KR101535338B1 - Novel tertiary structure of carbon nanostructure and composite comprising same - Google Patents

Abstract

The present invention relates to a novel type of carbon nanostructure tertiary structure, an aggregate thereof, and a composite material containing the same, wherein the tertiary structure according to the present invention comprises a plurality of carbon nanostructures (CNS) And a secondary structure formed to be assembled so as to form a spiral shape.
The novel tertiary structure, the aggregate thereof and the composite material containing the same according to the present invention are highly applicable to energy materials, functional composites, batteries, and semiconductor fields.

Description

TECHNICAL FIELD [0001] The present invention relates to a novel tertiary structure of carbon nanostructure and a composite material containing the same. BACKGROUND OF THE INVENTION [0002]

The present invention relates to a new type of carbon nanostructure tertiary structure and a composite material containing the same.

Carbon nanostructures (CNS) refer to nano-sized carbon structures with various shapes such as nanotubes, nanohair, fullerene, nanocone, nanohorn, and nano-rod. Since they have various properties, .

Particularly, carbon nanotubes (CNTs) are materials having carbon atoms arranged in a hexagonal shape in a tube shape and having a diameter of about 1 to 100 nm. Carbon nanotubes exhibit non-conductive, conductive, or semiconducting properties due to their unique chirality. They have strong tensile strengths greater than about 100 times greater than steel due to their strong covalent bonds, and are excellent in flexibility and elasticity, It is chemically stable.

Examples of carbon nanotubes include single-walled carbon nanotubes (SWCNTs) composed of one layer and having a diameter of about 1 nm, double-walled carbon nanotubes composed of two layers and having a diameter of about 1.4 to 3 nm walled carbon nanotubes (DWCNT), and multi-walled carbon nanotubes (MWCNTs) composed of a plurality of three or more plies and having a diameter of about 5 to 100 nm.

Carbon nanotubes have been commercialized and applied in various fields such as aerospace, fuel cell, composite material, biotechnology, medicine, electric / electronic and semiconductor due to their chemical stability, excellent flexibility and elasticity . However, the primary structure of carbon nanotubes has a limitation in directly controlling their diameters and lengths to the actual specifications that can be applied to industrial applications. Therefore, despite the excellent properties of carbon nanotubes, many applications There are restrictions.

Conventionally, in order to diversify the role of structural reinforcement and chemical functional substance of carbon nanostructure such as carbon nanotube, a method of collectively forming a primary structure of carbon nanostructure into a plate type and then physically raising it by a separate spinning process Was used [Zhang, X .; Li, Q .; Tu, Y .; Li, Y .; Coulter, JY; Zheng, L .; Zhao, Y .; Jia, Q .; Peterson, DE; Zhu, Y. Small , 2007 , 3 , 244]. However, this conventional method requires a secondary spinning process after the planar growth, so the productivity is very low. The carbon nanotube yarn produced by such a process has a multi-layered structure grown as a flat plate as shown in Fig. 1 [Adv. Mater. Vol. 22, 2010, pages 692-696 (2009.11.24.)

In addition, a method for producing carbon nanotube aggregates of various structures and sizes has been reported. The structure produced by these methods is shown in FIG. 2 ((a) Jia, Y .; He, L .; Kong, L .; Liu, J .; Guo, Z .; Meng, F .; Luo, T .; Li, M .; Liu, J. Carbon , 2009 , 47 , 1652; (b) Zhang, X .; Cao, A .; Li, Y .; Xu, C .; Liang, J .; Wu, D .; Wei, B. Chem . Phys . Lett ., 2002 , 351 , 183; (c) Kathyayini, H .; Willems, I .; Fonseca, A .; Nagy, JB; Nagaraju, N. Cat . Commun ., 2006 , 7 , 140; (d) Li, Y .; Zhang, XB; Tao, XY; Xu, JM; Huang, WZ; Luo, JH; Luo, ZQ; Li, T .; Liu, F .; Bao, Y .; Geise, HJ Carbon , 2005 , 43 , 295]. Although the structures and sizes of the structures are somewhat different from each other in FIG. 2, they are common in that they are hollow rather than hollow.

The hollow structure in nanochemistry has many advantages. Therefore, if a hollow structure can be formed using a carbon nanostructure excellent in chemical stability, elasticity, and flexibility, its utilization will be further increased.

Accordingly, the present invention provides a tertiary structure of a new type carbon nanostructure (CNS) that can be more effectively applied to energy materials, functional composites, batteries, semiconductors and the like, which are required to have various diameters, lengths, I want to.

In order to achieve the above object, the present invention provides a carbon nanostructure having a plurality of carbon nanostructures (CNS) formed in a spiral shape by a secondary structure formed by aggregating the carbon nanostructures Provides a tertiary structure.

According to a preferred embodiment of the present invention, the spiral may be a constant or a left-handed spiral with a constant or varying radius of curvature, and may also be conical or cylindrical spiral.

According to a preferred embodiment of the present invention, the secondary structure forming the tertiary structure may be a tangled structure in which a plurality of carbon nanostructures are tangled with each other.

According to a preferred embodiment of the present invention, the tube shape of the secondary structure may be such that the effective internal diameter is the diameter when the contrast ratio of the electron micrograph taken in the tube diameter direction is 90%.

According to a preferred embodiment of the present invention, the effective diameter of the secondary structure may be 0.1 to 30 탆.

According to a preferred embodiment of the present invention, the carbon nanostructure may be a carbon nanotube, a carbon nanorod, a carbon nanofiber, or a carbon nanofiber.

According to a preferred embodiment of the present invention, the carbon nanostructure may have a diameter of 0.1 to 200 nm and a length of 1 to 10 mm.

According to a preferred embodiment of the present invention, the secondary structure may be in the form of a tube having an outer diameter of 1 to 100 mu m and a length of 5 to 10,000 mu m.

According to a preferred embodiment of the present invention, the carbon nanostructure may be a single wall carbon nanotube (SWCNT), a double wall carbon nanotube (DWCNT), a multiwall carbon nanotube (MWCNT), or a mixture thereof.

The present invention also provides a composite material comprising the carbon nanostructure tertiary structure as described above.

The present invention also relates to a method for producing a carbon nanostructure tertiary structure, which comprises reacting a reaction gas containing a carbon source in the presence of a supported catalyst obtained by supporting a catalytic metal on a milled support, followed by pulverization and calcination, for 2 to 10 hours to provide.

According to a preferred embodiment of the present invention, the milled support may have a particle diameter (d ₅₀ ) of 0.1 to 1.5 탆.

According to a preferred embodiment of the present invention, the milled support may be an aluminum-based support.

According to a preferred embodiment of the present invention, the catalyst metal includes cobalt (Co) and molybdenum (Mo), and the content of cobalt (Co): molybdenum (Mo) may be 10 to 30: 1.

The CNS tertiary structure according to the present invention is a novel type which has not been conventionally used. Such a tertiary structure can exhibit new characteristics and can be applied to various fields such as energy materials, functional composites, medicines, batteries and semiconductors have.

1 is SEM photographs of CNT yarns manufactured according to the prior art.
2 is a SEM photograph of a CNT secondary structure manufactured according to the prior art.
3A and 3B are SEM photographs of a CNT secondary structure and a tertiary structure manufactured according to Example 1. FIG.
4 is a schematic diagram illustrating an initial stage of growth of a secondary structure for forming a CNS tertiary structure according to the present invention and an enlarged view of a CNS secondary structure included therein.
5 is a SEM photograph of a CNS secondary structure in which a center portion 301 and an outer frame portion 302 of a secondary structure for forming a CNS tertiary structure according to an embodiment of the present invention are shown.
6 is a SEM photograph of one side of a secondary structure for forming a CNS tertiary structure according to an embodiment of the present invention.
7 is an image photograph for explaining a method for measuring the effective inner diameter of a CNS secondary structure using a MATLAB-IPT.
8 is a graph showing a yield and an IG / ID change according to the reaction time of the CNT secondary structure produced according to Reference Experimental Example 1. FIG.
9 is a SEM photograph of the CMT secondary structure produced according to Reference Experimental Example 1. FIG.
10 is an SEM photograph of the CNT secondary structure produced according to Reference Experimental Example 2. FIG.
11 is SEM photographs of CNT secondary structure aggregates produced according to Comparative Examples 1 and 2. FIG.

Hereinafter, the CNS tertiary structure and the composite material containing the CNS tertiary structure according to the present invention will be described in detail.

The CNS tertiary structure according to the present invention is a structure in which a plurality of CNS entities are gathered to form a helical extension of a secondary structure having a tube shape in whole or in part.

Herein, the term " helical " includes both a conical or cylindrical helical, and a priority or a left-handed helical with a constant or varying radius of curvature.

The tube-shaped CNS secondary structure is also referred to as a hollow CNS bundle, where the 'tube shape' refers to the fact that the density of the CNS entities located at the center of the outer tube is low and the center appears empty (hollow or pore) ), And a shape having a length longer than the diameter of the secondary structure. Here, 'tube diameter' means 'tube outer diameter' unless otherwise noted.

The cross-section of the tubular shape may include circular or oval or hollow or pores formed in a somewhat distorted shape thereof, which hollow or pore may be circular or oval in shape, ≪ / RTI > It is difficult to see that the hollow or pore has a definite boundary since the distribution density of the carbon nanostructure is significantly lower than that of the outer portion.

Accordingly, in the present invention, the diameter of the hollow or pore of the cross section of the tube when viewed in a circle having a corresponding area is defined as the " effective inner diameter " of the tube. The effective inner diameter may be the effective inner diameter of the tube-shaped cross section formed by the secondary structure of the carbon nanostructure, when the contrast ratio of the electron micrograph is a predetermined level, for example, 90%.

On the other hand, the CNS secondary structure can be thickened or thinned along the direction in which the CNS constituting the CNS is grown from the supported catalyst, that is, along the longitudinal direction, so that the diameter of the central portion and the outer periphery thereof becomes thicker or thinner along the longitudinal direction .

A CNS secondary structure bundle according to another embodiment of the present invention is formed by assembling CNS secondary structures having a tube shape in whole or in part to form a three-dimensional shape that is tangled with each other.

According to the present invention, there is a cluster of catalyst particles of a certain size at the end of a tube-shaped CNS secondary structure (hollow CNS bundle). Therefore, the shape and length of the secondary structure produced by increasing the contact time with the reaction gas can be controlled.

The thickness of the thickest part of the CNS secondary structure aggregate forming the helical tertiary structure can be from a few micrometers (m) to thousands of micrometers, for example from 2 to 2000 m.

In addition, the length of the CNS secondary structure forming the spiral tertiary structure may be approximately several micrometers to several thousands of micrometers, excluding the supported catalyst, based on the direction in which the CNS secondary structure is grown, 5 to 10,000 占 퐉.

The composite according to another embodiment of the present invention may be a CNS tertiary structure or a cluster of CNS tertiary structures dispersed on a matrix. For example, the composite material may be obtained by melt-kneading a polymer polymer and a CNS tertiary structure to disperse CNS tertiary structure particles on a polymeric polymer matrix. The raw material of the matrix is not particularly limited, but may be a polymer, a metal, a ceramic, or a mixture thereof.

Hereinafter, the CNS tertiary structure will be described in detail with reference to the drawings.

3A and 3B are SEM photographs of a CNT secondary structure and a tertiary structure manufactured according to an embodiment of the present invention. As can be seen from FIG. 3B, the tertiary structure according to the present invention is a structure in which a plurality of CNS entities are gathered to form a spiral-shaped secondary structure having a tube shape in whole or in part.

4 is a diagram schematically showing a CNS secondary structure and its aggregate for forming a CNS tertiary structure according to the present invention. Reference numeral 100 in FIG. 4 denotes a supported catalyst used in the synthesis of the CNS, reference numeral 200 denotes a CNS secondary structure aggregate, reference numeral 300 denotes a CNS secondary structure, reference numeral 400 Refers to the CNS.

The CNS secondary structure 200 or the CNS secondary structure 300 formed according to an embodiment of the present invention may be present together with the supported catalyst 100 as shown in FIG. 4, However, those skilled in the art will recognize that they can be separated from the supported catalyst 100 separately by post treatment or the like.

As shown in FIG. 4, the CNS secondary structure 200 may be formed by densely gathering a plurality of CNS secondary structures 300, and some CNS secondary structures may be randomly entangled.

In an embodiment of the present invention, the CNS secondary structure aggregate may be formed by assembling the new type hollow CNS secondary structures according to the present invention, or the hollow CNS secondary structure according to the present invention, All filled CNS secondary structures may be included and configured.

In an embodiment of the present invention, the CNS secondary structure aggregate may include 10% or more of the hollow CNS secondary structure according to the present invention based on the number of all the CNS secondary structures in the CNS secondary structure aggregate, or 30% Or more, or 50% or more, or 80% or more.

The CNS secondary structure 300 constituting the CNS secondary structure 200 in FIG. 4 has a tangled structure in which a plurality of CNSs 400 grown together in the supported catalyst 100 are randomly gathered or tangled, , And a tubular shape that is roughly grown to one side is formed. 4, one end 311 of the CNS secondary structure 300 is connected to the supported catalyst 100 and has a length from one end 311 to the other end 312 A plurality of CNSs 400, which are approximately 5 to 10,000 占 퐉, are randomly gathered or tangled.

4 is an enlarged view of the CNS secondary structure 300 constituting the CNS secondary structure aggregate 200. In FIG. The CNS secondary structure 300 includes an empty central portion 301 and a tubular outer portion 302 surrounding the central portion 301.

5 is an SEM photograph of a CNS secondary structure showing a central portion 301 and an outer frame portion 302 of the CNS secondary structure according to an embodiment of the present invention, and FIG. 5 is a partial enlarged view of FIG. In one embodiment of the present invention, the central portion 301 of the CNS secondary structure 300 means that the distribution density of the CNS 400 present therein is relatively lower than the distribution density of the CNS present in the outer portion 302 . For example, the CNS distribution density of the central portion 301 may be about 1/3 or less, or 1/4 or less, or 1/5 or less of the CNS distribution density of the outer portion 302.

The low density of the CNS distribution in the center can be seen as the center being substantially empty. Specifically, the fact that the space corresponding to the center portion is substantially empty may mean that the space is more than 70% empty even if the CNS 400 is substantially present. For example, referring to FIGS. 5 and 6, the dark part of the SEM photograph is the central part 301, and the dark part of the center part is due to a small number of CNS entities present therein. Roughly the area occupied by the CNS entities in the central region 301 is less than 30% of the area of the central region 301. In addition, in an embodiment, the space substantially corresponding to the central portion may be substantially 80% or more, or 90% or more, even if the CNS is substantially present.

If there is no CNS 400 in comparison with the other parts, or if the CNS 400 exists, the distribution of which is negligible constitutes the central part 301 of the CNS secondary structure 300, which is roughly a cylindrical hollow or pore , The secondary structure has a tube shape in whole or in part. The diameter of the cylindrical pores, that is, the tubular inner diameter or effective inner diameter (a) is approximately 0.1 to 30 탆, or 0.5 to 9 탆, or 0.5 to 3 탆, or 0.5 to 2 탆, or 0.5 to 1.5 탆 Lt; / RTI >

According to one embodiment of the present invention, the effective internal diameter (a) can be measured using a Matlab-Image Processing Toolbox (Rafael C. Gonzalez, et al. Yoo Hyun-jung. "Digital Image Processing Using MATLAB", McGraw-Hill Korea, 2012, page 509)].

7, an electron microscope photograph as shown in FIG. 7 (a) is used as a virtual corresponding structure having an ideal circular shape which can be easily mathematically analyzed through a data input conversion process of an image process, (B). Using the space partition function of the image processing software, we define a circle with a certain radius at the center of the black part of the picture, digitize it as the number of black and white pixels, and then measure the ratio.

For example, if the number of black and white pixels (contrast ratio) according to the circle radius obtained by the above method is as shown in Table 1 below, the specific value of the contrast ratio can be defined as the effective inner diameter of the CNS secondary structure (for example, %).

Radius (㎛) Number of black and white pixels (contrast ratio) 0 98.9 0.5 96.6 One 94.8 1.5 93.2 2 6.4 2.5 1.9 3 1.1

The CNS secondary structure according to the present invention as well as the CNS secondary structure according to the present invention is a novel structure that has not been available in the past since it has a tube shape having an effective inner diameter.

In one embodiment, the length of the CNS secondary structure can be, for example, from 5 to 10,000 microns, or from 15 to 1000 microns, or from 20 to 500 microns.

Also, in one embodiment, the diameter of the CNS secondary structure, i.e., the tubular outer diameter ("b" in FIG. 3) is approximately 1 to 100 μm, or 1 to 30 μm, or 1 to 10 μm, Or 2 to 9 탆, or 3 to 8 탆. The outer diameter means the diameter of the circle forming the outermost of the tube shape.

According to one embodiment of the present invention, the thickness of the outer portion of the CNS secondary structure, i.e., the outer diameter of the CNS secondary structure excluding the inner diameter, is approximately 0.5 to 99.5 占 퐉, or 0.5 to 29.5 占 퐉, 9.5 占 퐉, or 1 to 8 占 퐉.

The CNS distribution density at the outer and central portions of the CNS secondary structure may be measured as the area occupied by the CNS per unit area in the direction perpendicular to the longitudinal direction of the CNS secondary structure, i.e., the radial direction of the tubular shape. The unit area may be, for example, 10 nm ² .

Alternatively, the CNS distribution density can be calculated by using the Matlab-Image Processing Toolbox and the Curve Fitting Toolbox to calculate the contrast ratio of the SEM photographs in the direction of increasing the diameter continuously from the inner center of the aggregate And the change of the first derivative of the change in the contrast ratio along the radial direction can be measured and converted into a density function for one side of the aggregate [Rafael C. Gonzalez, et al. Yoo Hyun-jung. "Digital Image Processing Using MATLAB", McGraw-Hill Korea, 2012, page 509).

In FIG. 4, reference numeral 400 denotes an enlarged SEM photograph of a part of the surface of the CNS secondary structure 300, which shows that the CNS 400 is closely connected to form a CNS secondary structure 300 . The CNS is preferably a CNT, and the CNT may be a single wall carbon nanotube (SWCNT), a double wall carbon nanotube (DWCNT), a multi wall carbon nanotube (MWCNT) or a mixture thereof. Nanotube (MWCNT).

In one embodiment, the length of the CNS 400 may be, for example, 1 to 10 mm, or 1 to 1 mm, and the diameter of the CNS 400 may be 0.1 to 200 nm, or 2 to 100 nm Lt; / RTI >

In one embodiment of the present invention, the CNS 400 may be a CNS containing less than 10% by weight of single-walled carbon nanotubes (SWCNTs) or 0.000001 to 10% by weight of single walled carbon nanotubes (SWCNTs) Gt; CNS < / RTI >

In another embodiment of the present invention, the CNS 400 may be a CNT containing less than 10% by weight of double walled carbon nanotubes (DWCNT), or a carbon nanotube (DWCNT) containing 0.0000001 to 10% CNS.

According to another embodiment of the present invention, the distribution density of the CNS in the central portion and the outer portion greatly varies, and the distribution density of the CNS on the main cylindrical portion of the CNS secondary structure irregularly protruding is not taken into account , The portion where the distribution density of the CNS changes most greatly from the center to the outer periphery of the CNS secondary structure may be the surface where the center portion and the outer portion are in contact with each other.

Hereinafter, a method of manufacturing the CNS tertiary structure according to the present invention will be described in detail. It will be apparent to those skilled in the art that the present invention will be better understood by reference to the following description.

In the CNS tertiary structure according to the present invention, the reaction gas containing a carbon source is reacted for a sufficient time, preferably 2 hours to 10 hours, more preferably 2 hours to 10 hours, in the presence of a supported catalyst obtained by carrying a catalyst metal on a milled support, Preferably 2 hours to 5 hours.

According to one embodiment of the present invention, the CNS manufacturing catalyst obtained by carrying an active metal on a milled support, preferably an aluminum-based support, and calcining it can be produced by chemical vapor deposition (CVD).

In order to produce a tertiary structure formed by spirally extending a tube-like CNS secondary structure in which a hollow (or pore) is formed at the center as described above, the support on which the active metal is supported can be milled.

The milling according to one embodiment of the present invention may be a ball milling process, may be performed at a condition of 100 rpm or more, or may be performed at a condition of 100 to 1000 rpm, or may be performed at a condition of 150 to 500 rpm have.

According to a preferred embodiment of the present invention, the support may be a milled AlO (OH) ₃ , Al (OH) ₃ or Al ₂ O ₃ . The milled AlO (OH), Al (OH) ₃ and Al ₂ O ₃ have a particle size (d ₅₀ ) of 0.1 to 1.5 μm, more preferably 0.15 to 0.6 μm, and most preferably 0.2 to 0.5 μm Lt; / RTI > Within this range, the CNS tertiary structure according to the present invention can be produced in a high content.

The particle size (d ₅₀ ) of the support prior to the milling treatment may be, for example, from 1 to 100 μm, more preferably from 3 to 60 μm. In addition, the surface area of the support prior to the milling process may be 10 to 1000 m ² / g, alternatively 50 to 600 m ² / g. And, the pore volume of the support before the milling treatment may be 0.1 to 2 mL / g, or 0.2 to 1.5 mL / g.

The particle size (d ₅₀ ) of Al (OH) ₃ before the milling treatment is, for example, 10 to 80 μm or 20 to 60 μm. The particle size (d ₅₀ ) of Al ₂ O ₃ before the milling treatment is, for example, 10 to 100 μm or 20 to 80 μm.

The catalytic metal according to one embodiment of the present invention is preferably, but not limited to, a Mo metal and a Co metal.

The molar ratio (Mo / Co) of the Mo metal and the Co metal is larger than 0 and smaller than 1, preferably 1/30 to 1/2, more preferably 1/30 to 1/5, and most preferably 1 / 25 to 1/10, and the distribution density of the central portion and the outer portion of the CNS secondary structure produced within this range is large, and the length growth effect is different in response to the reaction time, so that a spiral tertiary structure is formed Do.

The firing temperature according to an embodiment of the present invention may be more than 200 ° C to less than 800 ° C or may be 400 to 675 ° C or 550 to 650 ° C or 600 to 650 ° C, Gt; CNS < / RTI > secondary structure of the present invention can be produced with high content.

In addition, the CNS tertiary structure aggregate of the new type according to the present invention is formed by protruding catalyst particles into the outer space to facilitate the post-treatment process such as the step of cutting the CNS tertiary structure, and the polymer composite and solution dispersion type product There is an effect of excellent dispersibility in the production of

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are intended to be illustrative of the present invention and the scope of the invention as defined by the appended claims. It will be obvious to those skilled in the art that these modifications and variations are included in the scope of the appended claims.

[Example]

The following examples illustrate the case where carbon nanotubes (CNTs) are prepared as carbon nanostructures (CNS).

Example  One

≪ Synthesis of AlO (OH)

50 g of Al (O-sec-Bu) _{3 was} mixed with 25 ml of EtOH, stirred at 120 ° C for 30 minutes, and then 15 ml of distilled water was added thereto and cooled to room temperature. The cooled product was filtered with a glass filter to obtain a precipitate. The precipitate was washed several times with acetone and then dried at 120 ° C for 3 hours to produce AlO (OH).

≪ Preparation of Support >

The prepared AlO (OH) was ball-milled using a zirconia ball at 200 to 250 rpm. The particle size (d ₅₀ ) of the milled AlO (OH) support was 0.3 탆.

≪ Preparation of supported catalyst from AlO (OH)

Co (NO ₃ ) ₂ .6H ₂ O and (NH ₄ ) ₆ Mo ₇ O ₂₄ were completely dissolved in 50 mL of distilled water so that the molar ratio of Co and Mo was 20: 1, and milled AlO (OH) 1.0 g and then mixed at 60 DEG C under 85 mbar for 30 minutes and then mixed at 10 mb for 30 minutes to obtain a solid supported catalyst precursor. The obtained supported catalyst precursor was dried at 120 ° C. for 1 hour, pulverized and then calcined at 600 ° C. for 4 hours to prepare 1.12 g of supported catalyst.

≪ Synthesis of CNT secondary structure and tertiary structure >

2 mg of the prepared supported catalyst was placed in the middle of a quartz tube having an inner diameter of 55 mm in a laboratory scale fixed bed apparatus and then heated up to 700 ° C. in a nitrogen atmosphere and maintained under nitrogen (N ₂ ), hydrogen (H ₂ ) And ethylene (C ₂ H ₄ ) gas were mixed at a volume mixing ratio of 1: 1: 1 for 3 hours. FIG. 3A is a SEM photograph showing a CNT secondary structure formed in a tube shape after 1 hour of reaction, and FIG. 3B is a SEM photograph showing a CNT secondary structure formed by growing a length of a secondary structure as reaction time elapses. to be.

SEM photographs of the CNT tertiary structure aggregates thus prepared are shown in FIG. As shown in FIG. 7, it can be seen that the manufactured CNT secondary structure aggregate is composed of a plurality of CNT secondary structures, and each CNT secondary structure is tubular composed of a pore center portion and an outer circumferential portion enclosing the core portion. there was.

Reference Example  One

CNT was synthesized using the supported catalyst prepared in the same manner as in Example 1 except that the molar ratio of Co and Mo was 5: 1. Figure 8 shows the yield and IG / ID ratio over time of reaction. As shown in FIG. 8, when the reaction time was increased to 4 hours, the reaction yield was 5783%, which is twice the yield of 1 hour reaction. In addition, when the reaction time is increased, the similar IG / ID ratio value is shown. As a result, it can be confirmed that the CNT quality is not significantly different from the CNT grown within 1 h even if the reaction time is increased. However, during the increase of the reaction time, a large change in the length of the grown CNT bundle occurred. Specifically, the hollow CNT bundle grown for 1 hour with a catalyst of Co: Mo = 5: 1 was grown to a length of about 30 to 50 μm and a diameter of 3 to 5 μm, After 3 hours reaction, the length increased to about 150 ~ 200 ㎛. However, despite the reaction time of 3 hours, no spiral three-dimensional structure was formed (see FIG. 9).

Reference Example  2

CNT was synthesized using the supported catalyst prepared in the same manner as in Example 1, except that the molar ratio of Co to Mo was 7.5: 1. As shown in FIG. 10, it can be seen that the CNT secondary structure is grown in the longitudinal direction, but the helical tertiary structure is not formed.

Comparative Example  1 and 2

Except that Al (OH) ₃ and gamma-Al ₂ O ₃ not ball milled were used, respectively, to prepare a CNT secondary structure aggregate with reaction yields of 1463% and 480%, respectively Respectively. SEM photographs of the CNT secondary structure aggregates produced are shown in FIG.

11, relatively small bundles were observed in the CNT secondary structure aggregate (Comparative Example 1) produced using Al (OH) ₃ as the catalyst support, but the conventional CNT secondary structure , And a cluster of CNT secondary structures prepared using gamma-Al ₂ O ₃ as a catalyst support (Comparative Example 2) was produced in a small amount, and this aggregate was also formed in the same manner as in the case of a conventional CNT secondary structure (Thick bundles).

As shown in FIGS. 3 to 10, it can be seen that the CNT secondary structure according to the present invention is a new form having a hollow central portion unlike the conventional CNT secondary structure (Comparative Examples 1 and 2), and further, It can be seen that the helical tertiary structure shown is a hollow tube-shaped CNT secondary structure which is grown to form another new spiral structure.

[Test Methods]

1) The length and diameter (outer diameter) of the CNT secondary structure aggregate and the CNT secondary structure were measured by SEM (Scanning Electron Microscope). The SEM device used was FESEM (HITACHI S-4800). SEM observation conditions were acceleration voltage 5 ㎸, emission current 10 ㎂, working distance 8 ㎜, Detector SE.

2) The inner diameter of the CNT secondary structure is defined using a Matlab-Image Processing Toolbox, a function of the space division function of the image processing software, to define a circle having a certain radius at the center of the black portion of the picture The photograph was digitized as the number of black and white pixels, and then the contrast ratio was measured. The diameter at the contrast ratio of 90% was obtained.

3) The particle size (d ₅₀ ) of the support was measured using a particle size analyzer (Microtrac, Bluewave) Fluid (Water, 40%) and ultrasonic treatment (40 watt, 3 min).

100 supported catalyst surface
200 CNS secondary structure aggregate
301 The center of the secondary structure
302 Outer frame of secondary structure
311 One end of the CNS secondary structure in contact with the catalyst surface
312 Other end facing out of the CNS secondary structure
300 CNS secondary structure
400 CNS

Claims (16)

A tertiary structure of a carbon nanostructure in which a plurality of carbon nanostructures (CNS) are aggregated so as to form a tube shape in whole or in part, and a secondary structure is formed by spirally extending the carbon nanostructures.
The method according to claim 1,
Wherein the helical shape is a primary or left-handed spiral having a constant or varying radius of curvature.
The method according to claim 1,
Wherein the helical is a conical or cylindrical spiral, the tertiary structure of a carbon nanostructure.
The method according to claim 1,
Wherein the secondary structure is a tangled structure in which a plurality of carbon nanostructures are entangled with each other.
The method according to claim 1,
The tubular shape of the secondary structure has an effective inner diameter of a diameter at a contrast ratio of 90% of the electron microscope photograph taken in the tube diameter direction. The tertiary structure of the carbon nanostructure.
The method according to claim 1,
Wherein the secondary structure has an effective inner diameter of 0.1 to 30 占 퐉.
The method according to claim 1,
Wherein the carbon nanostructure is a carbon nanotube, a carbon nanorod, a carbon nanofiber, or a carbon nanofiber.
The method according to claim 1,
Wherein the carbon nanostructure has a diameter of 0.1 to 200 nm and a length of 1 to 10 mm.
The method according to claim 1,
Wherein the secondary structure is a tubular shape having an outer diameter of 1 to 100 탆 and a length of 5 to 10,000 탆.
The method according to claim 1,
The carbon nanostructure may be a single-wall carbon nanotube (SWCNT), a double wall carbon nanotube (DWCNT), a multiwall carbon nanotube (MWCNT), or a mixture thereof.
A composite material comprising the carbon nanostructure tertiary structure according to any one of claims 1 to 10.
The carbon nanostructure according to any one of claims 1 to 10, which comprises reacting a reaction gas containing a carbon source in the presence of a supported catalyst obtained by supporting a catalytic metal on a milled support, followed by pulverization and firing, for 2 to 10 hours A method for manufacturing a tertiary structure.
13. The method of claim 12,
Wherein the milled support has a particle diameter (d ₅₀ ) of 0.1 to 1.5 탆.
13. The method of claim 12,
Wherein the milled support is an aluminum support. ≪ RTI ID = 0.0 > 11. < / RTI >
13. The method of claim 12,
Wherein the catalyst metal comprises cobalt (Co) and molybdenum (Mo).
13. The method of claim 12,
Wherein the catalytic metal has a cobalt (Co): molybdenum (Mo) content of 10 to 30: 1.

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