CN111462941A - Carbon nano tube composite flexible conductive film and preparation method thereof - Google Patents
Carbon nano tube composite flexible conductive film and preparation method thereof Download PDFInfo
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Abstract
The invention provides a carbon nano tube composite flexible conductive film and a method thereof, wherein the carbon nano tube composite flexible conductive film comprises the following components: at least two carbon nanotube layers; and the composite material layer is arranged between the adjacent carbon nanotube layers, wherein the composite material layer comprises metal nanowires and graphene oxide. The sheet resistance of the obtained carbon nano tube composite flexible conductive film is 1-50ohm/sq, and the sheet resistance change rate is below 8%.
Description
Technical Field
The invention relates to the field of conductive films, in particular to the field of a carbon nano tube composite flexible conductive film.
Background
The carbon nano tube is an important nano material developed in the last 30 years, is also the most typical one-dimensional nano material, has the remarkable advantages of good heat conductivity and electrical conductivity, excellent mechanical property and the like, and is gradually applied in various fields. Around the industrial development of carbon nanotube materials, recent years have focused mainly on the fields of new energy batteries, conductive films, far infrared applications, and the like.
The carbon-based material far infrared product has great market potential, and is always the main heating body material in the far infrared health care field because the carbon-based material far infrared product can emit 'life light waves' absorbed by human bodies. In the process of using carbon nanotubes as far infrared devices, the morphology of the conductive film surrounding the carbon nanotubes is mainly divided into two categories: one is to attach carbon nanotubes on the surface of a substrate such as PET, PI, etc. to form a carbon nanotube conductive film; the other is to adopt a floating method to prepare the carbon nano tube, and form the flexible conductive film after rolling/multi-layer rolling. The former can not be self-supported due to the existence of the substrate, is limited by the performance of the substrate, and is not beneficial to manufacturing an ultra-flexible far infrared device with stronger distortion resistance; the second type of carbon nanotube conductive film has stronger anti-distortion performance after being compounded with the soft textile fabric. However, the second type of carbon nanotube conductive film is limited by the production process, and has high manufacturing cost (generally 6 or more layers of carbon nanotubes are required to be formed by hot pressing), poor uniformity of film resistance, and low yield.
Therefore, it is necessary to develop a carbon nanotube ultra-flexible conductive film with low cost, high yield and high performance for far infrared light application products such as protective clothing and clothes.
The statements in the background section are merely prior art as they are known to the inventors and do not, of course, represent prior art in the field.
Disclosure of Invention
The present invention is directed to one or more of the problems of the prior art and is directed to a carbon nanotube composite flexible conductive film.
The invention also aims to provide a preparation method of the carbon nano tube composite flexible conductive film.
The purpose of the invention is realized by the following technical scheme:
a carbon nanotube composite flexible conductive film, comprising:
at least two carbon nanotube layers;
and the composite material layer is arranged between the adjacent carbon nanotube layers and comprises metal nanowires and graphene oxide.
According to one aspect of the invention, the carbon nanotube layer is a single-layer carbon nanotube film.
According to one aspect of the invention, the mass ratio of the metal nanowire to the graphene oxide is (1-10): (1-50).
According to one aspect of the invention, the mass ratio of the metal nanowire to the graphene oxide is (3-6): (20-30).
According to one aspect of the present invention, the mass ratio of the metal nanowire to the graphene oxide is 5: 25.
according to an aspect of the present invention, the metal nanowire may be one or a mixture of silver nanowire, copper nanowire, nickel nanowire, and iron nanowire.
According to one aspect of the invention, the particle size of the graphene oxide is 1-100 microns, preferably 2-5 microns.
The preparation method of the carbon nano tube composite flexible conductive film comprises the following steps:
s1, preparing a carbon nano tube film;
s2, preparing a metal nanowire and graphene oxide mixed dispersion solution;
s3, uniformly coating the metal nanowire and graphene oxide mixed dispersion solution on the surface of a layer of carbon nanotube film, and then covering a layer of carbon nanotube film;
s4, carrying out heat treatment on the carbon nanotube film/the metal nanowire-graphene oxide/the carbon nanotube film in an argon/nitrogen protective atmosphere;
s5, performing rolling treatment on the carbon nanotube film/the metal nanowire-graphene oxide/carbon nanotube film after the heat treatment; and
s6, ultrasonic welding the rolled carbon nanotube film/metal nanowire-graphene oxide/carbon nanotube film to form a firm network structure between the carbon nanotube-graphene oxide-metal nanowire, so as to form the carbon nanotube composite flexible conductive film.
Preferably, the method for preparing the carbon nanotube composite flexible conductive film further comprises:
and S7, performing secondary rolling and shaping on the carbon nano tube flexible composite conductive film subjected to ultrasonic welding.
The graphene oxide can achieve deep or light reduction, depending on the temperature. In addition, for low-melting-point metal nanowires (such as silver nanowires), a small amount of melting may occur, and the melting may adhere to the surfaces of the carbon nanotubes and the graphene, so that the contact area is increased.
According to an aspect of the present invention, in step S1, the carbon nanotube film is prepared by a floating catalyst method, which includes:
s1-1, preparing a carbon source/catalyst solution: dissolving ferrocene and thiophene in a carbon source solvent, wherein the carbon source solvent can be absolute ethyl alcohol, ethylene glycol, methanol/benzyl alcohol, and preferably absolute ethyl alcohol; ferrocene content is 0.1-5 wt%, preferably 2 wt%; the thiophene content is from 0.1 to 5% by weight, preferably 1% by weight;
s1-2, heating the reaction cavity to the temperature of 1300 ℃ and preferably 1200 ℃, then introducing inert carrier gas, wherein the inert carrier gas is mixed gas of argon and hydrogen, the volume ratio of the argon to the hydrogen is 10 (8-10), preferably 10: 10, the flow rate of the inert carrier gas is 1-30L/min, preferably 10L/min, and then injecting the carbon source/catalyst solution into the reaction cavity at the injection rate of 10-40m L/h, preferably 20m L/h;
s1-3, the carbon nano tube film drifts out of the tube tail under the catalysis of inert carrier gas, and is continuously rolled into a film through a collecting roller.
According to an aspect of the present invention, in S2, a specific method for configuring a metal nanowire and graphene oxide mixed dispersion solution is as follows:
adding the metal nanowires and the graphene oxide powder into a solvent, adding a dispersing agent, and stirring and mixing uniformly.
Preferably, the metal nanowire can be one or a mixture of silver nanowire, copper nanowire, nickel nanowire and iron nanowire.
Preferably, the graphene oxide has a sheet diameter of 1 to 100 micrometers, preferably 2 to 5 micrometers.
Preferably, the solvent is water and/or N-methylpyrrolidone, and further preferably, the solvent is water and N-methylpyrrolidone according to a mass ratio of 10: 1.
Preferably, the dispersant is one or a mixture of several of polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), Sodium Dodecyl Sulfate (SDS) and carboxymethyl cellulose (CMC); more preferably, the dispersant is polyvinyl alcohol (PVA), and the mass concentration of the polyvinyl alcohol (PVA) in the mixed dispersion liquid is 0.05 wt%. The matching of the dispersant and the solvent ensures the dispersion of the metal nanowires.
Preferably, the mass concentration of the graphene oxide in the mixed dispersion liquid is 1-50 wt%, preferably 20-30 wt%, and most preferably 25 wt%.
Preferably, the mass concentration of the metal nanowires in the mixed dispersion is 1 to 10 wt%, preferably 4 to 6 wt%, and most preferably 5 wt%.
Preferably, the concentration of the dispersant in the mixed dispersion is 0.01 to 0.1 wt%, preferably 0.05 wt%.
According to an aspect of the invention, in the S3, the coating is performed by spraying.
According to one aspect of the invention, the spraying is to spray the metal nanowire and graphene oxide dispersion liquid on the surface of the carbon nanotube film, so that the average thickness of the coating formed on the surface of the carbon nanotube film by the metal nanowire and graphene oxide dispersion liquid is 500-10000nm, preferably 3000-5000 nm.
According to an aspect of the present invention, in S4, the heat treatment method includes:
s4-1, placing the coiled carbon nanotube composite film coated with the metal nanowires and the graphene oxide dispersion liquid into a vacuum heat treatment furnace;
s4-2, filling protective gas into the vacuum heat treatment furnace, heating to 100-1000 ℃, and then preserving heat for 10-60min, preferably, heating to 150-400 ℃, and then preserving heat for 30 min.
Preferably, the method for charging the protective gas into the vacuum heat treatment furnace comprises the following steps: and vacuumizing the vacuum heat treatment furnace, and introducing protective gas after the background vacuum degree reaches 3 Pa.
Preferably, the shielding gas is argon or nitrogen.
According to an aspect of the present invention, in the S5, the pressure of the roll press process is 2 to 20MPa, preferably 15 MPa.
According to an aspect of the present invention, in S6, the specific conditions of the ultrasonic welding process are:
the welding temperature is 50-200 ℃, preferably 80-100 ℃;
and/or the welding pressure is 2-8 × 105Pa, preferably 4-5 × 105 Pa;
and/or the welding time is 0.1 to 2s, preferably 0.8 to 1 s.
Preferably, the ultrasonic welding adopts a large-area rolling welding mode, and the rolling type online welding can be realized.
According to one aspect of the invention, the rolling pressure of the secondary rolling and shaping is 2-20MPa, preferably 15 MPa.
According to one aspect of the present invention, S3 and S4 are repeated one or more times to form a carbon nanotube composite flexible conductive film in which three or more layers of carbon nanotube films are alternated with two or more layers of composite material of metal nanowires and graphene oxide coating.
According to the invention, the gaps among the multi-layer carbon nanotube films are filled with the mixed material of the metal nanowires and the graphene oxide, and the carbon nanotube-metal nanowire-graphene are welded together by an ultrasonic welding method to form a three-dimensional network conductive structure, so that the uniformity of the graphene films is improved, and the cost of the flexible conductive films can be obviously saved. The sheet resistance of the obtained carbon nano tube composite flexible conductive film is 1-50ohm/sq, and the sheet resistance change rate is below 8%.
In the prior art, a pure floating catalysis method is adopted to prepare the carbon nanotube flexible conductive film, at least 6 layers of carbon nanotube stacks need to be prepared, namely, one heat conduction film needs at least six times of floating catalysis method preparation processes. And a process of laminating and hot-pressing a plurality of layers (more than or equal to 6 layers) of carbon nanotube films is required. The process cost is very high. In the improved method provided by the invention, the filler with moderate cost, namely graphene oxide (containing a very small amount of metal nanowires), is utilized in a large amount, so that the cost of the carbon nanotube conducting film prepared in the prior art can be reduced from 600 yuan per square meter to less than 350 yuan per square meter. The invention is improved, only 2 or 3 layers of carbon nanotube films are needed to achieve the same electrical property (see the table comparison effect). The carbon nanotube flexible conductive film prepared by the floating catalysis-multilayer superposition hot pressing method has poor sheet resistance uniformity and low yield in device application. The invention adopts the ultrasonic welding technology, and the carbon nano tube and the graphene are effectively connected by a network (see attached figure 3), so that more three-dimensional channels with freely moving charges are formed, the sheet resistance can be effectively reduced, and the uniformity of the sheet resistance of the film is improved (see table comparison effect).
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic view of a process flow of the carbon nanotube composite conductive film of the present invention;
FIG. 2 is a schematic cross-sectional view of a multi-layered carbon nanotube composite film according to the present invention;
FIG. 3 is a schematic diagram of the internal structure of the metal nanowire and graphene oxide coating according to the present invention;
wherein, 1 is a carbon nano tube film, 2 is a sprayed metal nano wire and graphene oxide coating, 101, 102 is a carbon nano tube film; 201- -graphene oxide nanoplatelets; 202-metal nanowires.
Detailed Description
In the following, only certain exemplary embodiments are briefly described. As those skilled in the art will recognize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. Accordingly, the drawings and description are to be regarded as illustrative in nature, and not as restrictive.
In the description of the present invention, it is to be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", and the like, indicate orientations and positional relationships based on those shown in the drawings, and are used only for convenience of description and simplicity of description, and do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be considered as limiting the present invention. Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, features defined as "first", "second", may explicitly or implicitly include one or more of the described features. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The following disclosure provides many different embodiments or examples for implementing different features of the invention. To simplify the disclosure of the present invention, the components and arrangements of specific examples are described below. Of course, they are merely examples and are not intended to limit the present invention. Furthermore, the present invention may repeat reference numerals and/or letters in the various examples, such repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed. In addition, the present invention provides examples of various specific processes and materials, but one of ordinary skill in the art may recognize applications of other processes and/or uses of other materials.
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.
Example 1:
a preparation method of a carbon nano tube composite conductive film is shown in figure 1, wherein A-E is a process flow, namely, a layer of metal nano wire and a graphene oxide coating are compounded from a single-layer carbon nano tube film, and then the process is repeated until a multi-layer composite carbon nano tube film is formed. The method specifically comprises the following steps:
1) preparing a carbon nanotube film by a floating catalysis method, and rolling the carbon nanotube film, wherein the rolling length is 200m, and the average thickness of a layer of carbon nanotube film on a rolling shaft is 2 microns;
2) preparing a mixed dispersion solution of nickel nanowires and graphene oxide, wherein the mass concentration of graphene is 25 wt%, and the mass concentration of carbon nanotubes is 5 wt%; adopting water as a solvent, Sodium Dodecyl Sulfate (SDS) as a dispersant, and stirring for dispersion, wherein the concentration of the dispersant is 0.05 wt%;
3) uniformly coating the mixed dispersion solution of the nickel nanowires and the graphene oxide on the surface of a layer of carbon nanotube film by adopting a spraying method, wherein the thickness of the coating is 5000nm, and then covering a layer of carbon nanotube film; repeatedly spraying the nickel nanowire and graphene oxide mixed dispersion solution, and repeatedly covering the carbon nanotube film, wherein the carbon nanotube film reaches 3 layers;
4) in the protective atmosphere of argon gas/nitrogen gas, carrying out heat treatment on the carbon nanotube film/nickel nanowire-graphene oxide/carbon nanotube film, wherein the heat treatment conditions are as follows: keeping the temperature at 200 ℃ for 30 min;
5) performing rolling treatment on the carbon nanotube film/nickel nanowire-graphene oxide/carbon nanotube film after heat treatment, wherein the rolling pressure is 15 MPa;
6) carrying out ultrasonic welding treatment on the rolled carbon nanotube film/nickel nanowire-graphene oxide/carbon nanotube film to form a firm networked structure between the carbon nanotube-graphene-nickel nanowire to form the carbon nanotube mixed flexible conductive film, wherein the ultrasonic welding conditions are as follows: temperature of welding100 ℃ and welding pressure of 5 × 105Pa; the welding time is 1 s;
7) and after the ultrasonic welding is finished, carrying out secondary shaping and rolling treatment on the carbon nano tube flexible composite conductive film, wherein the rolling pressure is 15 MPa.
As shown in fig. 2, the final product forms a composite structure of three layers of carbon nanotube films and two layers of nickel nanowires-graphene oxide, the sheet resistance of the composite structure is 3.0ohm/sq, and the variation rate of the sheet resistance is ± 12%.
Example 2:
a preparation method of a carbon nano tube composite conductive film is shown in figure 1, wherein A-E is a process flow, namely, a layer of metal nano wire and a graphene oxide coating are compounded from a single-layer carbon nano tube film, and then the process is repeated until a multi-layer composite carbon nano tube film is formed. The method specifically comprises the following steps:
1) preparing a carbon nanotube film by a floating catalysis method, and rolling the carbon nanotube film, wherein the rolling length is 200m, and the average thickness of a layer of carbon nanotube film on a rolling shaft is 2 microns;
2) preparing a mixed dispersion solution of copper nanowires and graphene oxide, wherein the mass concentration of graphene is 25 wt%, and the mass concentration of carbon nanotubes is 5 wt%; NMP is used as a solvent, polyvinyl alcohol (PVA) is used as a dispersing agent, the concentration of the dispersing agent is 0.05 wt%, and the NMP is stirred and dispersed;
3) uniformly coating the mixed dispersion solution of the copper nanowires and the graphene oxide on the surface of a layer of carbon nanotube film by adopting a spraying method, wherein the thickness of the coating is 5000nm, and then covering a layer of carbon nanotube film; repeatedly spraying the copper nanowire and graphene oxide mixed dispersion solution, and repeatedly covering a carbon nanotube film, wherein the carbon nanotube film reaches 3 layers;
4) in the protective atmosphere of argon gas/nitrogen gas, carrying out heat treatment on the carbon nanotube film/copper nanowire-graphene oxide/carbon nanotube film, wherein the heat treatment conditions are as follows: keeping the temperature at 200 ℃ for 30 min;
5) performing rolling treatment on the carbon nanotube film/copper nanowire-graphene oxide/carbon nanotube film after heat treatment, wherein the rolling pressure is 15 MPa;
6) for carbon nano treated by rollingCarrying out ultrasonic welding treatment on the rice tube film/copper nanowire-graphene oxide/carbon nanotube film to form a firm network structure between the carbon nanotube-graphene-nickel nanowire to form the carbon nanotube mixed flexible conductive film, wherein the ultrasonic welding conditions are that the welding temperature is 100 ℃ and the welding pressure is 5 × 105Pa; the welding time is 1 s;
7) and after the ultrasonic welding is finished, carrying out secondary shaping and rolling treatment on the carbon nano tube flexible composite conductive film, wherein the rolling pressure is 15 MPa.
As shown in fig. 2, the final product forms a composite structure of three layers of carbon nanotube films and two layers of copper nanowires-graphene oxide, the sheet resistance of the composite structure is 2.5ohm/sq, and the variation rate of the sheet resistance is ± 10%.
Example 3:
a preparation method of a carbon nano tube composite conductive film is shown in figure 1, wherein A-E is a process flow, namely, a layer of metal nano wire and a graphene oxide coating are compounded from a single-layer carbon nano tube film, and then the process is repeated until a multi-layer composite carbon nano tube film is formed. The method specifically comprises the following steps:
1) preparing a carbon nanotube film by a floating catalysis method, and rolling the carbon nanotube film, wherein the rolling length is 200m, and the average thickness of a layer of carbon nanotube film on a rolling shaft is 2 microns;
2) preparing a silver nanowire and graphene oxide mixed dispersion solution, wherein the mass concentration of graphene is 20 wt%, and the mass concentration of carbon nanotubes is 8 wt%; water and NMP (in a mass ratio of 10: 1) are used as solvents, Sodium Dodecyl Sulfate (SDS) is used as a dispersant, the concentration of the dispersant is 0.05 wt%, and the mixture is stirred and dispersed;
3) uniformly coating the mixed dispersion solution of the silver nanowires and the graphene oxide on the surface of a layer of carbon nanotube film by adopting a spraying method, wherein the thickness of the coating is 5000nm, and then covering a layer of carbon nanotube film; repeatedly spraying the silver nanowire and graphene oxide mixed dispersion solution, and repeatedly covering a carbon nanotube film, wherein the carbon nanotube film reaches 3 layers;
4) in the protective atmosphere of argon gas/nitrogen gas, carrying out heat treatment on the carbon nanotube film/silver nanowire-graphene oxide/carbon nanotube film, wherein the heat treatment conditions are as follows: keeping the temperature at 150 ℃ for 30 min;
5) performing rolling treatment on the carbon nanotube film/silver nanowire-graphene oxide/carbon nanotube film after heat treatment, wherein the rolling pressure is 15 MPa;
6) ultrasonic welding the rolled carbon nanotube film/silver nanowire-graphene oxide/carbon nanotube film to form a firm network structure between the carbon nanotube film and the graphene-silver nanowire to form the carbon nanotube mixed flexible conductive film, wherein the ultrasonic welding conditions are that the welding temperature is 100 ℃ and the welding pressure is 5 × 105Pa; the welding time is 1 s;
7) and after the ultrasonic welding is finished, carrying out secondary shaping and rolling treatment on the carbon nano tube flexible composite conductive film, wherein the rolling pressure is 15 MPa.
As shown in fig. 2, the final product forms a composite structure of three layers of carbon nanotube films + two layers of silver nanowires-graphene oxide, the sheet resistance of the composite structure is 1.8ohm/sq, and the variation rate of the sheet resistance is ± 8%.
Example 4:
a preparation method of a carbon nano tube composite conductive film is shown in figure 1, wherein A-E is a process flow, namely, a layer of metal nano wire and a graphene oxide coating are compounded from a single-layer carbon nano tube film, and then the process is repeated until a multi-layer composite carbon nano tube film is formed. The method specifically comprises the following steps:
1) preparing a carbon nanotube film by a floating catalysis method, and rolling the carbon nanotube film, wherein the rolling length is 200m, and the average thickness of a layer of carbon nanotube film on a rolling shaft is 2 microns;
2) preparing a mixed dispersion solution of nickel nanowires and graphene oxide, wherein the mass concentration of graphene is 25 wt%, and the mass concentration of carbon nanotubes is 5 wt%; water and NMP (the mass concentration ratio is 10: 1) are used as solvents, polyvinyl alcohol (PVA) is used as a dispersing agent, the concentration of the dispersing agent is 0.05 wt%, and the mixture is stirred and dispersed;
3) uniformly coating the mixed dispersion solution of the nickel nanowires and the graphene oxide on the surface of a layer of carbon nanotube film by adopting a spraying method, wherein the thickness of the coating is 5000nm, and then covering a layer of carbon nanotube film; repeatedly spraying the copper nanowire and graphene oxide mixed dispersion solution, and repeatedly covering a carbon nanotube film, wherein the carbon nanotube film reaches 3 layers;
4) in the protective atmosphere of argon gas/nitrogen gas, carrying out heat treatment on the carbon nanotube film/nickel nanowire-graphene oxide/carbon nanotube film, wherein the heat treatment conditions are as follows: keeping the temperature at 200 ℃ for 30 min;
5) performing rolling treatment on the carbon nanotube film/nickel nanowire-graphene oxide/carbon nanotube film after heat treatment, wherein the rolling pressure is 15 MPa;
6) ultrasonic welding the rolled carbon nanotube film/nickel nanowire-graphene oxide/carbon nanotube film to form a firm network structure between the carbon nanotube film and the graphene-nickel nanowire to form the carbon nanotube mixed flexible conductive film, wherein the ultrasonic welding conditions are that the welding temperature is 100 ℃ and the welding pressure is 5 × 105Pa; the welding time is 1 s;
7) and after the ultrasonic welding is finished, carrying out secondary shaping and rolling treatment on the carbon nano tube flexible composite conductive film, wherein the rolling pressure is 15 MPa.
As shown in fig. 2, the final product forms a composite structure of three layers of carbon nanotube films and two layers of nickel nanowires-graphene oxide, the sheet resistance of the composite structure is 2.4ohm/sq, and the variation rate of the sheet resistance is ± 10%.
Comparative example 1:
the carbon nano tube film is prepared by a floating catalysis method, and is rolled by a collecting roller. Then, a multilayer superposition method is adopted to prepare the uniform carbon nanotube film, and the specific method is as follows:
1) releasing (unreeling) the carbon nanotubes (1 layer) on the collecting roller on the surface of a substrate, such as the surface of a PET substrate, and flatly paving the carbon nanotubes on the surface of the PET substrate to form a first layer of carbon nanotube conductive film, wherein the unreeling direction is marked as the X direction;
2) because the carbon nanotube film has certain directionality after growing, in order to effectively reduce the sheet resistance of the conductive film and improve the uniformity, in the vertical direction (marked as Y direction) of the direction (X direction) of the carbon nanotube film released in 1), tiling a second layer of carbon nanotube film, and overlapping two layers of carbon nanotube films placed in 1) and 2) on a plane;
3) repeating the steps 1) and 2), namely, repeatedly overlapping the carbon nanotube film in a manner of vertically crossing the X direction and the Y direction until the carbon nanotube film reaches a 6-layer composite structure;
4) laminating the carbon nanotube film formed in the step 3) under the pressure of 0.5-15Mpa to form the compacted carbon nanotube multilayer composite film. The sheet resistance of the obtained carbon nano tube multilayer composite film is 2ohm/sq, and the variation rate of the sheet resistance is +/-15%.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A carbon nanotube composite flexible conductive film, comprising:
at least two carbon nanotube layers;
and the composite material layer is arranged between the adjacent carbon nanotube layers and comprises metal nanowires and graphene oxide.
2. The carbon nanotube composite flexible conductive film of claim 1, wherein the carbon nanotube layer is a single-layer carbon nanotube film;
preferably, the mass ratio of the metal nanowire to the graphene oxide is (1-10): (1-50);
preferably, the mass ratio of the metal nanowire to the graphene oxide is (3-6): (20-30);
further preferably, the mass ratio of the metal nanowire to the graphene oxide is 5: 25;
preferably, the metal nanowire can be one or a mixture of silver nanowire, copper nanowire, nickel nanowire and iron nanowire;
preferably, the particle size of the graphene oxide is 1-100 microns, preferably 2-5 microns;
preferably, the sheet resistance of the carbon nanotube composite flexible conductive film is 1-50ohm/sq, and the sheet resistance change rate is below 8%.
3. The method for preparing the carbon nanotube composite flexible conductive film according to claim 1 or 2, comprising:
s1, preparing a carbon nano tube film;
s2, preparing a metal nanowire and graphene oxide mixed dispersion solution;
s3, uniformly coating the metal nanowire and graphene oxide mixed dispersion solution on the surface of a layer of carbon nanotube film, and then covering a layer of carbon nanotube film;
s4, carrying out heat treatment on the carbon nanotube film/the metal nanowire-graphene oxide/the carbon nanotube film in an argon/nitrogen protective atmosphere;
s5, performing rolling treatment on the carbon nanotube film/the metal nanowire-graphene oxide/carbon nanotube film after the heat treatment; and
s6, ultrasonic welding the rolled carbon nanotube film/metal nanowire-graphene oxide/carbon nanotube film to form a firm network structure between the carbon nanotube-graphene oxide-metal nanowire, so as to form the carbon nanotube composite flexible conductive film.
4. The method for preparing the carbon nanotube composite flexible conductive film according to claim 3, further comprising:
and S7, performing secondary rolling and shaping on the carbon nano tube flexible composite conductive film subjected to ultrasonic welding.
5. The method for preparing the carbon nanotube composite flexible conductive film according to claim 3, wherein in the step S1, the carbon nanotube film is prepared by a floating catalysis method, and the specific method comprises:
s1-1, preparing a carbon source/catalyst solution: dissolving ferrocene and thiophene in a carbon source solvent, wherein the carbon source solvent can be absolute ethyl alcohol, ethylene glycol, methanol/benzyl alcohol, and preferably absolute ethyl alcohol; ferrocene content is 0.1-5 wt%, preferably 2 wt%; the thiophene content is from 0.1 to 5% by weight, preferably 1% by weight;
s1-2, heating the reaction cavity to the temperature of 1300 ℃ and preferably 1200 ℃, then introducing inert carrier gas, wherein the inert carrier gas is mixed gas of argon and hydrogen, the volume ratio of the argon to the hydrogen is 10 (8-10), preferably 10: 10, the flow rate of the inert carrier gas is 1-30L/min, preferably 10L/min, and then injecting the carbon source/catalyst solution into the reaction cavity at the injection rate of 10-40m L/h, preferably 20m L/h;
s1-3, the carbon nano tube film drifts out of the tube tail under the catalysis of inert carrier gas, and is continuously rolled into a film through a collecting roller.
6. The method for preparing the carbon nanotube composite flexible conductive film according to claim 3, wherein in the step S2, the specific method for preparing the metal nanowire and graphene oxide mixed dispersion solution comprises:
adding the metal nanowires and the graphene oxide powder into a solvent, adding a dispersing agent, and stirring and mixing uniformly;
preferably, the metal nanowire can be one or a mixture of silver nanowire, copper nanowire, nickel nanowire and iron nanowire;
preferably, the particle size of the graphene oxide is 1-100 microns, preferably 2-5 microns;
preferably, the solvent is water and/or N-methylpyrrolidone, and further preferably, the solvent is water and N-methylpyrrolidone according to a mass ratio of 10: 1, mixing;
preferably, the dispersing agent is one or a mixture of more of polyvinylpyrrolidone, polyvinyl alcohol, sodium dodecyl sulfate and carboxymethyl cellulose; more preferably, the dispersant is polyvinyl alcohol, and accounts for 0.05 wt% of the mixed dispersion liquid;
preferably, the mass concentration of the graphene oxide in the mixed dispersion liquid is 1-50 wt%, preferably 20-30 wt%, and most preferably 25 wt%;
preferably, the mass concentration of the metal nanowires in the mixed dispersion is 1-10 wt%, preferably 4-6 wt%, and most preferably 5 wt%;
preferably, the concentration of the dispersant in the mixed dispersion is 0.01 to 0.1 wt%, preferably 0.05 wt%.
7. The method for preparing a carbon nanotube composite flexible conductive film according to claim 3, wherein in the step S3, the coating is performed by spraying;
preferably, the metal nanowire and graphene oxide dispersion liquid is sprayed on the surface of the carbon nanotube film, so that a coating with the average thickness of 500-10000nm is formed on the surface of the carbon nanotube film by the metal nanowire and graphene oxide dispersion liquid, and the preferable coating thickness is 3000-5000 nm.
8. The method for preparing a carbon nanotube composite flexible conductive film according to claim 3, wherein in the step S4, the heat treatment method comprises:
s4-1, placing the coiled carbon nanotube composite film coated with the metal nanowires and the graphene oxide dispersion liquid into a vacuum heat treatment furnace;
s4-2, filling protective gas into the vacuum heat treatment furnace, heating to 100-1000 ℃, and then preserving heat for 10-60min, preferably, heating to 150-400 ℃, and then preserving heat for 30 min;
further preferably, the method for charging the protective gas into the vacuum heat treatment furnace comprises the following steps: vacuumizing the vacuum heat treatment furnace, and introducing protective gas after the background vacuum degree reaches 3 Pa;
further preferably, the shielding gas is argon or nitrogen.
9. The method for preparing a carbon nanotube composite flexible conductive film according to claim 3, wherein in the S5, the pressure of the rolling treatment is 2-20MPa, preferably 15 MPa;
preferably, in S6, the specific conditions of the ultrasonic welding process are:
the welding temperature is 50-200 ℃, preferably 80-100 ℃;
and/or the welding pressure is 2-8 × 105Pa, preferably 4-5 × 105 Pa;
and/or the welding time is 0.1 to 2s, preferably 0.8 to 1 s;
preferably, the ultrasonic welding adopts a large-area rolling welding mode, and the rolling type on-line welding can be realized;
further preferably, the rolling pressure of the secondary rolling and shaping is 2-20MPa, preferably 15 MPa.
10. The method of claim 3, wherein the steps of S3 and S4 are repeated one or more times to form a carbon nanotube composite flexible conductive film in which three or more layers of carbon nanotube films are alternated with two or more layers of metal nanowires and graphene oxide-coated composite materials.
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