CN103058182B - Method for preparing graphene by solution phase - Google Patents
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- CN103058182B CN103058182B CN201310031362.2A CN201310031362A CN103058182B CN 103058182 B CN103058182 B CN 103058182B CN 201310031362 A CN201310031362 A CN 201310031362A CN 103058182 B CN103058182 B CN 103058182B
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Abstract
The invention discloses a method for preparing graphene by a solution phase, and relates to grephene. The invention provide a method for preparing graphene by the solution phase, which is low in cost, simple and easy to implement, low in device requirements, and beneficial to large-scale industrial production. The method comprises the following steps: (1) adding graphite powder to a tetrahydrofuran solution and obtaining graphite-powder tetrahydrofuran dispersion liquid by carrying out ultrasonic dispersion under the protection of nitrogen gas; (2) adding alkali metal and naphthalene to the graphite-powder tetrahydrofuran dispersion liquid obtained in the step (1), stirring under the protection of the nitrogen gas to obtain the mixed solution; (3) adding halogenated organic reagent to the mixed solution obtained in the step (2), and reacting under the protection of the nitrogen gas to obtain a solid product; and (4) washing and drying the solid product obtained in the step (3) to obtain the graphene powder. According to the method disclosed by the invention, liquid-phase chemical intercalation is carried out to the graphite by using the graphite powder as material; and then, the chemical modification of the halogenated organic reagent to the graphite is utilized for further opening the graphite, so that the graphene can be prepared by peeling the graphite under the non-ultrasonic action or the light ultrasonic action.
Description
Technical field
The present invention relates to Graphene, especially relate to a kind of method that solution phase is prepared Graphene.
Background technology
Graphene is that one is completely by sp
2what hydridization carbon atom formed is only the New Two Dimensional carbon material of monatomic thickness.Since 2004 are prepared first, Graphene is just paid close attention to widely with its unique structure and excellent character, as high-specific surface area, high charge mobility, high strength and snappiness, high thermal conductivity coefficient etc., be expected to obtain widespread use in energy and material, nano electron device, matrix material, photoelectric device, sensor field.
Graphene is to separate (Novoselov K S etc., Science, 2004,306:666-669) by micromechanics stripping method from highly oriented pyrolytic graphite at first, but the method output is little, is only applicable to fundamental research.The low cost of Graphene, extensive preparation are still the key issue of this Materials of restriction and application.Based on Hummers method (Hummers W S etc., J.Am.Chem.Soc.80,1339) chemical oxidization method is a kind of graphene preparation method (the Stankovich S etc. that are widely adopted at present, Carbon45,1558-1565), graphite is carried out oxide treatment by the method, obtains graphite oxide, and then it is carried out to ultrasonic peeling off obtain graphene oxide.The method cost is low, output is large, but due to oxidising process can havoc the laminated structure of Graphene introduce many defects, even through chemical reduction and thermal reduction processing, the property indices of gained Graphene, as still unsatisfactory in electroconductibility etc.Using carbon compounds such as methane as carbon source, be also applied at present the preparation (Sutter P W etc., Nat.Mater.7,406-411) of Graphene by its chemical Vapor deposition process at the pyrolytic decomposition growing graphene of substrate surface.The Graphene area that this method prepares is larger, but often needs complicated equipment, and processing condition harshness, is difficult to extensive preparation.Except above-mentioned these methods, silicon carbide epitaxial growth method (Berger C etc., Science, 312,1191-1196), organic synthesis method (Zhi L J etc., J.Mater.Chem.18,1472-1484) etc. is also applied to the preparation of Graphene, but all there is the drawback of self in these methods, as complex process is difficult to control, yields poorly, high in cost of production.Therefore, develop a kind of can be on a large scale, that low cost is prepared the method for Graphene is very necessary.
Summary of the invention
The object of the present invention is to provide low cost, simple, not high to equipment requirements, a kind of solution phase that is beneficial to large-scale industrialization production is prepared the method for Graphene.
The present invention includes following steps:
1) Graphite Powder 99 is added in tetrahydrofuran solution, under nitrogen protection condition, carry out the ultrasonic Graphite Powder 99 tetrahydrofuran (THF) dispersion liquid that disperses to obtain;
2) in step 1) gained Graphite Powder 99 tetrahydrofuran (THF) dispersion liquid, add successively basic metal and naphthalene, under nitrogen protection, stir, obtain mixing solutions;
3) in step 2) add halo organic reagent in the mixing solutions of gained, under nitrogen protection condition, react, obtain solid product;
4) by the washing of step 3) gained solid product, dry, obtain graphene powder.
In step 1), described Graphite Powder 99 can adopt common commercially available Graphite Powder 99; It is the ultrasonic processor of 90W that described ultrasonic dispersion can adopt equipower, and ultrasonic time can be 3min.
In step 2) in, described basic metal can adopt metallic lithium or sodium Metal 99.5 etc.; In described Graphite Powder 99 tetrahydrofuran (THF) dispersion liquid, graphite (carbon atom) and alkali-metal mol ratio can be 1: (4～30), and the mol ratio of basic metal and naphthalene can >1; The time of described stirring can be 30～120min.
In step 3), described halo organic reagent can be selected from the one in halogenated alkane, halogenated carboxylic acid (salt), halogenated carboxylic ester, halogen ester, halohydrin, halogenated amine, halogen acid amide, halo ammonium salt etc.; Described halo organic reagent and alkali-metal mol ratio can be 1: 1; The time of described reaction can be 5～24h, and the molecular formula of described halogenated alkane is X (CH
2)
ncH
3, wherein X is halogen atom, n is integer, 1<n<20; The molecular formula of described halogenated carboxylic acid (salt) is X (CH
2)
ncOOR, wherein X is halogen atom, n is integer, 1<n<20, R is H or Na, K; The molecular formula of described halogenated carboxylic ester is X (CH
2)
ncOOR, wherein X is halogen atom, n is integer, 1<n<20, R is CH
3or C
2h
5; The molecular formula of described halohydrin is X (CH
2)
noH, wherein X is halogen atom, n is integer, 1<n<20; The molecular formula of described halo aliphatic amide is X (CH
2)
nnH
2, wherein X is halogen atom, n is integer, 1<n<20; The molecular formula of described halogen acid amide is X (CH
2)
ncONH
2, wherein X is halogen atom, n is integer, 1<n<20; The molecular formula of described halo ammonium salt is X (CH
2)
nn
+r
3br
-, wherein X is halogen atom, n is integer, and 1<n<20, R is CH
3or C
2h
5.
In step 4), described washing can be washed with ethanol, toluene, water and ethanol successively, described dry can being dried under 60 ° of C vacuum conditions; The number of plies of described graphene powder can be below 5 layers, preferred single layer.
The present invention, taking Graphite Powder 99 as raw material, carries out liquid phase chemical intercalation by graphite, then utilizes halo organic reagent to the chemical modification of graphite, graphite further to be strutted, and under not ultrasonic or slight ultrasonication, graphite can be peeled off and is prepared Graphene.
Compared with existing graphene preparation method, beneficial effect of the present invention is as follows:
(1) oxidising process that the Graphene that the present invention obtains does not pass through strong oxidizer, still less, quality is higher for graphene film layer defects, and all operations all carries out under room temperature, solution phase condition, and preparation method's energy consumption is low, efficiency is high.The Graphene obtaining like this has good dispersiveness in the aqueous solution or organic solvent (as chloroform, DMF (DMF), ethanol, chlorobenzene etc.), and the intercalation compound dispersion of formation and the degree of intercalation are higher.
(2) in the present invention, halo organic reagent further expands the interlamellar spacing of graphite to the chemical modification of graphite intercalation compound, does not need ultrasonic or short period of time, low power ultrasound can realize peeling off of Graphene.
(3) in the present invention, the intercalation of graphite and chemical modification all complete at solution phase, the completeness of reaction and good uniformity, and the efficiency of preparation is high.
(4) all operations of the present invention all at room temperature completes, and Graphene preparation technology energy consumption is low.
(5) preparation technology of the present invention is simple, low to production unit requirement, is easy to suitability for industrialized production.
Brief description of the drawings
Fig. 1 is the macro morphology figure (sample quality is respectively 10mg) of commercially available Graphite Powder 99 (a) and gained graphene powder of the present invention (b).
Fig. 2 is the scanning electron microscope diagram of gained Graphene of the present invention.In Fig. 2, scale is 1.00 μ m.
Fig. 3 is the transmission electron microscope figure of gained Graphene of the present invention.In Fig. 3, scale is 200nm.
Fig. 4 is the Raman spectrogram of gained Graphene of the present invention.In Fig. 4, X-coordinate is Raman shift Raman shift(cm
-1), ordinate zou is intensity I ntensity(a.u.)
Fig. 5 is the dispersion liquid figure of gained Graphene of the present invention in chloroform.
Embodiment
Embodiment 1
The tetrahydrofuran solution that adds 150mL fresh dried to cross 100mg Graphite Powder 99, ultrasonic dispersion 3min under nitrogen protection condition then adds successively 0.36g metallic lithium and 4.9g naphthalene in this dispersion liquid, continues to stir 35min.In said mixture, progressively add 12.5g1-bromododecane, under nitrogen protection condition, continue reaction 12h.
In above-mentioned reaction product, add ethanol to remove unreacted metallic lithium completely.Gained solid product is used ethanol, toluene, water and washing with alcohol successively, and dry under 60 ° of C vacuum conditions, obtains graphene powder.
Fig. 1 b is the macro morphology figure of gained graphene powder of the present invention, presents obvious puffy compared with the commercially available Graphite Powder 99 of Fig. 1 a.By scanning electronic microscope and transmission electron microscope observation for gained Graphene of the present invention, gained as shown in Figures 2 and 3.As can be seen from Figure 2, graphite is stripped from out after the chemical modification of liquid phase intercalation and halo organic reagent, and fold appears in Graphene surface.Fig. 3 is the transmission electron microscope figure of gained graphene film, can clearly find out Graphene profile.Fig. 4 is the Raman spectrogram of gained Graphene of the present invention, can find out, 2D peak is unimodal, and intensity is significantly higher than G peak, has the Raman spectrum characteristic of single-layer graphene.Fig. 5 is the chloroform dispersion liquid of gained Graphene of the present invention.
Embodiment 2
The tetrahydrofuran solution that adds fresh dried to cross 100mg Graphite Powder 99, ultrasonic dispersion 3min under nitrogen protection condition then adds successively 0.36g metallic lithium and 4.9g naphthalene in mixed solution, continues to stir 35min.In said mixture, progressively add 9.7g6-bromocaproic acid, under nitrogen protection condition, react 12h.
In above-mentioned reaction product, add ethanol to remove unreacted metallic lithium completely.Gained solid product is used ethanol, toluene, water and washing with alcohol successively, and dry under 60 ° of C vacuum conditions, obtains graphene powder.Gained graphene powder can be scattered in ethanol or the aqueous solution by supersound process.
Embodiment 3
The tetrahydrofuran solution that adds fresh dried to cross 100mg Graphite Powder 99, ultrasonic dispersion 3min under nitrogen protection condition then adds successively 0.36g metallic lithium and 4.9g naphthalene in mixed solution, continues to stir 35min.In said mixture, progressively add 11.6g6-bromocaproic acid methyl esters, under nitrogen protection condition, react 12h.
In above-mentioned reaction product, add ethanol to remove unreacted metallic lithium completely.Gained solid product is used ethanol, toluene, water, washing with alcohol successively, and dry under 60 ° of C vacuum conditions, obtains graphene powder.
Embodiment 4
The tetrahydrofuran solution that adds fresh dried to cross 100mg Graphite Powder 99, ultrasonic dispersion 3min under nitrogen protection condition then adds successively 0.36g metallic lithium and 4.9g naphthalene in mixed solution, continues to stir 35min.In said mixture, progressively add 11.2g9-bromine nonyl alcohol, under nitrogen protection condition, react 12h.
In above-mentioned reaction product, add ethanol to remove unreacted metallic lithium completely.Gained solid product is used ethanol, toluene, water, washing with alcohol successively, and dry under 60 ° of C vacuum conditions, obtains graphene powder.
Embodiment 5
The tetrahydrofuran solution that adds fresh dried to cross 100mg Graphite Powder 99, ultrasonic dispersion 3min under nitrogen protection condition then adds successively 0.36g metallic lithium and 4.9g naphthalene in mixed solution, continues to stir 35min.In said mixture, progressively add 9.7g6-bromohexane acid amides, under nitrogen protection condition, react 12h.
In above-mentioned reaction product, add ethanol to remove unreacted metallic lithium completely.Gained solid product is used ethanol, toluene, water, washing with alcohol successively, and dry under 60 ° of C vacuum conditions, obtains graphene powder.
Embodiment 6
The tetrahydrofuran solution that adds fresh dried to cross 100mg Graphite Powder 99, ultrasonic dispersion 3min under nitrogen protection condition then adds successively 0.36g metallic lithium and 4.9g naphthalene in mixed solution, continues to stir 20min.In said mixture, progressively add 14.5g(5-bromine amyl group) trimethylammonium bromide reacts 12h under nitrogen protection condition.
In above-mentioned reaction product, add ethanol to remove unreacted metallic lithium completely.Gained solid product is used ethanol, toluene, water, washing with alcohol successively, and dry under 60 ° of C vacuum conditions, obtains graphene powder.
Claims (9)
1. solution phase is prepared a method for Graphene, it is characterized in that comprising the following steps:
1) Graphite Powder 99 is added in tetrahydrofuran solution, under nitrogen protection condition, carry out the ultrasonic Graphite Powder 99 tetrahydrofuran (THF) dispersion liquid that disperses to obtain;
2) in step 1) gained Graphite Powder 99 tetrahydrofuran (THF) dispersion liquid, add successively basic metal and naphthalene, under nitrogen protection, stir, obtain mixing solutions; In described Graphite Powder 99 tetrahydrofuran (THF) dispersion liquid, graphite and alkali-metal mol ratio are 1: 4～30, the mol ratio > 1 of basic metal and naphthalene;
3) in step 2) add halo organic reagent in the mixing solutions of gained, under nitrogen protection condition, react, obtain solid product; Described halo organic reagent is selected from the one in halogenated alkane, halogenated carboxylic acid (salt), halogenated carboxylic ester, halohydrin, halo aliphatic amide, halogen acid amide, halo ammonium salt;
4) by the washing of step 3) gained solid product, dry, obtain graphene powder.
2. a kind of solution phase is prepared the method for Graphene as claimed in claim 1, it is characterized in that in step 1), and described ultrasonic dispersion is that to adopt equipower be the ultrasonic processor of 90 W, and ultrasonic time is 3 min.
3. a kind of solution phase is prepared the method for Graphene as claimed in claim 1, it is characterized in that in step 2) in, described basic metal adopts metallic lithium or sodium Metal 99.5.
4. a kind of solution phase is prepared the method for Graphene as claimed in claim 1, it is characterized in that in step 2) in, the time of described stirring is 30～120 min.
5. a kind of solution phase is prepared the method for Graphene as claimed in claim 1, it is characterized in that in step 3), and described halo organic reagent and alkali-metal mol ratio are 1: 1; The time of described reaction is 5～24 h.
6. a kind of solution phase is prepared the method for Graphene as claimed in claim 1, and the molecular formula that it is characterized in that described halogenated alkane is X (CH
2)
ncH
3, wherein X is halogen atom, n is integer, 1 < n <20; The molecular formula of described halogenated carboxylic acid (salt) is X (CH
2)
ncOOR, wherein X is halogen atom, n is integer, 1 < n <20, R is H or Na, K; The molecular formula of described halogenated carboxylic ester is X (CH
2)
ncOOR, wherein X is halogen atom, n is integer, 1 < n <20, R is CH
3or C
2h
5; The molecular formula of described halohydrin is X (CH
2)
noH, wherein X is halogen atom, n is integer, 1 < n <20; The molecular formula of described halo aliphatic amide is X (CH
2)
nnH
2, wherein X is halogen atom, n is integer, 1 < n <20; The molecular formula of described halogen acid amide is X (CH
2)
ncONH
2, wherein X is halogen atom, n is integer, 1 < n <20; The molecular formula of described halo ammonium salt is X (CH
2)
nn
+r
3br
-, wherein X is halogen atom, n is integer, and 1 < n <20, R is CH
3or C
2h
5.
7. a kind of solution phase is prepared the method for Graphene as claimed in claim 1, it is characterized in that in step 4), and described washing is washed with ethanol, toluene, water and ethanol successively, described being dried 60
odry under C vacuum condition.
8. a kind of solution phase is prepared the method for Graphene as claimed in claim 1, it is characterized in that in step 4), and the number of plies of described graphene powder is below 5 layers.
9. a kind of solution phase is prepared the method for Graphene as claimed in claim 8, and the number of plies that it is characterized in that described graphene powder is individual layer.
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Cited By (1)
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|---|---|---|---|---|
| CN106276885A (en) * | 2016-10-21 | 2017-01-04 | 兰州理工大学 | The fast preparation method of high conductivity nitrogen-doped graphene |
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| CN103253659B (en) * | 2013-05-23 | 2015-09-23 | 渤海大学 | A kind of ultrasonic wave peels off the method for preparing graphite alkene |
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| CN101433823A (en) * | 2008-11-28 | 2009-05-20 | 江苏工业学院 | Method for preparing CTAB modified expanded graphite and use in absorbing formaldehyde gas |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106276885A (en) * | 2016-10-21 | 2017-01-04 | 兰州理工大学 | The fast preparation method of high conductivity nitrogen-doped graphene |
| CN106276885B (en) * | 2016-10-21 | 2018-07-13 | 兰州理工大学 | The fast preparation method of high conductivity nitrogen-doped graphene |
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Address after: 363000 the southern tip of Xiamen University Zhangzhou campus, Zhangzhou, Fujian Patentee after: XIAMEN University Address before: Xiamen City, Fujian Province, 361005 South Siming Road No. 422 Patentee before: XIAMEN University |