CN102452649B - Preparation method for graphene - Google Patents
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- CN102452649B CN102452649B CN201010514807.9A CN201010514807A CN102452649B CN 102452649 B CN102452649 B CN 102452649B CN 201010514807 A CN201010514807 A CN 201010514807A CN 102452649 B CN102452649 B CN 102452649B
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Abstract
The invention relates to a preparation method for graphene. The preparation method is characterized in that: the method comprises the following steps: 1, placing graphite in a mixed solution comprising an oxidant and an intercalation agent, and carrying out treatments of impregnation, mechanical stirring or ultrasound to obtain a primary intercalation compound; 2, carrying out a treatment for the primary intercalation compound in the air, wherein the intercalation agent is rapidly decomposed, the primary separation of the graphite intercalation compound is achieved to obtain a primary stripping material; 3, adopting a secondary intercalation method or a mild oxidation method to treat the primary stripping material to obtain a secondary intercalation compound; 4, carrying out a treatment for the second intercalation compound in the air; 5, adopting a liquid phase ultrasonic treatment, solid mechanical grinding and ball milling to achieve the complete stripping of the graphite to obtain the graphene product. Compared to the prior art, the method of the present invention has the following advantages that: the prepared graphene has characteristics of less structural defects, good conductivity and high yield; the preparation process has characteristics of simple operation and low cost, and is applicable for the large-scale production.
Description
Technical field
The present invention relates to a kind of solution phase preparation method of Graphene.
Background technology
Graphene (being mono-layer graphite), since within 2004, being found first, has caused immediately the very big interest of scientific circles, and has become one of the most popular in recent years material.Graphene has high electric transmission speed because of its unique two dimensional crystal structure, and be the known the highest material of physical strength, simultaneously its stable chemical nature, transparent, thermal conductivity is outstanding, therefore in numerous fields, has extremely tempting application prospect.Basis and applied research around Graphene also worldwide launch in high gear.
The preparation of Graphene is the hot issue that people pay close attention to always, because this has been directly connected to the subsequent applications of material.The preparation method who has reported at present mainly contains mechanically peel (K.S.Novoselov, A.K.Geim, S.V.Morozov, D.Jiang, Y.Zhang, S.V.Dubonos, I.V.Grigorieva, A.A.Firsov, Science 2004, 306, 666), epitaxy (C.Berger, Z.M.Song, X.B.Li, X.S.Wu, N.Brown, C.Naud, D.Mayou, T.B.Li, J.Hass, A.N.Marchenkov, E.H.Conrad, P.N.First, W.A.de Heer, Science 2006, 312, 1191), chemical vapour deposition (K.S.Kim, Y.Zhao, H.Jang, S.Y.Lee, J.M.Kim, K.S.Kim, J.-H.Ahn, P.Kim, J.-Y.Choi, B.H.Hong, Nature 2009, 457, 706) and solution phase preparation (S.J.Park, R.S.Ruoff, Nature Nanotechnology 2009, advanced online publication, doi:10.1038/nnano.2009.58) several, see that application number is the preparation method > > (publication number: CN101139090A) of the open < < two-dimension single layer plumbago alkene of 200710052949.6 Chinese patent application.Although first three methods can obtain high-quality Graphene, be obviously difficult to realize the preparation of mass-producing.Solution phase redox preparation method is easy to expand a large amount of preparations, but has more defect and impurity through the Graphene product of redox processes, is difficult to obtain the highly purified product of high quality.
Recently; there is scientist to report and utilize super acids chlorsulfonic acid to realize directly peeling off of graphite; obtained the Graphene colloidal sol (N.Behabtu of concentration at 2mg/ml; et al., Nature Nanotechnology 2010,5; 406); but chlorsulfonic acid is extremely unstable in air, easily blast, must under protection of inert gas, operates, thereby limit its preparative scale amplification.
Summary of the invention
Technical problem to be solved by this invention is that a kind of preparation method of extensive high-quality graphene is provided for the above-mentioned state of the art.Gained Graphene is individual layer or several layers (number of plies is between 1～10 layer, and corresponding thickness is between 0.5～3 nanometer), and every layer by sp
2the carbon atom six side Mi Dui of hydridization form the carbon material of (identical with mono-layer graphite structure).
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of preparation method of Graphene, is characterized in that comprising the steps:
1. graphite is placed in to the mixing solutions being formed by oxygenant and intercalator, at 20～60 ℃ by dipping 0.5～5 hour, mechanical stirring 0.5-3 hour or supersound process 0.5～3 hour, obtain first insert layer compound, and the mass ratio of graphite, oxygenant and intercalator is 1: 0.2～10: 0.5～10;
2. above-mentioned first insert layer compound is processed in air, keeping temperature is 600～900 ℃, and in 10～60 seconds treatment times, intercalation reagent fast decoupled, realizes peeling off first of graphite intercalation compound, obtains overburden first;
3. adopt secondary intercalation method or mild oxidation method further to weaken the reactive force of graphene film interlayer in graphite above-mentioned overburden first, obtain secondary intercalation thing;
4. secondary intercalation thing need be processed in air, and keeping temperature is 600～900 ℃, 10～60 seconds treatment times, and realize the secondary of graphite and peel off, obtain secondary overburden;
5. use liquid phase supersound process, solid phase mechanical mill and ball milling to realize thoroughly peeling off of graphite, obtain product Graphene.
Further, the secondary intercalation method of step described in is 2.: first insert layer compound is placed in to the mixing solutions consisting of oxygenant and intercalator, at 20～60 ℃ by dipping 0.5～5 hour, mechanical stirring or supersound process 0.5～3 hour, obtain secondary intercalation compound, and the mass ratio of graphite, oxygenant and intercalator is 1: 0.2～10: 0.5～10.
As preferably, the oxygenant of step described in 1. can be at least one in mass percent 95～98% vitriol oils, hydrogen peroxide, potassium permanganate, mass percent 65%-68% concentrated nitric acid.
As preferably, step 1. described intercalator can be at least one in mass percent 95～98% vitriol oils, mass percent 65～68% concentrated nitric acids, Glacial acetic acid, diacetyl oxide.
The mild oxidation method of step described in is 2. specially: by first insert layer compound anneal in air again, keeping temperature is 400～700 ℃, 0.5～3 hour treatment time.
Further, it is 300～800 watts that the liquid phase supersound process of step described in 5. meets ultrasonic power, and the supersound process time is 5～30 minutes.
The liquid phase supersound process used solvent of step described in 5. can be N-Methyl pyrrolidone, N, dinethylformamide, N, at least one in N-N,N-DIMETHYLACETAMIDE, N-METHYLFORMAMIDE, methyl-sulphoxide, benzene,toluene,xylene, chloroform, methylene dichloride, ethanol, Virahol, acetone, water, and the mass percent concentration of Graphene in solvent is 0.1%-5%.
Further, in described solvent, be added with dispersion agent, the mass ratio of dispersion agent and Graphene is 0.1～10.
As preferably, described dispersion agent can be at least one macromolecule dispersing agent in polyvinylpyrrolidone, polyoxyethylene laurel ether, tween 80, triton X-100, Pluronic P123, Pluronic F127, Pluronic F68.
As preferably, the mechanical mill of step described in 5. or the time of ball milling are 0.5～2 hour.
Compared with prior art, the invention has the advantages that: prepared graphene-structured defect is few, good conductivity, and productive rate is high; Preparation process is easy and simple to handle, with low cost, is easy to large-scale production; Can meet Graphene at the needs of the field large-scale application such as lithium ion battery, ultracapacitor, functional composite material.
Accompanying drawing explanation
Fig. 1 is the atomic force microscope figure of the Graphene for preparing of embodiment 1.
Embodiment
Below in conjunction with accompanying drawing, embodiment is described in further detail the present invention.
Embodiment 1
The first step, in graphite: potassium permanganate: diacetyl oxide: the mass ratio of concentrated nitric acid is 1: 0.4: 1.7: 0.5 ratio above-mentioned four kinds of raw materials are evenly mixed at 30 ℃ after mechanical stirring 1.5 hours.Thin up, and add the hydrogen peroxide of 30wt.% extremely without Bubble formation.Water to neutral, is dried product washing.
Second step, by the product in the first step in air at 900 ℃ standing 30 seconds, is cooled to room temperature.
The 3rd step is placed the product in second step 2 hours in air at 500 ℃.
The 4th step, is scattered according to 1% mass percent the product obtaining in the 3rd step in N-Methyl pyrrolidone solvent, and supersound process 15 minutes obtains the suspension of Graphene.Centrifugal or filter and be dried after can obtain graphene powder material.
As shown in Figure 1, the Graphene of preparing is carried out to structural characterization and show, the thickness of graphene sheet layer is between 0.5-3 nanometer, and the number of plies is between 1-8 layer, and the distribution of sizes of graphene sheet layer is between 5-50 micron.The textural defect of this Graphene is obviously less than product prepared by solution phase redox, and electroconductibility also increases significantly, and the specific conductivity of product is about 10
3～10
4s/cm.
Embodiment 2
The first step, in graphite: the vitriol oil: the ratio that the mass ratio of hydrogen peroxide is 1: 5: 0.2 above-mentioned three kinds of raw materials are evenly mixed at 40 ℃ after mechanical stirring 1.5 hours.Water to neutral, is dried product washing.
Subsequent step is identical with embodiment 1.
Embodiment 3
The first step, in graphite: the vitriol oil: the ratio that the mass ratio of concentrated nitric acid is 1: 5: 0.2 above-mentioned four kinds of raw materials are evenly mixed at 30 ℃ after mechanical stirring 1.5 hours.Water to neutral, is dried product washing.
Subsequent step is identical with embodiment 1.
Embodiment 4
The first step, in graphite: potassium permanganate: Glacial acetic acid: the mass ratio of concentrated nitric acid is 1: 0.4: 2: 0.5 ratio above-mentioned four kinds of raw materials are evenly mixed at 30 ℃ after mechanical stirring 1.5 hours.Thin up, and add the hydrogen peroxide of 30wt.% extremely without Bubble formation.Water to neutral, is dried product washing.
Subsequent step is identical with embodiment 1.
Embodiment 5
Change the solvent in embodiment 1 the 4th step into DMF, other preparation process is identical with embodiment 1.
Embodiment 6
Change the solvent in embodiment 1 the 4th step into N,N-dimethylacetamide, other preparation process is identical with embodiment 1.
Embodiment 7
Change the solvent in embodiment 1 the 4th step into methyl-sulphoxide, other preparation process is identical with embodiment 1.
Embodiment 8
Change the solvent in embodiment 1 the 4th step into toluene, other preparation process is identical with embodiment 1.
Embodiment 9
Change the solvent in embodiment 1 the 4th step into chloroform, other preparation process is identical with embodiment 1.
Embodiment 10
Change the solvent in embodiment 1 the 4th step into ethanol, other preparation process is identical with embodiment 1.
Embodiment 11
Change the solvent in embodiment 1 the 4th step into acetone, other preparation process is identical with embodiment 1.
Embodiment 12
Graphene in embodiment 1 the 4th step is scattered in N-Methyl pyrrolidone solvent and carries out supersound process by 0.1% concentration, and other preparation process is identical with embodiment 1.
Embodiment 13
Graphene in embodiment 1 the 4th step is scattered in N-Methyl pyrrolidone solvent and carries out supersound process by 5% concentration, and other preparation process is identical with embodiment 1.
Embodiment 14
First three step is identical with first three step in embodiment 1.
The 4th step is scattered according to 1% mass percent the product obtaining in the 3rd step in N-Methyl pyrrolidone solvent, the polyvinylpyrrolidone that to add with Graphene mass ratio be 1: 1 simultaneously, and supersound process 10 minutes, obtains the suspension of Graphene.Centrifugal or filter and be dried after can obtain the powder body material of high-quality graphene.
Embodiment 15
Polyvinylpyrrolidone in embodiment 14 is replaced with to the polyoxyethylene laurel ether of equal in quality, other preparation process is identical with embodiment 14.
Embodiment 16
Polyvinylpyrrolidone in embodiment 14 is replaced with to the tween 80 of equal in quality, other preparation process is identical with embodiment 14.
Embodiment 17
Polyvinylpyrrolidone in embodiment 14 is replaced with to the triton X-100 of equal in quality, other preparation process is identical with embodiment 14.
Embodiment 18
Polyvinylpyrrolidone in embodiment 14 is replaced with to the Pluronic P123 of equal in quality, other preparation process is identical with embodiment 14.
Embodiment 19
Polyvinylpyrrolidone in embodiment 14 is replaced with to the Pluronic F127 of equal in quality, other preparation process is identical with embodiment 14.
Embodiment 20
Polyvinylpyrrolidone in embodiment 14 is replaced with to the Pluronic F68 of equal in quality, other preparation process is identical with embodiment 14.
Embodiment 21
By the water of the quality such as the solvent N-Methyl pyrrolidone in embodiment 14 replaces with, other preparation process is identical with embodiment 14.
Embodiment 22
By the ethanol of the quality such as the solvent N-Methyl pyrrolidone in embodiment 14 replaces with, other preparation process is identical with embodiment 14.
Embodiment 23
By the DMF of the quality such as the solvent N-Methyl pyrrolidone in embodiment 14 replaces with, other preparation process is identical with embodiment 14.
Embodiment 24
Change the mass ratio of polyvinylpyrrolidone and Graphene in embodiment 14 into 0.1: 1, other preparation process is identical with embodiment 14.
Embodiment 25
Change the mass ratio of polyvinylpyrrolidone and Graphene in embodiment 14 into 10: 1, other preparation process is identical with embodiment 14.
Embodiment 26
First three step is identical with first three step in embodiment 1.
The 4th step is placed in high-frequency resonance grinding machine for grinding 0.5 hour by the solid product obtaining in the 3rd step, can obtain high-quality Graphene product.
Embodiment 27
First three step is identical with first three step in embodiment 1.
The 3rd step is placed in high-energy planetary formula ball mill ball milling 0.5 hour by the solid product obtaining in second step, can obtain high-quality Graphene product.
Embodiment 28
The first two step is identical with the first two step of embodiment 1.
The 3rd step, carries out intercalation by the product of second step again according to the reaction raw materials proportioning with identical in the first step and reaction conditions.
The 4th step, by the product of the 3rd step according to again peeling off with operation identical in second step.
The 5th step is identical with the 4th step of embodiment 1.
Embodiment 29
The first two step is identical with the first two step of embodiment 2.
The 3rd step, carries out intercalation by the product of second step again according to the reaction raw materials proportioning with identical in the first step and reaction conditions.
The 4th step, by the product of the 3rd step according to again peeling off with operation identical in second step.
The 5th step is identical with the 4th step of embodiment 2.
Embodiment 30
The first two step is identical with the first two step of embodiment 1.
The 3rd step, in second step product: the vitriol oil: the ratio that the mass ratio of hydrogen peroxide is 1: 5: 0.2 above-mentioned three kinds of raw materials are evenly mixed at 40 ℃ after mechanical stirring 1.5 hours.Water to neutral, is dried product washing.
The 4th step, by the product of the 3rd step in air at 900 ℃ standing 30 seconds, is cooled to room temperature.
The 5th step is identical with the 4th step of embodiment 1.
Embodiment 31
Change the solvent in embodiment 28 the 5th step into DMF, other preparation process is identical with embodiment 36.
Embodiment 32
Change the solvent in embodiment 28 the 5th step into ethanol, other preparation process is identical with embodiment 36.
Embodiment 33
Front four steps are identical with front four steps in embodiment 28.
The 5th step is scattered according to 1% mass percent the product obtaining in the 4th step in N-Methyl pyrrolidone solvent, the polyvinylpyrrolidone that to add with Graphene mass ratio be 1: 1 simultaneously, and supersound process 10 minutes, obtains the suspension of Graphene.Centrifugal or filter and be dried after can obtain the powder body material of high-quality graphene.
Embodiment 34
Polyvinylpyrrolidone in embodiment 33 is replaced with to the polyoxyethylene laurel ether of equal in quality, other preparation process is identical with embodiment 33.
Embodiment 35
By the water of the quality such as the solvent N-Methyl pyrrolidone in embodiment 33 replaces with, other preparation process is identical with embodiment 33.
Embodiment 36
Front four steps are identical with front four steps in embodiment 28.
The 5th step is placed in high-frequency resonance grinding machine for grinding 0.5 hour by the solid product obtaining in second step, can obtain high-quality Graphene product.
Embodiment 37
Front four steps are identical with front four steps in embodiment 28.
The 5th step is placed in high-energy planetary formula ball mill ball milling 0.5 hour by the solid product obtaining in second step, can obtain high-quality Graphene product.
After testing, the Graphene of the gained in embodiment 2～36, is the number of plies between 1～10 layer, and every layer by sp
2the carbon atom six side Mi Dui of hydridization form the carbon material of (identical with mono-layer graphite structure), can meet the needs in field large-scale application such as lithium ion battery, ultracapacitor, functional composite materials.
Claims (6)
1. a preparation method for Graphene, is characterized in that comprising the steps:
1. graphite is placed in to the mixing solutions being formed by oxygenant and intercalator, at 20～60 ℃ by dipping 0.5～5 hour, mechanical stirring 0.5-3 hour or supersound process 0.5-3 hour, obtain first insert layer compound, and the mass ratio of graphite, oxygenant and intercalator is 1: 0.2～10: 0.5～10;
2. above-mentioned first insert layer compound is processed in air, keeping temperature is 600～900 ℃, and in 10～60 seconds treatment times, intercalation reagent fast decoupled, realizes peeling off first of graphite intercalation compound, obtains overburden first;
3. adopt secondary intercalation method further to weaken the reactive force of graphene film interlayer in graphite above-mentioned overburden first, obtain secondary intercalation thing;
4. secondary intercalation thing need be processed in air, and keeping temperature is 600～900 ℃, 10～60 seconds treatment times, and realize the secondary of graphite and peel off, obtain secondary overburden;
5. use liquid phase supersound process, solid phase mechanical mill and ball milling to realize thoroughly peeling off of graphite, obtain product Graphene;
The oxygenant of step described in is 1. a kind of in hydrogen peroxide, potassium permanganate;
Step 1. described intercalator is at least one in mass percent 95～98% vitriol oils, mass percent 65～68% concentrated nitric acids, Glacial acetic acid, diacetyl oxide;
The secondary intercalation method of step described in is 3.: first insert layer compound is placed in to the mixing solutions consisting of oxygenant and intercalator, at 20～60 ℃ by dipping 0.5～5 hour, mechanical stirring 0.5～3 hour or supersound process 0.5～3 hour, obtain secondary intercalation compound, and the mass ratio of graphite, oxygenant and intercalator is 1: 0.2～10: 0.5～10;
It is 300～800 watts that the liquid phase supersound process of step described in 5. meets ultrasonic power, and the supersound process time is 5～30 minutes;
The liquid phase supersound process used solvent of step described in is 5. N-Methyl pyrrolidone, N, dinethylformamide, N, at least one in N-N,N-DIMETHYLACETAMIDE, N-METHYLFORMAMIDE, methyl-sulphoxide, benzene,toluene,xylene, chloroform, methylene dichloride, ethanol, Virahol, acetone, water, and the mass percent concentration of Graphene in solvent is 0.1%-5%; In described solvent, be added with dispersion agent, the mass ratio of dispersion agent and Graphene is 0.1～10.
2. preparation method according to claim 1, is characterized in that described dispersion agent is at least one in polyvinylpyrrolidone, polyoxyethylene laurel ether, tween 80, triton X-100, Pluronic P123, Pluronic F127, Pluronic F68.
3. preparation method according to claim 1, the time that it is characterized in that the mechanical mill described in step 5. or ball milling is 0.5～2 hour.
4. a preparation method for Graphene, is characterized in that comprising the steps:
1. graphite is placed in to the mixing solutions being formed by oxygenant and intercalator, at 20～60 ℃ by dipping 0.5～5 hour, mechanical stirring 0.5-3 hour or supersound process 0.5-3 hour, obtain first insert layer compound, and the mass ratio of graphite, oxygenant and intercalator is 1: 0.2～10: 0.5～10;
2. above-mentioned first insert layer compound is processed in air, keeping temperature is 600～900 ℃, and in 10～60 seconds treatment times, intercalation reagent fast decoupled, realizes peeling off first of graphite intercalation compound, obtains overburden first;
3. above-mentioned overburden is first carried out to the reactive force that mild oxidation method further weakens graphene film interlayer in graphite, obtain secondary intercalation thing;
4. secondary intercalation thing need be processed in air, and keeping temperature is 600～900 ℃, 10～60 seconds treatment times, and realize the secondary of graphite and peel off, obtain secondary overburden;
5. use liquid phase supersound process, solid phase mechanical mill and ball milling to realize thoroughly peeling off of graphite, obtain product Graphene;
The oxygenant of step described in is 1. a kind of in hydrogen peroxide, potassium permanganate;
Step 1. described intercalator is at least one in mass percent 95～98% vitriol oils, mass percent 65～68% concentrated nitric acids, Glacial acetic acid, diacetyl oxide;
The mild oxidation method of step described in is 3.: by first insert layer compound anneal in air, keeping temperature is 400～700 ℃, 0.5～3 hour treatment time;
It is 300～800 watts that the liquid phase supersound process of step described in 5. meets ultrasonic power, and the supersound process time is 5～30 minutes;
The liquid phase supersound process used solvent of step described in is 5. N-Methyl pyrrolidone, N, dinethylformamide, N, at least one in N-N,N-DIMETHYLACETAMIDE, N-METHYLFORMAMIDE, methyl-sulphoxide, benzene,toluene,xylene, chloroform, methylene dichloride, ethanol, Virahol, acetone, water, and the mass percent concentration of Graphene in solvent is 0.1%-5%; In described solvent, be added with dispersion agent, the mass ratio of dispersion agent and Graphene is 0.1～10.
5. preparation method according to claim 4, is characterized in that described dispersion agent is at least one in polyvinylpyrrolidone, polyoxyethylene laurel ether, tween 80, triton X-100, Pluronic P123, Pluronic F127, Pluronic F68.
6. preparation method according to claim 4, the time that it is characterized in that the mechanical mill described in step 5. or ball milling is 0.5～2 hour.
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