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WO2015050352A1 - Method for preparing carbon nanotube-graphene composite, and carbon nanotube-graphene composite prepared thereby - Google Patents

Method for preparing carbon nanotube-graphene composite, and carbon nanotube-graphene composite prepared thereby Download PDF

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Publication number
WO2015050352A1
WO2015050352A1 PCT/KR2014/009154 KR2014009154W WO2015050352A1 WO 2015050352 A1 WO2015050352 A1 WO 2015050352A1 KR 2014009154 W KR2014009154 W KR 2014009154W WO 2015050352 A1 WO2015050352 A1 WO 2015050352A1
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carbon nanotube
graphene
graphene composite
mixture
oxide
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French (fr)
Korean (ko)
Inventor
윤동명
권순근
권지민
김민석
박영민
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Corning Precision Materials Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/10—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing sonic or ultrasonic vibrations
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • C01B32/162—Preparation characterised by catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/34—Length
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
    • H01M4/8673—Electrically conductive fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a method for producing a carbon nanotube-graphene composite and a carbon nanotube-graphene composite prepared by the present invention. More specifically, the carbon nanotubes are in a direction perpendicular to the graphene flakes having excellent electrical conductivity. By controlling the structure that is connected, that is, the carbon nanotubes stand up from the surface of the graphene flakes on the plane, carbon nanotubes that can produce a carbon nanotube-graphene composite having excellent electrical conductivity and electron mobility The present invention relates to a graphene composite production method and a carbon nanotube-graphene composite prepared thereby.
  • electrode materials of an energy storage medium such as an electric double layer capacitor and a fuel cell exhibit excellent characteristics when the passage of electrolyte ions is secured and the area (effective specific surface area) that can be adsorbed on the surface is wide.
  • the electrode material has excellent electrical conductivity, the capacitance characteristic is improved.
  • materials having high electrical conductivity such as carbon black were mixed and used as electrode materials.
  • graphene and carbon nanotubes are spotlighted as materials having excellent electrical conductivity and a large specific surface area of 100 times or more of copper.
  • an electrode material of an energy storage medium when the nano-materials such as graphene and carbon nanotubes are structured, not only a pore structure in which electrolyte ions can be easily moved, but also excellent electrical conductivity is used. The movement of is smooth, and the capacity characteristic can be maximized.
  • a carbon nanotube-graphene composite was prepared as an electrode material of an energy storage medium.
  • the direction in which the carbon nanotubes are formed on the graphene does not coincide with the direction in which the electrons move in the carbon nanotubes. .
  • an object of the present invention is a structure in which the carbon nanotubes are connected in a direction perpendicular to the graphene flakes in a direction excellent in electrical conductivity, that is, carbon Method of manufacturing a carbon nanotube-graphene composite that can produce a carbon nanotube-graphene composite having excellent electrical conductivity and electron mobility by controlling the nanotubes to stand up from the surface of the graphene flake on the plane and It is to provide a carbon nanotube-graphene composite prepared thereby.
  • the carbon nanotubes from the catalyst is distributed on the surface of the graphene oxide reduced in the mixture preparation step and the mixture heat-treatment step to prepare a mixture of graphene oxide and catalyst, the mixture manufacturing step It provides a carbon nanotube-graphene composite manufacturing method comprising a heat treatment step of forming a mixture.
  • the mixture may be heat treated at 600 ⁇ 900 °C.
  • the mixture heat treatment step may be performed in an inert atmosphere.
  • the mixture manufacturing step may further comprise a graphene oxide manufacturing step for producing the graphene oxide.
  • the graphene oxide manufacturing step may include a first process of acid-processing graphite to form graphite oxide, and a second process of layer-separating the graphene oxide from the graphite oxide.
  • the liquid phase ultrasonic treatment may be performed after adding the graphite oxide to the solvent.
  • the catalyst may be stirred in an aqueous solution containing the graphene oxide.
  • the catalyst in the step of preparing the mixture, may be dissolved in a solvent and then added to the aqueous solution.
  • the aqueous solution may be filtered and dried after the stirring.
  • the carbon nanotube-graphene composite may be acid treated and dried.
  • the carbon nanotubes may be formed to form a standing structure from the surface of the reduced graphene oxide.
  • carbon nanotubes characterized in that it comprises a graphene flake made of reduced graphene oxide and at least one carbon nanotube formed to form a structure standing up from the surface of the graphene flake on the plane It provides a graphene complex.
  • the carbon nanotubes may be formed to a length of 1 ⁇ 100nm.
  • the graphene flakes and the carbon nanotubes may form a structure that is sequentially stacked repeatedly in one direction.
  • the carbon nanotubes are connected in a direction perpendicular to the graphene flakes in the direction of excellent electrical conductivity, that is, the carbon nanotubes to form a structure standing up from the surface of the graphene flakes on the plane,
  • a carbon nanotube-graphene composite having excellent electrical conductivity and electron mobility can be manufactured, and high capacity and high output of a fuel cell employing the same as an electrode material can be manufactured.
  • FIG. 1 is a process flow chart illustrating a method for producing a carbon nanotube-graphene composite according to an embodiment of the present invention.
  • Figure 2 is a schematic diagram showing a carbon nanotube-graphene composite prepared by the carbon nanotube-graphene composite manufacturing method according to an embodiment of the present invention.
  • 3 and 4 are photographs taken with a runner electron microscope by varying the magnification of the surface of the carbon nanotube-graphene composite prepared by the carbon nanotube-graphene composite manufacturing method according to an embodiment of the present invention.
  • Figure 5 is a schematic diagram showing a comparison between the carbon nanotube-graphene composite prepared according to the embodiment of the present invention and the carbon nanotube-graphene composite prepared according to the prior art.
  • carbon nanotubes used as the electrode material of the energy storage medium, such as electric double layer capacitor or fuel cell -Graphene composite 100 is a method for manufacturing.
  • the carbon nanotube-graphene composite manufacturing method includes a mixture preparation step (S1) and a mixture heat treatment step (S2).
  • the mixture preparation step (S1) is a step of preparing a mixture of graphene oxide (graphene oxide) and the catalyst.
  • hydrophilic graphene oxide is dispersed in water.
  • an organic solvent including a carbon source for example, benzene, toluene, acetone, or the like is not mixed.
  • the catalyst is added to this aqueous solution and stirred.
  • the catalyst is dissolved in a solvent such as water and then added to an aqueous solution in which graphene oxide is dispersed.
  • iron oxide (Fe (III)) may be used as a catalyst that serves as a seed for carbon nanotube (CNT) growth. Accordingly, in the mixture preparation step (S1), for example, iron oxide (Fe (III)) may be dissolved in water at a concentration of 10 ⁇ M.
  • the hydroxylamine (hydroxylamine) as a reducing agent may also be dissolved together with iron oxide (Fe (III)) and added to an aqueous solution in which graphene oxide is dispersed. .
  • the hydroxylamine may be dissolved at 400 ⁇ M and then added to the aqueous solution in which graphene oxide is dispersed together with the iron oxide (Fe (III)) solution having a concentration of 10 ⁇ M.
  • the mixture preparation step (S1) in order to evenly disperse the iron oxide (Fe (III)) catalyst added to the aqueous solution in which graphene oxide is dispersed, it may be stirred using ultrasonic waves. Then, in the mixture preparation step (S1), the stirred aqueous solution is filtered to remove water from the mixture, and then dried through an oven, which is preferably dried in an oven maintained at 80 ° C. for about 1 hour.
  • the stirred aqueous solution is filtered to remove water from the mixture, and then dried through an oven, which is preferably dried in an oven maintained at 80 ° C. for about 1 hour.
  • the carbon nanotube-graphene composite manufacturing method may further comprise a graphene oxide manufacturing step for producing graphene oxide before the mixture preparation step (S1).
  • a graphene oxide manufacturing step graphite is first subjected to an acid treatment (Hummer's method) to produce graphite oxide having a hydroxyl group, an epoxide group, and a carboxyl group on the surface. Then, graphene oxide is obtained through layer separation from the produced graphite oxide.
  • the layer separation process may be performed by adding graphite oxide to distilled water, which is a solvent, at a concentration of approximately 0.1 g / L to 1 g / L, followed by liquid sonication.
  • a step of heat-treating the mixture is carried out.
  • the mixture heat treatment step (S2) without using a toxic gas such as carbonized gas such as methane or acetylene, and without using a special high-pressure device or electromagnetic waves, only heat in the mixture in an inert atmosphere Through the process of applying, to form the carbon nanotubes 120 of a short length on the surface of the graphene flakes (110). Accordingly, in the mixture heat treatment step (S2), for example, the mixture is heat treated at 600 to 900 ° C. in a firing furnace sufficiently flowed with nitrogen gas.
  • the produced carbon nanotube-graphene composite 100 can be acid treated and dried.
  • the carbon nanotube-graphene composite 100 may be immersed in a mild acid solution and dried at a temperature of 120 degrees or more.
  • FIG. 3 is an enlarged photo 10,000 times the surface of the prepared carbon nanotube-graphene composite
  • Figure 4 is an enlarged photo 50,000 times the surface of the prepared carbon nanotube-graphene composite.
  • FIG. 3 it can be seen that carbon nanotubes having a short length are formed on the surface of graphene oxide and are evenly distributed.
  • the material that appears evenly on the surface of graphene oxide, that is, the carbon nanotube is 100 nm or less It can be seen that it has a length of.
  • the carbon nanotube-graphene composite 100 prepared by the carbon nanotube-graphene composite manufacturing method according to the embodiment of the present invention is a graphene flake 110 made of reduced graphene oxide and It is formed to include at least one carbon nanotube 120 formed to form a structure standing up from the surface of the graphene flake 110 on the plane.
  • the graphene flakes 110 and the carbon nanotubes 120 form a stacked structure in order to repeat sequentially in one direction.
  • the carbon nanotubes 120 are formed to have a length (or height) of 1 to 100 nm from the surface of the graphene flakes 110.
  • the carbon nanotubes 120 form a structure standing up from the surface of the graphene flake 110 which is reduced graphene oxide, when the carbon nanotubes 120 are applied to the electrode material of the fuel cell, a space sufficient for the electrolyte ions to move is provided. It can be secured.
  • FIG. 5 is a schematic diagram showing a comparison between the carbon nanotube-graphene composite (a) and the carbon nanotube-graphene composite (b) according to the prior art prepared according to an embodiment of the present invention.
  • the carbon nanotubes 120 are formed in the graphene flakes 110 in the direction of carbon.
  • the nanotube 120 coincides with the direction in which the electrons move, that is, the carbon nanotubes 120 are connected to the graphene flakes 110, which are excellent in electrical conductivity, in a vertical direction, so that the movement of the electrons may be smooth.
  • the carbon nanotube-graphene composite (b) according to the prior art has a relatively excellent electrical properties compared to the carbon nanotube-graphene composite (b) according to the prior art.

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  • Organic Chemistry (AREA)
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Abstract

The present invention relates to a method for preparing a carbon nanotube-graphene composite, and a carbon nanotube-graphene composite prepared thereby, and more specifically, to a method for preparing a carbon nanotube-graphene composite, capable of preparing a carbon nanotube-graphene composite having remarkable electrical conductivity and electron mobility by controlling a structure, in which carbon nanotubes are connected in a direction vertical to graphene flakes which is the direction exhibiting remarkable electrical conductivity, that is, a structure in which the carbon nanotubes stand up from the surface of graphene flakes in the plane; and a carbon nanotube-graphene composite prepared thereby. To this end, the present invention provides a method for preparing a carbon nanotube-graphene composite and a carbon nanotube-graphene composite prepared thereby, the method comprising: a mixture preparation step of preparing a mixture of graphene oxide and a catalyst; and a mixture heat treatment step of forming carbon nanotubes from the catalyst distributed on the surface of the graphene oxide, which is reduced at the mixture preparation step.

Description

탄소나노튜브 그래핀 복합체 제조방법 및 이에 의해 제조된 탄소나노튜브 그래핀 복합체Carbon nanotube graphene composite manufacturing method and carbon nanotube graphene composite prepared by

본 발명은 탄소나노튜브-그래핀 복합체 제조방법 및 이에 의해 제조된 탄소나노튜브-그래핀 복합체에 관한 것으로서 더욱 상세하게는 탄소나노튜브가, 전기 전도도가 우수한 방향인 그래핀 플레이크에 수직한 방향으로 연결되는 구조, 즉, 탄소나노튜브가 평면 상의 그래핀 플레이크의 표면으로부터 기립된 구조를 이루도록 제어함으로써, 우수한 전기 전도도 및 전자 이동도를 갖는 탄소나노튜브-그래핀 복합체를 제조할 수 있는 탄소나노튜브-그래핀 복합체 제조방법 및 이에 의해 제조된 탄소나노튜브-그래핀 복합체에 관한 것이다.The present invention relates to a method for producing a carbon nanotube-graphene composite and a carbon nanotube-graphene composite prepared by the present invention. More specifically, the carbon nanotubes are in a direction perpendicular to the graphene flakes having excellent electrical conductivity. By controlling the structure that is connected, that is, the carbon nanotubes stand up from the surface of the graphene flakes on the plane, carbon nanotubes that can produce a carbon nanotube-graphene composite having excellent electrical conductivity and electron mobility The present invention relates to a graphene composite production method and a carbon nanotube-graphene composite prepared thereby.

일반적으로, 전기 이중층 커패시터와 연료전지 등과 같은 에너지 저장용 매체의 전극 소재는 전해질 이온의 이동 통로가 확보되고, 표면에 흡착할 수 있는 면적(유효 비표면적)이 넓으면 우수한 특성을 발현한다. 또한, 이러한 전극 소재는 전기 전도도가 우수할수록 용량 특성이 향상된다. 예를 들어, 종래에는 카본블랙 등 전기 전도도가 높은 물질을 혼합하여 전극 소재로 사용하였다.In general, electrode materials of an energy storage medium such as an electric double layer capacitor and a fuel cell exhibit excellent characteristics when the passage of electrolyte ions is secured and the area (effective specific surface area) that can be adsorbed on the surface is wide. In addition, as the electrode material has excellent electrical conductivity, the capacitance characteristic is improved. For example, in the past, materials having high electrical conductivity such as carbon black were mixed and used as electrode materials.

한편, 그래핀과 탄소나노튜브는 구리의 100배 이상의 우수한 전기 전도도와 큰 비표면적을 갖는 물질로 각광받고 있다. 에너지 저장용 매체의 전극 소재로 사용하기 위해, 이러한 그래핀과 탄소나노튜브 등과 같은 나노물질을 구조화할 경우, 전해액 이온의 이동이 용이한 기공구조를 확보할 수 있을 뿐만 아니라, 전기 전도도가 뛰어나 전자의 이동이 원활하여, 용량 특성이 극대화될 수 있다.On the other hand, graphene and carbon nanotubes are spotlighted as materials having excellent electrical conductivity and a large specific surface area of 100 times or more of copper. In order to use as an electrode material of an energy storage medium, when the nano-materials such as graphene and carbon nanotubes are structured, not only a pore structure in which electrolyte ions can be easily moved, but also excellent electrical conductivity is used. The movement of is smooth, and the capacity characteristic can be maximized.

이에 따라, 종래에는 에너지 저장용 매체의 전극 소재로 탄소나노튜브-그래핀 복합체를 제조하였다. 하지만, 종래의 탄소나노튜브-그래핀 복합체의 구조에서는 그래핀에 탄소나노튜브가 형성되어 있는 방향이 탄소나노튜브에서 전자가 이동하는 방향과 일치하지 않아, 전자의 이동이 원활하지 않은 문제점이 있었다.Accordingly, conventionally, a carbon nanotube-graphene composite was prepared as an electrode material of an energy storage medium. However, in the structure of the conventional carbon nanotube-graphene composite, the direction in which the carbon nanotubes are formed on the graphene does not coincide with the direction in which the electrons move in the carbon nanotubes. .

(선행기술문헌)(Prior art document)

일본 공개특허공보 제2012-199305호(2012.10.18.)Japanese Laid-Open Patent Publication No. 2012-199305 (2012.10.18.)

본 발명은 상술한 바와 같은 종래기술의 문제점을 해결하기 위해 안출된 것으로서, 본 발명의 목적은 탄소나노튜브가, 전기 전도도가 우수한 방향인 그래핀 플레이크에 수직한 방향으로 연결되는 구조, 즉, 탄소나노튜브가 평면 상의 그래핀 플레이크의 표면으로부터 기립된 구조를 이루도록 제어함으로써, 우수한 전기 전도도 및 전자 이동도를 갖는 탄소나노튜브-그래핀 복합체를 제조할 수 있는 탄소나노튜브-그래핀 복합체 제조방법 및 이에 의해 제조된 탄소나노튜브-그래핀 복합체를 제공하는 것이다.The present invention has been made to solve the problems of the prior art as described above, an object of the present invention is a structure in which the carbon nanotubes are connected in a direction perpendicular to the graphene flakes in a direction excellent in electrical conductivity, that is, carbon Method of manufacturing a carbon nanotube-graphene composite that can produce a carbon nanotube-graphene composite having excellent electrical conductivity and electron mobility by controlling the nanotubes to stand up from the surface of the graphene flake on the plane and It is to provide a carbon nanotube-graphene composite prepared thereby.

이를 위해, 본 발명은, 산화 그래핀과 촉매의 혼합물을 제조하는 혼합물 제조단계 및 상기 혼합물을 열처리하여, 상기 혼합물 제조단계 시 환원된 상기 산화 그래핀 표면에 분포되어 있는 상기 촉매로부터 탄소나노튜브를 형성시키는 혼합물 열처리단계를 포함하는 것을 특징으로 하는 탄소나노튜브-그래핀 복합체 제조방법을 제공한다.To this end, the present invention, the carbon nanotubes from the catalyst is distributed on the surface of the graphene oxide reduced in the mixture preparation step and the mixture heat-treatment step to prepare a mixture of graphene oxide and catalyst, the mixture manufacturing step It provides a carbon nanotube-graphene composite manufacturing method comprising a heat treatment step of forming a mixture.

여기서, 상기 혼합물 열처리단계에서는 상기 혼합물을 600~900℃로 열처리할 수 있다.Here, in the mixture heat treatment step, the mixture may be heat treated at 600 ~ 900 ℃.

이때, 상기 혼합물 열처리단계는 비활성 분위기에서 진행될 수 있다.At this time, the mixture heat treatment step may be performed in an inert atmosphere.

또한, 상기 혼합물 제조단계 전, 상기 산화 그래핀을 제조하는 산화 그래핀 제조단계를 더 포함할 수 있다.In addition, before the mixture manufacturing step, it may further comprise a graphene oxide manufacturing step for producing the graphene oxide.

이때, 상기 산화 그래핀 제조단계는, 흑연을 산처리하여 산화 흑연을 만드는 제1 과정, 및 상기 산화 흑연으로부터 상기 산화 그래핀을 층 분리시키는 제2 과정을 포함할 수 있다.In this case, the graphene oxide manufacturing step may include a first process of acid-processing graphite to form graphite oxide, and a second process of layer-separating the graphene oxide from the graphite oxide.

또한, 상기 제2 과정에서는 용매에 상기 산화 흑연을 첨가한 후 액상 초음파 처리할 수 있다.In addition, in the second process, the liquid phase ultrasonic treatment may be performed after adding the graphite oxide to the solvent.

그리고 상기 혼합물 제조단계에서는 상기 산화 그래핀을 포함하는 수용액에 상기 촉매를 넣고 교반할 수 있다.In the mixture preparation step, the catalyst may be stirred in an aqueous solution containing the graphene oxide.

이때, 상기 혼합물 제조단계에서는 상기 촉매를 용매에 용해시킨 후 상기 수용액에 첨가할 수 있다.In this case, in the step of preparing the mixture, the catalyst may be dissolved in a solvent and then added to the aqueous solution.

또한, 상기 혼합물 제조단계에서는 상기 교반 후 상기 수용액을 필터링 및 건조할 수 있다.In addition, in the mixture preparation step, the aqueous solution may be filtered and dried after the stirring.

그리고 상기 혼합물 열처리단계 후, 만들어진 탄소나노튜브-그래핀 복합체를 산처리 및 건조할 수 있다.After the mixture heat treatment step, the carbon nanotube-graphene composite may be acid treated and dried.

아울러, 상기 혼합물 열처리단계에서는 환원된 상기 산화 그래핀의 표면으로부터 기립된 구조를 이루도록 상기 탄소나노튜브를 형성시킬 수 있다.In addition, in the mixture heat treatment step, the carbon nanotubes may be formed to form a standing structure from the surface of the reduced graphene oxide.

한편, 본 발명은, 환원된 산화 그래핀으로 이루어진 그래핀 플레이크 및 평면 상의 상기 그래핀 플레이크의 표면으로부터 기립된 구조를 이루도록 형성되는 적어도 하나의 탄소나노튜브를 포함하는 것을 특징으로 하는 탄소나노튜브-그래핀 복합체를 제공한다.On the other hand, the present invention, carbon nanotubes, characterized in that it comprises a graphene flake made of reduced graphene oxide and at least one carbon nanotube formed to form a structure standing up from the surface of the graphene flake on the plane It provides a graphene complex.

여기서, 상기 탄소나노튜브는 1~100㎚ 길이로 형성될 수 있다.Here, the carbon nanotubes may be formed to a length of 1 ~ 100nm.

또한, 상기 그래핀 플레이크와 상기 탄소나노튜브는 일 방향을 따라 순차 반복적으로 적층된 구조를 이룰 수 있다.In addition, the graphene flakes and the carbon nanotubes may form a structure that is sequentially stacked repeatedly in one direction.

본 발명에 따르면, 탄소나노튜브가, 전기 전도도가 우수한 방향인 그래핀 플레이크에 수직한 방향으로 연결되는 구조, 즉, 탄소나노튜브가 평면 상의 그래핀 플레이크의 표면으로부터 기립된 구조를 이루도록 제어함으로써, 우수한 전기 전도도 및 전자 이동도를 갖는 탄소나노튜브-그래핀 복합체를 제조할 수 있고, 이를 전극 소재로 채용한 연료 전지의 고용량, 고출력 구현이 가능하다.According to the present invention, by controlling the carbon nanotubes are connected in a direction perpendicular to the graphene flakes in the direction of excellent electrical conductivity, that is, the carbon nanotubes to form a structure standing up from the surface of the graphene flakes on the plane, A carbon nanotube-graphene composite having excellent electrical conductivity and electron mobility can be manufactured, and high capacity and high output of a fuel cell employing the same as an electrode material can be manufactured.

또한, 본 발명에 따르면, 유독 기체, 고압 장치 및 전자기파 없이, 오직, 비활성 분위기 하에서 열을 가해줌으로써, 전극 소재로 적용 시 전해액의 이동 공간을 확보해주고 전자의 이동이 원활한 구조를 이루는 탄소나노튜브를 형성할 수 있다.In addition, according to the present invention, by applying heat only in an inert atmosphere, without the toxic gas, high pressure device and electromagnetic waves, to secure the moving space of the electrolyte when applied to the electrode material and to achieve a smooth structure of the carbon nanotube Can be formed.

도 1은 본 발명의 실시 예에 따른 탄소나노튜브-그래핀 복합체 제조방법을 나타낸 공정 순서도.1 is a process flow chart illustrating a method for producing a carbon nanotube-graphene composite according to an embodiment of the present invention.

도 2는 본 발명의 실시 예에 따른 탄소나노튜브-그래핀 복합체 제조방법을 통해 제조된 탄소나노튜브-그래핀 복합체를 나타낸 모식도.Figure 2 is a schematic diagram showing a carbon nanotube-graphene composite prepared by the carbon nanotube-graphene composite manufacturing method according to an embodiment of the present invention.

도 3 및 도 4는 본 발명의 실시 예에 따른 탄소나노튜브-그래핀 복합체 제조방법을 통해 제조된 탄소나노튜브-그래핀 복합체의 표면을 배율을 달리하여 주자전자현미경으로 촬영한 사진들.3 and 4 are photographs taken with a runner electron microscope by varying the magnification of the surface of the carbon nanotube-graphene composite prepared by the carbon nanotube-graphene composite manufacturing method according to an embodiment of the present invention.

도 5는 본 발명의 실시 예에 따라 제조된 탄소나노튜브-그래핀 복합체와 종래기술에 따라 제조된 탄소나노튜브-그래핀 복합체를 비교하여 나타낸 모식도.Figure 5 is a schematic diagram showing a comparison between the carbon nanotube-graphene composite prepared according to the embodiment of the present invention and the carbon nanotube-graphene composite prepared according to the prior art.

이하에서는 첨부된 도면들을 참조하여 본 발명의 실시 예에 따른 탄소나노튜브-그래핀 복합체 제조방법 및 이에 의해 제조된 탄소나노튜브-그래핀 복합체에 대해 상세히 설명한다.Hereinafter, a carbon nanotube-graphene composite manufacturing method and a carbon nanotube-graphene composite prepared thereby according to an embodiment of the present invention will be described in detail with reference to the accompanying drawings.

아울러, 본 발명을 설명함에 있어서, 관련된 공지 기능 혹은 구성에 대한 구체적인 설명이 본 발명의 요지를 불필요하게 흐릴 수 있다고 판단된 경우 그 상세한 설명은 생략한다.In addition, in describing the present invention, when it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the subject matter of the present invention, the detailed description thereof will be omitted.


도 1 및 도 2에 도시한 바와 같이, 본 발명의 실시 예에 따른 탄소나노튜브-그래핀 복합체 제조방법은, 전기 이중층 커패시터나 연료전지 등과 같은 에너지 저장용 매체의 전극 소재로 사용되는 탄소나노튜브-그래핀 복합체(100)를 제조하기 위한 방법이다. 이러한 탄소나노튜브-그래핀 복합체 제조방법은 혼합물 제조단계(S1) 및 혼합물 열처리단계(S2)를 포함한다.As shown in Figure 1 and 2, the carbon nanotube-graphene composite manufacturing method according to an embodiment of the present invention, carbon nanotubes used as the electrode material of the energy storage medium, such as electric double layer capacitor or fuel cell -Graphene composite 100 is a method for manufacturing. The carbon nanotube-graphene composite manufacturing method includes a mixture preparation step (S1) and a mixture heat treatment step (S2).


먼저, 혼합물 제조단계(S1)는 산화 그래핀(graphene oxide)과 촉매의 혼합물을 제조하는 단계이다. 혼합물 제조단계(S1)에서는 먼저, 친수성인 산화 그래핀을 물에 분산시킨다. 이때, 본 발명의 실시 예에서는 탄소 소스를 포함하는 유기용매, 예컨대, 벤젠, 톨루엔, 아세톤 등을 혼합하지 않는다. 그 다음, 이러한 수용액에 촉매를 넣고 교반한다. 이때, 혼합물 제조단계(S1)에서는 물과 같은 용매에 촉매를 용해시킨 후 산화 그래핀이 분산되어 있는 수용액에 첨가한다.First, the mixture preparation step (S1) is a step of preparing a mixture of graphene oxide (graphene oxide) and the catalyst. In the mixture preparation step (S1), first, hydrophilic graphene oxide is dispersed in water. At this time, in the embodiment of the present invention, an organic solvent including a carbon source, for example, benzene, toluene, acetone, or the like is not mixed. Then, the catalyst is added to this aqueous solution and stirred. At this time, in the mixture preparation step (S1), the catalyst is dissolved in a solvent such as water and then added to an aqueous solution in which graphene oxide is dispersed.

본 발명의 실시 예에서는 탄소나노튜브(CNT) 성장을 위한 시드(seed) 역할을 하는 촉매로 산화철(Fe(Ⅲ))을 사용할 수 있다. 이에 따라, 혼합물 제조단계(S1)에서는 예컨대, 10μM 농도로 산화철(Fe(Ⅲ))을 물에 용해시킬 수 있다. 또한, 본 발명의 실시 예에서는 산화 그래핀을 환원시키기 위해, 산화철(Fe(Ⅲ))과 함께 환원제인 하이드록실아민(hydroxylamine)도 용해시킨 후 산화 그래핀이 분산되어 있는 수용액에 첨가할 수 있다. 예를 들어, 혼합물 제조단계(S1)에서는 하이드록실아민을 400μM 농도로 용해시킨 후 10μM 농도의 산화철(Fe(Ⅲ)) 용액과 함께 산화 그래핀이 분산되어 있는 수용액에 첨가할 수 있다.In an embodiment of the present invention, iron oxide (Fe (III)) may be used as a catalyst that serves as a seed for carbon nanotube (CNT) growth. Accordingly, in the mixture preparation step (S1), for example, iron oxide (Fe (III)) may be dissolved in water at a concentration of 10 μM. In addition, in the embodiment of the present invention, in order to reduce the graphene oxide, the hydroxylamine (hydroxylamine) as a reducing agent may also be dissolved together with iron oxide (Fe (III)) and added to an aqueous solution in which graphene oxide is dispersed. . For example, in the preparation of the mixture (S1), the hydroxylamine may be dissolved at 400 μM and then added to the aqueous solution in which graphene oxide is dispersed together with the iron oxide (Fe (III)) solution having a concentration of 10 μM.

그리고 혼합물 제조단계(S1)에서는 산화 그래핀이 분산되어 있는 수용액에 첨가된 산화철(Fe(Ⅲ)) 촉매를 고르게 분산시키기 위해, 초음파를 이용하여 교반할 수 있다. 그 다음, 혼합물 제조단계(S1)에서는 교반시킨 수용액을 필터링하여, 혼합물로부터 물을 제거한 후, 이를 오븐을 통해 건조시키는데, 80℃로 유지되는 오븐에서 대략 1시간 동안 건조시키는 것이 바람직하다.In the mixture preparation step (S1), in order to evenly disperse the iron oxide (Fe (III)) catalyst added to the aqueous solution in which graphene oxide is dispersed, it may be stirred using ultrasonic waves. Then, in the mixture preparation step (S1), the stirred aqueous solution is filtered to remove water from the mixture, and then dried through an oven, which is preferably dried in an oven maintained at 80 ° C. for about 1 hour.

한편, 본 발명의 실시 예에 따른 탄소나노튜브-그래핀 복합체 제조방법은 혼합물 제조단계(S1) 전, 산화 그래핀을 제조하는 산화 그래핀 제조단계를 더 포함할 수 있다. 산화 그래핀 제조단계에서는 먼저, 흑연(graphite)을 산처리(Hummer's method)하여, 표면에 하이드록시기(hydroxyl group), 에폭시드기(epoxide group) 및 카르복시기(carbixylic group)를 갖는 산화 흑연을 만든다. 그 다음, 만들어진 산화 흑연으로부터의 층 분리를 통해 산화 그래핀을 얻는다. 이때, 층 분리 공정은 용매인 증류수에 산화 흑연을 대략 0.1g/L~1g/L 농도로 첨가한 후 액상 초음파 처리하는 방식으로 진행될 수 있다.On the other hand, the carbon nanotube-graphene composite manufacturing method according to an embodiment of the present invention may further comprise a graphene oxide manufacturing step for producing graphene oxide before the mixture preparation step (S1). In the graphene oxide manufacturing step, graphite is first subjected to an acid treatment (Hummer's method) to produce graphite oxide having a hydroxyl group, an epoxide group, and a carboxyl group on the surface. Then, graphene oxide is obtained through layer separation from the produced graphite oxide. In this case, the layer separation process may be performed by adding graphite oxide to distilled water, which is a solvent, at a concentration of approximately 0.1 g / L to 1 g / L, followed by liquid sonication.


다음으로, 혼합물 열처리단계(S2)는 혼합물 제조단계(S1) 시 환원된 산화 그래핀, 즉, 그래핀 플레이크(graphene flake)(110) 표면에 분포되어 있는 촉매로부터 탄소나노튜브(120)를 형성시키기 위해, 혼합물을 열처리하는 단계이다. 본 발명의 실시 예에 따른 혼합물 열처리단계(S2)에서는 메탄이나 아세틸렌 등의 탄화가스와 같은 유독한 기체를 사용하지 않고, 특수한 고압의 장치나 전자기파의 사용 없이, 오직, 비활성 분위기 하에서 혼합물에 열을 가해주는 공정을 통해, 그래핀 플레이크(110) 표면에 짧은 길이의 탄소나노튜브(120)를 형성한다. 이에 따라, 혼합물 열처리단계(S2)에서는 예컨대, 질소 가스를 충분히 흘려준 소성로 내에서 혼합물을 600~900℃로 열처리한다.Next, the mixture heat treatment step (S2) to form the carbon nanotubes 120 from the catalyst distributed on the graphene oxide, that is, graphene flake (110) surface reduced during the mixture production step (S1) In order to do so, a step of heat-treating the mixture is carried out. In the mixture heat treatment step (S2) according to the embodiment of the present invention, without using a toxic gas such as carbonized gas such as methane or acetylene, and without using a special high-pressure device or electromagnetic waves, only heat in the mixture in an inert atmosphere Through the process of applying, to form the carbon nanotubes 120 of a short length on the surface of the graphene flakes (110). Accordingly, in the mixture heat treatment step (S2), for example, the mixture is heat treated at 600 to 900 ° C. in a firing furnace sufficiently flowed with nitrogen gas.

도 2에 도시한 바와 같이, 비활성 분위기 하에서 600~900℃로 혼합물을 열처리하게 되면, 혼합물 내 그래핀 플레이크(110)의 손상된 탄소(defect)가 기화된다. 그리고 이와 같이 기화된 탄소는 그래핀 플레이크(110)의 표면에 분포되어 있는 촉매로부터 탄소나노튜브(120)로 형성되고, 이에 따라, 탄소나노튜브-그래핀 복합체(100)가 제조된다.As shown in FIG. 2, when the mixture is heat treated at 600 to 900 ° C. under inert atmosphere, damaged carbon of the graphene flakes 110 in the mixture is vaporized. In this way, the carbonized carbon is formed of carbon nanotubes 120 from a catalyst distributed on the surface of the graphene flakes 110, thereby producing a carbon nanotube-graphene composite 100.

한편, 혼합물 열처리단계(S2) 후, 제조된 탄소나노튜브-그래핀 복합체(100)로부터 촉매를 제거하기 위해, 만들어진 탄소나노튜브-그래핀 복합체(100)를 산처리 및 건조할 수 있다. 구체적으로, 탄소나노튜브-그래핀 복합체(100)를 마일드한 산용액에 담가두었다가, 120도 이상의 온도에서 건조시킬 수 있다.On the other hand, after the mixture heat treatment step (S2), in order to remove the catalyst from the prepared carbon nanotube-graphene composite 100, the produced carbon nanotube-graphene composite 100 can be acid treated and dried. Specifically, the carbon nanotube-graphene composite 100 may be immersed in a mild acid solution and dried at a temperature of 120 degrees or more.


실시 예1Example 1

산화 그래핀과, 산화철(Fe(Ⅲ)) 및 하이드록실아민을 혼합한 후, 이를 질소기체 분위기에서 900℃로 2시간 소성하여 탄소나노튜브-그래핀 복합체를 제조하였고, 이의 표면을 주사전자현미경(SEM)으로 분석하였다.Graphene oxide, iron oxide (Fe (III)), and hydroxylamine were mixed and calcined at 900 ° C. for 2 hours in a nitrogen gas atmosphere to prepare a carbon nanotube-graphene composite, and the surface thereof was scanned with an electron microscope. Analysis by (SEM).

도 3은 제조한 탄소나노튜브-그래핀 복합체의 표면을 10,000배로 확대한 사진이고, 도 4는 제조한 탄소나노튜브-그래핀 복합체의 표면을 50,000배로 확대한 사진이다. 도 3의 주사전자현미경 사진에서 보여지는 바와 같이, 산화 그래핀의 표면에 짧은 길이의 탄소나노튜브가 형성되어 고르게 분포되어 있는 것을 확인할 수 있다. 또한, 탄소나노튜브-그래핀 복합체의 표면으로부터 관찰 각도를 45도로 틸트(tilt)하여 관찰해보면(도 4), 산화 그래핀의 표면에 고르게 점으로 보이는 물질, 즉, 탄소나노튜브가 100㎚ 이하의 길이를 가지고 있음을 확인할 수 있다.3 is an enlarged photo 10,000 times the surface of the prepared carbon nanotube-graphene composite, Figure 4 is an enlarged photo 50,000 times the surface of the prepared carbon nanotube-graphene composite. As shown in the scanning electron micrograph of FIG. 3, it can be seen that carbon nanotubes having a short length are formed on the surface of graphene oxide and are evenly distributed. In addition, when observed from the surface of the carbon nanotube-graphene composite by tilting the observation angle at 45 degrees (FIG. 4), the material that appears evenly on the surface of graphene oxide, that is, the carbon nanotube is 100 nm or less It can be seen that it has a length of.


상술한 바와 같이, 본 발명의 실시 예에 따른 탄소나노튜브-그래핀 복합체 제조방법을 통해 제조된 탄소나노튜브-그래핀 복합체(100)는 환원된 산화 그래핀으로 이루어진 그래핀 플레이크(110) 및 평면 상의 그래핀 플레이크(110)의 표면으로부터 기립된 구조를 이루도록 형성된 적어도 하나의 탄소나노튜브(120)를 포함하여 형성된다. 이때, 그래핀 플레이크(110)와 탄소나노튜브(120)는 일 방향을 따라 순차 반복저긍로 적층된 구조를 이룬다. 또한, 탄소나노튜브(120)는 그래핀 플레이크(110)의 표면으로부터 1~100㎚ 길이(혹은 높이)로 형성된다. 이와 같이, 탄소나노튜브(120)가 환원된 산화 그래핀인 그래핀 플레이크(110)의 표면으로부터 기립된 구조를 이루면, 연료 전지의 전극 소재로 적용되는 경우, 전해액 이온이 이동하기에 충분한 공간을 확보할 수 있다.As described above, the carbon nanotube-graphene composite 100 prepared by the carbon nanotube-graphene composite manufacturing method according to the embodiment of the present invention is a graphene flake 110 made of reduced graphene oxide and It is formed to include at least one carbon nanotube 120 formed to form a structure standing up from the surface of the graphene flake 110 on the plane. In this case, the graphene flakes 110 and the carbon nanotubes 120 form a stacked structure in order to repeat sequentially in one direction. In addition, the carbon nanotubes 120 are formed to have a length (or height) of 1 to 100 nm from the surface of the graphene flakes 110. As such, when the carbon nanotubes 120 form a structure standing up from the surface of the graphene flake 110 which is reduced graphene oxide, when the carbon nanotubes 120 are applied to the electrode material of the fuel cell, a space sufficient for the electrolyte ions to move is provided. It can be secured.


한편, 도 5는 본 발명의 실시 예에 따라 제조된 탄소나노튜브-그래핀 복합체(a)와 종래기술에 따른 탄소나노튜브-그래핀 복합체(b)를 비교하여 나타낸 모식도이다. 도 5에 도시한 바와 같이, 본 발명의 실시 예에 따라 제조된 탄소나노튜브-그래핀 복합체(a)의 경우, 그래핀 플레이크(110)에 탄소나노튜브(120)가 형성되어 있는 방향이 탄소나노튜브(120)에서 전자가 이동하는 방향과 일치, 즉, 탄소나노튜브(120)가, 전기 전도도가 우수한 방향인 그래핀 플레이크(110)에 수직방향으로 연결되므로, 전자의 이동이 원활할 수 있고, 이에 따라, 이를 전극 소재로 채용하는 연료 전지의 고용량, 고출력 구현이 가능해진다. 이에 반해, 종래기술에 따른 탄소나노튜브-그래핀 복합체(b)의 경우에는 그래핀에 탄소나노튜브가 형성되어 있는 방향이 탄소나노튜브에서 전자가 이동하는 방향과 일치하지 않아, 본 발명의 실시 예에 따른 탄소나노튜브-그래핀 복합체(a)에 비해, 전자의 이동이 원활하게 이루어지지 않게 된다. 이에 따라, 본 발명의 실시 예에 따라 제조된 탄소나노튜브-그래핀 복합체(a)는 종래기술에 따른 탄소나노튜브-그래핀 복합체(b)에 비해 상대적으로 우수한 전기적 특성을 갖게 된다.On the other hand, Figure 5 is a schematic diagram showing a comparison between the carbon nanotube-graphene composite (a) and the carbon nanotube-graphene composite (b) according to the prior art prepared according to an embodiment of the present invention. As shown in FIG. 5, in the case of the carbon nanotube-graphene composite (a) manufactured according to the embodiment of the present invention, the carbon nanotubes 120 are formed in the graphene flakes 110 in the direction of carbon. The nanotube 120 coincides with the direction in which the electrons move, that is, the carbon nanotubes 120 are connected to the graphene flakes 110, which are excellent in electrical conductivity, in a vertical direction, so that the movement of the electrons may be smooth. As a result, a high capacity and high power output of the fuel cell employing the electrode material can be realized. On the contrary, in the case of the carbon nanotube-graphene composite (b) according to the prior art, the direction in which carbon nanotubes are formed in graphene does not coincide with the direction in which electrons move in the carbon nanotubes. Compared to the carbon nanotube-graphene composite (a) according to the example, the movement of electrons is not made smoothly. Accordingly, the carbon nanotube-graphene composite (a) prepared according to the embodiment of the present invention has a relatively excellent electrical properties compared to the carbon nanotube-graphene composite (b) according to the prior art.


이상과 같이 본 발명은 비록 한정된 실시 예와 도면에 의해 설명되었으나, 본 발명은 상기의 실시 예에 한정되는 것은 아니며, 본 발명이 속하는 분야에서 통상의 지식을 가진 자라면 이러한 기재로부터 다양한 수정 및 변형이 가능하다.As described above, although the present invention has been described with reference to the limited embodiments and the drawings, the present invention is not limited to the above embodiments, and those skilled in the art to which the present invention pertains various modifications and variations from such descriptions. This is possible.

그러므로 본 발명의 범위는 설명된 실시 예에 국한되어 정해져서는 아니 되며, 후술하는 특허청구범위뿐만 아니라 특허청구범위와 균등한 것들에 의해 정해져야 한다.Therefore, the scope of the present invention should not be limited to the described embodiments, but should be determined not only by the claims below but also by the equivalents of the claims.

Claims (14)

산화 그래핀과 촉매의 혼합물을 제조하는 혼합물 제조단계; 및
상기 혼합물을 열처리하여, 상기 혼합물 제조단계 시 환원된 상기 산화 그래핀 표면에 분포되어 있는 상기 촉매로부터 탄소나노튜브를 형성시키는 혼합물 열처리단계;
를 포함하는 것을 특징으로 하는 탄소나노튜브-그래핀 복합체 제조방법.A mixture preparation step of preparing a mixture of graphene oxide and a catalyst; And
Heat treating the mixture to form carbon nanotubes from the catalyst distributed on the graphene oxide surface reduced during the preparation of the mixture;
Carbon nanotubes-graphene composite manufacturing method comprising a. 제1항에 있어서,
상기 혼합물 열처리단계에서는 상기 혼합물을 600~900℃로 열처리하는 것을 특징으로 하는 탄소나노튜브-그래핀 복합체 제조방법.The method of claim 1,
In the mixture heat treatment step, the carbon nanotube-graphene composite manufacturing method characterized in that the mixture is heat-treated at 600 ~ 900 ℃. 제2항에 있어서,
상기 혼합물 열처리단계는 비활성 분위기에서 진행되는 것을 특징으로 하는 탄소나노튜브-그래핀 복합체 제조방법.The method of claim 2,
The mixture heat treatment step is a carbon nanotube-graphene composite manufacturing method characterized in that the progress in an inert atmosphere. 제1항에 있어서,
상기 혼합물 제조단계 전, 상기 산화 그래핀을 제조하는 산화 그래핀 제조단계를 더 포함하는 것을 특징으로 하는 탄소나노튜브-그래핀 복합체 제조방법.The method of claim 1,
Before the mixture manufacturing step, the carbon nanotube-graphene composite manufacturing method characterized in that it further comprises a graphene oxide manufacturing step for producing the graphene oxide. 제4항에 있어서,
상기 산화 그래핀 제조단계는,
흑연을 산처리하여 산화 흑연을 만드는 제1 과정, 및
상기 산화 흑연으로부터 상기 산화 그래핀을 층 분리시키는 제2 과정을 포함하는 것을 특징으로 하는 탄소나노튜브-그래핀 복합체 제조방법.The method of claim 4, wherein
The graphene oxide manufacturing step,
A first process of acid treating the graphite to produce graphite oxide, and
And a second process of layer separating the graphene oxide from the graphite oxide. 제5항에 있어서,
상기 제2 과정에서는 용매에 상기 산화 흑연을 첨가한 후 액상 초음파 처리하는 것을 특징으로 하는 탄소나노튜브-그래핀 복합체 제조방법.The method of claim 5,
In the second process, carbon nanotube-graphene composite manufacturing method characterized in that the liquid phase ultrasonic treatment after adding the graphite oxide to the solvent. 제1항에 있어서,
상기 혼합물 제조단계에서는 상기 산화 그래핀을 포함하는 수용액에 상기 촉매를 넣고 교반하는 것을 특징으로 하는 탄소나노튜브-그래핀 복합체 제조방법.The method of claim 1,
In the step of preparing the mixture, the carbon nanotube-graphene composite manufacturing method characterized in that the catalyst is added to the aqueous solution containing the graphene oxide and stirred. 제7항에 있어서,
상기 혼합물 제조단계에서는 상기 촉매를 용매에 용해시킨 후 상기 수용액에 첨가하는 것을 특징으로 하는 탄소나노튜브-그래핀 복합체 제조방법.The method of claim 7, wherein
In the step of preparing the mixture, carbon nanotube-graphene composite manufacturing method, characterized in that the catalyst is dissolved in a solvent and added to the aqueous solution. 제8항에 있어서,
상기 혼합물 제조단계에서는 상기 교반 후 상기 수용액을 필터링 및 건조하는 것을 특징으로 하는 탄소나노튜브-그래핀 복합체 제조방법.The method of claim 8,
In the step of preparing the mixture, the carbon nanotube-graphene composite manufacturing method of filtering and drying the aqueous solution after the stirring. 제1항에 있어서,
상기 혼합물 열처리단계 후, 만들어진 탄소나노튜브-그래핀 복합체를 산처리 및 건조하는 것을 특징으로 하는 탄소나노튜브-그래핀 복합체 제조방법.The method of claim 1,
After the mixture heat treatment step, the carbon nanotube-graphene composite manufacturing method, characterized in that the acid treatment and drying the carbon nanotube-graphene composite. 제1항에 있어서,
상기 혼합물 열처리단계에서는 환원된 상기 산화 그래핀의 표면으로부터 기립된 구조를 이루도록 상기 탄소나노튜브를 형성시키는 것을 특징으로 하는 탄소나노튜브-그래핀 복합체 제조방법.The method of claim 1,
The carbon nanotube-graphene composite manufacturing method of the mixture heat treatment step of forming a carbon nanotube to form a structure standing up from the surface of the reduced graphene oxide. 환원된 산화 그래핀으로 이루어진 그래핀 플레이크; 및
평면 상의 상기 그래핀 플레이크의 표면으로부터 기립된 구조를 이루도록 형성되는 적어도 하나의 탄소나노튜브;
를 포함하는 것을 특징으로 하는 탄소나노튜브-그래핀 복합체.Graphene flakes consisting of reduced graphene oxide; And
At least one carbon nanotube formed to form a structure standing up from the surface of the graphene flake on a plane;
Carbon nanotubes-graphene composite comprising a. 제12항에 있어서,
상기 탄소나노튜브는 1~100㎚ 길이로 형성되는 것을 특징으로 하는 탄소나노튜브-그래핀 복합체.The method of claim 12,
The carbon nanotubes are carbon nanotubes-graphene composite, characterized in that formed in 1 ~ 100nm length. 제12항에 있어서,
상기 그래핀 플레이크와 상기 탄소나노튜브는 일 방향을 따라 순차 반복적으로 적층된 구조를 이루는 것을 특징으로 하는 탄소나노튜브-그래핀 복합체.The method of claim 12,
The graphene flakes and the carbon nanotubes are carbon nanotube-graphene composite, characterized in that to form a structure that is sequentially repeatedly stacked in one direction.
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