EP1527014A2 - Verfahren zur öffnung der enden von kohlenstoffnanoröhren und deren verwendungen - Google Patents

Verfahren zur öffnung der enden von kohlenstoffnanoröhren und deren verwendungen

Info

Publication number
EP1527014A2
EP1527014A2 EP03758222A EP03758222A EP1527014A2 EP 1527014 A2 EP1527014 A2 EP 1527014A2 EP 03758222 A EP03758222 A EP 03758222A EP 03758222 A EP03758222 A EP 03758222A EP 1527014 A2 EP1527014 A2 EP 1527014A2
Authority
EP
European Patent Office
Prior art keywords
carbon nanotubes
nanotubes
oxidation
opening
carbon
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP03758222A
Other languages
English (en)
French (fr)
Inventor
François BEGUIN
Sandrine Delpeux
Katarzyna Szostak
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Centre National de la Recherche Scientifique CNRS
Original Assignee
Centre National de la Recherche Scientifique CNRS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Centre National de la Recherche Scientifique CNRS filed Critical Centre National de la Recherche Scientifique CNRS
Publication of EP1527014A2 publication Critical patent/EP1527014A2/de
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C01B32/168—After-treatment
    • C01B32/178—Opening; Filling
    • 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
    • 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

Definitions

  • the present invention relates generally to the post-treatment of carbon nanotubes and their applications.
  • the present invention relates to a process for opening carbon nanotubes at their ends and more especially multi-wall carbon nanotubes.
  • hollow carbon nanotubes can prove to be excellent reservoirs of gases, such as hydrogen, natural gas ... It is now well known that the presence of topological defects is necessary to close the graphene planes at the ends of carbon nanotubes. According to Euler's law, six pentagons are necessary to ensure the closure of the carbon nanotubes at each end. These regions of tension are of course the most useful sites for addition reactions, in particular on the double bonds connecting a pair of pentagons.
  • Oxidation in air or in oxygen is not selective enough. These treatments lead to a significant loss of material and the external graphene planes are often seriously damaged due to the uncontrollable nature of the reaction.
  • Oxidation is much more homogeneous when the carbon nanotubes are dispersed in an oxidizing solution.
  • carbon nanotubes obtained by decomposition of acetylene at 600 ° C on cobalt particles supported by zeolites often contain carbon impurities and have closed ends. It is then possible to carry out an attack with potassium permanganate both to partially remove these impurities by oxidation and to open part of the ends of the carbon nanotubes.
  • the object of the invention is therefore to provide a method making it possible to quickly and efficiently obtain the opening of carbon nanotubes, while preserving their morphology, their quality, and with reduced losses.
  • the process for opening carbon nanotubes according to the invention is characterized in that it comprises two oxidation stages, the first in the liquid phase in a concentrated acid, the second in the gas phase.
  • the oxidation stage in the liquid phase then makes it possible to directly obtain open nanotubes.
  • this has the advantage of making the major part of the residual metallic impurities enclosed at the ends accessible, for example following the syntheses carried out in the presence of catalyst.
  • the disordered carbon appearing during the oxidation reaction in the liquid phase is eliminated during the second stage in the gas phase.
  • the carbon nanotubes are multi-wall carbon nanotubes.
  • the concentrated acid is nitric acid.
  • concentrated nitric acid is used in excess.
  • this oxidation step is carried out at reflux, with stirring.
  • the reflux heating will last from 30 to 50 minutes, in particular approximately 35 minutes.
  • an additional step of gas phase oxidation is carried out at low temperature.
  • a particular implementation of this step consists of a treatment of approximately 1 to 2 hours, in particular under C0 2 to 500 to 600 ° C, in particular from 500 to 550 ° C and in particular from 525 ° C, to 1 at 1:40 min.
  • the method according to the invention will be implemented with a linear speed of said carbon dioxide of 40 to 100 cm / min, in particular from 50 to 70 cm / min, in particular of the order of 60 cm / min .
  • the method according to the invention comprises, between said first step of oxidation in the liquid phase and said second step of oxidation in the gas phase, an intermediate step of filtration and washing of the open nanotubes, in particular with distilled water.
  • the method according to the invention may include an additional step of treatment with hydrochloric acid in order to eliminate any metal particles, initially trapped in the central channel, and released during the opening of the nanotubes.
  • Figure 1 represents an image obtained by scanning electron microscopy (SEM) of carbon nanotubes after an HN0 3 + C0 2 treatment according to the invention
  • - Figure 2 represents a picture obtained by transmission electron microscopy (TEM) of nanotubes carbon after HN0 3 + C0 2 treatment according to the invention
  • FIG. 3 represents a MET radiograph (mode of network fringes C0 2 ) of an open end of a carbon nanotube after a treatment according to the method of the invention
  • FIG. 4 represents isothermal adsorption-desorption of nitrogen at 77K of the carbon nanotubes before (solid extract curve) and after implementation of the process according to the invention (dashed curve).
  • the process of the invention has been optimized on multi-wall carbon nanotubes synthesized by decomposition of acetylene at 600 ° C. on solid solutions of Co x Mg ( ⁇ _ x) 0.
  • the carbon nanotubes are dispersed in concentrated nitric acid and oxidized at reflux (130 ° C) for 35 minutes with continuous stirring (1 g of nanotubes in 1 liter of 69% acid by weight). Then, the mixture is filtered, then the solid is washed with distilled water until a neutral pH of the filtrate is obtained.
  • This first oxidation step allows the opening of the tubes.
  • a gentle oxidation is then carried out using a CO 2 current at low temperature.
  • the carbon nanotubes powder is placed in a quartz crucible equipped with a porous sintered glass disk allowing an upward flow of C0 2 to be introduced , at a linear speed of 60 cm / min, at 525 ° C .
  • the reaction is carried out for about 60 to 100 min. Selective oxidation of the disordered carbon nanostructures which are produced during the first oxidation reaction is obtained.
  • the porous texture of carbon nanotubes is characterized by the adsorption of nitrogen at 77 ° K (Micrometrics, ASAP 2000). Before the adsorption experiments, the samples are degassed at 350 ° C (10 ⁇ 6 bar) for 12 h.
  • Another heat treatment can be carried out at high temperature, at 1600-2800 ° C, for several hours, under nitrogen, to graphitize the aromatic layers of the walls and allow the sublimation of metallic Co.
  • the carbon nanotubes used have a strong entanglement.
  • the nitrogen adsorption isotherm at 77K is type IV, characteristic of a swelling mesoporous solid
  • the above method is applied to nanotubes having outside diameters of approximately 7 to 25 mm, but can be applied to nanotubes of larger diameters by adjusting the treatment time with nitric acid and C0 2 .
  • This process can of course be used with carbon nanotubes other than those obtained by catalytic processes.
  • the opening of carbon nanotubes with a very high crystallinity, in particular those which are synthesized by vaporization of graphite, will require longer reaction times.
  • the method according to the invention will then be effective in the context of the opening of carbon nanotubes. More particularly, the method according to the invention will be applied to the opening of multi-wall carbon nanotubes.
  • the method according to the invention will be applied to multi-wall carbon nanotubes having an outside diameter of between 7 and 25 nm.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Carbon And Carbon Compounds (AREA)
EP03758222A 2002-08-08 2003-08-08 Verfahren zur öffnung der enden von kohlenstoffnanoröhren und deren verwendungen Withdrawn EP1527014A2 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0210115 2002-08-08
FR0210115A FR2843382B1 (fr) 2002-08-08 2002-08-08 Procede d'ouverture de nanotubes de carbone a leurs extremites et applications
PCT/FR2003/002499 WO2004016550A2 (fr) 2002-08-08 2003-08-08 Procede d'ouverture de nanotubes de carbone a leurs extremite et applications

Publications (1)

Publication Number Publication Date
EP1527014A2 true EP1527014A2 (de) 2005-05-04

Family

ID=30471027

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03758222A Withdrawn EP1527014A2 (de) 2002-08-08 2003-08-08 Verfahren zur öffnung der enden von kohlenstoffnanoröhren und deren verwendungen

Country Status (7)

Country Link
US (1) US20050163697A1 (de)
EP (1) EP1527014A2 (de)
JP (1) JP2005535550A (de)
AU (1) AU2003274239A1 (de)
CA (1) CA2495094A1 (de)
FR (1) FR2843382B1 (de)
WO (1) WO2004016550A2 (de)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7488875B2 (en) * 2003-12-09 2009-02-10 Unidym, Inc. Process for purifying carbon nanotubes made on refractory oxide supports
FR2898139B1 (fr) * 2006-03-06 2008-05-30 Nanoledge Sa Procede de fabrication de produits extrudes composites polymeres et nanotubes de carbone
US8110170B2 (en) * 2006-09-22 2012-02-07 Snu R&Db Foundation Conductive polymer-carbon nanotube composite and manufacturing method thereof
ES2390099T3 (es) * 2007-05-11 2012-11-06 Grupo Antolín-Ingeniería, S.A. Nanofibras de carbono y procedimiento para obtener dichas nanofibras
CN104192818A (zh) * 2008-12-30 2014-12-10 独立行政法人产业技术综合研究所 取向单层碳纳米管集合体、块状取向单层碳纳米管集合体、粉体状取向单层碳纳米管集合体、及其制造方法
JP5605431B2 (ja) * 2010-08-05 2014-10-15 独立行政法人産業技術総合研究所 Ｃｎｔ集合体及び積層体
JP6354583B2 (ja) 2013-02-28 2018-07-11 東レ株式会社 カーボンナノチューブ集合体の製造方法
CN110071261A (zh) 2018-01-23 2019-07-30 清华大学 电池电极的制备方法
CN110065937B (zh) * 2018-01-23 2021-12-21 清华大学 氧化多壁碳纳米管的方法

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5346683A (en) * 1993-03-26 1994-09-13 Gas Research Institute Uncapped and thinned carbon nanotubes and process
JP2595903B2 (ja) * 1994-07-05 1997-04-02 日本電気株式会社 液相におけるカーボン・ナノチューブの精製・開口方法および官能基の導入方法
GB9418937D0 (en) * 1994-09-20 1994-11-09 Isis Innovation Opening and filling carbon nanotubes
WO1998005920A1 (en) * 1996-08-08 1998-02-12 William Marsh Rice University Macroscopically manipulable nanoscale devices made from nanotube assemblies
JPH10125321A (ja) * 1996-10-18 1998-05-15 Sony Corp 電池負極用炭素質材料及び非水電解液二次電池
JP2002515847A (ja) * 1997-05-29 2002-05-28 ウィリアム・マーシュ・ライス・ユニバーシティ 単層カーボンナノチューブ類から形成された炭素繊維類
AU6078700A (en) * 1999-07-21 2001-02-13 Hyperion Catalysis International, Inc. Methods of oxidizing multiwalled carbon nanotubes
JP2002097010A (ja) * 2000-09-20 2002-04-02 Japan Science & Technology Corp ハイブリッド単層カーボンナノチューブの作製方法
JP2002097008A (ja) * 2000-09-20 2002-04-02 Japan Science & Technology Corp 単層カーボンナノチューブの開孔方法
AU2002307283A1 (en) * 2001-04-12 2002-10-28 Honda Giken Kogyo Kabushiki Kaisha Purification of carbon filaments and their use in storing hydrogen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004016550A2 *

Also Published As

Publication number Publication date
FR2843382B1 (fr) 2005-12-23
CA2495094A1 (fr) 2004-02-26
FR2843382A1 (fr) 2004-02-13
AU2003274239A1 (en) 2004-03-03
WO2004016550A3 (fr) 2004-04-08
US20050163697A1 (en) 2005-07-28
WO2004016550A2 (fr) 2004-02-26
JP2005535550A (ja) 2005-11-24

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