WO2006037999A2 - Procede d'electroreduction - Google Patents

Procede d'electroreduction Download PDF

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Publication number
WO2006037999A2
WO2006037999A2 PCT/GB2005/003821 GB2005003821W WO2006037999A2 WO 2006037999 A2 WO2006037999 A2 WO 2006037999A2 GB 2005003821 W GB2005003821 W GB 2005003821W WO 2006037999 A2 WO2006037999 A2 WO 2006037999A2
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WO
WIPO (PCT)
Prior art keywords
electrode
electrolyte
oxide
electrolysis
metal
Prior art date
Application number
PCT/GB2005/003821
Other languages
English (en)
Other versions
WO2006037999A3 (fr
Inventor
Malcom Charles Ward Close
Daniel Robert Johnson
Alastair Bryan Godfrey
Original Assignee
Metalysis Limited
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.)
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Publication date
Application filed by Metalysis Limited filed Critical Metalysis Limited
Publication of WO2006037999A2 publication Critical patent/WO2006037999A2/fr
Publication of WO2006037999A3 publication Critical patent/WO2006037999A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B41/00—Obtaining germanium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C01B33/021—Preparation
    • C01B33/023—Preparation by reduction of silica or free silica-containing material
    • 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
    • C25B1/01—Products
    • C25B1/33—Silicon
    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B21/00—Obtaining aluminium
    • C22B21/0038—Obtaining aluminium by other processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B21/00—Obtaining aluminium
    • C22B21/02—Obtaining aluminium with reducing
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/20—Obtaining niobium, tantalum or vanadium
    • C22B34/22—Obtaining vanadium

Definitions

  • the present invention relates to a method for removing oxygen from metal oxides by electrolysis in a fused salt to produce elements or alloys of high purity, and to the products of such processes.
  • the invention relates in particular to the production of high purity silicon and other group IV elements from silica and other group IV oxides.
  • Electro-winning of elements from their ores has become well-established over the last two hundred years.
  • a new process has come to light in which a metal oxide is fabricated as an electrode with an electrolytic collector and is cathodically reduced to the metal in the presence of a fused electrolyte and applied direct current voltage.
  • Such an “electro-deoxidation” or “electro-reduction” process hereinafter generically referred to as an "EDO" process, is described in WO 99/64638 to Fray, and is generally- applicable to oxides of metals, metalloids and mixtures of oxides.
  • WO 99/64638 is especially concerned with the extraction of titanium from its oxide, although it teac ⁇ ies that the process may also be applied to decompose electrol ⁇ tically oxides of U, Mg, Al, Zr, Hf, Nb, Mo and rare earths such as Nd and Sm, as well as oxides of metalloids such as germanium and silicon.
  • EDO process may also be used to remove dissolved (e.g. interstitial) oxygen or other similar elements such as sulphur, nitrogen and carbon, it does not of course address the problem of dissolved metallic impurities.
  • High purity silicon is used widely in the electronics industry, for example in the production of semiconductors, integrated circuits and photovoltaic cells.
  • the required purity level depends upon the ultimate application.
  • the purity of photovoltaic grade silicon (>99.99999%) is lower than semiconductor • or integrated circuit grade silicon (>99.99999999%) .
  • Critical impurities requiring removal include the first row transition elements such as Cr, Fe, Mn, Ni as well as Al, B, P, ' Zr, Nb, Mo, Ta and W.
  • At present silicon is produced industrially by heating silicon dioxide with a reducing agent.
  • the low cost, metallurgical grade silicon obtained from the extraction process is then further purified, for example by the Siemens process.
  • the purification stage adds considerably to the cost of the final silicon product. Further processing stages may
  • a first aspect of the present invention provides a method for producing a metal, metalloid or alloy from a metal oxide, metalloid oxide or mixture of oxides of alloying elements forming a working electrode, by electrolysis in a fused salt or mixture of salts in the presence of a counter-electrode, the method comprising applying to the working electrode a plurality of electrolysis cycles, wherein at least one part of the electrolysis cycle is conducted at a cathodic potential relative to the counter-electrode under conditions so as to remove oxygen from the metal, metalloid or mixed oxide; and wherein at least one other part of the electrolysis cycle is conducted at an anodic voltage relative to the counter-electrode such that ionisation of metallic impurities from the oxide rather than removal of oxygen occurs and said impurities are released into the electrolyte.
  • the oxide electrode and secondary electrode are hereinafter referred to as the 'working electrode' and ⁇ counter-electrode' , respectively.
  • Either the working electrode is formed from the oxide or it is in electrical contact with the oxide, for example by threading oxide tiles onto a stainless steel rod.
  • the oxide typically has a porous or micro-porous structure produced, for example, by sintering oxide particles of suitable size. The micro-porosity decreases the length of diffusion paths for ions and other mobile species within the oxide, thus improving the diffusion efficiency of such species and aiding their removal from the electrode.
  • a high purity metal, metalloid or alloy can be produced directly from an oxide or mixed oxide by- applying a plurality of electrolysis cycles to a working electrode fabricated from, or contiguous with, said oxide or mixed oxide compound, wherein each electrolysis cycle comprises at least one cathodic electro-reduction phase in accordance with a typical EDO method and at least one anodic electro- oxidation phase for the ionisation and dissolution of metallic impurities.
  • each electrolysis cycle comprises at least one cathodic electro-reduction phase in accordance with a typical EDO method and at least one anodic electro- oxidation phase for the ionisation and dissolution of metallic impurities.
  • each electrolysis cycle comprises at least one cathodic electro-reduction phase in accordance with a typical EDO method and at least one anodic electro- oxidation phase for the ionisation and dissolution of metallic impurities.
  • the present invention has particular application to the production of silicon, especially photovoltaic grade silicon from silicon dioxide.
  • the method of the current invention is applicable to any element that can be extracted from its oxide by an EDO process and such elements include, for example, V, U, Mg, Al, Zr, Hf, Nb, Mo and rare earths such as Nd and Sm, as well as metalloids such as Ge and Si.
  • the type, rate and magnitude of electrode perturbation is chosen to achieve the reduction of the working electrode to the target element, whilst removing particular impurities according to their standard redox potentials in the particular electrolyte.
  • the present invention may be applied to any element or salt able to undergo this process and includes Group IV metalloids such as Si and Ge, which elements have redox potentials higher than typical metallic impurities such as, for example, transition elements.
  • the present method also applies to the extraction of high purity alloys from mixed oxides of alloying elements.
  • the cathodic voltage is set at a suitable level for an EDO process to take place, which level is sufficiently negative such that oxygen is removed from the cathode, but below the potential at which chlorine is evolved from the electrolyte.
  • the cathodic voltage suitably lies in the range 1.5V to 3.2V.
  • the anodic voltage applied to the working electrode is in the range 0.0 to 2.0V, referenced to a standard calomel electrode, and is sufficient to oxidise metallic impurities at the surface of the working electrode without re- oxidising the element undergoing extraction.
  • the anodic voltage applied to the working electrode is in the range 0.1 to 1.5V SCE, which voltage will remove a range of transition metal impurities, including, first row elements such as, for example, Cu, Pe, ,Cr 7 Mn, and Ni.
  • a reference electrode may not be used and the cell voltage may be selected having regard to the known redox potentials of target metallic impurities.
  • the use of cyclic polarisation of the working electrode causes the target element to form under cathodic polarisation and the metallic impurities to be removed from the reduced surface of the element under anodic polarisation.
  • the cathodic polarisation is set so that the element at the growing surface is momentarily formed. At this point the electrode is made to undergo a change in polarisation by altering the applied potential.
  • the removal of cathodic protection enables noble elements such as copper and iron, and other transition metals, to be ionised and thus be able to diffuse away from the growing surface of the silicon.
  • the re-adsorption of impurities into the working electrode will be governed, in part, by the concentration set up between the background concentration of the impurity in the electrolyte and those contained in the Helmholtz sphere at the electrode surface.
  • the cathodic voltage will usually be applied to the metal oxide, metalloid oxide or mixed oxide electrode for up to 100 seconds in each electrolysis cycle so as to reduce oxides at the electrode surface, but may be applied for only 10 to 100 milliseconds.
  • the cathodic deoxidation stage electrolytically reduces metallic impurities present at the working electrode as oxides or other salts, in addition to the target extractant, where their redox potentials are less cathodic.
  • the anodic voltage may be applied to the metal oxide, metalloid, oxide or mixed oxide electrode for up to 100 seconds, or for as little as 10 to 100 milliseconds, and may be of sufficient duration to deplete the double layer surrounding the working electrode of cationic impurities.
  • the plurality of electrolysis cycles conveniently comprises an alternating waveform, for example a sinusoidal, sawtooth or square waveform.
  • the plurality of electrolysis cycles comprises a pulsed or stepped waveform.
  • the plurality of electrolysis cycles preferably includes the condition of open circuit, which condition may aid the diffusion of impurities from the electrode bulk to the electrode surface.
  • the plurality of electrolysis cycles is applied until the required purity of the metal, metalloid or alloy product is obtained.
  • Th.e cycles may be of identical duration, or may vary, for example, getting progressively longer or shorter in duration.
  • the cycle lengths will get progressively longer with, time because, as the bulk concentration of impurities ⁇ n the working electrode decreases, the impurity concentration at the surface of the working electrode takes longer to build up.
  • the cycle rate may be directly proportional to the cell current and may be high initially.
  • the relative proportions of the anodic and cathodic phases may also be constant or vary, and the anodic phases may become shorter with successive cycles as fewer impur
  • the plurality of electrolysis cycles may be followed by a non-cyclic stage where the working electrode is maintained at a cathodic potential until substantially all of the oxygen has been removed from the oxide, for example, where a selected minimum impurity concentration threshold has been reached.
  • the temperature of the electrolysis cell should be maintained at 700-1000°C throughout the plurality of electrolysis cycles, thus aiding diffusion processes.
  • the electrolyte comprises a fused salt, or mixture of salts, which is more stable than the equivalent salt of the element that is being extracted.
  • the salt, or mixture of salts should have a wide difference between its melting and boiling point and a high temperature of operation to improve the diffusion of species in the electrode and elsewhere.
  • Suitable electrolytes include the chlorides of barium, calcium, caesium, lithium, strontium and yttrium. CaCl 2 is particularly suitable as an electrolyte, which electrolyte decomposes at approximately 3.3V at 700-1000 0 C.
  • the reduced species will be elemental calcium produced by the reduction of calcium oxide present in the electrolyte as an impmrity, which species getters oxygen and other impurities from the electrode surface. Once reoxidised through electrode cycling, these are removed into the electrolyte.
  • Electrode surface area, process temperature and the purity of the electrolyte all contribute to the efficiency of the out-diffusion processes, and electrolyte purity, in particular, provides a means of controlling concentration gradients and creating conditions suitable for gettering unwanted impurities from the electrode.
  • steps are preferably taken, on a continuous, semi-contzLnuous or batch basis, to maintain the purity of the electroDLyte in respect of target impurities.
  • the combination of electrode cycling and electrolyte purification can achieve high purity levels and preferably, purification of • the electrolyte occurs for at least the first two thirds, and preferably, the whole reaction time.
  • One method of doing this is to replace the electrolyte within the cell with pre-purified electrolyte from an erxternal supply. More advantageously, the electrolyte is, purified, using an additional purification means, which means may be Located within the electrolysis cell or externally.
  • the electrolyte is recycled through a purification means such as an ion exchange medium, for example a high melting point ion exchange resin such as Zeolite, located adjacent to the electrolysis cell.
  • a purification means such as a secondary plating electrode may be located within the cell and used to deposit metallic impurities from the electrolyte in situ.
  • a sacrificial electroactive material such as zinc or sodium may also be used to replace impurities in the electrolyte, which element will suitably be more electropositive than the impurities that it replaces, and have no impact (e.g. electrical impact in the case of Si) on the target element.
  • a suitable electroactive material is Zirconia loaded with sodium.
  • electrolyte purification means may optional.Iy comprise a filter to remove deposited salts from the electrolyte.
  • an EDO process is usually conducted using an anode comprising carbon.
  • a carbon counter electrode in the present invention may introduce disadvantageous additional impi ⁇ rities to the system, in which case an inert counter electrode may be used.
  • a counter electrode may comprise a pure metal, metal oxide or oxide- coated metal and more preferably the counter electrode comprises "Ebonex" , a conducting titanium oxide, or rhenium oxide.
  • the cell potential will need to be adjusted to account for the overpotential at an inert anode and suitable materials may be added to the electrolyte to improve the cell efficiency, as would be familiar to the skilled person.
  • the catriode material may be doped with elements such as phosphorous or boron, by the addition of suitable materials to the electrolyte.
  • the dopant-containing material is added to the electirolyte in excess concentration so that, for example, any phosphorous or boron removed from the working electrode during the anodic phase is more than replaced.
  • the purification method of the present invention proceeds via. surface mechanisms.
  • the working electrode is preferably fabricated with a high surface area.
  • Suitable electrode forms comprise flat, tiled, folded or cellular structures, for example pellets, foams, or single or multiple tiles threaded onto a steel conductor.
  • a thin layer of the oxide or mixed oxide is positioned on a conducting substrate such as a metal sheet and conveyed through and out of the reaction cell to speed throughput of material. This may be in the form of . a conducting belt, from which elemental material is subsequently removed, or a substrate coated with the element for permanency.
  • the working electrode is fabricated in the near net shape of the required metal, metalloid or alloy product.
  • Such electrodes are described j_n WO 99/64638.
  • a further aspect of the current invention provides a shaped component for a photovoltaic cell obtained by the process described above.
  • a final aspect of the current invention provides a method of doping a semiconductor.
  • Example 1 illustrates the invention.
  • a sample of compressed silicon dioxide on a steel cathode was electro-reduced to silicon in an electrochemical cell at 800° C using a fused impure CaCl 2 electrolyte and metal anode by the application of 3 volts dc.
  • a second sample of silicon was produced using high purity CaCl 2 electrolyte. The first sample exhibited a higher level of bulk impurities than the second.
  • a sample of compressed silicon dioxide on a steel cathode was electro-reduced to silicon in an electrochemical cell at 800 0 C using a fused pure CaCl 2 electrolyte and metal anode by the application of 3 volts dc.
  • the applied electrode potential was periodically switched off and ttie sample left at open circuit.
  • the impurities were found to have out diffused and accumulated at the surface of the silicon with the electrolyte.
  • Example 3 A sample of compressed silicon di.oxide on a steel cathode was electro-reduced to silicon in an electrochemical cell at 800° C using a fused pure CaCl 2 electrolyte and metal anode by the application of 3 volts dc.
  • the electrode was periodically cycled between cathodic and anodic potentials.
  • the impurities found to have accumulated at the surface of the silicon in example 2 had been removed from the bulk and surface of the silicon.
  • Powdered zinc was added to a fused and impure CaCl 2 electrolyte at 800° C.
  • the molten material was able to scavenge impurities from more noble metals and. thus purify the electrolyte whilst increasing its concentration in the CaCl 2 .
  • Example 6
  • Powdered sodium ion-containing zirc ⁇ nia was added to a fused and impure CaCl 2 electrolyte at 800 0 C. Impurities in the electrolyte were removed and the concentration of sodium ions increased.
  • Example 7 Powdered sodium ion-containing zirc ⁇ nia was added to a fused and impure CaCl 2 electrolyte at 800 0 C. Impurities in the electrolyte were removed and the concentration of sodium ions increased.
  • a sample of silicon dioxide was compressed with a small amount of sodium borate to form an electrode pellet on a steel cathode.
  • the sample was electro-reduced and found to contain mostly silicon but with additional boron species through its bulk suitable for further processing into various p-type semi ⁇ conducting phases.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Electrolytic Production Of Metals (AREA)

Abstract

L'invention concerne un procédé pour produire un métal, un métalloïde ou un alliage à partir d'un oxyde métallique, d'un oxyde de métalloïde ou d'un mélange d'oxydes d'éléments d'alliages formant une électrode de travail, par électrolyse dans un sel fusionné ou un mélange de sel en présence d'une contre-électrode. Ledit procédé comprend l'application d'une pluralité de cycles d'électrolyse sur une électrode de travail, au moins une partie du cycle d'électrolyse est effectuée sur un potentiel cathodique par rapport à la contre-électrode dans des conditions permettant d'éliminer l'oxygène du métal, du métalloïde ou de l'oxyde mélangé ; au moins une autre partie du cycle de l'électrolyse est effectué à une tension anodique par rapport à la contre-électrode, de sorte que l'ionisation des impuretés métalliques de l'oxyde soit effectuée au lieu de l'élimination de l'oxygène et lesdites impuretés sont éliminées dans l'électrolyte.
PCT/GB2005/003821 2004-10-06 2005-10-05 Procede d'electroreduction WO2006037999A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0422129.7 2004-10-06
GBGB0422129.7A GB0422129D0 (en) 2004-10-06 2004-10-06 Electro-reduction process

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WO2006037999A2 true WO2006037999A2 (fr) 2006-04-13
WO2006037999A3 WO2006037999A3 (fr) 2007-02-22

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010051759A1 (fr) * 2008-11-06 2010-05-14 北京有色金属研究总院 Procédé électrochimique de fabrication de nanopoudre, de nanofils et/ou de nanotubes de silicium
WO2010065989A1 (fr) * 2008-12-08 2010-06-17 University Of South Australia Fabrication de matériaux nanoporeux
WO2010069385A1 (fr) * 2008-12-18 2010-06-24 Silicon Fire Ag Procédé de préparation d'un vecteur d'énergie
WO2010069622A1 (fr) * 2008-12-18 2010-06-24 Silicon Fire Ag Procédé et installation permettant de produire une source d’énergie en utilisant du dioxyde de carbone comme source de carbone et en utilisant l’énergie électrique
WO2010069685A1 (fr) * 2008-12-18 2010-06-24 Silicon Fire Ag Silicium ou métaux élémentaires comme sources d'énergie
WO2010126597A1 (fr) * 2009-04-30 2010-11-04 Metal Oxygen Separation Technologies, Inc. Production primaire d'éléments
WO2017081160A1 (fr) 2015-11-10 2017-05-18 Stichting Energieonderzoek Centrum Nederland Fabrication additive d'objets métalliques
WO2018208155A1 (fr) 2017-05-10 2018-11-15 Admatec Europe B.V. Fabrication additive d'objets métalliques
WO2020055252A2 (fr) 2018-09-12 2020-03-19 Admatec Europe B.V. Objet tridimensionnel et son procédé de fabrication
DE102019107393A1 (de) * 2019-03-22 2020-09-24 Deutsches Zentrum für Luft- und Raumfahrt e.V. Verfahrenstechnik für Halogensalze mit zwei identischen Elektroden

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WO1999064638A1 (fr) * 1998-06-05 1999-12-16 Cambridge University Technical Services Limited Elimination d'oxygene d'oxydes metalliques et de solutions solides par electrolyse dans un sel fondu
WO2003048399A2 (fr) * 2001-12-01 2003-06-12 Cambridge University Technical Services Limited Procede et appareil de traitement de materiaux
WO2005019501A2 (fr) * 2003-08-20 2005-03-03 Materials & Electrochemical Research Corp. Procede thermique et electrochimique de production de metaux

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WO1999064638A1 (fr) * 1998-06-05 1999-12-16 Cambridge University Technical Services Limited Elimination d'oxygene d'oxydes metalliques et de solutions solides par electrolyse dans un sel fondu
WO2003048399A2 (fr) * 2001-12-01 2003-06-12 Cambridge University Technical Services Limited Procede et appareil de traitement de materiaux
WO2005019501A2 (fr) * 2003-08-20 2005-03-03 Materials & Electrochemical Research Corp. Procede thermique et electrochimique de production de metaux

Non-Patent Citations (1)

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X. JIN, P. GAO, D. WANG, X. HU, G. Z. CHEN: "Electrochemical Preparation of Silicon and Its Alloys from Solid Oxides in Molten Caclium Chloride" ANGEW. CHEM. INT. ED., [Online] vol. 43, no. 6, 27 January 2004 (2004-01-27), pages 733-736, XP002405077 Retrieved from the Internet: URL:http://www3.interscience.wiley.com/cgi -bin/fulltext/107561039/main.html,ftx_abs> [retrieved on 2006-10-27] *

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010051759A1 (fr) * 2008-11-06 2010-05-14 北京有色金属研究总院 Procédé électrochimique de fabrication de nanopoudre, de nanofils et/ou de nanotubes de silicium
WO2010065989A1 (fr) * 2008-12-08 2010-06-17 University Of South Australia Fabrication de matériaux nanoporeux
WO2010069385A1 (fr) * 2008-12-18 2010-06-24 Silicon Fire Ag Procédé de préparation d'un vecteur d'énergie
WO2010069622A1 (fr) * 2008-12-18 2010-06-24 Silicon Fire Ag Procédé et installation permettant de produire une source d’énergie en utilisant du dioxyde de carbone comme source de carbone et en utilisant l’énergie électrique
WO2010069685A1 (fr) * 2008-12-18 2010-06-24 Silicon Fire Ag Silicium ou métaux élémentaires comme sources d'énergie
US9631287B2 (en) 2008-12-18 2017-04-25 Silicon Fire Ag Method and facility system for providing an energy carrier by application of carbon dioxide as a carbon supplier of electric energy
US8795506B2 (en) 2009-04-30 2014-08-05 Infinium, Inc. Primary production of elements
US8460535B2 (en) 2009-04-30 2013-06-11 Infinium, Inc. Primary production of elements
CN102575364A (zh) * 2009-04-30 2012-07-11 金属氧分离技术公司 元素的初步生产方法
CN102575364B (zh) * 2009-04-30 2014-11-12 永能金属公司 元素的初步生产方法
WO2010126597A1 (fr) * 2009-04-30 2010-11-04 Metal Oxygen Separation Technologies, Inc. Production primaire d'éléments
WO2017081160A1 (fr) 2015-11-10 2017-05-18 Stichting Energieonderzoek Centrum Nederland Fabrication additive d'objets métalliques
WO2018208155A1 (fr) 2017-05-10 2018-11-15 Admatec Europe B.V. Fabrication additive d'objets métalliques
US11772157B2 (en) 2017-05-10 2023-10-03 Admatec Europe B.V. Additive manufacturing of metal objects
WO2020055252A2 (fr) 2018-09-12 2020-03-19 Admatec Europe B.V. Objet tridimensionnel et son procédé de fabrication
DE102019107393A1 (de) * 2019-03-22 2020-09-24 Deutsches Zentrum für Luft- und Raumfahrt e.V. Verfahrenstechnik für Halogensalze mit zwei identischen Elektroden

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WO2006037999A3 (fr) 2007-02-22
GB0422129D0 (en) 2004-11-03

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