WO2007046713A1 - Procede de production de matieres en carbone - Google Patents

Procede de production de matieres en carbone Download PDF

Info

Publication number
WO2007046713A1
WO2007046713A1 PCT/NO2006/000366 NO2006000366W WO2007046713A1 WO 2007046713 A1 WO2007046713 A1 WO 2007046713A1 NO 2006000366 W NO2006000366 W NO 2006000366W WO 2007046713 A1 WO2007046713 A1 WO 2007046713A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon
electrolyte
anode
cathode
oxygen
Prior art date
Application number
PCT/NO2006/000366
Other languages
English (en)
Inventor
Christian Rosenkilde
Original Assignee
Norsk Hydro Asa
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 Norsk Hydro Asa filed Critical Norsk Hydro Asa
Publication of WO2007046713A1 publication Critical patent/WO2007046713A1/fr

Links

Classifications

    • 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
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • C01B32/162—Preparation characterised by catalysts
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • 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

Definitions

  • the present invention relates to production of nano carbon materials such as nano fibres (CNF), carbon nano tubes (CNT), both multi and single walled (MWNT, SWNT), and other submicron particles.
  • CNF nano fibres
  • CNT carbon nano tubes
  • MWNT multi and single walled
  • SWNT single walled
  • nano carbon materials are produced by arc-discharge, laser ablation, catalytic growth from CO and other carbon containing gases by chemical vapour deposition, CVD, and electrolytic production from molten salts, as described in "ET. Thostenson, Z. Ren, and T-W. Chou, Composites Science and Technology, VoI 61 , 2001 , p. 1899.1912"
  • arc-method current is passed between a carbon anode and cathode in a suitable container filled with a suitable gas. An arc is created between the electrodes, and carbon evaporates from the anode and deposits on the cathode.
  • the cathode product is typically a mixture of different carbon nanostructures.
  • Subsequent separation and purification of the different structures can be made by e.g. liquid-liquid extraction methods.
  • a laser ablation method a laser is used to evaporate carbon from a graphite target. The evaporated carbon is carried by a gas flow to a cold collector, typically copper, where carbon nano structures are deposited. Separation and purification are normally also required.
  • CVD a carbon containing gas is decomposed and carbon nano structures are deposited on a suitable substrate. This method allows for high yields of desired structure, and purification may not be required. Continuous production is also possible.
  • the present invention also employs electrolysis in a molten salt for the production of carbon nano materials.
  • the mechanism of formation of the nano-structured carbon is, however, different from the prior art. This is due to the minimum level of dissolved oxygen, e.g. as oxide and/or carbonate, to be present in the electrolyte.
  • the anode can preferably be made of a carbonaceous material, e.g. graphite. Anodes commonly used for the electrolytic production of aluminium can also be used.
  • the cathode can in principle be any electronically conductive material that is sufficiently stable in the electrolyte, e.g. metals, carbon materials, conductive carbides, TiB 2 , etc.
  • the electrolyte should be able to dissolve CO 2 , preferably as carbonate ions, CO 3 2" . So far, CaCI 2 with dissolved CaO has been used, but in principle any MX y -M 2 Z y O electrolyte with sufficient M 2 ZyO solubility can be used.
  • M is typically an alkaline earth element (Mg, Ca, Sr, Ba) or an alkali element (Li, Na, K, Rb, Cs), and X a halogenide (F, Cl, Br, I). Fluorides are less desirable since they have poor water solubility.
  • the anode reaction is typically an alkaline earth element (Mg, Ca, Sr, Ba) or an alkali element (Li, Na, K, Rb, Cs), and X a
  • the CO 2 thus formed may react with the dissolved oxide, giving carbonate:
  • the product of this reaction is a dissolved carbon containing ion that can be transported to the cathode where it can be reduced:
  • the carbon thus formed may deposit in many configurations, of which some are valuable nano structures.
  • the total reaction of the above partial reaction simply is the transport of carbon from the anode to the cathode.
  • the anode reaction does not necessary require the formation of intermediate CO 2 ; carbonate ions may also form by the reverse of the latter reaction, i.e. by oxidation of oxide and reaction with the carbon in the anode.
  • Carbon deposition may take place on the cathode surface or in the vicinity of the cathode.
  • the specified electrolytes can typically dissolve alkaline earth and alkali metals.
  • the CaCI 2 - CaO electrolyte can for example dissolve Ca metal. Therefore, if the cathodic potential is sufficiently negative, formation of dissolved metal can take place on the cathode. At some point in the electrolyte between the anode and the cathode, dissolved CO 3 2" formed on or close to the anode may react with dissolved metal formed on the cathode, leading to carbon formation away from the cathode and anode surfaces.
  • a CaCI 2 -CaO electrolyte In the case of a CaCI 2 -CaO electrolyte:
  • the present invention does not rely on the cathode as a source of carbon.
  • CO 2 may be supplied to the electrolyte as a gas from an external source, e.g. by bubbling CO 2 through the electrolyte.
  • the CO 2 will react with the oxide dissolved in the electrolyte, leading to CO 3 2" formation.
  • This dissolved carbonate is no different than that formed by the anodic reaction on a carbon anode, and the reduction of CO 3 2" will be the same as if CO 2 is formed by the anodic reaction.
  • oxide dissolved in the electrolyte will oxidise to oxygen gas on the anode. In this case, the reactions are:
  • the oxygen producing anode may e.g. be Ni/NiO based, or an oxide ion conductor, e.g. CaO stabilized ZrO 2 , may be used.
  • the oxide ion conductor separates the molten salt from the oxygen gas.
  • Oxide ions from the molten salt enter the oxide ion conductor on the side facing the molten salt.
  • the oxide ions move through the oxide ion conductor towards the other side, where electrons are released and oxygen gas is produced.
  • the oxygen producing side of the wall must be electrically connected to the electrolysis circuit.
  • the oxygen production can be facilitated by catalysts commonly used on the air side in solid oxide fuel cells
  • Catalysts can also increase the yield of carbon nano tubes (CNT). It is known that catalysts of the transition metals, such as Ni, Co and Fe, work well. Such catalysts can be added to the electrolyte as a suitable salt in desirable amounts, or the cathode may be a pure metal or an alloy containing the catalytic elements. One can also place the catalyst material near the cathode to promote desired reactions between dissolved metal and dissolved CO 3 2" . If the catalysts are added as salts to the electrolyte, they can be reduced on or near the cathode. Reduction may either take place before production of carbon, thereby creating fresh catalysts, or by simultaneous reduction of carbon and catalyst, thereby continuously creating new catalytic sites for growth of desired carbon structures.
  • CNT carbon nano tubes
  • the advantage of the present invention over the prior art is that large quantities of carbon nano materials can be produced at a low cost. It is estimated that the cost may be in the range of common electrolytically produced metals. This is accomplished by the large solubility of the carbonates in the electrolyte. It has been demonstrated that the CaCl 2 -CaO electrolyte may dissolve as much as 6 w% CO 2 as carbonate at 900 0 C.
  • Fig. 1 discloses carbon nano particles resulting from operational conditions specified in Example 1 ,
  • Fig. 2 discloses carbon nano particles resulting from operational conditions specified in Example 2,
  • Fig. 3 discloses schematically a preferred design of an electrolysis cell for the claimed method, in side view and in top view.
  • the product is a mixture of different carbon nano structures. If desired, separation and purification should be made by normal methods, such as liquid-liquid extraction and/or partial oxidation.
  • An electrolytic cell containing 23 kg of CaCI 2 and 350 g CaO was heated to 85O 0 C.
  • a graphite anode and a steel cathode were immersed into the electrolyte.
  • a direct current of 120 A was applied between the electrodes, which resulted in a cell voltage of 5 V.
  • the surface area of the graphite anode was 350 cm 2 , giving an anodic current density of 4000 A/m 2 .
  • the area of the steel cathode was 230 cm 2 , giving a cathodic current density of 6100 AJm 2 .
  • a porous diaphragm was placed between the anode and the cathode, dividing the cell in two compartments.
  • Fig. 1 shows a scanning electron microscope (SEM) micrograph of the dried product. Large amounts of nano-structured carbon can be seen.
  • Example 2 The same cell, electrodes, temperature and electrolyte as in Example 1 were used. This time a one compartment cell was used since there was no diaphragm between the anode and the cathode. Direct currents ranging from 120 to 240 A were applied between the electrodes, resulting in anodic current densities between 3400 and 6860 A/m 2 , and cathodic current densities between 5200 and 10400 A/m 2 . The cell voltage was 4.8 - 7 V. After some time of operation, carbon collected on the top of the cathodic chamber. The carbon was skimmed off. It was treated the same way as in Example 1. Fig. 2 shows a scanning electron microscope (SEM) micrograph of the dried product. Large amounts of nano-structured carbon can be seen. It was roughly estimated that the total carbon production was 70 g over a time of 7 hrs. A rough estimate of the current efficiency (real production/theoretical production according to Faradays law) is 60-100%.
  • a suitable process for nano structured carbon production according to the present invention is described in the following.
  • the core of the process is the electrolytic cell.
  • an electrolytic cell with one or several flat carbon anodes placed parallel to the cathode(s) is a preferred design, as shown schematically in Fig. 3.
  • the anodes (1 ) are placed between the cathodes (3) and vice versa in a vertical configuration. Since the carbon anodes will be consumed by the anodic reaction, they should be relatively easy to replace. Therefore, the anodes should enter the cell at the top. Cathodes can enter the cell from the top, from the sides, or from the bottom.
  • Some sort of electrically insulating wall (2), preferably a ceramic material, separating the surface layer of the electrolyte (4) surrounding the anode and the cathode, may therefore be required. Such a separating wall may also be required to prevent contact between produced carbon and CO 2 gas coming from the anode since CO 2 and carbon reacts to form CO.
  • the cell can be lined with a ceramic material that is stable towards the electrolyte, e.g. MgO or AI 2 O 3 based refractory materials (5).
  • An oxygen producing anode will not be consumed to the same extent as a carbonaceous anode. Entry of such an anode from any side of the cell is therefore possible.
  • the same is the case for the cathode. Separation of the off gas from the anode and the electrolyte carrying the carbon from the cathode is required to avoid burning of the carbon by the oxygen gas. Separation can be made by a wall placed between the anode and cathode. The wall should be wider than the electrodes and extend from the top of the cell compartment and well into the electrolyte. This separation also allows for collection of the nearly pure oxygen produced for other suitable purposes.
  • CO 2 should be added to the electrolyte by bubbling, preferably using a gas dispersion unit creating small bubbles with slow rising velocities. It is preferred that the bubbling takes place some distance from the electrodes to avoid contact with the produced carbon and contamination of the produced oxygen. Bubbling in a separate chamber with electrolyte underflow to the electrode chamber(s) is another way to separate CO 2 gas from the anode(s) and cathode(s). Both bipolar and monopolar electrodes can be used. It is also possible to use an oxide ion conductive material to separate the electrolyte from the oxygen producing anode.
  • CaO stabilized ZrO 2 which is a ceramic oxide ion conductor, can be made into hollow shapes closed in one end and inserted into the electrolyte. The interior of the hollow shape will then not contain any molten salt. The wall of the oxide ion conductor will act as a membrane separating the electrolyte from the interior of the hollow shape. Only oxide ions (O 2" ) can be transported through the membrane.
  • a suitable catalyst for the oxide ion oxidation on the interior wall of the hollow shape such as those used in solid oxide fuel cells, and connecting this to the positive pole of the electric circuit, pure oxygen gas can also be produced during electrolysis.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Inorganic Fibers (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

La présente invention concerne la production de nanomatières en carbone telles que des nanofibres (CNF), des nanotubes de carbone (CNT) à parois multiples ou uniques (MWNT, SWNT) et d'autres particules d'une taille inférieure au micron. Cette invention porte notamment sur un procédé de production électrolytique de carbone dans lequel on utilise une anode et une cathode d'un matériau conducteur, l'électrolyte étant un halogénure alcalino-terreux ou un halogénure alcalin ou encore un mélange de ces derniers, le courant électrique passant entre les électrodes. La quantité d'oxygène dissous dans l'électrolyte est au moins égale à 0,1 % en poids. La source de carbone peut être une anode carbonée ou du CO2 gazeux.
PCT/NO2006/000366 2005-10-21 2006-10-20 Procede de production de matieres en carbone WO2007046713A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NO20054895A NO20054895L (no) 2005-10-21 2005-10-21 Fremgangsmate for fremstilling av karbonmaterialer
NO20054895 2005-10-21

Publications (1)

Publication Number Publication Date
WO2007046713A1 true WO2007046713A1 (fr) 2007-04-26

Family

ID=35428100

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NO2006/000366 WO2007046713A1 (fr) 2005-10-21 2006-10-20 Procede de production de matieres en carbone

Country Status (2)

Country Link
NO (1) NO20054895L (fr)
WO (1) WO2007046713A1 (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014191765A1 (fr) * 2013-05-30 2014-12-04 The University Of Manchester Procédé électrochimique de production de graphène
CN104419944A (zh) * 2013-08-19 2015-03-18 韩国原子力研究院 电化学制备硅膜的方法
CN105386076A (zh) * 2015-12-07 2016-03-09 东北石油大学 一种高温电解co2制碳纳米管系统的改进方法
CN105506665A (zh) * 2015-12-07 2016-04-20 东北石油大学 一种高温电解co2制碳纳米管系统
CN105624722A (zh) * 2016-01-05 2016-06-01 北京金吕能源科技有限公司 一种电解二氧化碳制备石墨烯或碳纳米管的方法
US9506156B2 (en) 2012-03-09 2016-11-29 The University Of Manchester Production of graphene
CN107849706A (zh) * 2015-02-26 2018-03-27 乔治华盛顿大学 制备碳纳米纤维的方法和系统
WO2018075123A1 (fr) * 2016-10-19 2018-04-26 Vanderbilt University Matériaux de carbone nanostructurés et leurs procédés de fabrication et d'utilisation
CN109072457A (zh) * 2016-02-17 2018-12-21 金属电解有限公司 制备石墨烯材料的方法
US20190039040A1 (en) * 2015-10-13 2019-02-07 C2Cnt Llc Methods and systems for carbon nanofiber production
US10415143B2 (en) 2013-08-06 2019-09-17 The University Of Manchester Production of graphene and graphane
CN115697900A (zh) * 2020-05-08 2023-02-03 C2Cnt有限责任公司 磁性碳纳米材料及其制备方法

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHEN G.Z. ET AL.: "Recent development in electrolytic formation of carbon nanotubes in molten salts", JOURNAL OF MINING AND METALLURGY, vol. 39, no. 1-2, 2003, pages 309 - 342, XP003009301 *
DIMITROV A.T. ET AL.: "A feasibility study of scaling-up the electrolytic production of carbon nanotubes in molten salts", ELECTROCHIMICA ACTA, vol. 48, 2002, pages 91 - 102, XP004392919 *
ITO Y. ET AL.: "Electrochemical formation of thin carbon film from molten chloride system", PROCEEDINGS ELECTROCHEMICAL SOCIETY (PROC. INT. SYMP. MOLTEN SALTS, 8TH, 1992), vol. 16, 1992, pages 574 - 585, XP003009314 *
MASSOT L. ET AL.: "Electrodeposition of carbon films from molten alkaline fluoride media", ELECTROCHIMICA ACTA, vol. 47, 2002, pages 1949 - 1957, XP004349346 *

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9506156B2 (en) 2012-03-09 2016-11-29 The University Of Manchester Production of graphene
CN105452533A (zh) * 2013-05-30 2016-03-30 曼彻斯特大学 生产石墨烯的电化学方法
WO2014191765A1 (fr) * 2013-05-30 2014-12-04 The University Of Manchester Procédé électrochimique de production de graphène
CN105452533B (zh) * 2013-05-30 2018-07-13 曼彻斯特大学 生产石墨烯的电化学方法
US10415143B2 (en) 2013-08-06 2019-09-17 The University Of Manchester Production of graphene and graphane
CN104419944A (zh) * 2013-08-19 2015-03-18 韩国原子力研究院 电化学制备硅膜的方法
CN104419944B (zh) * 2013-08-19 2017-06-16 韩国原子力研究院 电化学制备硅膜的方法
US10730751B2 (en) 2015-02-26 2020-08-04 C2Cnt Llc Methods and systems for carbon nanofiber production
CN107849706A (zh) * 2015-02-26 2018-03-27 乔治华盛顿大学 制备碳纳米纤维的方法和系统
US20190039040A1 (en) * 2015-10-13 2019-02-07 C2Cnt Llc Methods and systems for carbon nanofiber production
US11402130B2 (en) * 2015-10-13 2022-08-02 C2Cnt Llc Methods and systems for carbon nanofiber production
CN105506665A (zh) * 2015-12-07 2016-04-20 东北石油大学 一种高温电解co2制碳纳米管系统
CN105386076A (zh) * 2015-12-07 2016-03-09 东北石油大学 一种高温电解co2制碳纳米管系统的改进方法
CN105624722B (zh) * 2016-01-05 2018-10-02 北京金吕能源科技有限公司 一种电解二氧化碳制备石墨烯或碳纳米管的方法
CN105624722A (zh) * 2016-01-05 2016-06-01 北京金吕能源科技有限公司 一种电解二氧化碳制备石墨烯或碳纳米管的方法
CN109072457A (zh) * 2016-02-17 2018-12-21 金属电解有限公司 制备石墨烯材料的方法
WO2018075123A1 (fr) * 2016-10-19 2018-04-26 Vanderbilt University Matériaux de carbone nanostructurés et leurs procédés de fabrication et d'utilisation
US10995000B2 (en) 2016-10-19 2021-05-04 Vanderbilt University Nanostructured carbon materials and methods of making and use thereof
CN115697900A (zh) * 2020-05-08 2023-02-03 C2Cnt有限责任公司 磁性碳纳米材料及其制备方法

Also Published As

Publication number Publication date
NO20054895L (no) 2007-04-23
NO20054895D0 (no) 2005-10-21

Similar Documents

Publication Publication Date Title
WO2007046713A1 (fr) Procede de production de matieres en carbone
CN104919089B (zh) 通过电解还原生产金属的方法和设备
US4342637A (en) Composite anode for the electrolytic deposition of aluminum
CA2316901A1 (fr) Procede electrolytique de traitement de flux de dechets aqueux
JP6465816B2 (ja) ＨＣｌを生成する水素ガス拡散陽極の集成装置及び当該集成装置を含む電解セル
CN113832473B (zh) 一种联产金属/碳复合材料和氢气的熔盐电化学方法
Fray Molten salts and energy related materials
KR101147491B1 (ko) 전기분해수 제조장치
WO2024102397A1 (fr) Système et procédé d'extraction électrolytique durable de métal
US9315914B2 (en) Light metal production
Cheng et al. An efficient ammonium chloride roasting approach to separating salt from the electrolytic carbon in molten carbonate
EP3918113A1 (fr) Procédé de production d'aluminium
Namboothiri et al. Aluminium production options with a focus on the use of a hydrogen anode: a review
WO2002083989A1 (fr) Reduction electrolytique d'oxydes metalliques
GB2547637A (en) Methods of making graphene
WO2006003865A1 (fr) Procédé de production de métal par électrolyse ignée
RU2337182C2 (ru) Способ электрохимического выделения меди в хлористоводородном растворе
RU2797008C2 (ru) Способ производства алюминия
GB2051864A (en) Electrodeposition of Aluminium Using Molten Electrolyte
US11965258B1 (en) Sulfur dioxide depolarized electrolysis and electrolyzer therefore
JP5631167B2 (ja) ナトリウム精製用電解槽
US20240158935A1 (en) Dimensionally stable anode for electrolytic chlorine evolution in molten salts
HU177164B (en) Method for cleaning aluminium alloys
US618575A (en) Oiqrneys
Fray Innovative electrochemical processing using molten salts

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE