KR20030046858A - High yield purification of single-walled carbon nanotubes using a combined lquid- and gas-phase purification method - Google Patents
High yield purification of single-walled carbon nanotubes using a combined lquid- and gas-phase purification method Download PDFInfo
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- 239000002109 single walled nanotube Substances 0.000 title claims description 24
- 238000000746 purification Methods 0.000 title abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000012535 impurity Substances 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
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- 230000003647 oxidation Effects 0.000 claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 abstract description 10
- 229910021393 carbon nanotube Inorganic materials 0.000 abstract description 10
- 239000002071 nanotube Substances 0.000 abstract description 10
- 239000007791 liquid phase Substances 0.000 abstract description 6
- 239000004065 semiconductor Substances 0.000 abstract description 3
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 abstract description 2
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- 229910002804 graphite Inorganic materials 0.000 abstract description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 2
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
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- 239000002923 metal particle Substances 0.000 abstract 1
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- 229910052723 transition metal Inorganic materials 0.000 abstract 1
- 150000003624 transition metals Chemical class 0.000 abstract 1
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
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- 208000016169 Fish-eye disease Diseases 0.000 description 2
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- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
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Abstract
탄소나노튜브는 감긴 형태 및 직경에 따라 금속 또는 반도체의 성질을 가지며, 단중벽 탄소나노튜브(single-walled carbon nanotube, SWNT)와 다중벽 탄소나노튜브(multi-walled carbon nanotube, MWNT)로 나눈다. 특히, 탄소나노튜브는 속이 비어 있고, 길이가 길고, 기계적, 전기적, 화학적 특성이 우수하여 FED(Field Emission Display)와 수소저장용기, 2차 전지 전극 등에 이용이 가능한 재료로 알려져 있다. 그러나, 합성된 탄소나노튜브는 나노튜브 외에 여러 형태의 불순물(플러렌과 나노입자, 흑연, 비정질 탄소 등)을 포함한다. 따라서 전계방출소자나 전지전극등에 응용하기에 앞서 정제가 반드시 필요하다. 본 발명은 나노튜브 정제에 관한 것으로, 탄소성분을 포함하는 나노튜브를 높은 수율로 정제하는 것을 특징으로 하는 기술이다.Carbon nanotubes have metal or semiconductor properties depending on the shape and diameter of the wound, and are divided into single-walled carbon nanotubes (SWNTs) and multi-walled carbon nanotubes (MWNTs). In particular, carbon nanotubes are known as materials that can be used for FED (Field Emission Display), hydrogen storage vessel, secondary battery electrode, etc. because of their hollow, long length, and excellent mechanical, electrical, and chemical properties. However, the synthesized carbon nanotubes contain various types of impurities (fullerene and nanoparticles, graphite, amorphous carbon, etc.) in addition to the nanotubes. Therefore, purification is essential prior to application to field emission devices or battery electrodes. The present invention relates to nanotube purification, and is a technology characterized in that the purification of nanotubes containing a carbon component in a high yield.
본 발명은 액상-기상 혼합정제법으로서 SWNT 성장시 촉매로 사용된 전이금속 입자들을 액상법으로 제거하고, 나노튜브 성장 후에 남아 있는 불순 탄소입자들을 기상산화법으로 선택적으로 제거하는 공정으로 구성되어 있다. 본 발명에 의하면 금속 및 불순 탄소입자들을 효과적으로 제거하여 높은 순도의 단중벽 탄소나노튜브를 고수율로 정제할 수 있다. 본 발명은 탄소나노튜브를 제조하는 모든 공정에 적용될 수 있다.The present invention consists of a liquid-phase mixed purification process in which the transition metal particles used as catalysts during SWNT growth are removed by the liquid phase method, and the impurities which are removed after the nanotube growth are selectively removed by vapor phase oxidation. According to the present invention, the metal and the impurity carbon particles can be effectively removed to purify high purity single-walled carbon nanotubes with high yield. The present invention can be applied to all processes for producing carbon nanotubes.
Description
탄소나노튜브 정제는 제조한 나노튜브에 포함된 불순물들(금속촉매 입자, 비정질 탄소 물질, 흑연 성분, 탄소 미세 입자 및 풀러렌 등)을 제거하는 것이다. 일반적으로 다중벽 탄소나노튜브를 정제하기 위하여 기체상 열산화 방법을 이용하지만, 단중벽 탄소나노튜브는 벽이 하나밖에 없기 때문에 다중벽 탄소나노튜브에 비해 훨씬 빨리 산화된다. 따라서 열산화 방법을 단중벽 탄소나노튜브에 적용하기는 산화속도를 정교하게 제어해야 하는데, 이는 어려움이 많을 뿐만 아니라 정제 수율도 1％ 정도에 불과하다. 단중벽 탄소나노튜브 정제법으로는 나노튜브 성장의 촉매로 사용된 금속성분의 제거와 불순탄소 입자들의 제거를 위해 액상법이 주로 사용되고 있는데, 이는 초원심분리(ultracentrifugation), 초음파를 이용한 분리, 또는 십자류 여과(cross-flow filtration) 등과 같은 물리적인 분리방법을 복합적으로 사용하는 것이다. 그 외에도 농축된 산용액에 섞어 초음파 처리를 하고, 이를 다시 산용액에서 환류시키고 원심분리 및 여과 과정을 거쳐 정제하는 방법이 있다. 그러나 이러한 정제방법들은 공정이 복잡하고 수율이 낮을 뿐만 아니라 나노튜브의 길이가 짧아지는 단점이 있다. 또한 농축 산용액을 반복 사용하기 때문에 환경친화적이 아니다.Carbon nanotube purification is to remove impurities (metal catalyst particles, amorphous carbon material, graphite component, carbon fine particles and fullerene, etc.) contained in the prepared nanotubes. Generally, gas phase thermal oxidation is used to purify multi-walled carbon nanotubes, but single-walled carbon nanotubes are oxidized much faster than multi-walled carbon nanotubes because they have only one wall. Therefore, applying the thermal oxidation method to single-walled carbon nanotubes requires precise control of the oxidation rate, which is not only difficult, but also has a purification yield of about 1%. As the single-walled carbon nanotube refining method, the liquid phase method is mainly used to remove metal components used as a catalyst for nanotube growth and to remove impurity carbon particles, which are ultracentrifugation, ultrasonic separation, or cross. It is a combination of physical separation methods such as cross-flow filtration. In addition, there is a method of mixing in a concentrated acid solution and sonicating, refluxing it again in an acid solution, and purifying by centrifugation and filtration. However, these purification methods are disadvantageous in that the process is complicated, the yield is low, and the length of the nanotubes is shortened. It is also not environmentally friendly due to repeated use of concentrated acid solutions.
본 발명은 단중벽 탄소나노튜브가 반도체 소자, FED 등 디스플레이 소자, 2차 전지의 전극 재료 등으로 이용될 수 있도록 불순물을 효과적으로 제거하여 단중벽 탄소나노튜브를 고순도·고수율로 정제할 수 있는 방법을 개발하는 것을 목적으로 한다. 보다 상세하게는 산용액을 이용하는 액상법으로 금속촉매 입자들을 제거하고, 그 후에 산화속도를 제어할 수 있는 혼합기체를 사용하여 기상산화법으로 불순탄소 입자들을 제거하는 시키는 기술이다. 이 정제기술은 단중벽 탄소나노튜브를 제조하는 모든 공정(예, 아크 방전법, 화학증착법, 플라즈마 화학증착법, 레이저 증착법 등)에 적용될 수 있는 기술이다.The present invention provides a method for purifying single-walled carbon nanotubes with high purity and high yield by effectively removing impurities so that single-walled carbon nanotubes can be used as semiconductor devices, display devices such as FEDs, and electrode materials for secondary batteries. It is aimed at developing. More specifically, the metal catalyst particles are removed by a liquid phase method using an acid solution, and thereafter, a technique of removing impurity carbon particles by vapor phase oxidation using a mixed gas capable of controlling the oxidation rate. This purification technology is applicable to all processes (eg, arc discharge method, chemical vapor deposition, plasma chemical vapor deposition, laser deposition, etc.) for manufacturing single-walled carbon nanotubes.
[도 1]은 본 발명이 명시하는 액상-기상 혼합정제법의 공정흐름도.1 is a process flow diagram of a liquid-phase mixed purification method specified by the present invention.
[도 2]는 본 발명을 이용하여 아크 방전법으로 제조한 단중벽 탄소나노튜브를 정제처리하기 전과 처리한 후의 결과를 전자현미경(SEM)으로 찍은 결과도.FIG. 2 is a graph showing the results obtained before and after the purification of the single-walled carbon nanotubes prepared by the arc discharge method using the present invention with an electron microscope (SEM). FIG.
[도 3]은 아크 방전법으로 제조한 단중벽 탄소나노튜브를 본 발명에서 제안한 공정순서에 따라 처리하되, 기상산화공정에서 H2S-O2혼합기체를 사용한 경우에 각 공정 단계에서 채취한 시료를 분석한 프리에변환 라만(Fourier Transformed Raman, FT-Raman) 스펙트라 결과도.FIG. 3 is a single-walled carbon nanotube manufactured by the arc discharge method according to the process sequence proposed in the present invention, but the sample taken in each process step in the case of using the H 2 SO 2 mixed gas in the gas phase oxidation process Fourier transformed Raman (FT-Raman) spectra results analyzed.
[도 4]는 아크 방전법으로 제조한 단중벽 탄소나노튜브를 본 발명에서 제안한 공정순서에 따라 처리하되, 기상산화공정에서 O2-N2혼합기체를 사용한 경우에 각 공정 단계에서 채취한 시료를 분석한 FT-Raman 스펙트라 결과도.FIG. 4 is a sample taken at each process step when the single-walled carbon nanotubes prepared by the arc discharge method are treated according to the process sequence proposed in the present invention, but in which the O 2 -N 2 mixed gas is used in the gas phase oxidation process. FT-Raman spectra results analysis.
첨부한 도면들을 참조한 본 발명의 상세 설명은 다음과 같다.Detailed description of the invention with reference to the accompanying drawings is as follows.
이하 바람직한 실시예를 통해 본 발명의 목적 및 구성을 보다 잘 이해할 수 있을 것이다.Through the following preferred embodiments will be able to better understand the purpose and configuration of the present invention.
[도 1]은 본 발명이 명시하는 액상-기상 혼합정제법의 공정흐름도이다. 보다 상세하게는 불순물들을 포함하고 있는 합성된 단중벽 탄소나노튜브에서 금속(Ni, Co, Fe 등)촉매 입자들을 제거하기 위해 3M 염산용액에 담가두었다가 증류수로 세척한 후 건조시키는 제 1 공정, 그 후에 H2S-O2혼합기체를 이용하여 불순 탄소입자들을 제거하는 제 2 공정, 그 후에 3M 염산용액으로 린스(rinse) 하는 제 3 공정, 그 후에 건조시키는 제 4 공정으로 구성되어 있다.1 is a process flowchart of a liquid-phase mixed purification method specified by the present invention. More specifically, the first step of immersing in 3M hydrochloric acid solution to remove metal (Ni, Co, Fe, etc.) catalyst particles in the synthesized single-walled carbon nanotubes containing impurities, washed with distilled water and dried Later, a second step of removing impure carbon particles using H 2 SO 2 mixed gas, a third step of rinsing with 3M hydrochloric acid solution, and then a fourth step of drying.
[도 2]는 가장 불순물을 많이 함유하는 제조방법인 아크 방전법으로 제조한 단중벽 탄소나노튜브를 본 발명을 이용하여 정제처리 하기 전과 처리한 후의 결과를 전자현미경(SEM)으로 찍은 결과도이다. 단중벽 탄소나노튜브 제조시 촉매로 사용된 금속(Ni, Fe, Co 등)을 제 1공정에서 3M 염산용액으로 24시간 처리한 후 증류수로 세척하고 150 ℃에서 24시간 건조시킨 후, 제 2 공정에서 H2S-O2혼합기체를이용하여 500 ℃에서 열처리 한 후, 제 3 공정에서 3M 염산용액으로 1시간 처리한 후 제 4 공정에서 건조한 최종결과를 전자현미경으로 찍은 결과이다. 원료의 전자현미경 사진(A)을 보면, 불순 탄소입자들과 금속촉매 입자들에 뭉쳐있거나 엉켜있어서 탄소나노튜브가 구별이 잘 안되는 것을 알 수 있다. 그러나 본 발명을 이용하여 정제처리한 결과(B)를 보면, 금속 불순물과 탄소입자들이 거의 제거되었음을 알 수 있고, 단중벽 탄소나노튜브의 순도는 98 ％ 이상이었고, 전체 공정의 수율은 약 25 ％이었다.FIG. 2 is a diagram showing the results obtained by electron microscopy (SEM) before and after the purification of single-walled carbon nanotubes prepared by the arc discharge method, which is the method containing the most impurities, using the present invention. . The metal (Ni, Fe, Co, etc.) used as a catalyst for the production of single-walled carbon nanotubes was treated with 3M hydrochloric acid solution in the first step for 24 hours, washed with distilled water and dried at 150 ° C for 24 hours, and then in the second step. After heat treatment at 500 ℃ using H 2 SO 2 mixed gas at 3 hours in a 3M hydrochloric acid solution in the third step and the final result dried in the fourth step was taken with an electron microscope. Looking at the electron micrograph (A) of the raw material, it can be seen that the carbon nanotubes are indistinguishable because they are aggregated or entangled in the impurity carbon particles and the metal catalyst particles. However, when the purification process using the present invention (B) shows that the metal impurities and carbon particles were almost removed, the purity of the single-walled carbon nanotubes was 98% or more, and the yield of the entire process was about 25%. It was.
[도 3]은 아크 방전법으로 제조한 단중벽 탄소나노튜브를 본 발명에서 제안한 공정순서에 따라 처리하되, 기상산화공정에서 H2S-O2혼합기체를 사용한 경우에 각 공정 단계에서 채취한 시료를 분석한 프리에변환 라만(Fourier Transformed Raman, FT-Raman) 스펙트라 결과도이다. (a)는 아크방전법으로 제조한 불순물들이 포함되어 있는 상태의 단중벽 탄소나노튜브를 Raman 분석한 결과, (b)는 제 1 공정을 이용하여 금속 불순물을 제거한 후의 Raman 분석결과, (c)는 제 2 공정을 거친 후의 시료를 Raman 분석한 결과, (d)는 제 3 공정을 거치고 건조시킨 후 분석한 Raman 결과를 각각 나타낸다. 1590 cm-1에서 나타나는 주 peak와 그 왼쪽어깨에 걸쳐 있는 1580 cm-1및 1740 cm-1에서 나타나는 peak들은 단중벽 나노튜브가 제조되었음을 확인시켜주는 결과이다. 180 cm-1근처에서 나타나는 peak들은 단중벽 탄소나노튜브의 radial-breathing 모드로서 타노튜브의 직경을 계산하는데 사용하며, 본 발명의 실시예인 경우 1.27 nm이었다. 1290 cm-1에서의 peak은 불순탄소입자들을 나타낸다. 탄소나노튜브의 순도가 높을수록 1590 cm-1에서 나타나는 주 peak의 세기가 증가하고, 불순물 peak이 감소한다. 제 1 공정에서 염산처리로 금속을 제거한 후의결과(b)는 주 peak의 세기가 원료(a)에 비해 감소하였는데, 이는 나노튜브가 오랜 시간 강한 염산에 노출됨으로써 나노튜브도 일부 산화되었기 때문이다. 그러나, 제 1 공정을 거친 후에 제 2 공정에서 H2S-O2혼합기체로 500 ℃에서 1시간 산화처리하면, 주 peak의 세기가 현저하게 증가하였으며 불순물 peak도 감소하였다(c). 혹시 남아 있는 불순금속을 처리하기 위하여 제 2 공정을 거친 나노튜브를 제 3 공정에서 3M 염산용액으로 rinse한 후의 Raman 결과(d)는 제 2 공정을 거친 후의 결과와 비교할 때 별 차이가 없었다. 이는 제 3 공정을 거치지 않고도 탄소나노튜브를 정제할 수 있음을 나타내는 결과이다. 따라서 [도 1]의 공정도에서 제 3 공정은 생략 가능하다.FIG. 3 is a single-walled carbon nanotube manufactured by the arc discharge method according to the process sequence proposed in the present invention, but the sample taken in each process step in the case of using the H 2 SO 2 mixed gas in the gas phase oxidation process Fourier transformed Raman (FT-Raman) spectra results. (a) shows the results of Raman analysis of single-walled carbon nanotubes containing impurities prepared by the arc discharge method, (b) shows the results of Raman analysis after removing metal impurities using the first process, and (c) Is a Raman analysis of the sample after the second step, (d) shows the Raman results analyzed after drying after the third step. The main peaks appearing at 1590 cm -1 and the peaks appearing at 1580 cm -1 and 1740 cm -1 across the left shoulder confirm the production of single-walled nanotubes. The peaks appearing near 180 cm −1 are used to calculate the diameter of the tanotubes as a radial-breathing mode of the single-walled carbon nanotubes, which was 1.27 nm in the embodiment of the present invention. The peak at 1290 cm −1 represents impurity carbon particles. The higher the purity of the carbon nanotubes, the higher the intensity of the main peak appearing at 1590 cm -1 and the lower the impurity peak. After removing the metal by hydrochloric acid treatment in the first step (b), the intensity of the main peak was reduced compared to the raw material (a) because the nanotubes were partially oxidized due to exposure to strong hydrochloric acid for a long time. However, when the oxidation process was performed for 1 hour at 500 ° C. with H 2 SO 2 mixed gas in the second process after the first process, the intensity of the main peak was significantly increased and the impurity peak was also reduced (c). The Raman result (d) after rinse of the nanotubes subjected to the second process to 3M hydrochloric acid solution in the third process to treat the remaining impurity metals was not significantly different from the results after the second process. This is a result indicating that the carbon nanotubes can be purified without undergoing the third process. Therefore, the third process can be omitted in the process diagram of FIG. 1.
[도 4]는 아크 방전법으로 제조한 단중벽 탄소나노튜브를 본 발명에서 제안한 공정순서에 따라 처리하되, 기상산화공정에서 O2-N2혼합기체(또는 공기)를 사용한 경우에 각 공정 단계에서 채취한 시료를 분석한 FT-Raman 스펙트라 결과도이다. 원료의 Raman 분석결과와 비교하여 향상되지 않았음을 알 수 있는데, 이는 산소에 의해 단중벽 나노튜브가 상당부분 산화되었기 때문이다. 본 발명에서 제시한 H2S-O2혼합기체를 사용한 경우[도 3 참조]가 [도 4]와 비해 고순도의 정제된 단중벽 탄소나노튜브를 얻을 수 있는 이유는 다음과 같은 반응이 일어나기 때문이다.4 is a step of treating the single-walled carbon nanotubes prepared by the arc discharge method in accordance with the process sequence proposed in the present invention, in the case of using an O 2 -N 2 mixed gas (or air) in the gas phase oxidation process FT-Raman spectra results of the samples taken from Compared with the Raman analysis of the raw material, it can be seen that the improvement is due to the significant oxidation of the single-walled nanotubes by oxygen. In the case of using the H 2 SO 2 mixed gas presented in the present invention [see FIG. 3], a purified single-walled carbon nanotube having a higher purity than that of [FIG. 4] can be obtained because the following reaction occurs.
C(s) + H2S(g) + O2(g) → COS(g) + H2O(g) △Gr°= -403 kJ/molC (s) + H 2 S (g) + O 2 (g) → COS (g) + H 2 O (g) ΔG r ° = -403 kJ / mol
상기 반응은 정제반응기 출구쪽에 수증기(H2O)가 응축되는 것으로 확인할 수 있었다. 따라서 본 발명은 기존의 산소 또는 공기를 이용하여 600 ℃ 이상의 고온에서 불순물 탄소성분을 산화시키는 방법에 비해 저온(350 ℃ - 600 ℃)에서 H2S와 O2농도를 조절함으로써 불순물들을 선택적으로 산화반응시킬 수 있기 때문에 고순도의 탄소나노튜브를 정제할 수 있다. 또한 기체를 사용하기 때문에 액체를 사용하여 불순탄소들을 제거하는 기존의 정제공정에 비해 매우 간단하고 효율적이다.The reaction was confirmed to be condensation of water vapor (H 2 O) at the outlet of the purification reactor. Therefore, the present invention selectively oxidizes impurities by controlling H 2 S and O 2 concentrations at low temperature (350 ° C.-600 ° C.) compared to the method of oxidizing impurity carbon components at a high temperature of 600 ° C. or higher using conventional oxygen or air. Since it can react, it can refine | purify a high purity carbon nanotube. In addition, the use of gas is much simpler and more efficient than conventional refining processes that use liquids to remove impurities.
상술한 바와 같이 본 발명에 의하면 불순물을 다량 함유하는 단중벽 탄소나노튜브를 대량 처리할 수 있으며, 종래 방법들보다 공정이 간단하면서 수율이 높고, 98 ％이상의 고순도 단중벽 탄소나노튜브를 얻을 수 있다. 본 발명은 단중벽 탄소나노튜브를 제조하는 모든 방법에 적용할 수 있다. 나아가 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, it is possible to treat a large amount of single-walled carbon nanotubes containing a large amount of impurities, and the process is simpler than conventional methods, yields are high, and high purity single-walled carbon nanotubes of 98% or more can be obtained. . The present invention can be applied to all methods for producing single-walled carbon nanotubes. Furthermore, the present invention will improve 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 lowering manufacturing costs.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100745752B1 (en) * | 2005-06-28 | 2007-08-02 | 삼성전자주식회사 | Method for Purifying Carbonaceous Impurities in Carbon Nanotubes |
| KR100784791B1 (en) * | 2006-07-24 | 2007-12-14 | 세메스 주식회사 | Carbon nanotube post-treatment equipment, and carbon nanotube manufacturing equipment and method having the same |
| KR100827387B1 (en) * | 2006-09-04 | 2008-05-06 | 세종대학교산학협력단 | Method for Purifying Carbon Nanotubes Using Balls |
| DE102013214431A1 (en) * | 2013-07-24 | 2015-01-29 | Bayer Materialscience Aktiengesellschaft | Method of cleaning carbon nanotubes and carbon nanotube substrate and uses therefor |
| CN116022775A (en) * | 2022-12-29 | 2023-04-28 | 蜂巢能源科技(上饶)有限公司 | Carbon nano tube purification method and application |
| CN116462187A (en) * | 2023-03-27 | 2023-07-21 | 南京齐超环保科技有限公司 | Batch purification method of carbon nano tube |
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2001
- 2001-12-06 KR KR1020010077141A patent/KR20030046858A/en not_active Withdrawn
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100745752B1 (en) * | 2005-06-28 | 2007-08-02 | 삼성전자주식회사 | Method for Purifying Carbonaceous Impurities in Carbon Nanotubes |
| US7604790B2 (en) | 2005-06-28 | 2009-10-20 | Samsung Electronics Co., Ltd. | Method of removing carbonaceous impurities in carbon nanotubes |
| KR100784791B1 (en) * | 2006-07-24 | 2007-12-14 | 세메스 주식회사 | Carbon nanotube post-treatment equipment, and carbon nanotube manufacturing equipment and method having the same |
| KR100827387B1 (en) * | 2006-09-04 | 2008-05-06 | 세종대학교산학협력단 | Method for Purifying Carbon Nanotubes Using Balls |
| DE102013214431A1 (en) * | 2013-07-24 | 2015-01-29 | Bayer Materialscience Aktiengesellschaft | Method of cleaning carbon nanotubes and carbon nanotube substrate and uses therefor |
| CN116022775A (en) * | 2022-12-29 | 2023-04-28 | 蜂巢能源科技(上饶)有限公司 | Carbon nano tube purification method and application |
| CN116022775B (en) * | 2022-12-29 | 2024-02-09 | 蜂巢能源科技(上饶)有限公司 | Carbon nano tube purification method and application |
| CN116462187A (en) * | 2023-03-27 | 2023-07-21 | 南京齐超环保科技有限公司 | Batch purification method of carbon nano tube |
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