1 ︰ 3 ︰ 0.8 ︰ 0.4 according to mass ratio, add successively the there-necked flask that reflux condensate device and agitator are housed under constantly stirring in, put into the water bath with thermostatic control of 30 ℃, after stirring and reacting 60min, wash colourless to solution and pH value for neutral, suction filtration and in 50 ℃ of vacuum drying ovens dry 12 hours, obtain the formic acid intercalated graphite.
Getting the formic acid intercalated graphite joins in the stainless steel reaction container by the volume ratio of 5g/L, be 100Pa with being evacuated to vacuum tightness after the reactor sealing, be heated to 400 ℃, make the insertion material decomposes of intercalated graphite interlayer go out gas, kept 10 minutes, stopped heating and stop vacuumizing, cooling subsequently, collect solid product, described solid product is Graphene.
Fig. 1 is the SEM Electronic Speculum figure of the prepared Graphene of the embodiment of the present invention one, and as can be seen from Figure 1, intercalated graphite successfully has been stripped from into Graphene, and thickness is about 1～3nm, and width is about 0.5～3um.
Embodiment two
A kind of method for preparing Graphene comprises the following steps:
Adopt electrochemical production acetic acid intercalated graphite, namely the insertion material of intercalated graphite interlayer is acetic acid.Operating process is: with natural flake graphite, acetic acid, iron(ic) chloride and chromium trioxide, be 1 ︰ 4 ︰ 1.2 ︰ 0.5 according to mass ratio, add successively the there-necked flask that reflux condensate device and agitator are housed under constantly stirring in, put into the water bath with thermostatic control of 60 ℃, after stirring and reacting 120min, wash colourless to solution and pH value for neutral, suction filtration and in 50 ℃ of vacuum drying ovens dry 24 hours, obtain the acetic acid intercalated graphite.
Getting the acetic acid intercalated graphite and join in the stainless steel reaction container by the volume ratio of 8g/L, is 10 with being evacuated to vacuum tightness after the reactor sealing
-3Pa, be heated to 280 ℃, makes the insertion material decomposes of intercalated graphite interlayer go out gas, kept 8 minutes, and stopped heating and stop vacuumizing, cooling subsequently, collects solid product, and described solid product is Graphene.
Embodiment three
A kind of method for preparing Graphene comprises the following steps:
Adopt chemical method to prepare the propionic acid intercalated graphite, namely the insertion material of intercalated graphite interlayer is propionic acid.Operating process is: with natural flake graphite, propionic acid, iron(ic) chloride and chromium trioxide, be 1 ︰ 3 ︰ 1 ︰ 0.4 according to mass ratio, add successively the there-necked flask that reflux condensate device and agitator are housed under constantly stirring in, put into the water bath with thermostatic control of 30～60 ℃, after stirring and reacting 90min, wash colourless to solution and pH value for neutral, suction filtration and in 50 ℃ of vacuum drying ovens dry 18 hours, obtain the propionic acid intercalated graphite.
Getting the propionic acid intercalated graphite joins in the stainless steel reaction container by the volume ratio of 10g/L, be 1Pa with being evacuated to vacuum tightness after the reactor sealing, be heated to 320 ℃, make the insertion material decomposes of intercalated graphite interlayer go out gas, kept 5 minutes, stopped heating and stop vacuumizing, cooling subsequently, collect solid product, described solid product is Graphene.
Embodiment four
A kind of method for preparing Graphene comprises the following steps:
Adopt electrochemical production sulfuric acid intercalated graphite, namely the insertion material of intercalated graphite interlayer is sulfuric acid.Operating process is: adopt stainless steel substrates as collector, natural scale graphite is pressed into graphite flake as working electrode, use stereotype as to electrode, Hg/Hg
2SO
4As reference electrode, use sulfuric acid as electrolytic solution, three electrodes are put into electrolyzer and are fully immersed in electrolytic solution, under room temperature, at 5mA/cm
2Current density under, reacted 24 hours, can obtain the sulfuric acid intercalated graphite.
Getting the sulfuric acid intercalated graphite joins in the stainless steel reaction container by the volume ratio of 7g/L, be 10Pa with being evacuated to vacuum tightness after the reactor sealing, be heated to 350 ℃, make the insertion material decomposes of intercalated graphite interlayer go out gas, kept 8 minutes, stopped heating and stop vacuumizing, cooling subsequently, collect solid product, described solid product is Graphene.
Embodiment five
A kind of method for preparing Graphene comprises the following steps:
Adopt electrochemical production nitric acid intercalated graphite, namely the insertion material of intercalated graphite interlayer is nitric acid.Operating process is: adopt stainless steel substrates as collector, natural scale graphite is pressed into graphite flake as working electrode, use stereotype as to electrode, Hg/Hg
2SO
4As reference electrode, use nitric acid as electrolytic solution, three electrodes are put into electrolyzer and are fully immersed in electrolytic solution, under room temperature, at 20mA/cm
2Current density under, reacted 10 hours, can obtain the nitric acid intercalated graphite.
Getting the nitric acid intercalated graphite and join in the stainless steel reaction container by the volume ratio of 6g/L, is 10 with being evacuated to vacuum tightness after the reactor sealing
-1Pa, be heated to 360 ℃, makes the insertion material decomposes of intercalated graphite interlayer go out gas, kept 7 minutes, and stopped heating and stop vacuumizing, cooling subsequently, collects solid product, and described solid product is Graphene.
Embodiment six
A kind of method for preparing Graphene comprises the following steps:
Adopt chemical method to prepare the Nitromethane 99Min. intercalated graphite, namely the insertion material of intercalated graphite interlayer is Nitromethane 99Min..Operating process is: with natural flake graphite, Nitromethane 99Min., iron(ic) chloride and chromium trioxide, be 1 ︰ 3 ︰ 0.8 ︰ 0.4 according to mass ratio, add successively the there-necked flask that reflux condensate device and agitator are housed under constantly stirring in, put into the water bath with thermostatic control of 30 ℃, after stirring and reacting 60min, wash colourless to solution and pH value for neutral, suction filtration and in 50 ℃ of vacuum drying ovens dry 12 hours, obtain the Nitromethane 99Min. intercalated graphite.
Getting the Nitromethane 99Min. intercalated graphite and join in the stainless steel reaction container by the volume ratio of 10g/L, is 10 with being evacuated to vacuum tightness after the reactor sealing
-2Pa, be heated to 340 ℃, makes the insertion material decomposes of intercalated graphite interlayer go out gas, kept 6 minutes, and stopped heating and stop vacuumizing, cooling subsequently, collects solid product, and described solid product is Graphene.
Embodiment seven
A kind of method for preparing Graphene comprises the following steps:
Adopt electrochemical production sulfuric acid-nitric acid intercalated graphite, namely the insertion material of intercalated graphite interlayer is the mixture of sulfuric acid and nitric acid.Operating process is: adopt stainless steel substrates as collector, natural scale graphite is pressed into graphite flake as working electrode, use stereotype as to electrode, Hg/Hg
2SO
4As reference electrode, use sulfuric acid and nitric acid by volume as the mixture of 1:1 as electrolytic solution, three electrodes are put into electrolyzer and are fully immersed in electrolytic solution, under room temperature, 10mA/cm
2Current density under, reacted 16 hours, can obtain sulfuric acid-nitric acid intercalated graphite.
Getting sulfuric acid-nitric acid intercalated graphite joins in the stainless steel reaction container by the volume ratio of 5g/L, be 1Pa with being evacuated to vacuum tightness after the reactor sealing, be heated to 340 ℃, make the insertion material decomposes of intercalated graphite interlayer go out gas, kept 10 minutes, stopped heating and stop vacuumizing, cooling subsequently, collect solid product, described solid product is Graphene.
Embodiment eight
A kind of method for preparing Graphene comprises the following steps:
Adopt chemical method to prepare acetic acid-Nitromethane 99Min. intercalated graphite, namely the insertion material of intercalated graphite interlayer is the mixture of acetic acid and Nitromethane 99Min..Operating process is: with natural flake graphite, acetic acid, Nitromethane 99Min., iron(ic) chloride and chromium trioxide, be 1 ︰ 2 ︰ 1 ︰ 0.8 ︰ 0.4 according to mass ratio, add successively the there-necked flask that reflux condensate device and agitator are housed under constantly stirring in, put into the water bath with thermostatic control of 30 ℃, after stirring and reacting 60min, wash colourless to solution and pH value for neutral, suction filtration and in 50 ℃ of vacuum drying ovens dry 12 hours, obtain acetic acid-Nitromethane 99Min. intercalated graphite.
Getting acetic acid-Nitromethane 99Min. intercalated graphite joins in the stainless steel reaction container by the volume ratio of 8g/L, be 10Pa with being evacuated to vacuum tightness after the reactor sealing, be heated to 380 ℃, make the insertion material decomposes of intercalated graphite interlayer go out gas, kept 5 minutes, stopped heating and stop vacuumizing, cooling subsequently, collect solid product, described solid product is Graphene.
Claims (5)
1. a method for preparing Graphene, is characterized in that, comprises the following steps: getting intercalated graphite and be placed in reactor, is 10 with being evacuated to vacuum tightness after the reactor sealing
-3～100Pa, being heated to 280 ~ 400 ℃ makes the insertion material decomposes of intercalated graphite interlayer go out gas, the insertion material of described intercalated graphite interlayer is a kind of or arbitrary combination in formic acid, acetic acid, propionic acid, sulfuric acid, nitric acid and Nitromethane 99Min., stopped heating and stop vacuumizing subsequently, cooling, collect solid product, described solid product is Graphene.
2. the method for preparing Graphene as claimed in claim 1, is characterized in that, the material of described reactor is stainless steel.
3. the method for preparing Graphene as claimed in claim 1, is characterized in that, ratio adds described intercalated graphite in described reactor volume, being 5 ~ 10g/L.
4. the method for preparing Graphene as claimed in claim 1, is characterized in that, described described reactor was heated to 280 ~ 400 ℃ in 3 ~ 5 minutes.
5. the method for preparing Graphene as claimed in claim 1, is characterized in that, kept 5 ~ 10 minutes after described reactor is heated to 280 ~ 400 ℃, and stopped heating and stop vacuumizing, cooling subsequently.
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| CN103601179A (en) * | 2013-11-19 | 2014-02-26 | 厦门凯纳石墨烯技术有限公司 | Preparation method of size controllable graphene nanoplatelets |
| CN107857254A (en) * | 2017-09-19 | 2018-03-30 | 桂林理工大学 | A kind of preparation method of water-soluble graphene |
| CN108423663A (en) * | 2018-04-24 | 2018-08-21 | 江西理工大学 | A kind of method that electrochemistry prepares ultra-thin graphene nanometer sheet |
| CN112225205A (en) * | 2020-09-09 | 2021-01-15 | 宁波益德新材料有限公司 | Preparation method of graphene and graphene/PET composite material |
| CN114105135A (en) * | 2021-12-24 | 2022-03-01 | 湖南大学 | Method for electrochemically assisting preparation of low-defect expanded graphite paper |
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| CN114105135A (en) * | 2021-12-24 | 2022-03-01 | 湖南大学 | Method for electrochemically assisting preparation of low-defect expanded graphite paper |
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Application publication date: 20131113 |