WO2017048053A1 - Nanotube de carbone présentant une aptitude améliorée à la cristallisation - Google Patents

Nanotube de carbone présentant une aptitude améliorée à la cristallisation Download PDF

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WO2017048053A1
WO2017048053A1 PCT/KR2016/010338 KR2016010338W WO2017048053A1 WO 2017048053 A1 WO2017048053 A1 WO 2017048053A1 KR 2016010338 W KR2016010338 W KR 2016010338W WO 2017048053 A1 WO2017048053 A1 WO 2017048053A1
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carbon nanotubes
temperature
metal
carbon
chlorine
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Korean (ko)
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강경연
우지희
조동현
이승용
장형식
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주식회사 엘지화학
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    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size

Definitions

  • the present invention relates to carbon nanotubes having improved crystallinity by reacting and removing impurities contained in carbon nanotubes with chlorine-containing compounds.
  • carbon nanotubes are cylindrical carbon tubes having a diameter of about 3 to 150 nm, specifically about 3 to 100 nm, and having a length several times the diameter, for example, 100 times or more.
  • CNTs consist of layers of aligned carbon atoms and have different types of cores.
  • Such CNTs are also called, for example, carbon fibrils or hollow carbon fibers.
  • the CNT can be generally manufactured by an arc discharge method, a laser evaporation method, a chemical vapor deposition method, or the like.
  • the arc discharge method and the laser evaporation method is difficult to mass-produce, there is a problem that the economical efficiency is lowered due to excessive arc production cost or laser equipment purchase cost.
  • carbon nanostructures are typically produced by dispersing and reacting metal catalyst particles with a hydrocarbon-based feed gas in a high temperature fluidized bed reactor. That is, the metal catalyst is suspended in the fluidized bed reactor by the source gas and reacts with the source gas to grow carbon nanostructures.
  • Carbon nanotubes exhibit non-conductor, conductor or semiconducting properties according to their unique chirality, and the carbon atoms are connected by strong covalent bonds, so that their tensile strength is about 100 times greater than steel, and they have excellent flexibility and elasticity. It is also chemically stable, and because of its size and specific properties, it is industrially important in the manufacture of composites and has high utility in the field of electronic materials, energy materials and many other fields.
  • the carbon nanotubes may be applied to electrodes of an electrochemical storage device such as a secondary battery, a fuel cell or a super capacitor, an electromagnetic shield, a field emission display, or a gas sensor.
  • the catalytic metal used in the carbon nanotube fabrication process is treated as an impurity when attempting to use the carbon nanotubes, and the above-mentioned metal impurities cause a problem that the basic physical properties such as thermal stability and chemical stability are reduced. Therefore, at this time, there is a need for a method of improving the basic physical properties of carbon nanotubes by purifying only carbon nanotubes.
  • the present invention is to provide a carbon nanotube significantly improved thermal stability by going through the step of removing the residual metal contained in the carbon nanotubes.
  • the present invention comprises the steps of chlorinating the residual metal by reacting the metal remaining in the carbon nanotubes with a chlorine-containing compound at a first temperature (T 1 ) in a vacuum or inert atmosphere;
  • the second temperature T 2 may be performed at a temperature of T 1 + 300 ° C. or more.
  • the first temperature T 1 may be selected from 500 ° C. to 1000 ° C.
  • the second temperature may be selected from 800 ° C. to 1500 ° C.
  • the oxidation start temperature of the purified carbon nanotube may be 550 °C or more.
  • the metal impurity content remaining in the purified carbon nanotubes may be 50 ppm or less.
  • the purification step of evaporating the residual metal by reacting with the chlorine-containing compound may be performed in an N 2 gas or a vacuum atmosphere.
  • the carbon nanotubes may be manufactured using a metal catalyst containing cobalt (Co), and at least one metal component of iron (Fe), molybdenum (Mo), vanadium (V) and chromium (Cr). It may be to include more.
  • the carbon nanotubes may have a Co content of 40 ppm or less after the purification process.
  • the carbon nanotubes may be prepared by chemical vapor deposition (CVD) on a fluidized bed reactor.
  • CVD chemical vapor deposition
  • the carbon nanotubes may have an entangled shape or a bundle shape.
  • the chlorine-containing compound may be chlorine (Cl 2 ) gas or trichloromethane (CHCl 3 ) gas.
  • the first temperature may be performed at a temperature condition of 700 °C to 900 °C
  • the second temperature is 900 °C to 1500 °C.
  • the carbon nanotubes according to the present invention can remove residual metals generated in the manufacturing process of carbon nanotubes using a metal catalyst by reacting with a chlorine compound at a high temperature, thereby effectively removing impurities such as residual metals. Can be removed.
  • the chlorine gas treatment process that proceeds at a relatively low temperature of the first temperature and the metal chlorine removal process that proceeds to nitrogen (N 2 ) or the second temperature in a vacuum atmosphere can increase the metal removal efficiency remaining in the carbon nanotubes.
  • the second process is carried out in a nitrogen or vacuum atmosphere, the chlorine remaining in the carbon nanotubes can be removed together.
  • Purification process according to the present invention can further improve the physical properties of the carbon nanotubes, in particular, the oxidation stability stability and conductivity is improved by improving the crystallinity can be useful for use as a composite material of the metal composite and the conductive polymer.
  • Figure 1 shows the SEM images before and after the purification process of the carbon nanotubes of Example 1 and Comparative Example 1.
  • FIG. 2 is a graph showing TEM_EDX results of carbon nanotubes before and after the purification process.
  • FIG. 3 is a graph comparing G bands and D bands measured by Raman spectroscopy for carbon nanotubes of Example 1 and Comparative Example 1.
  • FIG. 3 is a graph comparing G bands and D bands measured by Raman spectroscopy for carbon nanotubes of Example 1 and Comparative Example 1.
  • Carbon nanotubes according to a preferred embodiment of the present invention
  • Chlorinating the residual metal by reacting the metal remaining in the carbon nanotubes with a chlorine-containing compound at a first temperature in a vacuum or inert atmosphere;
  • the average value of the intensity ratio (I G / I D ) of the G band and D band measured by Raman spectroscopy is characterized in that 20% or more compared to the carbon nanotubes before purification.
  • the present invention provides a method for removing residual metal generated from a metal catalyst used in a manufacturing process in a manufactured carbon nanotube, by using a method of reacting at a high temperature with a chlorine-containing compound to chlorinate the residual metal and evaporate it.
  • a method of reacting at a high temperature with a chlorine-containing compound to chlorinate the residual metal and evaporate it.
  • the physical property degradation due to metal impurities such as residual metals can be improved.
  • the oxidation start temperature of purified carbon nanotubes is refined, that is, remaining.
  • the carbon nanotube containing the metal can exhibit an increase rate of 100 °C or more, it can be used more efficiently, such as a flame retardant or metal composite that can be used in high temperature environment.
  • the first temperature may be selected from 500 °C to 1000 °C
  • the second temperature may be selected from 800 °C to 1500 °C.
  • the oxidation start temperature of the purified carbon nanotube may be 550 °C or more.
  • the metal impurity content remaining in the carbon nanotubes subjected to the purification process may be reduced by 10 to 100 times or more than before purification, that is, almost all of the metal remaining can be removed, which is a boiling point of the chlorinated metal
  • Chlorinating the residual metal by reacting the metal remaining in the prepared carbon nanotubes with a chlorine-containing compound at a first temperature in a vacuum or inert gas atmosphere; And evaporating and removing the chlorinated residual metal at a second temperature at a temperature higher than the first temperature.
  • the chlorine-containing compound may be chlorine (Cl 2 ) or trichloromethane (CHCl 3 ) gas. Since chlorine-containing compounds have low reactivity with carbon nanotubes, the damage to the manufactured carbon nanotubes can be further reduced.
  • a first temperature of the metal chlorination takes place (T 1) may be a 500 °C to 1000 °C, may be more preferably 700 °C to 900 °C. At temperatures below 500 ° C, chlorination of metal impurities such as catalyst metals in the carbon material may not be smooth.
  • the heating process after the chlorination of the metal is performed at a second temperature T 2 , which is higher than the first temperature T 1 , and specifically, T 2 may be a temperature of T 1 + 300 ° C. or more.
  • the second temperature may range from 800 ° C to 1500 ° C, preferably 900 ° C to 1500 ° C, and more preferably 900 ° C to 1400 ° C. If the reaction proceeds at a temperature below 900 ° C. or lower than the first temperature, the removal reaction of chlorinated metal is not smooth and residual metal and chlorinated metal may remain in the carbon nanotubes to act as impurities. Can be reduced. In addition, the catalyst graphitization by the residual metal occurs at a temperature higher than 1500 °C, it may not be easy to remove the metal.
  • the chlorination reaction carried out at the first temperature may be maintained for about 10 minutes to 1 hour to make the chlorination process of the residual metal more completely, and the total flow rate depends on the size of the charged carbon nanotubes and the reactor. I can regulate it.
  • the metal chlorination evaporation and removal reaction at the second temperature may be performed for 30 minutes to 300 minutes in an inert gas or vacuum atmosphere, and this may remove only the chlorinated residual metal without affecting carbon nanotubes. It should be within the range
  • the metal chlorine evaporation and removal reaction may proceed while alternately forming a vacuum atmosphere and an inert gas atmosphere, which may further increase the removal efficiency.
  • the chlorination reaction of the residual metal may occur in a vacuum or nitrogen gas atmosphere. More specifically, the reaction in which the residual metal is chlorinated by adding a chlorine-containing compound gas after heating the carbon nanotube-filled reactor or reactor to a first temperature in a vacuum or nitrogen atmosphere. In this case, in the chlorination process performed at the first temperature, only the chlorination reaction of the metal may occur, and the removal reaction by evaporation of the chlorinated residual metal may occur mainly at the second temperature. At this time, the step of evaporation and removal of the residual metal is to stop the addition of the chlorine-containing compound and proceed again by converting the reaction furnace or the inside of the reactor into a vacuum atmosphere, the evaporation of the metal chloride may occur more smoothly.
  • the vacuum atmosphere means a pressure of 1 torr or less
  • the inert gas means an inert gas such as nitrogen (N 2 ) or argon (Ar).
  • the second process in which the evaporation and chlorinated metal removal reaction occurs may be performed at a pressure of 500 tortor to 800 tor, preferably 600 to 700 torr.
  • the metal chloride and chlorine compound removal and evaporation processes proceeding to the second temperature may be alternately applied with a vacuum and an inert gas atmosphere, and may be pressured in the form of a pulse.
  • the inert gas is added again, the pressure is applied to 500torr, and the process of forming a vacuum again may be repeated. Residual metals can also be removed, resulting in higher purification efficiency.
  • the metal impurity content of the carbon nanotubes from which the residual metal is removed by the above method may be 50 ppm or less, and may be measured through the metal impurity ICP analysis of the carbon nanotubes.
  • the carbon nanotubes may be to use a metal catalyst containing a metal such as cobalt (Co), iron (Fe) as a main component, in this case, the content of the main component metal after purification is less than 40ppm each
  • the total content may be 50 ppm or less.
  • the carbon nanotube purification method as described above can effectively remove residual metals such as catalytic metals while using ultrasonic waves while suppressing damage or cutting of carbon nanotubes or solidifying carbon nanotubes to amorphous carbon materials. It can be purified without being able to suppress the physical damage or cutting of the carbon nanotubes, thereby providing a carbon nanotubes with improved mechanical and physical properties, in particular carbon nanotubes significantly improved in thermal stability Can be provided.
  • the carbon nanotubes according to the present invention may be prepared by growing carbon nanotubes by chemical vapor deposition (CVD) through decomposition of a carbon source using a supported catalyst, and the catalyst metal supported on the supported catalyst is carbon nanotubes. It will not be restrict
  • Examples of such a catalytic metal include at least one metal selected from the group consisting of Groups 3 to 12 of the Group 18 periodic table recommended by IUPAC in 1990. Among them, at least one metal selected from the group consisting of Groups 3, 5, 6, 8, 9, and 10 is preferable, and iron (Fe), nickel (Ni), cobalt (Co), chromium (Cr), and molybdenum are preferred. At least one metal selected from (Mo), tungsten (W), vanadium (V), titanium (Ti), ruthenium (Ru), rhodium (Rh), palladium (Pd), platinum (Pt) and rare earth elements Particularly preferred.
  • a catalyst metal precursor inorganic salts, such as nitrate, sulfate, and carbonate of a catalyst metal
  • organic salts such as acetate, organic complexes, such as an acetylacetone complex, an organometallic compound, etc. It will not specifically limit, if it is a compound containing a catalyst metal.
  • catalyst metals and catalyst metal precursor compounds For example, at least one element selected from iron (Fe), cobalt (Co) and nickel (Ni), and an element selected from titanium (Ti), vanadium (V) and chromium (Cr) and molybdenum (Mo) and tungsten What combined the element chosen from (W) can be illustrated.
  • it may be a metal catalyst containing cobalt (Co) as a main component and further including at least one metal selected from iron (Fe), molybdenum (Mo), chromium (Cr), and vanadium (V).
  • the catalyst used in the carbon nanotube generation step is specifically a catalytically active metal precursor, Co (NO 3 ) 2 -6H 2O , (NH 4 ) 6 Mo 7 O 24 -4H 2 O, Fe (NO 3 ) 2 -6H 2 O or (Ni (NO 3) 2 -6H 2 O) was dissolved in distilled water, etc., and then, this Al 2 O 3, by wet impregnation (wet impregnation) of the support, such as SiO 2 or MgO may be manufactured.
  • a catalytically active metal precursor Co (NO 3 ) 2 -6H 2O , (NH 4 ) 6 Mo 7 O 24 -4H 2 O, Fe (NO 3 ) 2 -6H 2 O or (Ni (NO 3) 2 -6H 2 O) was dissolved in distilled water, etc., and then, this Al 2 O 3, by wet impregnation (wet impregnation) of the support, such as SiO 2 or MgO may be manufactured.
  • the catalyst may be prepared by ultrasonically treating a catalytically active metal precursor with a carrier such as Al (OH) 3 , Mg (NO 3 ) 2, or colloidal silica.
  • a carrier such as Al (OH) 3 , Mg (NO 3 ) 2, or colloidal silica.
  • the catalyst is prepared by the sol-gel method using a chelating agent such as citric acid (citric acid), tartaric acid (tartaric acid), so that the catalytically active metal precursor in water can be dissolved smoothly, or a catalyst that is well dissolved It may be prepared by co-precipitation of the active metal precursor.
  • a chelating agent such as citric acid (citric acid), tartaric acid (tartaric acid)
  • the supported catalyst and the carbon-containing compound may be prepared by contacting under a heating zone.
  • a supported catalyst by impregnation method in which the bulk density of the catalyst itself is higher than that of the coprecipitation catalyst and fine powder of 10 microns or less unlike the coprecipitation catalyst when the supported catalyst is used. This is because it is possible to reduce the possibility of fine powder due to wear (attrition) that can occur in the fluidization process, and because the mechanical strength of the catalyst itself is also excellent, it has the effect of stabilizing the operation of the reactor.
  • the aluminum-based support that can be used in the present invention may be one or more selected from the group consisting of Al 2 O 3 , AlO (OH) and Al (OH) 3 , and preferably may be alumina (Al 2 O 3 ).
  • the aluminum (Al) -based support may further include one or more selected from the group consisting of ZrO 2 , MgO and SiO 2 .
  • the aluminum (Al) -based support may have a spherical or potato shape, and may be made of a material having a porous structure, a molecular sieve structure, a honeycomb structure, or another suitable structure to have a relatively high surface area per unit mass or volume.
  • (4) calcining the resultant obtained by the vacuum drying to form a supported catalyst can be prepared by a method comprising a.
  • Carbon nanotubes can be prepared by chemical vapor phase synthesis in which carbon nanotubes are grown by chemical vapor phase synthesis through decomposition of a carbon source using the catalyst.
  • the chemical vapor phase synthesis method is a carbon nanotube catalyst is introduced into a fluidized bed reactor and at least one carbon source selected from saturated or unsaturated hydrocarbons having 1 to 4 carbon atoms at 500 °C ⁇ 900 °C, or the carbon source and hydrogen and nitrogen It can be carried out by injecting a mixed gas.
  • the carbon nanotubes are grown by injecting a carbon source into the catalyst for preparing carbon nanotubes, which may be performed for 30 minutes to 8 hours.
  • the carbon source may be a saturated or unsaturated hydrocarbon having 1 to 4 carbon atoms, such as ethylene (C 2 H 4 ), acetylene (C 2 H 2 ), methane (C 2 H 4 ), propane (C 3 H 8 ), and the like. May be, but is not limited thereto.
  • the mixed gas of hydrogen and nitrogen transports a carbon source, prevents carbon nanotubes from burning at a high temperature, and assists decomposition of the carbon source.
  • the carbon nanotubes prepared using the supported catalyst according to the present invention may be obtained in the form of a potato or sphere aggregate having a particle size distribution (D cnt ) of 0.5 to 1.0.
  • a catalyst obtained by impregnating and calcining a catalyst component and an active ingredient in a spherical or potato granular support also has a spherical or potato form without significant change in shape, and the carbon nanotube aggregates grown on such a catalyst also have a shape.
  • Another feature is to have a spherical or potato shape with only a large diameter without a large change of.
  • the spherical or potato shape refers to a three-dimensional shape such as a spherical and ellipsoidal shape having an aspect ratio of 1.2 or less.
  • the particle size distribution value (D cnt ) of the carbon nanotubes is defined by Equation 1 below.
  • Dn 90 is the number average particle diameter measured under 90% in absorbing mode using a Microtrac particle size analyzer after 3 hours of CNT in distilled water
  • Dn 10 is the number average particle diameter measured under 10%
  • Dn 50 is the number average particle diameter measured on a 50% basis.
  • the particle size distribution value may be preferably 0.55 to 0.95, more preferably 0.55 to 0.9.
  • the carbon nanotubes may be a bundle type or a non-bundle type having a flatness of 0.9 to 1, and the term 'bundle' used in the present invention, unless otherwise stated, refers to a plurality of carbon nanotubes. It refers to a bundle or rope form, in which the tubes are arranged or intertwined side by side.
  • 'Non-bundle (entangled) type' is a form without a certain shape, such as a bundle or rope shape, in the case of a bundle type CNT bundle may have a diameter of 1 to 50 ⁇ m.
  • Flatness ratio shortest diameter through the center of CNT / maximum diameter through the center of CNT.
  • the carbon nanotubes are characterized in that the bulk density (bulk density) is 80 ⁇ 250kg / m 3 .
  • the bulk density is defined by the following Equation 3, the density distribution of the carbon nanotubes can provide a range unique to the present invention.
  • the carbon nanotubes may have an average particle diameter of 100 to 800 ⁇ m, and a strand diameter of the carbon nanotubes may be 10 to 50 nm.
  • the boiling point can be lowered, and the temperature above the boiling point of the metal chloride
  • the carbon nanotubes may be purified using a process of evaporation and removal under conditions, and the carbon nanotubes manufactured by this method may have improved physical properties, and in particular, thermal stability may be improved, such as high temperature flame retardants and metal composite materials. It can be usefully used for carbon composites used in the environment.
  • Carbon nanotube synthesis was tested in a laboratory scale fixed bed reactor using a Co / Fe-containing metal catalyst for CNT synthesis. Specifically, the catalyst for synthesizing CNT prepared in the above process was mounted in the middle of a quartz tube having an internal diameter of 55 mm, and then heated and maintained at 650 ° C. in a nitrogen atmosphere, while flowing hydrogen gas at a flow rate of 60 sccm. Synthesis was carried out for 2 hours to synthesize an entangled (non-bundle) type carbon nanotube aggregate. The shape of the carbon nanotubes is shown in FIG. 1.
  • I G / I D by Raman spectroscopy of carbon nanotubes of Example 1 and Comparative Example 1 was measured at a laser wavelength of 532 nm using DXR Raman Microscope (Thermo Electron Scientific Instruments LLC). Were shown in Figure 3 to the Raman analysis, obtaining the I G / I D values are shown in Table 1 below.
  • the I G / I D value of the carbon nanotubes of Example 1 purified by the purification method according to the present invention was increased by more than 20%, which was carbon nano purified by the method according to the present invention It shows that the crystallinity of the tube is significantly improved.
  • the numerical values of the standard deviation and the relative standard deviation% become smaller, indicating that the purification process was performed uniformly for the entire sample, and secondly, the effect of improving the crystallinity from the purification process was also obtained. It can be shown that the carbon nanotubes having more homogeneous crystallinity can be produced by exhibiting the effect evenly in the first half.
  • the method for purifying carbon nanotubes according to the present invention can provide carbon nanotubes having excellent crystallinity without changing the shape and elements of the carbon nanotubes.
  • the carbon nanotubes according to the present invention can remove residual metals generated in the manufacturing process of carbon nanotubes using a metal catalyst by reacting with a chlorine compound at a high temperature, thereby effectively removing impurities such as residual metals. Can be removed.
  • the oxidation stability and conductivity is improved by improving the crystallinity may be useful for use as a composite material of the metal composite and the conductive polymer.

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Abstract

La présente invention concerne un nanotube de carbone qui est purifié par un procédé comprenant les étapes consistant à : faire réagir du métal restant dans un nanotube de carbone avec un composé contenant du chlore à une première température sous vide ou dans une atmosphère inerte; chlorer le métal restant; et faire évaporer et enlever le métal restant chloré à une deuxième température qui est plus élevée que la première température, un nanotube de carbone étant utilisé qui présente une valeur moyenne d'un rapport d'intensité (IG/ID) d'une bande G et d'une bande D, telle que mesurée par spectroscopie Raman, qui est augmentée de 20 % ou plus par rapport au nanotube de carbone avant purification.
PCT/KR2016/010338 2015-09-15 2016-09-13 Nanotube de carbone présentant une aptitude améliorée à la cristallisation WO2017048053A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018178929A2 (fr) 2017-03-31 2018-10-04 HYDRO-QUéBEC Procédé de purification de nanotubes de carbone bruts
FR3064623A1 (fr) * 2017-03-31 2018-10-05 Arkema France Processus de purification de nanotubes de carbone bruts
WO2018178929A3 (fr) * 2017-03-31 2018-12-20 HYDRO-QUéBEC Procédé de purification de nanotubes de carbone bruts
US11661344B2 (en) 2017-03-31 2023-05-30 Hydro-Quebec Method for the purification of raw carbon nanotubes

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