CN103342358A - Method for quickly preparing large amount of layer number controllable high-quality graphene - Google Patents
Method for quickly preparing large amount of layer number controllable high-quality graphene Download PDFInfo
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Abstract
The invention relates to a method for quickly preparing a large amount of layer number controllable high-quality graphene. The method comprises the following steps of: preparing graphite oxide by adopting a Hummers method by using graphite as a raw material; centrifuging a solution in which oxydol is added to be neutral at a high speed by using the graphite oxide prepared by the Hummers method; then centrifuging mixed liquid at any rotating speed of 500-4000rpm for 20-40 minutes to obtain graphite oxide with a corresponding degree of oxidation; taking supernatant liquid, drying the obtained supernatant liquid and residual graphite oxide in a centrifuge bottle, then tearing the residual graphite oxide into pieces of 1cm<2>, and placing the graphite oxide pieces into an alumina ceramic crucible; fixing a crucible cover by using an adhesive tape, and pricking certain gaps by using a needle to ensure that air circulation is generated inside and outside the crucible; reducing the graphite oxide by using vacuum microwaves; and after reaction, releasing fluffy and flocculent graphene oxide with corresponding layers after vacuum treatment. According to the method, the graphite oxide with different degrees of oxidation can be obtained by controlling the centrifugal speed.
Description
Technical field
The present invention relates to the preparation of Graphene, particularly a large amount of preparations fast of Graphene.
Background technology
Carbon material is with its unique character and various form, becomes the outstanding person among the current type material, is widely used in industry-by-industries such as chemical industry, nuclear energy, electronics, metallurgy, machinery, aerospace.Graphene has peculiar two-dimensional layer crystalline structure, therefore the performance that has many excellences, as higher Young's modulus, thermal conductivity, higher carrier mobility, huge specific surface area, ferromegnetism etc., make Graphene become the research focus of chemistry, physics and Materials science, and predicted in fields such as matrix material, electron device, energy storage and sensors, be with a wide range of applications.
In order to advance Graphene in each Application for Field, prepare the key point that high-quality Graphene is problem fast.From two scientists of Britain in 2010 because since the work of Graphene obtained Nobel Prize in physics, short three or four years, it had become the most active science frontier of Materials science and physics field.Although the research of relevant Graphene is very many, how obtains high-quality Graphene in a large number and still have a lot of problems.Because the performance of Graphene is closely related with its number of plies, the Graphene of the different numbers of plies shows different performances.Individual layer and double-deck Graphene have only two kinds of current carriers of electronics and hole, and few layer graphene of 3 ~ 10 layers has multiple current carrier.Therefore, how the controlled high quality Graphene of the mass preparation number of plies is to make the Graphene industrialization and be applied to prerequisite and guarantee in each field.
Preparation method of graphene mainly contains mechanically peel method, oxidation reduction process, chemical Vapor deposition process, oxidation reduction process, silicon carbide epitaxial growth method, carbon nanotube patterning method etc. at present.Wherein the mechanically peel method can be prepared the Graphene lamella that can keep the perfect cystal structure, be widely used in the scientific effort, but preparation cycle is long, and productive rate is low, can't realize scale preparation, can not be used for suitability for industrialized production; Chemical Vapor deposition process technology is simple, is easy to patterning, but efficient is low, and output is few, and transitivity is poor, poor controllability; The silicon carbide epitaxial growth method can obtain large-area single-layer graphene, and quality is higher, but yields poorly and involve great expense; Carbon nanotube patterning method raw material is expensive and to the dependency height of equipment, efficient is low, the method for the mass preparation that neither suit Graphene.The gas mixture that Cheng Huiming etc. adopt pure hydrogen or hydrogen and argon gas in (CN101993061A) in " the high quality preparation method of graphene that a kind of number of plies is controlled " under 300 ~ 1000 ℃ atmosphere with graphite oxide reductase 12 0min ~ 10h, (6000 ~ 30000rpm) remove graphite and the thick graphite flake of not peeling off fully as yet by ultracentrifugal method again, obtain the controlled Graphene of the number of plies, but this method is to the equipment requirements height, recovery time is longer, and hydrogen is as inflammable gas, at high temperature reacting than danger and cost height, is not the method for suitable mass preparation Graphene.Yu Juan etc. " a kind of methods of utilizing graphite oxide prepare fast in a large number Graphene " (CN102502611A) in the employing microwave method of dissociating prepare Graphene fast, but this method reaches a few hours to the pretreatment time of graphite raw material, and the Graphene number of plies that obtains is uncontrollable, skewness has influenced the quality of product integral body.
Summary of the invention
The objective of the invention is to solve the Hummers legal system and be equipped with the degree of oxidation problem of non-uniform that exists in the graphite oxide process, the method of the controlled high quality Graphene of a large amount of numbers of plies of a kind of quick preparation is provided, the hydroxyl that inserts by the control graphite layers, carboxyl etc. contain the oxygen official can quantity, dissociate with microwave again, simple to operation.
Technical scheme of the present invention: the method for the high quality Graphene that a large amount of numbers of plies of a kind of quick preparation are controlled, comprise that with graphite be raw material, adopt the Hummers legal system to be equipped with graphite oxide, the Hummers legal system is equipped with graphite oxide will adds solution high speed centrifugation behind the hydrogen peroxide to neutral, and then mixing liquid is obtained the graphite oxide of corresponding oxidation degree with the centrifugal 20min ~ 40min of arbitrary rotating speed among 500rpm ~ 4000rpm, get supernatant liquid, will be torn into 1cm after the graphite oxide drying remaining in the supernatant liquid that obtain and the centrifugal bottle
2Fragment be positioned in the alumina-ceramic crucible, crucible cover is fixed and make inside and outside the crucible airiness is arranged with the certain space of pinprick with adhesive tape, vacuum microwave reduction-oxidation graphite after reaction finishes, discharges the graphene oxide that obtains the fluffy cotton-shaped corresponding number of plies after the vacuum.
Described graphite is synthetic graphite or natural flake graphite, is of a size of 30 ~ 600 μ m.
During described vacuum microwave, vacuum tightness is in the 0.1MPa, and microwave power is 4 ~ 6kW, and be 5 ~ 10s action time.
Described high speed centrifugation is centrifugal under the rotating speed of 8000rpm.
The concrete steps that described employing Hummers legal system is equipped with graphite oxide are:
(1) with there-necked flask with massfraction is 98% vitriol oil ice bath, the temperature of the control vitriol oil is below 3 ℃, slowly join the graphite of 1 part of quality in the vitriol oil, the ratio of graphite and the vitriol oil is 1g:(23 ~ 50) ml, after stirring 5min, the SODIUMNITRATE that slowly adds 0.5 ~ 2 part of quality, continue to stir 5min, the potassium permanganate that slowly adds 3 ~ 6 parts of quality again, stirring 15min ~ 4.5h below 3 ℃, the temperature of reaction system is transferred to 35 ℃, continue to stir 1 ~ 2h at 35 ℃, slowly add the deionized water of 46ml ~ 100ml in the reaction system with constant pressure funnel, guarantee that speed of dropping water is at 1 ~ 2 droplet/second, after water injection temperature of reaction system is risen to 95 ℃, continue to stop heating behind stirring 15 ~ 60min at 95 ℃;
(2) add the dilution of 500ml deionized water in the mixed solution, fluid temperature to be mixed is down to after 40 ℃ the hydrogen peroxide that adds mass concentration 30% in the mixed solution does not have bubble to produce to mixed solution.
Beneficial effect:
(1) degree of oxidation of graphite is controlled.Because being equipped with the technology of graphite oxide, the Hummers legal system all in liquid phase, finishes, in the process that stirs, it is identical everywhere that the stirring velocity of liquid internal can not reach, and this just causes the degree of mixing of graphite and oxygenant uncontrollable, and then cause the degree of oxidation of graphite uncontrollable.In the subsequent processes to graphite oxide, by the method for control centrifugal speed control the graphite layers hydroxyl (-OH), the carboxyl (-content of oxy radical such as COOH), can separate by the graphite oxide that degree of oxidation is different, make that the degree of oxidation of graphite is controlled.By high-power microwave radiation, bring out oxy radical and resolve into H rapidly again
2O, CO
2Etc. gas molecules, produce huge impact power, destroy the Van der Waals force combination of graphite layers, the graphite layers structure is opened, obtain Graphene, be applicable to the controlled high-quality Graphene of the macroscopic view preparation number of plies.
(2) be easy to industrialization.Whole reduction process is all finished in the furnace chamber of microwave oven, recovery time is in 10s, the method that chemistry dissociates needs poisonous reductive agents such as HI, hydrazine hydrate usually, and recovery time easily more than the 10h, production theory such as energy-conservation, the reduction of discharging that does not meet that present society vigorously advocates, environmental protection.And the method environmentally safe that microwave dissociates is low to the dependency of equipment, and use cost is low, and is simple to operation, can realize the magnanimity preparation of Graphene.
(3) can realize the magnanimity preparation of the Graphene that the high quality number of plies is controlled.As presoma, by the method that microwave dissociates, can realize the controlled preparation of the Graphene of the different numbers of plies with the graphite oxide of different degree of oxidations.The graphite oxide of different hydrophilic inserts the different amts of oxygen-containing functional group, and the surging force difference that produces when absorbing microwave causes the Graphene number of plies that obtains also different.This process only needs 5 ~ 10s can obtain the different high quality Graphene of the number of plies, thereby realizes the quick preparation of the high quality Graphene that the number of plies is controlled.Simple to operation, the cycle is short, and output is higher, and good stability is easy to industrialization.
Description of drawings
Fig. 1 is the XRD figure of different graphite oxides, as can be seen from the figure, adopts this method to separate the different graphite oxide of degree of oxidation, and rotating speed more the high oxidation degree is more high.
Fig. 2 is the transmission electron microscope picture of Graphene, and as can be seen from the figure, the Graphene surface of adopting this method to obtain is comparatively smooth, is the tulle shape, agglomeration do not occur.
Fig. 3 is the atomic force microscope images of Graphene.
Fig. 4 is the thickness curve of Graphene, as can be seen from the figure, adopt this method can obtain 1 ~ 2 layer Graphene, and the number of plies is evenly distributed.
Embodiment:
The invention provides a kind of high quality, the controlled preparation method of graphene of the number of plies, this method is raw material with synthetic graphite or natural flake graphite, is equipped with graphite oxide by the Hummers legal system.Because Hummers method preparation process all is to finish in liquid phase, stirring velocity can not be identical everywhere, and there is problem of non-uniform in the degree of oxidation of graphite, namely the hydroxyl that inserts of graphite layers (-OH), carboxyl (-COOH) wait the quantity that contains oxygen official energy inhomogeneous.Since the oxygen-containing functional group possess hydrophilic property, so the oxygen-containing functional group that graphite layers is inserted is more many, and the wetting ability of graphite is more good, need it could be separated from water by bigger centrifugal force.
Concrete technical process of the present invention may further comprise the steps:
(1) be 98% vitriol oil ice bath with there-necked flask with massfraction, the temperature of the control vitriol oil is below 3 ℃.The graphite of 1 part of quality is slowly joined in the vitriol oil, and the ratio of graphite and the vitriol oil is 1g:(23 ~ 50) ml, behind the stirring 5min, the SODIUMNITRATE that slowly adds 0.5 ~ 2 part of quality, continue to stir 5min, slowly add the potassium permanganate of 3 ~ 6 parts of quality again, stirring 15min ~ 4.5h below 3 ℃.The temperature of reaction system is transferred to 35 ℃, continue to stir 1 ~ 2h at 35 ℃.Slowly add the deionized water of 46 ~ 100ml in the reaction system with constant pressure funnel, guarantee speed of dropping water at 1 ~ 2 droplet/second, temperature of reaction system is risen to 95 ℃ after after water injection, stop heating at 95 ℃ after continuing to stir 15 ~ 60min.
(2) add the dilution of 500ml deionized water in the mixed solution, fluid temperature to be mixed is down to after 40 ℃ and is added 30% hydrogen peroxide in the mixed solution and do not have bubble to produce to mixed solution.
(3) mixing liquid in the step (2) is centrifugal to neutral under the rotating speed of 8000rpm.
(4) mixing liquid is centrifugal to obtain the graphite oxide of different degree of oxidations with the different rotating speeds between 500rpm ~ 4000rpm respectively again, for example respectively with the centrifugal 30min of the rotating speed of 3000rpm, 2000rpm, 1000rpm, 500rpm, get supernatant liquid respectively.The supernatant liquid that obtains and centrifugal back nubbin are namely obtained the graphite oxide of different degree of oxidations after 40 ℃ of following dryings.The more high then degree of oxidation of centrifugal rotational speed is also more high.Because rotating speed is a parameter of screening graphite oxidation degree, the degree of oxidation of the graphite oxide that the more big separation of rotating speed obtains is more high, but the amount of the graphite oxide that obtains also reduces thereupon, the highest centrifugal rotational speed that adopts 4000rpm of the present invention, Graphene difference on quality that rotating speed more than employing 4000rpm obtains is little, it is less that but amount compares, and therefore selects 4000 upper limits as centrifugal speed for use.
(5) graphite oxide is cut into 1cm
2Fragment, place in the alumina-ceramic crucible, cover crucible cover, crucible cover fixed and make inside and outside the crucible airiness is arranged with the certain space of pinprick with adhesive tape.
(6) crucible is placed in the microwave oven, close fire door, open vacuum valve, be evacuated in the 0.1MPa, add the microwave that power is 4 ~ 6kW, be 5 ~ 10s action time.
(7) after reaction finishes, open purging valve, open fire door after the stove internal gas pressure is returned to normal pressure, can obtain the Graphene of cotton-shaped fluffy state.
(8) graphite oxide of different degree of oxidations is operated according to the step of (5) ~ (7), can be obtained the Graphene of the different numbers of plies.
Measure the 250ml vitriol oil to going in the there-necked flask, adopt the mode of ice bath treat temperature be down to back below 3 ℃ in the vitriol oil successively at interval 5min slowly add 5g crystalline flake graphite (size≤600um), the 10g SODIUMNITRATE, 25g potassium permanganate, at stirring reaction 4.5h below 3 ℃, again at 35 ℃ of stirring reaction 2h.Reaction finishes the back and slowly add the 500ml deionized water in there-necked flask, temperature is risen to 95 ℃ again and continues stirring reaction 1h.Treat after the liquid cooling in there-necked flask, to add hydrogen peroxide no bubble generation to the liquid, with mixed solution centrifugal to the neutrality more respectively with the centrifugal 30min of the rotating speed of 4000rpm, 3000rpm, 2000rpm, 1000rpm, 500rpm, get nubbin in supernatant liquid and the centrifugal bottle 40 ℃ of forced air dryings.
Different graphite oxides is put into the different alumina-ceramic crucibles that volume is 1L, build the crucible cover rubber belt sealing, and prick at seal with pin and to have certain hole to make inside and outside the crucible airiness to be arranged, crucible is placed the furnace chamber of microwave oven, closing fire door is evacuated in the 0.1MPa, add the microwave that power is 6kW, be 10s action time.Close microwave then, discharge vacuum, sample is taken out from furnace chamber and crucible.
Observe sample as can be seen, 500rpm separates the remaining graphite oxide in back and is black, illustrates to contain a large amount of not oxidized graphite, and the above graphite oxide of 500rpm is brown, and oxidation effectiveness is better.Observation shows that the surface of Graphene shows comparatively smooth under the scanning electron microscope, and some areas fold to a certain degree occurs and curl, and the Graphene thickness of separating by 3000rpm is at 0.8 ~ 1.2nm, and the number of plies is about 2 ~ 3 layers, at thickness homogeneity is preferably arranged.The thickness of considering the monolayer carbon atom is 0.335nm, and the interlayer of Graphene has some spaces, can think that the graphite number of plies that obtains is at 1 ~ 2 layer.
Measure the 140ml vitriol oil to going in the there-necked flask, adopt the mode of ice bath to treat that temperature is down to below 3 ℃, in the vitriol oil successively at interval 5min slowly add 6g synthetic graphite (size≤30um), the 3g SODIUMNITRATE, 18g potassium permanganate, at stirring reaction 15min below 3 ℃, again at 35 ℃ of stirring reaction 1h.Reaction finishes the back and slowly add the 500ml deionized water in there-necked flask, temperature is risen to 95 ℃ again and continues stirring reaction 15min.Treat after the liquid cooling in there-necked flask, to add hydrogen peroxide no bubble generation to the liquid, with mixed solution centrifugal to the neutrality more respectively with the centrifugal 30min of the rotating speed of 4000rpm, 3000rpm, 2000rpm, 1000rpm, 500rpm, get the more shallow liquid of upper strata color and the nubbin in the centrifugal bottle 40 ℃ of forced air dryings.
Different graphite oxides is put into the different alumina-ceramic crucibles that volume is 1L, build the crucible cover rubber belt sealing, and prick at seal with pin and to have certain hole to make inside and outside the crucible airiness to be arranged, crucible is placed the furnace chamber of microwave oven, closing fire door is evacuated in the 0.1MPa, add the high pressure that power is 5kW, be 5s action time.Close microwave then, discharge vacuum, sample is taken out from furnace chamber and crucible.
XRD analysis shows that a large amount of not oxidized graphite are arranged in the remaining graphite oxide after 500rpm separates in the centrifugal bottle, and the degree of oxidation of the graphite oxide of separating more than the 500rpm increases along with the increase of centrifugal speed.Observation shows that the surface of Graphene is comparatively smooth under the transmission electron microscope, is the tulle shape.Utilize atomic force microscope as can be seen, the Graphene that the 2000rpm centrifugation obtains is mainly below 2 layers, and thickness is about 0.8nm, and the number of plies is about 1 ~ 2 layer, and the number of plies is evenly distributed.
Difference from Example 2 is:
(size≤30um) is raw material with synthetic graphite, according to graphite: SODIUMNITRATE: the potassium permanganate mass ratio is 1:1:6, add in the vitriol oil successively, at stirring reaction 15min below 3 ℃, 35 ℃ of stirring reaction 2h, in there-necked flask, slowly add the 500ml deionized water again, again at 95 ℃ of stirring reaction 15min.Remaining step is identical with embodiment 3.
Utilize the high resolution scanning Electronic Speculum as can be seen, the graphite number of plies after peeling off is less, shows as two-dimensional layered structure, and the surface of Graphene is comparatively smooth, and the subregion presents the phenomenon of curling with fold, can reduce its surface energy and make its stable existence.Utilize atomic force microscope as can be seen, the Graphene thickness that the 1000rpm separation obtains be about 3 ~ 4 layers, and the number of plies is evenly distributed about 1nm.
Claims (5)
1. quick method of the controlled high quality Graphene of a large amount of numbers of plies of preparation, comprise that with graphite be raw material, adopt the Hummers legal system to be equipped with graphite oxide, it is characterized in that, the Hummers legal system is equipped with graphite oxide will adds solution high speed centrifugation behind the hydrogen peroxide to neutral, and then mixing liquid is obtained the graphite oxide of corresponding oxidation degree with the centrifugal 20min ~ 40min of arbitrary rotating speed among 500rpm ~ 4000rpm, get supernatant liquid, will be torn into 1cm after the graphite oxide drying remaining in the supernatant liquid that obtain and the centrifugal bottle
2Fragment be positioned in the alumina-ceramic crucible, crucible cover is fixed and make inside and outside the crucible airiness is arranged with the certain space of pinprick with adhesive tape, vacuum microwave reduction-oxidation graphite after reaction finishes, discharges the graphene oxide that obtains the fluffy cotton-shaped corresponding number of plies after the vacuum.
2. according to the method for the controlled high quality Graphene of a large amount of numbers of plies of the described quick preparation of claim 1, it is characterized in that: described graphite is synthetic graphite or natural flake graphite, is of a size of 30 ~ 600 μ m.
3. according to the method for the controlled high quality Graphene of a large amount of numbers of plies of the described quick preparation of claim 1, it is characterized in that: during described vacuum microwave, vacuum tightness is in the 0.1MPa, and microwave power is 4 ~ 6kW, and be 5 ~ 10s action time.
4. according to the method for the controlled high quality Graphene of a large amount of numbers of plies of the described quick preparation of claim 1, it is characterized in that: described high speed centrifugation is centrifugal under the rotating speed of 8000rpm.
5. according to the method for the controlled high quality Graphene of a large amount of numbers of plies of the described quick preparation of claim 1, it is characterized in that: the concrete steps that described employing Hummers legal system is equipped with graphite oxide are:
Be 98% vitriol oil ice bath with massfraction with there-necked flask, the temperature of the control vitriol oil is below 3 ℃, slowly join the graphite of 1 part of quality in the vitriol oil, the ratio of graphite and the vitriol oil is 1g:(23 ~ 50) ml, after stirring 5min, the SODIUMNITRATE that slowly adds 0.5 ~ 2 part of quality, continue to stir 5min, the potassium permanganate that slowly adds 3 ~ 6 parts of quality again, stirring 15min ~ 4.5h below 3 ℃, the temperature of reaction system is transferred to 35 ℃, continue to stir 1 ~ 2h at 35 ℃, slowly add the deionized water of 46ml ~ 100ml in the reaction system with constant pressure funnel, guarantee that speed of dropping water is at 1 ~ 2 droplet/second, after water injection temperature of reaction system is risen to 95 ℃, continue to stop heating behind stirring 15 ~ 60min at 95 ℃;
Add the dilution of 500ml deionized water in the mixed solution, fluid temperature to be mixed is down to after 40 ℃ the hydrogen peroxide that adds mass concentration 30% in the mixed solution does not have bubble to produce to mixed solution.
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| CN104386676A (en) * | 2014-11-05 | 2015-03-04 | 北京化工大学 | Preparation method of graphene |
| CN105236398A (en) * | 2015-10-12 | 2016-01-13 | 青岛迈可威微波创新科技有限公司 | Method for microwave-assisted preparation of graphene |
| CN107416814A (en) * | 2017-08-03 | 2017-12-01 | 上海应用技术大学 | A kind of method that graphene is prepared using solid phase assisted microwave synthesis |
| CN113406079A (en) * | 2021-06-16 | 2021-09-17 | 南通第六元素材料科技有限公司 | Detection method and system for graphene oxide preparation process |
| CN114956063A (en) * | 2022-07-27 | 2022-08-30 | 湘潭大学 | Preparation method of nitrogen-doped fluorinated modified graphene potassium electrical anode material and battery |
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| CN113406079A (en) * | 2021-06-16 | 2021-09-17 | 南通第六元素材料科技有限公司 | Detection method and system for graphene oxide preparation process |
| CN114956063A (en) * | 2022-07-27 | 2022-08-30 | 湘潭大学 | Preparation method of nitrogen-doped fluorinated modified graphene potassium electrical anode material and battery |
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