CN103342355B - Method for preparing graphene and composite material thereof - Google Patents
Method for preparing graphene and composite material thereof Download PDFInfo
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- CN103342355B CN103342355B CN201310287025.XA CN201310287025A CN103342355B CN 103342355 B CN103342355 B CN 103342355B CN 201310287025 A CN201310287025 A CN 201310287025A CN 103342355 B CN103342355 B CN 103342355B
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Abstract
The invention discloses a method for preparing graphene and a composite material thereof, belonging to the technical field of graphene. The method adopts graphite oxide prepared by a Hummers method or improved Hummers method as a raw material and red aluminum as a reducing agent, and comprises the following steps of: firstly dispersing the graphite oxide prepared by the Hummers method or improved Hummers method in an organic solvent; and then reducing by use of the red aluminum, wherein different products are obtained by different washing processes; one product is graphene obtained by washing with aromatic hydrocarbons or esters, deionized water and diluted hydrochloric acid and drying; and the other product is a graphene/aluminum hydroxide composite material by directly washing with aromatic hydrocarbons or esters, deionized water and organic solvent an drying. According to the method disclosed by the invention, the red aluminum can be used as a reducing agent for reducing graphite oxide to obtain graphene, and the agglomeration of the prepared graphene is prevented by a functional graphite oxide mode; and meanwhile, the red aluminum can be used as a precursor of aluminum hydroxide to prepare graphene/aluminum hydroxide and graphene/aluminum oxide composite materials.
Description
Technical field
The invention belongs to technical field of graphene, relate to a kind of novel method preparing Graphene and matrix material thereof.
Background technology
Graphene (Graphene) a kind ofly forms ultra-thin superhard two-dimensional material in hexangle type honeycomb lattice by carbon atom with sp2 hybridized orbital, and the general graphite claiming less than ten layers is Graphene.Graphene is the essentially consist unit forming other carbon materials, it wraps up the soccerballene (Fullerene) forming zero dimension, roll the carbon nanotube (Carbon Nanotube) forming one dimension, stacked in multi-layers forms three-dimensional graphite (Graphite).Graphene and matrix material thereof are the study hotspots at present this field, all show good development prospect in electronics, optics, machinery and the field such as fire-retardant thereof.
From 2004, after the Andre Geim of Univ Manchester UK and Konstantin Novoselov uses mechanically peel method to obtain Graphene, people in succession propose the methods such as epitaxial growth method, chemical Vapor deposition process (CVD), liquid phase stripping method, chemical reduction method and prepare Graphene.The standby Graphene quality of mechanically peel legal system is high, but amount is few, is applicable to scientific research, can not meets a large amount of industrial requirements far away.Epitaxial growth method, CVD need the transfer process of high temperature and complexity, complex process and energy consumption is high.Liquid phase stripping method is consuming time and productive rate is low, limits its commercial applications.Chemical reduction method is considered to the most effective means that can realize suitability for industrialized production.Up to the present, investigators drop into sizable effort and energy development reduction method, and main method is for using reductive agent hydrazine hydrate (Stankovich S, etal.J.Mater.Chem.2006,16,155-158), dimethylhydrazine (Stankovich S, etal.Nature.2006,442,282 – 286), Resorcinol (G.X.Wang, etal.Carbon.2009,21,3514-3520), sodium borohydride (Si Y, etal.Nano Lett.2008,8,1679 – 1682), Lithium Aluminium Hydride (Ambrosi A, etal.Chem.Mater.2012,24,2292 – 2298), sulfide (W Chen, etal.J.Phys.Chem.C, 2010,114,19885 – 19890.), aluminium powder (Fan Z, etal, Carbon2010,48,1686 – 1689), xitix (Gao J, etal.Chem.Mater.2010,22,2213 – 2218), quadrol (Che J, etal.Mater.Chem.2010,20,1722 – 1727), reducing sugar (Zhu C, etal.ACS Nano.2010,4,2429 – 2437.), protein (Liu J, etal.J.Am.Chem.Soc.2010,132,7279 – 7281), Trisodium Citrate (Wan W, etal.New Carbon Mater.2011,26,16 – 20), iron (Fan Z, etal.ACS Nano.2011,5,191 – 198.) etc. acid or alkali and other as microwave, photochemical catalysis, biological chemistry, laser, plasma body, bacterial solution, N,O-Diacetylmuramidase, under triethylamine solution condition, Graphene is prepared in reduction.These reductive agents of hydrazine class, Resorcinol, sodium borohydride, Lithium Aluminium Hydride need long-time reaction could reduction-oxidation graphite thoroughly, there is long reaction time, the defects such as high toxicity, agglomeration are serious.There is the shortcomings such as reduction effect difference in sulfide, aluminium powder, quadrol, reducing sugar, protein, Trisodium Citrate, iron etc.Xitix is proved to be a kind of efficient, eco-friendly reductive agent, but xitix is expensive, is unfavorable for large-scale industrial production.
The present invention is directed to above problem, red aluminium is adopted to be reductive agent first, with with low cost, hold facile graphite oxide for raw material, while carrying out graphite oxide quick function, complete the reduction to it, thus selectivity obtains, and favorable dispersity, electroconductibility are good, area is micron-sized Graphene, Graphene/aluminium hydroxide and Graphene/alumina composite material.Preparation-obtained Graphene/the aluminium hydroxide of the present invention and Graphene/alumina composite material are expected to for fire retardant material, high-abrasive material and heavy-metal ion removal field.At present, such matrix material has been reported.Height as China Science & Technology University is superfine has prepared AlOOH-RGO matrix material, for removing Cd in tap water
2+, Pb
2+; Chinese patent " a kind of preparation method of graphene-epoxy resin composite material " (patent No. CN 101987908) reports and Graphene and epoxy resin is combined, the epoxy resin that the hardness of this material is more independent adds 50%, and resistance to punching property adds nearly 12 times.
Summary of the invention
The object of this invention is to provide a kind of method preparing Graphene, Graphene/aluminium hydroxide and Graphene/alumina composite material.Another object of the present invention simplifies Nano-composite materials technique namely to skip Graphene preparation section, prepares nano composite material with graphite oxide functionalization way selection ground one step.
For achieving the above object, technical scheme of the present invention is as follows:
One prepares Graphene or Graphene/aluminium hydroxide composite process, comprises the steps:
A. graphite oxide dispersion: obtain brown dispersion liquid by ultrasonic in organic solvent for graphite oxide;
B. graphite oxide reduction: join in the dispersion in organic solvent of the graphite oxide in steps A by red for reductive agent aluminium is 25-120 DEG C of reaction 5min-48h in temperature;
C. purification process: filtered by the dispersion liquid of step B, solid matter is successively through aromatic hydrocarbons or ether material (being preferably ether or tetrahydrofuran (THF)), deionized water, salt acid elution, and drying obtains Graphene.
Or: the dispersion liquid of step B is filtered, obtains Graphene/aluminium hydroxide through aromatic hydrocarbons or ethers (being preferably ether or tetrahydrofuran (THF)), deionized water wash, drying successively.
By Graphene obtained above/aluminium hydroxide matrix material, after roasting, Graphene/alumina composite material can be obtained.
Described graphite oxide adopts Hummers method or improve Hummers method to obtain.
Organic solvent described in steps A in aforesaid method is all selected from one or more in tetrahydrofuran (THF), ethylene glycol, toluene, second diether.Graphite oxide dispersion concentration is in organic solvent preferably 0.25mg/ml-1.5mg/ml.
Temperature of reaction described in steps A in aforesaid method is 25-120 DEG C, is preferably 25-80 DEG C.The described reaction times is 5min-48h, is preferably 30min-2h.
The mass ratio of the red aluminium described in the step B in aforesaid method and graphite oxide is (20-150) ︰ 1.
After aromatic hydrocarbons or ethers washing in step C in aforesaid method, also comprise through washing with alcohol, and then deionized water wash.
The postprocessing working procedures such as described separation, filtration, washing and drying are conventional treatment process.
When preparing Graphene/alumina composite material after Graphene/aluminium hydroxide matrix material roasting, roasting condition is preferably 500 DEG C.
Feature of the present invention is: in preparation process, and namely the red aluminium of reductive agent act as reductive agent, act as again the presoma of aluminium hydroxide or aluminum oxide, namely Graphene, Graphene/aluminium hydroxide and Graphene/alumina composite material optionally a step obtain.Therefore, major advantage of the present invention finds a kind of new reductive agent, and can reduce manufacturing cost, preparation technology is simple, easy to operate, selective, and the graphene dispersion prepared is good, sheet is large, electroconductibility is good.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of Graphene in the present invention;
Fig. 2 is the XRD figure spectrum of Graphene in the present invention/aluminium hydroxide matrix material;
Fig. 3 is the TEM photo of Graphene in the present invention;
Fig. 4 is the TEM photo of Graphene/aluminium hydroxide matrix material.
Embodiment
Embodiment 1
Take the graphite oxide of 100mg, the ratio being 1mg/1.25ml according to concentration measures a certain amount of anhydrous tetrahydro furan, after ultrasonic in ultrasonic cleaner, add the red aluminium of reductive agent of 2ml wherein, after temperature is 25 DEG C of reaction 2h, obtain homogeneous black dispersion liquid, centrifugal, ether, ethanol, deionized water, 1M dilute hydrochloric acid respectively wash three times successively, the Graphene after must reducing after vacuum-drying 24h, thinner from tem observation graphene film, size is 15 × 11 μm, favorable dispersity, and electric conductivity is 75s/cm.
Embodiment 2
Take the graphite oxide of 100mg, the ratio being 1mg/1ml according to concentration measures a certain amount of anhydrous second diether, after ultrasonic in ultrasonic cleaner, add the red aluminium of reductive agent of 5ml wherein, after temperature is 50 DEG C of reaction 1h, obtain homogeneous black dispersion liquid, centrifugal, tetrahydrofuran (THF), ethanol, deionized water wash, Graphene/aluminium hydroxide matrix material is obtained after vacuum-drying 24h, be deposited on graphene film or between graphene film uniformly from tem observation aluminium hydroxide, electric conductivity is 60s/cm, by its vacuum baking at 500 DEG C, obtain Graphene/alumina composite material, electric conductivity is 45s/cm.
Embodiment 3
Take the graphite oxide of 100mg, the ratio being 1mg/0.8ml according to concentration measures a certain amount of toluene, after ultrasonic in ultrasonic cleaner, add the red aluminium of reductive agent of 8ml wherein, after temperature is 70 DEG C of reaction 40min, obtain homogeneous black dispersion liquid, centrifugal, toluene, ethanol, deionized water, 1M dilute hydrochloric acid respectively wash three times, obtain Graphene after vacuum-drying 24h, thinner from tem observation graphene film, size is 9 × 11 μm, favorable dispersity, electric conductivity is 70s/cm.
Embodiment 4
Take the graphite oxide of 100mg, the ratio being 1mg/0.67ml according to concentration measures a certain amount of ethylene glycol, after ultrasonic in ultrasonic cleaner, add the red aluminium of reductive agent of 2ml wherein, after temperature is 80 DEG C of reaction 30min, obtain homogeneous black dispersion liquid, centrifugal, ether, ethanol, deionized water, 1M dilute hydrochloric acid respectively wash three times, the Graphene after must reducing after vacuum-drying 24h, size is 10 × 10 μm, and electric conductivity is 65s/cm.
Embodiment 5
Substantially the same manner as Example 4, the amount unlike the red aluminium added is 5ml, and the specific conductivity of preparation-obtained Graphene is larger, specific conductivity 90s/cm.
Embodiment 6
Substantially the same manner as Example 5, directly use ether, ethanol, deionized water wash unlike in post-processing step, vacuum-drying 24h draws Graphene/aluminium hydroxide matrix material, and its specific conductivity is 45s/cm.
In above-described embodiment Graphene XRD figure spectrum between Fig. 1; The XRD figure spectrum of Graphene/aluminium hydroxide matrix material is shown in Fig. 2; Fig. 3 is shown in by the TEM photo of Graphene; Fig. 4 is shown in by the TEM photo of Graphene/aluminium hydroxide matrix material.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (9)
1. prepare Graphene or Graphene/aluminium hydroxide composite process, it is characterized in that, comprise the steps:
A. graphite oxide dispersion: obtain brown dispersion liquid by ultrasonic in organic solvent for graphite oxide;
B. graphite oxide reduction: join in the dispersion in organic solvent of the graphite oxide in steps A by red for reductive agent aluminium is 25-120 DEG C of reaction 5min-48h in temperature;
C. purification process: the dispersion liquid of step B is filtered, solid matter is successively through aromatic hydrocarbons or ether material, deionized water, salt acid elution, and drying obtains Graphene;
Or: the dispersion liquid of step B is filtered, obtains Graphene/aluminium hydroxide through aromatic hydrocarbons or ethers, deionized water wash, drying successively.
2. according to the method for claim 1, it is characterized in that, the organic solvent described in steps A is selected from one or more in tetrahydrofuran (THF), ethylene glycol, toluene, second diether.
3. according to the method for claim 1, it is characterized in that, graphite oxide dispersion concentration is in organic solvent preferably 0.25mg/ml-1.5mg/ml.
4. according to the method for claim 1, it is characterized in that, the temperature of reaction described in steps A is 25-80 DEG C, and the reaction times is 30min-2h.
5. according to the method for claim 1, it is characterized in that, the mass ratio of the red aluminium described in step B and graphite oxide is (20-150) ︰ 1.
6. according to the method for claim 1, it is characterized in that, after aromatic hydrocarbons or ethers washing in the step C in aforesaid method, also comprise through washing with alcohol, and then deionized water wash.
7. according to the method for claim 1, it is characterized in that, described ethers is preferably ether or tetrahydrofuran (THF).
8. the preparation method of Graphene/alumina composite material, is characterized in that, Graphene claim 1 obtained/aluminium hydroxide matrix material, can obtain Graphene/alumina composite material after roasting.
9. according to the method for claim 7, it is characterized in that, roasting condition is preferably 500 DEG C.
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| CN103613097A (en) * | 2013-12-04 | 2014-03-05 | 天津大学 | Environment-friendly method for preparing sulfonated graphene |
| CN108530954A (en) * | 2018-04-10 | 2018-09-14 | 宁波工程学院 | A kind of preparation method of graphene coated aluminium hydrate nano composite material |
| CN109231191B (en) * | 2018-11-06 | 2021-12-14 | 新乡学院 | Preparation method of fatty amine modified graphene |
| CN109536141A (en) * | 2018-12-14 | 2019-03-29 | 宁波石墨烯创新中心有限公司 | A kind of graphene heat filling and its preparation method and application |
| CN112645373B (en) * | 2020-12-17 | 2023-05-02 | 安徽理工大学 | Gamma-AlOOH/RGO composite wave-absorbing material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2009085015A1 (en) * | 2008-01-03 | 2009-07-09 | National University Of Singapore | Functionalised graphene oxide |
| CN102826541A (en) * | 2012-09-13 | 2012-12-19 | 新乡学院 | Method for high-concentration graphene synthesis in oil-phase |
| CN103072981A (en) * | 2013-02-26 | 2013-05-01 | 武汉大学 | Preparation method for graphene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2009085015A1 (en) * | 2008-01-03 | 2009-07-09 | National University Of Singapore | Functionalised graphene oxide |
| CN102826541A (en) * | 2012-09-13 | 2012-12-19 | 新乡学院 | Method for high-concentration graphene synthesis in oil-phase |
| CN103072981A (en) * | 2013-02-26 | 2013-05-01 | 武汉大学 | Preparation method for graphene |
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