CN105600775A - Graphene film and method and device for continuous production of graphene film - Google Patents
Graphene film and method and device for continuous production of graphene film Download PDFInfo
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- CN105600775A CN105600775A CN201610005325.8A CN201610005325A CN105600775A CN 105600775 A CN105600775 A CN 105600775A CN 201610005325 A CN201610005325 A CN 201610005325A CN 105600775 A CN105600775 A CN 105600775A
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Abstract
The invention discloses a graphene film and a method and device for continuous production of the graphene film. The method comprises the steps that 1, a graphene oxide solution is sprayed on metal foil moving continuously, and the metal foil is heated at the same time, so that the graphene oxide solution forms a film, at least part of the solution is subjected to reduction, the metal foil coated with a graphene oxide layer is obtained, and the graphene oxide layer also contains graphene; 2, the metal foil coated with the graphene oxide layer moves continuously, an etching solution is used for etching the metal foil, and then a graphene oxide film is obtained; 3, the graphene oxide film is moved continuously, cleaned, dried and annealed to completely turn into the graphene film. Through the method, the graphene film with good flexibility and thermal conductivity can be prepared continuously and can be used as a high-performance heat conduction material.
Description
Technical field
The present invention relates to a kind of method and device of continuous production graphene film, and prepared by this methodGraphene film.
Background technology
Graphene has by carbon atom with sp2Hybridized orbit composition hexangle type is the plane stratiform of honeycomb latticeStructure. Graphene not only has higher specific area and loose structure, also has very excellent conductionProperty and mechanical property, make its application in multiple fields all attract domestic and international researcher's extensive concern.In addition, in Graphene, monolayer carbon atomic arrangement is tight, and has higher thermal conductivity, is a kind of non-The heat sink material that convention is thought. Graphene film is as a kind of radiator material of flexibility, can meet computer,The radiating requirements of the powerful devices such as hand-held terminal device, LED illuminating lamp.
At present, the method for preparing graphene film mainly contains filter deposition method, spin coating method and interfaceThe method of self assembly etc.
But these methods have limited the serialization of graphene film and have produced, and are difficult for realizing scale and produceContinuous graphene film. Moreover, prior art is in the reduction step of graphene film production processIn, conventionally using chemical reagent, the heat reduction of for example hydrazine hydrate, sodium-ammonia solution are in the dry ice bath conditionReduction under lower reduction, sodium borohydride alkali condition, the reduction of acetic acid-hydroiodic acid solution etc., these mistakesJourney needs to use poisonous chemical reagent in general, and loaded down with trivial details experimental procedure consumes considerable time,And may introduce more impurity in the process of electronation, affect its heat conductivility.
Can find out, need to improve the production method of graphene film, realize the serialization of graphene filmProduce and provide higher heat conductivility.
Summary of the invention
The object of the invention is for overcome prior art cannot realize graphene film serialization produce andReduction step needs the defect of poisonous chemical reagent, simultaneously for the graphene film obtaining is produced in serializationThe thermal conductivity factor having had, a kind of graphene film is provided and produce continuously graphene film method andDevice.
To achieve these goals, the invention provides a kind of method of continuous production graphene film, bagDraw together: (1) in the metal forming of continuous moving, heats described metal by graphene oxide solution spraying simultaneouslyPaper tinsel, so that described graphene oxide solution film forming also reduces at least partly, obtains applying graphene oxideThe metal forming of layer, described graphene oxide layer also contains Graphene; (2) described coating graphene oxide layerMetal forming continuous moving carry out metal forming etching by etching solution, obtain graphene oxide film; (3)Described graphene oxide film continuous moving, after cleaning and being dried, is annealed to change into completelyGraphene film.
The graphene film that the present invention also provides a kind of the inventive method to make, the leading of this graphene filmHot coefficient is 800-1300W/ (mK).
The present invention also provides a kind of device of continuous production graphene film, and this device comprises: the first volumeAxle 1, for discharging metal forming; Flush coater 2, for by graphene oxide solution spraying from describedIn the metal forming of the first spool; The first warm table 3, the graphite oxide for hot spraying in metal formingAlkene solution; The first glass guide channel 4, for splendid attire etching solution with etching the gold from described the first warm tableBelong to paper tinsel, obtain graphene oxide film; The second glass guide channel 5, for splendid attire cleaning fluid with clean from instituteState the graphene oxide film of the first glass guide channel; The second warm table 6, for will be from described the second glassThe graphene oxide film of groove is dried; High temperature furnace 7, for by the oxygen from described the second warm tableFunctionalized graphene film carries out annealing in process under argon gas exists, and obtains graphene film; And second spool8, for collecting the graphene film from described high temperature furnace; Wherein, the first spool 1 and the second spool 8Rotation makes metal forming, graphene oxide film and graphene film continuous moving, realizes graphene filmProduce continuously.
In method of the present invention, utilize the metal forming of continuous moving, the metal forming of coating graphene oxide layerRealize serialization with graphene oxide film and produced graphene film. And molten at spraying graphene oxideWhen liquid, carry out heat treated, realize the reduction of partial oxidation Graphene, can avoid using to have poisoningLearn reagent, and be conducive to annealing in process under follow-up hot conditions and do not affect the presentation quality of graphene filmAnd heat conductivility. Therefore, can obtain in the preparation that uses method of the present invention to carry out graphene filmFor clean graphene film, do not need the process of loaded down with trivial details processing chemical reagent. And this produces continuouslyGraphene film prepared by method can have good pliability and thermal conductivity, can be used as high-performance heat conductionMaterial, thermal conductivity factor can reach 800-1300W/ (mK).
Other features and advantages of the present invention are described in detail the detailed description of the invention part subsequently.
Brief description of the drawings
Accompanying drawing is to be used to provide a further understanding of the present invention, and forms a part for description, withDetailed description of the invention one is below used from explanation the present invention, but is not construed as limiting the invention. ?In accompanying drawing:
Fig. 1 is the process flow diagram of continuous production graphene film provided by the invention;
Fig. 2 is the graphene oxide film that obtains in embodiment 1 and the X-ray diffraction pair of graphene filmThan figure;
Fig. 3 is the Raman spectrum contrast of the graphene oxide film that obtains in embodiment 1 and graphene filmFigure;
Fig. 4 is the scanning electron microscope diagram of the graphene film that obtains in embodiment 1.
Description of reference numerals
1-the first spool, 2-flush coater, 3-the first warm table, 4-the first glass guide channel, 5-the second glass guide channel,6-the second warm table, 7-high temperature furnace, 8-the second spool
Detailed description of the invention
Below the specific embodiment of the present invention is elaborated. Should be understood that, retouch in this placeThe detailed description of the invention of stating only, for description and interpretation the present invention, is not limited to the present invention.
The invention provides a kind of method of continuous production graphene film, as shown in Figure 1, comprising: (1)Graphene oxide solution spraying, in the metal forming of continuous moving, is heated to described metal forming so that institute simultaneouslyState graphene oxide solution film forming and reduce at least partly, obtaining applying the metal of graphene oxide layerPaper tinsel, described graphene oxide layer also contains Graphene; (2) metal forming of described coating graphene oxide layerContinuous moving carries out metal forming etching by etching solution, obtains graphene oxide film; (3) described in inciting somebody to actionGraphene oxide film continuous moving, after cleaning and being dried, anneals to change into completely GrapheneFilm.
According to the present invention, in step (1), realize graphene oxide solution is carried out to continuous spraying, withTime control heating described metal forming. Described heating can be played the work of controlling graphene oxide solution film formingWith, ensure quality of forming film, further can make graphene oxide part reduce, prevent at high temperatureWhen processing, film expands and affects its heat conductivility. Wherein control the temperature of described heating: excess Temperature,The graphene oxide layer being transformed in described metal forming by graphene oxide solution there will be explosion and shadowRing the quality of final film; Temperature is too low, can make graphene oxide solution too much assemble and affect finalThe uniformity coefficient of film. Under preferable case, the temperature of described heating is 120-180 DEG C, is preferably140-150℃
Can be by being sprayed on the change color judgement of the graphene oxide solution in metal forming in the present inventionWhether there is the partial reduction of graphene oxide: the color of graphene oxide solution is brown, GrapheneColor is black, when the graphene oxide solution spraying in metal forming film forming and by brown under heat effectBecome black, can judge and in the graphene oxide layer of film forming, contain the Graphene that part obtains through reduction.
In step (1), can by change spray gun quantity, spraying rate, metal forming translational speed withAnd the concentration of graphene oxide solution, can realize the graphene film thickness of final acquisition is adjustedControl, the thickness of the graphene film that finally can obtain can minimum be low to moderate 10 μ m. Under preferable case,The speed of described graphene oxide solution spraying is 4-6mL/min. Spray gun quantity can be preferably 2-3.
According to the present invention, under preferable case, the translational speed of described metal forming is 0.5-2cm/min. ThisIn application, realize serialization and produce graphene film, therefore the gold of preferred follow-up coating graphene oxide layerThe translational speed that belongs to paper tinsel and graphene oxide film can be identical with the translational speed of described metal forming, i.e. instituteStating the metal forming of coating graphene oxide layer and the translational speed of described graphene oxide film is 0.5-2cm/min。
According to the present invention, under preferable case, the concentration of described graphene oxide solution is 0.5-5mg/mL.Preferred described graphene oxide solution can prepare for chemical oxidation graphite method (Hummers method).
In step of the present invention (2), pass through the metal forming of described coating graphene oxide layer and described quarterThe contact of erosion solution, removes metal forming, there is no substrate from the graphene oxide layer being coated in metal formingBecome graphene oxide film, wherein yet contain the Graphene that partial reduction obtains.
According to the present invention, under preferable case, described etching solution is that the salt of concentration 0.5-2mol/L is acid-solubleLiquid; Or described etching solution is hydrochloric and mixed solution iron chloride, hydrochloric acid in described mixed solutionConcentration is 0.5-2mol/L, and the concentration of iron chloride is 1-3mol/L.
According to the present invention, the cleaning in step (3) can be by being used cleaning fluid by described graphite oxideEtching solution residual on alkene film is removed, and described cleaning fluid is preferably water. Dry can by described inResidual cleaning fluid on graphene oxide film. Under preferable case, described dry temperature is80-120℃。
According to the present invention, under preferable case, described annealing is carried out under argon gas exists, the temperature of described annealingDegree is 900-1200 DEG C. Can make described graphene oxide film be reduced to graphene film completely. FrontDescribed in face step (1), under heat effect, first partial reduction graphene oxide is conducive to the height in annealingTemperature obtains the Graphene heat conduction film of better quality after processing.
According to the present invention, under preferable case, described metal forming is Copper Foil, aluminium foil or zinc paper tinsel.
The graphene film that the present invention also provides a kind of the inventive method to make, the leading of this graphene filmHot coefficient is 800-1300W/ (mK).
In the present invention, can be by regulating the size of metal forming to obtain the graphene film of desired width. LogicalCross method of the present invention and can carry out the consecutive production of graphene film.
The present invention also provides a kind of device of continuous production graphene film, as shown in Figure 1, and this deviceComprise: the first spool 1, for discharging metal forming; Flush coater 2, for spraying graphene oxide solutionBe coated in the metal forming from described the first spool; The first warm table 3, for hot spraying in metal formingOn graphene oxide solution; The first glass guide channel 4, for splendid attire etching solution with etching from describedThe metal forming of one warm table, obtains graphene oxide film; The second glass guide channel 5, for splendid attire cleaning fluidTo clean the graphene oxide film from described the first glass guide channel; The second warm table 6, for will be fromThe graphene oxide film of described the second glass guide channel is dried; High temperature furnace 7, for will be from describedThe graphene oxide film of two warm tables carries out annealing in process under argon gas exists, and obtains graphene film;And second spool 8, for collecting the graphene film from described high temperature furnace; Wherein, the first spool1 and second spool 8 rotate and make metal forming, graphene oxide film and graphene film continuous moving, realThe continuous production of existing graphene film.
According to the present invention, under preferable case, the first warm table 3 is below metal forming, and flush coater 2 existsThe top of metal forming and corresponding the first warm table 3.
In the present invention, the quantity of flush coater 2 can be 2-3.
In the present invention, the length of the first warm table 3 provides the appropriate heat treatment of described graphene oxide solution, the length of the first warm table 3 is 30-60cm.
In the present invention, the length of the first glass guide channel 4 is 20-60cm. Provide enough metal forming etchings to beCan.
In the present invention, the length of the second glass guide channel 5 is 15-30cm. Provide enough graphene oxide thinFilm cleans, and removes residual etching solution.
According to the present invention, under preferable case, the second warm table 6 is below graphene oxide film.
In the present invention, the length of the second warm table 6 is 20-40cm. Provide enough graphene oxide thinFilm is dry, removes residual cleaning fluid.
In the present invention, the length of high temperature furnace 7 is 60-120cm. Realization completes graphene oxide filmEnough annealing in process.
Carry in the present invention according to the method that continuous production graphene film of the present invention is described shown in Fig. 1 belowThe course of work on the device of the continuous production graphene film of confession.
The first spool 1 discharges after metal forming, and metal forming is drawn on the first warm table 3, fills oxidationThe flush coater 2 of graphene solution with evenly spray speed by graphene oxide solution spraying in metal forming, simultaneouslyThe first warm table 3 heats the graphene oxide solution spraying in metal forming, obtains being coated in goldBelong to the graphene oxide layer on paper tinsel; The metal forming that is coated with graphene oxide layer is guided to and filled etching solutionThe first glass guide channel 4 in carry out etching, after the complete metal forming of etching, the graphene oxide film obtaining is drawnClean to filling in the second glass guide channel 5 of water; Then, the graphene oxide film after cleaning is drawnBe dried to the second warm table 6, more dried graphene oxide film is passed to the height that passes into argon gasIn temperature stove 7, carry out annealing in process, finally obtain graphene film, and be collected on the second spool 8.Wherein, the first spool 1 and the second spool 8 rotate, to draw metal forming, to be coated with graphene oxide layerMetal forming and graphene oxide film in whole technological process, at the uniform velocity advance, through each preparation process.
Below will describe the present invention by embodiment.
In following examples,
The thermal diffusion coefficient of graphene film adopts the NETZSCHLFA449 laser method thermal conductivity factor that shinesMeasuring instrument records;
The specific heat capacity of graphene film adopts NETZSCHDSC200F3 differential scanning calorimeter to record;
The thickness of graphene film adopts the electronic digital display micrometer of wide land digital observing and controlling limited companyOr SEM (JSM-7001F SEM) records.
Below in conjunction with specific embodiment, the invention will be further elaborated.
Preparation example
The preparation method of the graphene oxide solution using in this preparation example explanation the inventive method.
After the sodium nitrate of the concentrated sulfuric acid of the graphite powder of 12g, 280mL and 6g is mixed, at ice-water bathLower stirring adds the potassium permanganate of 36g;
Continue to stir after 30min, temperature is adjusted to 35 DEG C, then continue to stir after 30min, add 600The distilled water of mL; Temperature is adjusted to 90 DEG C, continues to stir after 15min, then add the steaming of 2000mLHeat up in a steamer water, temperature is adjusted to normal temperature, continues to stir 1h;
After standing 1h, add again the hydrogen peroxide of 80mL, then suction filtration; Gained solid is dissolved inAfter 1200-3200mL distilled water, centrifuge washing is also dialysed, and obtains the graphene oxide of 8-12mg/mLSolution.
It is that the graphene oxide of 0.5-5mg/mL is molten that above-mentioned graphene oxide solution dilution is become concentration by waterLiquid.
Embodiment 1
The present embodiment illustrates the preparation method of graphene film of the present invention.
It is upper to the first warm table (length is 40cm) that (1) first spool discharges Copper Foil traction, by concentrationFor the graphene oxide solution of 2.5mg/mL at the uniform velocity sprays to 1.5 with 5ml/min through 2 flush coatersOn the Copper Foil that the speed of cm/min is pushed ahead, heat, heating-up temperature is 140 DEG C, obtains applying oxygenThe Copper Foil of functionalized graphene layer, can observe graphene oxide layer is black, illustrates and contains partial reductionGraphene;
(2) Copper Foil that applies graphene oxide layer is drawn to and fills 0.5mol/L hydrochloric acid and 3mol/LIn first glass guide channel (long × wide is 30 × 20cm) of the mixed solution of iron chloride, Copper Foil is carvedErosion; Copper Foil obtains graphene oxide film after being etched completely;
(3) (long × wide is 15 the graphene oxide film obtaining to be drawn to the second glass guide channel being filled with water× 20cm) in clean;
(4) graphene oxide film after cleaning being drawn to temperature is that (length is the second warm table40cm) be dried, dry temperature is 80 DEG C;
(5) be the height of 1200 DEG C by graphene oxide film after drying through passing into argon gas and temperatureIn temperature stove (length is 90cm), carry out annealing in process, obtain graphene film, and by graphene filmBe collected on the second spool.
The graphene oxide film sampling that step (1) is obtained is carried out X with the graphene film obtaining and is penetratedLine diffraction, Raman spectrum test.
Fig. 2 is that test result can for X-ray diffraction (X-ray diffractometer of German Brooker D8 series)To find out, after the high temperature anneal, the characteristic peak of graphene oxide disappears, and has occurred the spy of GrapheneLevy peak, illustrate that graphene oxide has been reduced into Graphene completely.
Fig. 3 is Raman spectrum (the burnt Raman light of RM2000 copolymerization of England (RenishawPLC)Spectrometer) test result can calculate the D peak intensity of graphene film and the ratio of G peak intensity(ID/IG); D peak represents SP3The vibration absorption peak of the one-tenth key model of hydridization carbon, as: " C-O ", " C=O "," O-C=O ", G peak represents SP2The vibration absorption peak of the one-tenth key model of hydridization carbon, that is: " C=C ", heightThe graphene film I that temperature obtains after processingD/IGValue be 1.49, and the I of graphene oxideD/IGValue is1.67, illustrate that graphene oxide has obtained reduction, the structure of Graphene has obtained reparation.
The graphene film obtaining is carried out to SEM (JSM-7001F scanning electron microscopyMirror) observe, obtain the photo of Fig. 4, can find out that graphene film has uniform layer structure, thickDegree is about 10 μ m.
Observable graphene film is that black does not expand, what can to bend length be 20cmFilm is bent into the minimum circular arc for 1.5cm of radius of curvature, has good pliability.
The thermal diffusion coefficient of the graphene film obtaining by test and specific heat capacity result, calculate thisThe thermal conductivity factor of film is 1302W/ (mK).
Embodiment 2
The present embodiment illustrates the preparation method of graphene film of the present invention.
It is upper to the first warm table (length is 30cm) that (1) first spool discharges aluminium foil traction, by concentrationFor the graphene oxide solution of 5mg/mL through 2 flush coaters 2 with 4ml/min at the uniform velocity spray toOn the aluminium foil that the speed of 2cm/min is pushed ahead, heat, heating-up temperature is 120 DEG C, is appliedThe aluminium foil of graphene oxide layer, can observe graphene oxide layer is black, illustrates and contains partial reductionThe Graphene becoming;
(2) aluminium foil that applies graphene oxide layer is drawn to the first glass guide channel that fills 2mol/L hydrochloric acidIn (long × wide is 60 × 20cm), aluminium foil is carried out to etching; Aluminium foil obtains oxygen after being etched completelyFunctionalized graphene film;
(3) (long × wide is 20 the graphene oxide film obtaining to be drawn to the second glass guide channel being filled with water× 20cm) in clean;
(4) graphene oxide film after cleaning being drawn to temperature is that (length is the second warm table30cm) be dried, dry temperature is 100 DEG C;
(5) be the height of 1000 DEG C by graphene oxide film after drying through passing into argon gas and temperatureIn temperature stove (length is 120cm), carry out annealing in process, obtain graphene film, and by graphene filmBe collected on the second spool.
The graphene oxide film sampling that step (1) is obtained is carried out X with the graphene film obtaining and is penetratedLine diffraction, Raman spectrum test, the photo obtaining is similar to Fig. 2, Fig. 3, not shown.
Can find out from X-ray diffraction test result, after the high temperature anneal, the spy of graphene oxideLevy peak and disappear, occurred the characteristic peak of Graphene, illustrate that graphene oxide has been reduced into graphite completelyAlkene.
Can calculate D peak intensity and the G peak intensity of graphene film from Raman spectrum test resultRatio (ID/IG) be 1.52, and the I of graphene oxideD/IGValue is 1.61, illustrates that graphene oxide obtainsReduction, the structure of Graphene has obtained reparation.
The thickness that can record graphene film with electronic digital display micrometer is 13 μ m.
Observable graphene film is that black does not expand, and the film obtaining with embodiment 1 is equally passableBend, there is good pliability.
The thermal diffusion coefficient of the graphene film obtaining by test and specific heat capacity result, calculate thisThe thermal conductivity factor of film is 993W/ (mK).
Embodiment 3
The present embodiment illustrates the preparation method of graphene film of the present invention.
It is upper to the first warm table 3 (length is 60cm) that (1) first spool discharges the traction of zinc paper tinsel, by denseDegree for the graphene oxide solution of 0.5mg/mL through 3 flush coaters with 6ml/min at the uniform velocity spray toOn the zinc paper tinsel that the speed of 0.5cm/min is pushed ahead, heat, heating-up temperature is 180 DEG C, is sprayedThe zinc paper tinsel that applies graphene oxide layer, can observe graphene oxide layer is black, illustrates and contains partThe Graphene being reduced into;
(2) the zinc paper tinsel that applies graphene oxide layer is drawn to and fills 1.5mol/L hydrochloric acid and 1mol/LIn first glass guide channel (long × wide is 20 × 20cm) of the mixed solution of iron chloride, zinc paper tinsel is carvedErosion; Zinc paper tinsel obtains graphene oxide film after being etched completely;
(3) (long × wide is 30 the graphene oxide film obtaining to be drawn to the second glass guide channel being filled with water× 20cm) in clean;
(4) graphene oxide film after cleaning being drawn to temperature is that (length is the second warm table20cm) be dried, dry temperature is 120 DEG C;
(5) be the high temperature of 900 DEG C by graphene oxide film after drying through passing into argon gas and temperatureIn stove (length is 60cm), carry out annealing in process, obtain graphene film, and graphene film is receivedCollection is on the second spool.
The graphene oxide film sampling that step (1) is obtained is carried out X with the graphene film obtaining and is penetratedLine diffraction, Raman spectrum test, the photo obtaining is similar to Fig. 2, Fig. 3, not shown.
Can find out from X-ray diffraction test result, after high-temperature process, the characteristic peak of graphene oxideDisappear, occurred the characteristic peak of Graphene, illustrate that graphene oxide has been reduced into Graphene completely.
Can calculate D peak intensity and the G peak intensity of graphene film from Raman spectrum test resultRatio (ID/IG) be 1.58, and the I of graphene oxideD/IGValue is 1.70, illustrates that graphene oxide obtainsReduction, the structure of Graphene has obtained reparation.
The thickness that can record graphene film with electronic digital display micrometer is 11 μ m.
Observable graphene film is that black does not expand, and the film obtaining with embodiment 1 is equally passableBend, there is good pliability.
The thermal diffusion coefficient of the graphene film obtaining by test and specific heat capacity result, calculate thisThe thermal conductivity factor of film is 812W/ (mK).
Embodiment 4
It is upper to the first warm table (length is 50cm) that (1) first spool discharges Copper Foil traction, by concentrationFor the graphene oxide solution of 1.5mg/mL at the uniform velocity sprays to 1.5 with 5ml/min through 3 flush coatersOn the Copper Foil that the speed of cm/min is pushed ahead, heat, heating-up temperature is 140 DEG C, obtains applying oxygenThe Copper Foil of functionalized graphene layer, can observe graphene oxide layer is black, illustrates and contains partial reductionGraphene;
(2) Copper Foil that applies graphene oxide layer is drawn to and fills 1mol/L hydrochloric acid and 2.5mol/LIn first glass guide channel (long × wide is 40 × 20cm) of the mixed solution of iron chloride, Copper Foil is carvedErosion; Copper Foil obtains graphene oxide film after being etched completely;
(3) graphene oxide film obtaining being drawn to the second glass guide channel of being filled with water (longly × wide is15 × 20cm) in clean;
(4) graphene oxide film after cleaning being drawn to temperature is that (length is the second warm table30cm) be dried, dry temperature is 90 DEG C;
(5) be the height of 1100 DEG C by graphene oxide film after drying through passing into argon gas and temperatureIn temperature stove (length is 90cm), carry out annealing in process, obtain graphene film, and by graphene filmBe collected on the second spool.
The graphene oxide film sampling that step (1) is obtained is carried out X with the graphene film obtaining and is penetratedLine diffraction, Raman spectrum test, the photo obtaining is similar to Fig. 2, Fig. 3, not shown.
Can find out from X-ray diffraction test result, after the high temperature anneal, the spy of graphene oxideLevy peak and disappear, occurred the characteristic peak of Graphene, illustrate that graphene oxide has been reduced into graphite completelyAlkene.
Can calculate D peak intensity and the G peak intensity of graphene film from Raman spectrum test resultRatio (ID/IG) be 1.48, and the I of graphene oxideD/IGValue is 1.68, illustrates that graphene oxide obtainsReduction, the structure of Graphene has obtained reparation.
The thickness that can record graphene film with electronic digital display micrometer is 10 μ m.
Observable graphene film is that black does not expand, and the film obtaining with embodiment 1 is equally passableBend, there is good pliability.
The thermal diffusion coefficient of the graphene film obtaining by test and specific heat capacity result, calculate thisThe thermal conductivity factor of film is 1086W/ (mK).
Embodiment 5
It is upper to the first warm table (length is 30cm) that (1) first spool discharges Copper Foil traction, by concentrationFor the graphene oxide solution of 4mg/mL through 2 flush coaters with 5ml/min at the uniform velocity spray toOn the Copper Foil that the speed of 1.5cm/min is pushed ahead, heat, heating-up temperature is 120 DEG C, is coated withCover the Copper Foil of graphene oxide layer, can observe graphene oxide layer is black, illustrates and also contains partThe Graphene of former one-tenth;
(2) Copper Foil that applies graphene oxide layer is drawn to and fills 2mol/L hydrochloric acid and 1mol/L chlorineChange in first glass guide channel (long × wide is 60 × 20cm) of the mixed solution of iron, Copper Foil is carried out to etching;Copper Foil obtains graphene oxide film after being etched completely;
(3) (long × wide is 20 the graphene oxide film obtaining to be drawn to the second glass guide channel being filled with water× 20cm) in clean;
(4) graphene oxide film after cleaning being drawn to temperature is that (length is the second warm table30cm) be dried, dry temperature is 100 DEG C;
(5) be the height of 1000 DEG C by graphene oxide film after drying through passing into argon gas and temperatureIn temperature stove (length is 120cm), carry out annealing in process, obtain graphene film, and by graphene filmBe collected on the second spool.
The graphene oxide film sampling that step (1) is obtained is carried out X with the graphene film obtaining and is penetratedLine diffraction, Raman spectrum test, the photo obtaining is similar to Fig. 2, Fig. 3, not shown.
Can find out from X-ray diffraction test result, after high-temperature process, the characteristic peak of graphene oxideDisappear, occurred the characteristic peak of Graphene, illustrate that graphene oxide has been reduced into Graphene completely.
Can calculate D peak intensity and the G peak intensity of graphene film from Raman spectrum test resultRatio (ID/IG) be 1.47, and the I of graphene oxideD/IGValue is 1.72, illustrates that graphene oxide obtainsReduction, the structure of Graphene has obtained reparation.
The thickness that can record graphene film with electronic digital display micrometer is 15 μ m.
Observable graphene film is that black does not expand, and the film obtaining with embodiment 1 is equally passableBend, there is good pliability.
The thermal diffusion coefficient of the graphene film obtaining by test and specific heat capacity result, calculate thisThe thermal conductivity factor of film is 1021W/ (mK).
Comparative example 1
(1) first spool discharges Copper Foil, and the graphene oxide solution that is 2.5mg/mL by concentration is through 2Individual flush coater at the uniform velocity sprays to 5ml/min on the Copper Foil of pushing ahead with the speed of 1.5cm/min;
(2) be 1200 DEG C by the Copper Foil that is coated with graphene oxide solution through passing into argon gas and temperatureIn high temperature furnace (length is 90cm), carry out annealing in process, obtain the Copper Foil of graphene coated film.
Copper Foil is removed and obtained graphene film and be collected on the second spool through etching.
Can observe graphene film has expansion out-of-flatness, and the thermal conductivity factor that measure and calculation obtains is250W/(m·K)。
Can be found out by above embodiment result, can realize continuous production graphene film, and obtainThermal conductivity factor is the graphene film of 800-1300W/ (mK). In comparative example 1, be not oxidized in sprayingWhen graphene solution, heat, do not have the graphene oxide solution of part spraying to be reduced, not shapeBecome Graphene, and the high temperature reduction of directly annealing, therefore, the graphene film that comparative example 1 obtainsOutward appearance and thermal conductivity factor not as the product of embodiment 1-5.
Claims (10)
1. a method of producing continuously graphene film, comprising:
(1) by graphene oxide solution spraying in the metal forming of continuous moving, heat described gold simultaneouslyBelong to paper tinsel so that described graphene oxide solution film forming also reduces at least partly, obtain applying graphite oxideThe metal forming of alkene layer, described graphene oxide layer also contains Graphene;
(2) the metal forming continuous moving of described coating graphene oxide layer carries out metal by etching solutionPaper tinsel etching, obtains graphene oxide film;
(3) by described graphene oxide film continuous moving through cleaning and dry after, anneal withChange graphene film completely into.
2. method according to claim 1, wherein, the speed of described graphene oxide solution sprayingDegree is 4-6mL/min, metal forming and the described oxidation of described metal forming, described coating graphene oxide layerThe translational speed of graphene film is 0.5-2cm/min, and the temperature of described heating is 120-180 DEG C.
3. method according to claim 1 and 2, wherein, described graphene oxide solution denseDegree is 0.5-5mg/mL, and described graphene oxide solution is that chemical oxidation graphite method prepares.
4. according to the method described in any one in claim 1-3, wherein, described etching solution isThe hydrochloric acid solution of concentration 0.5-2mol/L; Or described etching solution is hydrochloric molten with mixing of iron chlorideLiquid, in described mixed solution, concentration of hydrochloric acid is 0.5-2mol/L, the concentration of iron chloride is 1-3mol/L.
5. method according to claim 1, wherein, described dry temperature is 80-120 DEG C;Described annealing is carried out under argon gas exists, and the temperature of described annealing is 900-1200 DEG C.
6. method according to claim 1, wherein, described metal forming be Copper Foil, aluminium foil orZinc paper tinsel.
7. the graphene film that in claim 1-6, described in any one, method makes, this graphiteThe thermal conductivity factor of alkene film is 800-1300W/ (mK).
8. a device of producing continuously graphene film, this device comprises:
The first spool (1), for discharging metal forming;
Flush coater (2), for by graphene oxide solution spraying in the metal forming from described the first spoolOn;
The first warm table (3), the graphene oxide solution for hot spraying in metal forming;
The first glass guide channel (4), for splendid attire etching solution with etching the metal from described the first warm tablePaper tinsel, obtains graphene oxide film;
The second glass guide channel (5), for splendid attire cleaning fluid to clean from the oxidation stone of described the first glass guide channelChina ink alkene film;
The second warm table (6), for doing from the graphene oxide film of described the second glass guide channelDry;
High temperature furnace (7), for existing at argon gas from the graphene oxide film of described the second warm tableUnder anneal, obtain graphene film; And
The second spool (8), for collecting the graphene film from described high temperature furnace;
Wherein, the first spool (1) and the second spool (8) rotate and make metal forming, graphene oxide filmWith graphene film continuous moving, realize the continuous production of graphene film.
9. device according to claim 8, wherein, the first warm table (3) is under metal formingSide, flush coater (2) is above metal forming and corresponding the first warm table (3).
10. device according to claim 8, wherein, the second warm table (6) is at graphite oxideThe below of alkene film.
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