Carbon nanotube high-orientation ultra-thin broadening cluster body and preparation method and application thereof

Abstract

The invention discloses a carbon nanotube high-orientation ultrathin broadening cluster body and a preparation method and application thereof. The preparation method comprises the following steps: providing a plurality of original carbon nanotube fibers; carrying out mechanical pre-widening; enabling the pre-broadening cluster body to be in contact with a liquid-phase expansion medium to perform expansion broadening treatment; carrying out deexpansion treatment to remove part of the liquid-phase expansion medium; and carrying out cleaning treatment and heat treatment on the deexpanded cluster body to obtain the carbon nanotube high-orientation ultra-thin broadening cluster body. According to the method, mechanical broadening and expansion broadening are combined, the problems of dispersion, cracking and retraction in the expansion broadening process are avoided through the filling, lubricating, bonding and tension adjusting effects of a high-molecular polymer, a secondary removal mode is adopted when a liquid-phase expansion medium is removed, obvious retraction of a broadened cluster body is avoided, and the yield of the cluster body is improved. And finally, through thorough cleaning and heat treatment shaping, the carbon nanotube high-orientation ultra-thin broadening cluster body which is ultra-thin, high in orientation and uniform is obtained.

Description

Technical Field

[0001] The present invention relates to the technical field of carbon nanomaterials, and particularly to a highly oriented ultra-thin widened carbon nanotube bundle, a preparation method thereof, and an application thereof. Background Art

[0002] Carbon nanotubes, also known as buckytubes, are one-dimensional quantum materials with a special structure. Their radial size is on the nanometer scale, their axial size is on the micrometer scale, and both ends of the tubes are basically sealed. Carbon nanotubes are mainly composed of several to dozens of coaxial circular tubes formed by carbon atoms arranged in a hexagonal pattern.

[0003] Due to the excellent mechanical strength, high conductivity, and high thermal conductivity of carbon nanotubes, a large amount of research and development work on carbon nanotube materials has been carried out in the field. In particular, the fabrication of components by compounding carbon nanotubes with polymers such as resins has become a new breakthrough point in the fields of aerospace, electronics, and automobiles.

[0004] Some existing technologies have attempted to compound single carbon nanotubes or carbon nanotube films with resins. However, due to the too-small gaps between carbon nanotubes, it is difficult to achieve sufficient compounding, and the high-strength characteristics of carbon nanotubes cannot be fully utilized. Subsequently, some technical solutions have proposed a technical idea of fusing multiple carbon nanotubes to obtain a fused bundle for application. After fusion, multiple carbon nanotubes are intertwined and combined with each other to form an overall resultant force, making progress in mechanical properties and processability.

[0005] However, the above technical solutions can only obtain fibrous materials with a certain diameter or ribbon-like materials with a certain thickness. The relatively large cross-sectional macroscopic size limits the contact area of the carbon nanotube bundle in the composite material, resulting in physical properties that are not yet satisfactory. In the field of materials science, people often hope that the base materials used for compounding are as thin as possible. For example, for "hand-tearable steel", when the thickness is thin enough, the physical properties of the components made from it will change significantly compared to thicker homogeneous components.

[0006] Therefore, how to obtain a highly oriented carbon nanotube bundle with ultra-thin characteristics is a very worthy research topic. Summary of the Invention

[0007] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a highly oriented ultra-thin widened carbon nanotube bundle, a preparation method thereof, and an application thereof.

[0008] To achieve the foregoing invention purpose, the technical solutions adopted by the present invention include: In a first aspect, the present invention provides a preparation method for a highly oriented ultra-thin widened carbon nanotube bundle, which includes: Provided are multi-stranded original carbon nanotube fibers, and the original carbon nanotube fibers contain multiple carbon nanotube bundles; Mechanically pre-broadening the original carbon nanotube fibers to form a pre-broadened bundled body; Contacting the pre-broadened bundled body with a liquid-phase swelling medium for swelling and broadening treatment to form a swollen and broadened bundled body; a polymer is dissolved in the liquid-phase swelling medium, and during the swelling and broadening treatment, multiple carbon nanotube bundles repel and swell, the polymer enters between the multiple carbon nanotube bundles and adheres to the surfaces of the carbon nanotube bundles, and at the same time, the swollen fiber bundle composed of the multiple carbon nanotube bundles is subjected to a pressure in a first radial direction and spreads and broadens in a second radial direction, the first radial direction and the second radial direction intersect, and the swollen fiber bundle is subjected to a tensile force in the axial direction and elongates; Contacting the swollen and broadened bundled body with a de-swelling liquid for de-swelling treatment to remove part of the liquid-phase swelling medium to obtain a de-swollen bundled body; Performing a cleaning treatment and a heat treatment on the de-swollen bundled body to obtain a highly oriented and ultrathin broadened bundled body of carbon nanotubes.

[0009] In a second aspect, the present invention further provides a preparation device for a highly oriented and ultrathin broadened bundled body of carbon nanotubes for implementing the above preparation method, which includes, sequentially arranged along the process direction: A wire feeding device for providing multi-stranded original carbon nanotube fibers, and the original carbon nanotube fibers contain multiple carbon nanotube bundles; A pre-broadening device for mechanically pre-broadening the original carbon nanotube fibers to form a pre-broadened bundled body; A swelling and broadening device for contacting the pre-broadened bundled body with a liquid-phase swelling medium for swelling and broadening treatment to form a swollen and broadened bundled body; a polymer is dissolved in the liquid-phase swelling medium, and during the swelling and broadening treatment, multiple carbon nanotube bundles repel and swell, the polymer enters between the multiple carbon nanotube bundles and adheres to the surfaces of the carbon nanotube bundles, and at the same time, the swollen fiber bundle composed of the multiple carbon nanotube bundles is subjected to a pressure in a first radial direction and spreads and broadens in a second radial direction, the first radial direction and the second radial direction intersect, and the swollen fiber bundle is subjected to a tensile force in the axial direction and elongates; A de-swelling device for contacting the swollen and broadened bundled body with a de-swelling liquid for de-swelling treatment to remove part of the liquid-phase swelling medium to obtain a de-swollen bundled body; A cleaning device for performing a cleaning treatment on the de-swollen bundled body; A heat treatment device for performing a heat treatment on the de-swollen bundled body after the cleaning treatment to obtain a highly oriented and ultrathin broadened bundled body of carbon nanotubes; And a collecting device for collecting the highly oriented ultra-thin broadened carbon nanotube bundle.

[0010] In a third aspect, the present invention also provides a highly oriented ultra-thin broadened carbon nanotube bundle prepared by the above preparation method. The highly oriented ultra-thin broadened carbon nanotube bundle is a bundle formed by combining multiple carbon nanotube filaments, with a flat axial cross-section. There is a polymer filled between the carbon nanotube filaments, and the thickness of the highly oriented ultra-thin broadened carbon nanotube bundle is 500 nm - 10 μm.

[0011] In a fourth aspect, the present invention also provides a further application of the above technical solution, that is, a carbon nanotube composite member, which is formed by at least stacking and combining the above highly oriented ultra-thin broadened carbon nanotube bundles along the thickness direction.

[0012] Based on the above technical solution, compared with the prior art, the beneficial effects of the present invention at least include: The preparation method provided by the present invention realizes the preparation of the highly oriented ultra-thin broadened carbon nanotube bundle by combining preliminary mechanical pre-broadening and secondary expansion broadening under protonation expansion. During the expansion broadening treatment process, the filling, lubricating, bonding, and tension adjustment effects of the polymer are used to avoid problems such as dispersion, cracking, and retraction during the expansion broadening process. In addition, when removing the liquid-phase expansion medium, a secondary removal method is adopted to avoid removing a large amount of the liquid-phase expansion medium at one time, and to avoid obvious retraction of the broadened bundle. Finally, through thorough cleaning and heat treatment for shaping, a highly oriented ultra-thin and uniform carbon nanotube highly oriented ultra-thin broadened bundle is obtained, which shows excellent performance in the application of preparing composite materials.

[0013] The above description is only an overview of the technical solution of the present invention. In order to enable those skilled in the art to understand the technical means of the present application more clearly and to implement it in accordance with the content of the specification, the following is a detailed description of the preferred embodiments of the present invention in conjunction with the detailed drawings. Description of the Drawings

[0014] Figure 1 is a front view structural schematic diagram of a preparation device for a highly oriented ultra-thin broadened carbon nanotube bundle provided by a typical embodiment of the present invention; Figure 2 is a top view structural schematic diagram of a preparation device for a highly oriented ultra-thin broadened carbon nanotube bundle provided by a typical embodiment of the present invention; Figure 3 is a macroscopic morphology photograph of a highly oriented ultra-thin broadened carbon nanotube bundle provided by a typical embodiment of the present invention; Figure 4It is the electron microscope photograph of the highly oriented ultra-thin broadened carbon nanotube bundle provided by another typical embodiment of the present invention; Figure 5 It is the low-magnification cross-section and surface morphology electron microscope photograph of the highly oriented ultra-thin broadened carbon nanotube bundle provided by another typical embodiment of the present invention; Figure 6 It is the high-magnification surface morphology electron microscope photograph of the highly oriented ultra-thin broadened carbon nanotube bundle provided by another typical embodiment of the present invention; Figure 7 It is the mechanical property test diagram of the highly oriented ultra-thin broadened carbon nanotube bundle provided by another typical embodiment of the present invention.

[0015] Explanation of reference numerals: 1. Pay-off device; 2. Pre-broadening device; 3. Active traction assembly; 4. Lower yarn spreading rod; 5. Upper yarn spreading rod; 6. Swelling broadening device; 7. De-swelling device; 8. Cleaning device; 9. Environment sealing assembly; 10. Heat treatment device; 11. Take-up device. Detailed implementation manners

[0016] In the current prior art, there is no relevant research on the ultra-thin broadening of carbon nanotube fibers. As carbon materials, the methods for spreading carbon fibers include: hot roller method, mechanical spreading, ultrasonic spreading, air jet spreading, etc., but they are not suitable for the broadening preparation of carbon nanotubes. The problems faced currently include: (1) The mechanical properties of the carbon nanotube raw filaments directly prepared by the floating catalyst method are weak, and the existing carbon fiber spreading technologies cannot be directly used for continuous spreading, and the spreading efficiency is low; (2) The structural controllability is poor, and the fiber cannot be ultra-thin broadened; (3) The tension is too large during the broadening process, which damages the carbon tube structure inside the fiber, and the mechanical properties of the fiber are lost after broadening; (4) After broadening by the existing broadening equipment, the fibers cannot be fused and are still in a loose filament state, and the cross-scale performance transfer from macro to micro cannot be achieved, resulting in poor overall performance; (5) Although the chlorosulfonic acid protonation swelling technology is used in the existing technology to achieve the fusion of multi-strand carbon nanotube fibers and the preparation of fiber bundles, the fiber cross-section is multi-dimensional circular or elliptical or ribbon-shaped, and it is difficult to achieve ultra-thin. Once ultra-thin broadening is achieved, the problem of the interaction between tube interfaces during the ultra-thinning process needs to be solved. Otherwise, due to the action of interfacial tension during the preparation process, problems such as loose filaments, cracks, wrinkles, retraction or stacking are likely to occur, resulting in the failure of ultra-thin broadening.

[0017] In view of the deficiencies in the prior art, the inventors of this case have proposed the technical solution of the present invention through long-term research and a large number of practices. The following will further explain the technical solution, its implementation process and principle, etc.

[0018] In the following description, numerous specific details are set forth to provide a thorough understanding of the present invention. However, the present invention may be practiced in other ways than those specifically described herein, and thus, the scope of protection of the present invention is not limited by the specific embodiments disclosed below.

[0019] Moreover, relational terms such as "first" and "second" are only used to distinguish one component or method step with the same name from another, and do not necessarily require or imply any actual relationship or order between these components or method steps.

[0020] An embodiment of the present invention provides a method for preparing a highly oriented ultra-thin broadened carbon nanotube bundle, which includes the following steps: Provide multiple multi-stranded original carbon nanotube fibers, and the original carbon nanotube fibers contain multiple carbon nanotube bundles; Mechanically pre-broaden the original carbon nanotube fibers to form a pre-broadened bundle; Contact the pre-broadened bundle with a liquid-phase swelling medium for swelling and broadening treatment to form a swollen and broadened bundle; a polymer is dissolved in the liquid-phase swelling medium. During the swelling and broadening treatment, multiple carbon nanotube bundles repel and swell, the polymer enters between the multiple carbon nanotube bundles and adheres to the surface of the carbon nanotube bundles, and at the same time, the swollen fiber bundle composed of the multiple carbon nanotube bundles is subjected to a pressure in a first radial direction and spreads and broadens in a second radial direction, the first radial direction and the second radial direction intersect, and the swollen fiber bundle is subjected to a tensile force in the axial direction and elongates; Contact the swollen and broadened bundle with a deswelling liquid for deswelling treatment to remove part of the liquid-phase swelling medium and obtain a deswollen bundle; Wash and heat-treat the deswollen bundle to obtain a highly oriented ultra-thin broadened carbon nanotube bundle (hereinafter may be abbreviated as "bundle" or "ultra-thin bundle").

[0021] To achieve the above-mentioned objectives, the key technical points of the present invention are reflected in multiple aspects. One is the combination of two broadening methods. Through mechanical pre-broadening, first, multiple strands of original carbon nanotube fibers are relatively spread in the plane direction to avoid concentrated stacking, providing a prerequisite for obtaining a thin and uniform material through subsequent expansion broadening. The second lies in adding a certain amount of polymer to the liquid-phase expansion medium. The characteristics and appropriate concentration of this polymer can effectively regulate the interaction force and surface tension between carbon nanotube tows, as well as the viscosity of the liquid-phase expansion medium. It can also prevent the liquid-phase expansion medium from being removed too quickly from the expanded body during the deflation process. Under the combined action of multiple aspects, it can assist the spreading and shaping of carbon nanotube tows in the plane direction, and at the same time play a connecting role to prevent dispersion or dissociation after spreading, which is crucial for forming a thin and uniform cross-sectional state. In addition, in the present invention, the liquid-phase expansion medium is not removed in a one-time direct removal manner. Instead, a deflation liquid with mild dissolution characteristics is first used to remove a part of the liquid-phase expansion medium, and then the cleaning liquid is used to completely remove the liquid-phase expansion medium, avoiding problems such as retraction, wrinkling, and stacking caused by one-time removal of the liquid-phase expansion medium. Finally, with the systematic cooperation of various technical means, a uniform, ultra-thin, and highly oriented carbon nanotube highly oriented ultra-thin broadened bundle is successfully prepared.

[0022] In terms of mechanism, in the preparation method of the present invention, during the protonation expansion process, under the combined action of a series of forces such as the expansion force of superacid, the spreading force of yarn, the drawing force, and the polymer viscosity force; during the coagulation bath shrinkage process, the spreading force of yarn, the shrinkage force at the solvent evaporation interface, the shrinkage forces in the in-plane and thickness directions, the drawing force, and the polymer anchoring force, etc., ultra-thin broadening is achieved.

[0023] The research team where the inventor of the present invention is located has proposed some technical solutions regarding protonation treatment. For example, in the Chinese invention patent "Carbon Nanotube Bundle, Its Preparation Method and Application" with the publication number CN116905215A, a technical idea of using protonating reagents such as chlorosulfonic acid as the expansion medium to achieve the expansion and fusion of multiple strands of fibers is proposed. However, in this technical idea, no attempt is made to obtain an ultra-thin broadened material. Although the obtained material is shaped by a roller, it is still a ribbon-shaped material with a considerable thickness and does not reach the ultra-thin state required by the present invention. In terms of technical means, it does not specifically set technical means such as two-stage broadening, polymer-assisted broadening, and secondary removal of the expansion medium for the purpose of ultra-thin broadening. Therefore, the ultra-thin material provided by the present invention cannot be obtained.

[0024] Regarding the specific technical details in the more critical processes, in some embodiments, the liquid-phase expansion medium includes any one or a combination of two or more of chlorosulfonic acid, methanesulfonic acid, and fuming sulfuric acid.

[0025] In some embodiments, the polymer comprises any one or a combination of two or more of polyvinyl alcohol, polyacrylic acid, polystyrene, polyphenylene ether, phenolic resin, polyamide, and polyether ether ketone.

[0026] In some embodiments, the mass fraction of the polymer in the liquid-phase swelling medium is 0.01 - 1%, and typically 0.1 - 1% can be selected. In addition, generally, the polymer is commercially available, and the molecular weight range is generally in the range of 20,000 - 150,000, but it is not limited thereto. Since the concentration of the polymer is low, the influence of the molecular weight of the polymer on the liquid-phase viscosity is not very significant, and the selectable molecular weight range can be appropriately expanded, and similar effects can also be achieved.

[0027] In order to improve the effect of the polymer, the present invention also proposes a more preferred method, that is, by constructing active groups on the surface of the carbon nanotubes to improve the binding property of the polymer on the surface of the carbon nanotubes, thereby enhancing the effect of the polymer. Thus, in some embodiments, the preparation method may further include the following steps: Before performing the swelling and broadening treatment, the original carbon nanotube fiber is pre-oxidized to form oxygen-containing functional groups on the surface of the carbon nanotube tow.

[0028] Specifically, in some embodiments, the pre-oxidation treatment is carried out by an impregnation oxidation method, and the oxidant includes any one of concentrated sulfuric acid, concentrated nitric acid, and hydrogen peroxide, or a combination of any two with compatibility.

[0029] Regarding other process steps, in some embodiments, the mechanical pre-broadening is carried out by a method of rolling and broadening with a yarn spreading roller, and multiple original carbon nanotube fibers in the pre-broadening assembly are arranged side by side in a row.

[0030] In some embodiments, the swelling and broadening treatment is carried out by multiple yarn spreading rods immersed in the liquid-phase swelling medium. The swelling fiber bundle is wrapped around the yarn spreading rod and subjected to pressure, the wrapping curvature diameter is 1 - 100 mm, the wrapping angle of the swelling fiber bundle is 30 - 130°, and the draw ratio is 1:(1.1 - 1.2).

[0031] In some embodiments, the de-swelling treatment is carried out by an impregnation method with a de-swelling liquid, and the de-swelling liquid includes any one of chloroform, carbon tetrachloride, and nitrobenzene, or a combination of two or more.

[0032] In some embodiments, the cleaning treatment is carried out by an impregnation method with a cleaning liquid, and the cleaning liquid includes any one of acetone, ethanol, N-methylpyrrolidone, and water, or a combination of two or more.

[0033] In some embodiments, the temperature of the heat treatment is 100 - 550 °C.

[0034] In some embodiments, when performing the deflation treatment, the cleaning treatment, and the heat treatment, a drafting roller is used to pull while shaping the spreading state of the shaped bundle.

[0035] Moreover, in order to avoid adverse effects of moisture and oxygen in the air on the broadening process, in some embodiments, the swelling broadening treatment, the deflation treatment, and the cleaning treatment are all carried out in a protective atmosphere.

[0036] The second aspect of the embodiments of the present invention also provides a preparation device for a highly oriented ultra-thin broadened bundle of carbon nanotubes, which is used to implement the preparation method provided in any of the above embodiments. It includes, sequentially arranged along the process direction (usually a straight aligned direction, but not limited thereto): A wire feeding device for providing multiple stranded original carbon nanotube fibers, and the original carbon nanotube fibers contain multiple carbon nanotube filaments; A pre-broadening device for mechanically pre-broadening the original carbon nanotube fibers to form a pre-broadened bundle; A swelling broadening device for bringing the pre-broadened bundle into contact with a liquid-phase swelling medium (also referred to as a swelling liquid, or a protonating agent, etc. in some embodiments) for swelling broadening treatment to form a swollen broadened bundle; a polymer is dissolved in the liquid-phase swelling medium. When performing the swelling broadening treatment, multiple carbon nanotube filaments repel and expand from each other, the polymer enters between the multiple carbon nanotube filaments and adheres to the surface of the carbon nanotube filaments, and at the same time, the swollen fiber bundle composed of the multiple carbon nanotube filaments is subjected to a pressure in the first radial direction and spreads and broadens in the second radial direction, the first radial direction and the second radial direction intersect, and the swollen fiber bundle is subjected to a tensile force in the axial direction and elongates; A deflation device for bringing the swollen broadened bundle into contact with a deflation liquid for deflation treatment to remove part of the liquid-phase swelling medium and obtain a deflated bundle; A cleaning device for performing a cleaning treatment on the deflated bundle; A heat treatment device for performing heat treatment on the deflated bundle that has undergone the cleaning treatment to obtain a highly oriented ultra-thin broadened bundle of carbon nanotubes; Moreover, a collecting device for collecting the highly oriented ultra-thin broadened bundle of carbon nanotubes.

[0037] The third aspect of the embodiments of the present invention further provides a highly oriented ultra-thin widened carbon nanotube bundle prepared by the above preparation method. The highly oriented ultra-thin widened carbon nanotube bundle is a bundle with a flat axial cross-section formed by combining multiple carbon nanotube filaments. A polymer is filled between the carbon nanotube filaments. The thickness of the highly oriented ultra-thin widened carbon nanotube bundle is 500 nm - 10 μm.

[0038] As some typical application examples of the above technical solutions, specific embodiments of the present invention disclose a highly oriented ultra-thin widened carbon nanotube fiber, its preparation method and equipment. The preparation method includes: after the carbon nanotube fiber bundle is pre-oxidized, it is preliminarily widened by a pre-widening device, and then uniformly compounded, thinly widened, filament bundle fusion, and stretching orientation are carried out in an expanding solution with a spreading rod. While thinning, the mechanical properties are improved. Then, under continuous support force, it sequentially passes through a de-expanding solution, a cleaning solution, and high-temperature heat treatment annealing to gradually remove the residual protonated solution in the fiber in stages to achieve densification and shaping, and finally is transformed into a highly oriented ultra-thin widened carbon nanotube ribbon.

[0039] Among them, the pre-oxidation treatment is to immerse the carbon nanotube fiber bundle in an oxidant to graft functional groups on the surface of the carbon nanotubes to increase the binding force between the carbon nanotubes and the resin, thereby improving the mechanical properties of the fiber; the expanding solution is a protonated solvent in which a small amount of polymer is dissolved. The loose structure of the carbon nanotubes after expansion in the protonated solvent is used to achieve uniform compounding of the carbon nanotubes and the resin. The polymer can fill the space between the tubes. On the one hand, it reduces the pores between the fiber tubes, improves the ability of axial slip, increases the fiber orientation densification, and on the other hand, it can effectively improve the radial compound strength (adhesion force) of the interface between the carbon nanotubes, greatly reducing the situation of filament dispersion (there will be cracks) between the fiber bundles during the fiber widening and structure densification shrinkage processes, thereby improving the integration and mechanical properties of the fiber, and can also play a shaping role in subsequent processes to prevent problems such as retraction, wrinkling or stacking. The staged de-expanding reagent avoids the occurrence of the same problems such as retraction, wrinkling or stacking caused by excessive removal of the expanding medium at one time; the high-temperature annealing is to crosslink or cure the polymer on the surface of the carbon nanotubes while removing the temporarily retained protonated solvent, thereby improving the mechanical properties.

[0040] At the same time, the present invention also provides corresponding preparation equipment, such as Figure 1 and 2As shown in the figure, it includes: a wire pay-off device 1, a pre-spreading device 2, a main driving traction assembly 3, a lower yarn spreading rod 4, an upper yarn spreading rod 5, an expansion spreading device 6, a de-expansion device 7, a cleaning device 8, an environmental sealing assembly 9, a heat treatment device 10, a wire winding device 11, etc. Among them, by controlling the shape and size of the lower yarn spreading rod 4 and the upper yarn spreading rod 5, the wrap angle and the surrounding diameter of the carbon nanotube fiber tow are adjusted, so as to form tensions in different directions, and the spreading of multiple carbon nanotube fibers in the tow is realized in the pre-spreading yarn link in sequence, and the spreading of multiple carbon nanotubes in the fiber is realized in the carbon nanotube protonation expansion link, and finally the nano-scale ultra-thin limit spreading and stretching orientation of the fiber are realized to enhance the mechanical properties; through the upper and lower traction rollers (belonging to the main driving traction assembly 3) closely connected in the de-expansion device 7, the cleaning device 8, and the heat treatment device 10, the fiber is prevented from curling and coiling in the direction perpendicular to the fiber surface due to the supporting force during the solvent exchange and solvent volatilization densification process, and remains in a thin surface state macroscopically. At the same time, the traction shaft reduces the friction between the fiber and the roller during the process of removing the protonating reagent; through the dry inert gas atmosphere provided by the environmental sealing assembly 9, the moisture in the environment during the ultra-thin spreading process is reduced, thereby reducing the surface defects of the fiber.

[0041] In a more specific example, the structural composition of the device is as follows: Wire Pay-Out Device 1: The component pay-out end can be one or more, controlling the pay-out rate of all single filaments to be V1, and the pay-out rate range is 0.01 - 100 m / h; Pre-spreading Device 2: Conducts primary spreading on the tow, increasing the spreading efficiency of the tow. The shape of the pre-spreading yarn shaft can be cylindrical and polygonal column, the spreading surface can be flat and convex, and the rotating shaft can feed the wire actively, passively or not feed the wire; Active Traction Component 3: Conducts active traction on the tow, ensuring as much as possible that the tow is evenly stressed at all positions during the whole processing process and reducing the friction between the tow and the traction roller; Lower Spreading Yarn Rod 4: Introduces the tow into the solution tank. The shape of the lower spreading yarn rod 4 can be cylindrical and polygonal column, the spreading surface can be flat and convex, the rotating shaft can feed the wire actively, passively or not feed the wire, and the equivalent circle diameter of the lower traction ranges from 1 - 100 mm, and the general selection range is 10 - 50 mm; Upper Spreading Yarn Rod 5: Enables the tow to receive a force perpendicular to the axial direction of the traction shaft in the solution, and further spreads the tow. The vertical distance and spacing between the upper spreading yarn rod 4 and the lower spreading yarn rod 5 are controllable, and the wrap angle adjustment range can be 0° - 180° (greater than 0°), and the general wrap angle range during application is 30° - 130°; Swelling Spreading Device 6: Enables the tow fibers to swell and uniformly compound in the solution, providing a basis for further spreading and drawing. The material of the swelling tank can be one or several of quartz, polytetrafluoroethylene, etc., or other materials coated with quartz or polytetrafluoroethylene. The solute of the modified swelling solution can be one or several of resins such as polyvinyl alcohol, polyacrylic acid, polystyrene, polyphenylene ether, phenolic resin, polyamide, polyetheretherketone, etc. that can be dissolved in chlorosulfonic acid, and the solvent can be one or several of chlorosulfonic acid, methanesulfonic acid, fuming sulfuric acid, etc.; Deswelling Device 7: Eliminates the swelling effect of the tow in the swelling tank. The material of the deswelling tank can be one or several of quartz, polytetrafluoroethylene, etc., or other materials coated with quartz or polytetrafluoroethylene. The deswelling solution can be one or several of solvents such as chloroform, carbon tetrachloride, nitrobenzene, etc. that are miscible with chlorosulfonic acid but do not react, but cannot be a liquid medium with high affinity and high reactivity with the swelling medium such as chlorosulfonic acid in the subsequent cleaning tank to prevent the problem of curling caused by removing too large a proportion of the swelling medium at one time; Cleaning Device 8: Further removes the residual swelling solution and deswelling solution in the tow. The material of the deswelling tank can be one or several of quartz, polytetrafluoroethylene, etc., or other materials coated with quartz or polytetrafluoroethylene. The deswelling solution can be one or several of acetone, ethanol, N-methylpyrrolidone, water, etc.; Environmental Sealing Component 9: Provides an anhydrous environment for the whole experimental processing process. The material of the sealing device is all materials that do not react with the vapors of the swelling solution, deswelling solution, cleaning solution, etc., such as one or several of quartz, polytetrafluoroethylene, etc.Dry inert gas, such as one or more of nitrogen, argon, etc., is continuously introduced into the sealing device; Heat treatment device 10: Completely remove the liquid residue in the widened tow, and at the same time crosslink the resin on the surface of the carbon nanotubes in the tow to obtain a high-performance ultra-thin widened fiber with a stable structure. The annealing temperature range is 100 - 550 °C; Take-up device 11: The collection end of the widened tow, collect the obtained widened tow, and at the same time provide the drawing force during the treatment process. The collection speed V2 ranges from 0.01 to 100 m / h, where V1 < V2 (the specific ratio is set according to the draw ratio), so that the carbon nanotube fiber is drawn after protonation expansion to achieve high orientation.

[0042] The thickness of the obtained highly oriented ultra-thin widened carbon nanotube bundle is generally less than 5 μm (it may exceed this range depending on different process conditions), the tensile strength is generally greater than 6 GPa, and the conductivity is generally greater than 1.5 MS·m -1 , and the thermal conductivity is generally greater than 250 W·m -1 .K -1 .

[0043] Through the inter-tube modification and uniform compounding of a small amount of polymer, controlling the shape and size of the spreading roller, and the upper and lower traction roller shafts closely connected in the cleaning tank and annealing assembly, the present invention greatly realizes the ultra-thin limit widening of carbon nanotube fibers. Moreover, the process is stable throughout. This method can continuously and synchronously achieve effects such as the expansion and compounding, drawing orientation, ultra-thin widening, tow fusion, and densification crosslinking of carbon nanotube fibers, which is beneficial to the large-scale preparation of multifunctional carbon nanotube fibers. The prepared highly oriented carbon nanotube fibers have a uniform thickness that breaks through the thickness limit of carbon fibers, and excellent mechanical, electrical, and thermal properties. They can be continuously prepared and the thickness can be adjusted, etc.

[0044] Specific advantages are as follows: (1) Pretreatment with a modifier improves the bonding strength between carbon nanotubes and resins. Of course, in some implementation schemes, when the selected resin and carbon nanotubes themselves have certain affinity properties, pre-oxidation modification is also allowed, depending on the specific circumstances; (2) A small amount of resin or other polymer is added to the liquid expansion medium, and the carbon nanotubes in the carbon nanotube fiber bundle are expanded and rearranged to achieve uniform compounding of carbon nanotubes and polymers. At the same time, the addition of polymers is mainly to change the inter-tube interaction, interface properties and viscosity characteristics, etc., which is a key condition for achieving ultra-thin widening. Its concentration needs to be controlled in a relatively thin range, which is obviously different from the commonly used concentration range of traditional carbon nanotube-polymer swelling composites; (3) After the modified bundles are pre-spun, de-expanded and cleaned, they are uniformly compounded, ultra-thinly widened, highly oriented, fused and densified in an annealing device and then collected. The treatment process is continuous and highly controllable; (4) The entire treatment process is carried out in a dry inert gas environment to avoid water vapor and other factors affecting the bundle structure. (5) Through the adjustment of the processing technology, the thinnest nanometer-scale stretched fibers can be obtained, and usually bundles of several micrometers in thickness can be easily obtained, which far exceeds the thickness limit of carbon fiber and previous carbon nanotube bundle materials; (6) After ultra-thin stretching, the carbon nanotube bundles are highly oriented and fused to form a thin layer of ribbon-like carbon nanotube fiber structure. After further rearrangement and optimization, the fiber has excellent mechanical, electrical and thermal properties, and the homogeneity and bonding properties when used to prepare composite materials are very excellent, which is significantly stronger than other carbon nanotube materials with thicker radial dimensions (such as carbon fibers, carbon nanotube fibers, carbon nanotube films, carbon nanotube narrow strips, etc. with larger cross-sectional dimensions, which often require pre-impregnation winding or pre-impregnation lamination when resin composites are carried out. The fiber phase and the resin phase are macroscopically separated and cannot produce a combination close to homogenization. For ultra-thin materials, they will produce an extremely large contact area when used in the preparation of composite materials. The cross-section after bonding produces a similar homogeneous effect, and the mechanical strength, thermal conductivity and electrical conductivity will be significantly improved).

[0045] In addition, as an application of the above technical solution, the fourth aspect of the embodiment of the present invention also provides a carbon nanotube composite component, which is formed by stacking and combining the highly oriented ultra-thin widened carbon nanotube bundles provided by at least the above embodiment along the thickness direction.

[0046] The technical solution of the present invention is further described in detail below through several embodiments and in conjunction with the accompanying drawings. However, the selected embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention.

[0047] Example 1 Soak a roll of carbon nanotube fiber tow in a modifier for 24 h to graft oxygen-containing functional groups on the surface of the carbon nanotubes and increase the bonding force between the carbon nanotubes and the resin. The modifier is hydrogen peroxide; take out the carbon nanotube fiber tow and treat it in a vacuum oven at 150 °C for 1 h to remove the modifier.

[0048] Dissolve a small amount of polyvinyl alcohol in chlorosulfonic acid in a fume hood to prepare a modified swelling solution with a polyvinyl alcohol content of 0.5%.

[0049] Open the environmental sealing device. After fixing a roll of pretreated carbon nanotube fiber tow on the unwinding device, the tow ends pass through the pre-spreading yarn assembly, the active traction assembly, the swelling tank, the deswelling tank, the cleaning tank, and the annealing device respectively, and then are fixed on the empty reel of the collecting device; Select the shape and size of the pre-spreading yarn, the upper and lower spreading yarn rods, and the traction shaft according to the following parameters, and adjust them to the expected position so that the wrapping of the fiber conforms to the set wrap angle; Add acetone cleaning solution, carbon tetrachloride deswelling solution, and modified swelling solution to the solution tank in sequence, and then close the environmental sealing device; Introduce dry inert gas from the upper end of the environmental sealing device, and the gas discharges from the air outlets at both ends of the device. The gas needs to be introduced for a period of time (5 min in this embodiment) to completely discharge the humid air in the sealing device, and the gas flow rate is 5 SLM to ensure that there is no obvious moisture in the environment; Open the annealing furnace and heat it up to the target temperature of 300 °C; Set the traction speeds of the unwinding device, the collecting device, and all the active traction wheels according to the following parameters; Turn on the switches of the unwinding device, the collecting device, and all the active traction devices simultaneously to perform the width expansion treatment of the carbon nanotube fiber tow.

[0050] Specifically, in this embodiment, 100 strands of carbon nanotube fiber tow are used. During pre-width expansion, by adjusting the parameters, the 100 strands of fiber are basically close to a row in a straight arrangement. The spreading yarn rod, the upper and lower spreading yarn rods, and the traction shaft are all cylindrical flat shafts with a diameter of 50 mm. The spreading yarn rod is guided by an active traction method and adjusted to the expected position so that the wrap angle is 130°. The collecting speed is 60 m / h, and V2:V1 = 1.1:1 (that is, the collecting speed of the collecting device is 60 m / h, the unwinding speed of the unwinding device is 54.55 m / h, the active traction speed before entering the swelling solution is equal to the unwinding speed, and the active traction speed after the swelling solution is equal to the collecting speed). After width expansion, the width of the fiber tow is 3 mm, the thickness of the tow is 10 μm, and the finished product photo is as Figure 3 shown.

[0051] Example 2 This embodiment is generally the same as Embodiment 1, with the main difference being some parameter variations. 100 strands of carbon nanotube fiber tows are used (the number of tows can be arbitrarily changed depending on the specific width requirements, generally between 5 and 500 but not limited to this range), the polymer is polyether ether ketone, the addition amount is 1%, the cleaning liquid is ethanol, the de-swelling liquid is nitrobenzene, the yarn spreading rod is a cylindrical flat shaft with a diameter of 30 mm, the active traction method is used, the wrap angle is 110°, the collection speed is 50 m / h, and V2:V1 = 1.1:1. After spreading, the thickness of the fiber tow is 8 μm and the width is 3.75 mm.

[0052] Embodiment 3 This embodiment is generally the same as Embodiment 1, with the main difference being some parameter variations. 100 strands of carbon nanotube fiber tows are used, the polymer is polyamide, the addition amount is 0.1%, the cleaning liquid is water, the de-swelling liquid is chloroform, the yarn spreading rod is a cylindrical flat shaft with a diameter of 30 mm, the active traction method of the yarn spreading rod is used, the wrap angle is 60°, the collection speed is 40 m / h, and V2:V1 = 1.16:1. After spreading, the thickness of the fiber tow is 2 μm and the width is 15 mm.

[0053] Embodiment 4 This embodiment is generally the same as Embodiment 1, with the main difference being some parameter variations. 100 strands of carbon nanotube fiber tows are used, the yarn spreading rod is a convex panel with a thickness of 1 cm, the yarn spreading rod uses a non-actively rotating traction method, the wrap angle is 30°, the collection speed is 10 m / h, and V2:V1 = 1.2:1. After spreading, the thickness of the fiber tow is 500 nm and the width is 60 mm. Its cross-sectional morphology is as Figure 4 shown. It can be seen that its thickness has reached the nanometer level, and in such an ultrathin state, its cross-sectional thickness is very uniform, and the distribution of carbon nanotubes is also very uniform. Whether it is Figure 4 the cross-sectional morphology at a high magnification as shown, or the overall low-magnification cross-section as shown in Figure 5 no uneven phenomena such as particles, agglomerates, cracks, and depressions are observed. And combined with the surface morphology of the bundle shown in Figure 6 it can be seen that the carbon nanotubes have an obvious axial alignment orientation in it, and except for some burr regions on the surface, the distribution of carbon nanotubes is very dense.

[0054] The mechanical properties of this ultrathin spread bundle are tested, and its tensile curve is as Figure 7 shown, and it can reach a level of 6.6 GPa, belonging to a relatively high-strength fiber bundle material; however, the mechanical properties of the bundle provided by the present invention are not only manifested in the strength of a single bundle itself, but also in the composite strength after compounding, which is related to the composite performance under the ultrathin size shown above. For details, refer to the control experiment below.

[0055] Application Example This application example uses the composite material preparation of the ultra-thin carbon nanotube bundle provided in Example 4, and obtains a laminate by the way of bundle-resin layer-bundle cyclic lamination. The resin layer material is a bismaleimide resin, and a multi-layer composite material is obtained.

[0056] The mechanical strength of this multi-layer composite material is measured, and its tensile strength is 6 GPa, showing only a small decrease compared with the single ultra-thin carbon nanotube bundle.

[0057] As a control, this application example also provides the pre-impregnation winding composite of a high-strength carbon nanotube fiber (also with a strength of about 6.6 GPa) used in the past R & D process and the same resin. The mass ratio of the two is the same, and the hot pressing conditions are the same. The strength of the finally obtained composite material is 5 GPa, showing an obvious decrease.

[0058] It is analyzed that after the carbon nanotube fiber is broadened to an ultra-thin state, it has a larger specific surface area, and the probability of the resin infiltrating into the narrow band inside the carbon nanotube increases, increasing the interfacial composite strength with the resin. At the same time, its areal density is small, the mass is light, and the specific strength by mass is high. Compared with the traditional carbon fiber composite material, the resin content of the prepared composite material can be made lower, and the strength of the composite material under the same composite ratio is higher, and the mechanical retention rate is higher.

[0059] In addition, a high-strength narrow band bundle provided in the previous research is also used (specifically referring to the high-strength narrow band bundle prepared by the method shown in Example 1 of the Chinese invention patent "Carbon Nanotube Bundle, Its Preparation Method and Application" with the publication number of CN116905215 A. Samples with higher mechanical strength are selected from multiple batches, and its tensile strength is about 6 GPa). The thickness of this narrow band bundle is more than 50 μm, and the composite material is prepared under the same conditions. Its strength is 4.8 GPa, also showing an obvious decrease compared with the strength of the carbon nanotube bundle itself.

[0060] Comparative Example 1 This comparative example is generally the same as Example 4, and the main difference lies in: The pre-broadening process is cancelled, and 100 strands of bundled fibers are directly introduced into the expansion broadening device.

[0061] Finally, due to the lack of pre-broadening, the multi-strand fibers are physically stacked, and only relying on expansion broadening cannot obtain an ultra-thin bundle. The obtained product is similar to the plastic multi-strand fused fiber or strip in the previous invention.

[0062] Comparative Example 2 This comparative example is generally the same as Example 4, and the main difference lies in: No polymer was added to the liquid expansion medium.

[0063] Finally, during the de-expansion process, the expanded body shrank significantly, resulting in a significant increase in the thickness of the product. At the same time, in the expansion and widening device, the expanded body was also very easy to bifurcate and detach, making it impossible to prepare ultra-thin bundles. Obviously, the bonding, interface modification and viscosity control of the polymer are very critical in the preparation of ultra-thin bundles.

[0064] Comparative Example 3 This comparative example is substantially the same as Example 4, except that: Multiple tests were conducted with the addition ratio of polymer being 3%, 5%, and 10%.

[0065] It was found that in the expansion and widening device, the expansion body was obviously unable to fully spread in the width direction and encountered obvious widening resistance. The higher the polymer ratio, the more obvious this problem was, and ultimately only relatively thick narrow strips could be obtained.

[0066] The main function of the polymer is to regulate the interfacial force, provide cohesive force and viscosity, and solve problems such as widening and dispersion during the shrinkage process of the coagulation bath. However, its content should be controlled within a low range, otherwise it will easily lead to the inability to widen to an ultra-thin state.

[0067] Comparative Example 4 This comparative example is substantially the same as Example 4, except that: The de-expansion process is eliminated, and the expanded body directly enters the cleaning device after coming out of the expansion and widening device.

[0068] Finally, due to the rapid adsorption and removal rate of the liquid expansion medium by the cleaning liquid, the expansion body loses its expansion effect before it is shaped. Therefore, a very obvious shrinkage and stacking phenomenon will occur in the cleaning device, and ultimately an ultra-thin cluster cannot be obtained.

[0069] This shows that the removal of the liquid expansion medium is divided into two removal processes, inducing the fibers to gradually shrink and expand, achieving a slow and steady-state shrinkage process, and avoiding the excessive removal of the liquid expansion medium, which is crucial for achieving an ultra-thin and dense network structure.

[0070] Based on the above embodiments and comparative examples, it can be clearly seen that: (1) The embodiments of the present invention provide a solution for preparing ultra-thin bundles, which can continuously and synchronously achieve the effects of high orientation, ultra-thin widening, bundle fusion, densification, and cross-linking of carbon nanotube fibers, which is conducive to the large-scale preparation of multifunctional carbon nanotube bundles. The thickness is uniform, breaking through the thickness limit of carbon fiber, and has excellent mechanical, electrical, and thermal properties. It can be prepared continuously and the thickness is adjustable. (2) The embodiments of the present invention modify the carbon nanotube fiber tow and the swelling solution respectively, and achieve uniform composite of the resin in the state of the carbon nanotube fiber expanding and loosening, improving the uniformity and integrity of the ultra-thin limit broadening of the carbon nanotube fiber tow. (3) The embodiments of the present invention propose spreading rods with different shapes and sizes, which generate different tensions perpendicular to the fiber direction for the carbon nanotube tow by forming different wrap angles, realizing preliminary spreading among multiple strands of fibers in the tow in the pre-spreading part, and using the plastic property of the loose structure after the carbon nanotube fiber expands in the swelling tank to realize spreading among multiple carbon nanotubes in the carbon nanotube fiber, and multi-stage spreading thus realizes the ultra-thin limit broadening of the carbon nanotube fiber tow. (4) The embodiments of the present invention introduce adjacent and continuous active stretching components in the processes of de-swelling, cleaning and annealing, and at the same time avoid removing a large amount of liquid-phase swelling medium at one time, reducing the shrinkage of the thinned carbon nanotube fiber on the vertical fiber surface during the densification processes such as solvent exchange and solvent evaporation, maintaining the thickness and width of the carbon nanotube fiber in the swelling tank, and improving the uniformity of the ultra-thin broadened carbon nanotube fiber.

[0071] It should be understood that the above embodiments are only for explaining the technical concept and features of the present invention, and the purpose is to enable those who are familiar with this technology to understand the content of the present invention and implement it accordingly, and it cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit and essence of the present invention should be covered within the protection scope of the present invention.

Claims

1. A preparation method of a highly oriented ultrathin broadened carbon nanotube bundle, characterized in that, Comprising: Providing multiple multi-stranded raw carbon nanotube fibers, wherein the raw carbon nanotube fibers contain multiple carbon nanotube bundles; Mechanically pre-spreading the raw carbon nanotube fibers to form a pre-spread bundle; Bringing the pre-spread bundle into contact with a liquid-phase swelling medium for swelling and spreading treatment to form a swollen and spread bundle; a polymer is dissolved in the liquid-phase swelling medium. During the swelling and spreading treatment, multiple carbon nanotube bundles repel and swell, the polymer enters between the multiple carbon nanotube bundles and adheres to the surfaces of the carbon nanotube bundles, and at the same time, the swollen fiber bundle composed of the multiple carbon nanotube bundles is subjected to a pressure in the first radial direction and spreads and widens in the second radial direction, the first radial direction and the second radial direction intersect, and the swollen fiber bundle is subjected to a tensile force in the axial direction and elongates; Bringing the swollen and spread bundle into contact with a deflating liquid for deflating treatment to remove part of the liquid-phase swelling medium and obtain a deflated bundle; Performing a cleaning treatment and a heat treatment on the deflated bundle to obtain a highly oriented ultra-thin spread bundle of carbon nanotubes.

2. The preparation method according to claim 1, characterized in that, The liquid-phase swelling medium includes any one or a combination of two or more of chlorosulfonic acid, methanesulfonic acid, and fuming sulfuric acid; And / or, the polymer includes any one or a combination of two or more of polyvinyl alcohol, polyacrylic acid, polystyrene, polyphenylene ether, phenolic resin, polyamide, and polyetheretherketone; And / or, the mass fraction of the polymer in the liquid-phase swelling medium is 0.01-1%.

3. The preparation method according to claim 1, wherein, Also comprising: Before performing the swelling and spreading treatment, pre-oxidizing the raw carbon nanotube fibers to form oxygen-containing functional groups on the surfaces of the carbon nanotube bundles.

4. The preparation method according to claim 3, characterized in that, The pre-oxidation treatment is carried out by an impregnation oxidation method, and the oxidant includes any one or a compatible combination of any two of concentrated sulfuric acid, concentrated nitric acid, and hydrogen peroxide.

5. The preparation method according to claim 1, wherein The mechanical pre-spreading is carried out by rolling and spreading with a yarn spreading roller, and multiple raw carbon nanotube fibers in the pre-spread bundle are arranged side by side in a row.

6. The preparation method according to claim 1, wherein The swelling and spreading treatment is carried out by multiple yarn spreading rods immersed in the liquid-phase swelling medium. The swollen fiber bundle wraps around the yarn spreading rods and is subjected to pressure, the wrapping curvature diameter is 1-100 mm, the wrapping angle of the swollen fiber bundle is 30-130°, and the draw ratio is 1:(1.1-1.2).

7. The preparation method according to claim 1, characterized in that, The deflating treatment is carried out by impregnating with a deflating liquid, and the deflating liquid includes any one or a combination of two or more of chloroform, carbon tetrachloride, and nitrobenzene; And / or, the cleaning treatment is carried out by impregnating with a cleaning liquid, and the cleaning liquid includes any one or a combination of two or more of acetone, ethanol, N-methylpyrrolidone, and water; And / or, the temperature of the heat treatment is 100-550 °C; And / or, the swelling and spreading treatment, the deflating treatment, and the cleaning treatment are all carried out in a protective atmosphere; And / or, when performing the deflating treatment, the cleaning treatment, and the heat treatment, a drawing roller is used to pull and at the same time fix the spreading state of the bundle.

8. An apparatus for preparing a highly oriented ultra-thin broadened carbon nanotube bundle, which is used to implement the preparation method described in any one of claims 1-7, and is characterized in that, [[ID= A wire pay-off device for providing multiple multi-stranded raw carbon nanotube fibers, wherein the raw carbon nanotube fibers contain multiple carbon nanotube tows; A pre-spreading device for mechanically pre-spreading the raw carbon nanotube fibers to form a pre-spread bundle; An expansion spreading device for bringing the pre-spread bundle into contact with a liquid-phase expansion medium for expansion spreading treatment to form an expanded spread bundle; a polymer is dissolved in the liquid-phase expansion medium. During the expansion spreading treatment, multiple carbon nanotube tows repel and expand, the polymer enters between the multiple carbon nanotube tows and adheres to the surface of the carbon nanotube tows, and at the same time, the expanded fiber bundle composed of the multiple carbon nanotube tows is subjected to a pressure in a first radial direction to spread and widen in a second radial direction, the first radial direction and the second radial direction intersect, and the expanded fiber bundle is subjected to a tensile force in the axial direction to elongate; A de-expansion device for bringing the expanded spread bundle into contact with a de-expansion liquid for de-expansion treatment to remove part of the liquid-phase expansion medium to obtain a de-expanded bundle; A cleaning device for cleaning the de-expanded bundle; A heat treatment device for heat-treating the de-expanded bundle after cleaning treatment to obtain a carbon nanotube highly oriented ultra-thin spread bundle; And a collection device for collecting the carbon nanotube highly oriented ultra-thin spread bundle.

9. The carbon nanotube highly oriented ultra-thin widened bundle prepared by the preparation method according to any one of claims 1-7, characterized in that, The carbon nanotube highly oriented ultra-thin spread bundle is a bundle with a flat axial cross-section formed by combining multiple carbon nanotube tows, a polymer is filled between the carbon nanotube tows, and the thickness of the carbon nanotube highly oriented ultra-thin spread bundle is 500 nm - 10 μm.

10. A carbon nanotube composite component, characterized in that, The carbon nanotube composite member is at least formed by stacking and bonding the carbon nanotube highly oriented ultra-thin spread bundle according to claim 9 in the thickness direction.

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