CN103241732A - Method for large-scale preparation of high-quality graphene - Google Patents
Method for large-scale preparation of high-quality graphene Download PDFInfo
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- CN103241732A CN103241732A CN2013101390397A CN201310139039A CN103241732A CN 103241732 A CN103241732 A CN 103241732A CN 2013101390397 A CN2013101390397 A CN 2013101390397A CN 201310139039 A CN201310139039 A CN 201310139039A CN 103241732 A CN103241732 A CN 103241732A
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Abstract
The invention relates to a method for large-scale preparation of high-quality graphene. The technical process provided by the invention comprises the following steps of: regulating the pH value of a certain amount of graphite oxide solution to be 7-8 by utilizing an ammonia aqueous solution with the concentration of 10-30%; dispersing centrifuged precipitates into a small amount of hydrazine hydrate and carrying out ultrasonic processing for a plurality of hours, stripping graphite oxide to obtain few-layer or single-layer graphene oxide, then transferring the mixture solution into a reaction kettle, reacting for 24-60 hours at 150-250 DEG C, and after carrying out filtering and washing, obtaining a large number of black products, namely the high-quality grapheme. According to the method, the ammonia water is adopted to regulate the pH value of the graphite oxide solution to be neutral or alkaline, and in two aspects of the specific surface area and the specific capacitance, the grapheme prepared by utilizing the method is not inferior to the grapheme prepared by utilizing the conventional method. The method is simple and convenient to operate and is low in cost and high in yield.
Description
One, technical field
The present invention relates to a kind of a large amount of method for preparing the high quality Graphene, belong to the inorganic materials chemical field.
Two, background technology
Graphene has just caused scientist's very big concern rapidly since 2004 are found by Geim group, research boom continues so far.Graphene has only monoatomic layer thickness, piles up the crystal that forms in order by the two-dimension netted plane that carbon atom is formed, and can be used as the elementary cell of constructing other carbon material.Simultaneously, it still is a kind of zero bandgap semiconductor material.These structural performances make Graphene have a lot of excellent properties and special effects, as the quantum hall effect under: outstanding specific surface area, fabulous heat conductivity, high electron transport efficient, Di Lake fermion, two-shipper field-effect and the room temperature etc., thereby, be considered to have very tempting application prospect in fields such as biology, the energy, photoelectricity, machineries.
Preparation method of graphene mainly contains micromechanics and peels off method, epitaxy method, heating SiC method, chemical dispersion/reduction method and chemical Vapor deposition process etc. at present.Wherein chemical dispersion/reduction method because its required preparation condition is comparatively gentle and synthetic with low cost, is considered to be most appropriate to prepare in a large number the method for Graphene.That but this synthetic method also exists is time-consuming, water wasting, productive rate are low, and product Graphene surface imperfection is more, and electroconductibility has defectives such as certain loss.Therefore, chemical dispersion/reduction method will really realize industrialized Graphene mass preparation, must improve above weak point.
Three, summary of the invention
The present invention is directed to the deficiency of existing chemical dispersion/reduction preparation Graphene method, propose the method that a kind of ammonia scrubbing prepares the high quality Graphene in a large number.It is characterized in that having following process and step: 1) a large amount of preparations of neutral graphite oxide: drip 10%-30% ammoniacal liquor to a certain amount of acidic oxidation graphite solution, pH value to 7～8 of stirring and adjusting solution continue to stir 10～30 minutes, leave standstill 5-10 minute; With being washed till neutral graphite oxide solution in whizzer centrifugal 5～65 minutes, outwell supernatant liquor, namely obtain a large amount of neutral graphite oxide gelatinous precipitates; 2) a large amount of preparations of high quality Graphene: be that 85% hydrazine hydrate solution fully mixes ultra-sonic dispersion 30～300 minutes with the volume ratio of 1:5～5:1 and massfraction with the above-mentioned neutral graphite oxide gelatinous precipitate that makes; It is transferred in the band teflon-lined reactor, 150～250 ℃ of reactions 24～60 hours down, after filtration, washing, drying obtain the Graphene of a large amount of black, is stored in the moisture eliminator it standby.
The Graphene product of the present invention preparation has the structure of few layer even individual layer, productive rate is higher, specific surface area and than electric capacity all no less than the Graphene of traditional chemical oxidation-reduction method preparation.Principal feature of the present invention is: use the pH value of 10%-30% ammonia soln adjustment of acidity graphite oxide solution to neutrality or meta-alkalescence, not only shorten the centrifugation required time effectively, but also saved and be washed till neutral required water in a large number, can also guarantee the characteristic of product Graphene simultaneously substantially.And neutral graphite oxide undried processing just disperses in hydrazine hydrate solution, is guaranteeing the fully decentralized while of graphite oxide, has reduced the consumption of poisonous dispersion medium, has certain environment protection significance.The Graphene of the present invention preparation has been applied to adsorbing in the trade effluent heavy metal ion such as mercury, and has obtained certain effect.The present invention is simple to operate, with low cost, Graphene productive rate height.
Four, description of drawings
Fig. 1 is gained high quality Graphene transmission electron microscope of the present invention (TEM) photo.
Fig. 2 is gained high quality Graphene X-ray diffraction of the present invention (XRD) spectrogram.
Five, embodiment
Further describe feature of the present invention below by example.
Example 1:
Preparation process and step in the present embodiment are as described below:
Carefully add 20% ammonia soln while stirring to 50ml acidic oxidation graphite solution, the pH value to 8 of regulator solution continues to stir 30 minutes, leaves standstill a moment; With being washed till neutral graphite oxide solution under the rotating speed of 5000rpm centrifugal 45 minutes, outwell supernatant liquor, namely obtain a large amount of neutral graphite oxide gelatinous precipitates.Be that 85% hydrazine hydrate solution fully mixes ultra-sonic dispersion 3 hours with the above-mentioned neutral graphite oxide gelatinous precipitate that makes with the volume ratio of 2:1 and massfraction; After being uniformly dispersed it is transferred in the band teflon-lined reactor, and 180 ℃ of reactions 24 hours down, after filtration, washing, drying obtain the Graphene of a large amount of black, it is stored in the moisture eliminator.
Example 2
Preparation process in the present embodiment and step and above-mentioned example 1 are roughly the same.Different is: the centrifugation of neutral graphite oxide solution ultra-sonic dispersion time in hydrazine hydrate is 2 hours, finally makes a large amount of high quality Graphenes.
Example 3
Preparation process in the present embodiment and step and above-mentioned example 1 are roughly the same.Different is: the temperature that heats in reactor is 165 ℃, and the reaction times is 60 hours, finally makes a large amount of high quality Graphenes.
Example 4
Preparation process in the present embodiment and step and above-mentioned example 1 are roughly the same.Different is: the temperature that heats in reactor is 220 ℃, and the reaction times is 10 hours, finally makes a large amount of high quality Graphenes.
Example 1 obtained Graphene product characterization result is seen Fig. 1, Fig. 2 in the accompanying drawing.
Fig. 1 is gained high quality Graphene transmission electron microscope (TEM) photo figure.As we know from the figure, the gained Graphene number of plies is less, even is individual layer, and size is bigger, is close to clear, colorless.
Fig. 2 is gained high quality Graphene X-ray diffraction (XRD) spectrogram.As seen from the figure, ° located to occur the characteristic diffraction peak of Graphene (002) crystal face in 2 θ=25.6, interpret sample is the high quality Graphene; The diffraction peak broadening shows that the Graphene particle diameter of preparation is less.
Claims (1)
1. method for preparing in a large number the high quality Graphene is characterized in that having following process and step:
1) a large amount of preparations of neutral graphite oxide: drip 10%-30% ammoniacal liquor to a certain amount of acidic oxidation graphite solution, pH value to 7～8 of stirring and adjusting solution continue to stir 10～30 minutes, leave standstill 5-10 minute; With being washed till neutral graphite oxide solution in whizzer centrifugal 5～65 minutes, outwell supernatant liquor, namely obtain a large amount of neutral graphite oxide gelatinous precipitates;
2) a large amount of preparations of high quality Graphene: be that 85% hydrazine hydrate solution fully mixes ultra-sonic dispersion 30～300 minutes with the volume ratio of 1:5～5:1 and massfraction with the above-mentioned neutral graphite oxide gelatinous precipitate that makes; It is transferred in the band teflon-lined reactor, 150～250 ℃ of reactions 24～60 hours down, after filtration, washing, drying obtain the Graphene of a large amount of black, is stored in the moisture eliminator it standby.
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| CN2013101390397A CN103241732A (en) | 2013-04-19 | 2013-04-19 | Method for large-scale preparation of high-quality graphene |
| CN201310325054.0A CN103408003B (en) | 2013-04-19 | 2013-07-30 | Method for preparing graphene |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106006609A (en) * | 2016-05-17 | 2016-10-12 | 西南民族大学 | Method for preparing graphene with step-by-step purification method |
| CN107833759A (en) * | 2017-10-13 | 2018-03-23 | 南京旭羽睿材料科技有限公司 | A kind of silk screen print method prepares the preparation method of graphene electrode of super capacitor |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104977194B (en) * | 2014-04-10 | 2018-08-14 | 北京雷根生物技术有限公司 | A method of addition graphene accelerates sample process |
| CN105836855B (en) * | 2016-06-13 | 2019-02-15 | 西安工业大学 | A kind of preparation method and application of graphene gas-diffusion electrode |
| CN111055552A (en) * | 2019-06-08 | 2020-04-24 | 王雅静 | Batch preparation method of high-performance graphene film, graphene film and antenna |
| CN110980703A (en) * | 2019-12-30 | 2020-04-10 | 深圳市深瑞墨烯科技有限公司 | Graphene film batch production method and graphene film prepared by using same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2011159922A2 (en) * | 2010-06-16 | 2011-12-22 | The Research Foundation Of State University Of New York | Graphene films and methods of making thereof |
| CN102153077A (en) * | 2011-05-12 | 2011-08-17 | 北京工业大学 | Method for preparing single-layer graphene with high carbon-oxygen ratio |
| CN102275908B (en) * | 2011-07-07 | 2013-03-13 | 中南大学 | Preparation method of graphene material |
| CN102745675A (en) * | 2012-06-27 | 2012-10-24 | 合肥工业大学 | Preparation method of spinel-type magnetic MFe2O4/graphene composite material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106006609A (en) * | 2016-05-17 | 2016-10-12 | 西南民族大学 | Method for preparing graphene with step-by-step purification method |
| CN107833759A (en) * | 2017-10-13 | 2018-03-23 | 南京旭羽睿材料科技有限公司 | A kind of silk screen print method prepares the preparation method of graphene electrode of super capacitor |
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Application publication date: 20130814 |