WO2019132265A1 - Nanotubes de carbone de type enchevêtré et leur procédé de fabrication - Google Patents

Nanotubes de carbone de type enchevêtré et leur procédé de fabrication Download PDF

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WO2019132265A1
WO2019132265A1 PCT/KR2018/014738 KR2018014738W WO2019132265A1 WO 2019132265 A1 WO2019132265 A1 WO 2019132265A1 KR 2018014738 W KR2018014738 W KR 2018014738W WO 2019132265 A1 WO2019132265 A1 WO 2019132265A1
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carbon nanotube
entangled
carbon nanotubes
acid
precursor
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PCT/KR2018/014738
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English (en)
Korean (ko)
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김성진
조동현
윤재근
김태형
김옥신
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주식회사 엘지화학
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Priority claimed from KR1020180146925A external-priority patent/KR102379594B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP18896577.6A priority Critical patent/EP3620434B1/fr
Priority to US16/628,555 priority patent/US11618679B2/en
Priority to JP2019571542A priority patent/JP6888223B2/ja
Priority to CN201880018122.XA priority patent/CN110418767B/zh
Publication of WO2019132265A1 publication Critical patent/WO2019132265A1/fr
Priority to US18/115,184 priority patent/US20230406706A1/en

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    • 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
    • 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

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  • the present invention relates to an entangled carbon nanotube and a method for manufacturing the same, and more particularly, to an entangled carbon nanotube having improved dispersibility and conductivity by controlling a ratio of a tap density to a bulk density, and a method for manufacturing the same .
  • Carbon nanotubes which are one kind of fine carbon fibers, are tubular carbon having an average diameter of 1 ⁇ m or less. It is expected to be applied to various fields due to its high conductivity, tensile strength and heat resistance due to its specific structure. However, despite the availability of such carbon nanotubes, the use of carbon nanotubes is limited due to their low solubility and dispersibility.
  • the carbon nanotubes were linearly dispersed in a dispersion medium, and a conductive material dispersion was prepared and used. However, carbon nanotubes are not stable in dispersion medium due to strong Van der Waals attraction between them, and coagulation phenomenon occurs.
  • An object of the present invention is to provide an entangled carbon nanotube excellent in dispersibility and conductivity and a method for producing the same.
  • the present invention provides an entangled carbon nanotube having a bulk density of 31 to 85 kg / m 3 and satisfying the following formula 1:
  • X is the tap density (unit: kg / m < 3 >) of the entangled carbon nanotube
  • Y is the bulk density (unit: kg / m3) of the entangled carbon nanotube.
  • the present invention also relates to a process for preparing a mixture comprising mixing an organic acid and a vanadium precursor in a molar ratio of 1: 0.0463 to 1: 0.0875 to prepare a mixture; Mixing the mixture with a cobalt precursor to produce a catalyst precursor; Subjecting the aluminum hydroxide to a first heat treatment to produce a support; Supporting a catalyst precursor on the support, and then performing a second heat treatment to produce a supported catalyst; And reacting the supported catalyst with the carbon-based compound.
  • the present invention also provides a method for manufacturing the entangled carbon nanotube.
  • the entangled carbon nanotube according to the present invention is excellent in conductivity and dispersibility and can be contained in a high concentration in the carbon nanotube dispersion.
  • Example 1 is a scanning electron microscope image of a surface of an Entangled carbon nanotube of Example 3 magnified 400 times.
  • Example 2 is an image of a scanning electron microscope obtained by enlarging the surface of the entangled carbon nanotube of Example 3 1,000 times.
  • Example 3 is a scanning electron microscope image of the surface of the Entangled carbon nanotube of Example 4 magnified 400 times.
  • Example 4 is an image of a scanning electron microscope obtained by enlarging the surface of the entangled carbon nanotube of Example 4 1,000 times.
  • a carbon nanotube refers to a pristine carbon nanotube that has not been subjected to any further processing.
  • the entangled carbon nanotubes refer to a secondary structure in which a plurality of carbon nanotubes are entangled without a uniform shape such as a bundle or a rope.
  • the bundle-type carbon nanotubes are formed by arranging a plurality of carbon nanotubes in a bundle or rope-like secondary structure in which axes in the longitudinal direction of the unit are aligned in substantially the same orientation, Shape.
  • the unit of carbon nanotubes is a graphite sheet having a nano-sized diameter cylinder shape and has an sp 2 bonding structure. At this time, depending on the angle and structure of the graphite surface, the characteristics of the conductor or semiconductor may be exhibited.
  • the unit of the carbon nanotube may be a single-walled carbon nanotube (SWCNT), a double-walled carbon nanotube (DWCNT), or a multi-walled carbon nanotube (DWCNT) according to the number of walls MWCNT, and multi-walled carbon nanotubes. The thinner the wall thickness, the lower the resistance.
  • the bulk density of the carbon nanotubes can be measured according to ASTM B329, specifically, according to ASTM B329-06.
  • the bulk density can be measured using a Scott volumeter (Version USP 616).
  • the bulk density of the carbon nanotubes can be measured in accordance with the laboratory conditions, and substantially the same result as the result based on the above rule can be obtained.
  • the Tapped Bulk Density (TD) of carbon nanotubes is measured in accordance with ASTM B527-06, and specifically, can be measured using TAP-2S manufactured by LOGAN.
  • the tap density of the carbon nanotubes can be measured in accordance with the laboratory conditions, and even when the measurement is performed in accordance with the laboratory scale, substantially the same results as those based on the above rule can be obtained.
  • the specific surface area of the carbon nanotube is measured by the BET method and can be calculated from the amount of nitrogen gas adsorbed at a liquid nitrogen temperature (77 K) using, for example, BEL Japan's BELSORP-mino II .
  • the average diameter and length of the carbon nanotube unit can be measured using an electric field-type scanning electron microscope.
  • the entangled carbon nanotube according to an embodiment of the present invention has a bulk density of 31 to 85 kg / m 3 and satisfies the following formula 1:
  • X is the tap density (unit: kg / m < 3 >) of the entangled carbon nanotube
  • Y is the bulk density (unit: kg / m3) of the entangled carbon nanotube.
  • the carbon nanotubes can not be dispersed in the dispersion medium at a high concentration in the production of the carbon nanotube dispersion.
  • the carbon nanotube units constituting the entangled carbon nanotubes are too close to each other and are not easily released in the solvent. As a result, there is a high possibility that the carbon nanotube unit is broken during the dispersion process of the ingot-type carbon nanotubes, and as a result, the conductivity may be deteriorated.
  • the bulk density of the entangled carbon nanotubes may be preferably 32 to 80 kg / m < 3 >, more preferably 32 to 68 kg / m < 3 >.
  • the carbon nanotube dispersion can be sufficiently dispersed and dispersed at a high concentration in the production of the carbon nanotube dispersion.
  • the formula 1 is an index showing the morphology of the entangled carbon nanotube.
  • the value of the formula 1 may be 1.37 to 2.05, preferably 1.4 to 2.0, and more preferably 1.49 to 2.0.
  • the value of the formula 1 is less than the above-mentioned range, it means that the carbon nanotube units are entangled carbon nanotubes which are closely intertwined with each other. Therefore, it is difficult for the carbon nanotube units to be easily dispersed in the production of the carbon nanotube dispersion.
  • Entangled carbon nanotubes satisfying the above-described bulk density and Equation 1 have sufficient particle properties as conventional Entangled carbon nanotubes, and have a loose structure between carbon nanotubes like bundled carbon nanotubes Lt; / RTI > That is, the shape may be an entangled shape, or may have some characteristics of a bundled carbon nanotube. Accordingly, the entangled carbon nanotubes can be dispersed at a high concentration because the dispersion of the carbon nanotubes may occur slowly during the production of the carbon nanotube dispersion. Also, since the carbon nanotube units are loose, the carbon nanotube units can be more easily released than the conventional entangled carbon nanotube unit when dispersed in the dispersion medium.
  • the breakage of the carbon nanotube unit during the dispersion process is reduced, and as a result, the carbon nanotube unit having a relatively long length in the dispersion medium can be present. Accordingly, the conductivity of the carbon nanotube dispersion can be further improved.
  • the tap density of the entangled carbon nanotubes may be preferably 63 to 116 kg / m 3, and more preferably 65 to 102 kg / m 3.
  • the carbon nanotube unit is loosened between the carbon nanotube unit and the carbon nanotube unit in the dispersion medium, As a result, a relatively long carbon nanotube unit can be present in the dispersion medium. Accordingly, the conductivity of the carbon nanotube dispersion can be further improved.
  • the BET specific surface area of the entangled carbon nanotube may be 100 to 300 m 2 / g, preferably 150 to 280 m 2 / g, and more preferably 170 to 250 m 2 / g.
  • powder resistance is excellent, and it is advantageous for high-concentration dispersion.
  • the entangled carbon nanotubes may have a powder resistance value of 0.0171? ⁇ Cm or less, a maximum dispersion concentration of 3.3% by weight or more, preferably a powder resistance value of 0.0170? ⁇ Cm or less and a maximum dispersion concentration of 3.4% More preferably, the powder resistance value may be 0.0168? ⁇ cm m or less, and the maximum dispersion concentration may be 3.5% by weight or more.
  • the entangled carbon nanotubes having excellent conductivity can be contained in the carbon nanotube dispersion liquid at a high concentration, so that they may be more suitable than the conductive carbon nanotubes.
  • the maximum dispersion concentration of the entangled carbon nanotubes is determined by preparing a carbon nanotube dispersion by gradually injecting carbon nanotubes into N-methylpyrrolidone, and thereafter dispersing the maximum amount of carbon nanotubes dispersible in the carbon nanotube dispersion . ≪ / RTI > The powder resistance value of the ingot-type carbon nanotubes was measured by filling the insulating mold with the ingot-type carbon nanotubes at 1 g / cc, pressing the mixture, and then using Loresta-GX (trade name: MITSUBISHI CHEMICAL ANALYTECH) The surface current and voltage can be measured and calculated with four probes.
  • the average diameter of the unit bodies of the entangled carbon nanotubes may be preferably 30 nm or less, more preferably 10 to 30 nm. When the above-mentioned range is satisfied, the dispersibility and the conductivity can be improved.
  • the average length of the unit pieces of the entangled carbon nanotubes may be preferably 0.5 ⁇ m to 200 ⁇ m, more preferably 10 to 60 ⁇ m. When the above-mentioned range is satisfied, it is excellent in electrical conductivity and strength, and stable at room temperature and high temperature.
  • the entangled carbon nanotube unit preferably has an aspect ratio defined by the ratio of the length of the carbon nanotube unit (the length of the long axis passing through the center of the unit) to the diameter of the carbon nanotube unit (passing the center of the unit and the length of the minor axis perpendicular to the long axis) May be from 5 to 50,000, and more preferably from 10 to 20,000.
  • the average diameter and length of the carbon nanotube unit can be measured using an electric field scanning electron microscope.
  • the carbon nanotube layer surface per unit interval is a carbon crystal obtained by X-ray diffraction method (d 002) and to the O.335 O.342 nm, layer surface spacing (d 002) ⁇ O.3448-0.0028 (log ⁇ ) ( wherein , and? is the average diameter of the carbon nanotube unit), and the thickness Lc of the crystal in the C axis direction may be 40 nm or less.
  • the interplanar spacing (d 002 ) may preferably be less than 0.3444-0.0028 (1og ⁇ ), and more preferably less than 0.3441-0.0028 (log ⁇ ). When the above range is satisfied, the crystallinity of the carbon nanotube unit is improved, so that the conductivity of the entangled carbon nanotube including the same can be further improved.
  • the entangled carbon nanotube according to an embodiment of the present invention comprises: 1) mixing an organic acid and a vanadium precursor in a molar ratio of 1: 0.0463 to 1: 0.0875 to prepare a mixture; 2) preparing a catalyst precursor by mixing the mixture with a cobalt precursor; 3) subjecting the aluminum hydroxide to a first heat treatment to produce a support; 4) supporting a catalyst precursor on the support, and then performing a second heat treatment to produce a supported catalyst; 5) and reacting the supported catalyst with the carbon-based compound.
  • an organic acid and a vanadium precursor are mixed in a molar ratio of 1: 0.0463 to 1: 0.0875 to prepare a mixture.
  • the organic acid and the vanadium precursor can be mixed preferably in a molar ratio of 1: 0.047 to 1: 0.086, more preferably in a molar ratio of 1: 0.0475 to 1: 0.077.
  • a molar ratio of 1: 0.047 to 1: 0.086 more preferably in a molar ratio of 1: 0.0475 to 1: 0.077.
  • the particle size distribution of the catalyst particles becomes small.
  • the molar ratio of the organic acid to the vanadium precursor exceeds the above-mentioned range, bundle-type carbon nanotubes are produced in addition to the entangled carbon nanotubes.
  • the organic acid may be at least one member selected from the group consisting of citric acid, tartaric acid, fumaric acid, malic acid, acetic acid, butyric acid, palmitic acid and oxalic acid, of which citric acid is preferable.
  • the vanadium precursor may be a salt of a vanadium compound, preferably at least one selected from the group consisting of NH 4 VO 3 , NaVO 3 , V 2 O 5 and V (C 5 H 7 O 2 ) 3 , NH 4 VO 3 is more preferable.
  • the mixture and the cobalt precursor are then mixed to produce a catalyst precursor.
  • the mixture and the cobalt precursor may be mixed so that the molar ratio of vanadium and cobalt is 1: 1 to 1: 100, preferably 1: 5 to 1:20.
  • the above-mentioned range is satisfied, there is an advantage that the yield is increased.
  • the mixture and the cobalt precursor that is, the organic acid, the vanadium precursor, and the cobalt precursor can be used in the form of a solution dissolved in a solvent, and the solvent can be at least one kind selected from the group consisting of water, methanol and ethanol, desirable.
  • the concentration of the citric acid, vanadium precursor and cobalt precursor in the solution may be preferably 0.1 to 3 g / ml, more preferably 0.5 to 2 g / ml, even more preferably 0.7 to 1.5 g / ml .
  • Al (OH) 3 aluminum hydroxide (Al (OH) 3 ) is subjected to a first heat treatment to produce a support.
  • the aluminum hydroxide may be pretreated before performing the first heat treatment.
  • the pretreatment may be carried out at 50 to 150 ° C for 1 to 24 hours. By performing the pretreatment, the residual solvent or impurities that may be present on the surface of the aluminum hydroxide can be removed.
  • the aluminum hydroxide may have an average particle diameter of 20 to 200 ⁇ ⁇ , a porosity of 0.1 to 1.0 cm3 / g, and a specific surface area of less than 1 m2 / g.
  • the first heat treatment may be performed at 250 to 500 ° C, preferably 400 to 500 ° C. Also, the first heat treatment may be performed in an air atmosphere.
  • Aluminum (OH) 3 is contained in an amount of 30 wt% or more, Al (OH) 3 is 70 wt% or less, specifically, AlO (OH) 3 is contained in an amount of 60% by weight or less, but does not contain Al 2 O 3 .
  • the support may further include a metal oxide such as ZrO 2 , MgO, and SiO 2 .
  • the shape of the support is not particularly limited, but may be spherical or potato-shaped.
  • the support may have a porous structure, a molecular sieve structure, a honeycomb structure, or the like so as to have a relatively high surface area per unit mass or unit volume.
  • a catalyst precursor is supported on the support and then subjected to a second heat treatment to produce a supported catalyst.
  • the support may be such that the support and the catalyst precursor are uniformly mixed and aged for a predetermined time.
  • the mixing can be carried out specifically by rotating or stirring at a temperature of 45 to 80 ⁇ ⁇ .
  • the aging can be carried out for 3 to 60 minutes.
  • the catalyst precursor may be supported on the support and then dried.
  • the drying may be carried out at 60 to 200 ° C for 4 to 16 hours.
  • the second heat treatment may be performed in an air atmosphere for 1 to 6 hours.
  • the second heat treatment may preferably be performed at 700 to 800 ° C.
  • a supported catalyst in which the catalyst precursor is present in a state coated on the surface and the pores of the support is produced.
  • the final product, entangled carbon nanotubes manufactured using the supported catalyst satisfies the above-described bulk density and Equation (1).
  • the supported catalyst is reacted with the carbon-based compound.
  • the reaction of the supported catalyst with the carbon-based compound can be carried out by a chemical vapor synthesis method.
  • the supported catalyst is fed into a horizontal fixed bed reactor or a fluidized bed reactor, and the temperature of the catalyst is maintained at a temperature not lower than the pyrolysis temperature of the carbon-based compound in the gaseous state (hereinafter referred to as').
  • the gas-phase carbon compound or a gas mixture of the gas-phase carbon compound and a reducing gas (for example, hydrogen) and a carrier gas (for example, nitrogen) is injected to decompose the gas- And then growing the carbon nanotubes.
  • the carbon nanotubes produced by the chemical vapor synthesis method as described above have a crystal growth direction nearly parallel to the tube axis and a high crystallinity of the graphite structure in the tube length direction. As a result, the diameter of the unit is small, and the electrical conductivity and strength are high.
  • the production of the entangled carbon nanotubes may be performed at a temperature of 500 to 800 ° C, more specifically 550 to 750 ° C. In the reaction temperature range, the weight of the carbon nanotubes is maintained while maintaining the bulk size of the carbon nanotubes while minimizing the generation of amorphous carbon, so that the dispersibility according to the reduction of the bulk density can be further improved.
  • the heat source for the heat treatment induction heating, radiation heat, laser, IR, microwave, plasma, surface plasmon heating and the like can be used.
  • the carbon-based compound can supply carbon, and can be used without limitation, as long as it can exist in a vapor state at a temperature of 300 ° C or higher.
  • the carbon-based compound may be a carbon-based compound having a carbon number of 6 or less. More specifically, the carbon-based compound may be carbon monoxide, methane, ethane, ethylene, ethanol, acetylene, propane, propylene, butane, butadiene, pentane, pentene, cyclopentadiene, Cyclohexane, benzene, and toluene.
  • a removal step for removing metal impurities from the metal catalyst remaining in the entangled carbon nanotube can be selectively performed.
  • the metal impurity removing step may be performed according to a conventional method such as washing and acid treatment.
  • Aluminum hydroxide (Al (OH) 3 ) as an aluminum-based support precursor was first heat-treated at 450 DEG C for 4 hours in an air atmosphere to prepare an aluminum-based support containing AlO (OH) in an amount of 40 wt% or more.
  • NH 4 VO 3 aqueous solution was prepared by adding citric acid and NH 4 VO 3 in water at a molar ratio of 1: 0.0475 and dissolving them.
  • Co V molar ratio of 10: Co so that the 1 (NO 3) 2 ⁇ 6H 2 O and NH 4 VO 3 Aqueous solution to prepare a clear aqueous solution of catalyst precursor aqueous solution.
  • the support and the catalyst precursor aqueous solution were mixed such that the amount of Co and the amount of V in the catalyst precursor aqueous solution were 23 moles and 2.3 moles, respectively, based on 100 moles of Al in the support.
  • the catalyst precursor aqueous solution was supported on the support in a thermostatic chamber at 60 DEG C for 5 minutes and then dried in an air atmosphere at 120 DEG C for 12 hours. Subsequently, the supported catalyst was subjected to a second heat treatment at 720 ⁇ ⁇ for 4 hours in an air atmosphere to prepare a supported catalyst.
  • 0.1 g of the supported catalyst was placed in the center of a quartz tube having an inside diameter of 55 mm in diameter located in the fixed bed reactor.
  • the inside of the fixed bed reactor was heated to 650 ° C in a nitrogen atmosphere and maintained.
  • the mixture was stirred for 60 minutes while flowing nitrogen gas, ethylene gas, and hydrogen gas at a ratio of 1: 1: 1 at 0.3 l / min to prepare an entangled carbon nanotube ≪ / RTI >
  • Citrate and NH 4 VO 3 1 a molar ratio of 0.05 was put into water and NH 4 VO 3 was dissolved Except that an aqueous solution was prepared in the same manner as in Example 1, except that an aqueous solution was prepared.
  • Citrate and NH 4 VO 3 1 a molar ratio of 0.072 was added to the water and dissolved NH 4 VO 3 Except that an aqueous solution was prepared in the same manner as in Example 1, except that an aqueous solution was prepared.
  • Citrate and NH 4 VO 3 1 a molar ratio of 0.082 was added to the water and dissolved NH 4 VO 3 Except that an aqueous solution was prepared in the same manner as in Example 1, except that an aqueous solution was prepared.
  • Citrate and NH 4 VO 3 1 a molar ratio of 0.085 was added to the water and dissolved NH 4 VO 3 Except that an aqueous solution was prepared in the same manner as in Example 1, except that an aqueous solution was prepared.
  • Entangled carbon nanotubes were prepared in the same manner as in Example 1, except that NH 4 VO 3 aqueous solution was prepared by adding citric acid and NH 4 VO 3 to water at a molar ratio of 1: 0.045 and dissolving them to prepare an NH 4 VO 3 aqueous solution.
  • Entangled carbon nanotubes were prepared in the same manner as in Example 1, except that NH 4 VO 3 aqueous solution was prepared by adding citric acid and NH 4 VO 3 at a molar ratio of 1: 0.09 to water and dissolving them to prepare an NH 4 VO 3 aqueous solution.
  • Citrate and NH 4 VO 3 1 a molar ratio of 5.8 was added to water and dissolved NH 4 VO 3
  • the carbon nanotubes were prepared in the same manner as in Example 1 except that an aqueous solution was prepared, but the shape of the carbon nanotubes produced was of the bundle type.
  • Entangled carbon nanotubes (manufacturer: bayer, trade name: C150P) were used.
  • Entangled carbon nanotubes (manufacturer: LG Chem) were used.
  • Example 3 Entangled carbon nanotubes of Examples 3 and 4 were photographed by a scanning electron microscope (SEM), the results of Example 3 are shown in Figs. 1 and 2, and the results of Example 4 are shown in Figs. 3 and 4 .
  • SEM scanning electron microscope
  • FIGS. 1 and 3 are SEM images obtained by enlarging the surface of the Entangled carbon nanotube 400 times
  • FIGS. 2 and 4 are SEM images showing the surface of the Entangled carbon nanotube enlarged 1,000 times.
  • Specific surface area (m 2 / g): It can be calculated from the adsorption amount of nitrogen gas under liquid nitrogen temperature (77K) using BEL Japan's BELSORP-mino II.
  • Powder resistance value (ohm-cm @ 1 g / cc): An insulating mold was filled with carbon nanotubes at 1 g / cc and pressed. Using Loresta-GX (trade name: MITSUBISHI CHEMICAL ANALYTECH) The surface current and voltage were measured with four probes and the powder resistance was calculated.
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 The molar ratio of citric acid and NH 4 VO 3 1: 0.0475 1: 0.05 1: 0.072 1: 0.082 1: 0.085 Secondary structural feature Entangled Entangled Entangled Entangled Entangled Manufacturing yield 11 11 18.5 21.8 22.7 Bulk density (kg / m3) 32 36 61 76 80 Tap density (kg / m3) 64 65 93 111 112 Tap Density / Bulk Density 2.0 1.8 1.52 1.46 1.41 Powder resistance value (ohm ⁇ cm @ 1 g / cc) 0.0162 0.0161 0.0166 0.0170 0.0171 Maximum dispersion concentration (% by weight) 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5
  • the entangled carbon nanotubes of Examples 1 to 5 prepared by adding citric acid and NH 4 VO 3 at a molar ratio of 1: 0.0475 to 1: 0.085 had a bulk density of 32 to 80 Kg / m < 3 >
  • the entangled carbon nanotubes of Examples 1 to 5 have low powder resistance and a high maximum dispersion concentration, they are not only excellent in conductivity but can be contained in the dispersion at a high concentration. Therefore, It could be predicted that it was appropriate.
  • the carbon nanotubes of Comparative Example 3 were prepared by mixing citric acid and NH 4 VO 3 1: 5.8, it was confirmed to be a bundle type and did not satisfy the formula (1). Further, even though the bundle-type carbon nanotubes of Comparative Example 3 are low in the powder resistance value, they can not be contained in the dispersion at a high concentration, and therefore, it is predicted that they are not suitable for use as a conductive material dispersion.

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Abstract

La présente invention concerne un nanotube de carbone de type enchevêtré ayant une masse volumique apparente de 31 à 85 ㎏/㎥ en masse et un rapport de masse volumique tassée au masse volumique apparente de 1,37-2,05. L'invention porte également sur son procédé de fabrication.
PCT/KR2018/014738 2017-12-26 2018-11-27 Nanotubes de carbone de type enchevêtré et leur procédé de fabrication WO2019132265A1 (fr)

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Application Number Priority Date Filing Date Title
EP18896577.6A EP3620434B1 (fr) 2017-12-26 2018-11-27 Nanotubes de carbone de type enchevêtré et leur procédé de fabrication
US16/628,555 US11618679B2 (en) 2017-12-26 2018-11-27 Entangled-type carbon nanotubes and method for preparing the same
JP2019571542A JP6888223B2 (ja) 2017-12-26 2018-11-27 エンタングル型カーボンナノチューブ及びその製造方法
CN201880018122.XA CN110418767B (zh) 2017-12-26 2018-11-27 缠结型碳纳米管及其制备方法
US18/115,184 US20230406706A1 (en) 2017-12-26 2023-02-28 Entangled-type carbon nanotubes and method for preparing the same

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KR1020180146925A KR102379594B1 (ko) 2017-12-26 2018-11-26 인탱글형 탄소나노튜브 및 이의 제조방법

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