CN102351173A - Method for preparing high quality graphene in large scale - Google Patents
Method for preparing high quality graphene in large scale Download PDFInfo
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- CN102351173A CN102351173A CN2011101946854A CN201110194685A CN102351173A CN 102351173 A CN102351173 A CN 102351173A CN 2011101946854 A CN2011101946854 A CN 2011101946854A CN 201110194685 A CN201110194685 A CN 201110194685A CN 102351173 A CN102351173 A CN 102351173A
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Abstract
The invention provides a method for preparing high quality graphene in large scale, comprising the following steps: preparing common graphene with chemical exfoliation; then applying a pressure of 40-60 MPa on the common graphene with spark plasma sintering or vacuum sintering techniques under the pressure of 10-30 pa, and heating up to 1300-1500 DEG C, keeping for 5-30 min, so as to obtain the high quality graphene. The method has the advantages of simple operation, easy control, and low cost.
Description
Technical field
The invention belongs to the carbon material field, relate to a kind of a large amount of method for preparing the high quality Graphene.
Background technology
Graphene is a kind of special laminated structure; It found by scientist An Deliehaimu of Univ Manchester UK (Andre Geim) and Constantine Nuo Woxiaoluofu (Konstantin Novoselov) that (SCIENCE 2004 in 2004; 306; 666-669), and obtained Nobel prize for physics in 2010.They adopt the mechanically peel method, through repeatedly peeling off, have obtained the mono-layer graphite sheet that only is made up of one deck carbon atom, i.e. Graphene from highly oriented pyrolytic graphite.Discover that Graphene has the excellent attributes of various ultra current materials far away, for example: high speed electronic mobility under the thinnest in the world material (single-layer graphene is 0.335 nm only), material, the toughness fabulous (Young's modulus can reach 1.1 TPa) that known strength is the highest at present, excellent impermeability (the He atom can't pass), the thermal conductivity of giving prominence to, the room temperature, (the theoretical specific surface area of single-layer graphene is up to 2630m for high specific surface area
2/ g), the lightest charge carrier etc.Utilize Graphene, can research and develop a series of novel materials with special property.For example, the transistorized transmission speed of Graphene is expected to be applied to the research and development of brand-new supercomputer considerably beyond present silicon transistor.Utilize its good electroconductibility and great specific surface area, Graphene can be used to make electrode materials, sensor material.Compound with other material, Graphene also can be used for making the matrix material with property, thus make novel material thinner, gentlier, more high resilience, so its application prospect is very wide.Graphene not only brings an electronic material revolution, but also will greatly promote the development of automobile, aircraft and space industry.
Generally the number of plies is called " Graphene " at the graphite flake below 10 layers, one deck be called " single-layer graphene ", being called more than two layers " multi-layer graphene ".They all have the physics inequality with graphite, chemistry and mechanical property, and that the number of plies is higher than 10 layers the performance of graphite flake is identical with common graphite.Thus, the preparation for Graphene mainly is that the research number of plies is at the graphite flake below 10 layers with research.
At present, preparation method of graphene mainly contains: mechanically peel method, chemical stripping method, SiC epitaxial growth method, chemical vapour deposition etc.
The mechanically peel method : be that highly oriented pyrolytic graphite is cut into graphite flake, be bonded at the thin slice both sides, tear adhesive tape then thin slice is divided into two, repeat above process and just can obtain the Graphene below 10 layers with adhesive tape, or even the Graphene of individual layer.The advantage of this method: the graphene film that can obtain very high quality; Shortcoming: output is very low, and cost is very high.
The SiC epitaxial growth method : be to heat the SiC crystal in a vacuum; When temperature reaches 1200 ℃ ~ 1500 ℃; The C-Si key ruptures, and the Si atom that contains in the more plane of C atom is evaporated out, and remaining carbon atom can be arranged in six sides' graphene-structured on SiC crystal (0001) face.The advantage of this method: can prepare the Graphene of better quality and need not carry out the transfer of substrate; Shortcoming: yield poorly, cost is high, and graphene film is in uneven thickness.
Chemical Vapor deposition process : be to utilize the pyrolytic decomposition hydrocarbon gas, in nickel catalyzator or copper catalyst film as thin as a wafer, at first form carbon nickel saturated solid solution, in process of cooling, carbon atom is separated out from nickel or copper crystal gradually then, and obtains the Graphene lamella.The advantage of this method: when obtaining high-quality Graphene, can also reasonably obtain comparatively ideal productive rate under the cost, also possess certain potentiality aspect the large-area Graphene of preparation in addition.Shortcoming: 1) Zhi Bei Graphene need be transferred in other substrate usually, has increased the difficulty of preparation; 2) though the output of preparation Graphene is higher than mechanically peel method and epitaxial growth method, also can not satisfy the demand of people on using far away.
The chemical stripping method is claimed again " oxidation reduction process " : be meant and at first utilize strong oxidizer that common graphite is carried out oxide treatment, make its interlamellar spacing become big, be easy to separate; Utilize method such as ultrasonic to peel off oxidized graphite then, obtain graphene oxide; At last, perhaps in reducing solution, graphene oxide is carried out reduction reaction, make the graphite oxide reduction after peeling off obtain Graphene at high temperature.The advantage of this method: the Graphite Powder 99 starting material obtain easily, preparation technology simple, cost is lower, can be used for preparing in a large number Graphene.Shortcoming: the prepared graphene quality is low, defective is many, and the carbon atom arrangement degree of disorder is high, and these characteristics have reduced physics, chemistry and the mechanical property etc. of Graphene widely, have limited the further widespread use of Graphene, perhaps have influence on effect.
The monolayer carbon atomic building that Graphene is made up of sp2 hydridization; Belong to the ideal two dimensional crystal; And its perfect hexagonal lattice structure and two-dirnentional structure have been given its high electronic mobility, and this mobility makes Graphene under very little carrier concentration, also have good electroconductibility.But research shows that the existence meeting of defective seriously reduces electronic mobility.Defective in the Graphene mainly comprises: the introducing of five-ring, seven-membered ring, graphite layers lack of alignment and impurity atoms etc., they are considered to be in has introduced on the basis of sp2 hydridization that sp3 hydridization causes.Characterize judgement from Raman spectrum (Raman): defective high quality Graphene seldom only contains characteristic peaks such as G peak and 2D peak, very low of the value at D peak; And the big Graphene of defect concentration of poor quality, except that the G peak, the D peak is very obvious, the 2D peak a little less than.It is generally acknowledged influences the Graphene quality, and just the principal element of structural integrity is the kind and the quantity of " defective " in the Graphene.
In sum, from the present method for preparing Graphene, can obtain the method for high quality Graphene, its output is very low, and cost is high; And can prepare Graphene and the low method of cost in a large number, its Graphene second-rate has more defective, can not satisfy the needs of application.
Summary of the invention
In order to solve the contradiction of Graphene output and quality in the prior art, technical problem to be solved by this invention provides a kind of a large amount of method for preparing the high quality Graphene.
The present invention is on the chemical stripping method basis of (claiming oxidation reduction process again); Utilize the high temperature and high pressure technology that Graphene is handled again; Can eliminate the defective in the Graphene fully, obtain the high quality Graphene, thereby reach the target that big output and high quality get both.Application at aspects such as microelectronic device, matrix material, catalyzer, energy and materials has great importance to grapheme material for this.
The technical scheme that the present invention adopts in turn includes the following steps:
(1) preparation of graphene oxide;
(2) graphene oxide is placed 500 ~ 700 ℃ of inert atmospheres or reducing atmosphere, or graphene oxide is placed reducing solution, reduction obtains Graphene;
(3) adopt discharge plasma sintering or vacuum sintering technique, in the vacuum of 10 ~ 30Pa, the Graphene that (2) the are obtained 40 ~ 60Mpa that exerts pressure, and be heated to 1300 ~ 1500 ℃, kept acquisition high quality Graphene 5 ~ 30 minutes.
Said inert atmosphere comprises one or more in helium, nitrogen, the argon gas.
Said reducing atmosphere comprises one or more in hydrogen, carbon monoxide or the hydrogen sulfide.
Said reducing solution comprises hydrazine hydrate solution, pure hydrazine solution, Resorcinol solution, sodium borohydride solution or ethylene glycol solution.
The preparation process of said graphene oxide can specifically comprise:
1) mass concentration 98% vitriol oil and Graphite Powder 99 are mixed, and add activator and put into beaker and mix and stirred 0.5 ~ 1 hour, afterwards mixture is put into 80 ℃ of water-bath equipment, continue to stir four hours;
2) upwards obtain to add mass concentration 98% vitriol oil in the mixture in the step, and slowly add KMNO
4, maintain the temperature in the adition process below 20 ℃, operate in the ice-water bath and accomplish;
3) constant temperature is 35 ℃, stirs 2 hours, makes KMNO
4Fully contact with graphite, afterwards, in the distilled water with 60 ~ 70 ℃ of gains addings, kept 2 hours, add ydrogen peroxide 50, remove excessive KMNO
4
4) utilize on the ultra-sonic dispersion and obtain solution in the step, the time is 1 ~ 2 hour, is neutral with alcohol or distilled water wash until potential of hydrogen, 50 ~ 70 ℃ down the oven dry solution promptly get graphene oxide.
Described activator is K
2S
2O
4, P
2O
5In one or several.
Beneficial effect of the present invention is:
(1) on the basis of chemical stripping, for preparing the high quality Graphene provides a kind of new method in a large number;
(2) simple to operate, be easy to control, cost is lower.
Description of drawings
The transmission electron microscope shape appearance figure of the Graphene that Fig. 1 embodiment 1 makes;
The Raman spectrum curve of the Graphene that Fig. 2 embodiment 1 makes;
The transmission electron microscopy shape appearance figure of the Graphene that Fig. 3 embodiment 3 makes;
The Raman spectrum curve of the Graphene that Fig. 4 embodiment 3 makes.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is further set forth, but therefore do not limit the present invention within the described scope of embodiments.
Embodiment 1: at first take by weighing 0.2g graphite, 0.5gK
2S
2O
4, 0.5g P
2O
5, measure 2 ~ 4ml vitriol oil and mix and put into 80 ℃ of water-bath equipment and continue to stir after four hours and take out.Solution to after treatment goes out to add the 12ml vitriol oil, and slowly adds 2g KMNO
4, and remain temperature below 20 ℃, add KMNO
4After, 35 ℃ of constant temperature stirred 2 hours.Will be in the gains add in the 25ml distilled water, utilize the heat of vitriol oil suction heat release, make the graphite flake layer exhaustive oxidation with separate.Treat that heat release finishes, gains added in the 70ml distilled water, keep 60 ~ 70 ℃ 1 hour.In solution, add the 3ml ydrogen peroxide 50, remove excessive KMNO
4, utilize the alcohol wash sample to PH=7, utilized ultra-sonic dispersion 1 hour, dry solution down at 50 ~ 70 ℃ and obtain graphene oxide.The sample of oven dry is sent in the common heat treatment furnace, fed argon atmospher, and under argon atmospher, be heated to 700 degrees centigrade, kept 2 hours, obtain Graphene.Its pattern as shown in Figure 1, its Raman spectrum as shown in Figure 2, visible D peak is very strong among the figure, promptly the Graphene surface has a lot of defectives.
Embodiment 2: it is identical with embodiment 1 to press experiment condition, obtain Graphene after, put it into pyroprocessing in discharge plasma sintering (SPS) stove, treatment temp is 1300 ℃, the time is 5 minutes, vacuum tightness is 10 ~ 30Pa, applies the 50Mpa axle pressure.After treating cooling fast, obtain the Graphene of handling.
Embodiment 3: it is identical with embodiment 1 to press experiment condition, obtain Graphene after, put it into pyroprocessing among the SPS, treatment temp is 1500 ℃, the time is 5 minutes, vacuum tightness is 10 ~ 30Pa, applies the 50Mpa axle pressure.After treating cooling fast, obtain to handle Graphene.Graphene demonstrates perfect crystal mass, and its appearance structure as shown in Figure 3.Its Raman spectrum as shown in Figure 4.
Embodiment 4: it is identical with embodiment 1 to press experiment condition, obtain Graphene after, put it into pyroprocessing among the SPS, treatment temp is 1500 ℃, the time is 15 minutes, vacuum tightness is 10 ~ 30Pa, applies the 50Mpa axle pressure.After treating cooling fast, obtain the high quality Graphene of handling.
Embodiment 5: the experiment condition of preparation graphene oxide is identical with embodiment 1, in the sample adding hydrazine hydrate solution with oven dry, is heated to 90 degrees centigrade, pump around circuit 2 hours, and oven dry solution in back obtains Graphene.Put it into pyroprocessing in discharge plasma sintering (SPS) stove, treatment temp is 1300 ℃, and the time is 5 minutes, and vacuum tightness is 10 ~ 30Pa, applies the 50Mpa axle pressure.After treating cooling fast, obtain the high quality Graphene of handling.
Embodiment 6: it is identical with embodiment 1 to press experiment condition, obtain Graphene after, put it into pyroprocessing in the VPS stove, treatment temp is 1500 ℃, the time is 15 minutes, vacuum tightness is 10 ~ 30Pa, applies the 50Mpa axle pressure.After treating cooling fast, obtain the high quality Graphene of handling.
From on can find out, the Graphene of chemical stripping method (claiming oxidation reduction process again) preparation is carried out the vacuum high-temperature autoclaving can obtain a large amount of high-quality Graphenes.This produces the high quality Graphene for preparation in enormous quantities and has played promoter action.
Claims (6)
1. a method for preparing the high quality Graphene in a large number is characterized in that, in turn includes the following steps:
(1) preparation of graphene oxide;
(2) graphene oxide is placed 500 ~ 700 ℃ of inert atmospheres or reducing atmosphere, or graphene oxide is placed reducing solution, reduction obtains Graphene;
(3) adopt discharge plasma sintering or vacuum sintering technique, in the vacuum of 10 ~ 30Pa, the Graphene that (2) the are obtained 40 ~ 60Mpa that exerts pressure, and be heated to 1300 ~ 1500 ℃, kept acquisition high quality Graphene 5 ~ 30 minutes.
2. preparation method as claimed in claim 1 is characterized in that, said inert atmosphere is one or more in helium, nitrogen, the argon gas.
3. preparation method as claimed in claim 1 or 2 is characterized in that, said reducing atmosphere is one or more in hydrogen, carbon monoxide or the hydrogen sulfide.
4. preparation method as claimed in claim 1 or 2 is characterized in that, said reducing solution is hydrazine hydrate solution, pure hydrazine solution, Resorcinol solution, sodium borohydride solution or ethylene glycol solution.
5. preparation method as claimed in claim 1 or 2 is characterized in that, the preparation process of said graphene oxide specifically comprises:
1) mass concentration 98% vitriol oil and Graphite Powder 99 are mixed, and add activator and put into beaker and mix and stirred 0.5 ~ 1 hour, afterwards mixture is put into 80 ℃ of water-bath equipment, continue to stir four hours;
2) upwards obtain to add mass concentration 98% vitriol oil in the mixture in the step, and slowly add KMNO
4, maintain the temperature in the adition process below 20 ℃, operate in the ice-water bath and accomplish;
3) constant temperature is 35 ℃, stirs 2 hours, makes KMNO
4Fully contact with graphite, afterwards, in the distilled water with 60 ~ 70 ℃ of gains addings, kept 2 hours, add ydrogen peroxide 50, remove excessive KMNO
4
4) utilize on the ultra-sonic dispersion and obtain solution in the step, the time is 1 ~ 2 hour, is neutral with alcohol or distilled water wash until potential of hydrogen, 50 ~ 70 ℃ down the oven dry solution promptly get graphene oxide.
6. preparation method as claimed in claim 5 is characterized in that described activator is K
2S
2O
4, P
2O
5In one or several.
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102530937A (en) * | 2012-03-15 | 2012-07-04 | 武汉大学 | Method for preparing high-quality graphene on large scale |
| CN102602925A (en) * | 2012-04-13 | 2012-07-25 | 常州第六元素材料科技股份有限公司 | Method for preparing graphene by virtue of high-pressure reduction |
| CN103123830A (en) * | 2013-03-14 | 2013-05-29 | 南京科孚纳米技术有限公司 | Method for preparing graphene wire and cable |
| CN103387226A (en) * | 2013-07-05 | 2013-11-13 | 清华大学深圳研究生院 | Preparation method for graphene |
| CN103508441A (en) * | 2012-06-19 | 2014-01-15 | 海洋王照明科技股份有限公司 | Preparation method of graphene |
| CN103632852A (en) * | 2012-08-24 | 2014-03-12 | 海洋王照明科技股份有限公司 | Preparation methods of ruthenium oxide-graphene composite material and capacitor |
| CN103896257A (en) * | 2012-12-26 | 2014-07-02 | 海洋王照明科技股份有限公司 | Preparation method for graphene |
| CN103996546A (en) * | 2013-02-20 | 2014-08-20 | 海洋王照明科技股份有限公司 | Graphene composite material and preparation method thereof, electrochemical capacitor and electrode thereof |
| CN104031290A (en) * | 2014-06-27 | 2014-09-10 | 武汉大学 | Preparation method of graphene/polymer composite material with high strength and high low-temperature toughness |
| CN104261487A (en) * | 2014-09-23 | 2015-01-07 | 南昌航空大学 | Method for preparing ferroferric oxide/graphene magnetic nano composite material by solvothermal one-step method |
| CN106006621A (en) * | 2016-06-13 | 2016-10-12 | 华南理工大学 | Preparing method for multilayer graphene |
| CN108455575A (en) * | 2018-02-19 | 2018-08-28 | 桂林理工大学 | A kind of preparation method of reduced graphene |
| CN108504354A (en) * | 2018-03-20 | 2018-09-07 | 桂林理工大学 | A kind of preparation method of silicon doped graphene quantum dot |
| CN111366572A (en) * | 2020-03-27 | 2020-07-03 | 苏州聚龙能源科技有限公司 | Method for quantitatively analyzing content of graphene in graphene composite conductive slurry |
| CN113929087A (en) * | 2021-10-19 | 2022-01-14 | 深圳市汉嵙新材料技术有限公司 | Graphene sheet, and preparation method and application thereof |
| CN115057435A (en) * | 2022-08-03 | 2022-09-16 | 山东海科创新研究院有限公司 | Method for preparing graphene oxide by recycling concentrated sulfuric acid and application of obtained product |
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| JP2008285745A (en) * | 2007-04-17 | 2008-11-27 | Sumitomo Precision Prod Co Ltd | High thermal conductive composite material |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102530937A (en) * | 2012-03-15 | 2012-07-04 | 武汉大学 | Method for preparing high-quality graphene on large scale |
| CN102602925B (en) * | 2012-04-13 | 2016-01-13 | 常州第六元素材料科技股份有限公司 | The method of Graphene is prepared in a kind of high pressure reduction |
| CN102602925A (en) * | 2012-04-13 | 2012-07-25 | 常州第六元素材料科技股份有限公司 | Method for preparing graphene by virtue of high-pressure reduction |
| CN103508441A (en) * | 2012-06-19 | 2014-01-15 | 海洋王照明科技股份有限公司 | Preparation method of graphene |
| CN103632852A (en) * | 2012-08-24 | 2014-03-12 | 海洋王照明科技股份有限公司 | Preparation methods of ruthenium oxide-graphene composite material and capacitor |
| CN103896257A (en) * | 2012-12-26 | 2014-07-02 | 海洋王照明科技股份有限公司 | Preparation method for graphene |
| CN103996546A (en) * | 2013-02-20 | 2014-08-20 | 海洋王照明科技股份有限公司 | Graphene composite material and preparation method thereof, electrochemical capacitor and electrode thereof |
| CN103123830A (en) * | 2013-03-14 | 2013-05-29 | 南京科孚纳米技术有限公司 | Method for preparing graphene wire and cable |
| CN103387226A (en) * | 2013-07-05 | 2013-11-13 | 清华大学深圳研究生院 | Preparation method for graphene |
| CN104031290A (en) * | 2014-06-27 | 2014-09-10 | 武汉大学 | Preparation method of graphene/polymer composite material with high strength and high low-temperature toughness |
| CN104261487A (en) * | 2014-09-23 | 2015-01-07 | 南昌航空大学 | Method for preparing ferroferric oxide/graphene magnetic nano composite material by solvothermal one-step method |
| CN106006621A (en) * | 2016-06-13 | 2016-10-12 | 华南理工大学 | Preparing method for multilayer graphene |
| CN106006621B (en) * | 2016-06-13 | 2020-07-07 | 华南理工大学 | Preparation method of multilayer graphene |
| CN108455575A (en) * | 2018-02-19 | 2018-08-28 | 桂林理工大学 | A kind of preparation method of reduced graphene |
| CN108504354A (en) * | 2018-03-20 | 2018-09-07 | 桂林理工大学 | A kind of preparation method of silicon doped graphene quantum dot |
| CN111366572A (en) * | 2020-03-27 | 2020-07-03 | 苏州聚龙能源科技有限公司 | Method for quantitatively analyzing content of graphene in graphene composite conductive slurry |
| CN113929087A (en) * | 2021-10-19 | 2022-01-14 | 深圳市汉嵙新材料技术有限公司 | Graphene sheet, and preparation method and application thereof |
| CN115057435A (en) * | 2022-08-03 | 2022-09-16 | 山东海科创新研究院有限公司 | Method for preparing graphene oxide by recycling concentrated sulfuric acid and application of obtained product |
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Application publication date: 20120215 |