WO2015047042A1 - Nanotube de carbone ayant une surface spécifique élevée et son procédé de fabrication - Google Patents

Nanotube de carbone ayant une surface spécifique élevée et son procédé de fabrication Download PDF

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WO2015047042A1
WO2015047042A1 PCT/KR2014/009225 KR2014009225W WO2015047042A1 WO 2015047042 A1 WO2015047042 A1 WO 2015047042A1 KR 2014009225 W KR2014009225 W KR 2014009225W WO 2015047042 A1 WO2015047042 A1 WO 2015047042A1
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surface area
catalyst
carbon nanotubes
specific surface
carbon
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PCT/KR2014/009225
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English (en)
Korean (ko)
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김성진
손승용
우지희
이동철
강경연
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주식회사 엘지화학
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Priority claimed from KR20140129449A external-priority patent/KR101508101B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP14847473.7A priority Critical patent/EP3053877B1/fr
Priority to CN201480003597.3A priority patent/CN104870363B/zh
Priority to US14/438,165 priority patent/US11090635B2/en
Priority to JP2015544018A priority patent/JP6217755B2/ja
Publication of WO2015047042A1 publication Critical patent/WO2015047042A1/fr

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    • B01J35/40—
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B01J21/185—Carbon nanotubes
    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8906—Iron and noble metals
    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8913—Cobalt and noble metals
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

  • the present invention relates to a supported catalyst production method, particularly a carbon nanotube having a high specific surface area and a method for producing the same.
  • Carbon nanostructures refers to nanoscale carbon nanostructures having various shapes such as nanotubes, nanohairs, fullerenes, nanocones, nanohorns, and nanorods. High utilization in the technical field.
  • carbon nanotubes is a material in which the carbon atoms arranged in a hexagonal shape in the form of a tube, the diameter is approximately 1 to 100 nm.
  • CNTs carbon nanotubes
  • Such CNTs exhibit non-conductor, conductor or semiconducting properties depending on their unique chirality, and the carbon atoms are connected by strong covalent bonds, resulting in approximately 100 times greater tensile strength than steel, and excellent flexibility and elasticity. It is also chemically stable.
  • the type of CNT includes a single-walled carbon nanotube (SWCNT) composed of one layer and a diameter of about 1 nm, and a double-walled carbon composed of two layers and a diameter of about 1.4 to 3 nm.
  • nanotubes, DWCNTs) and multi-walled carbon nanotubes (MWCNTs) having a diameter of about 5 to 100 nm and consisting of three or more layers.
  • CNTs Due to characteristics such as chemical stability, excellent flexibility and elasticity, CNTs are being commercialized and applied in various fields, such as aerospace, fuel cells, composites, biotechnology, medicine, electrical and electronics, and semiconductors.
  • the primary structure of the CNT has a limit in directly adjusting its diameter or length to actual specifications for industrial applications, and thus, despite the excellent properties of the CNT, there are many limitations in industrial applications or applications.
  • the CNT is generally manufactured by arc discharge, laser ablation, chemical vapor deposition, or the like.
  • the arc discharge method and the laser evaporation method are difficult to mass-produce, and excessive arc production cost or laser equipment purchase cost is a problem.
  • the chemical vapor deposition method has a problem that the synthesis rate is very slow in the case of using a gas phase dispersion catalyst and the particles of the synthesized CNT are too small. There is a limit to mass production. Therefore, in order to increase the yield of CNT in chemical vapor deposition, studies on catalysts, reaction conditions, and the like are continuing.
  • CNTs having a high specific surface area and having a form that can be well dispersed and mixed during compounding are required.
  • an object of the present invention is to provide a method capable of providing a high yield of CNTs having a high specific surface area and having a bundled structure that can be well dispersed and mixed with a polymer.
  • Another object of the present invention is to provide a method for producing a CNT having the bundled structure.
  • the BET specific surface area is 200 m 2 / g or more, and the ratio of the G band peak integral (I G ) and the D band peak integral (I D ) (I G / I D ) by the BET specific surface area and Raman analysis is It provides a bundle of carbon nanotubes that satisfies the relationship.
  • y is the BET specific surface area
  • x is the I G / I D value
  • a is a constant from -400 to -500
  • b is a constant from 600 to 800.
  • the carbon nanotubes also satisfy the following relation.
  • y is the BET specific surface area (m 2 / g) and x is the I G / I D value.
  • a ratio (I G / I D ) of the G band peak integrated value (I G ) and the D band peak integrated value (I D ) of the carbon nanotubes may be 0.7 to 1.3.
  • the carbon nanotubes are formed by first firing a support precursor having a BET specific surface area of 1 m 2 / g or less at a first firing temperature of 100 ° C. to 450 ° C., and supporting a graphitized metal catalyst on the support. It may be prepared using a supported catalyst obtained by second firing at a second firing temperature of 100 ° C to 500 ° C.
  • the supported catalyst may be selected to have a particle size of 30 to 150 ⁇ m and a number average particle diameter (Mn) of 40 to 80 ⁇ m.
  • the support is aluminum-based, and in particular, the support precursor is preferably aluminum hydroxide [Al (OH) 3 ].
  • the second firing temperature is 100 °C to 300 °C.
  • the graphitized metal catalyst is nickel (Ni), cobalt (Co), iron (Fe), platinum (Pt), gold (Au), aluminum (Al), chromium (Cr), copper (Cu) ,
  • zirconium (Zr) may be at least one metal or alloy selected from the group consisting of.
  • the graphitized metal catalyst may be a multi-component metal catalyst including a main catalyst-catalyst.
  • the main catalyst may be at least one selected from Co and Fe, and the cocatalyst may be at least one selected from Mo and V.
  • the graphitized metal catalyst may be a binary metal catalyst selected from Co / Mo, Co / V, Fe / Mo and Fe / V.
  • the graphitized metal catalyst may have a content of 0.5 to 5 moles of a cocatalyst with respect to 10 moles of the main catalyst.
  • the graphitization catalyst may be 5 to 40 parts by weight based on 100 parts by weight of the supported catalyst.
  • the present invention also provides a support by forming a support by first baking a support precursor having a BET specific surface area of 1 m 2 / g or less at a first firing temperature of 100 ° C. to 450 ° C., after supporting the graphitized metal catalyst on the support, It provides a carbon nanotube manufacturing method comprising the step of contacting the supported catalyst obtained by the second firing at a second firing temperature of 100 °C to 500 °C contact with the gaseous carbon source to form carbon nanotubes (CNT).
  • a support precursor having a BET specific surface area of 1 m 2 / g or less at a first firing temperature of 100 ° C. to 450 ° C.
  • the specific surface area of the carbon nanotubes may increase.
  • the gaseous carbon source may be at least one selected from the group consisting of carbon monoxide, methane, ethane, ethylene, ethanol, acetylene, propane, propylene, butane, butadiene, pentane, pentene, cyclopentadiene, hexane, cyclohexane, benzene and toluene .
  • the reaction temperature may be 600 °C to 750 °C.
  • the present invention also provides a composite material including the bundled carbon nanotubes.
  • the present invention since a carbon nanotube (CNT) having a large specific surface area and having a shape that can be well dispersed and mixed can be obtained, it is possible to improve physical properties of the composite material including the CNT. As a result, the CNTs according to the present invention can be usefully used in various fields such as energy materials, functional composites, medicines, batteries, semiconductors, and display devices.
  • CNT carbon nanotube
  • 1 is a graph showing the relationship between the BET specific surface area and the IG / ID value of the carbon nanotube aggregate prepared according to an embodiment of the present invention.
  • FIG. 2 shows a SEM photograph of the bundled CNTs obtained in Example 3.
  • FIG. 3 shows the SEM photograph of the bundled CNT obtained in Example 12.
  • FIG. 4 shows the SEM photograph of the unbundled CNT obtained in Comparative Example 1.
  • FIG. 5 shows an SEM photograph of the unbundled CNT obtained in Comparative Example 2.
  • the present invention provides a method and method for producing the same, in which the specific surface area and form of the resulting CNTs can be suitably controlled by optimizing processes including pretreatment of the support, formation of the supported catalyst, and formation of the CNTs. It relates to CNT obtained by.
  • 'bundle type' refers to a secondary shape in the form of a bundle or a rope, in which a plurality of CNTs are arranged or intertwined side by side, unless otherwise stated.
  • 'Non-bundle or entangled type' means a shape without a certain shape, such as a bundle or a rope shape.
  • Raman analysis is a method for analyzing the structure of CNTs, which is useful for surface state analysis of CNTs.
  • the peak present in the region near the wavenumber of 1580 cm ⁇ 1 in the CNT Raman spectrum is called a G-band, which represents the SP 2 bond of the CNT, which represents a carbon crystal without structural defects.
  • the peak present in the region near the wave number 1360cm -1 in the Raman spectrum is called D-band, which indicates the SP 3 bond of CNTs, which represents carbon containing a structural bond.
  • the peak integrals of the G band and the D band are referred to as I G and I D , respectively.
  • the G band of the Raman spectrum for the CNT of the present invention may be a peak present in the wavenumber 1580 ⁇ 50 cm ⁇ 1 region, and the D band may be a peak present in the wavenumber 1360 ⁇ 50 cm ⁇ 1 region.
  • the wave range for the G band and the D band corresponds to a range that can be shifted according to the laser light source used in the Raman analysis.
  • the Raman value used in the present invention is not particularly limited, but is preferably measured at a laser wavelength of 532 nm using DXR Raman Microscope (Thermo Electron Scientific Instruments LLC).
  • the ratio of the G band peak integral value (I G ) and the D band peak integral value (I D ) of the Raman spectrum is 0.7 to 1.3. If less than 5, it means that the amorphous carbon is contained in a large amount or the crystallinity of the CNT is poor, but in the present invention, as the BET specific surface area is increased and the secondary shape of the bundled structure, the crystallinity of the CNT is good. It will have a range as described above.
  • the bundle type CNT according to the present invention has a BET specific surface area of 200 m 2 / g or more, and G band peak integral value (I G ) and D band peak integral value (I G ) by BET specific surface area and Raman analysis.
  • D ratio (I G / I D) of) a relationship that is inversely proportional at a predetermined ratio, and satisfy the following relation in detail.
  • y is the BET specific surface area
  • x is the I G / I D value
  • a is a constant from -400 to -500
  • b is a constant from 600 to 800.
  • a may be a constant of -400 to -450 or -450 to -500
  • b may be a constant of 600 to 700, or 650 to 750, or 700 to 800.
  • the carbon nanotubes also satisfy the following relation.
  • the specific surface area used in the present invention is measured by the BET method. Specifically, the specific surface area used is calculated by calculating the amount of nitrogen gas adsorption under liquid nitrogen temperature (77K) using BEL Japan's BELSORP-mini II. .
  • CNTs according to the invention have a BET specific surface area of 200 to 500 m 2 / g, or 200 to 300 m 2 / g, or 300 to 500 m 2 / g, or 300 to 400 m 2 / g, or 200 to 400 m Can be 2 / g.
  • CNTs according to the present invention have an I G / I D value of about 0.7 to about 1.3, or 0.7 to 1.1, or 0.7 to 1.0, or about 0.7 to 0.9, or 0.8 to 1.0, or 0.9 to 1.1, as determined by Raman analysis. It may have a range of.
  • Figure 1 graphically shows the relationship between the specific surface area and the I G / I D ratio of the CNT prepared according to the embodiment of the present invention.
  • Conventional CNTs tend to increase the I G / I D ratio as the BET specific surface area increases, but CNTs according to the present invention tend to constantly decrease the I G / I D ratio as the BET specific surface area increases. can confirm.
  • the ratio of the G band peak integral (I G ) and the D band peak integral (I D ) by the BET specific surface area and the Raman analysis method (I G / I D ) may satisfy the following relationship. have.
  • CNTs according to one embodiment may satisfy the following relationship.
  • the CNT may satisfy the following relationship.
  • the CNT may satisfy the following relationship.
  • a graphitization catalyst is supported on a support obtained therefrom, and then, at a temperature of 100 ° C. to 500 ° C.
  • a supported catalyst prepared by second firing at a temperature is prepared.
  • the supported catalyst may be contacted with a gaseous carbon source to prepare a bundle-type carbon nanotube having a BET specific surface area of preferably 200 m 2 / g or more.
  • the support precursor used in the preparation method serves to support the graphite catalyst, and can control the shape of the CNTs according to the type thereof.
  • an aluminum-based support precursor preferably aluminum hydroxide (aluminum-tri-hydroxide, ATH) can be used.
  • a support precursor can be used by drying for 1 hour to 24 hours at 50 °C to 150 °C.
  • the first firing temperature is preferably less than 500 ° C., much lower than 700 ° C., which is known to convert aluminum hydroxide to alumina. That is, the first firing may include a heat treatment process performed at a temperature of about 100 ° C to about 450 ° C, or about 120 ° C to about 400 ° C, or 200 to 450 ° C, or 300 to 450 ° C, or 200 to 400 ° C. Can be.
  • the aluminum-based support formed by the above process preferably contains 30 wt% or more of AlO (OH) converted from Al (OH) 3 and does not include 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 have 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.
  • the support precursor may have a primary particle size of about 20 to about 200 ⁇ m, porosity of about 0.1 to about 1.0 cm 3 / g, specific surface area of less than about 1 m 2 / g.
  • the first firing process may be performed for about 0.5 hours to about 10 hours, preferably about 1 hour to 5 hours, but is not limited thereto.
  • CNTs Contacting the graphitization catalyst used in the preparation method with a gaseous carbon source can form CNTs.
  • the growth process of CNTs is described above.
  • the carbonaceous material which is a gaseous carbon source
  • the graphite catalyst for example, a graphite metal catalyst
  • the carbonaceous material is thermally decomposed on the surface of the metal catalyst.
  • CNTs in which the carbon atom generated from the decomposed carbon-containing gas penetrates into the graphitized metal catalyst to be dissolved and then exceeds the solubility limit which is an inherent property of the graphitized metal catalyst.
  • the nucleation of the furnace occurs and grows into CNTs.
  • the graphitized metal catalyst serves to help the carbon components present in the carbonaceous material combine with each other to form a hexagonal ring structure, for example, to synthesize graphite, induce carbonization, or CNT It is possible to use the catalyst used to prepare the. More specifically, nickel (Ni), cobalt (Co), iron (Fe), platinum (Pt), gold (Au), aluminum (Al), chromium (Cr), copper (Cu), magnesium (Mg), With manganese (Mn), molybdenum (Mo), rhodium (Rh), silicon (Si), tantalum (Ta), titanium (Ti), tungsten (W), uranium (U), vanadium (V) and zirconium (Zr) One or more metals or alloys selected from the group consisting of can be used.
  • the graphitization catalyst may use a binary or ternary or higher polyvalent metal.
  • a binary or multi-part graphitization catalyst may be composed of a main catalyst and a promoter, Co, Fe, Ni, etc. may be used as the main catalyst, Mo, V, etc. may be used as the promoter.
  • Such binary or plural graphitization catalysts are Co / Mo, Co / V, Fe / Mo, Fe / V, Fe / Co, Fe / Co / V, Fe / Co / Mo, Co / Mo / V, Fe / Mo / V, Fe / Co / Mo / V, etc. are mentioned. Among these, it is more preferable that Co and V are included.
  • the component ratio thereof may be, for example, 0.1 to 10 moles or 0.5 to 5 moles of the cocatalyst based on 10 moles of the main catalyst.
  • the graphitization catalyst is supported on the support in the form of various precursors such as metal salts, metal oxides, or metal compounds.
  • various precursors such as metal salts, metal oxides, or metal compounds.
  • Fe salt, Fe oxide, Fe compound, Ni salt, Ni oxide, Ni compound, Co salt, Co oxide, Co compound, Mo oxide, Mo compound, Mo salt, V oxide, V compound, V salt, etc. can be illustrated.
  • Fe (NO 3 ) 2 ⁇ 6H 2 O, Fe (NO 3 ) 2 ⁇ 9H 2 O, Fe (NO 3 ) 3 , Fe (OAc) 2 , Ni (NO 3 ) 2 ⁇ 6H 2 O, Co (NO 3 ) 2 .6H 2 O, Co 2 (CO) 8 , [Co 2 (CO) 6 (t-BuC CH)], Co (OAc) 2 , (NH 4 ) 6 Mo 7 O 24 4H 2 O, Mo (CO) 6 , (NH 4 ) MoS 4 , NH 4 VO 3 , and the like can be used.
  • the precursor of the graphitization catalyst When the precursor of the graphitization catalyst is supported on the support in the form of a solution, and then undergoes a second firing process, it is mainly supported in the form of a metal oxide to form a supported catalyst.
  • a support for example a granular aluminum-based support in the precursor aqueous solution of the graphitization catalyst
  • the mixture is first baked at about 100 ° C. to about 450 ° C. to form a support, and the support is supported on a graphitized metal catalyst, which is then calcined at a second baking temperature of 100 ° C. to 500 ° C. To obtain a supported catalyst for producing CNTs obtained by impregnating and coating the graphitized catalyst component on the surface of the granular support and the pores.
  • the vacuum drying may be carried out by rotary evaporation in the range of about 30 minutes to about 12 hours under vacuum in the temperature range of about 40 to about 100 °C.
  • the method may include aging by rotation or stirring at about 45 to about 80 ° C. before the vacuum drying. For example, it may be performed for up to 5 hours, 20 minutes to 5 hours, or 1 to 4 hours.
  • the second firing process for forming the supported catalyst is performed at a temperature of about 100 ° C to about 500 ° C, and the lower the catalyst firing temperature, the higher the BET specific surface area.
  • the second firing temperature may be 100 to 500 ° C, or 100 to 400 ° C, or 100 to 300 ° C, or 100 to 200 ° C, or 200 to 300 ° C, or 200 to 400 ° C.
  • the particle size or average particle diameter measured before the second firing of the supported catalyst used in the preparation method is about 30 ⁇ m to about 150 ⁇ m, and the primary particle diameter of the granular support and the graphitization catalyst is about 10 nm to about 50 nm.
  • 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 supported catalyst when preparing a CNT according to the present invention using a fluidized bed reactor, in particular, has a particle diameter of about 30 ⁇ m to about 150 ⁇ m, a number average particle diameter (Mn) of 40 to 80 ⁇ m, or It can be used selectively to be 50 to 70 ⁇ m, or 50 to 70 ⁇ m. This is because it is important to ensure that the catalyst fluidized bed flows well without catalyst aggregation in the reaction zone in the fluidized bed reactor.
  • Mn number average particle diameter
  • the supported catalyst may include about 5 to about 40 parts by weight of the graphitization catalyst based on 100 parts by weight of the supported catalyst, but is not limited thereto.
  • the supported catalyst includes a Co-based graphitization catalyst
  • the content of Co may be about 3 to about 100 moles based on 100 moles of the support.
  • the graphitization catalyst may have a structure in which one or more layers are coated on the surface and pores of the granular support, preferably the aluminum-based support.
  • a supported catalyst using an impregnation method, in which the bulk density of the catalyst itself is higher than that of the coprecipitation catalyst and less than 10 microns, unlike the coprecipitation catalyst, when the supported catalyst is used. It is possible to reduce the possibility of fine powder due to attrition, which can occur during fluidization process because of the small amount of fine powder. Also, the mechanical strength of the catalyst itself is excellent, which makes it possible to stabilize the reactor operation.
  • CNTs may be prepared by growing CNTs by chemical vapor phase synthesis through decomposition of a carbon source using the supported catalyst as described above.
  • the CNT in the method for producing CNTs according to the chemical vapor phase synthesis method, after charging the graphitization catalyst in the reactor, the CNT can be prepared by supplying a gaseous carbon source under conditions of normal pressure and high temperature.
  • the growth of the CNTs is carried out by the process of infiltrating and saturating the pyrolyzed hydrocarbons by applying high temperature heat to the graphitization catalyst, and depositing carbons from the saturated graphitization catalyst to form a hexagonal ring structure.
  • the chemical vapor phase synthesis method is to add the supported catalyst to a horizontal fixed bed reactor or fluidized bed reactor and about 500 °C to about 900 °C, or about 500 °C to 800 °C, or about 600 °C to 800 °C, about 600 °C
  • One or more carbon sources selected from saturated or unsaturated hydrocarbons having 1 to 6 carbon atoms at a temperature of from about 750 ° C., or about 650 ° C. to about 700 ° C., or the carbon source with a reducing gas (eg, hydrogen) and a carrier gas ( For example, it may be carried out by injecting a mixed gas of nitrogen). Injecting a carbon source into the supported catalyst to grow the CNTs may be performed for 30 minutes to 8 hours.
  • the supply gas may be a carbon source and a reducing gas or a carrier gas, respectively, or a mixture thereof.
  • induction heating radiant heat, laser, IR, microwave, plasma, UV, surface plasmon heating, etc. can be used without limitation.
  • the carbon source used in the chemical vapor phase synthesis method may supply carbon, and any material that may exist in the gas phase at a temperature of 300 ° C. or higher may be used without particular limitation.
  • a gaseous carbonaceous substance any compound containing carbon may be used, and a compound having 6 or less carbon atoms is preferable, and more preferably a compound having 4 or less carbon atoms.
  • one or more selected from the group consisting of carbon monoxide, methane, ethane, ethylene, ethanol, acetylene, propane, propylene, butane, butadiene, pentane, pentene, cyclopentadiene, hexane, cyclohexane, benzene and toluene can be used. It is not limited.
  • the mixed gas of hydrogen and nitrogen transports the carbon source, prevents CNTs from burning at high temperatures, and assists in the decomposition of the carbon source.
  • Such gaseous carbon source, hydrogen and nitrogen can be used in various volume ratios, for example, the volume ratio of nitrogen: gaseous carbon source: hydrogen is 1: 0.1 to 10: 0 to 10, or 1: 0.5 to 1.5: 0.5 to 1.5 Can be used in the range of.
  • the flow rate of the reaction gas may use a range of about 100 to 500 sccm.
  • the CNTs are subjected to a cooling process.
  • the CNTs may be arranged more regularly by the cooling process.
  • Such cooling process may be natural cooling (removal of heat source), or cooling at a rate of about 5 ° C. to about 30 ° C. per minute.
  • a bundle type CNT having a BET specific surface area of about 200 m 2 / g or more, preferably about 200 m 2 / g to about 500 m 2 / g can be obtained.
  • the specific surface area can be measured by a conventional BET method.
  • the production method is capable of obtaining CNTs in high yield, for example, achieving a yield of about 5 to 50 times, or about 10 to 40 times.
  • the yield is obtained from the synthesized carbon nanotubes at room temperature and its content can be measured using an electronic balance.
  • the reaction yield can be calculated based on the weight of the supported catalyst used and the weight increase after the reaction based on the following formula.
  • the CNTs may be in a bundle having a flatness of about 0.9 to about 1, and each CNT strand diameter is about 2 nm to about 20 nm, preferably about 3 nm to about 8 nm, as the BET specific surface area increases. It may have a diameter.
  • the flatness may be defined by the following equation.
  • CNTs have a large BET specific surface area, that is, a low diameter, and have a bundle shape, so that the CNTs are well dispersed and mixed in other materials, for example, polymers, thereby improving physical properties when forming a composite material.
  • Electrode structures such as solar cells, fuel cells, lithium batteries and supercapacitors; Functional composite materials; Energy material; medicine; It can be usefully used for semiconductors such as FETs.
  • Co-V metal catalyst was prepared as a graphitization catalyst.
  • Citric acid was added to Flask A in which NH 4 VO 3 was dissolved in 20 ml water as the precursor material of V.
  • Co (NO 3 ) 2 .6H 2 O was added as a precursor material of Co so that the molar ratio of Co: V was 10: 1.
  • the prepared aqueous metal solution was observed as a clear solution without precipitation.
  • ATH400 obtained by calcining aluminum hydroxide (Aluminum-tri-hydroxide, Al (OH) 3 ) at 400 ° C for 4 hours as an aluminum-based support was prepared in Flask B. XRD analysis showed that after firing the support contained at least 40% by weight of AlO (OH).
  • CNT synthesis was tested in a laboratory scale fixed bed reactor using the supported catalyst prepared for CNT synthesis.
  • the catalyst for synthesizing CNT prepared in D was mounted in the middle of a quartz tube having an internal diameter of 55 mm, and then heated and maintained at 670 ° C. in a nitrogen atmosphere, and the volume of nitrogen, hydrogen, and ethylene gas was maintained.
  • the mixing ratio was synthesized for 1 hour while flowing 180 ml per minute in the same ratio to synthesize a predetermined amount of CNT aggregates.
  • the BET specific surface area was calculated by calculating the amount of nitrogen gas adsorption under liquid nitrogen temperature (77K) using BELSORP-mini II from BEL Japan.
  • I G / I D was measured at a laser wavelength of 532 nm using DXR Raman Microscope (Thermo Electron Scientific Instruments LLC).
  • Bundled CNTs were prepared by the same process as Example 1, except that the aluminum hydroxide was calcined at 300 ° C. instead of 400 ° C. (ATH300).
  • Bundled CNTs were prepared in the same manner as in Example 2, except that the reactor temperature was changed from 670 ° C to 690 ° C.
  • Bundled CNTs were prepared in the same manner as in Example 1, except that the reactor temperature was changed from 670 ° C. to 710 ° C.
  • Bundled CNTs were prepared in the same manner as in Example 1, except that the reactor temperature was changed from 670 ° C. to 690 ° C.
  • Bundled CNTs were prepared by the same process as Example 5, except that the molar ratio of Co: V was changed from 10: 1 to 20: 1.
  • Bundled CNT was prepared in the same manner as in Example 5 except that the molar ratio of Co: V was changed from 10: 1 to 5: 1.
  • Bundled CNTs were prepared in the same manner as in Example 7, except that Fe: Mo was used in a molar ratio of 5: 1 instead of Co: V in a molar ratio of 5: 1.
  • Bundled CNTs were prepared in the same manner as in Example 7, except that Co: V was used in a molar ratio of 5: 1 instead of Co: V in a molar ratio of 5: 1.
  • Bundled CNT was prepared by performing the same process as in Example 9 except that the calcining temperature of the supported catalyst was changed from 120 ° C. to 300 ° C.
  • a bundle-type CNT was prepared by performing the same process as in Example 9 except that the firing temperature of the supported catalyst was changed from 120 ° C. to 500 ° C.
  • Bundled CNTs were prepared in the same manner as in Example 9, except that 0 ml of nitrogen per minute, 60 ml of ethylene gas, and 120 ml of hydrogen per minute were flowed.
  • a CNT was prepared in the same manner as in Example 3 except that commercial boehmite was used as a support without performing a support calcining step.
  • a CNT was prepared in the same manner as in Example 3, except that commercial gamma-alumina was used as a support, and a support calcining process was not performed.
  • a CNT was prepared by performing the same process as in Example 9 except that the calcining temperature of the supported catalyst was changed from 120 ° C. to 700 ° C.
  • Example 1 Table 1 division Support Support firing temperature Catalytic metal Catalytic firing temperature Reactor temperature Mixed gas volume ratio (N 2 : C 2 H 4 : H 2 )
  • Example 1 ATH400 400 °C Co: V 10: 1 120 °C 670 °C 60:60:60 sccm
  • Example 4 ATH400 400 °C Co: V 10: 1 120 °C 710 °C 60:60:60 sccm
  • Example 5 ATH400 400 °C Co: V 10: 1 120 °C 690 °C 60:60:60 sccm
  • Example 6 ATH400 400 °C Co: V 20: 1 120 °C 690 °C 60:60:60 s
  • Examples 1, 2, 4, 5, and 8 satisfy the following relationship.
  • Example 3 satisfies the following relation.
  • Comparative Examples 1 to 6 have a specific surface area of 200 m 2 / g or more and bundle and satisfy the above relation.
  • Examples 3 and 5 in which the aluminum hydroxide support firing temperatures are 300 ° C. and 400 ° C., respectively, show different yields and BET surface areas, even though different process conditions are the same, It can be seen that it affects the yield and physical properties of the resulting CNTs.
  • Example 10 Example 11, Example 12 and Comparative Example 3, catalyst firing was performed at 120 ° C, 300 ° C, 500 ° C and 700 ° C, respectively, as the catalyst firing temperature was increased as shown in Table 2 above. It can be seen that the BET specific surface area decreases.
  • Examples 7 and 9 and 10 used binary catalysts of Co / V, Fe / Mo, and Co / Mo, respectively.
  • Examples 7 and 10, which are Co-based catalysts, have a high BET surface area and excellent yield. It can be seen that, especially in Example 7 using the CoV catalyst shows the best results.
  • Examples 5, 6 and 7 are Co: V ratios of 10: 1, 20: 1, and 5: 1, respectively, all of which show high BET specific surface area and high yield. It can be seen that the highest BET specific surface area is shown in Example 5 with a Co: V ratio of 10: 1.
  • Table 3 shows the yield, BET surface area, and I G / I D ratio of CNTs obtained using a catalyst prepared by varying the Co content (wt%) under the same reaction conditions as in Example 5.
  • Co content (wt%) was calculated as (Co impregnated weight / final catalyst weight) ⁇ 100.
  • Example 5 is referred to as Example 5-1 for convenience.
  • Example 7 and Example 12 only the mixing ratio of the reaction gas is different, it can be seen that the high specific surface area and yield are obtained in Example 7 where they are used in the same ratio.
  • Example 1 Example 4 and Example 5, the reaction temperature is 670 °C, 710 °C, and 690 °C, respectively, it can be seen that the highest BET specific surface area in Example 1, the temperature is 670 °C.
  • the present invention since a carbon nanotube (CNT) having a large specific surface area and having a shape that can be well dispersed and mixed can be obtained, it is possible to improve physical properties of the composite material including the CNT. As a result, the CNTs according to the present invention can be usefully used in various fields such as energy materials, functional composites, medicines, batteries, semiconductors, and display devices.
  • CNT carbon nanotube

Abstract

La présente invention concerne un procédé de production d'un catalyseur sur support capable de produire des nanotubes de carbone ayant une surface spécifique élevée, et des nanotubes de carbone obtenus en utilisant le catalyseur sur support. Les nanotubes de carbone peuvent être produits à un rendement élevé selon la présente invention, et peuvent donc être efficacement utilisés dans différents domaines.
PCT/KR2014/009225 2013-09-30 2014-09-30 Nanotube de carbone ayant une surface spécifique élevée et son procédé de fabrication WO2015047042A1 (fr)

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EP14847473.7A EP3053877B1 (fr) 2013-09-30 2014-09-30 Procédé de fabrication de nanotubes de carbone de type faisceau à surface spécifique élevée
CN201480003597.3A CN104870363B (zh) 2013-09-30 2014-09-30 具有高比表面积的碳纳米管及其制造方法
US14/438,165 US11090635B2 (en) 2013-09-30 2014-09-30 Carbon nanotube having high specific surface area and method for manufacturing same
JP2015544018A JP6217755B2 (ja) 2013-09-30 2014-09-30 高い比表面積を有する炭素ナノチューブ及びその製造方法

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US11171322B2 (en) 2015-12-10 2021-11-09 Lg Chem, Ltd. Positive electrode having improved pore structure in positive electrode active material layer
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CN107735890A (zh) * 2015-09-10 2018-02-23 Lg化学株式会社 用于二次电池的导电材料以及包含该导电材料的二次电池
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US11171322B2 (en) 2015-12-10 2021-11-09 Lg Chem, Ltd. Positive electrode having improved pore structure in positive electrode active material layer
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