CN104692371A - Method and device for continuously producing graphene film under micro-positive pressure - Google Patents
Method and device for continuously producing graphene film under micro-positive pressure Download PDFInfo
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- CN104692371A CN104692371A CN201510087684.8A CN201510087684A CN104692371A CN 104692371 A CN104692371 A CN 104692371A CN 201510087684 A CN201510087684 A CN 201510087684A CN 104692371 A CN104692371 A CN 104692371A
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Abstract
The invention discloses a method and a device for continuously producing a graphene film under micro-positive pressure. The device comprises a pre-heating chamber, a high-temperature settling chamber, a pre-cooling chamber and a quick cooling chamber which are tightly connected in sequence, wherein each working chamber is provided with a gas inlet tube, a gas outlet tube, a pressure meter, a flow rate meter, a timer and a thermometer; every two adjacent chambers are separated by a heat insulating partition plate; each working chamber is provided with a plurality of rotary roller shafts; a graphene substrate copper foil formed by roller shafts continopusly moves, so that a continuous production process of settling and moving the graphene is formed.
Description
Technical field
The invention belongs to grapheme material technical field, relate to a kind of method of pressure-fired continuous seepage graphene film, be specifically related to a kind of method and device of pressure-fired continuous seepage graphene film.
Background technology
Graphene-structured is highly stable, and up to now, investigator does not find the situation having carbon atom to lack in Graphene yet.Connection in Graphene between each carbon atom is very pliable and tough, and when applying external mechanical force, carbon atom face with regard to flexural deformation, thus makes carbon atom need not rearrange to adapt to external force, also just maintains Stability Analysis of Structures.This stable crystalline network makes carbon atom have outstanding electroconductibility.When electronics in Graphene moves in track, or foreign atom can not be introduced and scattering occurs because of lattice imperfection.Because interatomic force is very strong, at normal temperatures, even if around carbon atom telescopes, the interference that in Graphene, electronics is subject to is also very little, and meanwhile, Graphene is the thinnest in the world is also the hardest
nano material, it is almost completely transparent, only absorbs the light of 2.3%;
thermal conductivityup to 5300 W/(mK), higher than carbon nanotube and diamond, under normal temperature, its electronic mobility is more than 15 000 cm2/(Vs), again than CNT (carbon nano-tube) or silicon wafer height, and
resistivityonly about 10-6 Ω cm, than copper or silver lower, be the material that world resistivity is minimum.Because its resistivity is extremely low, the speed that electronics runs is exceedingly fast, and Graphene is electroconductibility best material in the world, and electronics movement velocity wherein reaches 1/300 of the light velocity, considerably beyond the movement velocity of electronics in general conductor.Because the advantages such as its high strength, high heat conductance, high conductivity and high-specific surface area receive the extensive attention of investigator.At present, the method preparing Graphene both at home and abroad mainly contains several as follows:
(1) micromechanics stripping method; The Graphene quality that this method obtains is high, but can only obtain a limited number of graphene film, and based on being only applicable to, the electrical properties of Graphene is probed in research.
(2) epitaxial growth method; This method preparation condition is harsh, all requires to carry out under high temperature high vacuum or certain condition such as particular atmosphere and single crystalline substrate, and obtained Graphene is not easily separated from substrate, can not prepare Graphene on a large scale.
(3) oxidation-reduction method; The method be at present comparatively common low-cost high-efficiency prepare the chemical process of large-area graphene layer material, but the Graphene obtained contains a large amount of oxy radicals and defect, its conductivity is lower, and reductive agent major part is poisonous, makes preparation process there is environmental pollution.
(4) chemical Vapor deposition process; This method can meet the requirement that high-quality graphene is prepared in mass-producing, but cost is higher, complex process.
(5) electrolytic process; This method can synthesize a large amount of Graphenes, but the surface of the Graphene synthesized is all with a large amount of positive ion negative ions or organism.Aforesaid method respectively has limitation part, therefore people urgently wish to develop a kind of environmental friendliness, technique simple, can the less Graphene method of large-scale production place defect and device.
(6) liquid phase ultrasonic stripping method is by the crushing effect of ultrasonic wave to powder, in organic solvent graphite flake layer is peeled off to the method (J.Mater.Chem.19,3367-3369,2009) preparing Graphene.Organic solvent not only provides preparation place, and can be played the effect promoting graphite linings separation, dispersion, protection, isolation Graphene by control condition.The method not only can carry out large volume preparation, and simultaneously owing to not introducing chemical process, Graphene crystalline structure have also been obtained better protecting, the Graphene of availability excellence.But it is high to there is energy consumption in this method, inefficient defect.And microwave liquid phase stripping method prepares Graphene, energy consumption is low, and product size is evenly distributed, and energy stable suspersion is in reaction solution.
These graphene preparation methods can obtain greatly the Graphene sample of use for laboratory under given conditions above, but, prepare big area fast, the method for high-quality graphene never makes a breakthrough, significantly limit efficiency, output and cost prepared by Graphene, hinder its further industrialized development.
China Patent No. CN201410139728.2, discloses a kind of continuous prodution graphene powder full scale plant and method thereof.The method is that the proportioning by controlling dispersion agent carrys out adjustment sheet surface tension, then obtains by the synergy of continuous ultrasound and microwave the Graphene that is uniformly dispersed after mixing with graphite; Add slurry and prepare slurry to graphene dispersing solution, adopt Frequency Conversion Technique of Centrifugal Spraying Drying Equipment to carry out spraying dry, granulation to slurry.This method can prepare graphene powder on a large scale, but does not possess and prepare graphene film condition on a large scale.Chinese patent CN201210561455.1, discloses a kind of volume to volume Graphene Preparation equipment, comprises airtight vacuum chamber; The roller system for driving graphene growth foil to move is provided with in described vacuum chamber, foil is driven to move by roller system, larger paper tinsel volume can be carried out produce, but the method still wants blowing out discharging after completing a volume graphene growth, and production carries out under airtight vacuum, equipment seal request is tight, high to the Copper Foil material purity requirement of the graphene-based end, production cost is high and control, still can not cannot apply on a large scale the quality of graphene film.Chinese patent CN201310290165.2, disclose the method for synthesizing graphite alkene under a kind of positive pressure, it is characterized in that: Graphene at the high temperature sedimentation indoor growing of chemical meteorology deposition system, growth conditions be in high temperature settling pocket pressure higher than the positive pressure of standard atmospheric pressure.Although the method is produced under positive pressure, owing to being carry out under sealing condition, still can not carry out suitability for industrialized production continuously, due in confined conditions, still can not understand the quality of graphene film in advance, and production cost be high.
Given this, the present invention is directed to the technical barrier of current continuous production big area, high-quality graphene film, and explore a kind of method and device of pressure-fired continuous seepage graphene film.The method and equipment is adopted to prepare Graphene; relative to existing method, there is advantage rapidly, continuously; the mass-producing growth of big area, high-quality graphene film can be carried out; this plays great prograding by numerous application of graphene film and industrialization thereof, produces far-reaching influence to the strategic field such as novel conductive film, nanometer integrated-optic device, information, the energy.
Summary of the invention
In order to solve existing graphene film continuous seepage Problems existing; the present invention proposes a kind of method and device of pressure-fired continuous seepage graphene film; there is the advantage of uninterrupted continuous production; and equipment is simple; operation simple and feasible; easily be automated and suitability for industrialized production, and the problem of high-quality graphene film large-scale production can be solved.
For achieving the above object, solution of the present invention is: a kind of method of pressure-fired continuous seepage graphene film and device, this device comprises by close-connected preheating chamber, high temperature settling pocket, fore-cooling room, fast cooling room successively, all there are inlet pipe, escape pipe, pressure warning unit, under meter, timing register and thermometer in each working spaces, fire wall is all had to separate between every adjacent chamber, all there is the roll shaft of multiple rotation each working spaces, form not stopping transport of Copper Foil of the graphene-based end by roll shaft dynamic, form the continuous flow procedure of sedimentation limit, Graphene limit motion.
Described preheating chamber is rectangle working spaces, it is characterized in that preheating chamber be whole device foremost, shell is that stainless steel is formed, liner thermal insulation material, there is wicket preheating chamber front end, so that a roll-leaf material is finished timely replacing, there is foil support preheating chamber front end, roll shaft is equipped with in two side, foil is positioned on indoor roll shaft, there are purgative gas inlet pipe and escape pipe in the side of preheating chamber, inlet pipe installs under meter and program-controlled electric magnet valve, preheating chamber top setting pressure meter and thermometer, preheating chamber and high temperature settling pocket abutting end are separated by fire wall, fire wall has charging gap at the same level place of roll shaft, foil enters high temperature settling pocket by gap.Preheating chamber length is 1-2 rice, and width is 0.5-1 rice, is highly 0.5-1 rice.
Described high temperature settling pocket is the groundwork room of Graphene sedimentation growth on foil, it is characterized in that high temperature settling pocket is rectangle working spaces, the front end of high temperature settling pocket is connected with preheating chamber, rear end is connected with fore-cooling room, high temperature settling pocket shell is that stainless steel is formed, liner thermal insulation material, there is manhole side, to keep in repair.There are inlet pipe and the escape pipe of purgative gas in the side of high temperature settling pocket, inlet pipe installs under meter and program-controlled electric magnet valve, the side bottom of high temperature settling pocket is provided with unstripped gas inlet pipe, unstripped gas inlet pipe is provided with under meter and program-controlled electric magnet valve, top setting pressure meter, thermometer, timing register and oxygen detection instrument, the two ends of high temperature settling pocket are separated by fire wall, the both sides of high temperature settling pocket are provided with 2-4 group roll shaft, foil is positioned on roll shaft, roundabout advance in high temperature settling pocket, foil is 30-120 minute in the roundabout time of high temperature settling pocket, the same level place of fire wall and hithermost roll shaft has charging gap and discharging gap, foil enters high temperature settling pocket by charging gap, gone out by discharging gap and enter next stage working spaces and fore-cooling room from high temperature settling pocket.High temperature settling pocket length is 2-5 rice, and width is 0.5-1 rice, is highly 0.5-1 rice.
Described high temperature settling pocket, is characterized in that there is nonstorage calorifier in high temperature settling pocket, and nonstorage calorifier is electric heater unit or high-temperature molten salt heating device for coil, and the temperature-controllable of heating unit is built in 800-1200 DEG C.
Described high temperature settling pocket, the purgative gas that it is characterized in that entering high temperature settling pocket is hydrogen, helium, the one of argon gas or gas mixture arbitrarily, and the unstripped gas entering high temperature settling pocket is the one of high-purity methane high purity acetylene or paraffin gasification gas.
Described fore-cooling room is the working spaces of subordinate of high temperature settling pocket, enter fore-cooling room from the high temperature settling pocket foil with Graphene thin layer out tentatively to cool, it is characterized in that fore-cooling room's shell is that stainless steel is formed, liner thermal insulation material, roll shaft is equipped with in two side, foil is positioned on indoor roll shaft, there are inlet pipe and escape pipe in the side of fore-cooling room, inlet pipe installs under meter and program-controlled electric magnet valve, top, fore-cooling room setting pressure meter and thermometer, fore-cooling room and high temperature settling pocket abutting end are separated by fire wall, fire wall has charging gap at the same level place of roll shaft.Preheating chamber length is 1-2 rice, and width is 0.5-1 rice, is highly 0.5-1 rice.
Described fast cooling room is last working spaces of this device, it is characterized in that fast cooling chamber enclosure is that stainless steel chuck is formed, chuck is built with cooling oil or water coolant, roll shaft is equipped with in two side, foil is positioned on indoor roll shaft, graphene film detector is installed above fast cooling room, in the sedimentation of the indoor cool to room temperature of fast cooling by the foil of Graphene thin layer through graphene film detector, detector detects Graphene thin layer quality in time, as satisfactory quality, then device is not reported to the police, as quality is undesirable, then detector is reported to the police, producers adjust whole apparatus system.Fast cooling room length is 1-2 rice, and width is 0.5-1 rice, is highly 0.5-1 rice.
Described roll shaft, it is characterized in that all roll shafts of whole device drag running by same motion-work wheel, the rotating speed of each roll shaft is identical, and the power of motion-work wheel is supplied by power set.
Described a kind of pressure-fired continuous seepage graphene film device, is characterized in that whole continuous seepage graphene film device internal pressure is 0.05-0.5Mpa.
Described foil, is characterized in that the material of foil is Copper Foil, and the thickness of Copper Foil is 0.1-0.5mm, and copper purity is greater than 97%.
A method for pressure-fired continuous seepage graphene film, its feature is: described graphene film is deposition growing in the high temperature settling pocket of chemical meteorology deposition system, and growth conditions is the pressure-fired condition of a little higher than standard atmospheric pressure of pressure in high temperature settling pocket.Be characterized in carrying out as follows:
1, the debug phase, Copper Foil is placed on the foil support of preheating chamber, and Copper Foil is positioned on corresponding roll shaft by the gap of each fire wall respectively, debugging transmission mechanism, setting speed, opens timing register, ON cycle refrigerating unit, power set is in state to be launched;
2, the cleaning systems stage, open the preheating apparatus of preheating chamber, and open intake valve and the air outlet valve of the purgative gas of each working spaces, pass into oxygenless gas to whole system and clean each working spaces, make to be oxygen-free environment in working spaces; To continue to be filled with in system in oxygenless gas to whole system as positive pressure and observe the oxygen gas component of oxygen detection instrument, if oxygen content is in setting range, then the intake valve of closure systems and air outlet valve;
3, the system temperature rise period, the high temperature sedimentation room temp of completing steps 2 was risen to 800-1300 DEG C in 50-150 minute, and keeps corresponding steady temperature 5-60 minute;
4, sedimentation growth phase, after the constant temperature stage terminates, thermostat temperature is kept to open intake valve and the extraction valve of the unstripped gas of high temperature settling pocket, the oxygenless gas of to be the carbonaceous gas of 50sccm-500sccm and flow by flow be 500sccm-4000sccm passes into 10-30 minute to high temperature settling pocket simultaneously, start transmission mechanism, each roll shaft rotates, and foil moves, and the system internal gas pressure of maintenance is less than 0.1MPa;
5, cooling detecting stage, continuous sedimentation growing graphene on foil in high temperature settling pocket, along with time lapse, when going out Graphene foil from high temperature settling pocket by fore-cooling room and fast cooling, at this moment Graphene coating temperature is down to room temperature, Graphene thin layer by Graphene detector to determine Graphene thin layer quality, as do not met specification of quality, then system is suitably adjusted, as conformed to quality requirements, then system continues steady running, until when the corresponding volume of production is long, take out foil, have graphene film in the surface growth of described Copper Foil.
Beneficial effect of the present invention is:
1, the present invention's synthesizing graphite alkene under pressure-fired condition, low to the specification of quality of Copper Foil, solving existing market only has the Copper Foil of individual species to can be used for the big area synthesis of copper substrate Graphene, multiple Copper Foil is made to can be used for the growth of Graphene, avoid Graphene suitability for industrialized production to limit by Copper Foil raw material, significant to the commercial application of Graphene;
2, the present invention adopts each stage to provide required environment to graphene growth, the motion of graphene growth foil is driven by arranging roll shaft, it is temperature required that the graphene growth foil be positioned on roll shaft is heated to graphene growth by high temperature settling pocket, and in this section of graphene growth foil, foil completes graphene growth in ceaselessly moving process, can meet Graphene rapidly, continuously with large-scale industrialized production demand.
3, by being arranged at fast cooling room Graphene detector, can in process of production, the quality of dynamic monitoring graphene film, guarantees graphene film reliable in quality, and with low cost.
Accompanying drawing explanation
Fig. 1 is method and the apparatus structure schematic diagram of a kind of pressure-fired continuous seepage of the present invention graphene film;
Number in the figure: 1, preheating chamber, 101, preheating chamber thermometer, 102, preheating chamber pressure warning unit, 103, timing register, 104, fire wall, 105, foil support, 2, high temperature settling pocket, 21, settling pocket thermometer, 22, settling pocket pressure warning unit, 23, settling pocket oxygen tester, 24, purgative gas escape pipe, 25, purgative gas inlet pipe, 26, under meter, 27, magnetic valve
3, fore-cooling room, 4, fast cooling room, 41, Graphene detector, 5, unstripped gas inlet pipe, 51, flow of feed gas gauge, 52 unstripped gas magnetic valves, 6, heating unit, 7, roll shaft, 8, foil, 9, power set.
Embodiment
For a better understanding of the present invention, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to following specific embodiment.
As shown in Figure 1, a kind of method of pressure-fired continuous seepage graphene film and device, this device comprises by close-connected preheating chamber 1, high temperature settling pocket 2, fore-cooling room 3, fast cooling room 4 successively, all there are purgative gas inlet pipe 24, escape pipe 25, pressure warning unit, under meter, timing register and thermometer in each working spaces, fire wall is all had to separate between every adjacent chamber, all there is the roll shaft 7 of multiple rotation each working spaces, form not stopping transport of copper foil tape of the graphene-based end by roll shaft 7 dynamic, form the continuous flow procedure of sedimentation limit, Graphene limit motion.
Described preheating chamber 1 is rectangle working spaces, it is characterized in that preheating chamber 1 for whole device foremost, shell is that stainless steel is formed, liner thermal insulation material, there is wicket preheating chamber 1 front end, so that a roll-leaf material 8 is finished timely replacing, there is foil support 105 preheating chamber 1 front end, roll shaft 7 is equipped with in two side, foil 8 is positioned on indoor roll shaft 8, there are purgative gas inlet pipe 24 and escape pipe 25 in the side of preheating chamber 1, inlet pipe installs under meter and program-controlled electric magnet valve, preheating chamber 1 top setting pressure meter 101, timing register, 103 and thermometer 102, preheating chamber 1 and high temperature settling pocket 2 abutting end are separated by fire wall 104, fire wall 104 has charging gap at the same level place of roll shaft 7, foil 8 enters high temperature settling pocket 2 by gap.Preheating chamber 1 length is 1-2 rice, and width is 0.5-1 rice, is highly 0.5-1 rice.
Described high temperature settling pocket 2 is Graphene sedimentation growth groundwork rooms on foil 8, it is characterized in that high temperature settling pocket 2 is for rectangle working spaces, the front end of high temperature settling pocket 2 is connected with preheating chamber 1, rear end is connected with fore-cooling room 3, high temperature settling pocket 2 shell is that stainless steel is formed, liner thermal insulation material, there is manhole side, to keep in repair.There are inlet pipe 24 and the escape pipe 25 of purgative gas in the side of high temperature settling pocket 2, inlet pipe installs under meter 26 and program-controlled electric magnet valve 27, the side bottom of high temperature settling pocket 2 is provided with unstripped gas inlet pipe 5, unstripped gas inlet pipe is provided with under meter 51 and program-controlled electric magnet valve 52, top setting pressure meter 21, thermometer 22, oxygen detection instrument 23, the two ends of high temperature settling pocket 2 are opened every 104 by fire wall, the both sides of high temperature settling pocket 2 are provided with 2-4 group roll shaft 7, foil 8 is positioned on roll shaft 7, roundabout advance in high temperature settling pocket 2, foil 8 is 30-120 minute in the roundabout time of high temperature settling pocket 2, the same level place of fire wall and hithermost roll shaft 7 has charging gap and discharging gap, foil 8 enters high temperature settling pocket 2 by charging gap, gone out by discharging gap and enter next stage working spaces and fore-cooling room 3 from high temperature settling pocket 2.High temperature sedimentation 2 Room length is 2-5 rice, and width is 0.5-1 rice, is highly 0.5-1 rice.
Described high temperature settling pocket, is characterized in that there is nonstorage calorifier 6 in high temperature settling pocket 2, and nonstorage calorifier 6 is electric heater unit or high-temperature molten salt heating device for coil, and the temperature-controllable of heating unit is built in 800-1200 DEG C.
Described high temperature settling pocket, the purgative gas that it is characterized in that entering high temperature settling pocket 2 is hydrogen, helium, the one of argon gas or gas mixture arbitrarily, and the unstripped gas entering high temperature settling pocket 2 is the one of high-purity methane high purity acetylene or paraffin gasification gas.
Described fore-cooling room 3 is working spacess of subordinate of high temperature settling pocket 2, enter fore-cooling room 3 from high temperature settling pocket 3 foil 8 with Graphene thin layer out tentatively to cool, it is characterized in that fore-cooling room's shell is that stainless steel is formed, liner thermal insulation material, roll shaft 7 is equipped with in two side, foil 8 is positioned on indoor roll shaft 7, there are inlet pipe and escape pipe in the side of fore-cooling room 3, inlet pipe installs under meter and program-controlled electric magnet valve, top, fore-cooling room setting pressure meter and thermometer, fore-cooling room and high temperature settling pocket abutting end are separated by fire wall, fire wall has charging gap at the same level place of roll shaft.Preheating chamber 3 length is 1-2 rice, and width is 0.5-1 rice, is highly 0.5-1 rice.
Described fast cooling room 4 is last working spaces of this device, it is characterized in that fast cooling room 4 shell is that stainless steel chuck is formed, chuck is built with cooling oil or water coolant, roll shaft 7 is equipped with in two side, foil 8 is positioned on indoor roll shaft 7, graphene film detector 41 is installed above fast cooling room, in fast cooling room 4 the sedimentation of cool to room temperature by the foil 8 of Graphene thin layer when the graphene film detector 41, detector detects Graphene thin layer quality in time, as satisfactory quality, then device is not reported to the police, as quality is undesirable, then detector is reported to the police, producers adjust whole apparatus system.Fast cooling room 4 length is 1-2 rice, and width is 0.5-1 rice, is highly 0.5-1 rice.
Described roll shaft 7, it is characterized in that all roll shafts 7 of whole device drag running by same motion-work wheel, the rotating speed of each roll shaft is identical, and the power of motion-work wheel is supplied by power set 9.
Described a kind of pressure-fired continuous seepage graphene film device, is characterized in that whole continuous seepage graphene film device internal pressure is 0.05-0.5Mpa.
Described foil 8, is characterized in that the material of foil 8 is Copper Foil, and the thickness of Copper Foil is 0.1-0.5mm.
Embodiment 1
The present embodiment, a kind of method of pressure-fired continuous seepage graphene film is carried out as follows:
1, the debug phase, long 50 meters wide 30 centimetres of Copper Foils are placed on the foil support of preheating chamber, and Copper Foil is positioned on corresponding roll shaft by the gap of each fire wall respectively, open timing register, debugging transmission mechanism, setting speed, makes foil be 40 minutes in the roundabout time of high temperature settling pocket, ON cycle refrigerating unit, power set is in state to be launched.
2, the cleaning systems stage, open the preheating apparatus of preheating chamber, and open intake valve and the air outlet valve of the purgative gas of each working spaces, pass into each working spaces of cleaning to whole system with 400sccm argon gas, make to be oxygen-free environment in working spaces; Continuing in system, be filled with pressure in argon gas to whole system is 0.1Mpa, and observes the oxygen gas component of oxygen detection instrument, and oxygen content, at below 0.01PPM, closes intake valve and the extraction valve of each working spaces; Air pressure is herein positive pressure, confirms through great many of experiments, and when positive pressure is 0.05MPa-0.25MPa, reaction effect is best, is preferably 0.1Mpa here.
3, the system temperature rise period, the high temperature sedimentation room temp of completing steps 2 is risen to 1000 DEG C in 50 minutes, and keep the steady temperature 30 minutes of 1000 DEG C.
4, sedimentation growth phase, after the constant temperature stage terminates, thermostat temperature is kept to open intake valve and the air outlet valve of the unstripped gas of high temperature settling pocket, the argon gas of to be the high-purity methane gas of 50sccm and flow by flow be 500sccm passes into 40 minutes to high temperature settling pocket simultaneously, start transmission mechanism, each roll shaft rotates, and foil moves, and the system internal gas pressure of maintenance is 0.01MPa.
5, cooling detecting stage, continuous sedimentation growing graphene on foil in high temperature settling pocket, along with time lapse, when going out Graphene foil from high temperature settling pocket by fore-cooling room and fast cooling, at this moment Graphene coating temperature has been down to room temperature about 25 DEG C, Graphene thin layer is detected by Graphene detector, to determine Graphene thin layer quality, as do not met specification of quality, then system is suitably adjusted, as conformed to quality requirements, then system continues steady running, until when the corresponding volume of production is long, take out foil, graphene film is had in the surface growth of described Copper Foil.
Embodiment 2
1, the debug phase, the extension Copper Foil of long 30 meters wide 20 centimetres is placed on the foil support of preheating chamber, and Copper Foil is positioned on corresponding roll shaft by the gap of each fire wall respectively, open timing register, debugging transmission mechanism, setting speed, makes foil be 30 minutes in the roundabout time of high temperature settling pocket, ON cycle refrigerating unit, power set is in state to be launched.
2, the cleaning systems stage, open the preheating apparatus of preheating chamber, and open intake valve and the air outlet valve of the purgative gas of each working spaces, pass into each working spaces of cleaning to whole system with 300sccm argon gas, make to be oxygen-free environment in working spaces; Continuing in system, be filled with pressure in argon gas to whole system is 0.1Mpa, and observes the oxygen gas component of oxygen detection instrument, and oxygen content, at below 0.015PPM, closes intake valve and the extraction valve of each working spaces; Air pressure is herein positive pressure, confirms through great many of experiments, and when positive pressure is 0.05MPa-0.25MPa, reaction effect is best, is preferably 0.15Mpa here.
3, the system temperature rise period, the high temperature sedimentation room temp of completing steps 2 is risen to 1100 DEG C in 40 minutes, and keep the steady temperature 30 minutes of 1100 DEG C.
4, sedimentation growth phase, after the constant temperature stage terminates, thermostat temperature is kept to open intake valve and the air outlet valve of the unstripped gas of high temperature settling pocket, the argon gas of to be the high-purity methane gas of 40sccm and flow by flow be 400sccm passes into 30 minutes to high temperature settling pocket simultaneously, start transmission mechanism, each roll shaft rotates, and foil moves, and the system internal gas pressure of maintenance is 0.01MPa.
5, cooling detecting stage, continuous sedimentation growing graphene on foil in high temperature settling pocket, along with time lapse, when going out Graphene foil from high temperature settling pocket by fore-cooling room and fast cooling, at this moment Graphene coating temperature has been down to 26 DEG C, Graphene thin layer is detected by Graphene detector, to determine Graphene thin layer quality, as do not met specification of quality, then system is suitably adjusted, as conformed to quality requirements, then system continues steady running, until when the corresponding volume of production is long, takes out foil, have graphene film in the surface growth of described Copper Foil.
Above-described embodiment just illustrates technical conceive of the present invention and feature, its objective is and those of ordinary skill in the art can be understood feature of the present invention and implement according to this, can not limit the scope of the invention with this.Every equivalence carried out according to the essence of content of the present invention changes or modifies, and all should be encompassed in protection scope of the present invention.
Claims (10)
1. the method for a pressure-fired continuous seepage graphene film and device, it is characterized in that this device comprises by close-connected preheating chamber, high temperature settling pocket, fore-cooling room, fast cooling room successively, all there are inlet pipe, escape pipe, pressure warning unit, under meter, timing register and thermometer in each working spaces, fire wall is all had to separate between every adjacent chamber, all there is the roll shaft of multiple rotation each working spaces, form not stopping transport of Copper Foil of the graphene-based end by roll shaft dynamic, form the continuous flow procedure of sedimentation limit, Graphene limit motion.
2. the method for a kind of pressure-fired continuous seepage graphene film according to claim 1 and device, it is characterized in that described preheating chamber is rectangle working spaces, shell is that stainless steel is formed, liner thermal insulation material, there is foil support preheating chamber front end, roll shaft is equipped with in two side, foil is positioned on indoor roll shaft, there are purgative gas inlet pipe and escape pipe in the side of preheating chamber, inlet pipe installs under meter and program-controlled electric magnet valve, preheating chamber top setting pressure meter and thermometer, preheating chamber and high temperature settling pocket abutting end are separated by fire wall, fire wall has charging gap at the same level place of roll shaft, foil enters high temperature settling pocket by gap, preheating chamber length is 1-2 rice, width is 0.5-1 rice, be highly 0.5-1 rice.
3. the method for a kind of pressure-fired continuous seepage graphene film according to claim 1 and device, it is characterized in that high temperature settling pocket is rectangle working spaces, the front end of high temperature settling pocket is connected with preheating chamber, rear end is connected with fore-cooling room, high temperature settling pocket shell is that stainless steel is formed, liner thermal insulation material, there is manhole side, there are inlet pipe and the escape pipe of purgative gas in the side of high temperature settling pocket, inlet pipe installs under meter and program-controlled electric magnet valve, the side bottom of high temperature settling pocket is provided with unstripped gas inlet pipe, unstripped gas inlet pipe is provided with under meter and program-controlled electric magnet valve, top setting pressure meter, thermometer, timing register and oxygen detection instrument, the two ends of high temperature settling pocket are separated by fire wall, the both sides of high temperature settling pocket are provided with 2-4 group roll shaft, foil is positioned on roll shaft, roundabout advance in high temperature settling pocket, foil is 30-120 minute in the roundabout time of high temperature settling pocket, the same level place of fire wall and hithermost roll shaft has charging gap and discharging gap, foil enters high temperature settling pocket by charging gap, gone out by discharging gap and enter next stage working spaces and fore-cooling room from high temperature settling pocket, high temperature settling pocket length is 2-5 rice, width is 0.5-1 rice, be highly 0.5-1 rice.
4. the method for a kind of pressure-fired continuous seepage graphene film according to claim 1 or 3 and device, described high temperature settling pocket, it is characterized in that there is nonstorage calorifier in high temperature settling pocket, nonstorage calorifier is electric heater unit or high-temperature molten salt heating device for coil, and the temperature-controllable of heating unit is built in 800-1200 DEG C.
5. the method for a kind of pressure-fired continuous seepage graphene film according to claim 1 or 3 and device, described high temperature settling pocket, the purgative gas that it is characterized in that entering high temperature settling pocket is hydrogen, helium, the one of argon gas or gas mixture arbitrarily, and the unstripped gas entering high temperature settling pocket is the one of high-purity methane high purity acetylene or paraffin gasification gas.
6. the method for a kind of pressure-fired continuous seepage graphene film according to claim 1 and device, described fore-cooling room is characterized in that fore-cooling room's shell is that stainless steel is formed, liner thermal insulation material, roll shaft is equipped with in two side, foil is positioned on indoor roll shaft, there are inlet pipe and escape pipe in the side of fore-cooling room, inlet pipe installs under meter and program-controlled electric magnet valve, top, fore-cooling room setting pressure meter and thermometer, fore-cooling room and high temperature settling pocket abutting end are separated by fire wall, fire wall has charging gap at the same level place of roll shaft, preheating chamber length is 1-2 rice, width is 0.5-1 rice, be highly 0.5-1 rice.
7. the method for a kind of pressure-fired continuous seepage graphene film according to claim 1 and device, described fast cooling room is characterized in that fast cooling chamber enclosure is that stainless steel chuck is formed, chuck is built with cooling oil or water coolant, roll shaft is equipped with in two side, foil is positioned on indoor roll shaft, graphene film detector is installed above fast cooling room, in the sedimentation of the indoor cool to room temperature of fast cooling by the foil of Graphene thin layer through graphene film detector, detector detects Graphene thin layer quality in time, fast cooling room length is 1-2 rice, width is 0.5-1 rice, be highly 0.5-1 rice.
8. the method for a kind of pressure-fired continuous seepage graphene film according to claim 1,2,3 or 6 and device, described roll shaft is characterized in that all roll shafts of whole device drag running by same motion-work wheel, the rotating speed of each roll shaft is identical, and the power of motion-work wheel is supplied by power set.
9. the method for a kind of pressure-fired continuous seepage graphene film according to claim 1 and device, is characterized in that whole continuous seepage graphene film device internal pressure is 0.05-0.5Mpa.
10. the method for a kind of pressure-fired continuous seepage graphene film according to claim 1, its feature is carried out as follows:
A, debug phase, Copper Foil is placed on the foil support of preheating chamber, and Copper Foil is positioned on corresponding roll shaft by the gap of each fire wall respectively, debugging transmission mechanism, setting speed, opens timing register, ON cycle refrigerating unit, power set is in state to be launched;
B, cleaning systems stage, open the preheating apparatus of preheating chamber, and open intake valve and the air outlet valve of the purgative gas of each working spaces, pass into oxygenless gas to whole system and clean each working spaces, make to be oxygen-free environment in working spaces; To continue to be filled with in system in oxygenless gas to whole system as positive pressure and observe the oxygen gas component of oxygen detection instrument, if oxygen content is in setting range, then the intake valve of closure systems and air outlet valve;
C, system temperature rise period, the high temperature sedimentation room temp of completing steps 2 was risen to 800-1300 DEG C in 50-150 minute, and keeps corresponding steady temperature 5-60 minute;
D, sedimentation growth phase, after the constant temperature stage terminates, thermostat temperature is kept to open intake valve and the extraction valve of the unstripped gas of high temperature settling pocket, the oxygenless gas of to be the carbonaceous gas of 50sccm-500sccm and flow by flow be 500sccm-4000sccm passes into 10-30 minute to high temperature settling pocket simultaneously, start transmission mechanism, each roll shaft rotates, and foil moves, and the system internal gas pressure of maintenance is less than 0.1MPa;
E, cooling detecting stage, continuous sedimentation growing graphene on foil in high temperature settling pocket, along with time lapse, when going out Graphene foil from high temperature settling pocket by fore-cooling room and fast cooling, at this moment Graphene coating temperature is down to room temperature, Graphene thin layer by Graphene detector to determine Graphene thin layer quality, as do not met specification of quality, then system is suitably adjusted, as conformed to quality requirements, then system continues steady running, until when the corresponding volume of production is long, take out foil, have Graphene in the surface growth of described Copper Foil.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104843691A (en) * | 2015-04-30 | 2015-08-19 | 深圳市德方纳米科技股份有限公司 | Graphene and preparation method thereof |
| CN107445147A (en) * | 2017-09-11 | 2017-12-08 | 张洪 | The preparation method and equipment of a kind of graphene |
| CN107732249A (en) * | 2017-09-11 | 2018-02-23 | 张洪 | Copper foil graphene collector and preparation method |
| CN109600866A (en) * | 2018-12-27 | 2019-04-09 | 中国科学院山西煤炭化学研究所 | Graphene infrared hot plate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN202297140U (en) * | 2011-11-01 | 2012-07-04 | 海洋王（东莞）照明科技有限公司 | Device capable of continuously preparing grapheme film |
| CN102976318A (en) * | 2012-12-21 | 2013-03-20 | 重庆绿色智能技术研究院 | Reel-to-reel graphene preparation apparatus |
| KR20140064132A (en) * | 2012-11-19 | 2014-05-28 | 삼성테크윈 주식회사 | Apparatus for manufacturing graphene |
| US20140367891A1 (en) * | 2013-06-13 | 2014-12-18 | Donald James Dawson | Method and apparatus for manufacturing graphene |
-
2015
- 2015-02-25 CN CN201510087684.8A patent/CN104692371B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN202297140U (en) * | 2011-11-01 | 2012-07-04 | 海洋王（东莞）照明科技有限公司 | Device capable of continuously preparing grapheme film |
| KR20140064132A (en) * | 2012-11-19 | 2014-05-28 | 삼성테크윈 주식회사 | Apparatus for manufacturing graphene |
| CN102976318A (en) * | 2012-12-21 | 2013-03-20 | 重庆绿色智能技术研究院 | Reel-to-reel graphene preparation apparatus |
| US20140367891A1 (en) * | 2013-06-13 | 2014-12-18 | Donald James Dawson | Method and apparatus for manufacturing graphene |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104843691A (en) * | 2015-04-30 | 2015-08-19 | 深圳市德方纳米科技股份有限公司 | Graphene and preparation method thereof |
| CN104843691B (en) * | 2015-04-30 | 2017-01-11 | 深圳市德方纳米科技股份有限公司 | Graphene and preparation method thereof |
| CN107445147A (en) * | 2017-09-11 | 2017-12-08 | 张洪 | The preparation method and equipment of a kind of graphene |
| CN107732249A (en) * | 2017-09-11 | 2018-02-23 | 张洪 | Copper foil graphene collector and preparation method |
| CN109600866A (en) * | 2018-12-27 | 2019-04-09 | 中国科学院山西煤炭化学研究所 | Graphene infrared hot plate |
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