CN102757038A - Method for preparing graphene - Google Patents
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- CN102757038A CN102757038A CN2011101087564A CN201110108756A CN102757038A CN 102757038 A CN102757038 A CN 102757038A CN 2011101087564 A CN2011101087564 A CN 2011101087564A CN 201110108756 A CN201110108756 A CN 201110108756A CN 102757038 A CN102757038 A CN 102757038A
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Abstract
The invention provides a method for preparing graphene. The method includes that graphite reacts in acid solution with an oxidant to obtain the graphene. Compared with the prior art, the method has the advantages that the graphene prepared by the method is good in quality, yield is greatly increased and productivity is greatly improved as compared with a mechanical exfoliation method, an epitaxial growth method and a chemical vapor deposition method; the quality of the graphene is greatly enhanced, structural defects of the graphene are greatly reduced, and electrical conductivity of the graphene is obviously improved as compared with a solution-phase oxidation reduction method; and the preparation process is simple, conditions are mild, cost is low, and large-scale production is realized easily. In addition, the graphene prepared by the method has an extremely broad prospect in fields of lithium ion batteries, super-capacitors, functional composites, transparent conductive thin films, microelectronic devices and the like.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related to a kind of method for preparing Graphene.
Background technology
Since Graphene came to light in 2004, caused the very big interest of scientific circles immediately as a kind of new carbon.Graphene has unique two-dimensional nanostructure, and its electric transmission speed is high, electroconductibility is outstanding, thermal conductivity is high, is the highest material of known physical strength, but also has the stable and good advantage of light transmission of chemical property.Graphene all has extremely tempting application prospect in various fields such as semi-conductor industry, energy storage material, functional composite material, transmitter and biological medicines.Therefore, basis and the applied research around Graphene becomes international research focus.
Preparation method of graphene is the key issue that can this material realize practical application.Along with deepening continuously of research, the various fields that comprises energy storage material and functional composite material has all proposed increasingly high requirement for the quality and the preparative-scale of Graphene.In the prior art, the preparation method of graphene of having reported has mechanically peel method (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), epitaxial growth method (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 Vapor deposition process (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, Nature2009; 457,706) and solution phase oxidation reduction preparation method (Nature Nanotechnology 2009,4,217 for S.J.Park, R.S.Ruoff) several kinds.
In the aforesaid method, mechanically peel method and epitaxial growth method preparation efficiency are very low, are difficult to satisfy large-scale needs.Though chemical Vapor deposition process can obtain large size successive graphene film, is applicable to micro-nano electron device or transparent conductive film, but can not satisfy the extensive demand in energy storage material and functional composite material field.
Compare with above-mentioned three kinds of methods; Solution phase oxidation reduction method has very big lifting on preparative-scale; But the intensive redox condition in the prior art in the disclosed solution phase oxidation method of reducing makes the Graphene product have more defective, has had a strong impact on quality and the performance such as the electroconductibility of Graphene; In addition, solution phase oxidation reduction method complex operation of the prior art, and also have suitable difficulty for the processing of waste reaction solution.To sum up, method of the prior art all is inappropriate for the high-quality Graphene of mass preparation.
Summary of the invention
The problem that the present invention will solve is to provide a kind of method for preparing Graphene; Compared with prior art, method preparation technology provided by the invention is simple, reaction conditions is gentle, and employed oxidizing condition is weaker than traditional solution phase oxidation method of reducing; Under the suboxide degree; Need not can prepare Graphene through reduction step, and the graphene-structured defective that makes is few, conductivity is good.
In order to solve above technical problem, the present invention provides a kind of method for preparing Graphene, comprising:
Graphite is reacted in the acid solution that oxygenant exists obtain Graphene.
Preferably, the ratio of the carbon Sauerstoffatom in the described reacted product is greater than 5.
Preferably, said oxygenant comprises one or more the combination in nitric acid, sulfuric acid, perchloric acid, hypochlorous acid, nitrous acid, chlorsulfonic acid, dichromate, perchlorate, oxymuriate, hypochlorite, persulphate, ydrogen peroxide 50, the superoxide.
Preferably, the acid in the described acid solution is one or more the combination in nitric acid, sulfuric acid, hydrochloric acid, perchloric acid, hypochlorous acid, nitrous acid, chlorsulfonic acid, acetic acid, the oxalic acid.
Preferably, the solvent in the described acid solution comprises one or more the combination in ethanol, tetracol phenixin, benzene, water, methyl alcohol, acetone, formaldehyde, acetaldehyde, the acetate.
Preferably, said graphite comprises one or more the combination in natural graphite, synthetic graphite or the expansible black lead.
Preferably, said graphite: oxygenant: acid: solvent is 1 according to mass ratio: 0.1-50: 0.1-50: 0.1-100.
Preferably, the temperature of said reaction is 0 ℃～90 ℃.
Preferably, the time of said reaction is 1 minute～10 hours.Preferably, also comprise mixed solution to neutral step behind the washing reaction.
Preferably, also comprise the step of the Graphene that obtains after the reaction being carried out lift-off processing.。
Preferably, said lift-off processing comprise that high temperature is peeled off, in mechanical mill or the supersound process one or more.
The present invention provides a kind of method for preparing Graphene, comprises that graphite is reacted in the acidic solution that oxygenant exists obtains Graphene.Compared with prior art, the invention has the advantages that: than mechanically peel, epitaxy and chemical gaseous phase depositing process, the Graphene of method preparation provided by the invention has good quality, and has significantly improved output and productive rate; Than solution phase oxidation method of reducing, Graphene quality of the present invention has tangible lifting, and textural defect significantly reduces, and electroconductibility significantly improves; And preparation technology is simple, mild condition, with low cost, very be easy to large-scale production.The Graphene of the present invention's preparation has very wide prospect in fields such as lithium ion battery, ultracapacitor, functional composite material, transparent conductive film, microelectronic devices.
Description of drawings
Fig. 1 is the Raman spectrogram of the Graphene of the embodiment of the invention 1 preparation;
Fig. 2 is the Raman spectrogram of the Graphene of comparative example 1 preparation of the present invention.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, describe just to further specifying feature and advantage of the present invention but should be appreciated that these, rather than to the restriction of claim of the present invention.
The present invention provides a kind of preparation method of graphene, comprising:
Graphite reacted in containing the acid solution of oxygenant obtain Graphene.
According to the present invention, the carbon Sauerstoffatom ratio in the described reacted product is greater than 5, more preferably greater than 10, more preferably greater than 14, more preferably greater than 16, more preferably greater than 20.
According to the present invention, the acid in the said acid solution is one or more combinations in nitric acid, sulfuric acid, perchloric acid, hypochlorous acid, nitrous acid, chlorsulfonic acid, acetic acid, the oxalic acid, but is not limited thereto.Said oxygenant is one or more the combination in nitric acid, sulfuric acid, perchloric acid, hypochlorous acid, nitrous acid, chlorsulfonic acid, dichromate, perchlorate, oxymuriate, hypochlorite, persulphate, ydrogen peroxide 50, the superoxide, but is not limited thereto.Solvent in the described acid solution comprises one or more the combination in ethanol, tetracol phenixin, benzene, water, methyl alcohol, acetone, formaldehyde, acetaldehyde, the acetate, but is not limited thereto.The object lesson of said dichromate such as sodium dichromate 99, SRM 935a, ammonium dichromate, but be not limited thereto.The object lesson of said perchlorate such as potassium perchlorate, sodium perchlorate, perchloric acid are pressed, calcium perchlorate, but are not limited thereto.Object lesson in the said oxymuriate such as Potcrate, VAL-DROP, ammonium chlorate, but be not limited thereto.The object lesson of said hypochlorite such as potassium hypochlorite, Youxiaolin, hypochlorous acid ammonium, but be not limited thereto.The object lesson of said persulphate such as Potassium Persulphate, Sodium Persulfate, ammonium persulphate, but be not limited thereto.The object lesson of said superoxide such as sodiumperoxide, Potassium peroxide 85, Peracetic Acid, but be not limited thereto.
According to the present invention, said graphite: oxygenant: acid: solvent is 1 according to mass ratio: 0.1-50: 0.1-50: 0.1-100, more preferably 1: 0.2～40: 1-40: 0.2-50, more preferably 1: 0.2～20: 0.5～20: 0.2-20; Said temperature of reaction is preferably 0 ℃～90 ℃, and more preferably 10 ℃～80 ℃, more preferably 20 ℃～70 ℃; The time of said reaction is preferably 1 minute～and 10 hours, more preferably 10 minutes～9 hours, more preferably 30 minutes～5 hours.
According to the present invention, after reaction, preferably reacted mixed solution is washed to the neutral step.Preferably; Also comprise the step of reacted product being carried out lift-off processing, said lift-off processing is preferably that high temperature is peeled off, a kind of in mechanical mill or the supersound process, also can above-mentioned several kinds of lift-off processing combined to handle; For order, the present invention does not have special restriction.
According to the present invention, use high temperature to peel off preferably according to following steps:
Product is heated to 500 ℃～1000 ℃ is incubated, preferably be heated to 650 ℃～950 ℃, more preferably be heated to 700 ℃～800 ℃, more preferably be heated to 750 ℃～800 ℃.Soaking time is preferably in 10 seconds at least, and more preferably 10 seconds～5 minutes, more preferably 50 seconds～3 minutes.
According to the present invention, when using mechanical mill to peel off, can use that high-energy ball milling, bead Jie sand milling, vibration are ground, in the impact grinding one or more; Milling time is preferably at least 10 minutes; More preferably at least 15 minutes, more preferably at least 20 minutes, more preferably 30 minutes～20 hours; More preferably 2 hours～15 hours, more preferably 10 hours～14 hours.
According to the present invention, when using ultrasonic peeling off, the supersound process time is preferably 1 minute～and 10 hours, more preferably 10 minutes～8 hours, more preferably 10 minutes～8 hours, more preferably 20 minutes～6 hours, more preferably 40 minutes～4 hours.
When said product is carried out ultrasonication; Solvent for use can be N-Methyl pyrrolidone, N; One or more combination in dinethylformamide, DMAC N,N, N-NMF, methyl-sulphoxide, benzene,toluene,xylene, tetracol phenixin, methylene dichloride, chloroform, acetonitrile, vinyl cyanide, methylene dichloride, chlorsulfonic acid, ethanol, terepthaloyl moietie, USP Kosher, Virahol, acetone or the water.
Compared with prior art, the invention has the advantages that: than mechanically peel, epitaxy and chemical gaseous phase depositing process, the Graphene of method preparation provided by the invention has good quality, and has significantly improved output and productive rate; Than solution phase oxidation method of reducing, Graphene quality of the present invention has tangible lifting, and textural defect significantly reduces, and electroconductibility significantly improves; And preparation technology is simple, mild condition, with low cost, very be easy to large-scale production.The Graphene of the present invention's preparation has very wide prospect in fields such as lithium ion battery, ultracapacitor, functional composite material, transparent conductive films.
Below with specific embodiment effect of the present invention is described, but protection scope of the present invention is not limited by the following examples.
Embodiment 1
The first step is mixed SRM 935a with the aqueous nitric acid of 69wt%, add graphite, graphite subsequently: nitric acid: SRM 935a: water is 1: 20: 10 according to weight ratio: 9, after 1 hour, be washed with water to neutral and dry 40 ℃ of reactions then;
In second step, the product that the first step is obtained is cooled to room temperature then in 900 ℃ of insulations 1 minute;
In the 3rd step, product in second step was ground 5 hours in high energy ball mill or sand mill;
The 4th step was scattered in product in the 3rd step in the ethanol, and supersound process 1 hour obtains Graphene, and productive rate is 96%, and the carbon Sauerstoffatom ratio of product is 21.2.
Embodiment 2
The first step; SRM 935a is mixed with aqueous nitric acid and a certain amount of ethanol of 69wt%, and add graphite, graphite subsequently: concentrated nitric acid: SRM 935a: water: ethanol is 1: 20: 10 according to weight ratio: 9: 10; After 1 hour, be washed with water to neutral and dry 40 ℃ of reactions then;
In second step, the product that the first step is obtained is cooled to room temperature then in 900 ℃ of insulations 1 minute;
In the 3rd step, product in second step was ground 5 hours in high energy ball mill or sand mill;
The 4th step was scattered in product in the 3rd step in the ethanol, and supersound process 1 hour obtains Graphene.
Embodiment 3
The first step; Aqueous nitric acid and a certain amount of methanol mixed with SRM 935a and 69wt% add graphite, graphite: concentrated nitric acid: SRM 935a: water subsequently: methyl alcohol is 1: 20: 10 according to weight ratio: 9: 10; After 1 hour, be washed with water to neutral and dry 40 ℃ of reactions then;
In second step, the product that the first step is obtained is cooled to room temperature then in 700 ℃ of insulations 1 minute;
In the 3rd step, product in second step was ground 5 hours in high energy ball mill or sand mill;
The 4th step was scattered in product in the 3rd step in the ethanol, and supersound process 1 hour obtains Graphene.
Embodiment 4
The first step; SRM 935a is mixed with aqueous nitric acid and a certain amount of acetate of 69wt%, and add graphite, graphite subsequently: concentrated nitric acid: SRM 935a: water: acetate is 1: 20: 10 according to weight ratio: 9: 20; After 1 hour, be washed with water to neutral and dry 40 ℃ of reactions then;
In second step, the product that the first step is obtained is cooled to room temperature then in 700 ℃ of insulations 1 minute;
In the 3rd step, product in second step was ground 5 hours in high energy ball mill or sand mill;
The 4th step was scattered in product in the 3rd step in the ethanol, and supersound process 1 hour obtains Graphene.
Embodiment 5
The first step is mixed sodium dichromate 99 with the vitriol oil of 98wt%, add graphite, graphite subsequently: the vitriol oil: sodium dichromate 99 is 1: 40: 20 according to weight ratio, after 1 hour, is washed with water to neutral and dry 80 ℃ of reactions then;
In second step, the product that the first step is obtained is cooled to room temperature then in 1000 ℃ of insulations 1 minute;
In the 3rd step, product in second step was ground 10 hours in high energy ball mill or sand mill;
The 4th step was scattered in product in the 3rd step in the ethanol, and supersound process 5 hours obtains Graphene.
Embodiment 6
The first step is mixed potassium perchlorate with the vitriol oil of 96wt%, add graphite, graphite subsequently: the vitriol oil: potassium perchlorate is 1: 10: 10 according to weight ratio, after 1 hour, is washed with water to neutral and dry 50 ℃ of reactions then;
In second step, the product that the first step is obtained is cooled to room temperature then 600 ℃ of 30 seconds of insulation;
In the 3rd step, product in second step was ground 1 hour in high energy ball mill or sand mill;
The 4th step was scattered in product in the 3rd step in the ethanol, and supersound process 1 hour obtains Graphene.
Embodiment 7
The first step is mixed ammoniumper chlorate with the vitriol oil of 96wt%, add graphite, graphite subsequently: the vitriol oil: ammoniumper chlorate is 1: 5: 0.5 according to weight ratio, after 2 hours, is washed with water to neutral and dry 20 ℃ of reactions then;
In second step, the product that the first step is obtained is cooled to room temperature then 800 ℃ of 30 seconds of insulation;
In the 3rd step, product in second step was ground 1 hour in high energy ball mill or sand mill;
The 4th step was scattered in product in the 3rd step in the N-Methyl pyrrolidone, and supersound process 1 hour obtains Graphene.
Embodiment 8
The first step is mixed Potcrate with the vitriol oil of 96wt%, add graphite, graphite subsequently: the vitriol oil: Potcrate is 1: 1: 0.5 according to weight ratio, after 0.5 hour, is washed with water to neutral and dry 40 ℃ of reactions then;
In second step, the product that the first step is obtained is cooled to room temperature then 800 ℃ of 30 seconds of insulation;
In the 3rd step, product in second step was ground 1 hour in high energy ball mill or sand mill;
The 4th step was scattered in product in the 3rd step in the N-Methyl pyrrolidone, and supersound process 1 hour obtains Graphene.
Embodiment 9
The first step; Potcrate is mixed with the vitriol oil of 96wt% and the aqueous nitric acid of 69wt%, add graphite, graphite subsequently: the vitriol oil: concentrated nitric acid: Potcrate: water is 1: 1: 0.5 according to weight ratio: 1: 0.22; After 1 hour, be washed with water to neutral and dry 60 ℃ of reactions then;
In second step, the product that the first step is obtained is cooled to room temperature then in 800 ℃ of insulations 1 minute;
In the 3rd step, product in second step was ground 1 hour in high energy ball mill or sand mill;
The 4th step was scattered in N with product in the 3rd step, and in the dinethylformamide, supersound process 1 hour obtains Graphene.
Embodiment 10
The first step is mixed VAL-DROP with the aqueous nitric acid of 69wt%, add graphite, graphite subsequently: nitric acid: VAL-DROP: water is 1: 2: 2 according to weight ratio: 0.9, after 1 hour, be washed with water to neutral and dry 60 ℃ of reactions then;
In second step, the product that the first step is obtained is cooled to room temperature then in 700 ℃ of insulations 1 minute;
In the 3rd step, product in second step was ground 5 hours in high energy ball mill or sand mill;
The 4th step was scattered in product in the 3rd step in the DMAC N,N, and supersound process 1 hour obtains Graphene.
Embodiment 11
The first step is mixed Potcrate with the aqueous nitric acid of 69wt%, add graphite, graphite subsequently: concentrated nitric acid: Potcrate: water is 1: 10: 20 according to weight ratio: 5.4, after 1 hour, be washed with water to neutral and dry 70 ℃ of reactions then;
In second step, the product that the first step is obtained is cooled to room temperature then in 700 ℃ of insulations 1 minute;
The 3rd step was scattered in product in second step in the N-Methyl pyrrolidone, and supersound process 1 hour obtains Graphene.
Embodiment 12
The first step; With aqueous nitric acid and a certain amount of mix of Potcrate with 69wt%, add graphite subsequently, graphite: concentrated nitric acid: Potcrate: water is 1: 10: 20 according to weight ratio: 4.5; After 1 hour, be washed with water to neutral and dry 70 ℃ of reactions then;
In second step, the product that the first step is obtained is cooled to room temperature then in 700 ℃ of insulations 1 minute;
The 3rd step was scattered in product in second step in the N-Methyl pyrrolidone, and supersound process 1 hour obtains Graphene.
Embodiment 13
The first step is mixed SRM 935a with the aqueous nitric acid of 69wt%, add graphite, graphite subsequently: concentrated nitric acid: SRM 935a: water is 1: 20: 20 according to weight ratio: 9, after 1 hour, be washed with water to neutral and dry 70 ℃ of reactions then;
In second step, the product that the first step is obtained is cooled to room temperature then in 700 ℃ of insulations 1 minute;
The 3rd step was scattered in product in second step in the ethanol, and supersound process 1 hour obtains Graphene.
Embodiment 14
The first step is mixed SRM 935a with the vitriol oil of 96wt%, add graphite, graphite subsequently: the vitriol oil: SRM 935a is 1: 10: 20 according to weight ratio, after 1 hour, is washed with water to neutral and dry 80 ℃ of reactions then;
In second step, the product that the first step is obtained ground in high energy ball mill 2 hours;
The 3rd step was scattered in product in second step in the N-Methyl pyrrolidone, and supersound process 1 hour obtains Graphene.
Embodiment 15
The first step is mixed SRM 935a with the vitriol oil and the acetate of 96wt%, add graphite, graphite subsequently: the vitriol oil: SRM 935a: acetate is 1: 10: 20 according to weight ratio: 5, after 1 hour, be washed with water to neutral and dry 80 ℃ of reactions then;
In second step, the product that the first step is obtained ground in high energy ball mill 2 hours;
The 3rd step was scattered in product in second step in the N-Methyl pyrrolidone, and supersound process 1 hour obtains Graphene.
Embodiment 16
The first step is mixed SRM 935a with the vitriol oil of 98wt%, add graphite, graphite subsequently: the vitriol oil: SRM 935a is 1: 20: 10 according to weight ratio, after 1 hour, is washed with water to neutral and dry 70 ℃ of reactions then;
In second step, the product that the first step is obtained was placed 2 minutes in 1000 ℃, was cooled to room temperature then;
The 3rd the step, with second the step product in high energy ball mill, ground 1 hour, can obtain Graphene.
Embodiment 17
The first step is mixed SRM 935a with the vitriol oil of 96wt%, add graphite, graphite subsequently: the vitriol oil: SRM 935a is 1: 20: 10 according to weight ratio, after 1 hour, is washed with water to neutral and dry 70 ℃ of reactions then;
In second step, the product that the first step is obtained ground in high energy ball mill 1 hour, can obtain Graphene.
Embodiment 18
The first step is mixed SRM 935a with the vitriol oil of 96wt%, add graphite, graphite subsequently: the vitriol oil: SRM 935a is 1: 20: 10 according to weight ratio, after 1 hour, is washed with water to neutral and dry 70 ℃ of reactions then;
In second step, the product that the first step is obtained is scattered in the N-Methyl pyrrolidone, and supersound process 1 minute can obtain Graphene.
Embodiment 19
The first step is mixed Potassium Persulphate with the vitriol oil of 96wt%, add graphite, graphite subsequently: the vitriol oil: Potassium Persulphate is 1: 30: 20 according to weight ratio, after 1 hour, is washed with water to neutral and dry 40 ℃ of reactions then;
In second step, the product that the first step is obtained is cooled to room temperature 800 ℃ of 30 seconds of held;
The 3rd step was scattered in product in second step in the ethanol, and supersound process 1 hour obtains Graphene.
Embodiment 20
The first step is mixed Sodium Persulfate with the vitriol oil of 96wt%, add graphite, graphite subsequently: the vitriol oil: Sodium Persulfate is 1: 20: 10 according to weight ratio, after 1 hour, is washed with water to neutral and dry 70 ℃ of reactions then;
In second step, the product that the first step is obtained is scattered in the ethanol, and supersound process 1 hour obtains Graphene.
Embodiment 21
The first step is mixed ammonium persulphate with the vitriol oil of 96wt%, add graphite, graphite subsequently: the vitriol oil: ammonium persulphate is 1: 30: 15 according to weight ratio, after 1 hour, is washed with water to neutral and dry 40 ℃ of reactions then;
In second step, the product that the first step is obtained is scattered in the ethanol, and supersound process 1 hour obtains Graphene.
Embodiment 22
The first step is mixed Potassium Persulphate with the vitriol oil of 96wt%, add graphite, graphite subsequently: the vitriol oil: Potassium Persulphate is 1: 30: 15 according to weight ratio, after 1 hour, is washed with water to neutral and dry 40 ℃ of reactions then;
In second step, the product that the first step is obtained is scattered in the N-Methyl pyrrolidone, and supersound process 1 hour obtains Graphene.
Embodiment 23
The first step is mixed Sodium Persulfate with the vitriol oil of 96wt%, add graphite, graphite subsequently: the vitriol oil: Sodium Persulfate is 1: 5: 5 according to weight ratio, after 1 hour, is washed with water to neutral and dry 40 ℃ of reactions then;
In second step, the product that the first step is obtained is scattered in water and the ethanol mixed solvent, and supersound process 1 hour obtains Graphene.
Embodiment 24
The first step; Sodium Persulfate is mixed with aqueous nitric acid and the acetate of 69wt%, add graphite, graphite subsequently: nitric acid: Sodium Persulfate: water: acetate is 1: 20: 20 according to weight ratio: 9: 10; After 1 hour, be washed with water to neutral and dry 40 ℃ of reactions then;
In second step, the product that the first step is obtained is scattered in the ethanol, and supersound process 1 hour obtains Graphene.
Embodiment 25
The first step; The aqueous hydrogen peroxide solution of 30wt% and the vitriol oil of 96wt% are mixed, and add graphite then, graphite: the vitriol oil: hydrogen peroxide: water is 1: 20: 3 according to weight ratio: 7; After 0.5 hour, be washed with water to neutral and dry 75 ℃ of reactions then;
In second step, the first step products therefrom was placed 1 minute in 800 ℃, and be cooled to room temperature.
The 3rd step was scattered in product in second step in the N-Methyl pyrrolidone, and supersound process obtained Graphene after 1 hour.
Embodiment 26
The first step is mixed the aqueous hydrogen peroxide solution of 30wt% and the aqueous nitric acid of 65wt%, adds graphite then; Graphite: nitric acid: hydrogen peroxide: water is 1: 15: 3 according to weight ratio: 15; Then 75 ℃ of reactions after 0.2 hour, leave standstill 5 hours after, be washed with water to neutral and dry;
In second step, the first step products therefrom was placed 1 minute in 850 ℃, and be cooled to room temperature.
The 3rd step was scattered in product in second step in the DMSO 99.8MIN., and supersound process obtained Graphene after 1 hour.
Embodiment 27
The first step, with the aqueous nitric acid mixing of sodiumperoxide and 65wt%, add graphite then, graphite: nitric acid: sodiumperoxide: water is 1: 20: 10 according to weight ratio: 9, after 0.2 hour, be washed with water to neutral and dry 75 ℃ of stirrings then;
In second step, the first step products therefrom was placed 1 minute in 850 ℃, and be cooled to room temperature.
The 3rd step was scattered in product in second step in the chloroform, and supersound process obtained Graphene after 1 hour.
Embodiment 28
The first step, with the aqueous nitric acid mixing of Potassium peroxide 85 and 65wt%, add graphite then, graphite: nitric acid: Potassium peroxide 85: water is 1: 10: 20 according to weight ratio: 4.5, after 0.2 hour, be washed with water to neutral and dry 75 ℃ of stirrings then;
In second step, the first step products therefrom was placed 1 minute in 850 ℃, and be cooled to room temperature.
The 3rd step, product in second step was ground in high energy ball mill 1 hour, can obtain the Graphene product.
Embodiment 29
The first step, with the aqueous nitric acid mixing of Peracetic Acid and 65wt%, add graphite then, graphite: nitric acid: Peracetic Acid: water is 1: 20: 10 according to weight ratio: 9, after 1.5 hours, be washed with water to neutral and dry 75 ℃ of stirrings then;
In second step, the first step products therefrom was placed 1 minute in 850 ℃, and be cooled to room temperature.
The 3rd step was scattered in product in second step in the Virahol, and ultrasonication 1 hour can obtain the Graphene product.
Embodiment 30
The first step, with high chloro acid solution's mixing of SRM 935a and 70wt%, add graphite then, graphite: perchloric acid: SRM 935a: water is 1: 30: 20 according to weight ratio: 12.9, after 1.5 hours, be washed with water to neutral and dry 75 ℃ of stirrings then;
In second step, the first step products therefrom was placed 1 minute in 850 ℃, and be cooled to room temperature.
In the 3rd step, product in second step was ground in high energy ball mill 3 hours;
The 4th step was scattered in product in the 3rd step in the ethanol, and supersound process 2 hours can obtain the Graphene product.
Embodiment 31
The first step is mixed Potassium Persulphate with the high chloro acid solution of 70wt%, add graphite, graphite then: perchloric acid: Potassium Persulphate: water is 1: 25: 15 according to weight ratio: 10.7, after 1.5 hours, be washed with water to neutral and dry 75 ℃ of stirrings then;
In second step, the first step products therefrom was placed 1 minute in 850 ℃, and be cooled to room temperature.
In the 3rd step, product in second step was ground in high energy ball mill 2 hours;
The 4th step was scattered in product in the 3rd step in the N-Methyl pyrrolidone, and supersound process 2 hours can obtain the Graphene product.
Embodiment 32
The first step is mixed Potcrate with chlorsulfonic acid, add graphite, graphite then: Potcrate: chlorsulfonic acid is 1: 30: 18 according to weight ratio, after 2 hours, is washed with water to neutral and dry 80 ℃ of stirrings then;
In second step, the first step products therefrom was placed 1 minute in 1000 ℃, and be cooled to room temperature.
The 3rd step was scattered in product in second step in the N-NMF, and supersound process can obtain Graphene after 2 hours.
Embodiment 33
The first step is mixed SRM 935a with the vitriol oil of 96wt%, add graphite, graphite then: the vitriol oil: SRM 935a is 1: 33: 20 according to weight ratio, after 2 hours, is washed with water to neutral and dry 80 ℃ of stirrings then;
In second step, the first step products therefrom was placed 1 minute in 1000 ℃, and be cooled to room temperature.
In the 3rd step, product in second step was ground in high energy ball mill 1 hour.
The 4th step was scattered in product in the 3rd step in the N-Methyl pyrrolidone, and supersound process 2 hours can obtain Graphene.
Comparative example 1 solution phase oxidation reduction method prepares Graphene
The first step takes by weighing 1.2 gram saltpetre, adds in the vitriol oil of 46 milliliters of 96wt%, adds 1.0 gram graphite then, after mixing, slowly adds 6.0 gram potassium permanganate under stirring.With mixture heating up to 40 ℃, continue to stir 6 hours then.Slowly splash into 80 ml waters again, stirred 30 minutes after system is warming up to 70 ℃.The ydrogen peroxide 50 that adds 200 ml deionized water and 6 milliliters of 30wt% stirs and stops after 5 minutes.Reacted product as for done time to system pH with deionized water wash reach 5, obtain graphite oxide.
In second step,, obtain graphene oxide colloidal sol with the graphite oxide that obtains supersound process 30 minutes in the aqueous solution.In said colloidal sol, add Hydrazine Hydrate 80, the mass ratio of Hydrazine Hydrate 80 and graphene oxide is 1: 1, after stirring, is positioned in 80 ℃ of baking ovens 12 hours; The product that obtains is centrifugal, the washing drying after, can obtain Graphene.
Comparative example 2 solution phase oxidation reduction methods prepare Graphene
The first step takes by weighing 1.0 gram graphite, adds in the vitriol oil of 20 milliliters of 96wt%, adds 3.0 gram potassium perchlorates subsequently, and stirring reaction is 2 hours in 0 ℃ ice-water bath.Subsequently system is warming up to 40 ℃, and under this temperature, continued stirring reaction 12 hours.Add 200 ml deionized water then, system is warming up to 90 ℃, and continue to stir 30 minutes postcooling to room temperature.Reaction product is spent deionised water to several times to system pH with deionized water reach 5, obtain graphite oxide.
In second step, in second step,, obtain graphene oxide colloidal sol with the graphite oxide that obtains supersound process 1 hour in the aqueous solution.In said colloidal sol, add Hydrazine Hydrate 80, the mass ratio of Hydrazine Hydrate 80 and graphene oxide is 1: 1, after stirring, is positioned in 80 ℃ of baking ovens 12 hours; The product that obtains is centrifugal, the washing drying after, can obtain Graphene.
Characterize and performance test
The Graphene of getting embodiment 1 preparation carries out structural characterization, and the thickness of Graphene lamella is the 2-3 nanometer, and the distribution of sizes of Graphene lamella is between the 1-50 micron.
The Graphene of getting embodiment 1 and comparative example 1 preparation carries out the Raman spectrum test, and the result is as depicted in figs. 1 and 2 respectively.Can find out that from the result of Fig. 1 and Fig. 2 the graphene-structured defective (the D peak that marks among the figure) of embodiment 1 preparation obviously is less than the Graphene that solution phase oxidation reduction obtains.The carbon Sauerstoffatom ratio that records the Graphene of embodiment 1 preparation through the x-ray photoelectron power spectrum is 21.2; And the carbon Sauerstoffatom ratio of the graphene oxide before the reduction is 1.2 in the comparative example 1; The carbon Sauerstoffatom of the Graphene after the reduction is merely 10.1 than also; Being the preparation method that provides of present embodiment is starkly lower than solution phase oxidation method of reducing for the degree of oxidation of Graphene, also much lower for the destructiveness of graphene-structured.In addition, the Graphene specific conductivity that records embodiment 1 preparation is 1000S/cm, and the specific conductivity of the Graphene of comparative example 1 preparation is 5S/cm, i.e. the specific conductivity of the Graphene of present embodiment preparation is far above the Graphene of oxide-reduction method preparation.
To embodiment 2-embodiment 33, the Graphene that reaches comparative example 2 preparations has carried out structure and performance characterization, and the result is as shown in table 1:
The Graphene performance characterization result of table 1 embodiment 2-embodiment 33 and comparative example 2 preparations
The high efficiency preparation method of a kind of high quality Graphene that the present invention proposes is described through embodiment; Person skilled obviously can be changed or suitably change and combination preparation method of graphene as herein described in not breaking away from content of the present invention, spirit and scope, realizes the present invention's technology.Special needs to be pointed out is, the replacement that all are similar and change apparent to those skilled in the artly, they all are regarded as and are included in spirit of the present invention, scope and the content.
Claims (11)
1. a method for preparing Graphene is characterized in that, comprising:
Graphite is reacted in the acid solution that oxygenant exists obtain Graphene.
2. method according to claim 1 is characterized in that, the carbon Sauerstoffatom ratio in the said reacted product is greater than 5, more preferably greater than 10, more preferably greater than 14, more preferably greater than 16, more preferably greater than 20.。
3. method according to claim 1 is characterized in that, the acid in the described acid solution comprises one or more the combination in nitric acid, sulfuric acid, perchloric acid, hypochlorous acid, nitrous acid, chlorsulfonic acid, acetic acid, the oxalic acid.
4. method according to claim 1; It is characterized in that said oxygenant comprises one or more the combination in nitric acid, sulfuric acid, perchloric acid, hydrochloric acid, hypochlorous acid, nitrous acid, chlorsulfonic acid, dichromate, perchlorate, oxymuriate, hypochlorite, persulphate, ydrogen peroxide 50, the superoxide.
5. method according to claim 1 is characterized in that, the solvent in the described acid solution comprises one or more the combination in ethanol, tetracol phenixin, benzene, water, methyl alcohol, acetone, formaldehyde, acetaldehyde, the acetate.
6. method according to claim 1, it is characterized in that graphite: acid: oxygenant: solvent is preferably 1 according to mass ratio: 0.1-50: 0.1-50: 0.1-100.
7. method according to claim 1 is characterized in that, the temperature of said reaction is 0 ℃～90 ℃.
8. method according to claim 1 is characterized in that, the time of said reaction is 1 minute～10 hours.
9. method according to claim 1 is characterized in that, also comprises mixed solution to the neutral step behind the washing reaction.
10. method according to claim 1 is characterized in that, also comprises the step of said reacted product being carried out lift-off processing.
11. method according to claim 9 is characterized in that, said lift-off processing comprises that high temperature is peeled off, in mechanical mill or the supersound process one or more.
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