CN105600775B - A kind of method and device of graphene film and continuous production graphene film - Google Patents
A kind of method and device of graphene film and continuous production graphene film Download PDFInfo
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Abstract
The invention discloses the method and device of a kind of graphene film and continuous production graphene film.This method includes：(1) graphene oxide solution is sprayed in the metal foil of continuous moving, simultaneously heat the metal foil so that the graphene oxide solution film forming and at least partly reduced, obtain coating the metal foil of graphene oxide layer, the graphene oxide layer also contains graphene；(2) metal foil of the coating graphene oxide layer continuously moves through etching solution and carries out metal foil etching, obtains graphene oxide film；(3) the graphene oxide film continuous moving is annealed to be completely transformed into graphene film after over cleaning and drying.This method can continuously prepare the graphene film with good pliability and thermal conductivity, can be used as 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 graphene prepared by this method are thin
Film.
Background technology
Graphene has by carbon atom with sp2Hybridized orbit composition hexangle type is in the plane layer structure of honeycomb lattice.Stone
Black alkene not only have higher specific surface area and loose structure, also with very excellent electric conductivity and mechanical property, make its
The application of multiple fields has all attracted the extensive concern of domestic and international researcher.In addition, single layer of carbon atom is arranged in graphene
Closely, it is a kind of ideal heat sink material and with higher thermal conductivity.Graphene film is used as a kind of flexible radiating
Body material, can meet the radiating requirements of the powerful devices such as computer, hand-held terminal device, LED illumination lamp.
At present, preparing the method for graphene film mainly has filter deposition method, spin coating method and interface self assembly
Method etc..
But these methods limit the continuous production of graphene film, it is difficult to produce continuous stone with realizing scale
Black alkene film.Moreover, prior art is in the reduction step of graphene film production process, usually using chemical reagent,
Reduction of the heating reduction, sodium-ammonia solution of such as hydrazine hydrate under the conditions of the dry ice bath under reduction, sodium borohydride alkalescence condition, second
Reduction of acid-hydroiodic acid solution etc., these processes need to use in general poisonous chemical reagent, cumbersome experimental procedure,
Consumption for quite a long time, and may introduce more impurity during electronation, influence its heat conductivility.
It can be seen that, it is necessary to improve the production method of graphene film, realizing the continuous production of graphene film and carrying
For higher heat conductivility.
The content of the invention
The invention aims to overcome prior art can not realize graphene film continuous production and reduction step
The defect of toxic chemical is needed, while the thermal conductivity factor having had for graphene film that continuous production is obtained, is carried
The method and device of a kind of graphene film and continuous production graphene film is supplied.
To achieve these goals, the invention provides a kind of method of continuous production graphene film, including：(1) will
Graphene oxide solution is sprayed in the metal foil of continuous moving, while heating the metal foil so that the graphene oxide is molten
Liquid film forming is simultaneously at least partly reduced, and obtains coating the metal foil of graphene oxide layer, and the graphene oxide layer also contains
Graphene；(2) metal foil of the coating graphene oxide layer continuously moves through etching solution and carries out metal foil etching, obtains
Graphene oxide film；(3) the graphene oxide film continuous moving is annealed with complete after over cleaning and drying
It is changed into graphene film.
Present invention also offers graphene film made from a kind of the inventive method, the thermal conductivity factor of the graphene film is
800-1300W/(m·K)。
Present invention also offers a kind of device of continuous production graphene film, the device includes：First spool 1, is used for
Discharge metal foil；Flush coater 2, for graphene oxide solution to be sprayed on into the metal foil from first spool；First
Warm table 3, for the graphene oxide solution of hot spraying on metal foil；First glass guide channel 4, for contain etching solution with
The metal foil from first warm table is etched, graphene oxide film is obtained；Second glass guide channel 5, for containing cleaning fluid
To clean the graphene oxide film from first glass guide channel；Second warm table 6, for second glass guide channel will to be come from
Graphene oxide film be dried；High temperature furnace 7, for by the graphene oxide film from second warm table in argon
Made annealing treatment in the presence of gas, obtain graphene film；And second spool 8, for collecting the stone from the high temperature furnace
Black alkene film；Wherein, the first spool 1 and the second spool 8, which are rotated, makes metal foil, graphene oxide film and graphene film continuous
It is mobile, realize the continuous production of graphene film.
In the method for the present invention, the metal foil of continuous moving, the metal foil of coating graphene oxide layer and oxidation stone are utilized
Black alkene film realizes continuous production graphene film.And carried out while graphene oxide solution is sprayed at heating
Reason, realizes the reduction of part graphene oxide, can avoid using toxic chemical, and under the conditions of being conducive to subsequent high temperature
Annealing does not influence the presentation quality and heat conductivility of graphene film.Therefore, graphite is being carried out using the method for the present invention
The preparation of alkene film can obtain more clean graphene film, it is not necessary to the process of cumbersome processing chemical reagent.And
Graphene film prepared by this continuous producing method can have good pliability and thermal conductivity, can be used as high-performance heat conduction material
Material, thermal conductivity factor can reach 800-1300W/ (mK).
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute a part for specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
The process flow diagram for the continuous production graphene film that Fig. 1 provides for the present invention；
Fig. 2 is the graphene oxide film obtained in embodiment 1 and the X-ray diffraction comparison diagram of graphene film；
Fig. 3 is the graphene oxide film obtained in embodiment 1 and the Raman spectrum comparison diagram of graphene film；
Fig. 4 is the scanning electron microscope diagram of the graphene film obtained in embodiment 1.
Description of reference numerals
The spools of 1- first, 2- flush coaters, the warm tables of 3- first, the glass guide channels of 4- first, the glass guide channels of 5- second, 6- second is heated
Platform, 7- high temperature furnaces, the spools of 8- second
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The present invention provides a kind of method of continuous production graphene film, as shown in figure 1, including：(1) by graphene oxide
Solution spraying is in the metal foil of continuous moving, while heating the metal foil so that the graphene oxide solution film forming and extremely
Small part is reduced, and obtains coating the metal foil of graphene oxide layer, and the graphene oxide layer also contains graphene；(2)
The metal foil of the coating graphene oxide layer continuously moves through etching solution and carries out metal foil etching, obtains graphene oxide
Film；(3) the graphene oxide film continuous moving is annealed to be completely transformed into graphite after over cleaning and drying
Alkene film.
Realized according to the present invention, in step (1) and continuously sprayed graphene oxide solution, while controlling heating institute
State metal foil.The heating can be played a part of controlling graphene oxide solution film forming, it is ensured that quality of forming film, further may be used
So that graphene oxide part is reduced, prevent the film expansion in high-temperature process and influence its heat conductivility.Wherein control
The temperature of the heating：Temperature is too high, the graphene oxide layer meeting being transformed into by graphene oxide solution in the metal foil
Appearance bursts and influences the quality of final film；Temperature is too low, graphene oxide solution can be made excessively to assemble and influence final
Film uniformity coefficient.Under preferable case, the temperature of the heating is 120-180 DEG C, preferably 140-150 DEG C
The color change of graphene oxide solution that can be by spraying on metal foil in the present invention judges whether occur
The partial reduction of graphene oxide：The color of graphene oxide solution is brown, and the color of graphene is black, when in metal foil
The graphene oxide solution of spraying film forming and is changed into black under heat effect from brown, it can be determined that the graphene oxide of film forming
Containing part through reducing obtained graphene in layer.
, can be by changing spray gun quantity, spraying rate, metal foil translational speed and graphene oxide in step (1)
The concentration of solution, it is possible to achieve regulate and control to the graphene film thickness finally obtained, the graphene that may finally be obtained is thin
The thickness of film can be minimum as little as 10 μm.Under preferable case, the speed of the graphene oxide solution spraying is 4-6mL/min.
Spray gun quantity preferably can be 2-3.
, according to the invention it is preferred in the case of, the translational speed of the metal foil is 0.5-2cm/min.Realized in the application
Continuous production graphene film, therefore the metal foil and graphene oxide film of preferably follow-up coating graphene oxide layer
Translational speed can be identical with the translational speed of the metal foil, i.e., the metal foil and the oxygen of described coating graphene oxide layer
The translational speed of graphite alkene film is 0.5-2cm/min.
, according to the invention it is preferred in the case of, the concentration of the graphene oxide solution is 0.5-5mg/mL.It is preferred that the oxygen
Graphite alkene solution can prepare for chemical oxidation graphite method (Hummers methods).
Pass through connecing metal foil and the etching solution of the coating graphene oxide layer in the step (2) of the present invention
Touch, metal foil is removed, graphene oxide film is turned into from the graphene oxide layer of coating on metal foil without substrate, wherein
The graphene yet obtained containing partial reduction.
, according to the invention it is preferred in the case of, the etching solution is concentration 0.5-2mol/L hydrochloric acid solution；Or it is described
Etching solution is that concentration of hydrochloric acid is 0.5-2mol/L, iron chloride in the hydrochloric mixed solution with iron chloride, the mixed solution
Concentration be 1-3mol/L.
According to the present invention, cleaning in step (3) can will be residual on the graphene oxide film by using cleaning fluid
The etching solution stayed is removed, and the cleaning fluid is preferably water.Drying will can be remained on the graphene oxide film
Cleaning fluid.Under preferable case, the temperature of the drying is 80-120 DEG C.
, according to the invention it is preferred in the case of, the annealing is carried out in the presence of argon gas, and the temperature of the annealing is 900-
1200℃.The graphene oxide film can be made to be reduced to graphene film completely.Heat and make described in preceding step (1)
Under, first partial reduction graphene oxide is conducive to the graphene heat conduction for obtaining better quality after the high-temperature process of annealing thin
Film.
, according to the invention it is preferred in the case of, the metal foil is copper foil, aluminium foil or zinc paper tinsel.
Present invention also offers graphene film made from a kind of the inventive method, the thermal conductivity factor of the graphene film is
800-1300W/(m·K)。
In the present invention, the graphene film of desired width can be obtained by adjusting the size of metal foil.Pass through the present invention
Method can carry out the consecutive production of graphene film.
Present invention also offers a kind of device of continuous production graphene film, as shown in figure 1, the device includes：First
Spool 1, for discharging metal foil；Flush coater 2, for graphene oxide solution to be sprayed on into the metal from first spool
On paper tinsel；First warm table 3, for the graphene oxide solution of hot spraying on metal foil；First glass guide channel 4, for containing
Etching solution obtains graphene oxide film to etch the metal foil from first warm table；Second glass guide channel 5, is used for
Cleaning fluid is contained to clean the graphene oxide film from first glass guide channel；Second warm table 6, it is described for that will come from
The graphene oxide film of second glass guide channel is dried；High temperature furnace 7, for by the graphite oxide from second warm table
Alkene film is made annealing treatment in the presence of argon gas, obtains graphene film；And second spool 8, for collecting from described
The graphene film of high temperature furnace；Wherein, the first spool 1 and the second spool 8, which are rotated, makes metal foil, graphene oxide film and graphite
Alkene film continuous moving, realizes the continuous production of graphene film.
, according to the invention it is preferred in the case of, the first warm table 3 is in the lower section of metal foil, and flush coater 2 is in the top of metal foil
And the first warm table 3 of correspondence.
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 the graphene oxide solution, first
The length of warm table 3 is 30-60cm.
In the present invention, the length of the first glass guide channel 4 is 20-60cm.Enough metal foil etchings are provided.
In the present invention, the length of the second glass guide channel 5 is 15-30cm.Enough graphene oxide film cleanings are provided, removed
The etching solution of residual.
, according to the invention it is preferred in the case of, the second warm table 6 is in the lower section of graphene oxide film.
In the present invention, the length of the second warm table 6 is 20-40cm.There is provided enough graphene oxide films to dry, remove
The cleaning fluid of residual.
In the present invention, the length of high temperature furnace 7 is 60-120cm.Realize the enough annealings for completing graphene oxide film
.
Below according to illustrate shown in Fig. 1 the present invention continuous production graphene film method the present invention provide it is continuous
Produce the course of work on the device of graphene film.
After first spool 1 release metal foil, metal foil is drawn on the first warm table 3, graphene oxide solution is filled
Flush coater 2 spray speed by graphene oxide solution spraying on metal foil with uniform, while 3 pairs of the first warm table sprays to metal
Graphene oxide solution on paper tinsel is heated, and obtains coating graphene oxide layer on metal foil；It is coated with aoxidizing stone
The metal foil of black alkene layer is guided to be performed etching in the first glass guide channel 4 for fill etching solution, has been etched after metal foil, by what is obtained
Graphene oxide film is guided to be cleaned in the second glass guide channel 5 for fill water；Then, by the graphene oxide film after cleaning
The second warm table 6 is guided to be dried, then by dried graphene oxide film through be passed through in the high temperature furnace 7 of argon gas carry out
Annealing, finally gives graphene film, and be collected on the second spool 8.Wherein, the first spool 1 and the second spool 8
Rotate, to draw metal foil, be coated with the metal foil and graphene oxide film of graphene oxide layer in whole technological process
At the uniform velocity promote, by each preparation process.
The present invention will be described in detail by way of examples below.
In following examples,
The thermal diffusion coefficient of graphene film using the laser of NETZSCH LFA 449 shine method thermal conductivity coefficient measurement instrument survey
；
The specific heat capacity of graphene film is measured using NETZSCH DSC 200F3 differential scanning calorimeters；
The thickness of graphene film is electric using the electronic digital display micrometer of the digital observing and controlling limited company in wide land or scanning
Sub- microscope (JSM-7001F SEM) measures.
With reference to 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 sodium nitrate of 12g graphite powder, the 280mL concentrated sulfuric acid and 6g is mixed, stirring adds 36g's under ice-water bath
Potassium permanganate；
Continue to stir after 30min, temperature is adjusted to 35 DEG C, be further continued for after stirring 30min, add 600mL distilled water；Will
Temperature is adjusted to 90 DEG C, continues to stir after 15min, then adds 2000mL distilled water, and temperature is adjusted to normal temperature, continues to stir 1h；
The hydrogen peroxide that 80mL is added after 1h is stood again, then suction filtration；Gained solid is dissolved in 1200-3200mL distilled water
Afterwards, centrifuge washing and dialyse, obtain 8-12mg/mL graphene oxide solution.
Above-mentioned graphene oxide solution is diluted to the graphene oxide solution that concentration is 0.5-5mg/mL with water.
Embodiment 1
This example demonstrates that the preparation method of the graphene film of the present invention.
(1) first spool release copper foil is drawn to the first warm table (length is 40cm), is 2.5mg/mL's by concentration
Graphene oxide solution is at the uniform velocity sprayed on the copper foil pushed ahead with 1.5cm/min speed through 2 flush coaters with 5ml/min
Heated, heating-up temperature is 140 DEG C, obtain coating the copper foil of graphene oxide layer, it is observed that graphene oxide layer is
Black, illustrate containing partial reduction into graphene；
(2) copper foil for coating graphene oxide layer is drawn to the mixing for filling 0.5mol/L hydrochloric acid and 3mol/L iron chloride
In the first glass guide channel (long × a width of 30 × 20cm) of solution, copper foil is performed etching；After copper foil is etched completely, aoxidized
Graphene film；
(3) obtained graphene oxide film is drawn in the second glass guide channel (long × a width of 15 × 20cm) being filled with water
Row cleaning；
(4) once purged graphene oxide film is drawn into temperature to be done for the second warm table (length is 40cm)
Dry, dry temperature is 80 DEG C；
(5) graphene oxide film after drying is passed through to the high temperature furnace (length for being passed through that argon gas and temperature are 1200 DEG C
For 90cm) in made annealing treatment, obtain graphene film, and by graphene film collection on the second spool.
Graphene film of the graphene oxide film sampling that step (1) is obtained with obtaining carries out X-ray diffraction, Raman
Spectrum test.
Fig. 2 is that X-ray diffraction (X-ray diffractometer of German Brooker D8 series) test result can be seen that high temperature and move back
After fire processing, the characteristic peak of graphene oxide disappears, and occurs in that the characteristic peak of graphene, illustrates that graphene oxide is complete
It has been reduced into graphene.
Fig. 3 is Raman spectrum (the Confocal laser-scanning microscopy instrument of RM 2000 of England (Renishaw PLC)) test result
It can calculate and obtain the ratio between the D peak intensities and G peak intensities of graphene film (ID/IG)；D peaks represent SP3The bonding model of hydridization carbon
Vibration absorption peak, such as：" C-O ", " C=O ", " O-C=O ", G peaks represent SP2The vibration absorption peak of the bonding model of hydridization carbon,
I.e.：The graphene film I obtained after " C=C ", high-temperature processD/IGValue be 1.49, and the I of graphene oxideD/IGIt is worth and is
1.67, illustrate that graphene oxide is reduced, the structure of graphene is repaired.
Obtained graphene film is scanned electron microscope (JSM-7001F SEM) observation, obtained
To Fig. 4 photo, it can be seen that graphene film has uniform layer structure, thickness is about 10 μm.
Observe obtained graphene film not expand for black, can be bent and be bent into length for 20cm film
The minimum 1.5cm of radius of curvature circular arc, with preferable pliability.
By testing the thermal diffusion coefficient and specific heat capacity result of obtained graphene film, calculating obtains leading for the film
Hot coefficient is 1302W/ (mK).
Embodiment 2
This example demonstrates that the preparation method of the graphene film of the present invention.
(1) first spool release aluminium foil is drawn to the first warm table (length is 30cm), by the oxygen that concentration is 5mg/mL
It is enterprising that graphite alkene solution at the uniform velocity sprays to the aluminium foil pushed ahead with 2cm/min speed through 2 flush coaters 2 with 4ml/min
Row heating, heating-up temperature is 120 DEG C, obtains coating the aluminium foil of graphene oxide layer, it is observed that graphene oxide layer is black
Color, illustrate containing partial reduction into graphene；
(2) aluminium foil for coating graphene oxide layer is drawn to the first glass guide channel (length × a width of for filling 2mol/L hydrochloric acid
60 × 20cm) in, aluminium foil is performed etching；After aluminium foil is etched completely, graphene oxide film is obtained；
(3) obtained graphene oxide film is drawn in the second glass guide channel (long × a width of 20 × 20cm) being filled with water
Row cleaning；
(4) once purged graphene oxide film is drawn into temperature to be done for the second warm table (length is 30cm)
Dry, dry temperature is 100 DEG C；
(5) graphene oxide film after drying is passed through to the high temperature furnace (length for being passed through that argon gas and temperature are 1000 DEG C
For 120cm) in made annealing treatment, obtain graphene film, and by graphene film collection on the second spool.
Graphene film of the graphene oxide film sampling that step (1) is obtained with obtaining carries out X-ray diffraction, Raman
Spectrum test, obtained photo is similar to Fig. 2, Fig. 3, not shown.
After X-ray diffraction test result can be seen that the high temperature anneal, the characteristic peak of graphene oxide disappears,
The characteristic peak of graphene is occurred in that, illustrates that graphene oxide has been reduced into graphene completely.
It can be calculated from Raman spectrum test result and obtain the ratio between the D peak intensities and G peak intensities of graphene film (ID/IG)
For 1.52, and the I of graphene oxideD/IGIt is worth for 1.61, illustrates that graphene oxide is reduced, the structure of graphene is obtained
Repair.
The thickness that can measure graphene film with electronic digital display micrometer is 13 μm.
Observe obtained graphene film not expand for black, the film that be the same as Example 1 is obtained can equally be bent,
With preferable pliability.
By testing the thermal diffusion coefficient and specific heat capacity result of obtained graphene film, calculating obtains leading for the film
Hot coefficient is 993W/ (mK).
Embodiment 3
This example demonstrates that the preparation method of the graphene film of the present invention.
(1) first spool release zinc paper tinsel is drawn to the first warm table 3 (length is 60cm), is 0.5mg/mL's by concentration
Graphene oxide solution is at the uniform velocity sprayed on the zinc paper tinsel pushed ahead with 0.5cm/min speed through 3 flush coaters with 6ml/min
Heated, heating-up temperature is 180 DEG C, obtain spraying the zinc paper tinsel for covering graphene oxide layer, it is observed that graphene oxide layer
For black, illustrate containing partial reduction into graphene；
(2) the zinc paper tinsel for coating graphene oxide layer is drawn to the mixing for filling 1.5mol/L hydrochloric acid and 1mol/L iron chloride
In the first glass guide channel (long × a width of 20 × 20cm) of solution, zinc paper tinsel is performed etching；After zinc paper tinsel is etched completely, aoxidized
Graphene film；
(3) obtained graphene oxide film is drawn in the second glass guide channel (long × a width of 30 × 20cm) being filled with water
Row cleaning；
(4) once purged graphene oxide film is drawn into temperature to be done for the second warm table (length is 20cm)
Dry, dry temperature is 120 DEG C；
(5) graphene oxide film after drying is passed through and is passed through argon gas and temperature (length is for 900 DEG C of high temperature furnace
Made annealing treatment in 60cm), obtain graphene film, and graphene film is collected on the second spool.
Graphene film of the graphene oxide film sampling that step (1) is obtained with obtaining carries out X-ray diffraction, Raman
Spectrum test, obtained photo is similar to Fig. 2, Fig. 3, not shown.
After X-ray diffraction test result can be seen that high-temperature process, the characteristic peak of graphene oxide disappears, and occurs
The characteristic peak of graphene, illustrates that graphene oxide has been reduced into graphene completely.
It can be calculated from Raman spectrum test result and obtain the ratio between the D peak intensities and G peak intensities of graphene film (ID/IG)
For 1.58, and the I of graphene oxideD/IGIt is worth for 1.70, illustrates that graphene oxide is reduced, the structure of graphene is obtained
Repair.
The thickness that can measure graphene film with electronic digital display micrometer is 11 μm.
Observe obtained graphene film not expand for black, the film that be the same as Example 1 is obtained can equally be bent,
With preferable pliability.
By testing the thermal diffusion coefficient and specific heat capacity result of obtained graphene film, calculating obtains leading for the film
Hot coefficient is 812W/ (mK).
Embodiment 4
(1) first spool release copper foil is drawn to the first warm table (length is 50cm), is 1.5mg/mL's by concentration
Graphene oxide solution is at the uniform velocity sprayed on the copper foil pushed ahead with 1.5cm/min speed through 3 flush coaters with 5ml/min
Heated, heating-up temperature is 140 DEG C, obtain coating the copper foil of graphene oxide layer, it is observed that graphene oxide layer is
Black, illustrate containing partial reduction into graphene；
(2) copper foil for coating graphene oxide layer is drawn to the mixing for filling 1mol/L hydrochloric acid and 2.5mol/L iron chloride
In the first glass guide channel (long × a width of 40 × 20cm) of solution, copper foil is performed etching；After copper foil is etched completely, aoxidized
Graphene film；
(3) obtained graphene oxide film is drawn in the second glass guide channel (long × a width of 15 × 20cm) being filled with water
Row cleaning；
(4) once purged graphene oxide film is drawn into temperature to be done for the second warm table (length is 30cm)
Dry, dry temperature is 90 DEG C；
(5) graphene oxide film after drying is passed through to the high temperature furnace (length for being passed through that argon gas and temperature are 1100 DEG C
For 90cm) in made annealing treatment, obtain graphene film, and by graphene film collection on the second spool.
Graphene film of the graphene oxide film sampling that step (1) is obtained with obtaining carries out X-ray diffraction, Raman
Spectrum test, obtained photo is similar to Fig. 2, Fig. 3, not shown.
After X-ray diffraction test result can be seen that the high temperature anneal, the characteristic peak of graphene oxide disappears,
The characteristic peak of graphene is occurred in that, illustrates that graphene oxide has been reduced into graphene completely.
It can be calculated from Raman spectrum test result and obtain the ratio between the D peak intensities and G peak intensities of graphene film (ID/IG)
For 1.48, and the I of graphene oxideD/IGIt is worth for 1.68, illustrates that graphene oxide is reduced, the structure of graphene is obtained
Repair.
The thickness that can measure graphene film with electronic digital display micrometer is 10 μm.
Observe obtained graphene film not expand for black, the film that be the same as Example 1 is obtained can equally be bent,
With preferable pliability.
By testing the thermal diffusion coefficient and specific heat capacity result of obtained graphene film, calculating obtains leading for the film
Hot coefficient is 1086W/ (mK).
Embodiment 5
(1) first spool release copper foil is drawn to the first warm table (length is 30cm), by the oxygen that concentration is 4mg/mL
It is enterprising that graphite alkene solution at the uniform velocity sprays to the copper foil pushed ahead with 1.5cm/min speed through 2 flush coaters with 5ml/min
Row heating, heating-up temperature is 120 DEG C, obtains coating the copper foil of graphene oxide layer, it is observed that graphene oxide layer is black
Color, illustrate containing partial reduction into graphene；
(2) by coat graphene oxide layer copper foil be drawn to fill 2mol/L hydrochloric acid and 1mol/L iron chloride mixing it is molten
In the first glass guide channel (long × a width of 60 × 20cm) of liquid, copper foil is performed etching；After copper foil is etched completely, obtain aoxidizing stone
Black alkene film；
(3) obtained graphene oxide film is drawn in the second glass guide channel (long × a width of 20 × 20cm) being filled with water
Row cleaning；
(4) once purged graphene oxide film is drawn into temperature to be done for the second warm table (length is 30cm)
Dry, dry temperature is 100 DEG C；
(5) graphene oxide film after drying is passed through to the high temperature furnace (length for being passed through that argon gas and temperature are 1000 DEG C
For 120cm) in made annealing treatment, obtain graphene film, and by graphene film collection on the second spool.
Graphene film of the graphene oxide film sampling that step (1) is obtained with obtaining carries out X-ray diffraction, Raman
Spectrum test, obtained photo is similar to Fig. 2, Fig. 3, not shown.
After X-ray diffraction test result can be seen that high-temperature process, the characteristic peak of graphene oxide disappears, and occurs
The characteristic peak of graphene, illustrates that graphene oxide has been reduced into graphene completely.
It can be calculated from Raman spectrum test result and obtain the ratio between the D peak intensities and G peak intensities of graphene film (ID/IG)
For 1.47, and the I of graphene oxideD/IGIt is worth for 1.72, illustrates that graphene oxide is reduced, the structure of graphene is obtained
Repair.
The thickness that can measure graphene film with electronic digital display micrometer is 15 μm.
Observe obtained graphene film not expand for black, the film that be the same as Example 1 is obtained can equally be bent,
With preferable pliability.
By testing the thermal diffusion coefficient and specific heat capacity result of obtained graphene film, calculating obtains leading for the film
Hot coefficient is 1021W/ (mK).
Comparative example 1
(1) first spool discharge copper foil, by concentration for 2.5mg/mL graphene oxide solution through 2 flush coaters with 5ml/
Min is at the uniform velocity sprayed on the copper foil pushed ahead with 1.5cm/min speed；
(2) copper foil for being coated with graphene oxide solution passes through to be passed through argon gas and temperature (long for 1200 DEG C of high temperature furnace
Spend for 90cm) in made annealing treatment, obtain the copper foil of graphene coated film.
The etched removing of copper foil is obtained into graphene film to collect on the second spool.
It is observed that graphene film has expansion out-of-flatness, the thermal conductivity factor that measure and calculation is obtained is 250W/ (mK).
It can be seen that by above example result, it is possible to achieve continuously produce graphene film, and obtain thermal conductivity factor
For 800-1300W/ (mK) graphene film.Do not carried out in comparative example 1 while graphene oxide solution is sprayed
Heating, the graphene oxide solution without part spraying is reduced, and does not form graphene, and the high temperature directly annealed is also
Original, therefore, the outward appearance and thermal conductivity factor of the graphene film that comparative example 1 is obtained are not so good as embodiment 1-5 product.
Claims (9)
1. a kind of method of continuous production graphene film, including：
(1) graphene oxide solution is sprayed in the metal foil of continuous moving, while heating the metal foil so that the oxygen
Graphite alkene solution film forming is simultaneously at least partly reduced, and obtains coating the metal foil of graphene oxide layer, the graphite oxide
Alkene layer also contains graphene；
(2) metal foil of the coating graphene oxide layer continuously moves through etching solution and carries out metal foil etching, obtains oxygen
Graphite alkene film；
(3) the graphene oxide film continuous moving is annealed to be completely transformed into graphite after over cleaning and drying
Alkene film；
The temperature heated described in step (1) is 120-180 DEG C.
2. according to the method described in claim 1, wherein, the speed of graphene oxide solution spraying is 4-6mL/min, institute
The translational speed for stating metal foil, the metal foil of coating graphene oxide layer and the graphene oxide film is 0.5-2cm/
min。
3. method according to claim 1 or 2, wherein, the concentration of the graphene oxide solution is 0.5-5mg/mL, institute
Graphene oxide solution is stated to prepare for chemical oxidation graphite method.
4. method according to claim 1 or 2, wherein, the etching solution is concentration 0.5-2mol/L hydrochloric acid solution；
Or the etching solution is that concentration of hydrochloric acid is 0.5-2mol/ in the hydrochloric mixed solution with iron chloride, the mixed solution
L, the concentration of iron chloride is 1-3mol/L.
5. method according to claim 3, wherein, the etching solution is concentration 0.5-2mol/L hydrochloric acid solution；Or
Etching solution described in person is that concentration of hydrochloric acid is 0.5-2mol/L in the hydrochloric mixed solution with iron chloride, the mixed solution,
The concentration of iron chloride is 1-3mol/L.
6. according to the method described in claim 1, wherein, the temperature of the drying is 80-120 DEG C；The annealing is deposited in argon gas
Carried out lower, the temperature of the annealing is 900-1200 DEG C.
7. according to the method described in claim 1, wherein, the metal foil be copper foil, aluminium foil or zinc paper tinsel.
8. a kind of device of continuous production graphene film, the device includes：
First spool (1), for discharging metal foil；
Flush coater (2), for graphene oxide solution to be sprayed on into the metal foil from first spool；
First warm table (3), for the graphene oxide solution of hot spraying on metal foil；
First glass guide channel (4), for containing etching solution to etch the metal foil from first warm table, obtains aoxidizing stone
Black alkene film；
Second glass guide channel (5), for containing cleaning fluid to clean the graphene oxide film from first glass guide channel；
Second warm table (6), for the graphene oxide film from second glass guide channel to be dried；
High temperature furnace (7), for the graphene oxide film from second warm table to be annealed in the presence of argon gas, is obtained
To graphene film；And
Second spool (8), for collecting the graphene film from the high temperature furnace；
Wherein, the first spool (1) and the second spool (8), which are rotated, makes metal foil, graphene oxide film and graphene film continuous
It is mobile, realize the continuous production of graphene film；
First warm table (3) is in the lower section of metal foil, and flush coater (2) is in the top of metal foil and the first warm table of correspondence (3).
9. device according to claim 8, wherein, the second warm table (6) is in the lower section of graphene oxide film.
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| CN108751172A (en) * | 2018-06-26 | 2018-11-06 | 哈尔滨万鑫石墨谷科技有限公司 | A kind of preparation method of graphene film and products thereof and purposes |
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| CN111085416A (en) * | 2019-12-02 | 2020-05-01 | 深圳石墨烯创新中心有限公司 | Graphene composite metal foil and preparation method thereof |
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