KR20000006701A - High yield purification of carbon nanotubes with H2S-mixed gases - Google Patents

High yield purification of carbon nanotubes with H2S-mixed gases Download PDF

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KR20000006701A
KR20000006701A KR1019990045696A KR19990045696A KR20000006701A KR 20000006701 A KR20000006701 A KR 20000006701A KR 1019990045696 A KR1019990045696 A KR 1019990045696A KR 19990045696 A KR19990045696 A KR 19990045696A KR 20000006701 A KR20000006701 A KR 20000006701A
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high yield
carbon nanotubes
gas
purification
carbon
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KR1019990045696A
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Korean (ko)
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한윤봉
정탁
이영희
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한윤봉
이영희
정탁
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B82B3/0009—Forming specific nanostructures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30

Abstract

PURPOSE: A refining method is provided to enhance price competitiveness of devices by refining a great amount of a carbon nano tube containing impurity with a high yield CONSTITUTION: The carbon nanotube of a mono wall or multiple walls is refined with a high yield at a lower temperature of about 350 to 650°C using H2S-mixed gas, wherein the yield is 40 percents and more. A supply concentration of H2S is controlled(1 percent H2S to 100 percents H2s) using N2 or other inert gas gases. A gas controlling reaction speed of CO and H2O and a monolithic reactor are simultaneously used.

Description

Ｈ2Ｓ-혼합기체를 이용한 탄소나노튜브의 고수율 정제법{High yield purification of carbon nanotubes with H2S-mixed gases}High yield purification of carbon nanotubes with H2S-mixed gases

탄소 나노튜브 정제는 제조한 나노튜브에 포함된 불순물들(비정질 탄소 물질, 흑연 성분, 탄소 미세 입자 및 풀러렌 등)을 제거하는 것이다. 정제법으로는 액상에서 고온 filtration이나 고체 크로마토그래피 등의 많은 방법들이 시도되어 왔으나 공정이 복잡해서 시간이 많이 소요되고, 수율도 낮았다. 또한 산을 이용한 액상 정제법은 기상 정제법보다 높은 수율(30 ∼ 50 %)로 정제할 수 있으나, 나노튜브의 길이를 짧게 하는 경향이 있으며 산을 쓰기 때문에 환경친화적이 아닌 과정이 복잡한 방법이다.Carbon nanotube purification is to remove impurities (amorphous carbon material, graphite component, carbon fine particles and fullerene, etc.) contained in the prepared nanotubes. As a purification method, many methods such as high temperature filtration and solid chromatography in the liquid phase have been tried, but the process is complicated and time-consuming and the yield is low. In addition, the liquid purification method using an acid can be purified in a higher yield (30-50%) than the gas phase purification method, but the process tends to shorten the length of the nanotubes and uses an acid, which is a complex process that is not environmentally friendly.

한편, 종래의 기체(공기 또는 산소)를 이용한 탄소 나노튜브 정제법은 탄소 나노튜브와 다른 탄소 물질의 산화온도 및 산화 속도의 차이를 이용한다. 즉, 산소나 공기 등을 공급하면서 고온(700 ℃ 이상)에서 불순물들을 반응시켜 처리하는 방법으로써 정제된 탄소나노튜브의 수율은 약 1% 정도에 불과하였다. 이는 탄소 나노튜브와 불순물들의 산화속도를 적절하게 조절할 수 없어서 시간이 지남에 따라 탄소 나노튜브도 함께 산화되기 때문이었다.Meanwhile, the conventional carbon nanotube purification method using gas (air or oxygen) uses a difference in oxidation temperature and oxidation rate of carbon nanotubes and other carbon materials. That is, the yield of purified carbon nanotubes was only about 1% as a method of reacting and treating impurities at high temperature (above 700 ° C.) while supplying oxygen or air. This is because the carbon nanotubes and the impurities can not be properly controlled so that the carbon nanotubes oxidize with time.

본 발명은 반도체 소자, FED 등 디스플레이 소자, 2차 전지의 전극 재료 등으로 이용될 수 있도록 불순물을 포함하는 탄소나노튜브를 높은 수율(40 - 80%)로 대량 정제할 수 있는 효과적인 정제기술을 개발하는데 목적이 있다.The present invention has developed an effective purification technology capable of mass refining carbon nanotubes containing impurities in high yield (40-80%) so that they can be used as semiconductor devices, display devices such as FEDs, and electrode materials for secondary batteries. The purpose is to.

대표도는 본 발명에 의한 탄소 나노튜브 정제를 위한 반응장치이다.Representative is a reactor for carbon nanotube purification according to the present invention.

[도 1]은 공급된 기체의 혼합 및 예열과 기체분산을 효과적으로 할 수 있으며 반응이 일어 나는 일체형 반응기를 나타낸다.1 shows an integrated reactor in which the mixing and preheating and gas dispersion of the supplied gas can be effectively performed and the reaction takes place.

[도 2]는 정제처리 하기 전의 아크방전법으로 제조한 다중벽(multi-walled) 탄소 나노튜브 raw sample을 전자현미경(SEM)으로 찍은 것이다.FIG. 2 is an electron microscope (SEM) of a multi-walled carbon nanotube raw sample prepared by an arc discharge method before purification.

[도 3]은 본 발명에서 제안한 방법으로 다중벽 탄소 나노튜브를 정제한 후 찍은 전자현미경 사진이다.3 is an electron micrograph taken after purification of multi-walled carbon nanotubes by the method proposed in the present invention.

대표도는 본 발명에 사용된 정제 반응장치를 나타내며, 공급기체 도입부, 기체의 혼합 및 예열과 분산을 효과적으로 할 수 있으며 반응이 일어 나는 일체형 반응기부, 반응온도를 일정하게 조절할 수 있는 가열부로 구성되어 있다. 특히 [도 1]은 기체의 혼합 및 예열과 분산을 효과적으로 할 수 있으며 반응이 일어 나는 일체형 반응기로서 탄소나노튜브 처리량에 따라 크기와 개수를 조정할 수 있다. 본 발명은 H2S-혼합기체를 사용하여 350 ℃ - 650 ℃ 이하의 저온에서 탄소나노튜브를 정제하는 기술로써 혼합기체는 H2S, O2, N2를 함유하며, 필요에 따라 CO, H2O 등을 첨가할 수 있다. 불순물은 탄소성분이므로 다음과 같이 반응부에서 H2S-혼합기체와 반응한다.Representative view shows the purification reaction apparatus used in the present invention, the feed gas introduction portion, the mixing and preheating and dispersion of the gas can be effectively and consists of an integral reactor portion that occurs the reaction, a heating portion that can constantly control the reaction temperature have. In particular, FIG. 1 can effectively mix, preheat, and disperse the gas, and adjust the size and number according to the throughput of the carbon nanotubes as an integrated reactor in which the reaction occurs. The present invention is a technology for purifying carbon nanotubes at a low temperature of 350 ℃-650 ℃ using H 2 S-mixed gas, the mixed gas contains H 2 S, O 2 , N 2 , CO, H 2 O and the like can be added. Since impurities are carbon components, they react with the H 2 S-mixed gas in the reaction section as follows.

C(s) + H2S(g) + O2(g) → COS(g) + H2O(g)C (s) + H 2 S (g) + O 2 (g) → COS (g) + H 2 O (g)

상기 반응식은 기존의 산소 또는 공기를 이용하여 700 ℃ 이상의 고온에서 불순물 탄소성분을 산화시키는 방법에 비해 저온(350 ℃ - 650 ℃)에서 H2S와 O2농도(또는 공급속도)를 조절함으로써 불순물들을 선택적으로 산화반응시킬 수 있기 때문에 높은 수율로 탄소나노튜브를 정제할 수 있다. 또한 기체를 사용하기 때문에 공정이 매우 간단하며 scale-up 하기가 쉽고, 공정의 자동화가 용이하다.The reaction formula is that impurities by adjusting the H 2 S and O 2 concentration (or feed rate) at low temperatures (350 ℃-650 ℃) compared to the conventional method of oxidizing the impurity carbon component at a high temperature of 700 ℃ or more using oxygen or air Since they can be selectively oxidized, the carbon nanotubes can be purified in high yield. The use of gas also makes the process very simple, easy to scale up, and easy to automate.

[도 2]와 [도 3]은 본 발명의 방법으로 정제하기 전의 아크 방전법으로 제조한 탄소나노튜브 raw sample과 정제한 후의 탄소나노튜브를 전자현미경(SEM)으로 찍은 사진을 각각 나타낸다. H2S와 50% 과잉 산소를 공급하면서 3시간 동안 처리한 결과([도 3])로서 수율은 약 70%이었다.2 and 3 are photographs taken of the carbon nanotube raw sample prepared by the arc discharge method before purification by the method of the present invention and the carbon nanotubes after purification by electron microscopy (SEM), respectively. As a result of treatment for 3 hours while supplying H 2 S and 50% excess oxygen (FIG. 3), the yield was about 70%.

상술한 바와 같이 본 발명에 의하면 불순물을 함유하는 탄소 나노튜브를 대량 처리할 수 있으며, 종래 방법들보다 공정이 간단하면서 높은 수율(40% 이상)을 얻을 수 있다. 이 발명은 반도체 소자, FED 등 디스플레이 소자, 2차 전지의 나노튜브 전극 등의 제조에 필요한 탄소나노튜브 원재료의 생산성을 향상시키고 제조원가를 낮춤으로써 이들 소자의 가격 경쟁력을 제고시킬 것이다.As described above, according to the present invention, carbon nanotubes containing impurities can be processed in large quantities, and the process is simpler than conventional methods, and a high yield (40% or more) can be obtained. The present invention will enhance the cost competitiveness of these devices by improving the productivity of carbon nanotube raw materials required for the manufacture of semiconductor devices, display devices such as FEDs, and nanotube electrodes of secondary batteries, and by reducing manufacturing costs.

Claims (2)

H2S-혼합기체를 사용하여 단일벽 또는 다중벽 탄소나노튜브를 저온(350-650 ℃)에서 40% 이상의 고수율로 정제하는 것.Purification of single-walled or multi-walled carbon nanotubes at low temperature (350-650 ° C) with high yield of at least 40% using H 2 S-mixed gas. H2S의 공급 농도를 N2또는 기타 불활성기체를 사용하여 조정하고(즉, 1% H2S에서부터 100% H2S까지 조정), CO, H2O 등 반응속도의 조절에 이용할 수 있는 기체를 사용하면서 일체형 반응기([도1])를 사용하는 것.The supply concentration of H 2 S can be adjusted using N 2 or other inert gas (ie from 1% H 2 S to 100% H 2 S), and can be used to control the reaction rate such as CO, H 2 O, etc. Using an integrated reactor (FIG. 1) while using gas.
KR1019990045696A 1999-10-20 1999-10-20 High yield purification of carbon nanotubes with H2S-mixed gases KR20000006701A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100385866B1 (en) * 2001-02-15 2003-06-02 일진나노텍 주식회사 Purifying method of singlewalled carbon nanotubes and thermal treatment apparatus used in the same
KR100385867B1 (en) * 1999-06-15 2003-06-02 일진나노텍 주식회사 Method of synthesizing highly purified carbon nanotubes
KR100513503B1 (en) * 2002-05-10 2005-09-08 한국화학연구원 Purification Method of Carbon Nanofibers for Hydrogen Storage

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100385867B1 (en) * 1999-06-15 2003-06-02 일진나노텍 주식회사 Method of synthesizing highly purified carbon nanotubes
KR100385866B1 (en) * 2001-02-15 2003-06-02 일진나노텍 주식회사 Purifying method of singlewalled carbon nanotubes and thermal treatment apparatus used in the same
KR100513503B1 (en) * 2002-05-10 2005-09-08 한국화학연구원 Purification Method of Carbon Nanofibers for Hydrogen Storage

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