CN103342355A - Method for preparing graphene and composite material thereof - Google Patents
Method for preparing graphene and composite material thereof Download PDFInfo
- Publication number
- CN103342355A CN103342355A CN201310287025XA CN201310287025A CN103342355A CN 103342355 A CN103342355 A CN 103342355A CN 201310287025X A CN201310287025X A CN 201310287025XA CN 201310287025 A CN201310287025 A CN 201310287025A CN 103342355 A CN103342355 A CN 103342355A
- Authority
- CN
- China
- Prior art keywords
- graphene
- graphite oxide
- organic solvent
- deionized water
- composite material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
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 the Graphene technical field, relate to a kind of novel method for preparing Graphene and matrix material thereof.
Background technology
Graphene (Graphene) is a kind ofly to form the ultra-thin superhard two-dimensional material that is hexangle type honeycomb lattice by carbon atom with the sp2 hybridized orbital, claims that generally the graphite below ten layers is Graphene.Graphene is the essentially consist unit that constitutes other carbon materials, and it wraps up the soccerballene (Fullerene) that forms zero dimension, rolls the carbon nanotube (Carbon Nanotube) that forms one dimension, and stacked in multi-layers forms three-dimensional graphite (Graphite).Graphene and matrix material thereof are the present research focuses in this field, have all shown bright development prospect at electronics, optics, machinery and field such as fire-retardant thereof.
From 2004, after the Andre Geim of Univ Manchester UK and Konstantin Novoselov used the mechanically peel method to obtain Graphene, people had proposed epitaxial growth method, chemical Vapor deposition process (CVD), liquid phase in succession and have peeled off methods such as method, chemical reduction method and prepare Graphene.The Graphene quality height of mechanically peel method preparation, but amount is few, is fit to scientific research, can not satisfy a large amount of industrial requirements far away.Epitaxial growth method, CVD method need high temperature and complicated transfer process, complex process and energy consumption height.It is consuming time and productive rate is low that liquid phase is peeled off method, limits its commercial applications.Chemical reduction method is considered to realize the effective means of suitability for industrialized production.Up to the present, investigators drop into sizable effort and energy development reduction method, 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, reduction preparation Graphene under the triethylamine solution condition.Defectives such as these reductive agents of hydrazine class, Resorcinol, sodium borohydride, Lithium Aluminium Hydride need long-time reaction reduction-oxidation graphite completely, exist long reaction time, and high toxicity, agglomeration are serious.There are 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, adopting red aluminium first is reductive agent, be raw material with graphite oxide with low cost, that obtain easily, when carrying out the graphite oxide quick functionization, finish the reduction to it, favorable dispersity, electroconductibility are good, area is micron-sized Graphene, Graphene/aluminium hydroxide and Graphene/alumina composite material thereby selectivity obtains.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 remove the heavy metal ion field.At present, the existing report of such matrix material.As the high superfine AlOOH-RGO matrix material that prepared of China Science ﹠ Technology University, be used for removing tap water Cd
2+, Pb
2+Chinese patent " a kind of preparation method of Graphene-epoxy resin composite material " (patent No. CN 101987908) has been reported Graphene and Resins, epoxy has been combined, the more independent Resins, epoxy of the hardness of this material has increased by 50%, has anti-ly increased nearly 12 times towards property.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing Graphene, Graphene/aluminium hydroxide and Graphene/alumina composite material.Another object of the present invention is to simplify nano composite material preparation technology namely to skip the Graphene preparation section, and optionally a step prepares nano composite material in graphite oxide functionalization mode.
For achieving the above object, technical scheme of the present invention is as follows:
A kind of preparation Graphene or Graphene/aluminium hydroxide composite process comprises the steps:
A. graphite oxide disperses: graphite oxide is obtained the brown dispersion liquid in organic solvent for ultrasonic;
B. graphite oxide reduction: the red aluminium of reductive agent is joined in the dispersion in organic solvent of the graphite oxide in the steps A, is 25-120 ℃ of reaction 5min-48h in temperature;
C. purification process: the dispersion liquid of step B is filtered, and through aromatic hydrocarbons or ether material (being preferably ether or tetrahydrofuran (THF)), deionized water, salt acid elution, drying obtains Graphene to solid matter successively.
Or: the dispersion liquid of step B is filtered, obtain Graphene/aluminium hydroxide through aromatic hydrocarbons or ethers (being preferably ether or tetrahydrofuran (THF)), deionized water wash, drying successively.
With the above-mentioned Graphene that obtains/aluminium hydroxide matrix material, can obtain Graphene/alumina composite material after the roasting.
Described graphite oxide adopts the Hummers method or improves the Hummers method and makes.
Organic solvent described in the steps A in the aforesaid method all is selected from one or more in tetrahydrofuran (THF), ethylene glycol, toluene, the second diether.The dispersion concentration of graphite oxide in organic solvent is preferably 0.25mg/ml-1.5mg/ml.
The described temperature of reaction of steps A in the aforesaid method is 25-120 ℃, is preferably 25-80 ℃.The described reaction times is 5min-48h, is preferably 30min-2h.
The mass ratio of the red aluminium described in the step B in the aforesaid method and graphite oxide is (20-150) ︰ 1.
After aromatic hydrocarbons or ethers washing, also comprise through washing with alcohol among the step C in the aforesaid method, and then deionized water wash.
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 ℃.
Characteristics of the present invention are: in preparation process, the red aluminium of reductive agent has namely served as reductive agent, has served as the presoma of aluminium hydroxide or aluminum oxide again, and namely optionally a step obtains for Graphene, Graphene/aluminium hydroxide and Graphene/alumina composite material.Therefore, major advantage of the present invention is to find a kind of new reductive agent, can reduce manufacturing cost, and preparation technology is simple, easy to operate, and is selective, and the Graphene good dispersity, the sheet that prepare are big, electroconductibility is good.
Description of drawings
Fig. 1 is the XRD figure spectrum of Graphene among the present invention;
Fig. 2 is the XRD figure spectrum of Graphene among the present invention/aluminium hydroxide matrix material;
Fig. 3 is the TEM photo of Graphene among the present invention;
Fig. 4 is the TEM photo of Graphene/aluminium hydroxide matrix material.
Embodiment
Embodiment 1
Take by weighing the graphite oxide of 100mg, be that the ratio of 1mg/1.25ml is measured a certain amount of anhydrous tetrahydro furan according to concentration, after ultrasonic in ultrasonic cleaner, to the red aluminium of the reductive agent that wherein adds 2ml, after temperature is 25 ℃ of reaction 2h, obtain the black dispersion liquid of homogeneous, centrifugal, ether, ethanol, deionized water, 1M dilute hydrochloric acid respectively wash three times successively, the Graphene after must reducing behind the vacuum-drying 24h, thinner from the tem observation graphene film, size is 15 * 11 μ m, favorable dispersity, and electric conductivity is 75s/cm.
Embodiment 2
Take by weighing the graphite oxide of 100mg, be that the ratio of 1mg/1ml is measured a certain amount of anhydrous second diether according to concentration, after ultrasonic in ultrasonic cleaner, to the red aluminium of the reductive agent that wherein adds 5ml, after temperature is 50 ℃ of reaction 1h, obtain the black dispersion liquid of homogeneous, centrifugal, tetrahydrofuran (THF), ethanol, deionized water wash gets Graphene/aluminium hydroxide matrix material behind the vacuum-drying 24h, be deposited on uniformly on the graphene film or between the graphene film from tem observation aluminium hydroxide, electric conductivity is 60s/cm, it at 500 ℃ of following vacuum bakings, is obtained Graphene/alumina composite material, and electric conductivity is 45s/cm.
Embodiment 3
Taking by weighing the graphite oxide of 100mg, is that the ratio of 1mg/0.8ml is measured a certain amount of toluene according to concentration, ultrasonic in ultrasonic cleaner after, to the red aluminium of the reductive agent that wherein adds 8ml, after temperature is 70 ℃ of reaction 40min, obtain the black dispersion liquid of homogeneous, centrifugal, toluene, ethanol, deionized water, 1M dilute hydrochloric acid respectively wash three times, get Graphene behind the vacuum-drying 24h, thinner from the tem observation graphene film, size is 9 * 11 μ m, favorable dispersity, electric conductivity are 70s/cm.
Embodiment 4
Take by weighing the graphite oxide of 100mg, be that the ratio of 1mg/0.67ml is measured a certain amount of ethylene glycol according to concentration, after ultrasonic in ultrasonic cleaner, to the red aluminium of the reductive agent that wherein adds 2ml, after temperature is 80 ℃ of reaction 30min, obtain the black dispersion liquid of homogeneous, centrifugal, ether, ethanol, deionized water, 1M dilute hydrochloric acid respectively wash three times, the Graphene after must reducing behind the vacuum-drying 24h, size is 10 * 10 μ m, and electric conductivity is 65s/cm.
Embodiment 5
Substantially the same manner as Example 4, the amount of the red aluminium that different is adds is 5ml, and the specific conductivity of preparation-obtained Graphene is more big, specific conductivity 90s/cm.
Embodiment 6
Substantially the same manner as Example 5, different is directly to use ether, ethanol, deionized water wash in the post-processing step, and vacuum-drying 24h draws Graphene/aluminium hydroxide matrix material, and its specific conductivity is 45s/cm.
Fig. 1 between the XRD figure of Graphene spectrum in above-described embodiment; The XRD figure spectrum of Graphene/aluminium hydroxide matrix material is seen Fig. 2; The TEM photo of Graphene is seen Fig. 3; The TEM photo of Graphene/aluminium hydroxide matrix material is seen Fig. 4.
The above only is preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle 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. one kind prepares Graphene or Graphene/aluminium hydroxide composite process, it is characterized in that, comprises the steps:
A. graphite oxide disperses: graphite oxide is obtained the brown dispersion liquid in organic solvent for ultrasonic;
B. graphite oxide reduction: the red aluminium of reductive agent is joined in the dispersion in organic solvent of the graphite oxide in the steps A, is 25-120 ℃ of reaction 5min-48h in temperature;
C. purification process: the dispersion liquid of step B is filtered, and through aromatic hydrocarbons or ether material, deionized water, salt acid elution, drying obtains Graphene to solid matter successively;
Or: the dispersion liquid of step B is filtered, obtain 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 the steps A is selected from one or more in tetrahydrofuran (THF), ethylene glycol, toluene, the second diether.
3. according to the method for claim 1, it is characterized in that the dispersion concentration of graphite oxide in organic solvent is preferably 0.25mg/ml-1.5mg/ml.
4. according to the method for claim 1, it is characterized in that the described temperature of reaction of steps A is 25-80 ℃, 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 the 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, also comprise through washing with alcohol among the step C in the aforesaid method, 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, with the resulting Graphene of claim 1/aluminium hydroxide matrix material, can obtain Graphene/alumina composite material after the roasting.
9. according to the method for claim 7, it is characterized in that roasting condition is preferably 500 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310287025.XA CN103342355B (en) | 2013-07-09 | 2013-07-09 | Method for preparing graphene and composite material thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310287025.XA CN103342355B (en) | 2013-07-09 | 2013-07-09 | Method for preparing graphene and composite material thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103342355A true CN103342355A (en) | 2013-10-09 |
| CN103342355B CN103342355B (en) | 2015-02-04 |
Family
ID=49277198
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310287025.XA Active CN103342355B (en) | 2013-07-09 | 2013-07-09 | Method for preparing graphene and composite material thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103342355B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109231191A (en) * | 2018-11-06 | 2019-01-18 | 新乡学院 | A kind of 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 |
| CN112645373A (en) * | 2020-12-17 | 2021-04-13 | 安徽理工大学 | Gamma-AlOOH/RGO composite wave-absorbing material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070131915A1 (en) * | 2005-11-18 | 2007-06-14 | Northwestern University | Stable dispersions of polymer-coated graphitic nanoplatelets |
| 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 |
-
2013
- 2013-07-09 CN CN201310287025.XA patent/CN103342355B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070131915A1 (en) * | 2005-11-18 | 2007-06-14 | Northwestern University | Stable dispersions of polymer-coated graphitic nanoplatelets |
| 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 |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109231191A (en) * | 2018-11-06 | 2019-01-18 | 新乡学院 | A kind of preparation method of fatty amine modified graphene |
| 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 |
| CN112645373A (en) * | 2020-12-17 | 2021-04-13 | 安徽理工大学 | Gamma-AlOOH/RGO composite wave-absorbing material and preparation method thereof |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103342355B (en) | 2015-02-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Dao et al. | Graphene prepared by thermal reduction–exfoliation of graphite oxide: Effect of raw graphite particle size on the properties of graphite oxide and graphene | |
| CN103342355B (en) | Method for preparing graphene and composite material thereof | |
| Zhang et al. | Preparation of few-layer graphene nanosheets by radio-frequency induction thermal plasma | |
| Wang et al. | Facile, mild and fast thermal-decomposition reduction of graphene oxide in air and its application in high-performance lithium batteries | |
| JP6359081B2 (en) | Boron nitride nanotube and method for producing the same | |
| Lü et al. | Low-temperature rapid synthesis of high-quality pristine or boron-doped graphene via Wurtz-type reductive coupling reaction | |
| CN102092710B (en) | Regular graphene and preparation method thereof | |
| CN111799464A (en) | MXene/graphene composite nanosheet, preparation method and application thereof, electrode plate and application thereof | |
| US10472243B2 (en) | Industrial method for preparing large-sized graphene | |
| CN103224230B (en) | A kind of preparation method of Graphene | |
| CN102431999A (en) | Method for preparing high-quality graphene | |
| JP2013500233A (en) | Production of graphene from metal alkoxides | |
| CN103935999A (en) | Preparation method of graphene | |
| CN104058399B (en) | Direct preparation method of high-purity high-quality graphene | |
| Yin et al. | Surface functionalization of bulk MoS2 sheets for efficient liquid phase exfoliation in polar micromolecular solvents | |
| Liu et al. | The preparation of holey phosphorene by electrochemical assistance | |
| Yang et al. | A facile one-step hydrothermal method to produce graphene–MoO3 nanorod bundle composites | |
| CN111039274B (en) | Liquid phase stripping method of graphdiyne | |
| CN103112844B (en) | Macro preparation method for mesoporous ordered graphene | |
| CN104936894A (en) | Carbon nano-tube production from carbon dioxide | |
| CN103553030A (en) | Preparation method of few-layer graphene | |
| Li et al. | Using glucosamine as a reductant to prepare reduced graphene oxide and its nanocomposites with metal nanoparticles | |
| CN105016331B (en) | Synthetic method of graphene microchip-diamond compound | |
| CN102320597B (en) | Preparation method of graphene | |
| Zhuo et al. | Facile reduction of graphene oxide at room temperature by ammonia borane via salting out effect |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |