CN107910129B - 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 and be film-made on the aqueous phase interface of instrument, obtain graphene oxide layer 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 oxide/carbon nano tube compound material obtained after static 10-30min；Then it lifted, be transferred in transparent substrates, reduction 0.5-48h is carried out through hydrazine hydrate under room temperature, graphene/carbon nano-tube compound transparent electricity conductive film is obtained, due to its transparency with higher and preferable photoelectric properties, can be applied to the preparation of flexible display device.Preparation method process of the invention is simple, strong operability.
Description
Technical field
The present invention relates to a kind of preparation methods of graphene/carbon nano-tube compound transparent electricity conductive film, belong to materialogy neck
Domain.
Background technique
Graphene refers to the tightly packed single layer of carbon atom at bi-dimensional cellular shape lattice structure, it is to construct 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, relatively by force
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.
At present there are many kinds of the preparation methods of compound transparent electricity conductive film, such as transfer printing method, dip coating method, spraying
Method, whirl coating, club rubbing method, electrophoretic deposition etc., however these methods all cannot control nanometer material in molecular level
The behavior of material, therefore prepared film is easy phenomena such as making raw material that accumulation occur, be unevenly distributed, 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 nanotube is lifted, therefore preparation process has preparation process complicated, exists simultaneously system
The standby technical problems such as the period is long, preparation efficiency is low.
Summary of the invention
An object of the present invention is to solve above-mentioned graphene/carbon nano-tube compound transparent electricity conductive film and prepared
Journey is complicated, exists simultaneously the technical problems such as long preparation period, low efficiency and provides and a kind of prepare graphite using L B masking technique
Alkene/carbon nanotube compound transparent electricity conductive film method, the preparation method have preparation process simple, strong operability, simultaneously
Have the advantages that short preparation period, high-efficient etc..
Technical solution of the present invention
A kind of preparation method of graphene/carbon nano-tube compound transparent electricity conductive film utilizes Langmuir-Blodgett
Transparent substrates are cleaned by ultrasonic, hydrophily processing, 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 nanotube is equably spread over to the water phase of L B film instrument again
On interface, static 0-30min, it is 0.1-10mm/ that obtained graphene oxide/carbon nanotube, which is then controlled pull rate, again
Min is transferred in the transparent substrates of drying after carrying out lifting 1-100 times, then passes through hydrazine hydrate reduction 0.5-48h at normal temperature,
Obtain graphene/carbon nano-tube compound transparent electricity conductive film, preparation process specifically includes the following steps:
(1), it successively uses acetone, deionized water, alcohol to be cleaned by ultrasonic 15min respectively transparent substrates, then uses volume hundred
Divide the ammonium hydroxide that specific concentration is 1-28% to impregnate 0.5-48h, is dried for standby controlled at 30-60 DEG C；
The transparent substrates are polyethylene terephthalate, light transmittance 70-98%；
Above-mentioned acetone, deionized water, the condition of alcohol ultrasonic cleaning are equal are as follows: are 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, obtaining concentration of volume percent is 35-95% methanol aqueous solution, spare；
(3), the preparation of graphene oxide water solution
It adds graphene oxide into water, jiggling is uniformly dissolved graphene oxide, and obtaining concentration is 0.01-
The graphene oxide water solution of 3mg/ml, it is spare；
(4), the preparation of carbon nano-tube aqueous solutions
Carbon nanotube is added to the water, obtaining concentration after mixing under conditions of ultrasonic disperse is 0.01-3mg/
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 nanotube is single-walled carbon nanotube or multi-walled carbon nanotube；
(5), the resulting methanol aqueous solution of step (2), step (3) resulting graphene oxide water solution mix
It is even, it is spare to obtain graphene oxide solution；
The amount of methanol aqueous solution used in above-mentioned mixing, graphene oxide water solution, by graphene oxide water solution
Graphene oxide: the ratio that methanol aqueous solution is 1g:10-1000ml calculates；
(6), the resulting methanol aqueous solution of step (2), step (4) resulting carbon nano-tube aqueous solutions mix
It is even, it is spare to obtain carbon nano-tube solution；
The dosage of methanol aqueous solution used in above-mentioned mixing, carbon nano-tube aqueous solutions, by the carbon in carbon nano-tube aqueous solutions
Nanotube: the ratio that methanol aqueous solution is 1g:10-1000ml calculates；
(7), 5-20ml step (5) resulting graphene oxide solution 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), 5-10ml step (6) resulting carbon nano-tube solution is taken, the graphite oxide in LB film instrument is equably added dropwise
On alkene lamella, static 10-30min obtains graphene oxide/carbon nano tube compound material on the aqueous phase interface of LB film instrument；
It (9), is 1-10mm/ by the resulting graphene oxide of step (8)/carbon nano tube compound material control pull rate
Min is transferred to through then passing through hydrazine hydrate also under room temperature in step (1) treated transparent substrates after carrying out lifting 1-100 time
Former 0.5-48h obtains graphene/carbon nano-tube compound transparent electricity conductive film.
Above-mentioned resulting graphene/carbon nano-tube compound transparent electricity conductive film, due to its transparency with higher and compared with
Good photoelectric properties, therefore its preparation that can be applied to flexible display device.
Beneficial effects of the present invention
It is 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 nanotube is eliminated
Aqueous treatment process, therefore have preparation method simple, the advantages of strong operability.
It is 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 simultaneously due to the present invention using two kinds of materials of graphene oxide and carbon nanotube, has preparation
Period short, high-efficient advantage.
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 nanotube compound transparent electricity conductive film, transparency with higher and preferable photoelectric properties.
In conclusion a kind of preparation method of graphene/carbon nano-tube compound transparent electricity conductive film of the invention, due to tool
Have that preparation method is simple, strong operability, while having many advantages, such as short preparation period, high-efficient, therefore be produced on a large scale.
Detailed description of the invention
Fig. 1 a, the atomic force of the obtained graphene/carbon nano-tube compound transparent electricity conductive film configuration of surface of embodiment 1 are aobvious
Micro mirror (AFM) photo；
The atom of Fig. 1 b, the obtained graphene/carbon nano-tube compound transparent electricity conductive film surface sections height of embodiment 1
Force microscope (AFM) photo；
The atom of Fig. 1 c, the obtained graphene/carbon nano-tube compound transparent electricity conductive film three-dimensional stereo topography of embodiment 1
Force microscope (AFM) photo；
The light transmission characterization of Fig. 2, the obtained graphene/carbon nano-tube compound transparent electricity conductive film of embodiment 1；
The photoelectric properties of the obtained graphene/carbon nano-tube compound transparent electricity conductive film of Fig. 3, embodiment 1-4 characterize.
Specific embodiment
The present invention is further illustrated below by specific embodiment and in conjunction with attached drawing, but is not intended to limit the present invention
Implementation.
LB used in various embodiments of the present invention is film-made instrument, and the sink size range of model Medium, LB film instrument is
Long 5-100cm, width 5-100cm, the production of KSV NIMA company.
Raw material used in various embodiments of the present invention is common commercially available.
Embodiment 1
A kind of preparation method of graphene/carbon nano-tube compound transparent electricity conductive film, specifically includes the following steps:
(1), transparent substrates are successively used acetone, deionized water, alcohol to be cleaned by ultrasonic 15min respectively, then with volume hundred
Divide the ammonium hydroxide that specific concentration is 28% to impregnate 0.5h, is 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 equal are as follows: controlled at 30 DEG C, frequency 130KHz；
(2), the preparation of methanol aqueous solution
Methanol is soluble in water, it is uniformly mixed, obtaining concentration of volume percent is 95% methanol aqueous solution, spare；
(3), the preparation of graphene oxide water solution
It adds graphene oxide into water, jiggling is uniformly dissolved graphene oxide, and obtaining concentration is 0.01mg/
The graphene oxide water solution of ml, it is spare；
(4), the preparation of carbon nano-tube aqueous solutions
Carbon nanotube is added to the water, is then that 20KHz ultrasonic mixing is uniform controlled at 30 DEG C, frequency, obtains
Concentration is the carbon nano-tube aqueous solutions of 0.01mg/ml, and the carbon nanotube is single-walled carbon nanotube；
(5), the resulting methanol aqueous solution of step (2), step (3) resulting graphene oxide water solution mix
It is even, it is spare to obtain graphene oxide solution；
The amount of methanol aqueous solution used in above-mentioned mixing, graphene oxide water solution, by graphene oxide water solution
Graphene oxide: the ratio that methanol aqueous solution is 1g:10ml calculates；
(6), the resulting methanol aqueous solution of step (2), step (4) resulting carbon nano-tube aqueous solutions mix
It is even, it is spare to obtain carbon nano-tube solution；
The dosage of methanol aqueous solution used in above-mentioned mixing, carbon nano-tube aqueous solutions, by the carbon in carbon nano-tube aqueous solutions
Nanotube: the ratio that methanol aqueous solution is 1g:10ml calculates；
(7), 5ml step (5) resulting graphene oxide solution is taken, is added dropwise on the aqueous phase interface of LB film instrument dropwise,
Static 10min, obtains graphene oxide layer；
(8), 5ml step (6) resulting carbon nano-tube solution is taken, the graphene oxide sheet in LB film instrument is equably added dropwise
On layer, static 10min obtains graphene oxide/carbon nano tube compound material on the aqueous phase interface of LB film instrument；
(9), by the resulting graphene oxide of step (8)/carbon nano tube compound material control pull rate be 1mm/min into
It is transferred to after row lifting 1 time through then carrying out reduction 0.5h through hydrazine hydrate under room temperature in step (1) treated transparent substrates,
Obtain graphene/carbon nano-tube compound transparent electricity conductive film.
Using Scanning Probe Microscope-NanoScope, Digital Instruments instrument to above-mentioned
Resulting graphene/carbon nano-tube compound transparent electricity conductive film configuration of surface is observed, resulting atomic force microscope (AFM)
Photo is as shown in Figure 1a, it can be seen that carbon nanotube 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 nanotube, therefore use LB film method of the invention is in graphene oxide sheet
The method that carbon nanotube and 1 lifting film are added dropwise on layer is feasible；
Using Scanning Probe Microscope-NanoScope, Digital Instruments instrument to above-mentioned
Resulting graphene/carbon nano-tube compound transparent electricity conductive film surface sections height is observed and divides its cross section
Analysis, resulting atomic force microscope (AFM) photo is as shown in Figure 1 b, it can be seen that film thickness average out to 2nm from Fig. 1 b；
Using Scanning Probe Microscope-NanoScope, Digital Instruments instrument to above-mentioned
Resulting graphene/carbon nano-tube compound transparent electricity conductive film three-dimensional stereo topography is observed, resulting atomic force microscope
(AFM) as illustrated in figure 1 c, it can be seen that carbon nanotube is evenly distributed in surface of graphene oxide from Fig. 1 c, soilless sticking is existing for photo
As occur, be indicated above using LB film method is added dropwise in graphene oxide layer carbon nanotube simultaneously 1 lifting it is obtained thin
Film is uniform；
Using Perkin Elmer Lambda 750UV-Vis spectrometer instrument to above-mentioned resulting graphene/
The light transmittance of carbon nanotube compound transparent electricity conductive film measures, resulting graphene/carbon nano-tube composite transparent conductive thin
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 the graphene/carbon nano-tube composite transparent as prepared by the present invention and leads
Conductive film light transmittance with higher.
Using Perkin Elmer Lambda 750UV-Vis spectrometer instrument and Scientific
The four-point probe instrument of Equipment&Services is respectively to above-mentioned resulting graphene/carbon nano-tube composite transparent conductive thin
The sheet resistance of film measures, photoelectric characteristic figure such as Fig. 3 institute of resulting graphene/carbon nano-tube compound transparent electricity conductive film
Show, as can be seen from Figure 3 graphene/carbon nano-tube compound transparent electricity conductive film when light transmittance is 85% or more, graphene/
The sheet resistance of carbon nanotube compound transparent electricity conductive film can achieve 600 Ω/sq, be indicated above the stone as prepared by the present invention
Black alkene/carbon nanotube 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 the following steps:
(1), transparent substrates are successively used acetone, deionized water, alcohol to be cleaned by ultrasonic 15min respectively, then with volume hundred
Divide the ammonium hydroxide that specific concentration is 20% to impregnate 10h, is 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 equal are as follows: controlled at 25 DEG C, frequency 100KHz；
(2), the preparation of methanol aqueous solution
Methanol is soluble in water, it is uniformly mixed, obtaining concentration of volume percent is 55% methanol aqueous solution, spare；
(3), the preparation of graphene oxide water solution
It adds graphene oxide into water, jiggling is uniformly dissolved graphene oxide, and obtaining concentration is 0.1mg/
The graphene oxide water solution of ml, it is spare；
(4), the preparation of carbon nano-tube aqueous solutions
Carbon nanotube is added to the water, is then that 30KHz ultrasonic mixing is uniform controlled at 25 DEG C, frequency, obtains
Concentration is the carbon nano-tube aqueous solutions of 0.1mg/ml, and the carbon nanotube is multi-walled carbon nanotube；
(5), the resulting methanol aqueous solution of step (2), step (3) resulting graphene oxide water solution mix
It is even, it is spare to obtain graphene oxide solution；
The amount of methanol aqueous solution used in above-mentioned mixing, graphene oxide water solution, by graphene oxide water solution
Graphene oxide: the ratio that methanol aqueous solution is 1g:40ml calculates；
(6), the resulting methanol aqueous solution of step (2), step (4) resulting carbon nano-tube aqueous solutions mix
It is even, it is spare to obtain carbon nano-tube solution；
The dosage of methanol aqueous solution used in above-mentioned mixing, carbon nano-tube aqueous solutions, by the carbon in carbon nano-tube aqueous solutions
Nanotube: the ratio that methanol aqueous solution is 1g:40ml calculates；
(7), 10ml step (5) resulting graphene oxide solution is taken, is added dropwise on the aqueous phase interface of LB film instrument dropwise,
Static 20min, obtains graphene oxide layer；
(8), 10ml step (6) resulting carbon nano-tube solution is taken, the graphene oxide in LB film instrument is equably added dropwise
On lamella, static 20min obtains graphene oxide/carbon nano tube compound material in the aqueous phase interface of LB film instrument；
(9), by the resulting graphene oxide of step (8)/carbon nano tube compound material control pull rate be 5mm/min into
It is transferred to after row lifting 3 times through then carrying out reduction 5h through hydrazine hydrate under room temperature, obtaining in step (1) treated transparent substrates
To graphene/carbon nano-tube compound transparent electricity conductive film.
Embodiment 3
A kind of preparation method of graphene/carbon nano-tube compound transparent electricity conductive film, specifically includes the following steps:
(1), transparent substrates are successively used acetone, deionized water, alcohol to be cleaned by ultrasonic 15min respectively, then with volume hundred
Divide the ammonium hydroxide that specific concentration is 10% to impregnate 25h, is 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 equal are as follows: controlled at 15 DEG C, frequency 80KHz；
(2), the preparation of methanol aqueous solution
Methanol is soluble in water, it is uniformly mixed, obtaining concentration of volume percent is 35% methanol aqueous solution, spare；
(3), the preparation of graphene oxide water solution
It adds graphene oxide into water, jiggling is uniformly dissolved graphene oxide, and obtaining concentration is 1mg/ml
Graphene oxide water solution, it is spare；
(4), the preparation of carbon nano-tube aqueous solutions
Carbon nanotube is added to the water, is then that 40KHz ultrasonic mixing is uniform controlled at 20 DEG C, frequency, obtains
Concentration is the carbon nano-tube aqueous solutions of 1mg/ml, and the carbon nanotube is single-walled carbon nanotube；
(5), the resulting methanol aqueous solution of step (2), step (3) resulting graphene oxide water solution mix
It is even, it is spare to obtain graphene oxide solution；
The amount of methanol aqueous solution used in above-mentioned mixing, graphene oxide water solution, by graphene oxide water solution
Graphene oxide: the ratio that methanol aqueous solution is 1g:500ml calculates；
(6), the resulting methanol aqueous solution of step (2), step (4) resulting carbon nano-tube aqueous solutions mix
It is even, it is spare to obtain carbon nano-tube solution；
The dosage of methanol aqueous solution used in above-mentioned mixing, carbon nano-tube aqueous solutions, by the carbon in carbon nano-tube aqueous solutions
Nanotube: the ratio that methanol aqueous solution is 1g:500ml calculates；
(7), 20ml step (5) resulting graphene oxide solution is taken, is added dropwise on the aqueous phase interface of LB film instrument dropwise,
Static 60min, obtains graphene oxide layer；
(8), 5ml step (6) resulting carbon nano-tube solution is taken, the graphene oxide sheet in LB film instrument is equably added dropwise
On layer, static 30min obtains graphene oxide/carbon nano tube compound material on the aqueous phase interface of LB film instrument；
It (9), is 10mm/min by the resulting graphene oxide of step (8)/carbon nano tube compound material control pull rate
It is transferred to after carrying out lifting 50 times through then being restored under room temperature through hydrazine hydrate in step (1) treated transparent substrates
30h obtains 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 the following steps:
(1), transparent substrates are successively used acetone, deionized water, alcohol to be cleaned by ultrasonic 15min respectively, then with volume hundred
Divide the ammonium hydroxide that specific concentration is 1% to impregnate 48h, is 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 equal are as follows: controlled at 10 DEG C, frequency 20KHz；
(2), the preparation of methanol aqueous solution
Methanol is soluble in water, it is uniformly mixed, obtaining concentration of volume percent is 35% methanol aqueous solution, spare；
(3), the preparation of graphene oxide water solution
It adds graphene oxide into water, jiggling is uniformly dissolved graphene oxide, and obtaining concentration is 3mg/ml
Graphene oxide water solution, it is spare；
(4), the preparation of carbon nano-tube aqueous solutions
Carbon nanotube is added to the water, is then that 60KHz ultrasonic mixing is uniform controlled at 10 DEG C, frequency, obtains
Concentration is the carbon nano-tube aqueous solutions of 3mg/ml, and the carbon nanotube is single-walled carbon nanotube；
(5), the resulting methanol aqueous solution of step (2), step (3) resulting graphene oxide water solution mix
It is even, it is spare to obtain graphene oxide solution；
The amount of methanol aqueous solution used in above-mentioned mixing, graphene oxide water solution, by graphene oxide water solution
Graphene oxide: the ratio that methanol aqueous solution is 1g:1000ml calculates；
(6), the resulting methanol aqueous solution of step (2), step (4) resulting carbon nano-tube aqueous solutions mix
It is even, it is spare to obtain carbon nano-tube solution；
The dosage of methanol aqueous solution used in above-mentioned mixing, carbon nano-tube aqueous solutions, by the carbon in carbon nano-tube aqueous solutions
Nanotube: the ratio that methanol aqueous solution is 1g:1000ml calculates；
(7), 20ml step (5) resulting graphene oxide solution is taken, is added dropwise on the aqueous phase interface of LB film instrument dropwise,
Static 60min, obtains graphene oxide layer；
(8), 5ml step (6) resulting carbon nano-tube solution is taken, the graphene oxide sheet in LB film instrument is equably added dropwise
On layer, static 30min obtains graphene oxide/carbon nano tube compound material on the aqueous phase interface of LB film instrument；
It (9), is 10mm/min by the resulting graphene oxide of step (10)/carbon nano tube compound material control pull rate
It is transferred to after carrying out lifting 100 times through then being restored under room temperature through hydrazine hydrate in step (1) treated transparent substrates
48h obtains 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 invention, and it is existing
Technology is compared, and eliminates the hydrophily treatment process of carbon nanotube, and lift simultaneously simultaneously using graphene oxide and carbon nanotube
Transfer, therefore have preparation method simple, strong operability has the advantages that short preparation period, high-efficient, while resulting stone
Black alkene/carbon nanotube compound transparent electricity conductive film light transmittance with higher and preferable photoelectric characteristic.
The principle of the present invention and its effect is only illustrated in above embodiments, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (7)
1. a kind of preparation method of graphene/carbon nano-tube compound transparent electricity conductive film, it is characterised in that:
Firstly, graphene oxide solution is spread on the aqueous phase interface of LB film instrument, after static 10-60min, instrument is film-made in LB
Aqueous phase interface on obtain graphene oxide layer；
Then, in the graphene oxide layer that carbon nano-tube solution is equably spread over to LB film instrument, static 10-30min,
Graphene oxide/the carbon nano tube compound material obtained on the aqueous phase interface of LB film instrument；
It then, is that 1-10mm/min is lifted by obtained graphene oxide/carbon nano tube compound material control pull rate
It is transferred in transparent substrates after 1-100 times, carries out reduction 0.5-48h through hydrazine hydrate under room temperature, it is multiple to obtain graphene/carbon nano-tube
Close transparent conductive film.
2. a kind of preparation method of graphene/carbon nano-tube compound transparent electricity conductive film as described in claim 1, 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, 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, then impregnates 0.5-48h, control temperature with the ammonium hydroxide that concentration of volume percent is 1-28%
Degree is dried for standby for 30-60 DEG C；
(2), the preparation of methanol aqueous solution
Methanol is soluble in water, it is uniformly mixed, obtaining concentration of volume percent is 35-95% methanol aqueous solution, spare；
(3), the preparation of graphene oxide water solution
It adds graphene oxide into water, jiggling is uniformly dissolved graphene oxide, and obtaining concentration is 0.01-3mg/ml
Graphene oxide water solution, it is spare；
(4), the preparation of carbon nano-tube aqueous solutions
Carbon nanotube is added to the water, obtaining concentration after mixing under conditions of ultrasonic disperse is 0.01-3mg/ml's
Carbon nano-tube aqueous solutions, it is spare；
The condition of ultrasonic disperse: controlled at 10-30 DEG C, frequency 20-60KHz；
The carbon nanotube is single-walled carbon nanotube or multi-walled carbon nanotube；
(5), the resulting methanol aqueous solution of step (2), step (3) resulting graphene oxide water solution are carried out it is uniformly mixed,
It is spare to obtain graphene oxide solution；
The amount of methanol aqueous solution used in above-mentioned mixing, graphene oxide water solution, by the oxidation in graphene oxide water solution
Graphene: the ratio that methanol aqueous solution is 1g:10-1000ml calculates；
(6), the resulting methanol aqueous solution of step (2), step (4) resulting carbon nano-tube aqueous solutions are carried out uniformly mixed, obtained
It is spare to carbon nano-tube solution；
The dosage of methanol aqueous solution used in above-mentioned mixing, carbon nano-tube aqueous solutions, by the carbon nanometer in carbon nano-tube aqueous solutions
Pipe: the ratio that methanol aqueous solution is 1g:10-1000ml calculates；
(7), 5-20ml step (5) resulting graphene oxide solution is taken, is added dropwise on the aqueous phase interface of LB film instrument dropwise, it is quiet
Only 10-60min obtains graphene oxide layer；
The sink size that LB is film-made instrument is long 5-100cm, width 5-100cm；
(8), 5-10ml step (6) resulting carbon nano-tube solution is taken, the graphene oxide sheet in LB film instrument is equably added dropwise
On layer, static 10-30min obtains graphene oxide/carbon nano tube compound material on the aqueous phase interface of LB film instrument；
(9), by the resulting graphene oxide of step (8)/carbon nano tube compound material control pull rate be 1-10mm/min into
It is transferred to after row lifting 1-100 time through in step (1) treated transparent substrates, then by hydrazine hydrate reduction 0.5- under room temperature
48h obtains 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, feature exist
In:
In step (1), successively it is controlled at 30 DEG C, frequency respectively with acetone, deionized water, alcohol by transparent substrates
130KHz carries out ultrasonic cleaning 15min, then 0.5h is impregnated with the ammonium hydroxide that concentration of volume percent is 28%, controlled at 40
It DEG C is dried for standby；
In step (2), the concentration of volume percent of methanol aqueous solution is 95%；
In step (3), the concentration of graphene oxide water solution is 0.01mg/ml；
In step (4), 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 nanotube is single-walled carbon nanotube；
In step (5), the amount of methanol aqueous solution used, graphene oxide water solution is mixed, by graphene oxide water solution
Graphene oxide: methanol aqueous solution be 1g:10ml ratio calculate；
In step (6), the dosage of methanol aqueous solution used, carbon nano-tube aqueous solutions is mixed, by carbon nano-tube aqueous solutions
Carbon nanotube: the ratio that methanol aqueous solution is 1g:10ml calculates；
In step (7), 5ml step (5) resulting graphene oxide solution is taken, the aqueous phase interface in LB film instrument is added dropwise dropwise
On, static 10min obtains graphene oxide layer；
In step (8), 5ml step (6) resulting carbon nano-tube solution is taken, the graphene oxide in LB film instrument is equably added dropwise
On lamella, static 10min obtains graphene oxide/carbon nano tube compound material on the aqueous phase interface of LB film instrument；
It is 1mm/min by the resulting graphene oxide of step (8)/carbon nano tube compound material control pull rate in step (9)
It is transferred to after carrying out lifting 1 time through then passing through hydrazine hydrate reduction 0.5h under room temperature in step (1) treated transparent substrates,
Obtain 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, feature exist
In:
In step (1), successively it is controlled at 25 DEG C, frequency respectively with acetone, deionized water, alcohol by transparent substrates
100KHz carries out ultrasonic cleaning 15min, then 10h is impregnated with the ammonium hydroxide that concentration of volume percent is 20%, controlled at 60
It DEG C is dried for standby；
In step (2), the concentration of volume percent of methanol aqueous solution is 55%；
In step (3), the concentration of graphene oxide water solution is 0.1mg/ml；
In step (4), 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 nanotube is multi-walled carbon nanotube；
In step (5), the amount of methanol aqueous solution used, graphene oxide water solution is mixed, by graphene oxide water solution
Graphene oxide: methanol aqueous solution be 1g:40ml ratio calculate；
In step (6), the dosage of methanol aqueous solution used, carbon nano-tube aqueous solutions is mixed, by carbon nano-tube aqueous solutions
Carbon nanotube: the ratio that methanol aqueous solution is 1g:40ml calculates；
In step (7), 10ml step (5) resulting graphene oxide solution is taken, the aqueous phase interface in LB film instrument is added dropwise dropwise
On, static 20min obtains graphene oxide layer；
In step (8), 10ml step (6) resulting carbon nano-tube solution is taken, the graphite oxide in LB film instrument is equably added dropwise
On alkene lamella, static 20min obtains graphene oxide/carbon nano tube compound material on the aqueous phase interface of LB film instrument；
It is 5mm/min by the resulting graphene oxide of step (8)/carbon nano tube compound material control pull rate in step (9)
It is transferred to after carrying out lifting 3 times through then passing through hydrazine hydrate reduction 5h under room temperature, obtaining in step (1) treated transparent substrates
To graphene/carbon nano-tube 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, feature exist
In:
In step (1), successively it is controlled at 15 DEG C, frequency respectively with acetone, deionized water, alcohol by transparent substrates
80KHz carries out ultrasonic cleaning 15min, then 25h is impregnated with the ammonium hydroxide that concentration of volume percent is 10%, controlled at 30 DEG C
It is dried for standby；
In step (2), the concentration of volume percent of methanol aqueous solution is 35%；
In step (3), the concentration of graphene oxide water solution is 0.01mg/ml；
In step (4), 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 nanotube is single-walled carbon nanotube；
In step (5), the amount of methanol aqueous solution used, graphene oxide water solution is mixed, by graphene oxide water solution
Graphene oxide: methanol aqueous solution be 1g:500ml ratio calculate；
In step (6), the dosage of methanol aqueous solution used, carbon nano-tube aqueous solutions is mixed, by carbon nano-tube aqueous solutions
Carbon nanotube: the ratio that methanol aqueous solution is 1g:500ml calculates；
In step (7), 20ml step (5) resulting graphene oxide solution is taken, the aqueous phase interface in LB film instrument is added dropwise dropwise
On, static 60min obtains graphene oxide layer；
In step (8), 5ml step (6) resulting carbon nano-tube solution is taken, the graphene oxide in LB film instrument is equably added dropwise
On lamella, static 30min obtains graphene oxide/carbon nano tube compound material on the aqueous phase interface of LB film instrument；
It is 10mm/ by the resulting graphene oxide of step (8)/carbon nano tube compound material control pull rate in step (9)
Min is transferred to through then passing through hydrazine hydrate reduction under room temperature in step (1) treated transparent substrates after carrying out lifting 50 times
30h obtains 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, feature exist
In:
In step (1), successively it is controlled at 10 DEG C, frequency respectively with acetone, deionized water, alcohol by transparent substrates
20KHz carries out ultrasonic cleaning 15min, then 48h is impregnated with the ammonium hydroxide that concentration of volume percent is 1%, controlled at 30 DEG C
It is dried for standby；
In step (2), the concentration of volume percent of methanol aqueous solution is 35%；
In step (3), the concentration of graphene oxide water solution is 3mg/ml；
In step (4), 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 nanotube is single-walled carbon nanotube；
In step (5), the amount of methanol aqueous solution used, graphene oxide water solution is mixed, by graphene oxide water solution
Graphene oxide: methanol aqueous solution be 1g:1000ml ratio calculate；
In step (6), the dosage of methanol aqueous solution used, carbon nano-tube aqueous solutions is mixed, by carbon nano-tube aqueous solutions
Carbon nanotube: the ratio that methanol aqueous solution is 1g:1000ml calculates；
In step (7), 20ml step (5) resulting graphene oxide solution is taken, the aqueous phase interface in LB film instrument is added dropwise dropwise
On, static 60min obtains graphene oxide layer；
In step (8), 5ml step (6) resulting carbon nano-tube solution is taken, the graphene oxide in LB film instrument is equably added dropwise
On lamella, static 30min obtains graphene oxide/carbon nano tube compound material on the aqueous phase interface of LB film instrument；
It is 10mm/ by the resulting graphene oxide of step (8)/carbon nano tube compound material control pull rate in step (9)
Min is transferred to through then passing through hydrazine hydrate reduction under room temperature in step (1) treated transparent substrates after carrying out lifting 100 times
48h obtains graphene/carbon nano-tube compound transparent electricity conductive film.
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