WO2007100306A1 - Nanotube(s) de carbone et leur procédé de fabrication - Google Patents

Nanotube(s) de carbone et leur procédé de fabrication Download PDF

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Publication number
WO2007100306A1
WO2007100306A1 PCT/SG2007/000059 SG2007000059W WO2007100306A1 WO 2007100306 A1 WO2007100306 A1 WO 2007100306A1 SG 2007000059 W SG2007000059 W SG 2007000059W WO 2007100306 A1 WO2007100306 A1 WO 2007100306A1
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cnts
pyrolysis
cnt
tube
catalyst
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PCT/SG2007/000059
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English (en)
Inventor
Hui Pan
Jianyi Lin
Yuan Ping Feng
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National University Of Singapore
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Publication of WO2007100306A1 publication Critical patent/WO2007100306A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • 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
    • C01B2202/02—Single-walled nanotubes
    • 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
    • C01B2202/06—Multi-walled nanotubes
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0234—Carbonaceous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1007—Fuel cells with solid electrolytes with both reactants being gaseous or vaporised
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to carbon nanotube(s) and to method(s) for making the same.
  • the carbon nanotube(s) according to the invention have applications in many fields, such as hybrid power sources for electrical energy, digital telecommunication systems, uninterruptible power supply (UPS) for computers, and pulse laser technique.
  • UPS uninterruptible power supply
  • Electrode materials for electrochemical capacitors have been extensively studied due to the increasing demand for new kind of energy storage devices with high specific power and long durability (B. E. Conway, 1999). These storage devices can be used in digital telecommunication systems, uninterruptible power supply (UPS) for computers, pulse laser technique, and the like.
  • the electrode materials can be conducting polymers (such as, polyacetylene, polypyrrole, and poiyaniline) (K. Lota et al., 2004; S. K. Ryu et al., 2003), oxides (such as RuO 2 and Co 3 O 4 ) (K. H. Chang et al., 2004; D. Rochefort and D. J. Guay, 2005; J. N. Broughton and M.
  • CNTs carbon nanotubes
  • electrochemical supercapacitor electrodes due to their unique properties, such as large surface area, high chemical stability, flexibility and high conductivity
  • the capacitance of CNTs strongly depends on the purity of the CNT and electrolyte (E. Frackowiak et al., 2001 ; J. N. Barisci et al., 2003; J. N. Barisci et al., 2004).
  • Functionalization of CNTs C. Niu et al., 1997; J.
  • CNT supercapacitors Y. Lee et al., 2003; E. Frackowiak et al., 2000; B. J. Yoon et al., 2004
  • modification of the CNTs with conducting polymers can also increase the capacitance of CNT supercapacitors because conducting polymers are also common electrode materials for supercapacitors and are known to create pseudocapacitance through Faradaic process (C. Zhou et al., 2005; M. Hughes et al., 2002; C. Downs et al., 1999).
  • the present invention seeks to address the problems above, and in particular provides tube(s)-in-tube carbon nanotubes (TiT-CNTs) for use in various applications including, but not limited to, hybrid power sources for electrical energy, digital telecommunication systems, uninterruptible power supply (UPS) for computers and pulse laser techniques.
  • TiT-CNTs may be prepared by a two-step pyrolysis process.
  • the present invention provides a method for preparing carbon nanotubes (CNTs) comprising the steps of:
  • the CNTs may comprise at least one outer tube and at least one inner tube.
  • CNTs comprising at least one tube may be formed after step (b).
  • CNTs comprising at least one outer tube and at least one inner tube may be formed after step (c).
  • the tube formed after step (b) may be the outer tube of the CNTs formed after step (c).
  • the CNTs may be tube(s)-in-tube CNTs (TiT- CNTs).
  • TiT-CNTs are formed after the at least one further pyrolysis.
  • the at least one outer tube and the at least one inner tube may be single-walled CNTs (SWCNTs) and/or multi-walled CNTs (MWCNTs).
  • the present invention provides a method for preparing tube(s)-in-tube carbon nanotubes (TiT-CNTs) comprising the steps of:
  • the at least one first carbon source and the at least one second carbon source are the same or different.
  • the CNTs formed from step (b) may be single-walled CNTs (SWCNTs) and/or multi-walled CNTs (MWCNTs).
  • the TiT-CNTs may comprise at least one outer tube and at least one inner tube.
  • the at least one outer tube and the at least one inner tube may be single-walled CNTs (SWCNTs) and/or multi-walled CNTs (MWCNTs).
  • the average diameter of: the at least one tube of the CNTs formed after step (b) of any method of the present invention; and/or the at least one outer tube of the CNTs formed after step (c) of any method of the present invention may be from 30 nm to 400 nm.
  • the average diameter of: the at least one inner tube of the CNTs formed after step (c) of any method of the present invention may be less than or equal to about 20 nm. More in particular, less than or equal to about 10 nm, and even more in particular, about 7 nm.
  • the first pyrolysis and/or the at least one further pyrolysis may be performed in the presence of a catalyst.
  • a catalyst Any suitable catalyst may be used.
  • the catalyst may be a transition metal.
  • the catalyst may be selected from a group consisting of: Ni, Fe, Co, Al, Mn, Pd, Mo, W, Cr and alloys thereof.
  • the catalyst may be deposited onto and/or inside the at least one nanotemplate.
  • the catalyst may be deposited onto the inner walls of the CNTs prepared from the first pyrolysis of step (b).
  • the catalyst may be deposited onto the inner walls of the CNTs formed after step (b) by immersing the at least one nanotemplate and/or CNTs into a catalyst-containing solution.
  • a catalyst-containing solution Any suitable catalyst-containing solution may be used.
  • the catalyst-containing solution may comprise at least one of the catalysts described above.
  • the catalyst-containing solution may be Ni2SO 4 .
  • the immersion may be carried out for a suitable period of time.
  • the at least one nanotemplate according to any aspect of the present invention may be porous.
  • the at least one nanotemplate may be anodic aluminium oxide and/or titanium oxide.
  • the average pore diameter of the nanotemplate may be from 10 nm to 400 nm.
  • the average thickness of the nanotemplate may be from 0.5 to 500 ⁇ m.
  • the carbon source may be a hydrocarbon source.
  • the at least one first carbon source and the at least one second carbon source may be independently selected from the group consisting of: alkane, alkene, alkyne, aromatic hydrocarbon, carbon monoxide, metal organic compound and a mixture thereof.
  • the at least one first carbon source and the at least one second carbon source may be independently selected from the group consisting of: methane, ethylene, benzene, acetylene, carbon monoxide, Co(CO) 5 , Fe(C 5 H 5 ) 2 and a mixture thereof.
  • the at least one first carbon source and/or the at least one second carbon source is ethylene, acetylene or a mixture thereof.
  • the first pyrolysis and the at least one further pyrolysis may be performed under the same or different conditions.
  • the conditions may include temperature and time.
  • the first pyrolysis and/or the at least one further pyrolysis may be performed at a temperature greater than 300 0 C.
  • the temperature may be from 400 0 C to 1000 0 C. Even more in particular, the temperature is from 500 0 C to 650 0 C.
  • the first pyrolysis and/or the at least one further pyrolysis may be performed from 10 to 120 minutes, in particular, the first pyrolysis and/or the at least one further pyrolysis may be performed from 30 to 80 minutes.
  • the first pyrolysis and/or the at least one further pyrolysis may be performed in the presence of a mixture of gases, the mixture comprising hydrogen gas and/or an inert gas.
  • the inert gas may be argon, helium, neon, nitrogen, krypton, xenon, radon, or a mixture thereof.
  • the method according to any aspect of the present invention may comprise the step of removing the CNTs formed after step (b) and/or step (c) from the at least one nanotemplate.
  • the present invention also provides carbon nanotubes (CNTs) obtainable by any method of the present invention.
  • CNTs carbon nanotubes
  • the present invention also provides a carbon nanotube (CNT) comprising at least one outer tube and at least one inner tube.
  • CNT carbon nanotube
  • the at least one outer tube and/or the at least one inner tube may be a single-walled CNT (SWCNT) or a multi-walled CNT (MWCNT).
  • the average diameter of the at least one outer tube of the CNTs may be from 30 nm to 400 nm.
  • the average diameter of the at least one inner tube of the CNTs may be less than or equal to about 20 nm. More in particular, less than or equal to about 10 nm, and even more in particular, about 7 nm.
  • the present invention also provides a use of carbon nanotubes (CNTs) comprising at least one outer tube and at least one inner tube in the manufacture of: electrodes; fuel cells; hydrogen storage devices; batteries; sorbents for air/water purification and/or gas separation systems; catalyst supports; and/or supercapacitors.
  • CNTs carbon nanotubes
  • the present invention also provides an electrode and/or a supercapacitor comprising at least one CNT prepared according to any method of the present invention.
  • the at least one CNT may comprise at least one outer tube and at least one inner tube.
  • the present invention also provides an electrode and/or a supercapacitor comprising at least one carbon nanotube (CNT), the at least one carbon nanotube comprising at least one outer tube and at least one inner tube.
  • CNT carbon nanotube
  • Figure 1 SEM images of the AAO-template after a first step of pyrolysis of ethylene: (a) 50 nm multi-walled carbon nanotubes (MWCNTs) are imbedded in the AAO template nanopores; and (b) after partially removing the surface of the AAO template.
  • Figure 2 SEM images of the tube-in-tube carbon nanotubes (TiT-CNTs) after the second step of pyrolysis of ethylene and total removal of the AAO template: (a) Sample ATM50: 50 nm outer diameter and (b) Sample ATM300: 300 nm outer diameter.
  • MWCNTs multi-walled carbon nanotubes
  • Figure 3 The cyclic voltammetry (CV) plots of five samples in 0.5M HbSO 4 at a scan rate of 50 mV/s.
  • Figure 4 Pore size distribution of five samples calculated using Barrett-Joyner- Halenda (BJH) method.
  • BJH Barrett-Joyner- Halenda
  • TiT-CNTs tube(s)-in-tube carbon nanotubes
  • the TiT- CNTs may be synthesized by a two-step chemical vapour deposition process or two-step pyrolysis of ethylene on AAO template.
  • large-diameter multi-walled carbon nanotubes MWCNTs
  • AAO anodic aluminium oxide
  • the TiT-CNTs may be fabricated by the second pyrolysis of ethylene (C 2 H 4 ).
  • the capacitance of the supercapacitors based on TiT-CNTs are related to the diameter and structure of the TiT-CNTs, which may be controllable in the two-step process.
  • the TiT-CNTs may comprise at least one outer tube and at least one inner tube.
  • the diameter of the tubes formed may be controlled, as desired.
  • This method is simple, easy and may be suitable for large scale production.
  • the present invention provides carbon nanotubes which can exhibit high capacitance. Such carbon nanotubes may have applications as hybrid power sources for electrical energy, in digital telecommunication systems, as uninterruptible power supply (UPS) for computers, and in pulse laser technique.
  • UPS uninterruptible power supply
  • the present invention provides a method for preparing carbon nanotubes (CNTs) comprising the steps of:
  • the at least one first carbon source and the at least one second carbon source are the same or different.
  • the CNTs may comprise at least one outer tube and at least one inner tube.
  • CNTs comprising at least one outer tube and at least one inner tube may be. formed after step (c).
  • the CNTs comprising at least one outer tube and at least one inner tube formed after step (c) may be referred to as tube(s)- in-tube CNTs (TiT-CNTs).
  • CNTs comprising at least one tube may be formed after step (b).
  • the at least one tube of the CNT formed after step (b) may be the at least one outer tube of the CNT formed after step (c).
  • the CNTs may be single-walled CNTs (SWCNTs) and/or multi-walled CNTs (MWCNTs).
  • the at least one outer tube and/or at least one inner tube may be SWCNTs or MWCNTs.
  • the at least one tube of the CNT formed after step (b) may be SWCNT or MWCNT.
  • the present invention provides a method for preparing tube(s)-in-tube carbon nanotubes (TiT-CNTs) comprising the steps of:
  • the at least one first carbon source and the at least one second carbon source are the same or different.
  • the CNTs formed from step (b) may be single-walled CNTs (SWCNTs) and/or multi-walled CNTs (MWCNTs).
  • the TiT-CNTs may be SWCNTs and/or MWCNTs.
  • the TiT-CNTs may comprise at least one outer tube and at least one inner tube. In particular, there may be a plurality of inner tubes.
  • the at least one inner tube are comprised within the at least one outer tube to form the TiT-CNTs:
  • the at least one outer tube and the at least one inner tube may be SWCNTs and/or MWCNTs.
  • CNTs carbon nanotubes
  • SWCNTs single-walled CNTs
  • MWCNTs multi-walled CNTs
  • SWCNTs are fullerenes consisting essentially of sp 2 -hybridized carbon typically arranged in hexagons and pentagons. These carbon cylindrical structures, known commonly as “buckytubes”, have extraordinary properties, including high electrical and thermal conductivity, as well as high strength and stiffness.
  • MWCNTs are nested single-wall carbon cylinders and possess some properties similar to SWCNTs. However, since SWCNTs have fewer defects than MWCNTs, SWCNTs are generally stronger and more conductive. Additionally, SWCNTs have considerably higher available surface area per gram of carbon than MWCNTs. Dispersing SWCNTs, however, is much more difficult than dispersing MWCNTs because the SWCNTs can "rope" together in aligned bundles of a few to many hundreds of nanotubes and be held tightly together by van der Waals forces.
  • the CNTs formed according to any method of the present invention may have an average diameter of less than 500 nm.
  • the average diameter of the at least one tube of the CNTs formed after step (b) and/or the average diameter of the at least one outer tube of the CNTs formed after step (c) may be from 30 nm to 400 nm.
  • the average diameter of the at least one tube and/or the at least one outer tube may be from 50 nm to 300 nm.
  • the average diameter of the at least one tube and/or the at least one outer tube is 50 nm or 300 nm.
  • the average diameter of the at least one tube and/or the at least one outer tube may depend on the average pore diameter of the at least one nanotemplate.
  • the average diameter of the at least one inner tube of the CNTs formed after step (c) may be less than or equal to the average diameter of the at least one outer tube.
  • the average diameter of the at least one inner tube may be less than or equal to 100 nm.
  • the average diameter of the at least one inner tube may be less than or equal to 20 nm. More in particular, less than or equal to 10 nm, and even more in particular, about 7 nm.
  • the term 'pyrolysis' is defined as the chemical decomposition of a compound by the action of heat.
  • the conditions under which pyrolysis is performed may be varied, such as catalyst (if used), temperature, time, pressure and/or flow rate of the material used in the pyrolysis.
  • the characteristics of the CNTs obtained may depend on the conditions of the first pyrolysis and/or the at least one further pyrolysis.
  • the first pyrolysis and the at least one further pyrolysis may be performed under the same or different conditions.
  • the first pyrolysis and/or the at least one further pyrolysis may be performed in the presence of a catalyst.
  • the first pyrolysis may be performed in the presence of a catalyst.
  • the catalyst may be deposited onto and/or inside the at least one nanotemplate.
  • the at least one further pyrolysis may be performed in the presence of a catalyst.
  • the catalyst may be deposited onto the inner walls of the CNTs formed after step (b).
  • the catalyst may be deposited onto the inner walls of the at least one tube of the CNTs formed after step (b).
  • the catalyst may be deposited by any suitable method.
  • the catalyst may be deposited by an impregnation process.
  • the catalyst may be deposited by immersing the at least one nanotemplate and/or CNTs into a catalyst-containing solution for a suitable period of time.
  • the immersion of the at least one nanotemplate and/or CNTs into the catalyst-containing solution may be carried out from 30 minutes to 4 hours.
  • the catalyst may be a transition metal.
  • the catalyst may be selected from the group consisting of: Ni, Fe, Co, Al, Mn, Pd, Mo, W, Cr, Ti, Ru, Re, Rh, V and alloys thereof.
  • the catalyst may be Ni or Co.
  • the catalyst- containing solution may be Ni 2 SO 4 solution.
  • the first pyrolysis and the at least one further pyrolysis may be carried out in the presence of a carbon source.
  • the carbon source used for each pyrolysis may be the same or different. Any suitable carbon source may be used.
  • the carbon source may be a hydrocarbon source.
  • the carbon source may include but is not limited to aliphatic hydrocarbons, aromatic hydrocarbons, carbonyls, halogenated hydrocarbons, silyated hydrocarbons, alcohols, ethers, aldehydes, ketones, acids, phenols, esters, amines, alkylnitriles, thioethers, cyanates, nitroalkyls, alkyl nitrates, and/or mixtures of one or more of the above.
  • the carbon source may be independently selected from the group consisting of: alkane, alkene, alkyne, aromatic hydrocarbon, carbon monoxide, metal organic compound and mixtures thereof.
  • the carbon source may be any one of the following or a mixture thereof: methane, ethane, propane, butane, ethylene, benzene, acetylene, methylsilane carbon monoxide, Co(CO) 5 and Fe(CsHs ⁇ . Even more in particular, the carbon source may be ethylene, acetylene or a mixture thereof.
  • the type of carbon source may determine the type of CNTs formed. For example, performing pyrolysis in the presence of some carbon sources may form higher quality CNTs compared to when other carbon sources are used due to better graphitization and/or carbonization during pyrolysis. In particular, ethylene forms better graphitized CNTs compared to acetylene (H. Pan et al, J.
  • the volumetric flow rate of the carbon source being supplied to the pyroiysis step may be controlled.
  • the volumetric flow rate may be from 1 seem to 100 seem.
  • the volumetric flow rate may be from 10 seem to 50 seem, more in particular, 16 seem.
  • the first pyrolysis and the at least one further pyrolysis may be carried out at a suitable temperature for a suitable period of time.
  • the temperature may be greater than 300 0 C. In particular, the temperature may be from 400 0 C to 1000 0 C. More in particular, the temperature may be from 500 0 C to 650°C.
  • the temperature at which pyrolysis is performed may depend on the carbon source used for the pyrolysis. For example, between the use of acetylene and ethylene for the carbon source, the temperature at which pyrolysis is conducted when acetylene is used as the carbon source is much lower than when ethylene is used.
  • the temperature required when acetylene is used may be greater than 550 0 C, whereas using ethylene, a temperature of greater than 850 0 C may be required. Methane, in turn, requires an even higher pyrolysis temperature.
  • the time period for which the first pyrolysis and/or the at least one further pyrolysis is carried out may be from 10 minutes to 120 minutes. In particular, pyrolysis may be carried out from 30 minutes to 80 minutes.
  • the first pyrolysis and/or the at least one further pyrolysis may be carried out in the presence of a gas or a mixture of gases.
  • the gas and/or mixture of gases may include, but may not be limited to, hydrogen gas and/or an inert gas.
  • the inert gas may be argon, helium, neon, nitrogen, krypton, xenon, radon and/or a mixture thereof.
  • the volumetric flow rate of the gas or mixture of gases may be controlled.
  • the volumetric flow rate may be from 10 seem to 300 seem.
  • the volumetric flow rate may be from 50 seem to 200 seem, more in particular, 100 seem.
  • the at least one nanotemplate used in any aspect of the present invention may be porous.
  • the nanotemplate may be anodic aluminium oxide (AAO) and/or titanium oxide.
  • AAO anodic aluminium oxide
  • the nanotemplate may be formed by any suitable method.
  • the AAO nanotemplate may be formed using a modified two-step anodization method as disclosed in H. Pan et al, J. Nanosci. Nanotech., 2004.
  • the average diameter of the nanopore of the at least one nanotemplate may determine the average diameter of the diameter of the at least one tube and/or the at least one outer tube of the CNTs formed from the method according to any aspect of the present invention.
  • the average diameter of the nanopores of the at least one nanotemplate may be from 10 nm to 600 nm. in particular, the average diameter may be from 30 nm to 400 nm. Even more in particular, the average diameter may be from 50 nm to 300 nm. The average diameter may be 50 nm or 300 nm. Further, the average thickness of the at least one nanotemplate may be from 0.5 to 500 ⁇ m.
  • the method of any aspect of the present invention further comprises a step of removing CNTs formed after step (b) and/or step (c) from the at least one nanotemplate.
  • Any suitable method of removal of the CNTs may be employed for the purposes of the present invention. This may include the use of any suitable solvent(s). For example, HF acid may be used to remove the CNTs from the nanotemplate. The CNTs may then be cleaned to a pH of about 7 by using distilled water. The CNTs may be dried. For example, the CNTs may be dried to a temperature of about 12O 0 C.
  • the present invention provides carbon nanotubes (CNTs) obtainable by any method of the present invention.
  • the present invention provides tube(s)-in-tube carbon nanotubes (TiT-CNTs) obtainable by any method of the present invention.
  • the average diameter, pore size (average pore diameter) and pore size distribution may be determined. Any suitable method may be used to determine the pore size and the pore size distribution.
  • the pore size distribution may be determined using the Barrett-Joyner-Halenda (BJH) method (E.P. Barrett et al, 1951; F. Rouquerol, 1999).
  • Pore size and pore size distribution can have different meanings. “Pore size” can be measured by (optical or electron) microscopy whereas pore size distribution and pore volume are determined statistically from counting in a field of view (of a representative portion of the material). Further, pore size of each pore usually refers to the average pore diameter. Pore size is determined by plotting pore volume (for large pore materials the volume of pores having a size of less than 100 nm can ignored) vs.
  • pore size and "average pore size” is the pore size at 50% of the existing pore volume (e.g., for a material that has a 40% pore volume, the "average pore size” is the size of the largest sized pore that adds with all smaller sized pores to reach 20% pore volume).
  • the pore size and pore volume are measured on a cross-section of the material that may be obtained with a diamond bladed saw.
  • the present invention also provides a carbon nanotube (CNT) comprising at least one outer tube and at least one inner tube.
  • the CNT may comprise at least one outer tube and a plurality of inner tubes.
  • the CNT may be a tube(s)-in-tube CNT (TiT-CNT).
  • the CNT may be a single-walled CNT (SWCNT) or multi-walled CNT (MWCNT).
  • the at least one outer tube and/or the at least one inner tube may be a SWCNT and/or MWCNT.
  • the CNT of the present invention may have an average diameter of less than 500 nm.
  • the average diameter of the at least one outer tube of the CNT may be from 30 nm to 400 nm. Even more in particular, the average diameter of the at least one outer tube may be. from 50 nm to 300 nm.
  • the average diameter of the at least one outer tube is 50 nm or 300 nm.
  • the average diameter of the at least one inner tube of the CNT may be less than or equal to the average diameter of the at least one outer tube.
  • the average diameter of the at least one inner tube may be less than or equal to 100 nm.
  • the average diameter of the at least one inner tube may be less than or equal to 20 nm. More in particular, less than or equal to 10 nm, and even more in particular, about 7 nm.
  • the CNT according to the present invention may have a specific capacitance greater than 50 F/g.
  • the specific capacitance of the CNT of the present invention is greater than 100 F/g. Even more in particular, greater than 350 F/g.
  • Specific capacitance of a device is the measure of the ability of the device to store energy in the form of an electrostatic field (such as charge) per unit weight of the device. Specific capacitance may be measured by any suitable method known to a person skilled in the art. An example of a method is provided in the Examples below.
  • the capacitance of the CNT of the present invention may be dependent on the average diameter of the CNT.
  • the capacitance of the CNT may be dependent on the average diameter of the at least one outer tube of the CNT.
  • the capacitance of the CNT may be higher for CNTs which have a smaller average diameter.
  • the specific capacitance of CNT with an average diameter of 50 nm (ATM50) is higher than the specific capacitance of CNT with an average diameter of 300 nm (ATM300).
  • the larger specific capacitance of the CNT with a smaller diameter may be contributed to the larger surface area, better pore size distribution and high conductivity.
  • the CNTs of the present invention may be used in digital telecommunication systems, uninterruptible power supply (UPS) for computers, pulse laser technique, and the like.
  • the CNTs may also be used for other applications such as in the construction of devices for practical applications in many fields including electron emitters, field-emission transistors, electrodes for photovoltaic cells and light emitting diodes, optoelectronic elements, bismuth actuators, chemical and biological sensors, gas and energy storages, molecular filtration membranes and energy-absorbing materials.
  • the present invention provides a use of carbon nanotubes (CNTs) according to any aspect of the present invention, comprising at least one outer tube and at least one inner tube in the manufacture of: electrodes; fuel cells; hydrogen storage devices; batteries; sorbents for air/water purification and/or gas separation systems; catalyst supports; and/or supercapacitors.
  • CNTs carbon nanotubes
  • the present invention also provides an electrode comprising at least one carbon nanotube (CNT) as described above.
  • the present invention also provides an electrode comprising at least one CNT prepared by any method of the present invention.
  • the at least one CNT may comprise at least one outer tube and at least one inner tube.
  • the present invention also provides a supercapacitor comprising at least one carbon nanotube (CNT) as described above.
  • CNT carbon nanotube
  • the present invention also provides a supercapacitor comprising at least one CNT prepared by any method of the present invention.
  • the at least one CNT may comprise at least one outer tube and at least one inner tube
  • Supercapacitors are electrochemical capacitors formed by two polarizable electrodes, a separator and an electrolyte.
  • the capacitance of a supercapacitor is the sum of double layer capacitance and pseudocapacitance. Double layer capacitance arises when a charge accumulation is achieved electrostatically on either side of the electrode and electrolyte interface, while pseudocapacitance is brought about by surface redox-reaction.
  • Carbon nanotubes were fabricated by a two-step pyrolysis of ethylene process at high temperatures on AAO template.
  • the AAO template was prepared using a modified two-step anodization process as described in H. Pan et al., IEEE Trans. Nanotech., 2004.
  • high purity (approximately 99.999%) aluminium foil was annealed under argon atmosphere at 500°-600°C for approximately 2 hours, in order to increase the grain size of the aluminium metal and to ensure the homogenous growth of nanopores over a large area.
  • the aluminium foil was electrochemically polished in a mixture of perchloric acid and ethanol (1 :4 in volume) under constant voltage of 20 V at 0 0 C for 4 minutes.
  • the first anodization of the aluminium foil was performed at 40 V in an oxalic acid solution of 3 weight% (wt%) at about 25 0 C for 6 hours.
  • the AAO template was then chemically etched in a mixed solution of phosphoric acid and chromic acid (3:1 by weight) at 6O 0 C to remove aluminium oxide formed.
  • the second anodization was performed under the same conditions as the first anodization except for 8 hours.
  • the average diameter of the nanopore of the AAO template obtained was about 40 nm.
  • the average thickness of the AAO template obtained was about 100 ⁇ m.
  • the remaining aluminium was removed in 10 wt% CuCI 2 solution.
  • a second AAO template was formed in the same manner as described above, except that the anodization was performed at 160 V instead of 40 V, and using 10 wt% phosphoric acid instead. This resulted in the formation of an AAO template with nanopores having an average diameter of about 300 nm.
  • Multi-walled carbon nanotubes (i) Multi-walled carbon nanotubes (MWGNTs)
  • MWCNTs were prepared following the procedure described in H. Pan et al, J. Nanosci. Nanotech., 2004. Generally, the growth of MWCNTs was carried out in a quartz tube (80 cm in length, 2.5 cm in diameter). The
  • AAO template was placed at the centre of the quartz tube, which was inserted into a horizontal high-temperature furnace (Carbolite 2416). A flow of Ar (95%) and H2 (5%) gas mixture at 100 seem was introduced to the quartz tube via stainless junctions and tubes (2 mm in diameter). The temperature of the furnace was increased to 600 0 C at a rate of 25°C/min.
  • the MWCNTs were removed from the AAO template using 10 wt% HF acid, cleaned to a pH of 7 using distilled water and dried at a temperature of about 12O 0 C.
  • Tube-in-tube carbon nanotubes (TiT-CNTs)
  • MWCNTs were produced following the procedure in (i) above, without removing the MWCNTs from the AAO template.
  • the AAO template was then immersed in N ⁇ 2 SO 4 solution for about 2 hours to enable the deposition of Ni catalyst onto the inner walls of MWCNTs.
  • a second pyrolysis was carried out under the same conditions as the first pyrolysis, except pyrolysis of ethylene was performed instead of that of acetylene. This step resulted in the formation of carbon nanotubes within the MWCNTs which were embedded in the nanopores of the AAO template and covered by Ni catalysts, forming TiT-CNTs.
  • the TiT-CNTs were removed from the AAO template using 10 wt% HF acid, cleaned to a pH of 7 using distilled water and dried at a temperature of about 12O 0 C.
  • the morphology of the CNTs was observed by scanning electron microscope (SEM, JEOL JSM-6700F).
  • FIG. 1 shows the SEM image of MWCNTs produced on the AAO template.
  • the average diameter of the MWCNTs is about 50 nm obtained after the first step of pyrolysis of ethylene.
  • FIG 1(a) clearly indicated that MWCNTs were formed within the nanopores in the AAO template.
  • the nanopores were widened, and the MWCNTs were exposed out after the AAO template was partially etched.
  • the exposed tips of the MWCNTs have equal length and are tangled together, as seen in Figure 1(b).
  • FIG 2 shows the SEM images of TiT-CNTs after totally removing the AAO template.
  • the surface of the TiT-CNTs is rough with a lot of smaller pores. From the open ends of TiT-CNTs, smaller carbon nanotubes within the MWCNTs are observable.
  • the MWCNTs of diameter of 300 nm confine a lot of smaller CNTs inside.
  • Some TiT-CNTs (diameter of 300 nm) were broken and smaller CNTs were released from inside during the removal of the AAO template in HF acid. This can be seen in Figure 2(b). The reason is because of the CNTs poor graphitization.
  • the average diameter of the smaller CNTs within the MWCNTs (300 nm) is about 20 nm.
  • the smaller CNTs within the MWCNTs (50 nm) was less than 10 nm in diameter ( Figure 2(a)).
  • the specific surface area of the samples was characterized by nitrogen isotherm at 77K (NOVA 3200, Quantachrome Corp) based on the Brunauer- Emmett-Teller (BET) method (S. Erunauer et a!, 1938).
  • BET Brunauer- Emmett-Teller
  • Cyclic voltammetry (CV) measurements were performed in an electrochemical measurement unit (Solartron SM 280B), a combined electrochemical interface and frequency response analyser (GCC 540, 724-01-004, Radiometer Analytical SAS), at room temperature with a scan rate of 50 mV/s.
  • AAO MWCNTs 50 nm in diameter
  • AAO MWCNTs 300 nm
  • AAO TiT-CNTs 50 nm
  • AAO TiT-CNTs 300 nm
  • commercial MWCNTs 10-20 nm
  • a working electrode was fabricated by casting a Nafion-impregnated sample onto a 3 mm diameter glassy carbon electrode. 4 mg of sample dispersed in 0.5 ml_ of aqueous ethanol solution (1 :1 volume/volume) was sonicated for 15 minutes (G Li and PG Pickup, 2003). This sample ink was dropped onto the glassy carbon electrode and the cast electrode was placed in a vacuum oven until the catalyst was totally dry for the CV measurement. The cast working electrode was then immersed in 0.5 M H 2 SO 4 which was de-aerated with high purity nitrogen gas for electrochemical measurement. A Pt foil and a saturated calomel electrode (SCE) were used as the counter electrode and reference electrode, respectively.
  • SCE saturated calomel electrode
  • Figure 3 shows the CV plots of the five samples in aqueous solution of 0.5 M H 2 SO 4 at a scan rate of 50 mV/s.
  • the CV plot of the background (glassy carbon electrode) is almost a straight line, as seen in the middle of Figure 3, indicating that the contribution of the glassy electrode to the results is negligible.
  • v is a constant of sweep rate applied for the CV measurements, i.e. — ; dt
  • i(V) is a current response depending on sweep voltage
  • the sweep potential is from -0.2 to 1.0 V, and thus the potential window (AV ) is 1.2 V.
  • the average specific capacitance of the commercial CNTs (10-20 nm in diameter) (CM20) was about 46 F/g, which was comparable to the value reported in literature (Liu T et al., 2003).
  • the CV plot of AM50 is very similar to that reported in Q. L. Chen et al., 2004.
  • the average specific capacitances of the remaining four samples were 183, 57, 406 and 117 F/g for AM50, AM300, ATM50 and ATM300, respectively.
  • the average specific capacitance of ATM50 is about 8 times that of CM20 and about twice the mean value of oxidatively purified single-wall carbon nanotubes functionalized with arylsulfonic acid moieties and then treated with pyrrole, as reported in C. Zhou, et al., 2005.
  • the CV plot of ATM50 is close to the rectangular shape of an ideal double layer capacitor.
  • An electrode of ATM50 was tested by the CV measurement for 5000 cycles in aqueous solution of 0.5 M H 2 SO 4 . A decrease of the specific capacitance was not observed, which indicated the cycling stability of ATM50.
  • the capacitance of carbon based electrochemical supercapacitors depends on two kinds of accumulated energy (E. Frackowiak and F. Beguin, Carbon 2001.): (a) the electrostatic attraction in electrical double layer capacitors (EDLC); and
  • the average pore diameters and average specific capacitance is shown in Table 1.
  • Table 1 The average pore diameters and average specific capacitance is shown in Table 1.
  • the average pore size distribution was calculated using the Barrett-Joyner-Halenda (BJH) method (E.P. Barrett et al, 1951 ). The results are shown in Figure 4, and summarised in Table 1.
  • Table 1 Specific surface area, average pore size, and capacitance of the carbon nanotubes.
  • the dominant pore diameter for AM50 and ATM50 is about 3.9 nm, but is about 2 nm for other samples. It is observed that the average specific capacitance for AM50 and ATM50 is larger than those of other samples. Also, it was found that capacitance increases with the increase of the specific surface area with the exception of ATM50. Electrical conductivity is one of the factors that affect the capacitance. It should be mentioned that the higher the specific surface area, the poorer the conductivity should be. This could be one of reasons for the capacitance of ATM50 being larger than that of AM50.
  • pseudocapacitance induced by faradaic reactions also contributes to the capacitance, which depends on the surface functionalization of the carbon nanostructures.
  • the redox peaks in the CV plots indicated the existence of oxygenated groups (H + or OH " ) on the surface of the carbon nanostructures, which leads to the remarkable pseudocapacitance (E. Frackowiak, et al., 2000).
  • the pseudocapacitance arises from the quick faradaic charge transfer reactions.
  • Pseudocapacitance is strongly related to the pore size, pore size distribution and the conductivity of the carbon materials, i.e. the CNTs. It is observed from Table 1 that ATM50 shows the highest average specific capacitance due to its high surface area, better pore size distribution and conductivity, as analyzed in the EDLC.
  • TiT-CNTs tube-in-tube carbon nanostructures
  • AAO-based MWCNTs produced by a one-step ethylene pyrolysis process.
  • the smaller diameter of TiT-CNTs exhibit better supercapacitance than TiT-CNTs with larger diameters.
  • the larger supercapacitance of ATM50 is contributed to their larger specific surface area, better pore size distribution and high conductivity. Accordingly, TiT-CNTs would be useful in satisfying power requirements in devices. References

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Abstract

La présente invention concerne un nanotube de carbone (CNT) comprenant au moins un tube externe et au moins un tube interne. En particulier, le nanotube de carbone est un nanotube de carbone à double tube (TiT-CNT). La présente invention concerne également un procédé de préparation de nanotubes de carbone (CNT) dont les étapes consistent à : (a) obtenir au moins un nanogabarit ; (b) réaliser une première pyrolyse en présence d'au moins une première source de carbone, la ou les première(s) source(s) de carbone étant en contact avec le(s) nanogabarit(s) ; et (c) réaliser au moins une pyrolyse supplémentaire en présence d'au moins une seconde source de carbone, la ou les première(s) source(s) de carbone et la ou les seconde(s) source(s) de carbone étant identiques ou différentes.
PCT/SG2007/000059 2006-03-01 2007-03-01 Nanotube(s) de carbone et leur procédé de fabrication WO2007100306A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100196780A1 (en) * 2009-01-30 2010-08-05 Mark Kaiser Protecting a pem fuel cell catalyst against carbon monoxide poisoning
WO2014133183A1 (fr) * 2013-03-01 2014-09-04 国立大学法人 東京大学 Film comprenant des nanotubes de carbone monocouches et présentant des parties denses et des parties clairsemées, procédé de production associé, matériau comprenant ledit film et procédé de production associé
CN105375028A (zh) * 2015-12-08 2016-03-02 武汉理工大学 收缩的可调内结构的介孔无机盐纳米管材料及其制备方法和应用
US20160251757A1 (en) * 2013-11-13 2016-09-01 Tokyo Electron Limited Process for producing carbon nanotubes and method for forming wiring
CN108217628A (zh) * 2018-02-10 2018-06-29 中国科学院合肥物质科学研究院 三维网状碳纳米管及其制备方法和用途

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20020004644A (ko) * 2000-07-06 2002-01-16 신정호 원격교육용 문제작성제공시스템 및 이를 이용한설문작성제공시스템
KR20020007237A (ko) * 2001-10-17 2002-01-26 (주) 나노텍 비표면적을 증가시킨 이중벽 탄소나노튜브 제조
CN1404174A (zh) * 2002-10-11 2003-03-19 清华大学 一种高能电池的活性材料
WO2004083113A1 (fr) * 2003-03-20 2004-09-30 Cheol-Jin Lee Procede de synthese massive de nanotubes de carbone a double paroi a l'aide de la croissance en phase vapeur
KR20040084114A (ko) * 2003-03-26 2004-10-06 한국전기연구원 리튬이차전지의 전극제조방법 및 이를 이용한 리튬이차전지
US20040197638A1 (en) * 2002-10-31 2004-10-07 Mcelrath Kenneth O Fuel cell electrode comprising carbon nanotubes
JP2004323258A (ja) * 2003-04-22 2004-11-18 Toray Ind Inc カーボンナノチューブの精製方法
KR20050001589A (ko) * 2003-06-26 2005-01-07 주식회사 디피아이 솔루션스 디스플레이용 유기 투명 전극의 제조방법
WO2005075663A2 (fr) * 2004-02-05 2005-08-18 The Provost, Fellows And Scholars Of The College Of The Holy And Undivided Trinity Of Queen Elizabeth, Near Dublin Matiere nanostructuree et procede de preparation correspondant
WO2005085130A2 (fr) * 2004-03-09 2005-09-15 Canatu Oy Nanotubes de carbone monoparoi, multiparois, fonctionnalises, dopes et composites de ces derniers
WO2005086982A2 (fr) * 2004-03-12 2005-09-22 Eikos, Inc. Solutions et procedes de decollage de nanotubes de carbone
EP1591418A1 (fr) * 2004-04-26 2005-11-02 Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. Nanostructures de carbone tube-dans-tube

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20020004644A (ko) * 2000-07-06 2002-01-16 신정호 원격교육용 문제작성제공시스템 및 이를 이용한설문작성제공시스템
KR20020007237A (ko) * 2001-10-17 2002-01-26 (주) 나노텍 비표면적을 증가시킨 이중벽 탄소나노튜브 제조
CN1404174A (zh) * 2002-10-11 2003-03-19 清华大学 一种高能电池的活性材料
US20040197638A1 (en) * 2002-10-31 2004-10-07 Mcelrath Kenneth O Fuel cell electrode comprising carbon nanotubes
WO2004083113A1 (fr) * 2003-03-20 2004-09-30 Cheol-Jin Lee Procede de synthese massive de nanotubes de carbone a double paroi a l'aide de la croissance en phase vapeur
KR20040084114A (ko) * 2003-03-26 2004-10-06 한국전기연구원 리튬이차전지의 전극제조방법 및 이를 이용한 리튬이차전지
JP2004323258A (ja) * 2003-04-22 2004-11-18 Toray Ind Inc カーボンナノチューブの精製方法
KR20050001589A (ko) * 2003-06-26 2005-01-07 주식회사 디피아이 솔루션스 디스플레이용 유기 투명 전극의 제조방법
WO2005075663A2 (fr) * 2004-02-05 2005-08-18 The Provost, Fellows And Scholars Of The College Of The Holy And Undivided Trinity Of Queen Elizabeth, Near Dublin Matiere nanostructuree et procede de preparation correspondant
WO2005085130A2 (fr) * 2004-03-09 2005-09-15 Canatu Oy Nanotubes de carbone monoparoi, multiparois, fonctionnalises, dopes et composites de ces derniers
WO2005086982A2 (fr) * 2004-03-12 2005-09-22 Eikos, Inc. Solutions et procedes de decollage de nanotubes de carbone
EP1591418A1 (fr) * 2004-04-26 2005-11-02 Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. Nanostructures de carbone tube-dans-tube

Non-Patent Citations (12)

* Cited by examiner, † Cited by third party
Title
AN K.H. ET AL.: "High-capacitance supercapacitor using a nanocomposite electrode of single-walled carbon nanotube and polypyrrole", JOURNAL OF THE ELECTROCHEMICAL SOCIETY, vol. 149, no. 8, 2002, pages A1058 - A1062 *
CHEN Y. ET AL.: "Patterned growth of carbon nanotubes on Si substrates without predeposition of metal catalysts", APPLIED PHYSICS LETTERS, vol. 87, 2005, pages 033103 *
DATABASE WPI Week 200267, Derwent World Patents Index; Class E36, AN 2002-624424 *
DATABASE WPI Week 200333, Derwent World Patents Index; Class E36, AN 2003-350441 *
DATABASE WPI Week 200344, Derwent World Patents Index; Class A85, AN 2003-458392 *
DATABASE WPI Week 200481, Derwent World Patents Index; Class A85, AN 2004-816667 *
DATABASE WPI Week 200512, Derwent World Patents Index; Class L03, AN 2005-108875 *
DATABASE WPI Week 200539, Derwent World Patents Index; Class A85, AN 2005-380746 *
DU C. ET AL.: "High power density supercapacitors using locally aligned carbon nanotube electrodes", NANOTECHNOLOGY, vol. 16, 2005, pages 350 - 353 *
HU W. ET AL.: "Growth of well-aligned carbon nanotube arrays on silicon substrates using porous alumina film as a nanotemplate", APPLIED PHYSICS LETTERS, vol. 79, no. 19, 5 November 2001 (2001-11-05), pages 3083 - 3085 *
SHAMOING HUANG: "Controllable 3D architecture of aligned carbon nanotube arrays by multi-step processes", CHEMICAL PHYSICS LETTERS, vol. 374, 2003, pages 157 - 163 *
WIKIPEDIA, FREE ENCYCLOPEDIA, Retrieved from the Internet <URL:http://www.en.wikipedia.org/wiki/Supercapacitor> *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100196780A1 (en) * 2009-01-30 2010-08-05 Mark Kaiser Protecting a pem fuel cell catalyst against carbon monoxide poisoning
US8273486B2 (en) * 2009-01-30 2012-09-25 Honeywell International, Inc. Protecting a PEM fuel cell catalyst against carbon monoxide poisoning
WO2014133183A1 (fr) * 2013-03-01 2014-09-04 国立大学法人 東京大学 Film comprenant des nanotubes de carbone monocouches et présentant des parties denses et des parties clairsemées, procédé de production associé, matériau comprenant ledit film et procédé de production associé
JPWO2014133183A1 (ja) * 2013-03-01 2017-02-09 国立大学法人 東京大学 密な部分及び疎な部分を有する単層カーボンナノチューブを有する膜及びその製造方法、並びに該膜を有する材料及びその製造方法
US9847181B2 (en) 2013-03-01 2017-12-19 The University Of Tokyo Film comprising single-layer carbon nanotubes and having dense portions and sparse portions, process for producing same, and material including said film and process for producing same
US20160251757A1 (en) * 2013-11-13 2016-09-01 Tokyo Electron Limited Process for producing carbon nanotubes and method for forming wiring
US10378104B2 (en) * 2013-11-13 2019-08-13 Tokyo Electron Limited Process for producing carbon nanotubes and method for forming wiring
CN105375028A (zh) * 2015-12-08 2016-03-02 武汉理工大学 收缩的可调内结构的介孔无机盐纳米管材料及其制备方法和应用
CN108217628A (zh) * 2018-02-10 2018-06-29 中国科学院合肥物质科学研究院 三维网状碳纳米管及其制备方法和用途
CN108217628B (zh) * 2018-02-10 2021-12-07 中国科学院合肥物质科学研究院 三维网状碳纳米管及其制备方法和用途

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