CN1436722A - Vacuum high-temperature process of purifying carbon nanotube - Google Patents
Vacuum high-temperature process of purifying carbon nanotube Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 45
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 26
- 230000008569 process Effects 0.000 title abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 23
- 150000003624 transition metals Chemical class 0.000 claims abstract description 23
- 239000002109 single walled nanotube Substances 0.000 claims abstract description 18
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 15
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 15
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- 239000002048 multi walled nanotube Substances 0.000 abstract description 15
- 229910052799 carbon Inorganic materials 0.000 abstract description 12
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000001066 destructive effect Effects 0.000 abstract 1
- 239000010439 graphite Substances 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 229910002804 graphite Inorganic materials 0.000 description 10
- 238000002411 thermogravimetry Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 241000209456 Plumbago Species 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- 229910021392 nanocarbon Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000007233 catalytic pyrolysis Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 229910017116 Fe—Mo Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
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- 239000007772 electrode material Substances 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
The present invention relates to the purification technology of coarse carbon nanotube product containing metal catalyst and metal oxide carrier. Through vacuum high-temperature process, transition metal catalyst, especially carbon layer coated transition metal catalyst, and metal oxide carrier in the carbon nanotube product can be eliminated effectively. The said process is simple, high in purification efficiency, non-destructive to carbon nanotube and suitable for both multi-wall and single-wall carbon nanotube. For example, multi-wall carbon nanotube sample with carbon content of 86% may be treated at 2300 deg.c for 5 hr to reach purity up to 99.93% and transition metal content as low as 0.05%.
Description
Technical field
The present invention relates to a kind of method of purifying carbon nano-tube, relate in particular to and a kind of the thick product of carbon nanotube that contains kish catalyzer and metal oxide carrier is carried out the method for purifying, belong to technical field of novel materials.
Background technology
Carbon nanotube is the seamless nanotube that is curled and formed by the single or multiple lift graphite flake.By the mono-layer graphite sheet curl form be called Single Walled Carbon Nanotube (SWNT), by the multilayer graphite flake curl form be called multi-walled carbon nano-tubes (MWNT).The adjacent layers spacing of multi-walled carbon nano-tubes is 0.34nm, near graphite layers distance (0.335nm).Carbon atom hexagonal array and carbon-coating spacing reflect the graphite feature that carbon nanotube keeps.Graphite is often used as high-temperature electrode material and lagging material.Under non-oxidizing atmosphere, carbon nanotube has the high temperature resistant character of similar graphite.
The diameter of carbon nanotube generally in several nanometers between tens nanometers, and length can reach the micron so that the millimeter magnitude, length-to-diameter ratio 100～10000 is considered to a kind of tubulose monodimension nanometer material.Theoretical analysis shows that high-purity perfect carbon nanotube has high strength, high-modulus, and favorable conductive, heat conductivility and field emission performance have the potential using value in a lot of fields.Carrying out its applied research at present both at home and abroad energetically.
The poly-group of nanometer fluidized-bed catalystic pyrolysis prepares the cheapness preparation (CN1327943A) that carbon nanotube technology has successfully realized carbon nanotube.It is a carbon source is decomposed carbon distribution on catalyzer process that catalystic pyrolysis prepares carbon nanotube, common working load type nano transition metal catalyzer, its active ingredient is nano grade transition metal (as: iron, cobalt, nickel, a molybdenum), and carrier is metal oxide (as: aluminum oxide, magnesium oxide, a silicon oxide).Follow the growth of carbon nanotube, metal active constituent can be coated by carbon-coating and cause catalyst deactivation, so residual inevitably in the thick product of carbon nanotube metal catalyst and metal oxide carrier is arranged.In order to obtain high pure nano-carbon tube, need carry out purifying to the thick product of catalystic pyrolysis preparation.
Many investigators attempt to utilize the catalyzer in the molten method removal carbon nanotube of acid.The result shows that acid is molten to have certain refining effect, but the purity that can reach is limited.We utilize electron microscope to observing through the sample of pickling repeatedly, see many transition-metal catalyst particles that remain in carbon nanotube inside or coated by carbon-coating.This is because under the barrier effect of carbon-coating, acid can not enter graphite linings inside and make the transition metal stripping.On the other hand, contain a large amount of carrier substance in the catalyzer, as aluminum oxide, silicon oxide etc.They are intermediate oxide, and the solubleness in acid is very low.Therefore utilize the molten method of acid can not obtain high-purity carbon nanotube product.
It has the good heat endurance energy atom composition of carbon nanotube and structures shape under nonoxidizing atmosphere.According to foreign study, multi-walled carbon nano-tubes can tolerate 3000 ℃ of high temperature, and Single Walled Carbon Nanotube can tolerate 1600～1800 ℃ temperature.There are some researches prove that below ultimate temperature the carbon nanotube sample being carried out that the high temperature crystallization handles not only not can destroying carbon nanometer tube, but also can further improve the degree of graphitization of carbon nanotube tube wall.People such as Andrews (R.Andrews, D.Jacques, D.Qian, E.C.Dikey, Carbon 2001; 39:1681-1687) when multi-walled carbon nano-tubes being carried out the processing of high temperature crystallization, find that the content of iron reduces to some extent in sample more than 1800 ℃.But their research work does not relate to the problem whether metal catalyst particles is coated by carbon-coating.According to their experimental result, can not infer that can the metallic particles that be coated by carbon-coating be removed by high temperature gasifying method.Their experiment is carried out under the nitrogen atmosphere condition, from very limited experimental data, the required temperature of iron level decline should be more than 1800 ℃ in the sample, and this temperature has surpassed the highest tolerable temperature of Single Walled Carbon Nanotube, obviously can not be used for the purifying Single Walled Carbon Nanotube.
Metal oxide (as: aluminum oxide, silicon oxide, magnesium oxide) is very common catalyst support material.Because the resistance toheat of these oxide compounds itself is good, is often used as refractory materials.The document of the relevant pyroprocessing carbon nanotube of having published does not all relate to the removal problem of metal oxide carrier, not about obtain the purity data of high pure nano-carbon tube by pyroprocessing yet.
Summary of the invention
The objective of the invention is at the transition-metal catalyst particle and the metal oxide carrier that remain in carbon nanotube thick product inside or coated by carbon-coating, a kind of method of utilizing the vacuum high-temperature purifying carbon nano-tube is provided, the transition-metal catalyst that this method can effectively be removed oxide carrier and be coated by carbon-coating, thus high pure nano-carbon tube obtained.
A kind of method of utilizing the vacuum high-temperature purifying carbon nano-tube, this method comprises the steps:
(1) carbon nanotube crude samples to be purified is placed in the High Temperature Furnaces Heating Apparatus, vacuumize and make that absolute pressure is lower than 20Pa in the stove;
(2) begin to be heated to 1100～3000 ℃ of predetermined treatment temps,, control the vacuum state in the stove simultaneously, and be incubated half an hour at least wherein for 1100～1800 ℃ of Single Walled Carbon Nanotube predetermined treatment temps;
(3) stop heating, lower the temperature under vacuum state, treat that temperature is reduced to below 200 ℃ in the stove, close vacuum pump, sample is taken out in the cooling back.
Vacuum state described in the above-mentioned steps (2) should satisfy the interior working pressure of stove and be lower than transition-metal catalyst and the saturation vapour pressure value of metal oxide carrier under this temperature.
The present invention utilizes the vacuum high-temperature operation, can effectively remove transition metal (Fe, Co, Ni, the Mo) catalyzer and metal oxide carrier (aluminum oxide, magnesium oxide, the silicon oxide), the particularly transition-metal catalyst that is coated by carbon-coating that mix in product.This method has overcome people and has thought the particularly aluminum oxide prejudice that is difficult to remove of under lower hot conditions metal oxide for a long time, for purifying carbon nano-tube provides a kind of new way.This method is easy and simple to handle, the purification efficiency height, and treating processes is to the carbon nanotube not damaged.Both be applicable to multi-walled carbon nano-tubes, also be applicable to Single Walled Carbon Nanotube.
Description of drawings
Fig. 1 is service temperature provided by the invention and the highest working pressure graph of a relation of permission.
Fig. 2 is the energy spectrum analysis of multi-walled carbon nano-tubes before the purifying.
Fig. 3 is the electromicroscopic photograph of multi-walled carbon nano-tubes before the purifying.
Fig. 4 a is the electromicroscopic photograph of multi-walled carbon nano-tubes behind the purifying.
Fig. 4 b is the electromicroscopic photograph of carbon-coating ghost behind the purifying.
Fig. 5 is the thermogravimetric analysis result before and after the multi-walled carbon nano-tubes sample purifying.
Embodiment
Further specify mechanism of the present invention and content thereof below in conjunction with drawings and Examples, understand the present invention with further.
The essential characteristic of this invention is under hot conditions, when working pressure is lower than saturation vapour pressure value under this temperature of transition-metal catalyst (Fe, Co, Ni, Mo) and metal oxide carrier (aluminum oxide, magnesium oxide, silicon oxide), transition-metal catalyst and oxide carrier can gasify in the ebullient mode and remove, thereby it is highly purified that the carbon nanotube sample is obtained.The present invention finds at 1100 ℃～2300 ℃ 10
-2Operation has purification to carbon nanotube in the scope of pa～20Pa.Along with temperature raises, the vapour pressure of transition-metal catalyst and metal oxide carrier increases, so gasification finish catalyzer and the required vacuum degree condition of carrier can decrease, and service temperature and pressure are according to Fig. 1 relation curve.According to foreign literature report, multi-walled carbon nano-tubes can heatproof to 3000 ℃, and along with service temperature raises, working pressure can further improve, and generally should be controlled at 1100～3000 ℃; During the purifying Single Walled Carbon Nanotube, its service temperature should be operated below the tolerable temperature of Single Walled Carbon Nanotube, generally should be controlled at 1100～1800 ℃.
Because the vacuum gasifying impellent is strong,, utilizes this method still transition metal can be gasified and remove even therefore when the transition metal catalyst is coated by carbon-coating.
Embodiment 1:
The carbon nanotube crude samples adopts by loading type catalyst Fe-Mo-Al
2O
3The multi-walled carbon nano-tubes that catalytic pyrolysis ethene makes.The EDAX results of Fig. 2 shows in this sample also to contain iron, molybdenum and aluminum oxide that except carbon component wherein the total content of metal Fe-Mo in catalyzer is lower than 10%.From the electromicroscopic photograph of Fig. 3, can see the metallics that is covered by carbon nanotube inside and carbon-coating inside.This sample is carried out vacuum high-temperature handle, treatment condition are: pressure 10Pa (cutting off), 1800 ℃ of temperature, 3 hours time.
Fig. 4 a, Fig. 4 b are the electromicroscopic photograph through sample after the pyroprocessing, and visible carbon nanotube inside does not have metallics from Fig. 4 a, can observe the ghost that carbon-coating forms from Fig. 4 b, illustrates that metallics has been removed in high-temperature process.
The purity data of sample utilizes the thermogravimetric analysis in the air atmosphere to obtain.In the thermogravimetric analysis process, sample is owing to the carbon nanotube burning produces weight loss.Therefore the burning weight loss of carbon nanotube finished before 750 ℃, non-volatile part of (transition-metal catalyst and oxide carrier) content in 800 ℃ of residual heavy reflection samples.Sample before and after the pyroprocessing is carried out thermogravimetric analysis, and the result as shown in Figure 5.Contain non-volatile part of 14.07% (wt.) before handling in the sample, the content of handling non-volatile part of back only is 0.03%.
Embodiment 2:
The carbon nanotube sample is with embodiment 1.The pyroprocessing condition is: pressure 20Pa (cutting off), 2300 ℃ of temperature, 5 hours time.The sample of getting after the 1g pyroprocessing burns test in air, residual heavy by 0.07% after burning through 800 ℃.Non-volatile part with after the excess acid dissolving with after the calcination utilizes icp analysis to detect levels of transition metals.The ICP test result shows behind the purifying that levels of transition metals is lower than 0.05% in the sample.Analytical results shows, the method for utilizing vacuum high-temperature to handle can obtain that purity is higher than 99.93%, levels of transition metals is lower than 0.05% carbon nanotube product.
Embodiment 3:
The carbon nanotube crude samples is by loaded catalyst Ni-SiO
2Catalytic pyrolysis ethene makes multi-walled carbon nano-tubes.The pyroprocessing condition is: pressure 1Pa (cutting off), 1900 ℃ of temperature, 4 hours time.The thermogravimetric analysis result proves that the non-carbon impurity in the sample reduces to 5% after the processing by 30% before handling.
Embodiment 4:
The Single Walled Carbon Nanotube sample is the Single Walled Carbon Nanotube that is made by the Fe-MgO catalytic cracking methane.This sample was handled 1 hour under 0.1Pa (cutting off), 1300 ℃ of conditions.The thermogravimetric analysis result proves that the non-carbon impurity in the sample reduces to 15% after the processing by 35% before handling.Electron microscopic observation proof Single Walled Carbon Nanotube is excellent.
Embodiment 5:
The Single Walled Carbon Nanotube sample is with embodiment 4.This sample was handled 0.5 hour under 0.01Pa (cutting off), 1800 ℃ of conditions.The thermogravimetric analysis result proves that the non-carbon impurity in the sample reduces to 1.5% after the processing by 35% before handling.Electron microscopic observation proof Single Walled Carbon Nanotube is excellent.
Embodiment 6:
The Single Walled Carbon Nanotube sample is with embodiment 4.This sample was handled 2 hours under 0.01Pa (cutting off), 1100 ℃ of conditions.The thermogravimetric analysis result proves that the non-carbon impurity in the sample reduces to 18% after the processing by 35% before handling.Electron microscopic observation proof Single Walled Carbon Nanotube is excellent.
The vacuum high-temperature treating processes of the foregoing description 1～6 is all carried out in the vacuum sintering furnace of Xiang magnificent, and this vacuum sintering furnace adopts the graphite piece heating, and graphite felt is heat insulation.Used carbon nanotube sample is the poly-group of nanometer bed catalystic pyrolysis and makes.
Reference example 1:
Accurately take by weighing the 1 gram alumina catalyst support plumbago crucible of packing into, processing is 2 hours under pressure 0.01Pa (cut off), 1100 ℃ of conditions of temperature, and the aluminum oxide in the plumbago crucible all disappears.Present embodiment proves that alumina supporter can gasify with this understanding and removes.
Reference example 2:
Accurately take by weighing the 4.25 gram alumina catalyst supports plumbago crucible of packing into, handled 0.5 hour under pressure 0.2Pa (cut off), 1380 ℃ of conditions of temperature, the aluminum oxide in the plumbago crucible only surplus 0.6896 restrains.Present embodiment proves that alumina supporter can gasify with this understanding and removes.
Claims (3)
1. method of utilizing the vacuum high-temperature purifying carbon nano-tube, this method comprises the steps:
(1) carbon nanotube crude samples to be purified is placed in the High Temperature Furnaces Heating Apparatus, vacuumize and make that absolute pressure is lower than 20Pa in the stove;
(2) begin to be heated to 1100～3000 ℃ of predetermined treatment temps,, control the vacuum state in the stove simultaneously, and be incubated half an hour at least wherein for 1100～1800 ℃ of Single Walled Carbon Nanotube predetermined treatment temps;
(3) stop heating, lower the temperature under vacuum state, treat that temperature is reduced to below 200 ℃ in the stove, close vacuum pump, sample is taken out in the cooling back.
2. according to the method for the described purifying carbon nano-tube of claim 1, it is characterized in that: vacuum state described in the step (2) should satisfy the interior working pressure of stove and be lower than transition-metal catalyst and the saturation vapour pressure value of metal oxide carrier under this temperature.
3. according to the method for the described purifying carbon nano-tube of claim 2, it is characterized in that: described transition-metal catalyst is Fe, Co, Ni, Mo; Described metal oxide carrier is aluminum oxide, magnesium oxide, silicon oxide.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7728497B2 (en) | 2004-11-15 | 2010-06-01 | Samsung Sdi Co., Ltd. | Carbon nanotube, electron emission source including the carbon nanotube, electron emission device including the electron emission source, and method of manufacturing the electron emission device |
| CN102020267A (en) * | 2010-12-30 | 2011-04-20 | 上海大学 | Purification method of single-wall carbon nano tube |
| CN105833871A (en) * | 2016-04-21 | 2016-08-10 | 长春吉大附中实验学校 | Defect-rich cobalt-inlaid carbon nano tube as well as preparation method and application thereof |
| CN107235488A (en) * | 2017-06-14 | 2017-10-10 | 中国科学院宁波材料技术与工程研究所 | A kind of purification process of graphene-based porous carbon |
| DE102017215665A1 (en) | 2016-09-06 | 2018-03-08 | Sk Global Chemical Co., Ltd. | METHOD FOR CLEANING CARBON NANOTUBES |
| CN109524667A (en) * | 2018-10-16 | 2019-03-26 | 上海力信能源科技有限责任公司 | A kind of preparation method of combined conductive agent and preparation method thereof, carbon nanotube |
| CN109553089A (en) * | 2018-12-29 | 2019-04-02 | 赛福纳米科技(徐州)有限公司 | Multi-purpose material heat treatment apparatus |
| CN109830685A (en) * | 2019-04-03 | 2019-05-31 | 哈尔滨万鑫石墨谷科技有限公司 | A kind of composite conducting slurry, preparation method and the usage |
| CN112563519A (en) * | 2020-07-23 | 2021-03-26 | 中国科学院苏州纳米技术与纳米仿生研究所 | Intermetallic compound-carbon nanotube composite material and preparation method and application thereof |
| EP4289786A2 (en) | 2022-06-06 | 2023-12-13 | Indian Oil Corporation Limited | A reagent solution for purification of carbon nanomaterials and a method thereof |
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2003
- 2003-03-21 CN CNB031208185A patent/CN1188345C/en not_active Expired - Lifetime
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| US7728497B2 (en) | 2004-11-15 | 2010-06-01 | Samsung Sdi Co., Ltd. | Carbon nanotube, electron emission source including the carbon nanotube, electron emission device including the electron emission source, and method of manufacturing the electron emission device |
| CN102020267A (en) * | 2010-12-30 | 2011-04-20 | 上海大学 | Purification method of single-wall carbon nano tube |
| CN105833871A (en) * | 2016-04-21 | 2016-08-10 | 长春吉大附中实验学校 | Defect-rich cobalt-inlaid carbon nano tube as well as preparation method and application thereof |
| CN105833871B (en) * | 2016-04-21 | 2018-06-08 | 长春吉大附中实验学校 | A kind of cobalt of richness defect inlays carbon nanotube, preparation method and applications |
| US10703632B2 (en) | 2016-09-06 | 2020-07-07 | Sk Innovation Co., Ltd. | Method of purifying carbon nanotubes |
| DE102017215665A1 (en) | 2016-09-06 | 2018-03-08 | Sk Global Chemical Co., Ltd. | METHOD FOR CLEANING CARBON NANOTUBES |
| CN107235488A (en) * | 2017-06-14 | 2017-10-10 | 中国科学院宁波材料技术与工程研究所 | A kind of purification process of graphene-based porous carbon |
| CN109524667A (en) * | 2018-10-16 | 2019-03-26 | 上海力信能源科技有限责任公司 | A kind of preparation method of combined conductive agent and preparation method thereof, carbon nanotube |
| CN109553089A (en) * | 2018-12-29 | 2019-04-02 | 赛福纳米科技(徐州)有限公司 | Multi-purpose material heat treatment apparatus |
| CN109830685A (en) * | 2019-04-03 | 2019-05-31 | 哈尔滨万鑫石墨谷科技有限公司 | A kind of composite conducting slurry, preparation method and the usage |
| CN112563519A (en) * | 2020-07-23 | 2021-03-26 | 中国科学院苏州纳米技术与纳米仿生研究所 | Intermetallic compound-carbon nanotube composite material and preparation method and application thereof |
| CN112563519B (en) * | 2020-07-23 | 2022-04-12 | 中国科学院苏州纳米技术与纳米仿生研究所 | Intermetallic compound-carbon nanotube composite material and preparation method and application thereof |
| EP4289786A2 (en) | 2022-06-06 | 2023-12-13 | Indian Oil Corporation Limited | A reagent solution for purification of carbon nanomaterials and a method thereof |
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|---|---|
| CN1188345C (en) | 2005-02-09 |
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