EP1794352B1 - Elektrolysezelle zur herstellung von alkalimetall - Google Patents

Elektrolysezelle zur herstellung von alkalimetall Download PDF

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Publication number
EP1794352B1
EP1794352B1 EP05787394A EP05787394A EP1794352B1 EP 1794352 B1 EP1794352 B1 EP 1794352B1 EP 05787394 A EP05787394 A EP 05787394A EP 05787394 A EP05787394 A EP 05787394A EP 1794352 B1 EP1794352 B1 EP 1794352B1
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EP
European Patent Office
Prior art keywords
tube
alkali metal
solid electrolyte
closure device
electrolysis cell
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.)
Not-in-force
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EP05787394A
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German (de)
English (en)
French (fr)
Other versions
EP1794352A2 (de
Inventor
Günther Huber
Reinhard Oettl
Manfred Munzinger
Heinz Neumann
Martina Schulz
Matthias Stahl
Gerhard Ruf
Ralph Hamleser
Hans-Jürgen Bender
Volker Esswein
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BASF SE
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BASF SE
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Publication of EP1794352A2 publication Critical patent/EP1794352A2/de
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Publication of EP1794352B1 publication Critical patent/EP1794352B1/de
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    • 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
    • C25C3/02—Electrolytic production, recovery or refining of metals by electrolysis of melts of alkali or alkaline earth metals
    • 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
    • C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
    • C25C3/08—Cell construction, e.g. bottoms, walls, cathodes
    • C25C3/12—Anodes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/005—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells for the electrolysis of melts
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/04—Diaphragms; Spacing elements

Definitions

  • the present invention relates to an electrolytic cell for the production of liquid alkali metal from a liquid alkali metal heavy metal alloy.
  • an alkali metal is to be understood as meaning in particular sodium, potassium or lithium.
  • Sodium is an important inorganic base product which can be used, inter alia, for the preparation of sodium compounds such as sodium peroxide, sodium hydride, sodium borohydride and sodium amide for the extraction of titanium by metallothermy, as well as for reduction purposes in the organic chemical industry, for the purification of hydrocarbons and used oil, for condensations, for alkoxide production, as a polymerization catalyst and in preparative organic chemistry.
  • the sodium extraction is carried out today mainly by the downs method by melt electrolysis of a ternary mixture of NaCl, CaCl 2 and BaCl 2 .
  • Lithium finds inter alia. Use in nuclear technology for the production of tritium, as an alloying addition to aluminum, lead or magnesium, in organic syntheses, for the synthesis of complex metal hydrides, for the preparation of organometallic compounds, for condensations, dehydrohalogenations, for the production of ternary amines or quaternary ammonium salts, in the mineral oil industry as a catalyst and for desulfurization, for the polymerization of isoprene to cis polymers, in the ceramic industry for controlling the expansion coefficient, lowering the melting temperature and the like, for the production of lubricants, as deoxidizing and cleaning agents in the metallurgy of iron, nickel, copper and their alloys.
  • Lithium is also produced in the prior art on an industrial scale by the Downs process by electrolysis of anhydrous alkali metal chloride melts, wherein the melting points of the molten salts are reduced by additions of alkali chlorides.
  • the service life of the known electrolysis cells is limited to 2 to 3 years. An interruption of the power supply or the shutdown of the cell usually leads to the destruction of the cell. Due to the melt additives, the sodium obtained after the Downs process has the disadvantage that it is primarily contaminated with calcium, whose residual content is reduced by subsequent purification steps, but never completely removed. In the case of the lithium obtained by the Downs process, a significant disadvantage is that the aqueous lithium chloride sols obtained in the chemical reaction of lithium must first be worked up to anhydrous lithium chloride before use in electrolysis.
  • Potassium is also an important inorganic base product used, for example, in the production of potassium alkoxides, potassium amides and potassium alloys.
  • the disadvantage is that the process operates at high temperatures.
  • the resulting potassium contains about 1% sodium as an impurity and must therefore be purified by another rectification.
  • the biggest disadvantage is that the sodium used is expensive. This is also due to the fact that sodium is obtained technically by electrolysis of molten common salt after the Downs process, which requires a great deal of energy.
  • GB 1,155,927 describes a process by which sodium metal can be obtained from sodium amalgam electrochemically using a solid sodium ion conductor with amalgam as the anode and sodium as the cathode.
  • the execution of in GB 1,155,927 does not lead to the results described there in terms of sodium conversion, product purity and current density.
  • the system described behaves unstable in the course of a few days, if the claimed temperature range is maintained.
  • Object of the present invention was to provide an electrolytic cell, which on the in the EP 1 114 883 A1 described method and the device disclosed therein, in which an effective separation of alkali metal-heavy metal alloy leading of alkali metal-leading components is achieved.
  • Another object of the present invention was to enable inexpensive and trouble-free maintenance of the electrolysis cell.
  • the electrolysis cell according to the invention makes it possible to operate the electrolysis on an industrial scale.
  • the closure device takes on a variety of functions, so that a simple construction of the electrolytic cell is achieved.
  • the electrolysis cell according to the invention is intended for continuous operation.
  • the flow of the liquid alkali metal heavy metal alloy is preferably driven by a pump located outside the electrolytic cell.
  • the inventive design of the electrolysis cell ensures that the alkali metal heavy metal alloy is guided so that the transport of the alkali metal dissolved in the heavy metal is ensured to the surface of the alkali metal ion conductive solid electrolyte for high current densities of industrial production.
  • a long service life can be achieved by the appropriate selection of materials for the construction of the electrolytic cell according to the invention, as is customary for devices of industrial chemistry.
  • the electrolysis can be interrupted at any time in the cell according to the invention without damaging the cell.
  • the cell according to the invention is supplied with a liquid alkali metal heavy metal alloy, in particular an alkali metal amalgam with sodium, potassium or lithium as alkali metal.
  • a liquid alkali metal heavy metal alloy in particular an alkali metal amalgam with sodium, potassium or lithium as alkali metal.
  • Other possible heavy metals as part of the liquid alkali metal heavy metal alloy are gallium or lead or alloys of gallium, lead and mercury.
  • the sodium concentration of this solution must be less than 1% by weight, preferably 0.2 to 0.5% by weight.
  • the potassium concentration of the solution is less than 1.5% by weight, preferably 0.3 to 0.6% by weight.
  • the lithium concentration of the solution is less than 0.19% by weight, preferably 0.02 to 0.06% by weight.
  • the material for the substantially horizontally disposed pipe preferably stainless steel or graphite is selected.
  • the material used for the solid electrolyte tube in the production of sodium ceramic materials such as NASICON ® into consideration, their composition in the EP-A 0 553 400 is specified.
  • Sodium ion-conducting glasses are also suitable as well as zeolites and feldspars.
  • potassium is also a variety of materials in question. Both the use of ceramics and the use of glasses are possible.
  • the following materials can be considered: KBiO 3 , gallium oxide-titanium dioxide-potassium oxide systems, alumina-titania-potassium oxide systems and KASICON ® glasses.
  • sodium ⁇ "-alumina, sodium ⁇ -alumina and sodium ⁇ / ⁇ " -alumina or potassium ⁇ "-alumina, potassium ⁇ -alumina and potassium ⁇ / ⁇ " -alumina preferred are sodium ⁇ "-alumina, sodium ⁇ -alumina and sodium ⁇ / ⁇ " -alumina or potassium ⁇ "-alumina, potassium ⁇ -alumina and potassium ⁇ / ⁇ " -alumina.
  • Potassium ⁇ "-alumina, potassium ⁇ -alumina or potassium ⁇ / ⁇ " -alumina can be prepared starting from sodium ⁇ "-alumina, sodium ⁇ -alumina and sodium ⁇ / ⁇ " -alumina, respectively, by cation exchange. In the production of lithium is also a variety of materials in question.
  • Li 4-x Si 1-x P x O 4 Li-beta "-Al 2 O 3, Li-beta-Al 2 O 3, lithium analogs of NASICON ® ceramics, lithium ion conductors with perovskite structure, and sulfidic glasses as lithium ion conductors.
  • the solid electrolyte tube is closed on one side and preferably thin-walled, but pressure-resistant and designed with a circular cross-section.
  • the tube has a length between 0.5 m and 2 m, preferably between 0.9 m and 1.1 m.
  • the inner diameter of the tube is between 35 mm and 130 mm, preferably between 65 mm and 75 mm.
  • the tube thickness (wall thickness) is between 1 mm and 30 mm, preferably between 2.5 mm and 3.6 mm when using commercially available welded tubes, and preferably between 15 and 20 mm when the tube is made by casting.
  • the solid electrolyte tube has an outer diameter between 30 mm and 100 mm, preferably between 55 mm and 65 mm.
  • the wall thickness of the solid electrolyte tube is between 0.9 mm and 2.5 mm, preferably between 1.2 mm and 1.8 mm. It has a length between 20 cm and 75 cm, preferably between 45 cm and 55 cm.
  • the alkali metal heavy metal alloy passes through the alkali metal heavy metal alloy feed into the first annular gap surrounding the solid electrolyte tube. From there, the alkali metal heavy metal alloy flows through the tube through the first annular gap and finally out of the tube via the alkali metal heavy metal alloy discharge.
  • the electrolysis is operated by applying an electric voltage between the outside of the solid electrolytic tube closed on one side composed of an alkali metal ion-conductive solid electrolyte and the inside so that the alkali metal heavy metal alloy flowing outside in the first annular gap in the longitudinal direction forms the positive pole the alkali metal formed forms the negative pole.
  • the voltage difference causes an electrolysis current which causes alkali metal to be oxidized at the alkaline metal-metal alloy-ion conductor interface, then transported through the ionic conductor as the alkali metal ion, and then reduced back to metal at the ionic conductor-alkali metal interface in the solid electrolyte tube.
  • the alkali metal heavy metal alloy stream is continuously depleted in terms of its alkali metal content in proportion to the flowing electrolysis stream.
  • the thus transferred to the inside of the solid electrolyte tube alkali metal can be removed continuously from there via the alkali metal.
  • the electrolysis is carried out at a temperature in the range of 260 to 400 ° C.
  • the temperature should be below the boiling point of mercury, preferably at 310 ° C to 325 ° C if the alkali metal is sodium, and 265 ° C to 280 ° C if the alkali metal is potassium, and 300 ° C to 320 ° C if the alkali metal is lithium.
  • the alkali metal heavy metal alloy is already preheated to 200 ° C to 320 ° C, preferably at 250 ° C to 280 ° C supplied to the electrolytic cell according to the invention.
  • the electrolysis cell can be assigned a heat exchanger, in particular a countercurrent heat exchanger, so that the alkali metal-depleted, leaving the tube of the electrolytic cell hot alkali metal heavy metal alloy heats the alkali metal heavy metal alloy supply of the tube.
  • Preheating of the alkali metal heavy metal alloy is also possible with the help of wound around the feed heating wires.
  • a closure device which is suitable, each one closed on one side solid electrolyte tube, consisting of an alkali metal ion-conducting solid electrolyte record.
  • the opening of the solid electrolyte tube is directed outward.
  • the closure device is designed in such a way that the space filled with alkali metal heavy metal alloy in the essentially horizontal tubes is sealed leak-free both to the environment and to the interior of the solid electrolyte tube.
  • the closure device also meets the requirement to seal the interior of the solid electrolyte tube against the environment. It contains a sealing system for sealing the interior of the solid electrolyte tube and the alkali metal removal against the first annular gap, the alkali metal-heavy metal alloy supply or removal and against the environment of the electrolysis cell.
  • the closure device includes a fixedly connected to the pipe part and a removable part, wherein the firmly connected to the pipe part of the closure device is integrally or integrally connected to the tube.
  • the closure device includes a removable part, access to the arranged in the tube components of the electrolytic cell is made possible, in particular for their repair, replacement or maintenance.
  • the removable part of the closure device comprises a T-shaped neck containing the alkali metal removal. Via the alkali metal removal molten alkali metal can be removed from the interior of the solid electrolyte tube.
  • the T-shaped socket is preferably made of an electrically conductive material, so that it can be used as an electrical connection for the cathode.
  • a first isolation ring and a second isolation ring are arranged in the closure device so as to electrically isolate the T-shaped connection from other electrically conductive components of the closure device.
  • the T-shaped connecting piece is used as an electrical connection for the cathode, it is electrically insulated from the electrically conductive components of the electrolysis cell connected to the anode, for example with respect to the pipe, so that a short circuit is avoided.
  • the insulating rings are preferably made of an electrically non-conductive ceramic material. In particular, they consist of sintered Al 2 O 3 , ZrO 2 , magnesium oxide or boron nitride.
  • the sealing system which is arranged in the closure device, preferably comprises two applied on two sides of the first insulating ring sealing rings.
  • It is for example commercially available gasket rings flnxibler graphite sheets, reinforced with steel sheets, for example SIGRAFLEX® ®.
  • gasket rings flnxibler graphite sheets, reinforced with steel sheets, for example SIGRAFLEX® ®.
  • SIGRAFLEX® ® steel sheets
  • suitable sealing rings are laminated mica seals as KLINGERmilam ®.
  • an annular space for guiding a pressure-supplied inert gas, in particular nitrogen, is arranged adjacent to the first insulating ring between the two sealing rings.
  • the inert gas is passed under pressure into the annulus.
  • alkali metal heavy metal alloy can be forced into the annulus via the one seal ring nor alkali metal over the other seal ring if the pressure of the inert gas is set sufficiently high.
  • the inert gas is injected at a higher pressure than counterpressure on the alkali metal heavy metal alloy side or on the alkali metal side is to be expected.
  • a displacement body is arranged in the interior of the solid electrolyte tube so that there is a second annular gap for receiving the liquid alkali metal between the outside of the displacement body and the inside of the solid electrolyte tube.
  • a displacement body can serve a solid metal body.
  • This metal body has the further advantage that it can be used as a cathode when the electrolysis is started with a solid electrolyte tube not yet filled with alkali metal.
  • As a displacement body but can also serve a closed hollow body. This hollow body has the advantage that it can be more easily inserted into the solid electrolyte tube due to its lower weight, without damaging them.
  • As a displacement body can serve a one-sided closed, exactly to the shape of the interior of the solid electrolyte tube adapted thin-walled sheet metal tube, which is inserted into the solid electrolyte tube, so that forms a very narrow second annular gap. In the thin-walled sheet metal tube, another body can be used for reinforcement.
  • the displacement body designed as a sheet metal tube has the advantage that the amount of alkali metal that is mixed in the failure of the solid electrolyte tube with alkali metal heavy metal alloy, is very low.
  • two solid electrolyte tubes are arranged in the tube, which each face with the opening to one end of the tube.
  • the invention relates to an electrolysis device having a plurality of electrolysis cells, wherein the electrolysis cells are connected to one another in such a way that the liquid alkali metal heavy metal alloy is guided as a meandering current through the electrolysis cells.
  • the electrolysis device according to the invention has the advantage that it is modular. At least two cells arranged one above the other are connected to form an electrolysis unit which is flowed through by a volume flow of alkali metal-heavy metal alloy from the first to the last tube.
  • the number of electrolysis cells can be increased arbitrarily. Similarly, the number of parallel used electrolysis units are arbitrarily increased. This makes it possible to produce alkali metals on an industrial scale.
  • the electrolysis device preferably comprises 2 to 100 tubes, more preferably 5 to 25 tubes per electrolysis unit. It contains n electrolysis units arranged in parallel with n preferably between 1 and 100, more preferably between 5 and 20.
  • the present invention further relates to the use of an electrolytic cell according to the invention for the production of sodium, potassium or lithium from a liquid alkali metal amalgam.
  • FIG. 1 shows a section of an electrolytic cell according to the invention for the production of liquid alkali metal from a liquid alkali metal heavy metal alloy.
  • the electrolytic cell comprises a substantially horizontally arranged tube 1.
  • FIG. 1 only one end of the tube 1 with a closure device 4 is shown.
  • the electrolysis cell according to the invention is constructed substantially symmetrically with another (not shown) closure device 4 at the other end of the tube 1.
  • a solid electrolyte tube 12 is concentrically arranged, which is closed at its (not shown) end and on the other (shown ) End has an opening 11. The opening 11 faces the end of the tube 1.
  • a first annular gap 13 for guiding the anodes forming liquid alkali metal heavy metal alloy, the passes through the alkali metal heavy metal alloy supply 8 in the tube 1 and flows through the first annular gap 13 along the solid electrolyte tube 12 up to an alkali metal (not shown) heavy metal alloy discharge 9 at the other end of the tube 1.
  • the interior 14 of the solid electrolyte tube 12 serves to accommodate during the electrolysis there formed liquid alkali metal, which is usable as the cathode of the electrolytic cell.
  • a holding means for the solid electrolyte tube 12 an alkali metal discharge 15 connected to the inner space 14 of the solid electrolyte tube 12 and a sealing system are integrated.
  • the closure device 4 contains a part 20 fixedly connected to the tube 1 and a detachable part, wherein the part 20 of the closure device 4 fixedly connected to the tube 1 is firmly bonded to the tube 1.
  • the detachable part of the closure device 4 can be fastened with the aid of a clamping ring 3 to the part 20 of the closure device 4 fixedly connected to the tube 1.
  • the clamping ring 3 is by means of two in each case a threaded bore 10 in the firmly connected to the tube 1 part 20 of the closure device 4 screwed threaded bolt 21 which extend through a respective bore 22 in the clamping ring 3 and by means of a nut 23 and a clamping plate 24 at the Locking device 4 clamped.
  • the removable part of the closure device 4 comprises a T-shaped stub 25 containing the alkali metal discharge 15.
  • the T-shaped socket 25 is preferably made of an electrically conductive material, so that it can be used as an electrical connection for the cathode. He contacted directly in the interior 14 in the electrolysis resulting alkali metal.
  • a first insulating ring 26 and a second insulating ring 27 are arranged in the closure device 4, that they electrically isolate the T-shaped socket 25 against other electrically conductive components of the closure device 4.
  • the first insulating ring 26 is connected to the opening 11 having the end of the solid electrolyte tube 12 by means of an electrically non-conductive adhesive 28.
  • the adhesive 28 is a glass.
  • the removable part of the closure device 4 comprises in addition to the clamping ring 3 and the T-shaped socket 25 and the second insulating ring 27.
  • the clamping ring 3 presses the second insulating ring 27, the T-shaped socket 25 and the first insulating ring 26 against the fixed
  • These components thus form a holding device for the solid electrolyte tube 12, which is held by the pressure on the associated with her first insulating ring 26 on the fixed to the pipe 1 part 20 of the closure device 4.
  • a further sealing ring 38 is arranged between the clamping ring 3 and the second insulating ring 27, a further sealing ring 38 is arranged.
  • the electrolysis cell according to the invention further includes a resilient support device 29, which facilitates the concentric installation of the ion-conducting solid electrolyte tube 12 in the tube 1 and the weight forces in the empty state and the buoyancy force in the filled state of the interior space 14 of the solid electrolyte tube 12 partially receives.
  • the sealing system of the closure device 4 comprises two sealing rings 30, 31 resting on two sides of the first insulating ring 26. Adjacent to the first insulating ring 26, an annular space 32 for guiding a pressurized inert gas is arranged between the two sealing rings 30, 31. The inert gas is supplied via a gas line 33 to the annular space 32 under pressure.
  • the alkali metal heavy metal alloy supply 8 and -Ab arrangement 9 is connected.
  • an alkali metal heavy metal alloy feed 8 is shown over which the alkali metal heavy metal alloy flows into an alloy annulus 34 that is separated from the first annular gap 13 by a rotating screen 35.
  • This structure is advantageous for the distribution of the alkali metal-heavy metal alloy flow over the cross section of the first annular gap 13 serving as a reaction zone. Furthermore, this arrangement prevents disturbing solid particles from entering the reaction zone and leading to blockages there.
  • the inner space 14 of the solid electrolyte tube 12 is almost completely filled by a displacement body 36, so that only a second annular gap 37 remains free between the outside of the displacement body 36 and the inside of the solid electrolyte tube 12 for the resulting alkali metal.
  • FIG. 2 shows a schematic representation of an electrolysis device according to the invention.
  • the electrolyzer includes a plurality of tubes 1 forming an electrolysis unit 2. There are three superimposed tubes 1 an electrolysis unit 2 shown. In each tube 1 are two closed at one end, at the other end an opening 11 having solid electrolyte tubes 12 are present. The solid electrolyte tubes 12 are arranged concentrically in the tube 1 and with the opening 11 each one end of the tube 1 faces.
  • a first annular gap 13 for guiding the anodes forming liquid alkali metal heavy metal alloy 6 from the alloy manifold 5 via the outlet port 7 and the alkali metal heavy metal alloy supply 8 in the uppermost Pipe 1 passes and flows through the annular gap 13 on the solid electrolyte tubes 12 along to the alkali metal heavy metal alloy discharge 9 and from there into the next lower tube 1.
  • the alkali metal heavy metal alloy is guided through the illustrated arrangement of the electrolysis device according to the invention as a meandering current through the electrolysis unit 2.
  • Each shutter 4 serves as a support for a solid electrolyte tube 12 which is detachable, so that a defective solid electrolyte tube 12 can be easily exchanged.
  • the interior 14 of the solid electrolyte tube 12 is sealed against the alkali metal heavy metal alloy-carrying parts of the electrolysis unit 2, as above FIG. 1 described.
  • the interior space 14 serves to absorb liquid alkali metal formed there during the electrolysis, which can be used as the cathode of the electrolysis device.
  • the interior space 14 is connected to an alkali-metal outlet 15, which via a discharge line 16 directs the alkali metal to an alkali metal collector 17 positioned above the alloy distributor 5.
  • the alkali metal collector 17 is preferably filled with an inert gas under pressure.
  • the alkali metal collector 17 is in the in FIG.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
EP05787394A 2004-09-14 2005-09-12 Elektrolysezelle zur herstellung von alkalimetall Not-in-force EP1794352B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004044405A DE102004044405A1 (de) 2004-09-14 2004-09-14 Elektrolysezelle zur Herstellung von Alkalimetall
PCT/EP2005/009786 WO2006029792A2 (de) 2004-09-14 2005-09-12 Elektrolysezelle zur herstellung von alkalimetall

Publications (2)

Publication Number Publication Date
EP1794352A2 EP1794352A2 (de) 2007-06-13
EP1794352B1 true EP1794352B1 (de) 2008-02-27

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EP05787394A Not-in-force EP1794352B1 (de) 2004-09-14 2005-09-12 Elektrolysezelle zur herstellung von alkalimetall

Country Status (10)

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US (1) US7981260B2 (zh)
EP (1) EP1794352B1 (zh)
KR (1) KR101253787B1 (zh)
CN (1) CN101018893B (zh)
AR (1) AR054312A1 (zh)
AT (1) ATE387521T1 (zh)
DE (2) DE102004044405A1 (zh)
ES (1) ES2300052T3 (zh)
TW (1) TWI404831B (zh)
WO (1) WO2006029792A2 (zh)

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US9758881B2 (en) * 2009-02-12 2017-09-12 The George Washington University Process for electrosynthesis of energetic molecules
JP2013531738A (ja) * 2010-06-30 2013-08-08 シー アメンドラ スティーヴン リチウム金属の電解生成
CN104313645B (zh) * 2014-10-28 2017-08-08 苏州萨伯工业设计有限公司 含钪铝合金材料的制备装置及制备工艺
CN105742727B (zh) * 2014-12-09 2018-05-22 中国科学院物理研究所 一种二次电池、用途及其负极的制备方法
CN104805469B (zh) * 2015-05-11 2017-04-05 中国东方电气集团有限公司 一种电解制备金属钠装置的阴极电解槽
CN106972192A (zh) * 2017-03-16 2017-07-21 江苏大学 为锂离子储能器件负极预制锂的方法及电解池装置、锂离子储能器件
WO2022155752A1 (en) * 2021-01-21 2022-07-28 Li-Metal Corp. Electrorefining apparatus and process for refining lithium metal
CA3179470C (en) * 2021-01-21 2023-05-09 Li-Metal Corp. Process for production refined lithium metal
US11976375B1 (en) 2022-11-11 2024-05-07 Li-Metal Corp. Fracture resistant mounting for ceramic piping
CN116695185B (zh) * 2023-08-04 2023-10-17 四川澳晟新材料科技有限责任公司 一种金属锂熔盐电解工艺参数模拟仿真测试装置

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DE1114330B (de) 1959-05-06 1961-09-28 Dr Dr E H Karl Ziegler Verfahren zur kathodischen Abscheidung von Natrium durch Elektrolyse von natriumhaltigen organischen Aluminiumverbindungen
GB1155927A (en) 1967-02-20 1969-06-25 Ici Ltd Electrolytic manufacture of alkali metals.
US4089770A (en) * 1977-07-11 1978-05-16 E. I. Du Pont De Nemours And Company Electrolytic cell
CN1204700A (zh) * 1997-07-08 1999-01-13 国营建中化工总公司 一种金属锂电解槽
DE19859563B4 (de) 1998-12-22 2008-01-24 Basf Ag Verbessertes Verfahren zur elektrochemischen Herstellung von Alkalimetall aus Alkalimetallamalgam
DE19926724A1 (de) * 1999-06-11 2000-12-14 Basf Ag Elektrolysezelle zur Herstellung eines Alkalimetalls

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ATE387521T1 (de) 2008-03-15
DE502005003027D1 (de) 2008-04-10
DE102004044405A1 (de) 2006-03-30
US20070246368A1 (en) 2007-10-25
KR20070055592A (ko) 2007-05-30
AR054312A1 (es) 2007-06-20
US7981260B2 (en) 2011-07-19
CN101018893B (zh) 2010-08-11
KR101253787B1 (ko) 2013-04-15
TWI404831B (zh) 2013-08-11
EP1794352A2 (de) 2007-06-13
TW200624606A (en) 2006-07-16
WO2006029792A2 (de) 2006-03-23
ES2300052T3 (es) 2008-06-01
CN101018893A (zh) 2007-08-15
WO2006029792A3 (de) 2006-08-03

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