CN103508447A - Preparation method of graphene - Google Patents
Preparation method of graphene Download PDFInfo
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- CN103508447A CN103508447A CN201210213260.8A CN201210213260A CN103508447A CN 103508447 A CN103508447 A CN 103508447A CN 201210213260 A CN201210213260 A CN 201210213260A CN 103508447 A CN103508447 A CN 103508447A
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Abstract
The invention discloses a preparation method of graphene. The method comprises the following steps: obtaining graphene oxide and a substrate; preparing pulp from the graphene oxide and coating the pulp on the surface of the substrate; preparing the graphene by a laser reduction method. The preparation method has the beneficial effects that the graphene is prepared by adopting the laser reduction method, so that the time of reaction for generating the graphene is short, thus the production efficiency is improved, the production cost is reduced and the environment-friendly effect is achieved; the graphene oxide is coated on the surface of the substrate to form a dry graphene oxide layer, so that irreversible agglomeration, caused by Van der Waals force, of the generated graphene with high specific surface area is effectively avoided in the laser reduction process, thus the yield of the graphene is increased; meanwhile, the preparation method of the graphene is combined with transmission equipment, thus achieving continuous operation of graphene production, reducing energy waste, shortening the production time, being beneficial to achievement of automatic macro production and increasing the yield.
Description
Technical field
The invention belongs to carbon material technical field, specifically relate to a kind of preparation method of Graphene.
Background technology
Graphene is a kind of Two-dimensional Carbon atomic crystal of the discoveries such as the strong K sea nurse of the peace moral of Univ Manchester UK in 2004 (Andre K.Geim), and obtains the physics Nobel prize in 2010, again causes carbon material research boom.Because its unique structure and photoelectric property become the study hotspot in the fields such as carbon material, nanotechnology, Condensed Matter Physics and functional materials, many scientific workers have been attracted.Graphene has good conduction, heat conductivility and low thermal expansivity, and its theoretical specific surface area is up to 2630m
2/ g, can be used for effect transistor, electrode materials, matrix material, liquid crystal display material, sensor.But the subject matter running in using the process of Graphene is cannot produce in a large number it at present.
In order to improve the turnout of Graphene, occurred that at present employing chemistry redox method carries out extensive preparation and produce, but the Graphene that the method prepares easily occurs to reunite and is difficult to disperse, owing to existing Van der Waals to interact, the Graphene with high-specific surface area trends towards forming irreversible caking, even again pile up to form graphite, thereby affected a large amount of production of Graphene, same restrict its application.In addition, the reductive agent that this chemistry redox method adopts is toxic, and environment is caused to certain pollution.
Summary of the invention
The object of the invention is to overcome the above-mentioned deficiency of prior art, the method for the quick macroscopic preparation of graphene of a kind of energy is provided.
In order to realize foregoing invention object, technical scheme of the present invention is as follows:
A preparation method for Graphene, comprises the steps:
Obtain graphene oxide and substrate;
Described graphene oxide is mixed with to slurry, and is coated in described substrate surface;
Laser reduction reaction is carried out in the laser reactive chamber that adopts transmission equipment to send into successively oven drying, oxygen-free environment the described substrate that is coated with slurry, generates Graphene; Wherein, the optical maser wavelength of launching in described laser reactive chamber is 157～780nm, and adopts the mode of linear time base sweep with the rate scanning graphene oxide of 5～20cm/min.
The preparation method of Graphene of the present invention adopts laser reduction legal system for Graphene, and the reaction times that makes to generate Graphene is short, has improved production efficiency, has reduced production cost, has avoided the use of toxic reductive agent, environmental protection.Graphene oxide is coated in to substrate surface and forms dry graphene oxide layer, make the Graphene of its high-specific surface area of effectively avoiding generation in laser reduction process because irreversible reunion occurs Van der Waals force, thereby improved the yield of Graphene.Meanwhile, this graphene preparation method combines transmission equipment, thus realized that Graphene of the present invention produces uninterrupted, work continuously, reduce energy wastage, reduced the production time, be conducive to realize automatization magnanimity and produce, improve output.In addition, this graphene preparation method is low for equipment requirements, and condition is easy to control, and its technique is simple.
Accompanying drawing explanation
Fig. 1 is preparation method's process flow diagram of embodiment of the present invention Graphene;
Fig. 2 is Graphene electron-microscope scanning (SEM) figure of embodiment 1 preparation.
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Example of the present invention provides a kind of method of quick macroscopic preparation of graphene.Preparation method's technical process of this Graphene refers to Fig. 1, comprises the steps:
S01, obtain graphene oxide and substrate;
S02, graphene oxide prepared by step S01 are mixed with slurry, and are coated in this substrate surface;
S03, laser reduction graphene oxide: laser reduction reaction is carried out in the laser reactive chamber that adopts transmission equipment to send into successively oven drying, oxygen-free environment this substrate that is coated with slurry, generates Graphene; Wherein, the optical maser wavelength of launching in described laser reactive chamber is 157～780nm, and adopts the mode of linear time base sweep with the rate scanning graphene oxide of 5～20cm/min.
Concrete, in above-mentioned steps S01, graphene oxide is preferably prepared as follows and obtains:
Step 1): by Graphite Powder 99, potassium permanganate and the vitriol oil according to 1 (g): 2～4 (g): the add-on of 15～31 (ml) is mixed at the temperature lower than 10 ℃, obtains mixing solutions;
Step 2): at room temperature (20 ℃～25 ℃) water-bath mixing solutions, stir after 20～48h again, under condition of ice bath, in mixing solutions, add deionized water, then add the deionized water solution that contains hydrogen peroxide to remove the complete potassium permanganate of unreacted, finally carry out solid-liquid separation, washing, obtain graphene oxide.
In one embodiment, this graphene oxide preparation method step:
0.5g 500 order Graphite Powder 99s are added in 0 ℃, the vitriol oil of 11.5mL, add again 1.5g potassium permanganate, the temperature of mixture remains on below 10 ℃, stir 2h, then in room-temperature water bath, stir after 24h, under condition of ice bath, slowly add 46mL deionized water, after 15min, add again 140mL deionized water (wherein contain 2.5mL concentration be 30% hydrogen peroxide), mixture color becomes glassy yellow afterwards, suction filtration, then with the hydrochloric acid that 250ml concentration is 10% wash, suction filtration, until filtrate is neutral.
In the preparation method of above-mentioned graphene oxide, Graphite Powder 99 can make natural graphite powder, expanded graphite powder etc.In addition, consider the size of Graphene in order to improve speed prepared by graphene oxide, the particle diameter of Graphite Powder 99 is preferably 500 orders left and right and is advisable simultaneously.Certainly, this graphene oxide Ye Ke market is bought and is obtained.Substrate in this step S01 is preferably one or more in silicon chip, quartz glass plate, titanium dioxide silicon chip.
Further, before this substrate surface applies graphene oxide slurry, the pre-treatment of preferably it being carried out decon and being degreased.This pretreated method is preferably as follows:
Substrate is removed to surface impurity in 30 minutes with acid soak, then use respectively ethanol, acetone and deionized water ultrasonic 20 minutes wipe oils in ultrasonic cleaning instrument, be then placed in vacuum drying oven and be dried 10 minutes in 80 ℃.Wherein, at least one in the hydrochloric acid that acid solution preferred concentration is 0.5～1mol/L, nitric acid, sulfuric acid.
This substrate, after above-mentioned pre-treatment, can effectively be removed the impurity and the grease that stick to substrate surface, reaches the effect on clean substrate surface, thereby has avoided participating in of in the reaction of follow-up laser reduction impurity, has improved the purity of Graphene.
In above-mentioned steps S02, the concentration of slurry is preferably 10～50g/L.The slurry preparation of graphene oxide is preferably dispersed in graphene oxide in deionized water according to the concentration of slurry.More even for graphene oxide is disperseed, can adopt sonic oscillation to process.In addition, the solvent of slurry, except deionized water, also can adopt volatile organic solvent, as volatile organic solvents such as ethanol, methyl alcohol, ether.For graphene oxide can be distributed in solvent rapidly and uniformly, can this graphene oxide of ultrasonic dispersion.
In this step S02, the thickness that applies slurry at substrate surface is preferably 0.1～5 μ m, and in a specific embodiment, the thickness that applies slurry at substrate surface is 2 μ m.This slurry coating thickness can affect the effect of laser reduction reaction.If thickness is excessive, can affects the effect that adds penetration of heat of laser in following step S03, thereby make graphene oxide reduction not thorough, thereby affect yield and the purity of Graphene.If thickness is too thin, can affect the output of Graphene within the unit time, also can cause in addition energy consumption relatively high, increased unnecessary cost.Therefore, above-mentioned preferred slurry thickness can improve yield and the purity of Graphene, can reduce production costs again, improves the output of Graphene within the unit time.
In this step S02, slurry preferably adopts thin film coated machine to be coated in substrate surface.Can guarantee like this homogeneity of graphene oxide slurry coat thickness, can also effectively shorten the time of the coating of slurry, improve the production efficiency of Graphene.
In above-mentioned steps S03, baking oven and laser reactive chamber should connect into an individual system with transfer equipment, by the transmission of transfer equipment, make graphene oxide first by oven drying, then through carrying out reduction reaction in laser reactive chamber.As embodiments of the invention, the surface-coated that above-mentioned steps S02 is processed has the substrate of graphene oxide slurry to be placed on the travelling belt of transfer equipment, open transfer equipment, by travelling belt, this substrate is delivered in 80～120 ℃ of baking boxes, governing speed, making the residence time of substrate in baking box is 10～30 minutes, thereby the solvent in graphene oxide slurry is thoroughly volatilized, dry slurry, and make slurry form graphene oxide layer at substrate surface.The more important thing is that this dry graphene oxide that can also make, owing to there is no solvent, in follow-up laser reduction reaction, effectively avoided Graphene because Van der Waals force is reunited, and purity and yield high.
In this step S03, in the process of laser reduction reaction, the moment high-energy that pulse laser produces, is radiated on the skeleton of graphite oxide, and the oxy radical on its skeleton is reduced.Particularly, graphite oxide is after the irradiation certain hour of high energy pulse laser, and its inner oxy radical is removed substantially, generates the gases such as carbonic acid gas, water, is finally reduced into Graphene.Accordingly, in a preferred embodiment, the optical maser wavelength of launching in laser reactive chamber is preferably 157～353nm, and the width of laser rays is greater than base widths, in the mode of line sweep, scans heated oxide graphite.In the process of line sweep, the speed of adjusting travelling belt is 5～20cm/min, that is to say to make this laser the speed with 5～20cm/min scans graphene oxide layer with the relative graphene oxide layer of mode that adopts linear time base sweep.Like this, the width of this line sweep and laser rays is greater than base widths and all graphene oxides in surface, base all can be included in its sweep limit, improves preparation efficiency and the purity of Graphene; By adjusting laser scanning speed and optical maser wavelength, quadrature two is gone back Etio. Ag, oxygen groups in graphite oxide can be effectively reduced, realize the quick macroscopic preparation of graphene of pipeline system, wherein, on the basis of this scanning speed, the oxygen groups that the laser energy of this optimal wavelength improves in graphite oxide is significantly reduced efficiency.
In this step S03, in laser reactive chamber, build anaerobic sublimity, its objective is laser reduction reaction and oxygen are completely cut off, prevent that the Graphene generating is oxidized.Preferably, this anaerobic sublimity can be the oxygen-free environment that is full of protective gas, as is full of one or more the oxygen-free environment of protective gas in nitrogen, argon gas, helium.The gas of this protectiveness is the participation of starvation effectively, and laser reduction reaction is carried out under the condition of anaerobic, guarantees the generation of Graphene, makes the condition of this laser reduction reaction more easily control simultaneously, reduces production costs.Certainly, this oxygen-free environment can be also the environment of vacuum.
After this step S03 laser reduction, this substrate is sent laser reactive chamber by travelling belt, and the Graphene of producing after reduction is separated with substrate, collects Graphene, and this substrate can reuse.Wherein, the Graphene mode separated with substrate can adopt automatic scraper that Graphene is scraped from substrate surface.
From the above mentioned, the preparation method of above-mentioned Graphene adopts laser reduction legal system for Graphene, and the reaction times that makes to generate Graphene is short, has improved production efficiency, has reduced production cost, has avoided the use of toxic reductive agent, environmental protection.Graphene oxide is coated in to substrate surface and forms dry graphene oxide layer, make the Graphene of its high-specific surface area of effectively avoiding generation in laser reduction process because irreversible reunion occurs Van der Waals force, thereby improved the yield of Graphene, thereby effectively overcome the deficiency of polluting sublimity and occurring to lump in the chemistry redox method of existing a large amount of production Graphenes.Simultaneously, this graphene preparation method combines transmission equipment and passes through to adjust laser scanning speed and optical maser wavelength, quadrature two is gone back Etio. Ag, and the oxygen groups in graphite oxide can be effectively reduced, and realizes the quick macroscopic preparation of graphene of pipeline system, thereby the pipeline system of having realized Graphene production of the present invention is worked continuously, and reduces energy wastage, has reduced the production time, be conducive to realize automatization magnanimity and produce, improve output.In addition, this graphene preparation method is low for equipment requirements, and condition is easy to control, and its technique is simple.
By concrete a plurality of embodiment, graphene preparation method is described below.
Embodiment 1
A preparation method for Graphene, its preparation method concrete steps are as follows:
S11. the preparation of graphite oxide:
0.5g 500 order Graphite Powder 99s are added in 0 ℃, the vitriol oil of 11.5mL, add again 1.5g potassium permanganate, the temperature of mixture remains on below 10 ℃, stir 2h, then in room-temperature water bath, stir after 24h, under condition of ice bath, slowly add 46mL deionized water, after 15min, add again 140mL deionized water (wherein contain 2.5mL concentration be 30% hydrogen peroxide), mixture color becomes glassy yellow afterwards, suction filtration, then with the hydrochloric acid that 250ml concentration is 10% wash, suction filtration, until filtrate is neutral;
S12. the pre-treatment of substrate: silicon chip is removed to surface impurity in 30 minutes by 0.5M salt acid soak, then use respectively ethanol, acetone and deionized water ultrasonic 20 minutes wipe oils in ultrasonic cleaning instrument, be then placed in vacuum drying oven and be dried 10 minutes in 80 ℃;
S13. step S11 is made to the slurry that graphite oxide and deionized water are mixed with 10g/L, with thin film coated machine, slurry is coated on dried silicon chip, the thickness that applies slurry is 2 μ m, this silicon chip is put on travelling belt, by travelling belt, silicon chip is delivered in 80 ℃ of baking boxes, governing speed, making the residence time of silicon chip in baking box is 30 minutes, be dried, make graphene oxide will expect to form graphene oxide layer at silicon chip surface;
S14. having toasted rear continuation delivers to silicon chip in the laser reactive case that is full of nitrogen by travelling belt, open the laser apparatus in reaction box, emission wavelength is 300nm laser rays, and the width of laser rays is greater than silicon chip width, in the mode of line sweep, with 10cm/min rate scanning heated oxide graphite, make graphene oxide be reduced into Graphene;
S15. after silicon chip leaves reaction box, with automatic scraper, the product of silicon chip surface is scraped, collected and obtain Graphene, silicon chip can reuse again after the processing of step S12.Wherein, the output of per minute Graphene is=the distance * thickness=10g/L*D*10cm*2um of slurry concentration * silicon chip width * per minute scanning.
The present embodiment 1 Graphene is carried out to electron-microscope scanning, and the SEM figure obtaining as shown in Figure 2.As can be seen from Figure 2, Graphene is successfully preparation, and graphene film layer thickness is about 2～4nm, and lamella is wider, is about 2～10um.From the preparation method of this Graphene, this graphene preparation method combines transmission equipment, thus realized that Graphene of the present invention produces uninterrupted, work continuously, reduce energy wastage, reduced the production time, be conducive to realize automatization magnanimity and produce, improve output, and environmental protection.
Embodiment 2
A preparation method for Graphene, its preparation method concrete steps are as follows:
S21. the preparation of graphite oxide:
0.5g 500 order Graphite Powder 99s are added in 0 ℃, the vitriol oil of 8mL, add 1g potassium permanganate, the temperature of mixture remains on below 10 ℃ again, stirs 4h, then in room-temperature water bath, stir after 24h, under condition of ice bath, slowly add 46mL deionized water, after 15min, then add 95mL deionized water (wherein contain 2.5mL concentration be 30% hydrogen peroxide), mixture color becomes glassy yellow afterwards, suction filtration, then with the hydrochloric acid that 200ml concentration is 10% wash, suction filtration, until filtrate is neutral;
S22. the pre-treatment of substrate: silicon chip is removed to surface impurity in 30 minutes with 1M nitric acid dousing, then use respectively ethanol, acetone and deionized water ultrasonic 20 minutes wipe oils in ultrasonic cleaning instrument, be then placed in vacuum drying oven and be dried 10 minutes in 80 ℃;
S23. step S21 is made to the slurry that graphite oxide and deionized water are mixed with 30g/L, with thin film coated machine, slurry is coated on dried quartz glass plate, the thickness that applies slurry is 2 μ m, this silicon chip is put on travelling belt, by travelling belt, silicon chip is delivered in 90 ℃ of baking boxes, governing speed, making the residence time of silicon chip in baking box is 25 minutes, be dried, make graphene oxide will expect to form graphene oxide layer at silicon chip surface;
S24. having toasted rear continuation delivers to silicon chip in the laser reactive case that is full of helium by travelling belt, open the laser apparatus in reaction box, emission wavelength is 353nm laser rays, and the width of laser rays is greater than silicon chip width, in the mode of line sweep, with 20cm/min rate scanning heated oxide graphite, make graphene oxide be reduced into Graphene;
S25. after silicon chip leaves reaction box, with automatic scraper, the product of silicon chip surface is scraped, collected and obtain Graphene, silicon chip can reuse again after the processing of step S22.Wherein, the output of per minute Graphene is=the distance * thickness=10g/L*D*20cm*2um of slurry concentration * silicon chip width * per minute scanning.
Embodiment 3
A preparation method for Graphene, its preparation method concrete steps are as follows:
S31. the preparation of graphite oxide:
0.5g 600 order Graphite Powder 99s are added in 0 ℃, the vitriol oil of 15mL, add again 2g potassium permanganate, the temperature of mixture remains on below 10 ℃, stir 4h, then in room-temperature water bath, stir after 48h, under condition of ice bath, slowly add 46mL deionized water, after 15min, add again 190mL deionized water (wherein contain 2.5mL concentration be 30% hydrogen peroxide), mixture color becomes glassy yellow afterwards, suction filtration, then with the hydrochloric acid that 300ml concentration is 10% wash, suction filtration, until filtrate is neutral;
S32. the pre-treatment of substrate: silicon chip is soaked and removes surface impurity in 30 minutes with 0.8M sulfuric acid, then use respectively ethanol, acetone and deionized water ultrasonic 20 minutes wipe oils in ultrasonic cleaning instrument, be then placed in vacuum drying oven and be dried 10 minutes in 80 ℃;
S33. step S31 is made to the slurry that graphite oxide and deionized water are mixed with 50g/L, with thin film coated machine, slurry is coated on dried silicon chip, the thickness that applies slurry is 2 μ m, this silicon chip is put on travelling belt, by travelling belt, silicon chip is delivered in 100 ℃ of baking boxes, governing speed, making the residence time of silicon chip in baking box is 20 minutes, be dried, make graphene oxide will expect to form graphene oxide layer at silicon chip surface;
S34. having toasted rear continuation delivers to silicon chip in the laser reactive case that is full of argon gas by travelling belt, open the laser apparatus in reaction box, emission wavelength is 780nm laser rays, and the width of laser rays is greater than silicon chip width, in the mode of line sweep, with 5cm/min rate scanning heated oxide graphite, make graphene oxide be reduced into Graphene;
S35. after silicon chip leaves reaction box, with automatic scraper, the product of silicon chip surface is scraped, collected and obtain Graphene, silicon chip can reuse again after the processing of step S32.Wherein, the output of per minute Graphene is=the distance * thickness=10g/L*D*5cm*2um of slurry concentration * silicon chip width * per minute scanning.
Embodiment 4
A preparation method for Graphene, its preparation method concrete steps are as follows:
S41. the preparation of graphite oxide: referring to the step S11 in embodiment 1;
S42. the pre-treatment of substrate: silicon chip is removed to surface impurity in 30 minutes by 1M salt acid soak, then use respectively ethanol, acetone and deionized water ultrasonic 20 minutes wipe oils in ultrasonic cleaning instrument, be then placed in vacuum drying oven and be dried 10 minutes in 80 ℃;
S43. step S41 is made to the slurry that graphite oxide and deionized water are mixed with 20g/L, with thin film coated machine, slurry is coated on dried titanium dioxide silicon chip, the thickness that applies slurry is 2 μ m, this silicon chip is put on travelling belt, by travelling belt, silicon chip is delivered in 120 ℃ of baking boxes, governing speed, making the residence time of silicon chip in baking box is 10 minutes, be dried, make graphene oxide will expect to form graphene oxide layer at silicon chip surface;
S44. having toasted rear continuation delivers to silicon chip in the laser reactive case that is full of nitrogen by travelling belt, open the laser apparatus in reaction box, emission wavelength is 157nm laser rays, and the width of laser rays is greater than silicon chip width, in the mode of line sweep, with 15cm/min rate scanning heated oxide graphite, make graphene oxide be reduced into Graphene;
S45. after silicon chip leaves reaction box, with automatic scraper, the product of silicon chip surface is scraped, collected and obtain Graphene, silicon chip can reuse again after the processing of step S32.Wherein, the output of per minute Graphene is=the distance * thickness=10g/L*D*15cm*2um of slurry concentration * silicon chip width * per minute scanning.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. a preparation method for Graphene, comprises the steps:
Obtain graphene oxide and substrate;
Described graphene oxide is mixed with to slurry, and is coated in described substrate surface;
Laser reduction reaction is carried out in the laser reactive chamber that adopts transmission equipment to send into successively oven drying, oxygen-free environment the described substrate that is coated with slurry, generates Graphene; Wherein, the optical maser wavelength of launching in described laser reactive chamber is 157～780nm, and adopts the mode of linear time base sweep with the rate scanning graphene oxide of 5～20cm/min.
2. the preparation method of Graphene according to claim 1, is characterized in that: the thickness that described slurry is coated in described substrate surface is 0.1～5 μ m.
3. the preparation method of Graphene according to claim 1, is characterized in that: the concentration of described slurry is 10～50g/L.
4. according to the preparation method of any described Graphene of claim 1～3, it is characterized in that: described slurry is to adopt thin film coated machine to be coated in described substrate surface.
5. the preparation method of Graphene according to claim 1 or 5, is characterized in that: the optical maser wavelength of launching in described laser reactive chamber is 157～353nm.
6. the preparation method of Graphene according to claim 1 or 5, is characterized in that: described oxygen-free environment is one or more the oxygen-free environment being full of in nitrogen, argon gas, helium.
7. the preparation method of Graphene according to claim 1, is characterized in that: described dry temperature is 80～120 ℃, and the time is 10～30min.
8. the preparation method of Graphene according to claim 1, is characterized in that: the acquisition methods of described graphene oxide is as follows:
Graphite Powder 99, potassium permanganate and the vitriol oil are mixed at the temperature lower than 10 ℃ according to the add-on of 1g:2g～4g:15ml～31ml, obtain mixing solutions;
After the stirring in water bath mixing solutions 20～48h of 20 ℃～25 ℃, under condition of ice bath, in mixing solutions, add deionized water again, then add the deionized water solution that contains hydrogen peroxide, finally carry out solid-liquid separation, washing, obtain graphene oxide.
9. the preparation method of Graphene according to claim 1, is characterized in that: described substrate is one or more in silicon chip, quartz glass plate, titanium dioxide silicon chip.
10. according to the preparation method of the Graphene described in claim 1 or 9, it is characterized in that: apply the step of slurry at described substrate surface before, also comprise described substrate is carried out to decon and the pretreated step that degreases.
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