CN105271209A - Graphene film and method and device for continuously producing graphene film - Google Patents
Graphene film and method and device for continuously producing graphene film Download PDFInfo
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- CN105271209A CN105271209A CN201510824701.1A CN201510824701A CN105271209A CN 105271209 A CN105271209 A CN 105271209A CN 201510824701 A CN201510824701 A CN 201510824701A CN 105271209 A CN105271209 A CN 105271209A
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Abstract
The invention discloses a graphene film and a method and a device for continuously producing the graphene film. The method comprises the following steps: (1) spraying a graphene oxide solution on a metal foil which continuously moves, simultaneously heating the metal foil, forming the film by the graphene oxide solution and at least partially carrying out reduction, so as to obtain a graphene oxide layer-coated metal foil, wherein the graphene oxide layer also contains graphene; (2) enabling the graphene oxide layer-coated metal foil to continuously move and carrying out metal foil etching through an etching solution, so as to obtain the graphene oxide film; and (3) enabling the graphene oxide film to continuously move, cleaning and drying the graphene oxide film, and carrying out annealing to completely convert into the graphene film. According to the method, the graphene film with good flexibility and thermal conductivity can be continuously prepared, 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 seepage graphene film, and graphene film prepared by this method.
Background technology
Graphene has by carbon atom with sp
2hybridized orbital composition hexangle type is the plane laminate structure of honeycomb lattice.Graphene not only has higher specific surface area and vesicular structure, also has very excellent electroconductibility and mechanical property, its application in multiple field is all the attracted extensive concern of domestic and international investigator.In addition, in Graphene, monolayer carbon atomic arrangement is tight, and has higher thermal conductivity, is a kind of ideal heat sink material.Graphene film, as a kind of radiator material of flexibility, can meet the radiating requirements of the powerful devices such as computer, hand-held terminal device, LED illumination lamp.
At present, the method preparing graphene film mainly contains the method etc. of filter deposition method, spin coating method and interface self-assembly.
But these methods limit the continuous prodution of graphene film, produce continuous print graphene film with not easily realizing mass-producing.Moreover, prior art is in the reduction step of graphene film production process, usual use chemical reagent, heat reduction, the sodium-ammonia solution of such as hydrazine hydrate reduce under the dry ice bath condition, reduction under sodium borohydride alkaline condition, acetic acid-hydroiodic acid HI solution reduction etc., these processes need to use poisonous chemical reagent in general, loaded down with trivial details experimental procedure, consume considerable time, and more impurity may be introduced in the process of chemical reduction, affect its heat conductivility.
Can find out, need the production method improving graphene film, realize the continuous prodution of graphene film and higher heat conductivility is provided.
Summary of the invention
The object of the invention is cannot realize graphene film continuous prodution and reduction step needs the defect of toxic chemical to overcome prior art, the thermal conductivity that the graphene film simultaneously obtained in order to continuous prodution has had, provides method and the device of a kind of graphene film and continuous seepage graphene film.
To achieve these goals, the invention provides a kind of method of continuous seepage graphene film, comprise: graphene oxide solution is sprayed in the tinsel of continuous moving by (1), heat described tinsel to make described graphene oxide solution film forming and to reduce at least partly simultaneously, obtain the tinsel applying graphene oxide layer, described graphene oxide layer is also containing Graphene; (2) tinsel of described coating graphene oxide layer continuously moves through etching solution and carries out tinsel etching, obtains graphene oxide film; (3) by described graphene oxide film continuous moving through cleaning and drying after, carry out annealing to change graphene film into completely.
Present invention also offers the graphene film that a kind of the inventive method is obtained, the thermal conductivity of this graphene film is 800-1300W/ (mK).
Present invention also offers a kind of device of continuous seepage graphene film, this device comprises: the first spool 1, for discharging tinsel; Spraying machine 2, for being sprayed on the tinsel from described first spool by graphene oxide solution; First warm table 3, for hot spraying graphene oxide solution on metal foil; First glass guide channel 4, for splendid attire etching solution with the tinsel of etching from described first warm table, obtains graphene oxide film; Second glass guide channel 5, for splendid attire scavenging solution with the graphene oxide film of cleaning from described first glass guide channel; Second warm table 6, for carrying out drying by the graphene oxide film from described second glass guide channel; High Temperature Furnaces Heating Apparatus 7, for the graphene oxide film from described second warm table is carried out anneal under argon gas exists, obtains graphene film; And second spool 8, for collecting the graphene film from described High Temperature Furnaces Heating Apparatus; Wherein, the first spool 1 and the second spool 8 rotate and make tinsel, graphene oxide film and graphene film continuous moving, realize the continuous seepage of graphene film.
In method of the present invention, the tinsel of the tinsel of continuous moving, coating graphene oxide layer and graphene oxide film is utilized to achieve continuous prodution graphene film.And while spraying graphene oxide solution, carry out heat treated, realize the reduction of part graphene oxide, can avoid using toxic chemical, and the anneal be conducive under subsequent high temperature condition does not affect visual appearance and the heat conductivility of graphene film.Therefore, comparatively clean graphene film can be obtained in the preparation using method of the present invention to carry out graphene film, not need the process of loaded down with trivial details process chemical reagent.And graphene film prepared by this continuous production method can have good snappiness and thermal conductivity, can be used as High-performance heat conduction material, thermal conductivity can reach 800-1300W/ (mK).
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the process flow diagram of continuous seepage graphene film provided by the invention;
Fig. 2 is the X-ray diffraction comparison diagram of graphene oxide film and the graphene film obtained in embodiment 1;
Fig. 3 is the Raman spectrum comparison diagram of graphene oxide film and the graphene film obtained in embodiment 1;
Fig. 4 is the scanning electron microscope diagram of the graphene film obtained in embodiment 1.
Description of reference numerals
1-first spool, 2-spraying machine, 3-first warm table, 4-first glass guide channel, 5-second glass guide channel, 6-second warm table, 7-High Temperature Furnaces Heating Apparatus, 8-second spool
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of method of continuous seepage graphene film, as shown in Figure 1, comprise: graphene oxide solution is sprayed in the tinsel of continuous moving by (1), heat described tinsel to make described graphene oxide solution film forming and to reduce at least partly simultaneously, obtain the tinsel applying graphene oxide layer, described graphene oxide layer is also containing Graphene; (2) tinsel of described coating graphene oxide layer continuously moves through etching solution and carries out tinsel etching, obtains graphene oxide film; (3) by described graphene oxide film continuous moving through cleaning and drying after, carry out annealing to change graphene film into completely.
According to the present invention, realize graphene oxide solution to carry out continuous print spraying in step (1), control the described tinsel of heating simultaneously.Described heating can play the effect of controlled oxidization graphene solution film forming, ensures quality of forming film, graphene oxide part further can be made to reduce, prevent the film expansion when pyroprocessing and affect its heat conductivility.Wherein control the temperature of described heating: temperature is too high, the graphene oxide layer be transformed in described tinsel by graphene oxide solution there will be explosion and affects the quality of final film; Temperature is too low, and graphene oxide solution can be made too much to assemble and affect the degree of uniformity of final film.Under preferable case, the temperature of described heating is 120-180 DEG C, is preferably 140-150 DEG C
Can judge whether by the colour-change of spraying graphene oxide solution on metal foil the partial reduction that graphene oxide occurs: the color of graphene oxide solution is brown in the present invention, the color of Graphene is black, when the graphene oxide solution that tinsel sprays film forming and become black from brown under heat effect, can to judge in the graphene oxide layer of film forming containing part through reducing the Graphene obtained.
In step (1), can by changing the concentration of spray gun quantity, spraying rate, tinsel translational speed and graphene oxide solution, can realize regulating and controlling the final graphene film thickness obtained, the thickness of the graphene film that finally can obtain minimumly can be low to moderate 10 μm.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 tinsel is 0.5-2cm/min.Continuous prodution graphene film is realized in the application, the tinsel of therefore preferably follow-up coating graphene oxide layer can be identical with the translational speed of described tinsel with the translational speed of graphene oxide film, and namely the described tinsel of coating graphene oxide layer and the translational speed of described graphene oxide film are 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).
Pass through the described tinsel of coating graphene oxide layer and the contact of described etching solution in step of the present invention (2), tinsel is removed, substrate is not had to become graphene oxide film from the graphene oxide layer applied on metal foil, wherein yet containing the Graphene that partial reduction obtains.
According to the present invention, under preferable case, described etching solution is the hydrochloric acid soln of concentration 0.5-2mol/L; Or described etching solution is mixing solutions that is hydrochloric and iron(ic) chloride, and in described mixing solutions, concentration of hydrochloric acid is 0.5-2mol/L, the concentration of iron(ic) chloride is 1-3mol/L.
According to the present invention, etching solution residual on described graphene oxide film can be removed by using scavenging solution by the cleaning in step (3), and described scavenging solution is preferably water.The dry scavenging solution that can will described graphene oxide film remain.Under preferable case, the temperature of described drying is 80-120 DEG C.
According to the present invention, under preferable case, described annealing is carried out under argon gas exists, and the temperature of described annealing is 900-1200 DEG C.Described graphene oxide film can be made to be reduced to graphene film completely.Under heat effect described in preceding step (1), first partial reduction graphene oxide is conducive to the Graphene heat conduction film obtaining better quality after the pyroprocessing of annealing.
According to the present invention, under preferable case, described tinsel is Copper Foil, aluminium foil or zinc paper tinsel.
Present invention also offers the graphene film that a kind of the inventive method is obtained, the thermal conductivity of this graphene film is 800-1300W/ (mK).
In the present invention, can by the graphene film regulating the size of tinsel to obtain desired width.The consecutive production of graphene film can be carried out by method of the present invention.
Present invention also offers a kind of device of continuous seepage graphene film, as shown in Figure 1, this device comprises: the first spool 1, for discharging tinsel; Spraying machine 2, for being sprayed on the tinsel from described first spool by graphene oxide solution; First warm table 3, for hot spraying graphene oxide solution on metal foil; First glass guide channel 4, for splendid attire etching solution with the tinsel of etching from described first warm table, obtains graphene oxide film; Second glass guide channel 5, for splendid attire scavenging solution with the graphene oxide film of cleaning from described first glass guide channel; Second warm table 6, for carrying out drying by the graphene oxide film from described second glass guide channel; High Temperature Furnaces Heating Apparatus 7, for the graphene oxide film from described second warm table is carried out anneal under argon gas exists, obtains graphene film; And second spool 8, for collecting the graphene film from described High Temperature Furnaces Heating Apparatus; Wherein, the first spool 1 and the second spool 8 rotate and make tinsel, graphene oxide film and graphene film continuous moving, realize the continuous seepage of graphene film.
According to the present invention, under preferable case, the first warm table 3 is in the below of tinsel, and spraying machine 2 is above tinsel and corresponding first warm table 3.
In the present invention, the quantity of spraying machine 2 can be 2-3.
In the present invention, the length of the first warm table 3 provides the appropriate thermal treatment of described graphene oxide solution, and 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.Enough tinsels are provided to etch.
In the present invention, the length of the second glass guide channel 5 is 15-30cm.Enough graphene oxide film cleanings are provided, remove residual etching solution.
According to the present invention, under preferable case, the second warm table 6 is in the below of graphene oxide film.
In the present invention, the length of the second warm table 6 is 20-40cm.Enough graphene oxide film dryings are provided, remove residual scavenging solution.
In the present invention, the length of High Temperature Furnaces Heating Apparatus 7 is 60-120cm.Enough anneal of graphene oxide film are realized.
Following the working process of the method for continuous seepage graphene film of the present invention on the device of continuous seepage graphene film provided by the invention is described according to Fig. 1.
After first spool 1 discharges tinsel, tinsel is drawn on the first warm table 3, fill the spraying machine 2 of graphene oxide solution evenly to spray speed by graphene oxide solution spraying on metal foil, first warm table 3 heats the graphene oxide solution sprayed in tinsel simultaneously, obtains the graphene oxide layer applied on metal foil; The tinsel being coated with graphene oxide layer is guided in the first glass guide channel 4 filling etching solution and etch, after having etched tinsel, the graphene oxide film obtained is guided in the second glass guide channel 5 filling water and clean; Then, the graphene oxide film after cleaning is guided to the second warm table 6 and carried out drying, more dried graphene oxide film is carried out anneal through in the High Temperature Furnaces Heating Apparatus 7 passing into argon gas, finally obtain graphene film, and be collected on the second spool 8.Wherein, the first spool 1 and the second spool 8 rotate, and drawing tinsel, are coated with the tinsel of graphene oxide layer and graphene oxide film at the uniform velocity advances in whole technical process, through each preparation process.
Below will be described the present invention by embodiment.
In following examples,
The thermal diffusivity of graphene film adopts the NETZSCHLFA449 laser method thermal conductivity coefficient measurement instrument that shines to record;
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 numeral observing and controlling limited-liability company or scanning electronic microscope (JSM-7001F scanning electronic microscope) to record.
Below in conjunction with specific embodiment, the invention will be further elaborated.
Preparation example
This preparation example illustrates the preparation method of the graphene oxide solution used in the inventive method.
After the SODIUMNITRATE of the Graphite Powder 99 of 12g, the vitriol oil of 280mL and 6g being mixed, under ice-water bath, stir the potassium permanganate adding 36g;
After continuing to stir 30min, temperature is adjusted to 35 DEG C, then after continuing to stir 30min, adds the distilled water of 600mL; Temperature is adjusted to 90 DEG C, after continuing to stir 15min, then add the distilled water of 2000mL, temperature is adjusted to normal temperature, continues to stir 1h;
The hydrogen peroxide of 80mL is added, then suction filtration after leaving standstill 1h again; After gained solid is dissolved in 1200-3200mL distilled water, centrifuge washing is also dialysed, and obtains the graphene oxide solution of 8-12mg/mL.
With water, above-mentioned graphene oxide solution is diluted to the graphene oxide solution that concentration is 0.5-5mg/mL.
Embodiment 1
The present embodiment illustrates the preparation method of graphene film of the present invention.
(1) first spool release Copper Foil traction is on the first warm table (length is 40cm), be that the graphene oxide solution of 2.5mg/mL at the uniform velocity to spray to 5ml/min through 2 spraying machines on the Copper Foil of pushing ahead with the speed of 1.5cm/min and heats by concentration, Heating temperature is 140 DEG C, obtain the Copper Foil applying graphene oxide layer, can observe graphene oxide layer is black, and the Graphene become containing partial reduction is described;
(2) Copper Foil of coating graphene oxide layer is drawn in first glass guide channel (long × wide is 30 × 20cm) of the mixing solutions filling 0.5mol/L hydrochloric acid and 3mol/L iron(ic) chloride, Copper Foil is etched; Copper Foil is etched completely, obtains graphene oxide film;
(3) graphene oxide film obtained is drawn in the second glass guide channel (long × wide is 15 × 20cm) be filled with water and cleans;
(4) graphene oxide film after cleaning being drawn to temperature is that the second warm table (length is 40cm) carries out drying, and dry temperature is 80 DEG C;
(5) by graphene oxide film after drying through passing into argon gas and temperature is carry out anneal in the High Temperature Furnaces Heating Apparatus (length is 90cm) of 1200 DEG C, obtain graphene film, and graphene film be collected on the second spool.
Step (1) is obtained graphene oxide film sampling with obtain graphene film carries out X-ray diffraction, Raman spectrum is tested.
Fig. 2 is that X-ray diffraction (X-ray diffractometer of German Brooker D8 series) test result can be found out, after the high temperature anneal, the characteristic peak of graphene oxide disappears, and has occurred the characteristic peak of Graphene, has illustrated that graphene oxide has been reduced into Graphene completely.
Fig. 3 is that Raman spectrum (the RM2000 Confocal laser-scanning microscopy instrument of England (RenishawPLC)) test result can calculate the D peak intensity of graphene film and the ratio (I of G peak intensity
d/ I
g); D peak represents SP
3the vibration absorption peak of the one-tenth key model of hydridization carbon, as: " C-O ", " C=O ", " O-C=O ", G peak represents SP
2the vibration absorption peak of the one-tenth key model of hydridization carbon, i.e.: " C=C ", the graphene film I obtained after pyroprocessing
d/ I
gvalue be 1.49, and the I of graphene oxide
d/ I
gvalue is 1.67, illustrates that graphene oxide obtains reduction, and the structure of Graphene obtains reparation.
The graphene film obtained is carried out scanning electronic microscope (JSM-7001F scanning electronic microscope) to observe, obtain the photo of Fig. 4, can find out that graphene film has uniform laminate structure, thickness is about 10 μm.
Observable graphene film is that black does not expand, and can carry out bending by length is that the film of 20cm is bent into the minimum circular arc for 1.5cm of radius-of-curvature, has good snappiness.
By testing thermal diffusivity and the specific heat capacity result of the graphene film obtained, the thermal conductivity calculating this film is 1302W/ (mK).
Embodiment 2
The present embodiment illustrates the preparation method of graphene film of the present invention.
(1) first spool release aluminium foil traction is on the first warm table (length is 30cm), be that the graphene oxide solution of 5mg/mL at the uniform velocity to spray to 4ml/min through 2 spraying machines 2 on the aluminium foil of pushing ahead with the speed of 2cm/min and heats by concentration, Heating temperature is 120 DEG C, obtain the aluminium foil applying graphene oxide layer, can observe graphene oxide layer is black, and the Graphene become containing partial reduction is described;
(2) aluminium foil of coating graphene oxide layer is drawn in the first glass guide channel (long × wide is 60 × 20cm) filling 2mol/L hydrochloric acid, aluminium foil is etched; Aluminium foil is etched completely, obtains graphene oxide film;
(3) graphene oxide film obtained is drawn in the second glass guide channel (long × wide is 20 × 20cm) be filled with water and cleans;
(4) graphene oxide film after cleaning being drawn to temperature is that the second warm table (length is 30cm) carries out drying, and dry temperature is 100 DEG C;
(5) by graphene oxide film after drying through passing into argon gas and temperature is carry out anneal in the High Temperature Furnaces Heating Apparatus (length is 120cm) of 1000 DEG C, obtain graphene film, and graphene film be collected on the second spool.
Step (1) is obtained graphene oxide film sampling with obtain graphene film carries out X-ray diffraction, Raman spectrum is tested, the photo obtained is similar to Fig. 2, Fig. 3, not shown.
As can be seen from X-ray diffraction test result, after the high temperature anneal, the characteristic peak of graphene oxide disappears, and has occurred the characteristic peak of Graphene, has illustrated that graphene oxide has been reduced into Graphene completely.
The D peak intensity of graphene film and the ratio (I of G peak intensity can be calculated from Raman spectrum test result
d/ I
g) be 1.52, and the I of graphene oxide
d/ I
gvalue is 1.61, illustrates that graphene oxide obtains reduction, and the structure of Graphene obtains reparation.
The thickness that can record graphene film with electronic digital display micrometer is 13 μm.
Observable graphene film is that black does not expand, and the film obtained with embodiment 1 equally can bend, and has good snappiness.
By testing thermal diffusivity and the specific heat capacity result of the graphene film obtained, the thermal conductivity calculating this film is 993W/ (mK).
Embodiment 3
The present embodiment illustrates the preparation method of graphene film of the present invention.
(1) first spool release zinc paper tinsel traction is on the first warm table 3 (length is 60cm), be that the graphene oxide solution of 0.5mg/mL at the uniform velocity to spray to 6ml/min through 3 spraying machines on the zinc paper tinsel of pushing ahead with the speed of 0.5cm/min and heats by concentration, Heating temperature is 180 DEG C, obtain spraying the zinc paper tinsel covering graphene oxide layer, can observe graphene oxide layer is black, and the Graphene become containing partial reduction is described;
(2) the zinc paper tinsel of coating graphene oxide layer is drawn in first glass guide channel (long × wide is 20 × 20cm) of the mixing solutions filling 1.5mol/L hydrochloric acid and 1mol/L iron(ic) chloride, zinc paper tinsel is etched; Zinc paper tinsel is etched completely, obtains graphene oxide film;
(3) graphene oxide film obtained is drawn in the second glass guide channel (long × wide is 30 × 20cm) be filled with water and cleans;
(4) graphene oxide film after cleaning being drawn to temperature is that the second warm table (length is 20cm) carries out drying, and dry temperature is 120 DEG C;
(5) by graphene oxide film after drying through passing into argon gas and temperature is carry out anneal in the High Temperature Furnaces Heating Apparatus (length is 60cm) of 900 DEG C, obtain graphene film, and graphene film be collected on the second spool.
Step (1) is obtained graphene oxide film sampling with obtain graphene film carries out X-ray diffraction, Raman spectrum is tested, the photo obtained is similar to Fig. 2, Fig. 3, not shown.
As can be seen from X-ray diffraction test result, after pyroprocessing, the characteristic peak of graphene oxide disappears, and has occurred the characteristic peak of Graphene, has illustrated that graphene oxide has been reduced into Graphene completely.
The D peak intensity of graphene film and the ratio (I of G peak intensity can be calculated from Raman spectrum test result
d/ I
g) be 1.58, and the I of graphene oxide
d/ I
gvalue is 1.70, illustrates that graphene oxide obtains reduction, and the structure of Graphene obtains reparation.
The thickness that can record graphene film with electronic digital display micrometer is 11 μm.
Observable graphene film is that black does not expand, and the film obtained with embodiment 1 equally can bend, and has good snappiness.
By testing thermal diffusivity and the specific heat capacity result of the graphene film obtained, the thermal conductivity calculating this film is 812W/ (mK).
Embodiment 4
(1) first spool release Copper Foil traction is on the first warm table (length is 50cm), be that the graphene oxide solution of 1.5mg/mL at the uniform velocity to spray to 5ml/min through 3 spraying machines on the Copper Foil of pushing ahead with the speed of 1.5cm/min and heats by concentration, Heating temperature is 140 DEG C, obtain the Copper Foil applying graphene oxide layer, can observe graphene oxide layer is black, and the Graphene become containing partial reduction is described;
(2) Copper Foil of coating graphene oxide layer is drawn in first glass guide channel (long × wide is 40 × 20cm) of the mixing solutions filling 1mol/L hydrochloric acid and 2.5mol/L iron(ic) chloride, Copper Foil is etched; Copper Foil is etched completely, obtains graphene oxide film;
(3) graphene oxide film obtained is drawn in the second glass guide channel (long × wide is 15 × 20cm) be filled with water and cleans;
(4) graphene oxide film after cleaning being drawn to temperature is that the second warm table (length is 30cm) carries out drying, and dry temperature is 90 DEG C;
(5) by graphene oxide film after drying through passing into argon gas and temperature is carry out anneal in the High Temperature Furnaces Heating Apparatus (length is 90cm) of 1100 DEG C, obtain graphene film, and graphene film be collected on the second spool.
Step (1) is obtained graphene oxide film sampling with obtain graphene film carries out X-ray diffraction, Raman spectrum is tested, the photo obtained is similar to Fig. 2, Fig. 3, not shown.
As can be seen from X-ray diffraction test result, after the high temperature anneal, the characteristic peak of graphene oxide disappears, and has occurred the characteristic peak of Graphene, has illustrated that graphene oxide has been reduced into Graphene completely.
The D peak intensity of graphene film and the ratio (I of G peak intensity can be calculated from Raman spectrum test result
d/ I
g) be 1.48, and the I of graphene oxide
d/ I
gvalue is 1.68, illustrates that graphene oxide obtains reduction, and the structure of Graphene obtains reparation.
The thickness that can record graphene film with electronic digital display micrometer is 10 μm.
Observable graphene film is that black does not expand, and the film obtained with embodiment 1 equally can bend, and has good snappiness.
By testing thermal diffusivity and the specific heat capacity result of the graphene film obtained, the thermal conductivity calculating this film is 1086W/ (mK).
Embodiment 5
(1) first spool release Copper Foil traction is on the first warm table (length is 30cm), be that the graphene oxide solution of 4mg/mL at the uniform velocity to spray to 5ml/min through 2 spraying machines on the Copper Foil of pushing ahead with the speed of 1.5cm/min and heats by concentration, Heating temperature is 120 DEG C, obtain the Copper Foil applying graphene oxide layer, can observe graphene oxide layer is black, and the Graphene become containing partial reduction is described;
(2) Copper Foil of coating graphene oxide layer is drawn in first glass guide channel (long × wide is 60 × 20cm) of the mixing solutions filling 2mol/L hydrochloric acid and 1mol/L iron(ic) chloride, Copper Foil is etched; Copper Foil is etched completely, obtains graphene oxide film;
(3) graphene oxide film obtained is drawn in the second glass guide channel (long × wide is 20 × 20cm) be filled with water and cleans;
(4) graphene oxide film after cleaning being drawn to temperature is that the second warm table (length is 30cm) carries out drying, and dry temperature is 100 DEG C;
(5) by graphene oxide film after drying through passing into argon gas and temperature is carry out anneal in the High Temperature Furnaces Heating Apparatus (length is 120cm) of 1000 DEG C, obtain graphene film, and graphene film be collected on the second spool.
Step (1) is obtained graphene oxide film sampling with obtain graphene film carries out X-ray diffraction, Raman spectrum is tested, the photo obtained is similar to Fig. 2, Fig. 3, not shown.
As can be seen from X-ray diffraction test result, after pyroprocessing, the characteristic peak of graphene oxide disappears, and has occurred the characteristic peak of Graphene, has illustrated that graphene oxide has been reduced into Graphene completely.
The D peak intensity of graphene film and the ratio (I of G peak intensity can be calculated from Raman spectrum test result
d/ I
g) be 1.47, and the I of graphene oxide
d/ I
gvalue is 1.72, illustrates that graphene oxide obtains reduction, and the structure of Graphene obtains reparation.
The thickness that can record graphene film with electronic digital display micrometer is 15 μm.
Observable graphene film is that black does not expand, and the film obtained with embodiment 1 equally can bend, and has good snappiness.
By testing thermal diffusivity and the specific heat capacity result of the graphene film obtained, the thermal conductivity calculating this film is 1021W/ (mK).
Comparative example 1
Concentration is that the graphene oxide solution of 2.5mg/mL at the uniform velocity to spray on the Copper Foil of pushing ahead with the speed of 1.5cm/min with 5ml/min through 2 spraying machines by (1) first spool release Copper Foil;
(2) by the Copper Foil being coated with graphene oxide solution through passing into argon gas and temperature is carry out anneal in the High Temperature Furnaces Heating Apparatus (length is 90cm) of 1200 DEG C, obtain the Copper Foil of graphene coated film.
Copper Foil is obtained graphene film through etching removing be collected on the second spool.
Can observe graphene film and have expansion unfairness, the thermal conductivity that measure and calculation obtains is 250W/ (mK).
As can be seen from above embodiment result, continuous seepage graphene film can be realized, and obtain the graphene film that thermal conductivity is 800-1300W/ (mK).Do not heat while spraying graphene oxide solution in comparative example 1, the graphene oxide solution of part spraying is not reduced, do not form Graphene, and directly carry out the high temperature reduction of annealing, therefore, the outward appearance of graphene film that obtains of comparative example 1 and thermal conductivity are not as the product of embodiment 1-5.
Claims (10)
1. a method for continuous seepage graphene film, comprising:
(1) graphene oxide solution is sprayed in the tinsel of continuous moving, heat described tinsel to make described graphene oxide solution film forming and to reduce at least partly simultaneously, obtain the tinsel applying graphene oxide layer, described graphene oxide layer is also containing Graphene;
(2) tinsel of described coating graphene oxide layer continuously moves through etching solution and carries out tinsel etching, obtains graphene oxide film;
(3) by described graphene oxide film continuous moving through cleaning and drying after, carry out annealing to change graphene film into completely.
2. method according to claim 1, wherein, the speed of described graphene oxide solution spraying is 4-6mL/min, described tinsel, the described tinsel of coating graphene oxide layer and the translational speed of described graphene oxide film are 0.5-2cm/min, and the temperature of described heating is 120-180 DEG C.
3. method according to claim 1 and 2, wherein, the concentration of described graphene oxide solution is 0.5-5mg/mL, and described graphene oxide solution is that chemical oxidation graphite method prepares.
4. according to the method in claim 1-3 described in any one, wherein, described etching solution is the hydrochloric acid soln of concentration 0.5-2mol/L; Or described etching solution is mixing solutions that is hydrochloric and iron(ic) chloride, and in described mixing solutions, concentration of hydrochloric acid is 0.5-2mol/L, the concentration of iron(ic) chloride is 1-3mol/L.
5. method according to claim 1, wherein, the temperature of described drying 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 tinsel is Copper Foil, aluminium foil or zinc paper tinsel.
7. the graphene film that in claim 1-6, method described in any one is obtained, the thermal conductivity of this graphene film is 800-1300W/ (mK).
8. a device for continuous seepage graphene film, this device comprises:
First spool (1), for discharging tinsel;
Spraying machine (2), for being sprayed on the tinsel from described first spool by graphene oxide solution;
First warm table (3), for hot spraying graphene oxide solution on metal foil;
First glass guide channel (4), for splendid attire etching solution with the tinsel of etching from described first warm table, obtains graphene oxide film;
Second glass guide channel (5), for splendid attire scavenging solution with the graphene oxide film of cleaning from described first glass guide channel;
Second warm table (6), for carrying out drying by the graphene oxide film from described second glass guide channel;
High Temperature Furnaces Heating Apparatus (7), for being annealed under argon gas exists by the graphene oxide film from described second warm table, obtains graphene film; And
Second spool (8), for collecting the graphene film from described High Temperature Furnaces Heating Apparatus;
Wherein, the first spool (1) and the second spool (8) rotate and make tinsel, graphene oxide film and graphene film continuous moving, realize the continuous seepage of graphene film.
9. device according to claim 8, wherein, the first warm table (3) is in the below of tinsel, and spraying machine (2) is above tinsel and corresponding first warm table (3).
10. device according to claim 8, wherein, the second warm table (6) is in the below of graphene oxide film.
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