CN114206775A - Composite carbon nanotube film, preparation method thereof and layered heating device - Google Patents
Composite carbon nanotube film, preparation method thereof and layered heating device Download PDFInfo
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Abstract
A preparation method of a composite carbon nanotube film, the composite carbon nanotube film and a layered heating device. The preparation method of the composite carbon nanotube film comprises the following steps: obtaining a carbon nanotube base film (120), wherein the carbon nanotube base film (120) comprises a layer of carbon nanotube film or a plurality of layers of carbon nanotube films which are arranged in a stacked mode, and the carbon nanotube film is provided with first carbon nanotubes which are arranged in an oriented mode; obtaining carbon nanotube slurry, wherein the carbon nanotube slurry comprises a solvent, a second carbon nanotube uniformly dispersed in the solvent and a binder; and coating carbon nanotube slurry on the surface of the carbon nanotube-based film (120), and removing the solvent in the carbon nanotube slurry to prepare the composite carbon nanotube film. The composite carbon nanotube film prepared by the preparation method successfully realizes the composite carbon nanotube film which adopts the oriented carbon nanotube film as the substrate, and the conductivity of the composite carbon nanotube film is obviously higher than that of the traditional carbon nanotube film.
Description
Technical Field
The application relates to the technical field of carbon materials, in particular to a composite carbon nanotube film, a preparation method thereof and a layered heating device.
Background
Carbon nanotubes are a typical one-dimensional nanomaterial and have extremely high strength, electrical conductivity, and thermal conductivity in the length direction of the carbon nanotubes. However, in many application scenarios, the carbon nanotubes are often required to be further manufactured into products with macroscopic dimensions to be further used, such as carbon nanotube films further prepared from a plurality of carbon nanotubes. The carbon nanotube film has the advantages of light weight, high strength, free bending, cutting into any shape, small occupied space, high temperature resistance, corrosion resistance, long service life, difficult deformation at high temperature, high heat conductivity and the like. The carbon nanotube film can be used for preparing a heating core layer material of a heating device, efficiently converts electric energy into heat energy and timely disperses the heat energy thanks to better electric conductivity and heat conductivity.
Conventional carbon nanotube films are often carbon nanotube films formed by pressing carbon nanotube slurry or carbon nanotube powder. The heat generation performance of such carbon nanotube films is still limited. Specifically, since the conductivity is not high, the amount of heat that can be generated at a low voltage is limited, and the temperature rise is also limited. Such carbon nanotube films thus tend to remain difficult to meet practical requirements.
Disclosure of Invention
Based on this, in order to improve the electric conductivity of the carbon nanotube film and further improve the heating performance of the carbon nanotube film, the invention provides a preparation method of a composite carbon nanotube film with higher electric conductivity and a corresponding composite carbon nanotube film.
According to one embodiment of the present invention, a method for preparing a composite carbon nanotube film includes the steps of:
obtaining a carbon nanotube base film, wherein the carbon nanotube base film comprises a layer of carbon nanotube film or a plurality of layers of carbon nanotube films which are stacked, and the carbon nanotube film is provided with first carbon nanotubes which are arranged in an oriented manner;
obtaining carbon nanotube slurry, wherein the carbon nanotube slurry comprises a solvent, and a second carbon nanotube and a binder which are uniformly dispersed in the solvent;
and coating the carbon nanotube slurry on the surface of the carbon nanotube base film, and removing the solvent in the carbon nanotube slurry to prepare the composite carbon nanotube film.
In one embodiment, the viscosity of the carbon nanotube slurry is 4000cp to 8000 cp.
In one embodiment, in the carbon nanotube slurry, the mass ratio of the second carbon nanotubes is 0.3% to 20%, and the mass ratio of the binder is 0.1% to 5%.
In one embodiment, the carbon nanotube slurry further includes a dispersant in a mass ratio of 0.1% to 5%, the dispersant being used to promote dispersibility of the second carbon nanotubes in the solvent.
In one embodiment, the binder is selected from polyvinylidene fluoride, and/or the dispersant is selected from polyvinylpyrrolidone.
In one embodiment, the carbon nanotube-based film comprises a plurality of layers of the carbon nanotube film, and the method for preparing the carbon nanotube-based film comprises the steps of: and laminating a plurality of single-layer carbon nanotube films and rolling to obtain the densified multi-layer carbon nanotube-based film.
In one embodiment, the method further comprises the step of wetting the carbon nanotube film with an alcohol liquid during the rolling of the plurality of single-layer carbon nanotube films.
In one embodiment, in the process of rolling the plurality of single-layer carbon nanotube films, the pressure of the pressing roller to the carbon nanotube film is 0.2MPa to 1MPa, and the moving speed of the pressing roller is 0.1m/min to 6 m/min.
In one embodiment, the carbon nanotube-based film comprises a plurality of carbon nanotube films, and the included angle between the orientations of any two carbon nanotube films is less than or equal to 15 degrees.
In one embodiment, the thickness of the carbon nanotube-based film is 1 μm to 50 μm.
And, a composite carbon nanotube film, comprising:
the carbon nanotube base film comprises one or more layers of carbon nanotube films, and the carbon nanotube films are provided with first carbon nanotubes which are arranged in an oriented manner; and
the carbon nanotube enhancement layer comprises a second carbon nanotube and a binder, wherein the second carbon nanotube in the carbon nanotube enhancement layer is bonded on the surface of the carbon nanotube base film through the binder, or the second carbon nanotube in the carbon nanotube enhancement layer is bonded on the surface of the carbon nanotube base film through the binder and part of the second carbon nanotube is inserted into the surface layer of the carbon nanotube base film.
In one embodiment, the composite carbon nanotube film is prepared by the preparation method according to any one of the above embodiments.
Further, a layered heat generating device comprising a heat generating core layer converting electrical energy into thermal energy, the heat generating core layer comprising the composite carbon nanotube film according to any of the embodiments described above.
The composite carbon nanotube film of the above embodiment has the following beneficial effects:
the composite carbon nanotube film of the embodiment has the oriented carbon nanotube film, and the oriented carbon nanotube film has the conductivity in the orientation direction which is obviously higher than that of the traditional carbon nanotube film with carbon nanotubes randomly distributed, so that the heating performance of the carbon nanotube film can be obviously improved. In addition, in the orientation direction, the heat conduction performance and the mechanical performance of the carbon nanotube film are also obviously superior to those of the traditional carbon nanotube film.
Further, in order to meet the use requirement, the tensile strength of the composite carbon nanotube film prepared by the method for preparing a composite carbon nanotube film according to the above embodiment in the vertical orientation direction can be significantly improved. In the composite carbon nanotube film, the second carbon nanotube and the binder play a role of an intermediate connector, so that the first carbon nanotubes arranged side by side are connected more tightly. Specifically, the first carbon nanotube and the second carbon nanotube which are originally arranged side by side are connected, and meanwhile, the second carbon nanotube is fixedly connected with other second carbon nanotubes through the adhesive, when an external force acts on the carbon nanotube base film in a non-oriented direction, the bonding force between the first carbon nanotube and the second carbon nanotube is required to be overcome, so that the tensile strength of the composite carbon nanotube film in the non-oriented direction is remarkably improved. Meanwhile, as the second carbon nanotube is used as the intermediate connector, the conductivity between the carbon nanotube base films is still similar to that of the original carbon nanotube base films, and the significant reduction caused by introducing other non-insulating substances can be avoided.
The details of one or more embodiments of the application are set forth in the accompanying drawings and the description below. Other features, objects, and advantages of the application will be apparent from the description and drawings, and from the claims.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain drawings of other embodiments based on these drawings without any creative effort.
In the drawings:
fig. 1 is a schematic structural diagram of a composite carbon nanotube film according to an embodiment of the present invention;
fig. 2 is a schematic surface topography of the composite carbon nanotube film of embodiment 1 of the present invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless otherwise defined, in the description of the present invention, terms indicating orientation or positional relationship such as "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., are based on the orientation or positional relationship shown in the drawings of the present invention, which are only for convenience and simplicity in describing the contents of the invention and for the reader's understanding in conjunction with the drawings, and do not define or imply that the device or element referred to must have a specific orientation and therefore should not be construed as limiting the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items. "Multi", as used herein, means a combination of two or more items. Unless explicitly indicated or otherwise generally understood by those skilled in the art, the ratios or concentrations in this application are to be considered mass ratios or mass concentrations.
The conventional carbon nanotube film is often prepared by coating carbon nanotube slurry or pressing carbon nanotube powder, so that carbon nanotubes in the prepared carbon nanotube film are randomly arranged, the electrical conductivity and the thermal conductivity of a single carbon nanotube are high, but the electrical conductivity of the integral carbon nanotube film formed by the random arrangement of the carbon nanotubes is poor. This is because the carbon nanotube film has microscopically many interfaces that increase the resistance of the carbon nanotube film.
Based on this, one embodiment of the present invention proposes to replace the conventional carbon nanotube film with a carbon nanotube film having an orientation to obtain a carbon nanotube film having a higher conductivity. However, the carbon nanotube film with orientation has some problems, which results in that it cannot be directly applied to replace the conventional carbon nanotube film. The details are as follows.
Compared with the carbon nanotube film formed by the carbon nanotubes arranged randomly, the carbon nanotubes in the carbon nanotube film formed by pulling out the carbon nanotube array have a certain orientation, namely, the carbon nanotube film is oriented. In the orientation direction, the whole carbon nanotube film has obviously higher electrical conductivity, thermal conductivity and mechanical strength, so that the oriented carbon nanotube film can meet the use occasions with higher performance requirements. However, such an aligned carbon nanotube film needs to be bonded together by van der waals force between adjacent carbon nanotubes in a non-aligned direction, particularly in a direction perpendicular to the aligned direction, and thus the strength of the aligned carbon nanotube film in the non-aligned direction is much lower than that in the aligned direction, which makes it extremely vulnerable to damage during the manufacturing process. This not only puts extremely high demands on the processing process, but also limits the practical application scenarios of the oriented carbon nanotube film products.
The mechanical property of the carbon nanotube film can also be improved by some traditional technical means, for example, a high polymer material layer is adopted for coating, and the carbon nanotube film is shaped by the aid of the mechanical property of the high polymer material; and for example, coating an adhesive on the surface of the carbon nanotube film to enhance the tensile resistance of the whole carbon nanotube film. However, the composite carbon nanotube films formed by these methods generally have significantly reduced overall electrical properties, and are difficult to continue to be used as materials for the heat-generating core layer.
According to one embodiment of the invention, a method for preparing a composite carbon nanotube film comprises the following steps.
Step S1, obtaining a carbon nanotube-based film, where the carbon nanotube-based film includes a carbon nanotube film or a plurality of carbon nanotube films stacked one on another. The carbon nanotube film is provided with first carbon nanotubes which are arranged in an orientation mode.
In one specific example, the carbon nanotube-based film includes a plurality of carbon nanotube films, and the plurality of carbon nanotube films are stacked one on another. Generally, the thickness of one layer of oriented carbon nanotube base film is relatively limited, so that the bulk resistance of the oriented carbon nanotube base film is relatively large, the overall strength is low, and the oriented carbon nanotube base film is not suitable for partial application scenes, and therefore, the overall thicker carbon nanotube base film can be formed by overlapping a plurality of layers of carbon nanotube films. Optionally, the number of the oriented carbon nanotube film layers is 20 to 500. The number of the layers of the film can be selected according to actual requirements. In general, the larger the number of carbon nanotube thin films, the lower the resistance of the entire carbon nanotube-based film composed of the carbon nanotube thin films.
In one specific example, the carbon nanotube-based film comprises a plurality of layers of oriented carbon nanotube films, and the orientation included angle is less than or equal to 15. Preferably, the included angle between the orientations of any two layers of carbon nanotube films is less than or equal to 15 degrees. Namely, the orientation of the first carbon nanotube in one layer of carbon nanotube film is taken as a reference direction, and the included angle between the orientation of the first carbon nanotube in other layers of carbon nanotube films and the reference direction is less than or equal to 15 degrees. More preferably, the orientation of the plurality of aligned carbon nanotube films in the carbon nanotube-based film is the same. The arrangement of the plurality of carbon nanotube films in the same orientation has the following advantages. On one hand, the carbon nanotube film with the same orientation is more convenient to operate and lower in cost during preparation. If different directions are adopted for superposition, especially when the orientation included angle is 90 degrees, the operation difficulty is higher, the efficiency is low, and the actual size of the base film can be limited. Also, the carbon nanotube film stacked in the same or similar direction has more excellent mechanical and electrical properties in that direction.
In one specific example, the carbon nanotube-based film includes a plurality of layers of aligned carbon nanotube films, and the method of preparing the carbon nanotube-based film includes the step of rolling the plurality of layers of carbon nanotube films to densify the carbon nanotube films. In the rolling and compacting process, the pressure applied by the pressing roller is 0.2-1 MPa. Furthermore, in the process of rolling and compacting, the laminated multilayer oriented carbon nanotube film can be wetted by alcohol liquid to enhance the bonding force between the carbon nanotube films. The alcoholic liquid may be selected from ethanol. Correspondingly, the speed of the press rolls may be selected from 0.1m/min to 6 m/min. When the press roll speed exceeds this range, the alcohol is not easily volatilized completely. Meanwhile, some problems possibly occurring in the rolling process are not easy to find in time, and the stability of the film is influenced. Further, in the process of rolling and compacting, the alcohol liquid can be removed by adopting a drying mode. The drying temperature can be 100-200 ℃, the drying temperature is set in cooperation with the speed of a compression roller, and when the speed of the compression roller is low, the drying is carried out at a lower temperature; when the speed of the press roller is high, the film needs to be dried at a higher temperature, and the film drying alcohol is completely volatilized.
In one specific example, the thickness of the carbon nanotube-based film is 0.5 μm to 100 μm. Further optionally, the thickness of the carbon nanotube-based film is 1 μm to 50 μm.
In one specific example, the carbon nanotube film may be prepared from a carbon nanotube array. The carbon nanotube array is an aggregate of a plurality of carbon nanotubes grown in a specific direction. The carbon nanotube array has uniform growth direction, so that the carbon nanotubes in the carbon nanotube array have orientation, and a carbon nanotube film further prepared by the carbon nanotube array also has certain orientation. The length of the carbon nano tube in the carbon nano tube array can be selected according to actual preparation conditions, for example, the length of the carbon nano tube array is 100-1000 μm, and the diameter of the carbon nano tube in the carbon nano tube array is 6-15 nm.
More specifically, the method for preparing the oriented carbon nanotube film by using the carbon nanotube array may be: and clamping the carbon nanotubes from the carbon nanotube array, and dragging the carbon nanotubes along a direction perpendicular to the growth direction of the carbon nanotube array to prepare the carbon nanotube film. When the clamping tool stretches the carbon nanotubes, the carbon nanotubes drive the modified carbon nanotube array to be continuously pulled out through van der waals force, and the carbon nanotube film prepared by the method has intrinsic orientation along the growth direction of the carbon nanotube array.
In one particular example, the carbon nanotube array may be a carbon nanotube array grown by chemical vapor deposition. More specifically, the catalyst layer is deposited, for example, using an electron beam evaporation method, and the material of the catalyst layer may be selected from at least one of iron, cobalt, and nickel. The thickness of the catalyst layer may be 20nm to 23 nm. And heating the substrate with the catalyst layer to 550-900 ℃, and introducing carbon source gas for reaction to prepare the carbon nanotube array. The carbon source gas may include ethylene and hexane, and a gas partial pressure ratio of ethylene to hexane is 1.25:1 to 8: 1. The flow rate of the carbon source gas is 5mL/min to 15mL/min, and the time for introducing the carbon source gas to react is 10min to 25 min. The carbon nano tube array prepared by the preparation method has better mechanical property.
The carbon nanotube array grown by the chemical vapor deposition method has a highly oriented structure, and due to van der waals forces between the carbon nanotubes, adjacent carbon nanotubes can be pulled from the carbon nanotube array along a specific direction to form an oriented carbon nanotube film connected end to end. The carbon nanotube film is used for reinforcing the composite material, so that the composite material has better processability, and the fracture toughness of the composite material can be effectively improved.
Step S2, spreading carbon nanotube slurry on the surface of the carbon nanotube-based film, where the carbon nanotube slurry includes a solvent and a dispersoid dispersed in the solvent, and the dispersoid includes a second carbon nanotube and a binder.
It is understood that in the art of carbon nanotube slurry, "solvent" and "solute" are generally used
In the broad sense, it is understood that in a mixture where a solid is dispersed in a liquid, the liquid is a "solvent," the solid is a "solute," and the solid may be present as dissolved in the liquid or as smaller particles suspended in the liquid.
In one specific example, carbon nanotube slurry is applied to both surfaces of the carbon nanotube-based film opposite to each other. The method for coating the carbon nanotube slurry may be specifically coating. For example, a doctor blade is used to coat the carbon nanotube-based film with the carbon nanotube slurry. More specifically, the double-sided coating is performed by a small roll-to-roll doctor blade casting roll system. The coating speed may be 0.1m/min to 0.8 m/min.
In one specific example, the method further comprises the step of removing the solvent in the carbon nanotube slurry after the carbon nanotube slurry is coated. The solvent may be removed by drying. The drying temperature can be 100-200 ℃. The coating speed is matched with the drying temperature, and when the coating speed is low, the drying is carried out at a low temperature; when the coating speed is high, high-temperature drying is needed, so that the solvent in the slurry is completely volatilized.
In one specific example, the viscosity of the carbon nanotube slurry is 4000cp to 8000cp, for example, 4000cp, 5000cp, 6000cp, 7000cp, 8000cp or a range therebetween. When the viscosity is too low, the slurry is thinner, and when the carbon nanotube film is coated with the slurry, the slurry is not easy to bond with each other and can be scattered around, so that the slurry sizing rate is low, and the coating is too thin. When the viscosity is too high, the slurry is too easy to bond, and the coating effect is poor.
In one specific example, in the carbon nanotube slurry, the mass ratio of the carbon nanotubes is 0.3 to 20%, and the mass ratio of the binder is 0.1 to 5%.
In one specific example, the carbon nanotube slurry further includes a dispersant in an amount of 0.1 to 5% by mass. For example, the dispersant may be a surfactant, and the dispersant is used to improve dispersibility of the carbon nanotubes in the solvent.
In one specific example, the carbon nanotube slurry includes, by mass, 0.3% to 20% of carbon nanotubes, 0.1% to 5% of a binder, 0.1% to 5% of a dispersant, and the balance of a solvent.
In one specific example, the binder may be selected from materials having viscosity, such as polyvinylidene fluoride (PVDF) or sodium alginate. In one specific example, the solvent may be selected from one or more of Nitrogen Methyl Pyrrolidone (NMP), ethanol, and water. For example, in order to improve the dispersibility of the carbon nanotubes, the solvent may be selected from lipophilic solvents, azomethylpyrrolidone, and the binder may be selected from polyvinylidene fluoride.
In one specific example, the dispersant may be selected from polyvinylpyrrolidone. The polyvinylpyrrolidone can better promote the dispersibility of the second carbon nanotubes in the N-methyl pyrrolidone, so that the second carbon nanotubes can be fully separated and finally uniformly distributed on the surface layer of the carbon nanotube base film.
In one specific example, the thickness of the coated carbon nanotube paste is 50 μm to 400 μm. This thickness is the thickness of the coated wet film. The coating after drying can have different coating thicknesses due to differences in solids content and viscosity. Generally, the higher the solids content and the higher the viscosity, the higher the coating thickness after baking. Too thick a coating results in a cured film that is stiff and not flexible, and the coating is susceptible to cracking during subsequent solvent removal due to non-uniform solvent evaporation.
Further, another embodiment of the present invention further provides a composite carbon nanotube film prepared by the above method for preparing a composite carbon nanotube film.
For example, referring to fig. 1, the carbon nanotube film includes: a carbon nanotube-based film 120, wherein the carbon nanotube-based film 120 includes one or more carbon nanotube films, and the carbon nanotube films have first carbon nanotubes aligned therein; and
the carbon nanotube enhancement layer comprises a second carbon nanotube and a binder, wherein the second carbon nanotube in the carbon nanotube enhancement layer is bonded on the surface of the carbon nanotube base film through the binder, or the second carbon nanotube in the carbon nanotube enhancement layer is bonded on the surface of the carbon nanotube base film through the binder and has a part of the second carbon nanotube inserted into the surface layer of the carbon nanotube base film.
In the present embodiment, the first carbon nanotube reinforcing layer 110 and the second carbon nanotube reinforcing layer 130 are simultaneously disposed on the opposite side surfaces of the carbon nanotube-based film 120. In other embodiments, it may be disposed on one of the side surfaces.
In one specific example, a portion of the second carbon nanotubes are disposed in contact with the first carbon nanotubes in the carbon nanotube-based film.
The tensile strength of the composite carbon nanotube film prepared by the preparation method of the composite carbon nanotube film of the embodiment in the direction perpendicular to the carbon orientation direction can be significantly improved. Specifically, when the composite carbon nanotube film is prepared, the adhesive in the carbon nanotube enhancement layer may penetrate into the carbon nanotube base film 120 to connect the first carbon tubes, and the solvent may slightly shrink the film during the volatilization process, thereby shortening the distance between the first carbon tubes and increasing van der waals force; meanwhile, in the composite carbon nanotube film, the second carbon nanotube plays a role of an intermediate connector, and the first carbon nanotube and the second carbon nanotube which are originally arranged side by side are connected.
Meanwhile, the second carbon nanotubes are fixedly connected with other second carbon nanotubes through a binder, the second carbon nanotubes are irregularly overlapped together to form a net shape, the strength of the carbon nanotube reinforcing layer in each direction is similar, the second carbon nanotubes are bonded with the first carbon nanotubes through the binder, the tensile strength of the composite carbon nanotube film in the non-orientation direction is also improved, when external force acts on the carbon nanotube base film in the non-orientation direction, the bonding force between the first carbon nanotubes and the second carbon nanotubes is also required to be overcome, and therefore the tensile strength of the composite carbon nanotube film in the non-orientation direction is remarkably improved.
In addition, in the technical scheme, the second carbon nanotube not only plays a role of an intermediate connector to enhance the tensile strength of the carbon nanotube film in the non-orientation direction, but also plays a role of an intermediate conductor at the same time, and ensures that the carbon nanotube enhancement layer does not significantly affect the electrical property of the carbon nanotube base film. Experiments prove that the carbon nanotube enhancement layer can improve the tensile strength in the direction perpendicular to the orientation direction of the carbon nanotube base film on the basis of ensuring that the composite carbon nanotube film has at least the electrical property similar to that of the carbon nanotube base film.
For a better understanding and appreciation of the invention, reference is also made to the following more detailed examples, which are easier to be construed to practice. The advantages of the invention will also be apparent from the description of specific examples and comparative examples below and from the performance results.
The starting materials used in the following examples and comparative examples were all conventionally available from the market unless otherwise specified.
Example 1
Drawing a carbon nanotube film with the width of about 10cm from the carbon nanotube array, repeating the step, overlapping 50 layers of carbon nanotube films, simultaneously adding ethanol for infiltration and rolling to enable the overlapped carbon nanotube films to be more compact, and then drying to prepare a carbon nanotube base film; wherein the pressure intensity of the compression roller is 0.4MPa, and the moving speed of the compression roller is 2 m/min; the drying temperature is 150 ℃.
Coating carbon nanotube slurry on two sides of the obtained carbon nanotube base film by a small roll-to-roll scraper type tape-casting coating rolling system; wherein, the carbon nanotube slurry comprises the following components in percentage by mass: 5% of carbon nano tube and 1% of PVP; 2.2% PVDF and balance NMP; the viscosity of the carbon nano tube slurry is 4520 cp; the coating thickness of the scraper is 200 mu m; the coating speed of a scraper is 0.2m/min, and the drying temperature is 150 ℃.
Example 2
Drawing a carbon nanotube film with the width of about 10cm from the carbon nanotube array, repeating the step, overlapping 50 layers of carbon nanotube films, simultaneously adding ethanol for infiltration and rolling to enable the overlapped carbon nanotube films to be more compact, and then drying to prepare a carbon nanotube base film; wherein the pressure intensity of the compression roller is 0.4MPa, and the moving speed of the compression roller is 2 m/min; the drying temperature is 150 ℃.
Coating carbon nanotube slurry on two sides of the obtained carbon nanotube base film by a small roll-to-roll scraper type tape-casting coating rolling system; wherein, the carbon nanotube slurry comprises the following components in percentage by mass: 10% of carbon nano tube, 3.2% of PVP; 2.5% PVDF and balance NMP; the viscosity of the carbon nano tube slurry is 7558 cp; the coating thickness of the scraper is 200 mu m; the coating speed of a scraper is 0.2m/min, and the drying temperature is 150 ℃.
Example 3
Drawing a carbon nanotube film with the width of about 10cm from the carbon nanotube array, repeating the step, overlapping 50 layers of carbon nanotube films, simultaneously adding ethanol for infiltration and rolling to enable the overlapped carbon nanotube films to be more compact, and then drying to prepare a carbon nanotube base film; wherein the pressure intensity of the compression roller is 0.4MPa, and the moving speed of the compression roller is 2 m/min; the drying temperature is 150 ℃.
Coating carbon nanotube slurry on two sides of the obtained carbon nanotube base film by a small roll-to-roll scraper type tape-casting coating rolling system; wherein, the carbon nanotube slurry comprises the following components in percentage by mass: 7.5% of carbon nano tube, 2% of PVP, 2.2% of PVDF and the balance of NMP, wherein the viscosity of the carbon nano tube slurry is 5953 cp; the coating thickness of the scraper is 200 mu m; the coating speed of a scraper is 0.2m/min, and the drying temperature is 150 ℃.
Example 4
Drawing a carbon nanotube film with the width of about 10cm from the carbon nanotube array, repeating the step, overlapping 50 layers of carbon nanotube films, simultaneously adding ethanol for infiltration and rolling to enable the overlapped carbon nanotube films to be more compact, and then drying to prepare a carbon nanotube base film; wherein the pressure intensity of the compression roller is 0.4MPa, and the moving speed of the compression roller is 2 m/min; the drying temperature is 150 ℃.
Coating carbon nanotube slurry on two sides of the obtained carbon nanotube base film by a small roll-to-roll scraper type tape-casting coating rolling system; wherein, the carbon nanotube slurry comprises the following components in percentage by mass: 1% of carbon nano tube and 0.5% of PVP; 0.5% PVDF and balance NMP; the viscosity of the carbon nano tube slurry is 2137 cp; the coating thickness of the scraper is 200 mu m; the coating speed of a scraper is 0.2m/min, and the drying temperature is 150 ℃.
Example 5
Drawing a carbon nanotube film with the width of about 10cm from the carbon nanotube array, repeating the step and overlapping 50 layers of carbon nanotube films, and adopting a rolling mode to make the laminated carbon nanotube film more compact to prepare a carbon nanotube base film; wherein the pressure intensity of the compression roller is 0.4MPa, and the moving speed of the compression roller is 2 m/min; the drying temperature is 150 ℃.
Coating carbon nanotube slurry on two sides of the obtained carbon nanotube base film by a small roll-to-roll scraper type tape-casting coating rolling system; wherein, the carbon nanotube slurry comprises the following components in percentage by mass: 5% of carbon nano tube and 1% of PVP; 2.2% PVDF and balance NMP; the viscosity of the carbon nano tube slurry is 4520 cp; the coating thickness of the scraper is 200 mu m; the coating speed of a scraper is 0.2m/min, and the drying temperature is 150 ℃.
Example 6
Drawing a carbon nanotube film with the width of about 10cm from the carbon nanotube array, repeating the step, overlapping 50 layers of carbon nanotube films, simultaneously adding ethanol for infiltration and rolling to enable the overlapped carbon nanotube films to be more compact, and then drying to prepare a carbon nanotube base film; wherein the pressure intensity of the compression roller is 0.4MPa, and the moving speed of the compression roller is 2 m/min; the drying temperature is 150 ℃.
Coating carbon nanotube slurry on two sides of the obtained carbon nanotube base film by a small roll-to-roll scraper type tape-casting coating rolling system; wherein, the carbon nanotube slurry comprises the following components in percentage by mass: 5% of carbon nanotubes, 2.2% of PVDF and the balance of NMP; the coating thickness of the scraper is 200 mu m; the coating speed of a scraper is 0.2m/min, and the drying temperature is 150 ℃.
Comparative example 1
Drawing a carbon nanotube film with the width of about 10cm from the carbon nanotube array, repeating the step, overlapping 50 layers of carbon nanotube films, simultaneously adding ethanol for infiltration and rolling to enable the overlapped carbon nanotube films to be more compact, and then drying to prepare a carbon nanotube base film; wherein the pressure intensity of the compression roller is 0.4MPa, and the moving speed of the compression roller is 2 m/min; the drying temperature is 150 ℃.
Comparative example 2
Drawing a carbon nanotube film with the width of about 10cm from the carbon nanotube array, repeating the step, overlapping 50 layers of carbon nanotube films, simultaneously adding ethanol for infiltration and rolling to enable the overlapped carbon nanotube films to be more compact, and then drying to prepare a carbon nanotube base film; wherein the pressure intensity of the compression roller is 0.4MPa, and the moving speed of the compression roller is 2 m/min; the drying temperature is 150 ℃.
Coating carbon nanotube slurry on two sides of the obtained carbon nanotube base film by a small roll-to-roll scraper type tape-casting coating rolling system; wherein, the binder slurry comprises the following components in percentage by mass: 5% of carbon nano tube, 1% of PVP and the balance of NMP; the coating thickness of the scraper is 200 mu m; the coating speed of a scraper is 0.2m/min, and the drying temperature is 150 ℃.
Comparative example 3
Drawing a carbon nanotube film with the width of about 10cm from the carbon nanotube array, repeating the step, overlapping 50 layers of carbon nanotube films, simultaneously adding ethanol for infiltration and rolling to enable the overlapped carbon nanotube films to be more compact, and then drying to prepare a carbon nanotube base film; wherein the pressure intensity of the compression roller is 0.4MPa, and the moving speed of the compression roller is 2 m/min; the drying temperature is 150 ℃.
Coating graphene slurry on the two sides of the obtained carbon nanotube base film through a small roll-to-roll scraper type tape-casting coating rolling system; wherein, the binder slurry comprises the following components in percentage by mass: 5% of conductive carbon black, 1% of PVP, 2.2% of PVDF and the balance of NMP; the coating thickness of the scraper is 200 mu m; the coating speed of a scraper is 0.2m/min, and the drying temperature is 150 ℃.
Test examples
The carbon nanotube films of the above examples and comparative examples were tested for resistance in the orientation direction; the carbon nanotube films prepared in the above examples and comparative examples were connected to a circuit, and the stable temperature of the entire composite carbon nanotube film was measured at 5V and 12V, with the current direction along the alignment direction. In addition, the tensile strength perpendicular to the carbon nanotube alignment direction on the carbon nanotube-based film was tested, and the results can be seen in table 1.
TABLE 1
As shown in table 1, the difference between example 1 and comparative example 1 is whether the carbon nanotube slurry is coated on the surface of the carbon nanotube-based film, and example 1 and comparative example 1 show a significant improvement in tensile strength in the vertical alignment direction without a significant increase in conductive properties. In comparative example 2, the coated carbon nanotube slurry does not contain a binder, and the electrical conductivity is not significantly improved, which indicates that the introduction of the binder can significantly improve the tensile strength of the carbon nanotube base film by improving the binding force between the second carbon nanotubes and the first carbon nanotubes. In comparative example 3, the introduction of the conductive carbon black not only failed to improve the tensile strength of the carbon nanotube-based film, but also even resulted in a decrease in the overall electrical performance of the composite carbon nanotube film, indicating that the simultaneous introduction of the carbon nanotubes and the binder can effectively improve the tensile strength in the vertical orientation direction without decreasing the electrical conductivity of the oriented carbon nanotubes.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only represent a preferred embodiment of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (13)
1. A preparation method of a composite carbon nanotube film is characterized by comprising the following steps:
obtaining a carbon nanotube base film, wherein the carbon nanotube base film comprises a layer of carbon nanotube film or a plurality of layers of carbon nanotube films which are stacked, and the carbon nanotube film is provided with first carbon nanotubes which are arranged in an oriented manner;
obtaining carbon nanotube slurry, wherein the carbon nanotube slurry comprises a solvent, and a second carbon nanotube and a binder which are uniformly dispersed in the solvent;
and coating the carbon nanotube slurry on the surface of the carbon nanotube base film, and removing the solvent in the carbon nanotube slurry to prepare the composite carbon nanotube film.
2. The method of claim 1, wherein the carbon nanotube paste has a viscosity of 4000cp to 8000 cp.
3. The method of manufacturing a composite carbon nanotube film according to claim 1, wherein the second carbon nanotube is 0.3 to 20% by mass and the binder is 0.1 to 5% by mass in the carbon nanotube slurry.
4. The method of manufacturing a composite carbon nanotube film according to claim 3, wherein the carbon nanotube slurry further comprises a dispersant in an amount of 0.1 to 5% by mass, the dispersant being for promoting dispersibility of the second carbon nanotubes in the solvent.
5. The method of claim 4, wherein the binder is selected from polyvinylidene fluoride, and/or the dispersant is selected from polyvinylpyrrolidone.
6. The method for preparing the composite carbon nanotube film according to any one of claims 1 to 5, wherein the carbon nanotube-based film comprises a plurality of layers of the carbon nanotube thin film, and the method for preparing the carbon nanotube-based film comprises the following steps: laminating a plurality of single-layer carbon nanotube films and rolling, thereby obtaining a densified multi-layer carbon nanotube-based film.
7. The method of claim 6, further comprising the step of wetting the carbon nanotube film with an alcohol liquid during the step of rolling the plurality of carbon nanotube films.
8. The method of claim 7, wherein the pressure of the pressing roller against the carbon nanotube film is 0.2 to 1MPa, and the moving speed of the pressing roller is 0.1 to 6m/min, during the rolling of the plurality of carbon nanotube films.
9. The method of any one of claims 1 to 5 and 7 to 8, wherein the carbon nanotube-based film comprises a plurality of carbon nanotube films, and an included angle between orientations of any two carbon nanotube films is not greater than 15 °.
10. The method for producing a composite carbon nanotube film according to any one of claims 1 to 5 and 7 to 8, wherein the thickness of the carbon nanotube-based film is 1 μm to 50 μm.
11. A composite carbon nanotube film, comprising:
the carbon nanotube base film comprises one or more layers of carbon nanotube films, and the carbon nanotube films are provided with first carbon nanotubes which are arranged in an oriented manner; and
the carbon nanotube enhancement layer comprises a second carbon nanotube and a binder, wherein the second carbon nanotube in the carbon nanotube enhancement layer is bonded on the surface of the carbon nanotube base film through the binder, or the second carbon nanotube in the carbon nanotube enhancement layer is bonded on the surface of the carbon nanotube base film through the binder and part of the second carbon nanotube is inserted into the surface layer of the carbon nanotube base film.
12. The composite carbon nanotube film according to claim 11, wherein the composite carbon nanotube film is produced by the production method according to any one of claims 1 to 10.
13. A layered heat-generating device comprising a heat-generating core layer that converts electric energy into heat energy, the heat-generating core layer comprising the composite carbon nanotube film according to claim 11 or 12.
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