CN102452649A - Preparation method for graphene - Google Patents
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- CN102452649A CN102452649A CN2010105148079A CN201010514807A CN102452649A CN 102452649 A CN102452649 A CN 102452649A CN 2010105148079 A CN2010105148079 A CN 2010105148079A CN 201010514807 A CN201010514807 A CN 201010514807A CN 102452649 A CN102452649 A CN 102452649A
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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) has caused the very big interest of scientific circles immediately, and has become one of the most popular in recent years material since being found first in 2004.Graphene has high electric transmission speed because of its unique two dimensional crystal structure; And be the highest material of known physical strength; Its chemical property is stable, transparent simultaneously, thermal conductivity is outstanding, therefore in numerous fields extremely tempting application prospect is arranged all.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, and 706) prepare (S.J.Park mutually with solution; R.S.Ruoff, Nature Nanotechnology 2009, advanced online publication, sees that application number is open " a kind of preparation method of two-dimension single layer plumbago alkene " (publication number: CN101139090A) of China's invention application of 200710052949.6 by doi:10.1038/nnano.2009.58) several kinds.Though first three methods can both obtain high-quality Graphene, obviously be difficult to realize the preparation of mass-producing.Solution phase oxidation reducing preparation method is easy to enlarge 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 utilizes the 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, be prone to blast, and must under protection of inert gas, operate, thereby limit its preparative scale amplification.
Summary of the invention
Technical problem to be solved by this invention is to the above-mentioned state of the art a kind of extensive high quality preparation method of graphene to be provided.The 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 constitute the carbon material of (identical with the mono-layer graphite structure).
The present invention solves the problems of the technologies described above the technical scheme that is adopted: a kind of preparation method of graphene is characterized in that comprising the steps:
1. graphite is placed the mixing solutions that is made up of oxygenant and intercalator; At 20～60 ℃ down through dipping 0.5～5 hour, mechanical stirring 0.5-3 hour or supersound process 0.5～3 hour; Obtain one time intercalation compound; And the mass ratio of graphite, oxygenant and intercalator is 1: 0.2～10: 0.5～10;
2. an above-mentioned intercalation compound is handled in air, keeping temperature is 600～900 ℃, and in 10～60 seconds treatment times, intercalation reagent decomposes fast, 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 the graphite above-mentioned overburden first, obtain the secondary intercalation thing;
4. the secondary intercalation thing needs in air, to handle, and keeping temperature is 600～900 ℃, 10～60 seconds treatment times, realize that the secondary of graphite is peeled off, and obtain the secondary overburden;
5. use liquid phase supersound process, solid phase mechanical mill and ball milling to realize thoroughly peeling off of graphite, obtain the product Graphene.
Further; The secondary intercalation method of step described in 2. is: an intercalation compound is placed the mixing solutions that is made up of oxygenant and intercalator; At 20～60 ℃ down through dipping 0.5～5 hour, mechanical stirring or supersound process 0.5～3 hour; Obtain the 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 a in mass percent 95～98% vitriol oils, ydrogen peroxide 50, potassium permanganate, the mass percent 65%-68% concentrated nitric acid.
As preferably, the 1. described intercalator of step can be at least a in mass percent 95～98% vitriol oils, mass percent 65～68% concentrated nitric acids, Glacial acetic acid min. 99.5, the diacetyl oxide.
The mild oxidation method of step described in 2. is specially: with intercalation compound anneal in the 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. satisfies 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 a in N-N,N-DIMETHYLACETAMIDE, N-NMF, methyl-sulphoxide, benzene,toluene,xylene, chloroform, methylene dichloride, ethanol, Virahol, acetone, the water; And the mass percent concentration of Graphene in solvent is 0.1%-5%.
Further, be added with dispersion agent in the described solvent, the mass ratio of dispersion agent and Graphene is 0.1～10.
As preferably, described dispersion agent can be at least a macromolecule dispersing agent among Vinylpyrrolidone polymer, polyoxyethylene laurel ether, tween 80, Triton X100, Pluronic P123, Pluronic F127, the 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: the prepared graphene textural defect is few, good conductivity, and productive rate is high; The preparation process operation is easy, with low cost, is easy to large-scale production; Can satisfy the needs of Graphene in field large-scale application such as lithium ion battery, ultracapacitor, functional composite materials.
Description of drawings
The AFM figure of the Graphene that Fig. 1 prepares for embodiment 1.
Embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
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 is with above-mentioned four kinds of raw materials mechanical stirring 1.5 hours behind 30 ℃ of following uniform mixing.Thin up, and the ydrogen peroxide 50 of adding 30wt.% produces to there being bubble.Water is extremely neutral with the product washing, drying.
Second step, the product in the first step was left standstill under 900 ℃ 30 seconds in air, be cooled to room temperature.
The 3rd step, with the product in second step in air 500 ℃ of held 2 hours.
The 4th step was scattered in the product that obtains in the 3rd step in the N-Methyl pyrrolidone solvent according to 1% mass percent, and supersound process 15 minutes obtains the suspension-s of Graphene.Centrifugal or filtration also can obtain the Graphene powder body material after the drying.
As shown in Figure 1, the Graphene of preparing is carried out structural characterization show, the thickness of Graphene lamella is between the 0.5-3 nanometer, and promptly the number of plies is between the 1-8 layer, and the distribution of sizes of Graphene lamella is between the 5-50 micron.The textural defect of this Graphene obviously is less than the product of solution phase oxidation reduction preparation, 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 mass ratio of ydrogen peroxide 50 is that 1: 5: 0.2 ratio is with above-mentioned three kinds of raw materials mechanical stirring 1.5 hours behind 40 ℃ of following uniform mixing.Water is extremely neutral with the product washing, drying.
Subsequent step is identical with embodiment 1.
Embodiment 3
The first step, in graphite: the vitriol oil: the mass ratio of concentrated nitric acid is that 1: 5: 0.2 ratio is with above-mentioned four kinds of raw materials mechanical stirring 1.5 hours behind 30 ℃ of following uniform mixing.Water is extremely neutral with the product washing, drying.
Subsequent step is identical with embodiment 1.
Embodiment 4
The first step, in graphite: potassium permanganate: Glacial acetic acid min. 99.5: the mass ratio of concentrated nitric acid is 1: 0.4: 2: 0.5 ratio is with above-mentioned four kinds of raw materials mechanical stirring 1.5 hours behind 30 ℃ of following uniform mixing.Thin up, and the ydrogen peroxide 50 of adding 30wt.% produces to there being bubble.Water is extremely neutral with the product washing, drying.
Subsequent step is identical with embodiment 1.
Embodiment 5
Change the solvent of embodiment 1 in the 4th step into N, dinethylformamide, other preparation process is identical with embodiment 1.
Embodiment 6
Change the solvent of embodiment 1 in the 4th step into DMAC N,N, other preparation process is identical with embodiment 1.
Embodiment 7
Change the solvent of embodiment 1 in the 4th step into methyl-sulphoxide, other preparation process is identical with embodiment 1.
Embodiment 8
Change the solvent of embodiment 1 in the 4th step into toluene, other preparation process is identical with embodiment 1.
Embodiment 9
Change the solvent of embodiment 1 in the 4th step into chloroform, other preparation process is identical with embodiment 1.
Embodiment 10
Change the solvent of embodiment 1 in the 4th step into ethanol, other preparation process is identical with embodiment 1.
Embodiment 11
Change the solvent of embodiment 1 in the 4th step into acetone, other preparation process is identical with embodiment 1.
Embodiment 12
With embodiment 1 the 4th in the step Graphene be scattered in by 0.1% concentration and carry out supersound process in the N-Methyl pyrrolidone solvent, other preparation process is identical with embodiment 1.
Embodiment 13
With embodiment 1 the 4th in the step Graphene be scattered in by 5% concentration and carry out supersound process in the N-Methyl pyrrolidone solvent, other preparation process is identical with embodiment 1.
Embodiment 14
First three step is identical with first three step among the embodiment 1.
The 4th step was scattered in the product that obtains in the 3rd step in the N-Methyl pyrrolidone solvent according to 1% mass percent, and adding simultaneously with the Graphene mass ratio is 1: 1 Vinylpyrrolidone polymer, and supersound process 10 minutes obtains the suspension-s of Graphene.Centrifugal or filter and drying after can obtain the powder body material of high quality Graphene.
Embodiment 15
Vinylpyrrolidone polymer among the embodiment 14 is replaced with the polyoxyethylene laurel ether of equal in quality, and other preparation process is identical with embodiment 14.
Embodiment 16
Vinylpyrrolidone polymer among the embodiment 14 is replaced with the tween 80 of equal in quality, and other preparation process is identical with embodiment 14.
Embodiment 17
Vinylpyrrolidone polymer among the embodiment 14 is replaced with the Triton X100 of equal in quality, and other preparation process is identical with embodiment 14.
Embodiment 18
Vinylpyrrolidone polymer among the embodiment 14 is replaced with the Pluronic P123 of equal in quality, and other preparation process is identical with embodiment 14.
Embodiment 19
Vinylpyrrolidone polymer among the embodiment 14 is replaced with the Pluronic F127 of equal in quality, and other preparation process is identical with embodiment 14.
Embodiment 20
Vinylpyrrolidone polymer among the embodiment 14 is replaced with the Pluronic F68 of equal in quality, and other preparation process is identical with embodiment 14.
Embodiment 21
With the water of quality such as the solvent N-Methyl pyrrolidone among the embodiment 14 replaces with, other preparation process is identical with embodiment 14.
Embodiment 22
With the ethanol of quality such as the solvent N-Methyl pyrrolidone among the embodiment 14 replaces with, other preparation process is identical with embodiment 14.
Embodiment 23
With the N of quality such as the solvent N-Methyl pyrrolidone among the embodiment 14 replaces with, dinethylformamide, other preparation process is identical with embodiment 14.
Embodiment 24
Change the mass ratio of Vinylpyrrolidone polymer and Graphene among the embodiment 14 into 0.1: 1, other preparation process is identical with embodiment 14.
Embodiment 25
Change the mass ratio of Vinylpyrrolidone polymer and Graphene among the embodiment 14 into 10: 1, other preparation process is identical with embodiment 14.
Embodiment 26
First three step is identical with first three step among the embodiment 1.
The 4th step placed the high-frequency resonance grinding machine for grinding 0.5 hour with the solid product that obtains in the 3rd step, can obtain high-quality Graphene product.
Embodiment 27
First three step is identical with first three step among the embodiment 1.
The 3rd step placed high-energy planetary formula ball mill ball milling 0.5 hour with the solid product that obtains 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 the step, with second the step product according to the first step in identical reaction raw materials proportioning and reaction conditions carry out intercalation once more.
In the 4th step, the product in the 3rd step is peeled off according to identical operations in going on foot with second once more.
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 the step, with second the step product according to the first step in identical reaction raw materials proportioning and reaction conditions carry out intercalation once more.
In the 4th step, the product in the 3rd step is peeled off according to identical operations in going on foot with second once more.
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.
In the 3rd step, go on foot product by second: the vitriol oil: the mass ratio of ydrogen peroxide 50 is that 1: 5: 0.2 ratio is with above-mentioned three kinds of raw materials mechanical stirring 1.5 hours behind 40 ℃ of following uniform mixing.Water is extremely neutral with the product washing, drying.
The 4th the step, with the 3rd the step product in air, under 900 ℃, left standstill 30 seconds, be cooled to room temperature.
The 5th step is identical with the 4th step of embodiment 1.
Embodiment 31
Change the solvent of embodiment 28 in the 5th step into N, dinethylformamide, other preparation process is identical with embodiment 36.
Embodiment 32
Change the solvent of embodiment 28 in the 5th step into ethanol, other preparation process is identical with embodiment 36.
Embodiment 33
Preceding four steps are identical with preceding four steps among the embodiment 28.
The 5th step was scattered in the product that obtains in the 4th step in the N-Methyl pyrrolidone solvent according to 1% mass percent, and adding simultaneously with the Graphene mass ratio is 1: 1 Vinylpyrrolidone polymer, and supersound process 10 minutes obtains the suspension-s of Graphene.Centrifugal or filter and drying after can obtain the powder body material of high quality Graphene.
Embodiment 34
Vinylpyrrolidone polymer among the embodiment 33 is replaced with the polyoxyethylene laurel ether of equal in quality, and other preparation process is identical with embodiment 33.
Embodiment 35
With the water of quality such as the solvent N-Methyl pyrrolidone among the embodiment 33 replaces with, other preparation process is identical with embodiment 33.
Embodiment 36
Preceding four steps are identical with preceding four steps among the embodiment 28.
The 5th step placed the high-frequency resonance grinding machine for grinding 0.5 hour with the solid product that obtains in second step, can obtain high-quality Graphene product.
Embodiment 37
Preceding four steps are identical with preceding four steps among the embodiment 28.
The 5th step placed high-energy planetary formula ball mill ball milling 0.5 hour with the solid product that obtains in second step, can obtain high-quality Graphene product.
Through detecting, the Graphene of the gained among the 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 constitute the carbon material of (identical with the mono-layer graphite structure), can satisfy the needs in field large-scale application such as lithium ion battery, ultracapacitor, functional composite materials.
Claims (10)
1. a preparation method of graphene is characterized in that comprising the steps:
1. graphite is placed the mixing solutions that is made up of oxygenant and intercalator; At 20～60 ℃ down through dipping 0.5～5 hour, mechanical stirring 0.5-3 hour or supersound process 0.5-3 hour; Obtain one time intercalation compound; And the mass ratio of graphite, oxygenant and intercalator is 1: 0.2～10: 0.5～10;
2. an above-mentioned intercalation compound is handled in air, keeping temperature is 600～900 ℃, and in 10～60 seconds treatment times, intercalation reagent decomposes fast, 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 the graphite above-mentioned overburden first, obtain the secondary intercalation thing;
4. the secondary intercalation thing needs in air, to handle, and keeping temperature is 600～900 ℃, 10～60 seconds treatment times, realize that the secondary of graphite is peeled off, and obtain the secondary overburden;
5. use liquid phase supersound process, solid phase mechanical mill and ball milling to realize thoroughly peeling off of graphite, obtain the product Graphene.
2. preparation method according to claim 1; It is characterized in that the secondary intercalation method described in step 2. is: an intercalation compound is placed the mixing solutions that is made up of oxygenant and intercalator; At 20～60 ℃ down through dipping 0.5～5 hour, mechanical stirring 0.5～3 hour or supersound process 0.5～3 hour; Obtain the secondary intercalation compound, and the mass ratio of graphite, oxygenant and intercalator is 1: 0.2～10: 0.5～10.
3. preparation method according to claim 1 and 2 is characterized in that the oxygenant described in step 1. is at least a in mass percent 95～98% vitriol oils, ydrogen peroxide 50, potassium permanganate, the mass percent 65%-68% concentrated nitric acid.
4. preparation method according to claim 1 and 2 is characterized in that the 1. described intercalator of step is at least a in mass percent 95～98% vitriol oils, mass percent 65～68% concentrated nitric acids, Glacial acetic acid min. 99.5, the diacetyl oxide.
5. preparation method according to claim 1 is characterized in that the mild oxidation method described in step 2. is: with intercalation compound anneal in air, keeping temperature is 400～700 ℃, 0.5～3 hour treatment time.
6. preparation method according to claim 1 is characterized in that it is 300～800 watts that the liquid phase supersound process described in step 5. satisfies ultrasonic power, and the supersound process time is 5～30 minutes.
7. preparation method according to claim 6; It is characterized in that the used solvent of the liquid phase supersound process described in step 5. is N-Methyl pyrrolidone, N; Dinethylformamide, N; At least a in N-N,N-DIMETHYLACETAMIDE, N-NMF, methyl-sulphoxide, benzene,toluene,xylene, chloroform, methylene dichloride, ethanol, Virahol, acetone, the water, and the mass percent concentration of Graphene in solvent is 0.1%-5%.
8. preparation method according to claim 7 is characterized in that being added with dispersion agent in the described solvent, and the mass ratio of dispersion agent and Graphene is 0.1～10.
9. preparation method according to claim 8 is characterized in that described dispersion agent is at least a among Vinylpyrrolidone polymer, polyoxyethylene laurel ether, tween 80, Triton X100, Pluronic P123, Pluronic F127, the Pluronic F68.
10. preparation method according to claim 1, the time that it is characterized in that mechanical mill described in step 5. or ball milling is 0.5～2 hour.
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