CN107910129A - A kind of preparation method of graphene/carbon nano-tube compound transparent electricity conductive film - Google Patents
A kind of preparation method of graphene/carbon nano-tube compound transparent electricity conductive film Download PDFInfo
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Abstract
The present invention discloses a kind of preparation method of graphene/carbon nano-tube compound transparent electricity conductive film, i.e., graphene oxide solution is spread over LB first is film-made on the aqueous phase interface of instrument, and graphene oxide layer is obtained after static 10 60min；Then, carbon nano-tube solution is equably spread over to LB to be film-made in the graphene oxide layer of instrument, the Graphene/carbon nanotube composite material obtained after static 10 30min；Then lifted, be transferred in transparent substrates, under room temperature 0.5 48h of reduction is carried out through hydrazine hydrate, graphene/carbon nano-tube compound transparent electricity conductive film is obtained, since it has higher transparency and preferable photoelectric properties, can be applied to the preparation of flexible display device.The preparation method process of the present invention is simple, workable.
Description
Technical field
The present invention relates to a kind of preparation method of graphene/carbon nano-tube compound transparent electricity conductive film, belongs to materialogy neck
Domain.
Background technology
Graphene, refers to the tightly packed single layer of carbon atom into bi-dimensional cellular shape lattice structure, it is to build other raws material of wood-charcoal
The basic structural unit of material.Because of its special two dimensional crystal structure, and excellent performance, such as higher Young's modulus, stronger
Mechanical strength, high electron mobility, high thermal conductivity coefficient, high-specific surface area, the high grade of transparency, magnet etc., graphene is transparent
Before conductive film, composite material, catalysis material, energy storage material, gas sensor and gas field of storage have development well
Scape.
The preparation method of compound transparent electricity conductive film has many kinds, such as transfer printing method, dip coating method, spraying at present
Method, whirl coating, club rubbing method, electrophoretic deposition etc., but these methods all cannot control nanometer material in molecular level
The behavior of material, therefore phenomena such as prepared film easily makes raw material that accumulation, skewness occur, so as to cause prepared
Transparent conductive film transparency is high, electric conductivity is restricted；Yang et al. prepares graphene/carbon with L B film analysis instrument
Nanotube compound transparent electricity conductive film (RSC Advances, 2015,5,23650-23657), using first lifting one layer of oxidation stone
Black alkene, then the stepping mode progress of one layer of carbon nanotubes is lifted, therefore preparation process has preparation process complexity, while there is system
The standby technical problem such as the cycle is long, preparation efficiency is low.
The content of the invention
An object of the present invention was prepared to solve above-mentioned graphene/carbon nano-tube compound transparent electricity conductive film
Journey is complicated, while provides one kind there are the technical problem such as long preparation period, efficiency is low and prepare graphite using L B masking techniques
The method of alkene/carbon nanotubes compound transparent electricity conductive film, the preparation method is simple with preparation process, workable, at the same time
There are the advantages of short preparation period, efficiency height etc..
Technical scheme
A kind of preparation method of graphene/carbon nano-tube compound transparent electricity conductive film, that is, utilize Langmuir-Blodgett
Transparent substrates, are cleaned by ultrasonic, hydrophily is handled, drying by masking technique first；Then graphene oxide is spread over L B
It is film-made on the aqueous phase interface of instrument, after static 0-60min, then carbon nanotubes is equably spread over to the water phase of L B film instrument again
On interface, static 0-30min, then again by obtained graphene/carbon nano-tube control pull rate for 0.1-10mm/min into
Row is transferred in the transparent substrates of drying after lifting 1-100 times, is then passed through hydrazine hydrate reduction 0.5-48h at normal temperatures, is obtained
Graphene/carbon nano-tube compound transparent electricity conductive film, its preparation process specifically include following steps：
(1), transparent substrates are cleaned by ultrasonic 15min respectively with acetone, deionized water, alcohol successively, then with volume hundred
Divide the ammonium hydroxide that specific concentration is 1-28% to soak 0.5-48h, be dried for standby controlled at 30-60 DEG C；
The transparent substrates are polyethylene terephthalate, light transmittance 70-98%；
The condition that above-mentioned acetone, deionized water, alcohol are cleaned by ultrasonic is：It is controlled at 10-30 DEG C, frequency
20-130KHz；
(2), the preparation of methanol aqueous solution
Methanol is soluble in water, it is uniformly mixed, it is 35-95% methanol aqueous solutions to obtain concentration of volume percent, spare；
(3), the preparation of graphene oxide water solution
Add graphene oxide into water, jiggling is uniformly dissolved graphene oxide, and it is 0.01- to obtain concentration
The graphene oxide water solution of 3mg/ml, it is spare；
(4), the preparation of carbon nano-tube aqueous solutions
Carbon nanotubes is added to the water, it is 0.01-3mg/ to obtain concentration after mixing under conditions of ultrasonic disperse
The carbon nano-tube aqueous solutions of ml, it is spare；
The condition of ultrasonic disperse：Controlled at 10-30 DEG C, frequency 20-60KHz；
The carbon nanotubes is single-walled carbon nanotube or multi-walled carbon nanotube；
(5), the methanol aqueous solution obtained by step (2), the graphene oxide water solution obtained by step (3) mix
It is even, it is spare to obtain graphene oxide solution；
The amount of methanol aqueous solution, graphene oxide water solution used in above-mentioned mixing, by graphene oxide water solution
Graphene oxide：Methanol aqueous solution is 1g:The ratio of 10-1000ml calculates；
(6), the methanol aqueous solution obtained by step (2), the carbon nano-tube aqueous solutions obtained by step (4) mix
It is even, it is spare to obtain carbon nano-tube solution；
The dosage of methanol aqueous solution, carbon nano-tube aqueous solutions used in above-mentioned mixing, by the carbon in carbon nano-tube aqueous solutions
Nanotube：Methanol aqueous solution is 1g:The ratio of 10-1000ml calculates；
(7), the graphene oxide solution obtained by 5-20ml steps (5) is taken, the aqueous phase interface in LB film instrument is added dropwise dropwise
On, static 10-60min, obtains graphene oxide layer；
The sink size of LB film instrument ranges preferably from long 5-100cm, width 5-100cm；
(8), the carbon nano-tube solution obtained by 5-10ml steps (6) is taken, the graphite oxide in LB film instrument is equably added dropwise
On alkene lamella, static 10-30min, Graphene/carbon nanotube composite material is obtained on the aqueous phase interface of LB film instrument；
(9), by the Graphene/carbon nanotube composite material obtained by step (8) control pull rate for 1-10mm/min into
Row is transferred to after lifting 1-100 times in the transparent substrates after step (1) processing, and hydrazine hydrate reduction 0.5- is then passed through under room temperature
48h, obtains graphene/carbon nano-tube compound transparent electricity conductive film.
The graphene/carbon nano-tube compound transparent electricity conductive film of above-mentioned gained, due to its have higher transparency and compared with
Good photoelectric properties, therefore it can be applied to the preparation of flexible display device.
Beneficial effects of the present invention
Compared with prior art, a kind of preparation method of graphene/carbon nano-tube compound transparent electricity conductive film of the invention,
Since the present invention is that hydrophobic carbon nano-tube solution is added dropwise on graphene oxide layer, the parent of carbon nanotubes is eliminated
Aqueous treatment process, therefore there is the advantages of preparation method is simple, workable.
Further, compared with prior art, a kind of system of graphene/carbon nano-tube compound transparent electricity conductive film of the invention
Preparation Method, is shifted after being lifted at the same time using two kinds of materials of graphene oxide and carbon nanotubes due to the present invention, is had and is prepared
The advantages of cycle is short, efficient.
Further, the stone that a kind of preparation method of graphene/carbon nano-tube compound transparent electricity conductive film of the invention obtains
Black alkene/carbon nanotubes compound transparent electricity conductive film, has higher transparency and preferable photoelectric properties.
In conclusion a kind of preparation method of graphene/carbon nano-tube compound transparent electricity conductive film of the present invention, due to tool
Have that preparation method is simple, it is workable, while there is short preparation period, efficient, therefore be produced on a large scale.
Brief description of the drawings
The atomic force of the obtained graphene/carbon nano-tube compound transparent electricity conductive film configuration of surface of Fig. 1 a, embodiment 1 is shown
Micro mirror (AFM) photo；
The atom of the obtained graphene/carbon nano-tube compound transparent electricity conductive film surface sections height of Fig. 1 b, embodiment 1
Force microscope (AFM) photo；
The atom of the obtained graphene/carbon nano-tube compound transparent electricity conductive film three-dimensional stereo topography of Fig. 1 c, embodiment 1
Force microscope (AFM) photo；
The light transmission characterization of the obtained graphene/carbon nano-tube compound transparent electricity conductive film of Fig. 2, embodiment 1；
The photoelectric properties characterization of the obtained graphene/carbon nano-tube compound transparent electricity conductive film of Fig. 3, embodiment 1-4.
Embodiment
The present invention is further illustrated below by specific embodiment and with reference to attached drawing, but is not intended to limit the present invention
Implementation.
LB used film instrument in various embodiments of the present invention, the sink size scope of model Medium, LB film instrument are
Long 5-100cm, the production of width 5-100cm, KSV NIMA companies.
Raw material used is common commercially available in various embodiments of the present invention.
Embodiment 1
A kind of preparation method of graphene/carbon nano-tube compound transparent electricity conductive film, specifically includes following steps：
(1), transparent substrates are cleaned by ultrasonic 15min and then with volume hundred respectively with acetone, deionized water, alcohol successively
Divide the ammonium hydroxide that specific concentration is 28% to soak 0.5h, be then dried for standby controlled at 40 DEG C；
The transparent substrates are polyethylene terephthalate, light transmittance 70-98%；
Acetone, deionized water, the condition of alcohol ultrasonic cleaning are：Controlled at 30 DEG C, frequency 130KHz；
(2), the preparation of methanol aqueous solution
Methanol is soluble in water, it is uniformly mixed, it is 95% methanol aqueous solution to obtain concentration of volume percent, spare；
(3), the preparation of graphene oxide water solution
Add graphene oxide into water, jiggling is uniformly dissolved graphene oxide, and it is 0.01mg/ to obtain concentration
The graphene oxide water solution of ml, it is spare；
(4), the preparation of carbon nano-tube aqueous solutions
Carbon nanotubes is added to the water, it is then uniform for 20KHz ultrasonic mixings controlled at 30 DEG C, frequency, obtain
Concentration is the carbon nano-tube aqueous solutions of 0.01mg/ml, and the carbon nanotubes is single-walled carbon nanotube；
(5), the methanol aqueous solution obtained by step (2), the graphene oxide water solution obtained by step (3) mix
It is even, it is spare to obtain graphene oxide solution；
The amount of methanol aqueous solution, graphene oxide water solution used in above-mentioned mixing, by graphene oxide water solution
Graphene oxide：Methanol aqueous solution is 1g:The ratio of 10ml calculates；
(6), the methanol aqueous solution obtained by step (2), the carbon nano-tube aqueous solutions obtained by step (4) mix
It is even, it is spare to obtain carbon nano-tube solution；
The dosage of methanol aqueous solution, carbon nano-tube aqueous solutions used in above-mentioned mixing, by the carbon in carbon nano-tube aqueous solutions
Nanotube：Methanol aqueous solution is 1g:The ratio of 10ml calculates；
(7), the graphene oxide solution obtained by 5ml steps (5) is taken, is added dropwise dropwise on the aqueous phase interface of LB film instrument,
Static 10min, obtains graphene oxide layer；
(8), the carbon nano-tube solution obtained by 5ml steps (6) is taken, the graphene oxide sheet in LB film instrument is equably added dropwise
On layer, static 10min, Graphene/carbon nanotube composite material is obtained on the aqueous phase interface of LB film instrument；
(9), pull rate is controlled to be carried for 1mm/min the Graphene/carbon nanotube composite material obtained by step (8)
It is transferred to after drawing 1 time in the transparent substrates after step (1) processing, then carries out reduction 0.5h through hydrazine hydrate under room temperature, obtain
Graphene/carbon nano-tube compound transparent electricity conductive film.
Using Scanning Probe Microscope-NanoScope, Digital Instruments instruments to above-mentioned
The graphene/carbon nano-tube compound transparent electricity conductive film configuration of surface of gained is observed, the atomic force microscope (AFM) of gained
Photo as shown in Figure 1a, it can be seen that carbon nanotubes is evenly distributed on graphene oxide from Fig. 1 a, is indicated above the film
It is combined for one layer of graphene oxide and one layer of carbon nanotubes, therefore the use LB of the present invention is film-made method in graphene oxide sheet
The method that carbon nanotubes and 1 lifting film are added dropwise on layer is feasible；
Using Scanning Probe Microscope-NanoScope, Digital Instruments instruments to above-mentioned
The graphene/carbon nano-tube compound transparent electricity conductive film surface sections of gained are highly observed and its cross section are divided
Analysis, atomic force microscope (AFM) photo of gained as shown in Figure 1 b, can be seen that film thickness average out to 2nm from Fig. 1 b；
Using Scanning Probe Microscope-NanoScope, Digital Instruments instruments to above-mentioned
The graphene/carbon nano-tube compound transparent electricity conductive film three-dimensional stereo topography of gained is observed, the atomic force microscope of gained
(AFM) as illustrated in figure 1 c, it can be seen that carbon nanotubes is evenly distributed in surface of graphene oxide from Fig. 1 c, soilless sticking is existing for photo
As occurring, it is indicated above that carbon nanotubes is added dropwise in graphene oxide layer using LB film methods and 1 lifting is obtained thin
Film is uniform；
Using Perkin Elmer Lambda 750UV-Vis spectrometer instruments to the graphene of above-mentioned gained/
The light transmittance of carbon nanotubes compound transparent electricity conductive film measures, the graphene/carbon nano-tube composite transparent conductive thin of gained
The light transmission situation of film is as shown in Fig. 2, as can be seen from Figure 2 graphene/carbon nano-tube compound transparent electricity conductive film is in light
Wavelength is that the light transmittance at 550nm is 93%, is indicated above being led as the graphene/carbon nano-tube composite transparent prepared by the present invention
Conductive film has higher light transmittance.
Using 750 UV-Vis spectrometer instruments of Perkin Elmer Lambda and Scientific
The four-point probe instrument of Equipment＆Services is respectively to the graphene/carbon nano-tube composite transparent conductive thin of above-mentioned gained
The sheet resistance of film measures, photoelectric characteristic figure such as Fig. 3 institutes of the graphene/carbon nano-tube compound transparent electricity conductive film of gained
Show, as can be seen from Figure 3 graphene/carbon nano-tube compound transparent electricity conductive film when light transmittance is more than 85%, graphene/
The sheet resistance of carbon nanotubes compound transparent electricity conductive film can reach 600 Ω/sq, be indicated above as the stone prepared by the present invention
Black alkene/carbon nanotubes compound transparent electricity conductive film has preferable photoelectric characteristic.
Embodiment 2
A kind of preparation method of graphene/carbon nano-tube compound transparent electricity conductive film, specifically includes following steps：
(1), transparent substrates are cleaned by ultrasonic 15min and then with volume hundred respectively with acetone, deionized water, alcohol successively
Divide the ammonium hydroxide that specific concentration is 20% to soak 10h, be then dried for standby controlled at 60 DEG C；
The transparent substrates are polyethylene terephthalate, light transmittance 70-98%；
Acetone, deionized water, the condition of alcohol ultrasonic cleaning are：Controlled at 25 DEG C, frequency 100KHz；
(2), the preparation of methanol aqueous solution
Methanol is soluble in water, it is uniformly mixed, it is 55% methanol aqueous solution to obtain concentration of volume percent, spare；
(3), the preparation of graphene oxide water solution
Add graphene oxide into water, jiggling is uniformly dissolved graphene oxide, and it is 0.1mg/ to obtain concentration
The graphene oxide water solution of ml, it is spare；
(4), the preparation of carbon nano-tube aqueous solutions
Carbon nanotubes is added to the water, it is then uniform for 30KHz ultrasonic mixings controlled at 25 DEG C, frequency, obtain
Concentration is the carbon nano-tube aqueous solutions of 0.1mg/ml, and the carbon nanotubes is multi-walled carbon nanotube；
(5), the methanol aqueous solution obtained by step (2), the graphene oxide water solution obtained by step (3) mix
It is even, it is spare to obtain graphene oxide solution；
The amount of methanol aqueous solution, graphene oxide water solution used in above-mentioned mixing, by graphene oxide water solution
Graphene oxide：Methanol aqueous solution is 1g:The ratio of 40ml calculates；
(6), the methanol aqueous solution obtained by step (2), the carbon nano-tube aqueous solutions obtained by step (4) mix
It is even, it is spare to obtain carbon nano-tube solution；
The dosage of methanol aqueous solution, carbon nano-tube aqueous solutions used in above-mentioned mixing, by the carbon in carbon nano-tube aqueous solutions
Nanotube：Methanol aqueous solution is 1g:The ratio of 40ml calculates；
(7), the graphene oxide solution obtained by 10ml steps (5) is taken, is added dropwise dropwise on the aqueous phase interface of LB film instrument,
Static 20min, obtains graphene oxide layer；
(8), the carbon nano-tube solution obtained by 10ml steps (6) is taken, the graphene oxide in LB film instrument is equably added dropwise
On lamella, static 20min, Graphene/carbon nanotube composite material is obtained in the aqueous phase interface of LB film instrument；
(9), pull rate is controlled to be carried for 5mm/min the Graphene/carbon nanotube composite material obtained by step (8)
It is transferred to after drawing 3 times in the transparent substrates after step (1) processing, then carries out reduction 5h through hydrazine hydrate under room temperature, obtain stone
Black alkene/carbon nanotubes compound transparent electricity conductive film.
Embodiment 3
A kind of preparation method of graphene/carbon nano-tube compound transparent electricity conductive film, specifically includes following steps：
(1), transparent substrates are cleaned by ultrasonic 15min and then with volume hundred respectively with acetone, deionized water, alcohol successively
Divide the ammonium hydroxide that specific concentration is 10% to soak 25h, be then dried for standby controlled at 30 DEG C；
The transparent substrates are polyethylene terephthalate, light transmittance 70-98%；
Acetone, deionized water, the condition of alcohol ultrasonic cleaning are：Controlled at 15 DEG C, frequency 80KHz；
(2), the preparation of methanol aqueous solution
Methanol is soluble in water, it is uniformly mixed, it is 35% methanol aqueous solution to obtain concentration of volume percent, spare；
(3), the preparation of graphene oxide water solution
Add graphene oxide into water, jiggling is uniformly dissolved graphene oxide, and it is 1mg/ml to obtain concentration
Graphene oxide water solution, it is spare；
(4), the preparation of carbon nano-tube aqueous solutions
Carbon nanotubes is added to the water, it is then uniform for 40KHz ultrasonic mixings controlled at 20 DEG C, frequency, obtain
Concentration is the carbon nano-tube aqueous solutions of 1mg/ml, and the carbon nanotubes is single-walled carbon nanotube；
(5), the methanol aqueous solution obtained by step (2), the graphene oxide water solution obtained by step (3) mix
It is even, it is spare to obtain graphene oxide solution；
The amount of methanol aqueous solution, graphene oxide water solution used in above-mentioned mixing, by graphene oxide water solution
Graphene oxide：Methanol aqueous solution is 1g:The ratio of 500ml calculates；
(6), the methanol aqueous solution obtained by step (2), the carbon nano-tube aqueous solutions obtained by step (4) mix
It is even, it is spare to obtain carbon nano-tube solution；
The dosage of methanol aqueous solution, carbon nano-tube aqueous solutions used in above-mentioned mixing, by the carbon in carbon nano-tube aqueous solutions
Nanotube：Methanol aqueous solution is 1g:The ratio of 500ml calculates；
(7), the graphene oxide solution obtained by 20ml steps (5) is taken, is added dropwise dropwise on the aqueous phase interface of LB film instrument,
Static 60min, obtains graphene oxide layer；
(8), the carbon nano-tube solution obtained by 5ml steps (6) is taken, the graphene oxide sheet in LB film instrument is equably added dropwise
On layer, static 30min, Graphene/carbon nanotube composite material is obtained on the aqueous phase interface of LB film instrument；
(9), pull rate is controlled to be carried out for 10mm/min the Graphene/carbon nanotube composite material obtained by step (8)
It is transferred to after lifting 50 times in the transparent substrates after step (1) processing, then carries out reduction 30h through hydrazine hydrate under room temperature, obtain
To graphene/carbon nano-tube compound transparent electricity conductive film.
Embodiment 4
A kind of preparation method of graphene/carbon nano-tube compound transparent electricity conductive film, specifically includes following steps：
(1), transparent substrates are cleaned by ultrasonic 15min and then with volume hundred respectively with acetone, deionized water, alcohol successively
Divide the ammonium hydroxide that specific concentration is 1% to soak 48h, be then dried for standby controlled at 30 DEG C；
The transparent substrates are polyethylene terephthalate, light transmittance 70-98%；
Acetone, deionized water, the condition of alcohol ultrasonic cleaning are：Controlled at 10 DEG C, frequency 20KHz；
(2), the preparation of methanol aqueous solution
Methanol is soluble in water, it is uniformly mixed, it is 35% methanol aqueous solution to obtain concentration of volume percent, spare；
(3), the preparation of graphene oxide water solution
Add graphene oxide into water, jiggling is uniformly dissolved graphene oxide, and it is 3mg/ml to obtain concentration
Graphene oxide water solution, it is spare；
(4), the preparation of carbon nano-tube aqueous solutions
Carbon nanotubes is added to the water, it is then uniform for 60KHz ultrasonic mixings controlled at 10 DEG C, frequency, obtain
Concentration is the carbon nano-tube aqueous solutions of 3mg/ml, and the carbon nanotubes is single-walled carbon nanotube；
(5), the methanol aqueous solution obtained by step (2), the graphene oxide water solution obtained by step (3) mix
It is even, it is spare to obtain graphene oxide solution；
The amount of methanol aqueous solution, graphene oxide water solution used in above-mentioned mixing, by graphene oxide water solution
Graphene oxide：Methanol aqueous solution is 1g:The ratio of 1000ml calculates；
(6), the methanol aqueous solution obtained by step (2), the carbon nano-tube aqueous solutions obtained by step (4) mix
It is even, it is spare to obtain carbon nano-tube solution；
The dosage of methanol aqueous solution, carbon nano-tube aqueous solutions used in above-mentioned mixing, by the carbon in carbon nano-tube aqueous solutions
Nanotube：Methanol aqueous solution is 1g:The ratio of 1000ml calculates；
(7), the graphene oxide solution obtained by 20ml steps (5) is taken, is added dropwise dropwise on the aqueous phase interface of LB film instrument,
Static 60min, obtains graphene oxide layer；
(8), the carbon nano-tube solution obtained by 5ml steps (6) is taken, the graphene oxide sheet in LB film instrument is equably added dropwise
On layer, static 30min, Graphene/carbon nanotube composite material is obtained on the aqueous phase interface of LB film instrument；
(9), pull rate is controlled to be carried out for 10mm/min the Graphene/carbon nanotube composite material obtained by step (10)
It is transferred to after lifting 100 times in the transparent substrates after step (1) processing, then carries out reduction 48h through hydrazine hydrate under room temperature, obtain
To graphene/carbon nano-tube compound transparent electricity conductive film.
In conclusion a kind of preparation method of graphene/carbon nano-tube compound transparent electricity conductive film of the present invention, and it is existing
Technology is compared, and eliminates the hydrophily processing procedure of carbon nanotubes, and lifted at the same time simultaneously with carbon nanotubes using graphene oxide
Transfer, thus it is simple with preparation method, it is workable, there is short preparation period, efficient, while the stone of gained
Black alkene/carbon nanotubes compound transparent electricity conductive film has higher light transmittance and preferable photoelectric characteristic.
The principle of the present invention and its effect is only illustrated in above example, not for the limitation present invention.It is any ripe
Know the personage of this technology all can carry out modifications and changes under the spirit and scope without prejudice to the present invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete without departing from disclosed spirit and institute under technological thought such as
Into all equivalent modifications or change, should by the present invention claim be covered.
Claims (7)
- A kind of 1. preparation method of graphene/carbon nano-tube compound transparent electricity conductive film, it is characterised in that：First, graphene oxide solution is spread on the aqueous phase interface of LB film instrument, after static 10-60min, is film-made in LB Graphene oxide layer is obtained on the aqueous phase interface of instrument；Then, in the graphene oxide layer that carbon nano-tube solution is equably spread over to LB film instrument, static 10-30min, The Graphene/carbon nanotube composite material obtained on the aqueous phase interface of LB film instrument；Then, pull rate is controlled to carry out lifting 1-100 for 1-10mm/min obtained Graphene/carbon nanotube composite material It is transferred to after secondary in transparent substrates, carries out reduction 0.5-48h through hydrazine hydrate under room temperature, it is compound to obtain graphene/carbon nano-tube Bright conductive film.
- 2. a kind of preparation method of graphene/carbon nano-tube compound transparent electricity conductive film as claimed in claim 1, its feature exist In the transparent substrates be polyethylene terephthalate, light transmittance 70-98%.
- 3. a kind of preparation method of graphene/carbon nano-tube compound transparent electricity conductive film as claimed in claim 2, its feature exist In specifically comprising the following steps：（1）, by transparent substrates successively with acetone, deionized water, alcohol respectively controlled at 10-30 DEG C, frequency 20- 130KHz carries out ultrasonic cleaning 15min, and the ammonium hydroxide for being then 1-28% with concentration of volume percent soaks 0.5-48h, controls temperature It is dried for standby for 30-60 DEG C；（2）, methanol aqueous solution preparationMethanol is soluble in water, it is uniformly mixed, it is 35-95% methanol aqueous solutions to obtain concentration of volume percent, spare；（3）, graphene oxide water solution preparationAdd graphene oxide into water, jiggling is uniformly dissolved graphene oxide, and it is 0.01-3mg/ml to obtain concentration Graphene oxide water solution, it is spare；（4）, carbon nano-tube aqueous solutions preparationCarbon nanotubes is added to the water, it is 0.01-3mg/ml's to obtain concentration after mixing under conditions of ultrasonic disperse Carbon nano-tube aqueous solutions, it is spare；The condition of ultrasonic disperse：Controlled at 10-30 DEG C, frequency 20-60KHz；The carbon nanotubes is single-walled carbon nanotube or multi-walled carbon nanotube；（5）, by step（2）The methanol aqueous solution of gained, step（3）The graphene oxide water solution of gained is uniformly mixed, It is spare to obtain graphene oxide solution；The amount of methanol aqueous solution, graphene oxide water solution used in above-mentioned mixing, by the oxidation in graphene oxide water solution Graphene：Methanol aqueous solution is 1g:The ratio of 10-1000ml calculates；（6）, by step（2）The methanol aqueous solution of gained, step（4）The carbon nano-tube aqueous solutions of gained are uniformly mixed, and are obtained It is spare to carbon nano-tube solution；The dosage of methanol aqueous solution, carbon nano-tube aqueous solutions used in above-mentioned mixing, by the carbon nanometer in carbon nano-tube aqueous solutions Pipe：Methanol aqueous solution is 1g:The ratio of 10-1000ml calculates；（7）, take 5-20ml steps（5）The graphene oxide solution of gained, is added dropwise on the aqueous phase interface of LB film instrument dropwise, quiet Only 10-60min, obtains graphene oxide layer；The sink size of LB film instrument is long 5-100cm, width 5-100cm；（8）, take 5-10ml steps（6）The carbon nano-tube solution of gained, is equably added dropwise the graphene oxide sheet in LB film instrument On layer, static 10-30min, Graphene/carbon nanotube composite material is obtained on the aqueous phase interface of LB film instrument；（9）, by step（8）The Graphene/carbon nanotube composite material of gained controls pull rate to be carried for 1-10mm/min It is transferred to after drawing 1-100 times through step（1）In transparent substrates after processing, hydrazine hydrate reduction 0.5-48h is then passed through under room temperature, Obtain graphene/carbon nano-tube compound transparent electricity conductive film.
- 4. a kind of preparation method of graphene/carbon nano-tube compound transparent electricity conductive film as claimed in claim 3, its feature exist In：Step（1）In, it is controlled at 30 DEG C, frequency respectively with acetone, deionized water, alcohol successively by transparent substrates 130KHz carries out ultrasonic cleaning 15min, then 0.5h is soaked with the ammonium hydroxide that concentration of volume percent is 28%, controlled at 40 DEG C it is dried for standby；Step（2）In, the concentration of volume percent of methanol aqueous solution is 95%；Step（3）In, the concentration of graphene oxide water solution is 0.01mg/ml；Step（4）In, the concentration of carbon nano-tube aqueous solutions is 0.01mg/ml；The condition of ultrasonic disperse：Controlled at 30 DEG C, Frequency is 20KHz；The carbon nanotubes is single-walled carbon nanotube；Step（5）In, methanol aqueous solution used, the amount of graphene oxide water solution are mixed, by graphene oxide water solution Graphene oxide：Methanol aqueous solution is 1g:The ratio of 10ml calculates；Step（6）In, methanol aqueous solution used, the dosage of carbon nano-tube aqueous solutions are mixed, by carbon nano-tube aqueous solutions Carbon nanotubes：Methanol aqueous solution is 1g:The ratio of 10ml calculates；Step（7）In, take 5ml steps（5）The graphene oxide solution of gained, is added dropwise the aqueous phase interface in LB film instrument dropwise On, static 10min, obtains graphene oxide layer；Step（8）In, take 5ml steps（6）The carbon nano-tube solution of gained, is equably added dropwise the graphene oxide in LB film instrument On lamella, static 10min, Graphene/carbon nanotube composite material is obtained on the aqueous phase interface of LB film instrument；Step（9）In, by step（8）The Graphene/carbon nanotube composite material of gained controls pull rate to be carried out for 1mm/min It is transferred to after lifting 1 time through step（1）In transparent substrates after processing, hydrazine hydrate reduction 0.5h is then passed through under room temperature, is obtained Graphene/carbon nano-tube compound transparent electricity conductive film.
- 5. a kind of preparation method of graphene/carbon nano-tube compound transparent electricity conductive film as claimed in claim 3, its feature exist In：Step（1）In, it is controlled at 25 DEG C, frequency respectively with acetone, deionized water, alcohol successively by transparent substrates 100KHz carries out ultrasonic cleaning 15min, then 10h is soaked with the ammonium hydroxide that concentration of volume percent is 20%, controlled at 60 DEG C It is dried for standby；Step（2）In, the concentration of volume percent of methanol aqueous solution is 55%；Step（3）In, the concentration of graphene oxide water solution is 0.1mg/ml；Step（4）In, the concentration of carbon nano-tube aqueous solutions is 0.1mg/ml；The condition of ultrasonic disperse：Controlled at 25 DEG C, frequency Rate is 30KHz；The carbon nanotubes is multi-walled carbon nanotube；Step（5）In, methanol aqueous solution used, the amount of graphene oxide water solution are mixed, by graphene oxide water solution Graphene oxide：Methanol aqueous solution is 1g:The ratio of 40ml calculates；Step（6）In, methanol aqueous solution used, the dosage of carbon nano-tube aqueous solutions are mixed, by carbon nano-tube aqueous solutions Carbon nanotubes：Methanol aqueous solution is 1g:The ratio of 40ml calculates；Step（7）In, take 10ml steps（5）The graphene oxide solution of gained, is added dropwise the aqueous phase interface in LB film instrument dropwise On, static 20min, obtains graphene oxide layer；Step（8）In, take 10ml steps（6）The carbon nano-tube solution of gained, is equably added dropwise the graphite oxide in LB film instrument On alkene lamella, static 20min, Graphene/carbon nanotube composite material is obtained on the aqueous phase interface of LB film instrument；Step（9）In, by step（8）The Graphene/carbon nanotube composite material of gained controls pull rate to be carried out for 5mm/min It is transferred to after lifting 3 times through step（1）In transparent substrates after processing, hydrazine hydrate reduction 5h is then passed through under room temperature, obtains stone Black alkene/carbon nanotubes compound transparent electricity conductive film.
- 6. a kind of preparation method of graphene/carbon nano-tube compound transparent electricity conductive film as claimed in claim 3, its feature exist In：Step（1）In, it is controlled at 15 DEG C, frequency respectively with acetone, deionized water, alcohol successively by transparent substrates 80KHz carries out ultrasonic cleaning 15min, then 25h is soaked with the ammonium hydroxide that concentration of volume percent is 10%, controlled at 30 DEG C It is dried for standby；Step（2）In, the concentration of volume percent of methanol aqueous solution is 35%；Step（3）In, the concentration of graphene oxide water solution is 0.01mg/ml；Step（4）In, the concentration of carbon nano-tube aqueous solutions is 1mg/ml；The condition of ultrasonic disperse：Controlled at 20 DEG C, frequency For 40KHz；The carbon nanotubes is single-walled carbon nanotube；Step（5）In, methanol aqueous solution used, the amount of graphene oxide water solution are mixed, by graphene oxide water solution Graphene oxide：Methanol aqueous solution is 1g:The ratio of 500ml calculates；Step（6）In, methanol aqueous solution used, the dosage of carbon nano-tube aqueous solutions are mixed, by carbon nano-tube aqueous solutions Carbon nanotubes：Methanol aqueous solution is 1g:The ratio of 500ml calculates；Step（7）In, take 20ml steps（5）The graphene oxide solution of gained, is added dropwise the aqueous phase interface in LB film instrument dropwise On, static 60min, obtains graphene oxide layer；Step（8）In, take 5ml steps（6）The carbon nano-tube solution of gained, is equably added dropwise the graphene oxide in LB film instrument On lamella, static 30min, Graphene/carbon nanotube composite material is obtained on the aqueous phase interface of LB film instrument；Step（9）In, by step（8）The Graphene/carbon nanotube composite material of gained control pull rate for 10mm/min into Row is transferred to through step after lifting 50 times（1）In transparent substrates after processing, hydrazine hydrate reduction 30h is then passed through under room temperature, is obtained To graphene/carbon nano-tube compound transparent electricity conductive film.
- 7. a kind of preparation method of graphene/carbon nano-tube compound transparent electricity conductive film as claimed in claim 3, its feature exist In：Step（1）In, it is controlled at 10 DEG C, frequency respectively with acetone, deionized water, alcohol successively by transparent substrates 20KHz carries out ultrasonic cleaning 15min, then with concentration of volume percent be 1% ammonium hydroxide soak 48h, controlled at 30 DEG C into Row is dried for standby；Step（2）In, the concentration of volume percent of methanol aqueous solution is 35%；Step（3）In, the concentration of graphene oxide water solution is 3mg/ml；Step（4）In, the concentration of carbon nano-tube aqueous solutions is 3mg/ml；The condition of ultrasonic disperse：Controlled at 10 DEG C, frequency For 60KHz；The carbon nanotubes is single-walled carbon nanotube；Step（5）In, methanol aqueous solution used, the amount of graphene oxide water solution are mixed, by graphene oxide water solution Graphene oxide：Methanol aqueous solution is 1g:The ratio of 1000ml calculates；Step（6）In, methanol aqueous solution used, the dosage of carbon nano-tube aqueous solutions are mixed, by carbon nano-tube aqueous solutions Carbon nanotubes：Methanol aqueous solution is 1g:The ratio of 1000ml calculates；Step（7）In, take 20ml steps（5）The graphene oxide solution of gained, is added dropwise the aqueous phase interface in LB film instrument dropwise On, static 60min, obtains graphene oxide layer；Step（8）In, take 5ml steps（6）The carbon nano-tube solution of gained, is equably added dropwise the graphene oxide in LB film instrument On lamella, static 30min, Graphene/carbon nanotube composite material is obtained on the aqueous phase interface of LB film instrument；Step（9）In, by step（8）The Graphene/carbon nanotube composite material of gained control pull rate for 10mm/min into Row is transferred to through step after lifting 100 times（1）In transparent substrates after processing, hydrazine hydrate reduction 48h is then passed through under room temperature, is obtained To graphene/carbon nano-tube compound transparent electricity conductive film.
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