KR101779668B1 - 3-dimensional carbon composite and preparing method thereof - Google Patents

3-dimensional carbon composite and preparing method thereof Download PDF

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KR101779668B1
KR101779668B1 KR1020150138419A KR20150138419A KR101779668B1 KR 101779668 B1 KR101779668 B1 KR 101779668B1 KR 1020150138419 A KR1020150138419 A KR 1020150138419A KR 20150138419 A KR20150138419 A KR 20150138419A KR 101779668 B1 KR101779668 B1 KR 101779668B1
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carbon material
dimensional
dimensional carbon
metal oxide
oxide layer
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KR20170039375A (en
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박지선
이철승
신권우
김윤진
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전자부품연구원
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Abstract

An electrically conductive three-dimensional organic / inorganic hybrid carbon material having a maximized specific surface area and a method for producing the same are disclosed. A three-dimensional organic / inorganic hybrid carbon material according to an embodiment of the present invention is a three-dimensional organic / inorganic hybrid carbon material formed by placing a one-dimensional carbon material on a two-dimensional carbon material. A porous metal oxide layer is formed on the surface of the three- .

Description

[0001] The present invention relates to a three-dimensional organic or inorganic hybrid carbon material,

The present invention relates to a three-dimensional organic-inorganic hybrid carbon material and a method of manufacturing the same, and more particularly, to an electrically conductive three-dimensional organic-inorganic hybrid carbon material having a maximized specific surface area and a method of manufacturing the same.

Carbon materials such as graphene, fullerene or carbon nanotubes have excellent physical properties and thus can be applied to a wide range of fields such as photovoltaic cells, field emission devices (FEDs), capacitors or batteries, Is progressing actively.

As a method for synthesizing carbon nanotubes among carbon materials, a metal oxide / metal catalyst carrier is prepared by supporting a transition metal (Fe, Co, or Ni) on a metal oxide support (Al 2 O 3 or MgO) There is a method of synthesizing by exposing / reacting to a high temperature carbon source. When carbon nanotubes are synthesized in this manner, carbon nanotubes having a yield of 500% or more can be obtained.

However, in the case of synthesized carbon nanotubes, the metal oxide itself used as a support for supporting the metal catalyst acts as an inorganic impurity, thereby deteriorating the purity of the carbon nanotubes. Accordingly, a complex purification process for removing inorganic impurities may be required. Therefore, synthesis of carbon nanotubes with a high yield while minimizing the amount of unnecessary metal oxide is advantageous for various applications of carbon nanotubes in the future.

If the support supporting the transition metal is replaced with a carbon material different from the carbon nanotubes which are not metal oxides, the purity of the synthesized carbon nanotubes can be improved . In addition, since the support itself is an electrically conductive and thermally conductive material, it may function as a conductive filler rather than an impurity, even if a support is detached from the carbon nanotube.

However, it is very unstable in terms of reproducibility and reliability to uniformly support the transition metal in a carbon material having low reactivity. Carbon nanotubes have been synthesized by surface treatment of carbon materials. Carbon nanotubes have been surface-treated by surface treatment using a functional group introduction by chemical treatment, introduction of an organic buffer layer or plating, A transition metal precursor such as ferrocene has been applied at high temperature by directly depositing the carbon precursor on a carbon material through a physical adsorption method.

This surface-treated carbon material was effective in the impurity problem, but there is a problem in synthesizing carbon nanotubes having a high yield on a carbon material because the yield of the carbon nanotubes after synthesizing the carbon nanotubes is less than 100% of the initial catalyst carrier mass there was.

On the other hand, the carbon material having a high specific surface area in the energy storage and catalyst fields has excellent characteristics in terms of output and reaction speed because of easy contact and accessibility with the surrounding medium. However, attempts have been made to composite various carbon-based materials in order to obtain the desired properties. In this case, phase separation and coagulation phenomena occur in the medium due to the difference in density, and thus the excellent specific surface properties of the one- The problem also occurred.

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and an object of the present invention is to provide an electrically conductive three-dimensional organic-inorganic hybrid carbon material having a maximized specific surface area and a method for manufacturing the same.

In order to achieve the above object, a three-dimensional organic / inorganic hybrid carbon material according to one aspect of the present invention is a three-dimensional organic / inorganic hybrid carbon material formed by placing a one-dimensional carbon material on a two-dimensional carbon material, A metal oxide layer is formed.

The porous metal oxide layer may be formed on the entire surface of the one-dimensional carbon material. Alternatively, the porous metal oxide layer may be formed in the form of a cylindrical micelle on the surface of the one-dimensional carbon material.

The porous metal oxide layer may include SiO 2, TiO 2, MgO, RuO 2, MnO 2, at least one of Co 3 O 4, and NiO.

The one-dimensional carbon material may be a carbon nanotube, and the two-dimensional carbon material may be any one selected from graphene, oxide graphene, reduced graphene oxide, graphene nanoplate, graphite and expanded graphite.

According to another aspect of the present invention, there is provided a three-dimensional organic / inorganic hybrid carbon material formed by placing a one-dimensional carbon material on a two-dimensional carbon material, wherein the one-dimensional carbon material comprises a three-dimensional organic / inorganic hybrid carbon material having a porous metal oxide layer formed on its surface A lithium ion battery is provided.

According to another aspect of the present invention, there is provided a method of manufacturing a carbon material, comprising: forming a one-dimensional carbon material growth support on a two-dimensional carbon material; Supporting a one-dimensional carbon material growth catalyst on a one-dimensional carbon material growth lag; Growing a one-dimensional carbon material on a one-dimensional carbon material growth support supporting a growth catalyst of a one-dimensional carbon material to produce a three-dimensional carbon material; And forming a porous metal oxide layer on the surface of the three-dimensional carbon material.

The step of forming the porous metal oxide layer includes: forming a polymer layer on the surface of the three-dimensional carbon material; Forming a metal oxide layer on the polymer layer; And removing all or a part of the polymer of the polymer layer to form a pore.

According to the method for manufacturing a three-dimensional organic / inorganic hybrid carbon material according to an embodiment of the present invention, a support for synthesizing carbon nanotubes can be replaced with a carbon material having the same component as that of a conventional metal oxide to reduce the amount of inorganic impurities in the carbon nanotube, And high-yield carbon nanotubes can be synthesized on a carbon material, thereby enabling commercial mass production.

In addition, since the carbon support itself includes an electrically conductive and thermally conductive carbon material, the carbon nanotube can be used as a hybrid carbon nanotube composite without separating the carbon nanotube from the carbon support even after the carbon nanotube is grown. It is not necessarily required and the performance can be further improved.

In addition, various carbon materials having different dimensions can be applied in various fields that exhibit electrical conductivity while having high specific surface area characteristics, while being homogeneously hybridized with functional inorganic material while maintaining dispersibility without phase separation and aggregation in the medium. In addition, since the functional inorganic material hybridized with the carbonaceous material has a microporous structure including micro- and nano-sized pores, it is possible to maximize the specific surface area and to suppress the volume change in the reaction accompanied by the volume expansion of the inorganic material, Is improved.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view for explaining a three-dimensional carbon material of a three-dimensional organic / inorganic hybrid carbon material according to an embodiment of the present invention.
FIG. 2 is a view showing a three-dimensional organic / inorganic hybrid carbon material having a porous metal oxide layer formed on the three-dimensional carbon material produced in FIG.
Figs. 3A and 3B are a SEM image (10.0 mu m) of a three-dimensional carbon material produced according to the embodiment and an enlarged image thereof (500 nm), respectively.
4A and 4B are a SEM image (10.0 mu m) and an enlarged image (500 nm) of a three-dimensional carbon material having a metal oxide layer formed according to an embodiment, respectively.
5 shows the result of EDX analysis of the surface of the three-dimensional carbon material having the metal oxide layer formed thereon.
6 is a result of XRD analysis of the surface of the three-dimensional carbon material having the metal oxide layer formed thereon.
7A and 7B are a TEM image (50 nm) and an enlarged image thereof (10 nm) of a three-dimensional carbon material in which the metal oxide layer is formed to a thickness of 3 nm.
8A and 8B are a TEM image (50 nm) and an enlarged image (10 nm) of a three-dimensional carbon material in which the metal oxide layer is formed to a thickness of 7 nm, respectively.
9A and 9B are a TEM image (50 nm) and an enlarged image (10 nm) of a three-dimensional carbon material in which the metal oxide layer is formed to a thickness of 16 nm.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. However, the embodiments of the present invention can be modified into various other forms, and the scope of the present invention is not limited to the embodiments described below. The embodiments of the present invention are provided to enable those skilled in the art to more fully understand the present invention. It should be understood that while the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, The present invention is not limited thereto.

FIG. 1 is a view for explaining a three-dimensional carbon material of a three-dimensional organic / inorganic hybrid carbon material according to an embodiment of the present invention. FIG. 2 is a cross-sectional view of a three- Hybrid carbon material.

The three-dimensional organic / inorganic hybrid carbon material according to the present invention is a three-dimensional organic / inorganic hybrid carbon material formed by placing a one-dimensional carbon material on a two-dimensional carbon material, and a porous metal oxide layer is formed on the surface of the three-dimensional carbon material. The three-dimensional organic / inorganic hybrid carbon material according to the present invention can be produced by hybridizing a porous metal oxide on a surface of a three-dimensional carbon material having excellent electrical conductivity and a large specific surface area in a thin film form, Can be used as a high specific surface area material.

According to the present invention, there is also provided a method of manufacturing a carbon material, comprising: forming a one-dimensional carbon material growth support on a two-dimensional carbon material; Supporting a one-dimensional carbon material growth catalyst on a one-dimensional carbon material growth lag; Growing a one-dimensional carbon material on a growth support of a one-dimensional carbon material carrying a growth catalyst of a one-dimensional carbon material; And forming a porous metal oxide layer on the surface of the three-dimensional carbon material. Hereinafter, a three-dimensional organic-inorganic hybrid carbon material according to the present invention and a method for producing the same will be described.

The three-dimensional organic-inorganic hybrid carbon material according to the present invention is a three-dimensional carbon material formed by hybridizing a two-dimensional carbon material and a one-dimensional carbon material, and has a porous metal oxide layer formed on its surface. Such a three-dimensional organic-inorganic hybrid carbon material can be obtained, for example, by first preparing a three-dimensional carbon material and forming a porous metal oxide thin film on the surface of the three-dimensional carbon material.

The three-dimensional organic / inorganic hybrid carbon material may be formed by synthesizing a one-dimensional carbon material on a two-dimensional carbon material to form a three-dimensional structure, forming a metal oxide thin film on the surface, and then imparting porosity to the metal oxide thin film.

For example, referring to FIG. 1, a three-dimensional organic-inorganic hybrid carbon material may be obtained by forming a one-dimensional carbon material growth support body 120 on a two-dimensional carbon material 110 and growing a one-dimensional carbon material growth material 120 on the one- Dimensional carbon material 150 may be obtained by growing a one-dimensional carbon material 140 on the one-dimensional carbon material growth support 120 on which the one-dimensional carbon material growing catalyst 130 is carried.

In order to produce a three-dimensional carbon material having a one-dimensional carbon material formed on a two-dimensional carbon material according to the present invention, a two-dimensional carbon material (110) is used as a support for growth of the one-dimensional carbon material. Examples of the carbon-based material include carbon isotopes such as graphene and graphite. Specifically, two-dimensional carbon materials such as graphene, oxide graphene, graphene nanoplate, graphite, or expanded graphite can be exemplified .

On the two-dimensional carbon material 110, a one-dimensional carbon material growth support 120 for growing a one-dimensional carbon material is formed. The one-dimensional carbon material growth supporting member 120 is for supporting a catalyst that is a seed of a one-dimensional carbon material. Usually, a metal catalyst is used as a catalyst. In order to support such a metal catalyst, Metal oxides may be used. The one-dimensional carbon material 140 is obtained by separating the one-dimensional carbon material 140 after the one-dimensional carbon material 140 is supported by supporting the catalyst on the metal oxide itself. However, A metal oxide having low electrical conductivity or low thermal conductivity remains and can act as an inorganic impurity.

Accordingly, in the present invention, a support is formed of the same carbon material as the one-dimensional carbon material 140 without using a metal oxide as a support, a metal oxide layer is formed on the surface of the two-dimensional carbon material 110, A one-dimensional carbon material 140 is grown.

The one-dimensional carbon material growth supporting member 120 can be formed, for example, by coating a metal oxide thin film on the two-dimensional carbon material 110 using a hydrolysis reaction.

The metal oxide used as the one-dimensional carbon material growth supporting member 120 may be selected from Al 2 O 3 , MgO, SiO 2 , CaO, ZrO 2 and CaCO 3. What is the porous metal oxide capable of supporting the metal catalyst Can also be used. Since the purity of the one-dimensional carbon material 140 produced according to the residual metal oxide may be lowered, it is preferable that the metal oxide is contained in the entire process as small as possible, but the metal oxide should be sufficiently supported. Therefore, a metal oxide thin film layer may be formed on the surface of the two-dimensional carbon material 110 to maximize the area required for growth of the one-dimensional carbon material 140 and minimize the amount of the metal oxide.

The one-dimensional carbon material growth catalyst 130 may be a metal catalyst. The transition metal may be a single metal such as Fe, Mo, Ti, V, Cr, Mn, Ni, Co, Cu, Cd, Zn, Ru, Pd, Ag, Pt and Au, have. The one-dimensional carbon material growth catalyst 130 can be used in consideration of the obtained amount of the one-dimensional carbon material 140 to be produced. When the amount of the metal catalyst carried on the one-dimensional carbon material growth promoter 120 is adjusted, 140 can also be controlled.

The one-dimensional carbon material 140 is grown on the one-dimensional carbon material growth catalyst 130 carried by the one-dimensional carbon material growth promoter 120. The one-dimensional carbon material 140 may be carbon nanotubes. The shape of the one-dimensional carbon material 140 to be manufactured is not limited. For example, a shape of the single-wall carbon nanotube, a functionalized single wall carbon nanotube, a double wall carbon nanotube, a functionalized double wall carbon nanotube, Or functionalized multi-walled carbon nanotubes.

As a method of growing the one-dimensional carbon material 140, chemical vapor deposition (CVD) may be used. The chemical vapor deposition process can be performed by any one of a variety of chemical vapor deposition methods such as chemical vapor deposition (TCVD), rapid chemical vapor deposition (RTCVD), inductively coupled plasma chemical vapor deposition (ICP-CVD), low pressure chemical vapor deposition (LPCVD), atmospheric pressure chemical vapor deposition Vapor deposition (MOCVD), or plasma chemical vapor deposition (PECVD).

In order to grow the one-dimensional carbon material 140, a carbon support carrying the one-dimensional carbon material growth catalyst 130 is introduced into the growth reactor, the temperature of the reactor is increased to a predetermined temperature, and then a carbon source The one-dimensional carbon material 140 can be grown by flowing the reactive gas. At this time, it is possible to control the diameter or length of the one-dimensional carbon material 140 by controlling the pressure of the reactor or the flow rate of the reactive gas. The carbon source may be an aliphatic hydrocarbon or an aromatic hydrocarbon. Examples of such carbon sources include, but are not limited to, methane, ethane, propane, butane, ethylene, acetylene, and benzene.

Since the two-dimensional carbon material 110 is also a carbon-based material, it exhibits properties such as thermal conductivity and electrical conductivity similar to the one-dimensional carbon material 140. Therefore, the two-dimensional carbon material 110 can be used as one three-dimensional carbon material without a separate purification process.

Unlike the above-described method, the three-dimensional carbon material used in the three-dimensional organic-inorganic hybrid carbon material according to the present invention may be a one-dimensional carbon material directly grown on the two-dimensional carbon material. In this case, the step of forming the one-dimensional carbon material growth lag among the above-described methods may be performed except for the step of forming the one-dimensional carbon material growth lag. However, since the reactivity of the support two-dimensional carbon material is low, it is difficult to support the growth catalyst and the yield is low. However, the three-dimensional carbon material is formed of only pure carbon material and has an advantage of exhibiting high electrical conductivity.

These three-dimensional carbon materials exhibit high electrical conductivity and can be used in a wide range of fields such as solar cells, field emission devices (FEDs), capacitors, batteries, fillers for composites, or electrode materials. In addition, since the carbon nanotube composite has a very large specific surface area, it can exhibit high physical properties even when a small amount is added to other composite materials.

The three-dimensional organic-inorganic hybrid carbon material according to the present invention is a carbon material in which a porous metal oxide layer is formed on the surface of the above-mentioned three-dimensional carbon material. Referring to FIG. 2, a porous metal oxide layer 160 is formed on the surface of a three-dimensional carbon material 140 formed on a two-dimensional carbon material 110 to obtain a three-dimensional organic / inorganic hybrid material 170 .

The three-dimensional organic / inorganic hybrid carbon material 170 is excellent in dispersibility so that the three-dimensional carbon material 150 has a large specific surface area and does not cause a problem of phase separation of individual materials due to density difference, Including the layer 160, because of the micro and nano-sized pores due to the porous structure, the specific surface area is higher than that of the three-dimensional carbon material and can exhibit more excellent characteristics.

The step of forming the porous metal oxide layer 160 on the three-dimensional carbon material 150 includes the steps of: forming a polymer layer on the surface of the three-dimensional carbon material; Forming a metal oxide layer on the polymer layer; And removing all or a part of the polymer of the polymer layer to form a pore.

The porous metal oxide layer may be formed on the entire surface of the three-dimensional carbon material. Alternatively, the porous metal oxide layer may be formed over the entire surface of the one-dimensional carbon material of the three-dimensional carbon material. In particular, the porous metal oxide layer may be formed in the form of a cylindrical micelle on the surface of the one-dimensional carbon material. That is, the porous metal oxide layer is formed on the surface of the one-dimensional carbon material. When the one-dimensional carbon material is the same as the long-type structure such as the carbon nanotube, the porous metal oxide layer is formed so as to surround the outside of the one- So that the total specific surface area of the three-dimensional carbon material is increased. On the other hand, if the porous metal oxide layer is formed flat while covering the entire surface of the three-dimensional carbon material, the specific surface area of the porous metal oxide layer becomes smaller than that of the one-dimensional carbon material when the porous metal oxide layer is formed in a cylindrical shape.

The metal oxide used for the porous metal oxide layer is not particularly limited, but it is preferably a metal oxide which can be formed as a thin film on the surface of a three-dimensional carbon material, particularly a one-dimensional carbon material, and is capable of forming a porous structure. For example, the porous metal oxide layer may include at least one of SiO 2 , TiO 2 , MgO, RuO 2 , MnO 2 , Co 3 O 4 , and NiO, but is not limited thereto. In particular, it is more preferable that the metal oxide used for the porous metal oxide layer is a metal oxide which can be formed into a cylindrical micellar shape while surrounding the surface of the one-dimensional carbon material as described above.

The method of forming the porous metal oxide layer in a cylindrical micellar form on the surface of the one-dimensional carbon material can be carried out, for example, in the following manner. For example, if SiO 2 is formed as a metal oxide, the surface of the three-dimensional carbon material is coated with a positively charged CTAB by using a surfactant such as hexadecyltrimethylammonium bromide (CTAB) ) Can be made. When tetraethyl orthosilicate (TEOS), which is a metal oxide source, is added, negatively charged TEOS reacts with CTAB by electrostatic attraction and reacts on the surface of the three-dimensional carbon material as follows.

[Reaction Scheme 1]

Si (OC 2 H 5) 4 + 2H 2 O → SiO 2 + 4C 2 H 5 OH

In this case, since the CTAB surrounds the surface of the three-dimensional carbon material, and particularly, it surrounds the surface of the one-dimensional carbon material, the resulting SiO 2 layer is formed into a cylindrical micelle shape. Especially, when the reaction is carried out in a basic solution such as NH 4 OH, a positive charge CTAB and a negative charge of TEOS react with each other to obtain a micellar SiO 2 layer.

Thereafter, if a high temperature is applied to the three-dimensional carbon material having the metal oxide layer formed thereon, the organic substance CTAB is removed, and the position of the CTAB is formed as a pore, so that the porous SiO 2 thin film can be formed. Accordingly, a three-dimensional organic / inorganic hybrid carbon material including a cylindrical porous metal oxide layer surrounding the surface of the one-dimensional carbon material can be obtained.

According to another aspect of the present invention, there is provided a three-dimensional organic / inorganic hybrid carbon material formed by placing a one-dimensional carbon material on a two-dimensional carbon material, wherein the one-dimensional carbon material comprises a three-dimensional organic / inorganic hybrid carbon material having a porous metal oxide layer formed on its surface A lithium ion battery is provided.

The three-dimensional organic / inorganic hybrid carbon material of the present invention can be used for an electrode of an energy reservoir. Electrode material is one of the most important factors that determine performance in energy storage devices. Conventionally, activated carbon or graphite has been used as an electrode in an energy storage device. However, there are micropores which are difficult to adsorb and desorb in activated carbon, and there is a limit in specific surface area. To improve this, carbon nanotubes or two- And the like have been proposed.

In the case of graphene, which is a two-dimensional carbon material, it has a very high specific surface area (2,630 m 2 / g), a high thermal conductivity and a high electric conductivity, so that theoretically, a very high capacitor capacity can be obtained. That is, graphene has a large specific surface area, and a large amount of ions can be adsorbed and desorbed on the active layer, and since the electrical conductivity is high, the resistance of the electrode is low, so it is effective to move the charge. However, when the carbon material based on the graphene material is applied, unlike the theoretical value, there are problems in application to manufacturing of actual products.

This is due to the uniaxial orientation characteristic of the graphene material, which causes problems such as electrode bias, handleability of materials, and adherence of materials during electrode production. That is, due to the characteristics of graphene, when electrodes are formed, they are mixed with a binder or other additive, applied to a current collector, and laminated when stacked. As a result, the graphenes are stacked in one direction to exhibit bias, and the specific surface area of the surface is not as high as the theoretical value.

However, in the case of the three-dimensional carbon material of the present invention, a one-dimensional carbon material such as a carbon nanotube is randomly oriented on a two-dimensional carbon material such as graphene. Therefore, when the electrode is formed by mixing with a binder or the like to prevent lamination at the time of forming an electrode, the specific surface area becomes close to the theoretical value, and accordingly, it has a high energy density. In addition, since the metal oxide layer having a porous structure is included on the surface, the lithium ion and the like can be easily adsorbed and desorbed with a wider specific surface area, and high efficiency can be obtained.

The energy reservoir in which the three-dimensional organic / inorganic hybrid carbon material of the present invention can be used is an element affected by the specific surface area of the electrode. The energy reservoir may be any one of a lithium ion battery, an electric double layer capacitor, a pseudo capacitor, and a hybrid capacitor.

A lithium ion battery is a secondary battery in which an organic electrolyte is interposed between a cathode (lithium cobalt oxide) and a cathode (carbon) to repeat charging and discharging through the movement of lithium ions. The three-dimensional organic / inorganic hybrid carbon material according to the present invention has high reaction speed and high energy density due to high contact and accessibility of lithium ions and the like due to its large specific surface area and porous structure. In addition, the porous structure of the metal oxide layer, which is a functional inorganic material thin-coated on the three-dimensional carbon material, can suppress the volume change in the reaction accompanied by the volume expansion, thereby improving the durability of the lithium ion battery, have.

For example, a cathode material is mainly used as a cathode material of a lithium ion battery, and a lithium material having a theoretical capacity of 372 mAh / g is relatively low. Therefore, when hybridizing a metal oxide (> 3700 mAh / g) which is relatively easy to manufacture while having a relatively large lithium storage capacity in a carbon material having a larger lithium storage capacity than a graphite based material, the carbon nano- The effect of increasing the storage capacity of lithium can be obtained. In addition, when the porous structure is provided, the structure breakdown of the electrode material due to the volumetric expansion phenomenon occurring in the process of inserting and discharging lithium ions (charge / discharge process) is suppressed, thereby improving the cycle performance of the battery.

Hereinafter, specific test examples of the present invention will be described. However, the following test examples do not limit the present invention.

A method for manufacturing a three-dimensional organic-inorganic hybrid carbon material according to an embodiment of the present invention includes

(1) a three-dimensional carbon material manufacturing step and

(2) forming a porous metal oxide layer.

[Production of three-dimensional carbon material]

A solution of magnesium methoxide (Mg (OCH 3 ) 2 ) diluted to 6-8% in methanol was uniformly mixed with a graphene nanoplate in a plate at a mass ratio of 18: 1, and water was added to the mixed solution Slowly introduce the following hydrolysis reaction.

Mg (OCH 3) 2 + H 2 O → Mg (OH) (OCH 3) + CH 3 OH,

Mg (OH) (OCH 3) + H 2 O → Mg (OH) 2 + CH 3 OH

Mg (OH) 2 is uniformly coated on the surface of the graphene nanoplate by the hydrolysis reaction. The solvent of the reaction solution is selectively removed by using a rotary condenser, and finally the surface is treated with Mg (OH) 2 To obtain graphene nanoplate powder.

The graphene nanoparticle powder surface treated with Mg (OH) 2 was ultrasonically dispersed in water, and then ammonium molybdate tetrahydrate (NH 3 ) 6 Mo 7 O 24 .4H 2 O), iron nitrate (Fe (NO 3 ) 3 .9H 2 O), and polyethylene glycol (PEG) were successively mixed and homogeneously mixed for 1 hour under stirring on a hot plate at 110 ° C. The homogeneous mixed solution was transferred to an alumina boat, and water and methanol as a solvent were removed from the hot plate at 150 ° C., followed by heat treatment in a high temperature drying furnace at 650 ° C. for 10 minutes. Finally, (Fe-Mo) is supported on the carbon material / metal catalyst carrier.

The prepared carbon material / metal catalyst carrier is reacted with a carbon source in a high temperature quartz tube through thermal chemical vapor deposition (thermal CVD). That is, after annealing for 40 minutes in an atmosphere of Ar (500 sccm) at 900 ° C., carbon nanotubes were synthesized for 60 to 180 minutes under a CH 4 / H 2 mixed gas (500 sccm / 25 sccm) To form a hybridized three-dimensional carbon material.

Figs. 3A and 3B are a SEM image of the surface (10.0 mu m) and an enlarged image thereof (500 nm) of the three-dimensional carbon material. In FIG. 3A, a carbon nanotube having a carbon nanotube formed on a graphene nanoplate can be identified. In FIG. 3B, a carbon nanotube can be confirmed by enlarging the surface.

[Formation of Porous Metal Oxide Layer]

First, a metal oxide layer is formed on the prepared three-dimensional carbon material. The above-prepared three-dimensional carbon material (0.3 wt%) was added to an aqueous solution (3 wt%) of hexadecyltrimethylammonium bromide (CTAB), and the mixture was homogeneously mixed to uniformly coat the surface of the 3D carbon material with CTAB ). When a small amount of ethanol and ammonia water (NH 4 OH) is added and tetraethyl orthosilicate (TEOS) is added to the thickness of the thin film to be coated, a SiO 2 layer is formed on the surface of the carbon nanotube do.

After 12 hours of reaction, unreacted TEOS residues are washed with water to finally obtain a three-dimensional carbonaceous material-SiO 2 hybrid material coated with SiO 2 on the surface of the three-dimensional carbon nanostructure, in particular, on the surface of the carbon nanotube. 4A and 4B are a SEM image (10.0 mu m) and an enlarged image thereof (500 nm) of a three-dimensional carbon material on which the metal oxide layer is formed. In FIG. 4B, the surface of the carbon nanotube was enlarged to confirm the SiO 2 layer surrounding the carbon nanotube. 5 shows the result of EDX analysis of the surface of the three-dimensional carbon material having the metal oxide layer formed thereon. In FIG. 5, it was confirmed through EDX analysis that the surface of the three-dimensional carbon material was coated with SiO 2 . FIG. 6 is a result of XRD analysis of the surface of the three-dimensional carbon material having the metal oxide layer. It was confirmed by XRD analysis that amorphous SiO 2 was formed on the surface of the three-dimensional carbon material.

Removing the three-dimensional carbon material having a metal oxide, SiO 2 thin film on the surface of a three-dimensional carbon material -SiO 2 hybrid material CTAB organic material by sintering at high temperature more than 400 ℃, public (cavity) it is formed on the porous SiO 2 film on the spot CTAB . Accordingly, a three-dimensional organic / inorganic hybrid carbon material including a porous metal oxide layer having pores formed in the metal oxide layer can be obtained.

7A and 7B are a TEM image (50 nm) and an enlarged image (10 nm) of a three-dimensional carbon material in which the metal oxide layer is formed to a thickness of 3 nm, and FIGS. 8A and 8B, respectively, (50 nm) and an enlarged image thereof (10 nm) of a three-dimensional carbon material formed from a three-dimensional carbon material, and FIGS. 9A and 9B are TEM images (50 nm) (10 nm). In the above-mentioned process, the amount of TEOS was adjusted to adjust the thickness of the metal oxide layer to 3 nm, 7 nm, and 16 nm, respectively, to prepare a three-dimensional organic / inorganic hybrid carbon material, and TEM images thereof were obtained. The results of the BET analysis of such a three-dimensional organic / inorganic hybrid carbon material are as follows. In addition, the specific surface area in the case of using only a graphene nanoplate (GNP) and the case of using GNP and CNT together were also measured and shown as a result.

Sample CNT Diameter (nm) Thickness of SiO 2 Thin Film (nm) Specific surface area (m 2 / g) GNP - - 86.7 GNP-CNT 23 - 150.8 GNP-CNT-SiO 2 30 3 210.4 GNP-CNT-SiO 2 40 7 691.3 GNP-CNT-SiO 2 49 16 780.8

In Table 1, it can be seen that the three-dimensional carbon material hybridized with carbon nanotubes, which are one-dimensional carbon materials, had an effect of increasing the specific surface area by about twice as compared with the case of using only two-dimensional carbon materials, GNP. In addition, when the porous SiO 2 layer is formed, the specific surface area is higher, and as the thickness of the thin film is increased, the specific surface area is further increased. The specific surface area was increased to about 10 when the SiO 2 layer was thicker than 16 nm in the case of GNP alone, and it was found that a high specific surface area could be obtained due to the porous structure of the metal oxide layer.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, many modifications and changes may be made by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims. The present invention can be variously modified and changed by those skilled in the art, and it is also within the scope of the present invention.

110 Two-dimensional carbon material
120 One-Dimensional Carbon Material Growth Delay
130-dimensional carbon material growth catalyst
140 one-dimensional carbon material
150 three-dimensional carbon material
160 Porous metal oxide layer
170 Three-dimensional organic / inorganic hybrid carbon material

Claims (8)

Dimensional carbon material formed by placing a one-dimensional carbon material on a two-dimensional carbon material, wherein the three-dimensional carbon material has a porous metal oxide layer formed on a surface thereof.
The method according to claim 1,
Wherein the porous metal oxide layer is formed on the entire surface of the one-dimensional carbon material.
The method according to claim 1,
Wherein the porous metal oxide layer is formed on the surface of the one-dimensional carbon material in the form of a cylindrical micelle.
The method according to claim 1,
The porous metal oxide layers are SiO 2, TiO 2, MgO, RuO 2, MnO 2, Co 3 O 4, and at least one of a three-dimensional inorganic hybrid carbon material of NiO.
The method according to claim 1,
Wherein the one-dimensional carbon material is a carbon nanotube.
The method according to claim 1,
Wherein the two-dimensional carbon material is any one selected from graphene, oxide graphene, reduced graphene oxide, graphene nanoplate, graphite and expanded graphite.
Forming a one-dimensional carbon material growth lag on the two-dimensional carbon material;
Supporting a one-dimensional carbon material growth catalyst on the one-dimensional carbon material growth supporting member;
Growing the one-dimensional carbon material on the one-dimensional carbon material growth support having the one-dimensional carbon material growth catalyst carried thereon to produce a three-dimensional carbon material; And
And forming a porous metal oxide layer on the surface of the three-dimensional carbon material.
The method of claim 7,
Wherein forming the porous metal oxide layer comprises:
Forming a polymer layer on a surface of the three-dimensional carbon material;
Forming a metal oxide layer on the polymer layer; And
And removing the entire polymer or part of the polymer layer to form a pore.
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KR101470830B1 (en) 2013-11-01 2014-12-17 한국에너지기술연구원 Fabrication method of three-dimensional carbon structure and the structure thereof
WO2015069227A1 (en) 2013-11-05 2015-05-14 The Regents Of The University Of California Metal-oxide anchored graphene and carbon-nanotube hybrid foam

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KR101470830B1 (en) 2013-11-01 2014-12-17 한국에너지기술연구원 Fabrication method of three-dimensional carbon structure and the structure thereof
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