CN107585756B - Device and method for preparing graphene by laser impact of carbon material in liquid medium - Google Patents
Device and method for preparing graphene by laser impact of carbon material in liquid medium Download PDFInfo
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- CN107585756B CN107585756B CN201710637532.XA CN201710637532A CN107585756B CN 107585756 B CN107585756 B CN 107585756B CN 201710637532 A CN201710637532 A CN 201710637532A CN 107585756 B CN107585756 B CN 107585756B
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Abstract
The invention relates to a device and a method for preparing graphene on a large scale by using carbon materials in a liquid medium through laser impact. After laser generated by a high-power pulse laser generating device is reflected by a light mirror, a laser beam is vertically focused on a proper position on the upper surface of a graphite block target in an aqueous solution medium, a direct current electric field with the voltage of direct current of 24V is added at two ends of the graphite target, one end of the electric field is fixed at one end of a reaction tank, the other end of the electric field adopts a copper foil, the copper foil is driven by a motor to move at a fixed speed, a high-temperature and high-pressure plasma can be formed between the graphite and the aqueous medium at the moment when the graphite is impacted by the laser, the plasma can be attached to the surface of the copper foil under the driving of the electric field and can be continuously attached, the copper foil continuously moves, and finally the.
Description
Technical Field
The invention belongs to a technology for efficiently preparing graphene, and particularly relates to a device and a method for preparing graphene by using carbon materials in a liquid medium through laser impact.
Background
Graphene, which is a novel carbon nanomaterial with a thickness of only a single atomic layer, is paid much attention to by researchers in the last decade, and the thickness of the single layer is only 0.3554 nm. Graphene not only has the unique properties of nano materials, but also has extremely high hardness, is the highest-strength material understood in the world today, and has the tensile strength of 125GPa and the elastic modulus of 1.1 TPa. Moreover, the thermal conductivity of graphene under normal environmental conditions is 5x 103W/(mK), which is an order of magnitude higher than the thermal conductivity of copper under equivalent conditions. The graphene has excellent optical transparency (the absorptivity of light is only 2.3 percent), high conductivity and the like and can reach 2630m2Theoretical specific surface area in g.
Laser energy is gathered to a point within a short time, the laser power density at the point is extremely high, the temperature and the pressure at the point are rapidly increased to form plasma, the high-temperature and high-pressure plasma plume is broken out in a laser pulse gap to release enough heat and energy to promote the graphite crystal to be converted to the graphene structure, and the preparation process of the graphene is completed within a very short time of pulse laser. However, the fine graphene cannot really exert its superior properties, and thus, research on the preparation of large-sized, high-efficiency graphene is necessary.
Under the action of nanosecond pulse laser, a graphite crystal absorbs a large amount of laser energy in a very short time, and is limited by surrounding water media, heat cannot be transmitted, and a high-temperature and high-pressure plasma region is formed on the surface of graphite, so that the graphite is induced to be converted into graphene. The transformation process is mainly divided into two stages: the first stage is a temperature and pressure raising process, and covalent bonds among carbon atoms on the surface layer of the graphite are broken into free carbon atoms; the second stage is a temperature and pressure reduction process, and carbon atoms are hybridized to form graphene through sp 2.
Disclosure of Invention
The invention aims to provide a method and a device for preparing graphene by laser impact of a carbon material in a liquid medium, which are used for improving the preparation efficiency of the graphene.
The technical scheme adopted by the invention is as follows: the device for preparing graphene by using carbon materials in a liquid medium through laser impact comprises a three-dimensional moving platform and a reaction container, wherein the reaction container is positioned on the three-dimensional moving platform, a highly-oriented pyrolytic graphite block and a lead screw are arranged in the reaction container, a supporting plate is in threaded connection with the lead screw, a second motor is installed at the tail end of the lead screw, a second rotating shaft and a first rotating shaft are installed on the supporting plate, a copper foil is wound on the second rotating shaft, a first motor is installed on the first rotating shaft, and the copper foil is wound on the first rotating shaft from the second rotating shaft by means of the rotation of the first motor; the high-power pulse laser generator is arranged above the reaction container, a copper column is arranged in the reaction container, and the copper column and the first rotating shaft are respectively connected with two poles of a power supply.
In the above scheme, still include flow regulator, liquid reserve tank and charge pump, flow regulator one end links to each other with the liquid reserve tank, and the other end passes through the charge pump and links to each other with the water inlet of reaction vessel, the delivery port of reaction vessel links to each other with the liquid reserve tank.
In the scheme, laser beams emitted by the high-power pulse laser generating device are radiated to the high-orientation pyrolytic graphite block from a laser processing head after passing through the collimation beam expanding lens and the total reflection lens.
In the above scheme, the water outlet of the reaction vessel is connected with the liquid storage tank, one end of the flow regulator is connected with the liquid storage tank, and the other end of the flow regulator is connected with the water inlet of the reaction vessel through the electric pump.
In the above scheme, the power supply is connected with a power transformer, the three-dimensional mobile platform, the first motor, the second motor and the power transformer are all connected with a digital controller, and the digital controller, the high-power pulse laser generating device and the flow regulator are all connected with a computer.
The invention also provides a method for preparing graphene by laser impact of carbon materials in liquid media, which comprises the following steps: A. preparing a dilute sulfuric acid solution; B. setting a reaction device: placing the highly oriented pyrolytic graphite block in a reaction container, and adjusting the support plate along the Y axis through a second motor to keep a specified distance between the copper foil and the highly oriented pyrolytic graphite block; C. adjusting the three-dimensional moving platform to enable the laser focus to be located on the upper surface of the highly-oriented pyrolytic graphite block, so that the laser beam is vertically incident on the upper surface of the highly-oriented pyrolytic graphite block; D. injecting a dilute sulfuric acid solution into the reaction vessel: adjusting the flow regulator to set the flow at 0.65-1L/s, and starting the electric pump to inject the sulfuric acid solution into the reaction container until the liquid level exceeds the upper surface of the highly oriented pyrolytic graphite block; E. connecting the positive pole of a power supply with a copper column at the front end of the reaction container through a wire, connecting the negative pole of the power supply with the tail end of the first rotating shaft, and turning on the power supply through a digital controller to form an electric field environment in the reaction container; F. opening a high-power pulse laser generating device, setting laser parameters through a computer, focusing laser on the upper surface of the high-orientation pyrolytic graphite block by the aid of laser emitted by the high-power laser generating device through a laser processing head, controlling the three-dimensional moving platform to perform feed motion along the X-axis direction by a digital controller, moving the three-dimensional moving platform for a light spot distance along the Y-axis direction after impacting a certain distance, continuously impacting, starting to rotate a first motor, and repeating the steps after feeding of the high-orientation pyrolytic graphite block in the X-axis direction is completed; G. and closing all the devices, taking down the copper foil, and carrying out subsequent graphene transfer and purification treatment.
The method for preparing graphene by laser impact on carbon material in liquid medium according to claim 6, wherein the impact interval of the laser beam is 5 seconds, the moving distance in the X-axis direction is a light spot distance, and after the impact in the X-axis direction is finished, the next round of laser impact treatment is performed, and the process is repeated until the impact on the whole surface is finished.
The method for preparing graphene by laser impact on carbon material in liquid medium according to claim 6, wherein the material of the first rotating shaft (18) is copper;
the method for preparing graphene by laser impact on carbon material in liquid medium according to claim 6, wherein laser parameters of laser emitted by the high-power laser generating device are as follows: laser wavelength 1064nm, pulse width 10ns, spot diameter 3mm, laser energy 1J, frequency 10 Hz.
The invention has the beneficial effects that: 1. the laser power density is extremely high, high-temperature and high-pressure plasma is formed between graphite and a dilute sulfuric acid solution medium at the moment of laser shock treatment of the highly-oriented pyrolytic graphite in the dilute sulfuric acid solution, so that the graphite crystal is promoted to be converted into a graphene structure, and the preparation process of the graphene is completed in a very short time of pulse laser; 2. the plasma can be attached to the surface of the copper foil under the driving of the electric field, and is continuously attached, and the copper foil continuously moves, so that the aim of continuously preparing the graphene on a large scale is finally fulfilled.
Drawings
FIG. 1 is a schematic diagram of the structure of the device of the present invention.
In the figure: 1. a water outlet; 2. a water inlet; 3. a power source; 4. an electric pump; 5. a power transformer; 6. a liquid storage tank; 7. a water pipe; 8. a flow regulator; 9. a computer; 10. a digital controller; 11. a high power pulsed laser generating device; 12. a collimating beam expander; 13. a focusing lens; 14. a convex lens; 15. a laser beam; 16. a total reflection mirror; 17. a support plate; 18. a first rotating shaft; 19. an insulating shaft sleeve; 20. a first motor; 21. a second motor; 22. a bearing; 23. copper foil; 24. a second rotation shaft; 25. a lead screw; 26. highly oriented pyrolysis graphite blocks; 27. a reaction vessel; 28. a copper pillar; 29. a three-dimensional mobile platform; 30. a laser processing head; 31. a focusing lens; 32. and (4) protective glasses.
Detailed Description
The technical solution of the present invention will be described in more detail below with reference to the accompanying drawings, but the present invention is not limited thereto.
As shown in fig. 1, the laser generator comprises a laser generating system and a reaction vessel 27 located below the laser generating system, wherein two sides of the bottom of the reaction vessel 27 are provided with a lead screw 25 in a Y-axis direction, the lead screw 25 is provided with a support plate 17, the support plate 17 can be driven by a second motor 21 to move back and forth in the Y-axis direction on the lead screw 25, the support plate 17 is provided with a second rotating shaft 24 and a first rotating shaft 18, the second rotating shaft 24 is wound with a copper foil 23, the first rotating shaft 18 is provided with a first motor 20, the copper foil 23 is wound on the first rotating shaft 18 from the second rotating shaft 24 by the rotation of the first motor 20, the first motor 20 is connected with the right end of the first rotating shaft 18 through an insulating shaft sleeve 19, the first rotating shaft 18 is connected with the positive pole of a power supply 3, two ends of the first rotating shaft 18 are provided with bearings and fixed on the, bearings are also arranged at two ends of the second rotating shaft 24 and fixed on the supporting plate 17, a copper column 28 is arranged at one side in front of the interior of the reaction container 27 and connected with the negative electrode of the power supply 3, and the power supply 3 is connected with the power supply transformer 5 so as to ensure that the voltage of the power supply 3 is 24V; a highly oriented pyrolytic graphite block 26 is placed in the reaction vessel 27, and the support plate 17 provided with the copper foil is moved to a proper position with the highly oriented pyrolytic graphite block 26 through the lead screw 25; the reaction container 27 is filled with a dilute sulfuric acid solution, and the solution depth exceeds the height of the highly oriented pyrolytic graphite block 26; high oriented pyrolytic graphite piece 26 top fixed mounting has high power pulse laser generating device 11, the laser beam 15 that high power pulse laser generating device 11 sent radiates to from laser beam processing head 30 behind collimation beam expanding lens 12, the total reflection mirror 16 on the high oriented pyrolytic graphite piece 26, wherein, collimation beam expanding lens 12 comprises focusing lens 13 and concave lens 14. Preferably, the device further comprises a flow regulator 8, a liquid storage tank 6 and an electric pump 4, wherein one end of the flow regulator 8 is connected with the liquid storage tank 6, the other end of the flow regulator is connected with the water inlet 2 of the reaction container 27 through the electric pump 4, and the water outlet 1 of the reaction container 27 is connected with the liquid storage tank 6. In order to realize intelligent control, the power supply 3 is connected with a power transformer 5, the three-dimensional mobile platform 29, the first motor 20, the second motor 21 and the power transformer 5 are all connected with a digital controller 10, and the digital controller 10, the high-power pulse laser generating device 11 and the flow regulator 8 are all connected with a computer 9.
When graphene is prepared, preparing 98% concentrated sulfuric acid and water according to the proportion of 1: 10; placing the highly oriented pyrolytic graphite block in a reaction container, and adjusting the support plate along the Y axis through a second motor to keep a proper distance between the copper foil of the highly oriented pyrolytic graphite block and the highly oriented pyrolytic graphite block; adjusting the three-dimensional moving platform to enable the laser focus to be located on the upper surface of the highly-oriented pyrolytic graphite block, so that the laser beam is vertically incident on the upper surface of the highly-oriented pyrolytic graphite block; injecting a dilute sulfuric acid solution into the reaction container, adjusting the flow regulator to set the flow to be 0.8L/s, and opening the electric pump to inject the sulfuric acid solution into the reaction container until the liquid level exceeds the upper surface of the highly oriented pyrolytic graphite block by 12 cm; connecting the positive pole of a power supply with a copper column at the front end of the reaction container through a wire, connecting the negative pole of the power supply with the tail end of the first rotating shaft, and turning on the power supply through a digital controller to form an electric field environment in the reaction container; turning on a high-power pulse laser generating device, and setting laser parameters through a computer, wherein the laser wavelength is 1064nm, the pulse width is 10ns, the spot diameter is 3mm, the laser energy is 1J, and the frequency is 10 Hz; the high-power laser generating device emits laser, the laser is focused on the upper surface of the high-orientation pyrolytic graphite block through the laser processing head, the three-dimensional moving platform is controlled by the digital controller to move in the X-axis direction for a feeding distance of 3mm, after the three-dimensional moving platform impacts a certain distance, the three-dimensional moving platform moves for 3mm in the Y-axis direction, the impact is continued, meanwhile, the first motor rotates for a distance of 6mm, and after the feeding of the high-orientation pyrolytic graphite block in the X-axis direction is finished, the steps are repeated; and closing all the devices, taking down the copper foil, and carrying out subsequent graphene transfer treatment.
Claims (9)
1. The device for preparing graphene by laser impact of carbon materials in liquid media is characterized by comprising a three-dimensional moving platform (29) and a reaction vessel (27), the reaction vessel (27) is positioned on the three-dimensional moving platform (29), a highly oriented pyrolytic graphite block (26) and a lead screw (25) are arranged in the reaction vessel (27), the screw rod (25) is in threaded connection with the support plate (17), the tail end of the screw rod (25) is provided with a second motor (21), a second rotating shaft (24) and a first rotating shaft (18) are arranged on the supporting plate (17), a copper foil (23) is wound on the second rotating shaft (24), a first motor (20) is installed on the first rotating shaft (18), the copper foil (23) is wound from the second rotating shaft (24) to the first rotating shaft (18) by means of the rotation of the first motor (20); high power pulse laser generating device (11) are equipped with to reaction vessel (27) top, be equipped with copper post (28) in reaction vessel (27), copper post (28) with first rotation axis (18) link to each other with the two poles of the earth of power (3) respectively.
2. The device for preparing graphene by laser impact on carbon material in liquid medium according to claim 1, further comprising a flow regulator (8), a liquid storage tank (6) and an electric pump (4), wherein one end of the flow regulator (8) is connected with the liquid storage tank (6), the other end of the flow regulator is connected with a water inlet (2) of a reaction vessel (27) through the electric pump (4), and a water outlet (1) of the reaction vessel (27) is connected with the liquid storage tank (6).
3. The device for preparing graphene by laser impact on carbon material in liquid medium according to claim 1 or 2, wherein the laser beam (15) emitted by the high-power pulse laser generating device (11) passes through the collimating beam expander (12) and the holophote (16) and then is radiated from a laser processing head (30) onto the high-orientation pyrolytic graphite block (26).
4. The device for preparing graphene by laser impact on carbon material in liquid medium according to claim 1 or 2, characterized in that the water outlet (1) of the reaction vessel (27) is connected with a liquid storage tank (6), one end of a flow regulator (8) is connected with the liquid storage tank (6), and the other end is connected with the water inlet (2) of the reaction vessel (27) through an electric pump (4).
5. The device for preparing graphene by laser impact on carbon material in liquid medium according to claim 4, wherein the power supply (3) is connected with a power transformer (5), the three-dimensional moving platform (29), the first motor (20), the second motor (21) and the power transformer (5) are all connected with a digital controller (10), and the digital controller (10), the high-power pulse laser generation device (11) and the flow regulator (8) are all connected with a computer (9).
6. A method for preparing graphene by laser impact of carbon materials in a liquid medium comprises the following steps: s1, preparing a dilute sulfuric acid solution; s2, setting the reaction device: placing the highly oriented pyrolytic graphite block (26) in a reaction container (27), and adjusting a support plate (17) along the Y axis through a second motor (21) to keep a specified distance between a copper foil (23) and the highly oriented pyrolytic graphite block (26); s3, adjusting the three-dimensional moving platform (29) to enable the laser focus to be positioned on the upper surface of the highly oriented pyrolytic graphite block (26), so that the laser beam is vertically incident on the upper surface of the highly oriented pyrolytic graphite block (26); s4, injecting a dilute sulfuric acid solution into the reaction container (27): adjusting the flow regulator (7) to set the flow at 0.65-1L/s, and opening the electric pump (5) to inject the sulfuric acid solution into the reaction container (27) until the liquid level exceeds the upper surface of the highly oriented pyrolytic graphite block (26); s5, connecting the positive pole of the power supply with the copper column (28) at the front end of the reaction container (27) through a lead, connecting the negative pole of the power supply with the tail end of the first rotating shaft (18), and turning on the power supply (3) through the digital controller (10) to form an electric field environment in the reaction container (27); s6, turning on a high-power pulse laser generating device (11), setting laser parameters through a computer (9), focusing laser on the upper surface of a highly-oriented pyrolytic graphite block (26) by the laser emitted by the high-power laser generating device through a laser processing head (32), controlling the three-dimensional moving platform (29) to perform feed motion along the X-axis direction by a digital controller (10), moving the three-dimensional moving platform (29) for a spot distance along the Y-axis direction after impacting for a certain distance, continuing impacting, starting to rotate a first motor (20) at the same time, and repeating the steps after the feeding of the highly-oriented pyrolytic graphite block (26) along the X-axis direction is finished; and S7, closing all devices, taking down the copper foil (23), and carrying out subsequent graphene transfer and purification treatment.
7. The method for preparing graphene by laser impact on carbon material in liquid medium according to claim 6, wherein the impact interval of the laser beam is 5 seconds, the moving distance in the X-axis direction is a light spot distance, and after the impact in the X-axis direction is finished, the next round of laser impact treatment is performed, and the process is repeated until the impact on the whole surface is finished.
8. The method for preparing graphene by laser impact on carbon material in liquid medium according to claim 6, wherein the material of the first rotating shaft (18) is copper.
9. The method for preparing graphene by laser impact on carbon material in liquid medium according to claim 6, wherein laser parameters of laser emitted by the high-power laser generating device are as follows: laser wavelength 1064nm, pulse width 10ns, spot diameter 3mm, laser energy 1J, frequency 10 Hz.
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| CN108516537A (en) * | 2018-03-29 | 2018-09-11 | 江苏大学 | A kind of continuous apparatus and method for quickly preparing graphene film on copper foil |
| CN109444202A (en) * | 2018-09-13 | 2019-03-08 | 江苏大学 | A kind of experimental detection device and method preparing graphene using laser |
| CN110373714B (en) * | 2019-06-03 | 2020-12-18 | 杭州电子科技大学 | Method for rapidly preparing large-size high-quality single-layer graphene at room temperature |
| CN110828374B (en) * | 2019-11-29 | 2020-07-07 | 广东工业大学 | Method and device for repairing open circuit defect of chip internal circuit |
| CN111716715B (en) * | 2020-05-14 | 2021-12-28 | 青岛科技大学 | Laser micro-nano deposition printing method based on liquid phase optical drive |
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