CN110451484B - Preparation device and method of carbon nanotube film - Google Patents
Preparation device and method of carbon nanotube film Download PDFInfo
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- CN110451484B CN110451484B CN201910831831.6A CN201910831831A CN110451484B CN 110451484 B CN110451484 B CN 110451484B CN 201910831831 A CN201910831831 A CN 201910831831A CN 110451484 B CN110451484 B CN 110451484B
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
Abstract
The invention discloses a preparation device and a preparation method of a carbon nanotube film, the device comprises a container main body (1), a buffer clapboard (4), the buffer clapboard (4) is positioned at the lower part of the container main body (1), and a solvent guiding part (5) is communicated with the inside of the container main body (1) through a through hole on the side wall of the container main body (1) and extends to the outside of the container main body (1). By adopting the device and the method, the liquid level descending speed can be controlled by controlling the length of the semi-permeable pipeline, so that the self-assembly speed of the carbon nano tube on the surface of the substrate is controlled. Has the characteristics of stable liquid level drop, simple structure, low cost, suitability for large-area preparation and the like.
Description
Technical Field
The invention relates to the field of carbon nanotubes, in particular to a device and a method for preparing a carbon nanotube film.
Background
Carbon nanotubes are a novel carbon material discovered by Iijima of NEC corporation of japan in 1991 and can be classified into single-walled carbon nanotubes and multi-walled carbon nanotubes. The special structure of the carbon nanotube determines the special properties of the carbon nanotube, such as high tensile strength and high thermal stability; the carbon nanotubes may exhibit metallic or semiconducting properties, etc., according to the change in the helical form of the carbon nanotubes. Because the carbon nano tube has an ideal one-dimensional structure and excellent properties in the fields of mechanics, electricity, thermal engineering and the like, the carbon nano tube has a wide application prospect in the fields of interdisciplines such as material science, chemistry, physics and the like, and is more and more concerned in scientific research and industrial application, but the carbon nano tube prepared under the general condition is granular or powdery, which causes great inconvenience to the application of people.
At present, Caoqing et al in the prior art use an LS method to prepare a carbon nanotube membrane, which is extruded back and forth at a certain speed by a push-pull plate; then, the carbon tube array on the solution is transferred to the substrate in parallel by the Langmuir-Schaefer method. Hongsik Park et al use trenching to allow carbon tubes to enter the trenches. Arnold et al, university of wisconsin, usa, uses the principle of evaporation to prepare a strip-shaped carbon tube. However, the preparation method in the prior art still has various defects, the carbon nanotube film prepared by the method of Caoqing et al has large-area nonuniformity, and the carbon nanotube film is multi-layer and has bad influence on the electrical performance (transistor).
The method of Hongsik Park or Arnold et al is disadvantageous in that the carbon nanotube obtained by the method is not a continuous film but a strip shape, and is not suitable for industrial large-area processing; and the minimum size of the groove in the method of Arnold et al can only be made to 70nm, which has great limitation. Therefore, there is a need for an apparatus and method suitable for large-area production of carbon nanotube thin films.
Disclosure of Invention
The invention aims to provide a device and a method for preparing a carbon nanotube film, which have simple structure and low cost, are suitable for large-area preparation, and can effectively avoid the problem of uneven thickness of the carbon nanotube film.
According to an aspect of the present invention, there is provided an apparatus for manufacturing a carbon nanotube film, including a container body, including:
the buffer clapboard is positioned at the lower part of the container main body;
and a solvent leading-out part which is communicated with the inside of the container body through a through hole of the side wall of the container body and extends to the outside of the container body.
Preferably, the buffer clapboard is lapped, bonded, buckled or integrally formed with the inner wall of the container main body.
Preferably, the upper surface of the buffer partition plate is provided with a raised strip-shaped fixing piece and a plurality of through holes.
Preferably, the perforations are 1-3mm in diameter.
Preferably, the solvent lead-out part is located between the buffer partition plate and the bottom of the container main body.
Preferably, the solvent lead-out portion is perpendicular to or at an angle to a central axis of the container body.
The invention also provides a method for preparing the in-line carbon nanotube film by using the device, which comprises the following steps:
firstly, adding a carbon nanotube solution into a container main body of the device;
vertically placing a base inside a container body;
adding a sealing liquid which is incompatible with the carbon nanotube solution (5) along the substrate or the side wall of the container body to form a double liquid layer;
leading out the solvent by using the solvent leading-out part to ensure that the liquid level of the carbon nano tube solution gradually descends, thereby forming a layer of carbon nano tube film on the substrate; and finally, cleaning the formed film.
Preferably, the carbon nanotube solution is prepared by dissolving carbon nanotubes in one or more halogenated hydrocarbon solvents selected from one or more of chloroform, dichloroethane, trichloroethane, chlorobenzene, dichlorobenzene and bromobenzene.
Preferably, the sealing liquid is one or more of polyalcohol, amine solution or water. Preferably, the temperature of the carbon nanotube film preparation process is from the freezing point of the liquid to the boiling point of the carbon nanotube solution.
In addition, another aspect of the present invention provides a method for preparing a carbon nanotube film by using a specific solution formulation in combination with a pulling method, in step S1, injecting a carbon nanotube solution into a container, and adding a substance that interacts with carbon nanotubes; then dispersing for 5min by adopting a water area ultrasonic or probe ultrasonic mode; the substance forming interaction with the carbon nano tube is polyalcohol or mercaptan, and preferably 1-70% of 3-methyl-propylene glycol.
Drawings
The above and other objects, features and advantages of the present invention will become more apparent by describing embodiments thereof with reference to the accompanying drawings in which:
FIG. 1 is a schematic structural diagram of an apparatus for manufacturing a carbon nanotube film according to the present invention;
FIG. 2 shows a perspective view of the container body;
FIG. 3 shows a perspective view of a buffer spacer;
fig. 4 shows a flow chart of a carbon nanotube film preparation process.
Reference numerals
1-a container; 2-a substrate; 3-carbon nanotube solution; 4-a buffer baffle; 5-semi-permeable pipeline; 6-sealing liquid; 7-a through hole; 8-perforating; 9-convex strip.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings and examples.
Fig. 1 shows an apparatus for preparing a carbon nanotube film according to the present invention, and a detailed description will be given of an embodiment of the present invention with reference to the structure shown in fig. 1 and fig. 2 to 4.
As shown in fig. 1, the present invention provides a carbon nanotube film manufacturing apparatus, which includes a container body 1, wherein a carbon nanotube solution 3 is contained therein, the shape of which can be set according to the shape of a substrate 2, the requirement of a factory site, etc., and can be a rectangular parallelepiped, a cube, a cylinder, etc., and the rectangular parallelepiped shape is adopted in this embodiment.
In the present invention, the carbon nanotube film is formed mainly based on the change of the liquid level in the container 1, and in order to ensure the gradual fall of the liquid level and to form a more uniform carbon nanotube film, a buffer partition plate 4 is provided at the lower part of the container body 1, and the peripheral edge of the buffer partition plate 4 is connected to the inner wall of the container body 1 and is positioned above the solvent leading-out part 3. The buffer partition plate 4 and the inner wall of the container body 1 can be lapped, bonded, fastened or integrally formed. If the inner wall of the container body 1 is provided with a bulge along the periphery of the inner wall, the buffer partition plate 4 can be directly lapped on the bulge.
Fig. 3 shows the structure of the baffle 4 in detail, and the upper surface of the baffle 4 is provided with a plurality of through holes 8 and a raised strip-shaped fixing piece 9. The arrangement of the through holes 8 can prevent the liquid from directly approaching the solvent leading-out part 3, which causes the uneven leading-out speed of the solvent and the uneven thickness of the carbon nano tube film, and the through holes 8 can be randomly distributed on the main body of the buffer partition plate 4, preferably uniformly distributed in an array; the perforations are preferably 1-3mm in diameter, and with holes of this size, the rate of liquid passage is relatively flat and uniform.
A solvent lead-out part 5 is arranged between the buffer clapboard 4 and the bottom of the container body 1, and the solvent lead-out part 5 is communicated with the inside of the container body 1 through a through hole 7 of the side wall of the container body 1 and extends to the outside of the container body 1. The connection position of the solvent lead-out portion 5 to the container body 1 is preferably near the bottom wall of the container body 1 in consideration of the gravity action of the solvent and the pressure of the liquid in the container body 1. Of course, the number of the solvent leading-out parts 5 may be adjusted according to the quality requirement of the film layer and the film forming efficiency, and may be one, two or more, and in the present embodiment, one solvent leading-out part is taken as an example.
The length of the solvent derivation part 5 is controlled to control the liquid level descending speed, thereby controlling the self-assembly film forming speed of the carbon nano tube on the surface of the substrate 2. The length of the solvent derivation part is preferably greater than 1cm, more preferably 1 to 30 cm, and still more preferably 20 cm. The solvent lead-out section 5 can lead out only the solvent in the carbon nanotube solution 3, and the carbon nanotubes cannot be led out and remain in the container 1, and the carbon nanotubes can be recovered and reused later.
The solvent leading-out part 5 can be a pipeline with a semi-permeable function, a semi-permeable membrane, a pipeline provided with a throttle or a pipeline connected with a peristaltic pump, so that the solvent in the carbon nano tube solution 5 can be quantitatively led out, and the accurate liquid level descending speed can be realized. In another embodiment, the solvent outlet 3 is preferably a semi-permeable pipe, which is perpendicular to or at an angle with respect to the central axis of the container 1, and the angle with respect to the central axis may be an acute angle or an obtuse angle. For ease of installation and maximum passage of solvent through the semi-permeable conduit, it is preferably substantially vertical. The semi-permeable pipeline has the advantages of stable liquid level descending, simple structure, low cost, suitability for large-area preparation and the like.
In another embodiment of the present invention, a method for preparing a carbon nanotube film by using the above apparatus is provided, and the specific steps are shown in fig. 4. Firstly, adding a carbon nanotube solution 3 into a container body 1 of the device, then vertically placing a substrate 2 into the container body 1, and then adding a sealing liquid 6 which is incompatible with the carbon nanotube solution 3 along the substrate 2 or the side wall of the container body 1 to form a double liquid layer. The carbon nanotube solution 3 is formed by dissolving carbon nanotubes in one or more halogenated hydrocarbons, preferably chloroform, dichloroethane, trichloroethane, chlorobenzene, dichlorobenzene, or bromobenzene. The sealing liquid 6 is one or more of polyhydric alcohol, amine solution or water, and is not dissolved in the carbon nano tube solution 3. In addition, the temperature of the carbon nanotube film in the preparation process is from the freezing point of the liquid to the boiling point of the carbon nanotube solution, and the freezing point refers to the freezing point temperature with the higher freezing point in the sealing liquid 6 and the carbon nanotube solution 3.
The principle of forming the carbon nanotube film in the invention is that the acting force between the sealing liquid 6 and the carbon nanotube solution 3 is utilized, the acting force is intermolecular acting force (hydrogen bond/Van der Waals force/other non-covalent bond) and covalent bond or ionic bond acting force, two mutually insoluble liquids of the sealing liquid 6 and the carbon nanotube solution 3 form a double liquid layer, the carbon nanotubes in the solution are firstly adsorbed on an interface close to the double liquid layer, the carbon nanotube solvent seeps out along with the solvent leading-out part 5, the liquid level in the container main body 1 gradually drops, and the carbon nanotubes on the interface are arranged on the substrate 2 in sequence, so that the carbon nanotube film is formed. Finally, cleaning the formed film.
In another embodiment of the present invention, the carbon nanotube solution 3 is first prepared, the components are selected as in embodiment 1, and then a substance forming an interaction with the carbon nanotube-dispersant complex is added to the carbon nanotube solution, wherein the substance forming an interaction with the carbon nanotube is a polyol or thiol, preferably 1% -70% 3-methyl-propanediol. Then dispersing for 5min by adopting a water area ultrasonic or probe ultrasonic mode to form a carbon nano tube solution 16 with a dispersing agent. Then, the substrate 2 is vertically placed inside the container body 1, and then a sealing liquid 6 incompatible with the carbon nanotube solution 3 is added along the substrate 2 or the side wall of the container body 1 to form a double liquid layer. The carbon nanotube solvent gradually drops down the liquid surface in the container body 1 as the solvent lead-out portion 5 bleeds out, and the carbon nanotubes on the interface are lined up on the substrate 2, thereby forming a carbon nanotube film. Finally, cleaning the formed film.
According to the technical scheme of the invention, the descending speed of the carbon nanotube solution is controlled by controlling the length of the solvent leading-out part, so that the self-assembly speed of the carbon nanotubes on the surface of the substrate is controlled, and the preparation of the large-area in-line carbon nanotube film with stable liquid level descending, simple structure and low cost can be realized.
Although the invention has been described in detail hereinabove with respect to specific embodiments thereof, it will be apparent to those skilled in the art that modifications and improvements can be made thereto without departing from the scope of the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (13)
1. A carbon nanotube film production apparatus comprising a container body (1), characterized by comprising:
the buffer partition plate (4) is positioned at the lower part of the container main body (1), and a raised strip-shaped fixing piece (7) and a plurality of through holes (8) are formed in the upper surface of the buffer partition plate (4);
the solvent leading-out part (5) is located between the buffer partition plate (4) and the bottom of the container body (1), is communicated with the inside of the container body (1) through a through hole in the side wall of the container body (1) and extends to the outside of the container body (1), and the solvent leading-out part (5) is a pipeline with a semi-permeable effect and has the length range of 1cm to 30 cm.
2. The apparatus for preparing carbon nanotube film according to claim 1, wherein the buffer partition plate (4) is overlapped, bonded, fastened or integrally formed with the inner wall of the container body (1).
3. The apparatus for manufacturing a carbon nanotube film according to claim 1, wherein the diameter of the through-hole (8) is 1-3 mm.
4. The apparatus for producing a carbon nanotube film according to claim 1, wherein the solvent leading-out part (5) is one or more.
5. The apparatus for producing a carbon nanotube film according to claim 1, wherein the solvent lead-out part (5) has a length of 20 cm.
6. The apparatus for manufacturing a carbon nanotube film according to claim 1, wherein the solvent leading-out part (5) comprises a semi-permeable membrane, a pipe provided with a gate, or a pipe connected to a peristaltic pump.
7. The apparatus for producing a carbon nanotube film according to claim 1, wherein the solvent lead-out part (5) is at an angle to a central axis of the container body (1).
8. A method for preparing an aligned carbon nanotube film using the apparatus of any one of claims 1 to 7,
dissolving carbon nanotubes in one or more halogenated hydrocarbon solvents to form a carbon nanotube solution (3), adding the carbon nanotube solution (3) into a container main body (1) of the device, adding a dispersing agent to form the carbon nanotube solution with the dispersing agent, then adding polyhydric alcohol or mercaptan which forms interaction with a carbon nanotube-dispersing agent compound as an additive, and then dispersing the solution by adopting a water-area ultrasonic or probe ultrasonic mode;
vertically placing a substrate (2) into the container body (1);
adding a sealing liquid (6) which is insoluble with the carbon nanotube solution (3) along the side wall of the substrate (2) or the container main body (1) to form a double-liquid layer;
leading out the solvent by using a solvent leading-out part (5) to ensure that the liquid level of the carbon nano tube solution (3) gradually descends, thereby forming a layer of in-line carbon nano tube film on the substrate (2);
and finally, cleaning the formed film.
9. The method for preparing the aligned carbon nanotube film according to claim 8, wherein the halogenated hydrocarbon solvent is selected from one or more of chloroform, dichloroethane, trichloroethane, chlorobenzene, dichlorobenzene and bromobenzene.
10. The method for preparing the aligned carbon nanotube film according to claim 8, wherein the sealing liquid (6) is one or more of a polyol, an amine solution or water.
11. The method of claim 8, wherein the temperature of the carbon nanotube film is from the freezing point of the liquid to the boiling point of the carbon nanotube solution.
12. The method for preparing the in-line carbon nanotube film according to any one of claims 8 to 11, wherein the carbon nanotube solution with the dispersant is dispersed for 5min by water ultrasound or probe ultrasound.
13. The method of preparing an aligned carbon nanotube film of claim 8, wherein said polyol is 1% to 70% 3-methyl-propylene glycol.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910831831.6A CN110451484B (en) | 2019-09-04 | 2019-09-04 | Preparation device and method of carbon nanotube film |
| US17/640,219 US20220332584A1 (en) | 2019-09-04 | 2020-09-04 | Method for manufacturing high-density in-line carbon nanotube thin film |
| US17/640,224 US20220314265A1 (en) | 2019-09-04 | 2020-09-04 | Apparatus and method for manufacturing high-density in-line carbon nanotube thin film |
| PCT/CN2020/113380 WO2021043235A1 (en) | 2019-09-04 | 2020-09-04 | Method for manufacturing high-density in-line carbon nanotube thin film |
| PCT/CN2020/113382 WO2021043236A1 (en) | 2019-09-04 | 2020-09-04 | Apparatus and method for manufacturing high-density in-line carbon nanotube thin film |
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| CN201910831831.6A CN110451484B (en) | 2019-09-04 | 2019-09-04 | Preparation device and method of carbon nanotube film |
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| CN110451484A CN110451484A (en) | 2019-11-15 |
| CN110451484B true CN110451484B (en) | 2021-05-25 |
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| CN1214985C (en) * | 2003-01-20 | 2005-08-17 | 清华大学 | Method for preparing zirconium oxide nano ball stack blank by carbon nano-tube auxiliary double liquid phase precipitation |
| CN101143358A (en) * | 2007-10-26 | 2008-03-19 | 上海大学 | Method for preparing article surface membrane by liquid level descent method |
| KR100948086B1 (en) * | 2007-12-27 | 2010-03-16 | 세메스 주식회사 | Fluidizing bed apparatus and method for prosucting carbon nano tube |
| CN101623682B (en) * | 2008-07-09 | 2011-05-25 | 北京石油化工学院 | Device for preparing membrane by liquid level sedimentation method |
| CN101884969B (en) * | 2010-06-25 | 2012-07-04 | 北京航空航天大学 | Device for preparing thin film by liquid level drawdown method |
| CN103771387B (en) * | 2012-10-19 | 2016-08-03 | 清华大学 | The preparation method of carbon nano-tube film |
| CN104497337A (en) * | 2014-11-26 | 2015-04-08 | 王秋芹 | Preparation method of carbon nanotube-based biodegradable composite membrane used in garden |
| CN105457844B (en) * | 2015-12-24 | 2019-01-11 | 中国科学院宁波材料技术与工程研究所 | A kind of device of liquid level sedimentation plated film |
| CN109081329B (en) * | 2018-09-29 | 2020-03-27 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method and system for separating carbon nano tube from polymer |
| CN110171815A (en) * | 2019-06-19 | 2019-08-27 | 昆明物理研究所 | A kind of preparation method of the high-purity carbon nano-tube film of low cost |
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