CN103011124B - The preparation method of carbon nano-tube compound film - Google Patents
The preparation method of carbon nano-tube compound film Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of carbon nano-tube compound film, comprise the following steps: provide a carbon nano-tube film, this carbon nano-tube film comprises multiple carbon nanotube being parallel to its surface; And formation electro-conductive material is attached to described carbon nano-tube film surface.
Description
Technical field
The present invention relates to a kind of preparation method of composite membrane, particularly relate to a kind of preparation method of carbon nano-tube compound film.
Background technology
Since the early 1990s, be that the nano material of representative causes people with the structures and characteristics of its uniqueness and pays close attention to greatly with carbon nanotube.In recent years, along with deepening continuously of carbon nanotube and nano materials research, its wide application prospect constantly displayed.Such as, due to the performance such as electromagnetism, optics, mechanics, chemistry of the uniqueness that carbon nanotube has, in a large number about its applied research in fields such as field emitting electronic source, sensor, novel optical material, soft ferromagnetic materials is constantly in the news.
Especially, the compound of carbon nanotube and other materials such as metal, semi-conductor or polymkeric substance etc. can realize mutual supplement with each other's advantages or the reinforcement of material.Carbon nanotube has larger length-to-diameter ratio and the structure of hollow, has excellent mechanical property, can be used as a kind of super fiber, play enhancement to matrix material.In addition, carbon nanotube has excellent heat conductivility, utilizes the heat conductivility of carbon nanotube to make this matrix material have good heat conductivity.But carbon nanotube is except having excellent heat conductivility, and it also has good conductivity, so carbon nanotube and the other materials matrix material that such as metal, semi-conductor or polymkeric substance etc. are formed also has excellent conductivity.
The preparation method of carbon nano tube compound material has situ aggregation method, solution blended process and melt blending method usually.Carbon nano-tube compound film is a kind of important form of carbon nano tube compound material practical application.Carbon nano-tube compound film is generally got rid of painting method, pyrolysis of carbonaceous material method or liquid-phase chemistry deposition technique formed by silk screen print method, rotation.The carbon nano-tube compound film formed has the good and uniformly dispersed good advantage of compactness.
But the preparation method of existing carbon nano-tube compound film is comparatively complicated, and carbon nanotube is randomly dispersed in carbon nano-tube compound film along all directions.Such carbon nanotube disperses uneven in carbon nano-tube compound film, causes the electric property etc. affecting carbon nano-tube compound film.By the carbon nano-tube compound film prepared after carrying out chemical modification to carbon nanotube, refer to " SurfaceResistivityandRheologicalBehaviorsofCarboxylatedM ultiwallCarbonNanotube-filledPETCompositeFilm ", DaeHoShin, JournalofAppliedPolymerScience, V99n3, p900-904 (2006)), although electric property increases, but owing to will carry out under the condition of heating, thus limit the type with the material of carbon nanotube compound.
Summary of the invention
In view of this, necessaryly provide a kind of carbon nano-tube compound film and preparation method thereof, prepared carbon nano-tube compound film has good conductivity, and this preparation method simple, be easy to large-scale production.
A preparation method for carbon nano-tube compound film, comprises the following steps: provide a carbon nano-tube film, and this carbon nano-tube film comprises multiple carbon nanotube being parallel to its surface; And formation electro-conductive material is attached to described carbon nano-tube film surface.
A preparation method for carbon nano-tube compound film, comprises the following steps: provide a carbon nano-tube film, and this carbon nano-tube film comprises multiple carbon nanotube, has gap between adjacent carbon nanotube, and this carbon nano-tube film has self supporting structure; And formation electro-conductive material is attached to described carbon nano-tube film surface.
Compared with prior art, described carbon nano-tube compound film is attached to described carbon nano-tube film surface prepares by directly forming electro-conductive material, and preparation method is simple, be easy to large-scale production.In addition, described carbon nano-tube compound film comprises electro-conductive material and is attached to described carbon nano-tube film surface, therefore described carbon nano-tube compound film has good conductivity.Method due to described formation carbon nano-tube compound film does not need heating, thus in the present invention with carbon nano-tube film can the scope of material of compound wider.
Accompanying drawing explanation
Fig. 1 is the structural representation of embodiment of the present invention carbon nano-tube compound film.
Fig. 2 is the structural representation of single-root carbon nano-tube in embodiment of the present invention carbon nano-tube compound film.
Fig. 3 is the schema of the preparation method of embodiment of the present invention carbon nano-tube compound film.
Fig. 4 is the preparation facilities structural representation of embodiment of the present invention carbon nano-tube compound film.
Fig. 5 is the stereoscan photograph of the carbon nano-tube film of the embodiment of the present invention.
Fig. 6 is the stereoscan photograph of embodiment of the present invention carbon nano-tube compound film.
Fig. 7 is the transmission electron microscope photo of carbon nanotube in embodiment of the present invention carbon nano-tube compound film.
Embodiment
Structure of embodiment of the present invention carbon nano-tube compound film and preparation method thereof is described in detail below with reference to accompanying drawing.
The embodiment of the present invention provides a kind of carbon nano-tube compound film, and this carbon nano-tube compound film is made up of carbon nanotube and electro-conductive material.Refer to Fig. 1, this carbon nanotube 111 is parallel to carbon nano-tube compound film 100 surface alignment, and described electro-conductive material is coated on described carbon nanotube 111 surface.Particularly, this carbon nano-tube compound film 100 comprises multiple carbon nanotube 111, and the plurality of carbon nanotube 111 forms the carbon nano-tube film of a self-supporting.Further, each carbon nanotube 111 surfaces be clad at least layer of conductive material.In this carbon nano-tube compound film 100, carbon nanotube 111 is arranged of preferred orient along same direction.Particularly, in this carbon nano-tube compound film 100, each carbon nanotube 111 has roughly equal length, and is joined end to end by Van der Waals force.
So-called " self-supporting " i.e. this carbon nano-tube film, without the need to by a support body supports, also can keep self specific shape.The carbon nano-tube film of this self-supporting comprises multiple carbon nanotube, and the plurality of carbon nanotube is attracted each other by Van der Waals force and joins end to end, thus makes carbon nano-tube film have specific shape.
Please simultaneously see Fig. 2, each root carbon nanotube 111 surfaces be clad at least layer of conductive material in this carbon nano-tube compound film 100.Particularly, this at least layer of conductive material can comprise the wetting layer 112 directly combined with carbon nanotube 111 surface, the transition layer 113 be arranged on outside wetting layer, the anti oxidation layer 115 that is arranged on the conductive layer 114 outside transition layer 113 and is arranged on outside conductive layer 114.
Because the wettability between carbon nanotube 111 and most metals is bad, therefore, acting as of above-mentioned wetting layer 112 makes conductive layer 114 better be combined with carbon nanotube 111.The material forming this wetting layer 112 can be the metal good with carbon nanotube 111 wettability or their alloys such as iron, cobalt, nickel, palladium or titanium, and the thickness of this wetting layer 112 is 1 ~ 10 nanometer (nm).In the present embodiment, the material of this wetting layer 112 is nickel, and thickness is about 2 nanometers.Be appreciated that this wetting layer 112 is optional structure.
Acting as of above-mentioned transition layer 113 makes wetting layer 112 better be combined with conductive layer 114.The material forming this transition layer 113 can be the material that all can better be combined with wetting layer 112 material and conductive layer 114 material, and the thickness of this transition layer 113 is 1 ~ 10 nanometer.In the present embodiment, the material of this transition layer 113 is copper, and thickness is 2 nanometers.Be appreciated that this transition layer 113 is optional structure.
Acting as of above-mentioned conductive layer 114 makes carbon nano-tube compound film 100 have good conductivity.The material forming this conductive layer 114 can be the metal of copper, silver or the good conductivity such as golden or its alloy, and the thickness of this conductive layer 114 is 1 ~ 20 nanometer.In the present embodiment, the material of this conductive layer 114 is silver, and thickness is about 10 nanometers.
Acting as of above-mentioned anti oxidation layer 115 prevents conductive layer 114 in the manufacturing processed of carbon nano-tube compound film 100 oxidized in atmosphere, thus the conductivity of carbon nano-tube compound film 100 is declined.The material forming this anti oxidation layer 115 can be stable metal not oxidizable in atmosphere or their alloys such as gold or platinum, and the thickness of this anti oxidation layer 115 is 1 ~ 10 nanometer.In the present embodiment, the material of this anti oxidation layer 115 is platinum, and thickness is 2 nanometers.Be appreciated that this anti oxidation layer 115 is optional structure.
Further, for improving the intensity of carbon nano-tube compound film 100, one strengthening layer 116 can be set further in described at least layer of conductive material outward.The material forming this strengthening layer 116 can be the polymkeric substance that polyvinyl alcohol (PVA), polyhenylene benzo dioxazole (PBO), polyethylene (PE) or polyvinyl chloride (PVC) equal strength are higher, and the thickness of this strengthening layer 116 is 0.1 ~ 1 micron.In the present embodiment, the material of this strengthening layer 116 is polyvinyl alcohol (PVA), and thickness is 0.5 micron.Be appreciated that this strengthening layer 116 is optional structure.
Refer to Fig. 3 and Fig. 4, in the embodiment of the present invention, the preparation method of carbon nano-tube compound film 222 mainly comprises the following steps:
Step one a: carbon nano-tube film 214 is provided.
Described carbon nano-tube film 214 comprises multiple carbon nanotube, has gap between adjacent carbon nanotube, and this carbon nanotube is parallel to the surface of described carbon nano-tube film 214.Distance between described adjacent carbon nanotube can be greater than the diameter of carbon nanotube.Described carbon nano-tube film 214 can have self supporting structure.
The preparation method of described carbon nano-tube film 214 can comprise the following steps:
First, provide a carbon nano pipe array 216, preferably, this array is super in-line arrangement carbon nano pipe array.
The carbon nano pipe array 216 that the embodiment of the present invention provides is one or more in single-wall carbon nanotube array, double-walled carbon nano-tube array and array of multi-walled carbon nanotubes.In the present embodiment, the preparation method of this super in-line arrangement carbon nano pipe array adopts chemical Vapor deposition process, its concrete steps comprise: (a) provides a smooth substrate, this substrate can select P type or N-type silicon base, or select the silicon base being formed with zone of oxidation, the present embodiment is preferably the silicon base of employing 4 inches; B () evenly forms a catalyst layer at substrate surface, this catalyst layer material can select one of alloy of iron (Fe), cobalt (Co), nickel (Ni) or its arbitrary combination; C the above-mentioned substrate being formed with catalyst layer is annealed about 30 minutes ~ 90 minutes by () in the air of 700 ~ 900 ° of C; D the substrate processed is placed in Reaktionsofen by (), be heated to 500 ~ 740 ° of C under protective gas, and then pass into carbon-source gas reaction about 5 ~ 30 minutes, growth obtains super in-line arrangement carbon nano pipe array, and it is highly 200 ~ 400 microns.This super in-line arrangement carbon nano-pipe array is classified as multiple parallel to each other and pure nano-carbon tube array that is that formed perpendicular to the carbon nanotube of substrate grown.By above-mentioned control growth conditions, substantially not containing impurity in this super in-line arrangement carbon nano pipe array, as agraphitic carbon or residual catalyst metal particles etc.Carbon nanotube in this super in-line arrangement carbon nano pipe array forms array each other by Van der Waals force close contact.This super in-line arrangement carbon nano pipe array is substantially identical with above-mentioned area of base.
The hydrocarbon polymer that in the present embodiment, carbon source gas can select the chemical property such as acetylene, ethene, methane more active, the preferred carbon source gas of the present embodiment is acetylene; Shielding gas is nitrogen or rare gas element, and the preferred shielding gas of the present embodiment is argon gas.
Secondly, adopt a stretching tool to pull from described carbon nano pipe array 216 and obtain a carbon nano-tube film 214.
The preparation method of described carbon nano-tube film 214 comprises the following steps: adopt a stretching tool to pull from carbon nano pipe array 216 and obtain a carbon nano-tube film 214.It specifically comprises the following steps: (a) from a carbon nano pipe array 216 selected or have multiple carbon nanotubes of one fixed width, and the present embodiment is preferably and adopts adhesive tape, tweezers or the clip contact carbon nano pipe array 216 with one fixed width with selected one or have multiple carbon nanotubes of one fixed width; B () to stretch this selected carbon nanotube with certain speed, thus form end to end multiple carbon nanotube fragment, and then forms a continuous print carbon nano-tube film 214.This pulls direction along the direction of growth being basically perpendicular to carbon nano pipe array 216.
In above-mentioned drawing process, while the plurality of carbon nanotube fragment departs from substrate gradually along draw direction under a stretching force, due to van der Waals interaction, these selected multiple carbon nanotube fragments are drawn out end to end continuously with other carbon nanotube fragment respectively, thus are formed one continuously, evenly and have the carbon nano-tube film 214 of one fixed width.This carbon nano-tube film 214 comprises multiple end to end carbon nanotube, and this carbon nanotube arranges along draw direction substantially.Refer to Fig. 5, this carbon nano-tube film 214 comprises multiple carbon nanotube be arranged of preferred orient.Further, described carbon nano-tube film 214 comprises multiple joining end to end and the carbon nanotube fragment aligned, and carbon nanotube fragment two ends are interconnected by Van der Waals force.This carbon nanotube fragment comprises multiple carbon nanotube be arranged parallel to each other.The thickness of described carbon nano-tube film 214 is about 0.5 nanometer ~ 100 micron.The width of multiple carbon nanotubes selected in the size of the length of described carbon nano-tube film and width and this carbon nano pipe array 216 and step (a) is relevant, the maximum diameter being no more than this carbon nano pipe array 216 of the width of described carbon nano-tube film, the length of described carbon nano-tube film can reach more than 100 meters.The carbon nano-tube film 214 of the preferred orientation that this uniaxial direct tensile obtains has better homogeneity and conductivity than unordered carbon nano-tube film.The method of the carbon nano-tube film 214 of this uniaxial direct tensile acquisition is simultaneously simple and quick, is suitable for carrying out industrial applications.
Step 2: form electro-conductive material and be attached to described carbon nano-tube film 214 surface.
The method that described formation electro-conductive material is attached to described carbon nano-tube film 214 surface can adopt physical method, as physical vaporous deposition (PVD) comprises vacuum evaporation or ion sputtering etc., also can adopt chemical process, as plating or electroless plating etc.Preferably, the present embodiment adopts the vacuum vapour deposition in physical method to form described electro-conductive material and is attached to described carbon nano-tube film 214 surface.
The method that described employing vacuum vapour deposition formation electro-conductive material is attached to described carbon nano-tube film 214 surface comprises the following steps: first, one vacuum vessel 210 is provided, this vacuum vessel 210 has between a sedimentary province, between this sedimentary province, bottom and top are placed to a few evaporation source 212 respectively, this at least one evaporation source 212 is arranged along the draw direction of carbon nano-tube film 214 successively by the sequencing forming electro-conductive material, and each evaporation source 212 is all by a heating unit (not shown) heating.Above-mentioned carbon nano-tube film 214 is arranged at upper and lower evaporation source 212 centre and keeps at a certain distance away, and wherein carbon nano-tube film 214 is just arranged upper and lower evaporation source 212.This vacuum vessel 210 is bled by an external vacuum pump (not shown) and is reached predetermined vacuum tightness.Described evaporation source 212 material is electro-conductive material to be deposited.Secondly, by heating described evaporation source 212, after making its melting, evaporation or distillation form electro-conductive material steam, after this electro-conductive material steam runs into cold carbon nano-tube film 214, in the cohesion of carbon nano-tube film 214 upper and lower surface, form electro-conductive material and be attached to described carbon nano-tube film 214 surface.Owing to there is gap between the carbon nanotube in carbon nano-tube film 214, and carbon nano-tube film 214 thinner thickness, electro-conductive material can penetrate among described carbon nano-tube film 214, thus is deposited on every root carbon nano tube surface.The microsctructural photograph of the carbon nano-tube compound film 222 after deposits conductive material refers to Fig. 6 and Fig. 7.
Being appreciated that the distance by regulating between the distance of carbon nano-tube film 214 and each evaporation source 212 and evaporation source 212, each evaporation source 212 can be made to have a sedimentary province.When needs deposit multilayer electro-conductive material, multiple evaporation source 212 can be heated simultaneously, make described carbon nano-tube film 214 continue through the sedimentary province of multiple evaporation source, so formed described electro-conductive material be attached to described carbon nano-tube film 214 surface.Therefore this vacuum vessel 210 can realize the continuous seepage that carbon nano tube surface has the carbon nano-tube film 214 of at least layer of conductive material.
For improving electro-conductive material vapour density and preventing electro-conductive material oxidized, in vacuum vessel 210, vacuum tightness should reach more than 1 handkerchief (Pa).In the embodiment of the present invention, the vacuum tightness in described vacuum vessel is 4 × 10
-4pa.
Be appreciated that and also the carbon nano pipe array 216 in step one directly can be put into above-mentioned vacuum vessel 210.First, in vacuum vessel 210, adopt a stretching tool from described carbon nano pipe array 216, pull the carbon nano-tube film 214 obtaining one fixed width.Then, heat at least one evaporation source 212 above-mentioned, deposit at least layer of conductive material surperficial in described carbon nano-tube film 214.Constantly from described carbon nano pipe array 216, pull carbon nano-tube film 214 with certain speed, and make described carbon nano-tube film 214 continually by the sedimentary province of above-mentioned evaporation source 212, and then realize the continuous seepage of carbon nano-tube compound film 222.
The step that described employing vacuum vapour deposition forms electro-conductive material can specifically comprise the following steps: form one deck wetting layer in described carbon nano-tube film 214 surface; Form one deck transition layer in the outside surface of described wetting layer; Form one deck conductive layer in the outside surface of described transition layer; Form one deck anti oxidation layer in the outside surface of described conductive layer.Wherein, the step of above-mentioned formation wetting layer, transition layer and anti oxidation layer is selectable step.Particularly, the sedimentary province of the evaporation source that above-mentioned carbon nano-tube film 214 can be formed continually by above-mentioned layers of material.In the embodiment of the present invention, the step that described employing vacuum vapour deposition forms electro-conductive material can specifically comprise the following steps: form one deck wetting layer in described carbon nano-tube film 214 surface; And form one deck conductive layer in the outside surface of described transition layer.
In addition, at the described electro-conductive material of formation after the surface of described carbon nano-tube film 214, the step that described electro-conductive material outside surface forms strengthening layer can be included in further.Particularly, the step of described formation strengthening layer specifically comprises the following steps: the device 220 carbon nano-tube film 214 being formed with electro-conductive material being equipped with polymers soln by, make polymers soln infiltrate whole carbon nano-tube film 214, this polymers soln adheres to the outside surface of described electro-conductive material by Intermolecular Forces; And cure polymer solution, form a strengthening layer.
Obtained carbon nano-tube compound film 222 can be collected on reel 224 further.Collection mode is for be wrapped in carbon nano-tube compound film 222 on described reel 260.
Selectively, the forming step of the above-mentioned forming step of carbon nano-tube film 214, the forming step of electro-conductive material and strengthening layer all can be carried out in above-mentioned vacuum vessel, and then realizes the continuous seepage of carbon nano-tube compound film 222.
Selectively, for increasing the light transmission rate of the carbon nano-tube compound film 222 obtained, after pulling acquisition one carbon nano-tube film 214 and before the carbon nano tube surface of carbon nano-tube film 214 forms electro-conductive material, a pair carbon nano-tube film 214 can be comprised further and carry out the thinning step of laser.In the present embodiment, wavelength can be adopted to be the infrared laser of 1064 nanometers, and the peak power output of laser is 20 milliwatts, sweep velocity be 10 millimeters per second, meanwhile, for avoiding the energy of lasers that focuses on too high and damage carbon nano-tube film completely, the focusing unit of laser apparatus is removed.The laser irradiated over the carbon nanotube film is the circular light spot dispersed, and diameter is about 3 millimeters.Table 1 is square resistance and the light transmission rate contrast table of the composite membrane 222 and pure nano-carbon tube film 214 obtained after the different electro-conductive material of evaporation rear with process before laser treatment.Described light transmission rate refers to that described carbon nano-tube compound film 222 is to the transmitance of the light of 550 nanometers.
Table 1
| Numbering | Whether adopt laser treatment | Wetting layer metal species/thickness | Conductive layer metal species/thickness | Square resistance (Ω) | Light transmission rate (%) |
| 1 | Untreated | -- | -- | 1684 | 85.2 |
| 2 | Untreated | Ni/2nm | -- | 1656 | 79.0 |
| 3 | Untreated | Ni/2nm | Au/3nm | 504 | 74.6 |
| 5 | Untreated | Ni/2nm | Au/5nm | 216 | 72.5 |
| 6 | Process | Ni/2nm | Au/5nm | 2127 | 92.8 |
| 7 | Process | Ni/2nm | Au/10nm | 1173 | 92.7 |
| 8 | Process | Ni/2nm | Au/15nm | 495 | 90.7 |
| 9 | Process | Ni/2nm | Au/20nm | 208 | 89.7 |
Can be found by above-mentioned table 1, by making the resistance of this carbon nano-tube compound film 222 improve compared to the resistance of pure nano-carbon tube film 214 in the carbon nano tube surface deposits conductive material of carbon nano-tube film 214, but the light transmission rate of this carbon nano-tube compound film 222 declines to some extent along with the increase of electro-conductive material thickness, after adopting this carbon nano-tube film 214 of laser treatment, deposits conductive material forms carbon nano-tube compound film 222 again, and the light transmission rate of this carbon nano-tube compound film 222 is improved.Through great many of experiments test, the resistance of this carbon nano-tube compound film 222 is 50 Europe, Europe ~ 2000, and visible light transmissivity is 70%-95%.
In the present embodiment, the resistance of the carbon nano-tube film 214 before non-deposits conductive material is greater than 1600 ohms, when the resistance of the carbon nano-tube compound film 222 formed after deposits conductive material Ni/Au can be down to 200 ohms, visible light transmissivity is 90%, therefore the carbon nano-tube compound film 222 formed has lower resistance and good visible light transmissivity, can be used as nesa coating.
Compared with prior art, carbon nano-tube compound film that the embodiment of the present invention provides and preparation method thereof has the following advantages: one, comprise multiple being joined end to end by Van der Waals force and the carbon nanotube be arranged of preferred orient in carbon nano-tube compound film, thus make carbon nano-tube compound film have better physical strength and toughness.They are two years old, in carbon nano-tube compound film, every root carbon nano tube surface is all formed with electro-conductive material, has better electroconductibility, in addition than unordered carbon nano-tube compound film of the prior art, this carbon nano-tube compound film also has good visible light transmissivity, therefore can be used as nesa coating.Its three, because carbon nano-tube compound film directly pulls from carbon nano pipe array and manufactures, the method is simple, cost is lower.Its four, the step of described stretching carbon nano-tube film and deposits conductive material all can be carried out in a vacuum vessel, is conducive to the large-scale production of carbon nano-tube compound film.Its four, because the method forming described carbon nano-tube compound film does not need heating, thus in the present invention with carbon nano-tube film can the scope of material of compound wider.
In addition, those skilled in the art also can do other change in spirit of the present invention, and these changes done according to the present invention's spirit, all should be included in the present invention's scope required for protection certainly.
Claims (16)
1. a preparation method for carbon nano-tube compound film, comprises the following steps:
There is provided the carbon nano-tube film that has a self supporting structure, this carbon nano-tube film comprises multiple carbon nanotube, has gap between adjacent carbon nanotube;
Form the surface that electro-conductive material is attached to the carbon nanotube in described carbon nano-tube film, make the visible light transmissivity of this carbon nano-tube compound film be 70%-95%.
2. the preparation method of carbon nano-tube compound film as claimed in claim 1, is characterized in that, the step of described formation electro-conductive material is form the surface that electro-conductive material is attached to each carbon nanotube in described carbon nano-tube film.
3. the preparation method of carbon nano-tube compound film as claimed in claim 1, is characterized in that, the step of described formation electro-conductive material comprises formation one deck conductive layer in the surface of described carbon nano-tube film.
4. the preparation method of carbon nano-tube compound film as claimed in claim 3, it is characterized in that, the material of described conductive layer is gold and silver, copper or its alloy, and the thickness of this conductive layer is 1 ~ 20 nanometer.
5. the preparation method of carbon nano-tube compound film as claimed in claim 3, it is characterized in that, before the step of described formation conductive layer, the step of described formation electro-conductive material comprises formation one deck wetting layer further in the step on described carbon nano-tube film surface, and above-mentioned conductive layer is formed in the outside surface of described wetting layer.
6. the preparation method of carbon nano-tube compound film as claimed in claim 5, it is characterized in that, the material of this wetting layer is iron, cobalt, nickel, palladium, titanium or their alloy, and the thickness of this wetting layer is 1 ~ 10 nanometer.
7. the preparation method of carbon nano-tube compound film as claimed in claim 5, it is characterized in that, before the step of described formation conductive layer, after forming the step of wetting layer, the step of described formation electro-conductive material comprises formation one deck transition layer further in the outside surface of described wetting layer, and above-mentioned conductive layer is formed in the outside surface of described transition layer.
8. the preparation method of carbon nano-tube compound film as claimed in claim 5, is characterized in that, after the step of described formation conductive layer, the step of described formation electro-conductive material comprises formation one deck anti oxidation layer further in the outside surface of described conductive layer.
9. the preparation method of carbon nano-tube compound film as claimed in claim 1, is characterized in that, at described formation electro-conductive material after described carbon nano-tube film surface, is included in the step that described electro-conductive material outside surface forms strengthening layer further.
10. the preparation method of carbon nano-tube compound film as claimed in claim 9, it is characterized in that, the step of described formation strengthening layer specifically comprises the following steps: the device carbon nanotube structure being formed with electro-conductive material being equipped with polymers soln by, make polymers soln infiltrate whole carbon nanotube structure, this polymers soln adheres to the outside surface of described electro-conductive material by Intermolecular Forces; And cure polymer solution, form a strengthening layer.
The preparation method of 11. carbon nano-tube compound films as claimed in claim 1, is characterized in that, before formation electro-conductive material is attached to the surface of described carbon nanotube, comprises further and carries out the thinning step of laser to carbon nano-tube film.
The preparation method of 12. carbon nano-tube compound films as claimed in claim 1, is characterized in that, the method for described formation electro-conductive material comprises the one in physical vaporous deposition, electroless plating and plating.
The preparation method of 13. carbon nano-tube compound films as claimed in claim 1, it is characterized in that, the method for described formation electro-conductive material comprises vacuum vapour deposition or sputtering method.
The preparation method of 14. carbon nano-tube compound films as claimed in claim 13, it is characterized in that, the method for described formation electro-conductive material is vacuum vapour deposition, and it comprises the following steps:
There is provided a vacuum vessel, this vacuum vessel has between a sedimentary province, and between this sedimentary province, bottom and top are placed to a few evaporation source respectively, and the material of described evaporation source is electro-conductive material to be deposited;
Arranging above-mentioned carbon nano-tube film in the middle of the upper and lower evaporation source keeps at a certain distance away, and carbon nano-tube film is just arranged upper and lower evaporation source; And
Heat described evaporation source, after making its melting, evaporation or distillation form electro-conductive material steam, and after this electro-conductive material steam runs into cold carbon nano-tube film, lower surface cohesion over the carbon nanotube film, forms electro-conductive material and be attached to described carbon nano-tube film surface.
The preparation method of 15. carbon nano-tube compound films as claimed in claim 1, is characterized in that, described in there is self supporting structure carbon nano-tube film be that employing one stretching tool pulls and obtains from carbon nano pipe array.
The preparation method of 16. carbon nano-tube compound films as claimed in claim 1, it is characterized in that, the plurality of carbon nanotube is parallel to this carbon nano-tube compound film surface alignment, and is arranged of preferred orient along same direction and is joined end to end by Van der Waals force.
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| CN103395240B (en) * | 2013-08-14 | 2015-11-11 | 苏州捷迪纳米科技有限公司 | The preparation method of carbon nano-composite material and corresponding carbon nano-composite material |
| CN106337215A (en) * | 2016-06-06 | 2017-01-18 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon nanotube composite fiber and production method thereof |
| CN109427983B (en) * | 2017-08-30 | 2020-08-11 | 清华大学 | Organic light emitting diode |
| CN109979644B (en) * | 2019-03-26 | 2020-10-13 | 武汉华星光电半导体显示技术有限公司 | Conductive film preparation method and conductive film |
| CN110337234B (en) * | 2019-07-09 | 2020-11-06 | 中国科学院苏州纳米技术与纳米仿生研究所 | Damp-heat-resistant electromagnetic shielding film, composite material, preparation method and application thereof |
| CN114639937B (en) * | 2022-03-10 | 2023-02-21 | 西安电子科技大学 | Ultrathin breathable flexible butterfly antenna with stretching and temperature sensing functions and preparation method thereof |
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