WO2016126133A1 - Nanotubes de carbone de type faisceau à haute densité et leur procédé de préparation - Google Patents

Nanotubes de carbone de type faisceau à haute densité et leur procédé de préparation Download PDF

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WO2016126133A1
WO2016126133A1 PCT/KR2016/001278 KR2016001278W WO2016126133A1 WO 2016126133 A1 WO2016126133 A1 WO 2016126133A1 KR 2016001278 W KR2016001278 W KR 2016001278W WO 2016126133 A1 WO2016126133 A1 WO 2016126133A1
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catalyst
carbon nanotubes
spherical
carbon
supported catalyst
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Korean (ko)
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강경연
조동현
이승용
차진명
우지희
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주식회사 엘지화학
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Publication of WO2016126133A1 publication Critical patent/WO2016126133A1/fr

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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8877—Vanadium, tantalum, niobium or polonium
    • B01J35/30—
    • B01J35/51—
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/32—Specific surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/36—Diameter
    • 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
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/10—Solid density

Definitions

  • the present invention relates to a high density bundled carbon nanotubes and a method of manufacturing the same.
  • 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. Refers to. These CNTs consist of layers of aligned carbon atoms and have different types of cores. Such CNTs are also called carbon fibrils or hollow carbon fibers, for example.
  • CNTs are industrially important in the production of composites due to their size and specific properties, and have high utility in the field of electronic materials, energy materials and many other fields.
  • 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.
  • the catalyst used in the chemical vapor deposition method may be a carbon nanotube catalyst, a co-precipitation catalyst, etc., in which the catalytically active component has an oxide form, a partially or completely reduced form, or a hydroxide form, and can be generally used for preparing CNTs.
  • a double carbon nanotube catalyst which is because when the carbon nanotube catalyst is used, the bulk density of the catalyst itself is higher than that of the coprecipitation catalyst, and unlike the coprecipitation catalyst, the fineness of less than 10 microns is reduced, which may occur in the fluidization process. This is because the possibility of fine powder generation by attrition can be reduced, and the mechanical strength of the catalyst itself is also excellent, which can stabilize the reactor operation.
  • the prepared catalyst has a problem that the efficiency is low because a high metal loading amount compared to the amount produced during CNT synthesis.
  • the present invention to solve the above problems,
  • It provides a carbon nanotubes having a BET specific surface area of 1 to 50 m 2 / g and a bulk density of 60 to 250 kg / m 3 .
  • the carbon nanotubes may have a secondary structure in the form of a bundle.
  • the supported catalyst can be obtained by an impregnation method.
  • the total content of the catalyst component and the active ingredient may be 10 to 25 parts by weight based on 100 parts by weight of the spherical ⁇ -alumina.
  • the weight ratio of the catalyst component and the active ingredient may be 10 to 30: 1 to 14.
  • the catalyst component may be at least one of Fe, Co or Ni.
  • the ultrasonic fraction of the supported catalyst may be within 5%.
  • It provides a method for producing carbon nanotubes comprising the step of growing carbon nanotubes by decomposition of the carbon source injected on the catalyst surface.
  • the concentration of the aqueous metal solution may be 0.1 to 0.4 g / ml.
  • the aging impregnation process may be performed for 30 minutes to 15 hours at a temperature of 20 °C to 100 °C.
  • the firing temperature may be 550 °C to 800 °C.
  • after the vacuum drying process and before the firing process may further comprise the step of performing at least one preliminary baking at 250 to 400 °C.
  • the supported catalysts of the present invention can obtain CNT yields equal to or higher than those of low metals by using a spherical ⁇ -alumina support. Furthermore, the supported catalyst for synthesizing CNTs of the present invention can efficiently control CNT growth to synthesize bundle type high density CNTs.
  • FIG. 2 shows an SEM image of the supported catalyst obtained in Example 1.
  • FIG. 3 shows an SEM image of the support used in Comparative Example 1.
  • FIG. 4 shows an SEM image of the supported catalyst obtained in Comparative Example 1.
  • FIG. 5 shows a low magnification SEM image of CNTs obtained in Comparative Example 1.
  • FIG. 6 shows a high magnification SEM image of CNTs obtained in Comparative Example 1.
  • FIG. 7 shows a low magnification SEM image of the CNT obtained in Example 1.
  • FIG. 8 shows a high magnification SEM image of the CNT obtained in Example 1.
  • FIG. 9 shows a low magnification SEM image of CNTs obtained in Example 2.
  • FIG. 10 shows a high magnification SEM image of the CNT obtained in Example 2.
  • FIG. 11 shows a low magnification SEM image of CNTs obtained in Example 3.
  • FIG. 12 shows a high magnification SEM image of the CNT obtained in Example 3.
  • FIG. 13 shows a low magnification SEM image of CNTs obtained in Example 4.
  • FIG. 14 shows a high magnification SEM image of the CNT obtained in Example 4.
  • FIG. 15 shows an SEM image of the CNT obtained in Example 1.
  • FIG. 16 shows an SEM image of region A of FIG. 15.
  • FIG. 17 shows an SEM image of region B of FIG. 15.
  • the supported catalyst for synthesizing CNTs is supported on an Al-based support with a catalyst component and an active component
  • the Al-based support may include spherical ⁇ -alumina.
  • alumina having a chemical formula of Al 2 O 3 is present in several different phases, for example ⁇ -, ⁇ -, ⁇ -, ⁇ -, ⁇ - and ⁇ -alumina.
  • ⁇ -alumina corundum
  • the oxide ions form a hexagonally packed structure and the alumina ions are symmetrically distributed in the octahedral gap.
  • ⁇ -alumina has a "defective" spinel structure (the cation free spinel structure).
  • the support of the catalyst may comprise ⁇ -alumina.
  • ⁇ -alumina has high utility as a catalyst support due to its high porosity
  • ⁇ -alumina is known to have a very low utility as a catalyst support due to its very low porosity.
  • the CNT production method using the same as the catalyst support produces a high yield of CNTs even with a low metal loading when compared to a process using alumina having a different form and crystal structure as the catalyst support. It has been found that a bundle type spherical shape can be selectively obtained also in the shape of the resultant CNT.
  • the term "spherical" includes a case that is substantially spherical in addition to a perfect sphere, and may include a case having an elliptic cross section such as a potato shape.
  • the spherical ⁇ -alumina can be prepared by methods known in the art.
  • the Bayer method for producing alumina from bauxite is widely used industrially.
  • spherical ⁇ -alumina can be prepared by heating ⁇ -Al 2 O 3 or any hydrogen oxide above 1000 ° C.
  • the spherical ⁇ -alumina is dissolved in water-soluble precursors such as aluminum chloride or aluminum nitrate in water, and then the pH is about 8 or more, preferably about 9 or more, more preferably about 10 using an aqueous ammonia solution or a caustic soda solution.
  • the powder may be prepared by spray drying and then calcined at a temperature of about 1000 ° C. or higher, preferably 1100 to 1300 ° C., more preferably about 1200 ° C., but It is not limited.
  • the spherical ⁇ -alumina used as the support in the present invention may be of any suitable dimension.
  • a spherical ⁇ - alumina used in this invention as measured by the BET method may have a surface area of from about 1m 2 / g to about 50m 2 / g, for example, 1 to 30m 2 / g, for example 1 to 20 m 2 / g, for example 1 to 10 m 2 / g.
  • the spherical ⁇ - alumina used as the support has a very low porosity is smooth and even surface, unlike a conventional support, for example from 0.001 to 0.1cm 3 / g, for example from 0.005 to 0.05cm 3 / g It can have a pore volume of.
  • the spherical ⁇ -alumina which is a support, may be loaded with a relatively low content of metal, for example, about 10 to 25 parts by weight of the catalyst component and the active component based on 100 parts by weight of the spherical ⁇ -alumina, Or in an amount of about 15 to 20 parts by weight. Sufficient catalytic activity can be exhibited at such supported contents.
  • the catalyst component and the active component supported on the spherical ⁇ -alumina can be used in a weight ratio of 10 to 30: 1 to 14, and can exhibit better CNT production activity in this content range.
  • the catalyst component used in the present invention may be one or more selected from Fe, Co and Ni, for example Fe salt, Fe oxide, Fe compound, Co salt, Co oxide, Co compound, Ni salt, Ni oxide, Ni compound It may be one or more selected from the group consisting of, and as another example Fe (NO 3 ) 2 ⁇ 6H 2 O, Fe (NO 3 ) 2 ⁇ 9H 2 O, Ni (NO 3 ) 2 ⁇ 6H 2 O, Co (NO 3 ) a nitride such as 2 ⁇ 6H 2 O, or the like.
  • the active ingredient used in the present invention may be, for example, one or more of Mo and V, another example may be Mo salt, Mo oxide, Mo compound, V salt, V oxide, V compound, etc.
  • Mo salt Mo oxide
  • Mo compound Mo compound
  • V salt V oxide
  • V compound etc.
  • Nitrogen such as (NH 4 ) 6 Mo 7 O 24 4H 2 O and the like can be dissolved and used in distilled water.
  • the supported catalyst for synthesizing CNTs of the present invention as described above can be prepared by the impregnation method.
  • a method for preparing a supported catalyst for synthesizing CNTs wherein the Al-based support is spherical ⁇ -alumina.
  • the aqueous solution is formed by mixing the Al-based support in the aqueous metal solution containing the catalyst component precursor and the active component precursor, wherein the catalyst component, active Components and spherical ⁇ -alumina supports, which have already been described above.
  • the concentration of the metal aqueous solution is more efficient to use, for example, 0.1 to 0.4 g / ml, or 0.1 to 0.3 g / ml.
  • the content of the spherical ⁇ -alumina support mixed with the aqueous metal solution may be, for example, about 10 to 25 parts by weight based on 100 parts by weight of the spherical ⁇ -alumina, or It can be used to be supported in an amount of about 15 to 20 parts by weight.
  • step (2) of the preparation method Aging impregnation of the supported catalyst precursor solution in step (2) of the preparation method to obtain a mixture, wherein the impregnation is not limited to this, but 30 °C in the temperature range of 20 °C to 100 °C, or 60 to 100 °C It can be carried out for minutes to 15 hours, or 1 to 15 hours, it is possible to provide a high supporting efficiency in this range.
  • step (3) of the production method the mixture resulting from the aging impregnation obtained in step (2) is vacuum dried to coat the catalyst component and the active ingredient on the surface of the support.
  • the vacuum drying is to dry by rotary evaporation under vacuum, for example, can be carried out within 1 hour, or 1 minute to 1 hour under 45 to 80 °C, drying the excess metal salt remaining without impregnation in the support.
  • the process makes it possible to provide a coating impregnation of a uniform alumina surface.
  • vacuum in the vacuum drying described herein is not particularly limited as long as it corresponds to the vacuum range that is typically applied to vacuum drying.
  • step (4) of the production method the resultant obtained by vacuum drying in step (3) is fired to form a supported catalyst of the present invention, which is a final result, and such firing is about 550 to 800 ° C, or about 600 It may be carried out in the range of °C to 700 °C, it can be carried out in the air or under an inert atmosphere.
  • the firing time is not limited thereto, but may be performed within about 30 minutes to 5 hours.
  • the pre-baking may be carried out one or more times at about 250 to 400 °C, in this case immediately before the pre-firing Up to 50% of the supported catalyst precursor aqueous solution is impregnated with the spherical ⁇ -alumina support, and the remainder of the supported catalyst precursor aqueous solution is impregnated with the spherical ⁇ -alumina support immediately after or immediately before firing. It is desirable in terms of efficiency.
  • the bulk shape of the supported catalyst prepared as described above depends on the bulk shape of the spherical ⁇ -alumina support used. That is, the supported catalyst for synthesizing CNTs may have a spherical bulk shape and mainly have a structure in which a catalyst component is coated on one or multiple layers (two or three or more layers) on the surface of the support, and these may not have a continuous coating layer structure. It may be desirable to have a discontinuous coating structure in terms of CNT synthesis.
  • the supported catalyst for preparing CNTs provided by the present invention may have, for example, a particle size or an average particle diameter of about 30 to about 150 ⁇ m, and a surface particle size of SEM observation in a range of about 10 to 100 nm, in which CNT diameter Preferred in terms of control and catalytic activity.
  • the supported catalyst coated with the catalyst component and the active ingredient on the surface of the spherical ⁇ -alumina support is ultrasonic (ultrasonic) having a particle size of 32 ⁇ m or less based on the particle size measurement standard in consideration of the particle size or the average particle size range of the alumina support.
  • the number average particle size measurement may have a range of 5% or less, specifically 3% or less.
  • the fine powder is an aggregate of the catalyst material and the active material attached to the catalyst, and is not filtered out when sieved, but is different in particle size and catalyst activity from the catalyst-active material well coated on the support.
  • island-like aggregates attached to the catalyst significantly lower the yield of CNTs, and because the materials are rather weakly attached to the catalyst, they are separated at the time of ultrasonication to generate fine powder.
  • the ultrasonic differential amount refers to the number average particle diameter differential amount measured by the particle size analyzer after the ultrasonic treatment, wherein the support includes a multilayer support.
  • the supported catalyst for synthesizing CNTs obtained by the present invention is preferably spherical in consideration of specific surface area, and as shown in the SEM photograph of FIG. 1, the supported catalyst for synthesizing CNTs synthesized in the present invention is also spherical, almost spherical, Or substantially close to a sphere.
  • the process for preparing CNTs from the supported catalyst obtained by the above-described method includes, but is not limited to:
  • the reactor may be a fixed bed reactor or a fluidized bed reactor without limitation.
  • CNTs of the present invention obtained according to the production method is a potato or spherical bundle type having a bulk density of 60 to 250 kg / m 3 , flatness 0.9 to 1.0, particle size distribution (Dcnt) 0.5 to 1.0 (bundle type).
  • the term "bulk density” used in the present invention is defined by the following Equation 1, and because the amount of fine powder of the supported catalyst for synthesizing CNTs according to the present invention is small, the density distribution of CNTs grown therefrom may also have a specific range. .
  • the flatness and the bundle type can be obtained by a unique process prepared using the supported catalyst of the present invention described above.
  • the flatness ratio is defined by the following Equation 2.
  • Flatness shortest diameter through the center of CNT / maximum diameter through the center of CNT.
  • the particle size distribution value Dcnt may be defined by Equation 3 below.
  • Dn90 is the number average particle diameter measured under 90% in absorbing mode using Microtrac particle size analyzer after 3 hours of CNT in distilled water
  • Dn10 is the number average particle diameter measured under 10% reference
  • Dn50 is the number average particle diameter measured on a 50% basis.
  • the CNT obtained by the above production method may satisfy a particle diameter or an average particle diameter of 100 to 800 ⁇ m and a strand diameter of the CNTs of 10 to 50 nm.
  • the CNT of the present invention can be used as a raw material in the electric field, the electronic field, the energy field, etc., and can also be used as the reinforcing material in the plastic field.
  • Flask A was prepared completely dissolved in 15.0 ml.
  • Example 1 Spherical ⁇ -Al 2 O 3 680 0.01 4.9
  • Example 2 Spherical ⁇ -Al 2 O 3 660 0.01 4.9
  • Example 3 Spherical ⁇ -Al 2 O 3 620 0.01 4.9
  • Example 4 Spherical ⁇ -Al 2 O 3 600 0.01 4.9 Comparative Example 1 ⁇ -Al 2 O 3 680 0.55 185
  • FIG. 1 shows SEM images of the spherical ⁇ -alumina used as the support in Examples 1 to 4, and it can be seen that the support has a shape that is almost spherical.
  • FIG. 2 shows an SEM image of the supported catalyst obtained according to Example 1, and it can be seen that it has a substantially spherical shape similarly to the support.
  • Figure 3 shows an SEM image of the ⁇ -alumina used as the support in Comparative Example 1, it can be seen that the shape of the support has a rather irregular shape rather than spherical.
  • 4 shows an SEM image of the supported catalyst obtained according to Comparative Example 1, and it can be seen that the shape has a somewhat irregular shape similarly to the support.
  • Carbon nanotube synthesis was tested in a laboratory scale fixed bed reactor using the catalysts for synthesizing CNTs prepared in Examples 1 to 4 and Comparative Example 1. Specifically, the catalyst for synthesizing CNT prepared in the above process was mounted in the middle of a quartz tube having an inner diameter of 55 mm, and then heated up to 650 ° C. in a nitrogen atmosphere and maintained therein, and hydrogen gas was flowed at a flow rate of 60 sccm. Synthesizing for 3 hours while flowing to synthesize a predetermined amount of carbon nanotube aggregates. The CNT yield and bulk density at this time are described in Table 4 below.
  • Example 1 15.3 87 91.2
  • Example 2 15.3 60 102
  • Example 3 15.3 51 100
  • Example 4 15.3 27 60 Comparative Example 1 23.2 85 111.9
  • the supported catalysts obtained in Examples 1 to 4 showed better CNT yields even though the amount of metal supported was less than that of Comparative Example 1, and the bulk density was lower to obtain a larger diameter CNT. It can be seen that.
  • FIGS. 7 and 8 show low and high magnification SEM images of the CNT aggregates obtained in Example 1
  • FIGS. 9 and 10 show low and high magnification SEM images of the CNT aggregates obtained in Example 2
  • FIGS. 11 and FIG. 12 shows low and high magnification SEM images of the CNT aggregates obtained in Example 3
  • FIGS. 13 and 14 show low and high magnification SEM images of the CNT aggregates obtained in Example 14.
  • FIG. 7 to FIG. 14 when the CNT is prepared using the supported catalyst obtained according to the present invention, it can be confirmed that a large diameter CNT having a shape substantially close to a spherical shape and having a larger diameter is obtained. .
  • FIG. 15 is a SEM image of the CNT obtained in Example 1
  • FIG. 16 is an enlarged view of region A of FIG. 15
  • FIG. 17 is an enlarged view of region B of FIG. 15. It can be seen from FIGS. 16 and 17 that the CNTs obtained using the supported catalyst of the present invention have a secondary structure in the form of bundles.

Abstract

La présente invention concerne : des nanotubes de carbone, qui sont cultivés sur un catalyseur supporté ayant un composant de catalyseur et un composant actif supporté sur un support d'α-alumine sphérique, et ont une aire de surface spécifique BET de 1 à 50 m2/g et une densité en vrac de 60 à 250 kg/m3; et un procédé de préparation correspondant.
PCT/KR2016/001278 2015-02-06 2016-02-05 Nanotubes de carbone de type faisceau à haute densité et leur procédé de préparation WO2016126133A1 (fr)

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CN114618516A (zh) * 2022-03-17 2022-06-14 无锡东恒新能源科技有限公司 一种微球状催化剂的合成方法

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WO2018169366A1 (fr) * 2017-03-17 2018-09-20 주식회사 엘지화학 Nanotube de carbone de type faisceau et sa méthode de production
KR102124951B1 (ko) 2017-03-17 2020-06-22 주식회사 엘지화학 번들형 탄소나노튜브 및 이의 제조방법
KR102450747B1 (ko) 2018-07-27 2022-10-06 주식회사 엘지화학 탄소나노튜브의 제조방법
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