WO2016061577A1 - Procédé et appareil pour une connexion d'électrode métallique liquide dans la production ou le raffinage de métaux - Google Patents

Procédé et appareil pour une connexion d'électrode métallique liquide dans la production ou le raffinage de métaux Download PDF

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Publication number
WO2016061577A1
WO2016061577A1 PCT/US2015/056230 US2015056230W WO2016061577A1 WO 2016061577 A1 WO2016061577 A1 WO 2016061577A1 US 2015056230 W US2015056230 W US 2015056230W WO 2016061577 A1 WO2016061577 A1 WO 2016061577A1
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WO
WIPO (PCT)
Prior art keywords
metal
conduit
liquid
container
aluminum
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Application number
PCT/US2015/056230
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English (en)
Inventor
Gregory Hardie
Adam Clayton Powell
Matthew Earlam
Robert Steve TUCKER
Alton TABEREAUX
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Infinium, Inc.
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Application filed by Infinium, Inc. filed Critical Infinium, Inc.
Publication of WO2016061577A1 publication Critical patent/WO2016061577A1/fr

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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
    • C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
    • C25C3/24—Refining
    • 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
    • C25C3/04—Electrolytic production, recovery or refining of metals by electrolysis of melts of magnesium
    • 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
    • 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
    • C25C3/18—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
    • C25C3/34—Electrolytic production, recovery or refining of metals by electrolysis of melts of metals not provided for in groups C25C3/02 - C25C3/32
    • 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
    • C25C7/02—Electrodes; Connections thereof
    • C25C7/025—Electrodes; Connections thereof used in cells for the electrolysis of melts

Definitions

  • the invention relates to apparatuses and methods for production of metals via molten salt electrolysis.
  • the Hall-Heroult cell revolutionized aluminum production in 1886 (U.S. Patent No. 400,664; herein incorporated by reference in its entirety) by reducing aluminum oxide dissolved in a molten salt electrolyte, with a consumable carbon anode that reacts with the oxygen to form carbon dioxide.
  • the Hall-Heroult molten salt electrolysis remains limited in cost and energy efficiency for several reasons.
  • the Hall-Heroult process electrical energy efficiency is below 55% ("U.S. Energy Requirements for Aluminum Production," U.S. Department of Energy, EERE Report, Feb.
  • This cathode arrangement works well when the molten salt electrolyte is less dense than the liquid aluminum product, such that there is a large graphite area and low current density through the graphite. In contrast, if the molten salt electrolyte is more dense than the liquid aluminum product, the aluminum floats to the top of the cell. In a conventional cell, this is problematic because it would be difficult to connect the carbon anode to the bath without either shorting it to the floating aluminum or creating a large distance between the floating aluminum cathode and broad carbon anode in the bath below it.
  • cermets generally of doped nickel ferrites with base/noble metal alloys, transition metals which form conducting surface oxides, composites which combine these two, aluminum bronzes generally with copper, and porous graphite with fuel gas flow to the outer surface. See, e.g., US Patents 4,397,729; 4,960,494; 5,254,232; 5,865,980; 6,030,518; 6,113,758; 6,126,799; 6,217,739; 6,248,227;
  • solid electrolyte enabling new classes of inert anodes or the use of natural gas reductant, eliminating carbon anode costs and contaminants, reducing or eliminating direct greenhouse gas emissions, clean anode emissions and no perfluorocarbon generation, reducing thermal losses by using an insulated steel vessel, simplified feeding, stabilizing the cell during oxide depletion due to lower zirconia resistance at high temperature, and vertical electrodes leading to much higher productivity per unit cell footprint.
  • the floating aluminum pad can further simplify metal collection, enable use of sintered oxide fines in some cases, reduce contamination due to broken solid electrolyte tubes and release of anode material, and increase magnetic field for improved magneto-hydrodynamic stirring (MHD) (see, e.g., U.S. Provisional Patent Application
  • the process as applied to metal production consists of a metal cathode, a molten salt electrolyte bath that dissolves the metal oxide that is in electrical contact with the cathode, a solid electrolyte oxygen ion conducting membrane (SOM) typically consisting of zirconia stabilized by yttria (YSZ) or other low valence oxide-stabilized zirconia, for example, magnesia- or calcia-stabilized zirconia (MSZ or CSZ, respectively) in ion-conducting contact with the molten salt bath, an anode in ion- conducting contact with the SOM, and a power source for establishing a potential between the cathode and anode.
  • SOM solid electrolyte oxygen ion conducting membrane
  • Metal cations are reduced to metal at the cathode, and oxygen ions migrate through the membrane to the anode where they are oxidized to produce oxygen gas or other oxides.
  • the SOM blocks back-reaction between anode and cathode products. It also blocks ion cycling, which is the tendency for subvalent cations to be re-oxidized at the anode, by removing the electronic connection between the anode and the metal ion containing molten salt because the SOM conducts only oxide ions, not electrons (see, U.S. Patent Nos. 5,976,345, and
  • the SOM electrolysis can proceed with high- or low-density electrolytes, and in some embodiments combines several desired characteristics of metal oxide reduction technology including, for example, 1) low-cost, low-toxicity metal oxide feedstock to avoid costs of producing, dehydrating and handling toxic metal chlorides; 2) insulated molten salt containment to reduce heat loss from the frozen sidewall; 3) separation between anode gas and molten salt for reduced emission of HF contaminated gases and heat recovery from the voluminous anode gas; 4) low anode-cathode distance for low resistance and excess heat production; 5) scale-down ability to mini-mills and on-site sale of liquid metal to customers; 6) ability to retrofit existing metal smelters; 7) use of clean, inexpensive fuel (e.g., natural gas) with high energy content and half the CHG emissions of expensive carbon anodes, optionally with uncontaminated carbon dioxide capture for sequestration or sale as a by-product; and/or 8) optional oxygen-producing inert anode without contamination of the
  • advantages particular to primary production of metal include, e.g., eliminating carbon anode costs, clean emissions with no anode effect from SOM selectivity, anode flexibility and energy efficiency, reduction of thermal loss, simpler metal collection, simplified feeding and improved electrode geometry.
  • the zirconia solid electrolyte tubes can accommodate either liquid silver or perovskite inert anodes that produce pure oxygen byproduct or fueled (e.g., natural gas) anodes emitting only water and carbon dioxide.
  • Hot swapping anode assemblies are also contemplated, as is exchanging current collectors while leaving zirconia tubes in place to change between inert and fueled (e.g., natural gas) operation for GHG and cost savings.
  • molten salt (cryolite) bath used in the Hall-Heroult cell requires a "frozen sidewall" of cryolite for containment since it dissolves all refractory oxides and accelerates oxidation of most metals. This frozen sidewall withdraws an enormous amount of thermal energy from the process, which increases energy consumption dramatically.
  • SOM technology oxygen originates inside the SOM tube(s), and the bath produces little to no gas.
  • a metal container can contain the salts without a frozen side wall, there is no oxidant (e.g., oxygen, carbon dioxide or water) outside of the tube(s) that would oxidize the metal container, and anode gas originates in the SOM and does not pick up corrosive volatiles (e.g., HF) so it is easy to seal and inert the container using very little inert gas, e.g., argon or nitrogen, preventing oxidation of a metal container.
  • a floating liquid aluminum cathode would require connection through the top of the cell, as side connection would lead to very high current density and overpotential through a graphite side- wall.
  • a traditional carbon block cathode would have very high current density and overpotential. High overpotential reduces cell energy efficiency. If connecting through the top, cathode bus connections must be interspersed with anode bus connections in a complex top plate.
  • the Hoopes cell (U.S. Patent 1,534,320; herein incorporated by reference in its entirety) employs graphite connectors and is in widespread use for production of high-purity aluminum. While possible to operate at high current density, the Hoopes cell requires very high voltage and energy consumption in part due to the high overpotential in these conductors.
  • the present invention provides a high-conductivity metal connection to the floating or submerged aluminum pad, resulting in low overpotential and energy usage, and a less complex top plate and manifold.
  • an apparatus comprising: (a) a conduit having a first end and a second end; (b) a liquid first metal disposed at the first end of the conduit and within the conduit; (c) a solid first metal disposed at the second end of the conduit and within the conduit; (d) a solid conductor portion in electrical contact with the solid first metal; and (e) a cooling mechanism disposed at the second end of the conduit; wherein at least a portion of the liquid first metal and the solid first metal are in electrical contact, and the solid conductor disposed to provide electrical contact between the solid first metal and an electrical source outside the conduit.
  • the conduit does not dissolve into the first metal more than about 5% by weight.
  • the conduit comprises carbon, silicon carbide, titanium diboride, boron nitride, silicon nitride, aluminum nitride, aluminum oxide or an aluminum-bearing compound with an element that does not dissolve into the first metal.
  • the apparatus further comprises a conduit sheath disposed around at least a portion of the conduit.
  • the cooling mechanism comprises a jacket disposed around a portion of the conduit, wherein the jacket has an inlet and an outlet.
  • air, gas, and/or a cooling liquid are disposed within at least a portion of the jacket.
  • the solid conductor comprises the first metal.
  • the apparatus further comprises a first container configured to contain at least a portion of the liquid first metal.
  • the first container comprises a well, tube or ledge extending from a second container.
  • the apparatus further comprises a vacuum port disposed along at least a portion of the conduit.
  • At least a portion of the conduit and solid conductor portion comprise a mould for extraction of the solid first metal.
  • the apparatus further comprises a second container for holding a molten electrolyte, the second container having an interior surface; an anode in ion- conducting contact with the molten electrolyte; and a power source for generating an electric potential between the anode and the liquid first metal.
  • the first metal is recovered from an oxide of the first metal dissolved in the molten electrolyte and the first metal collects on the floor of the second container.
  • the first metal is recovered from an oxide of the first metal dissolved in the molten electrolyte and the first metal collects on a top surface of the molten electrolyte when the electrolyte is disposed in the second container.
  • a portion of a side wall of the second container defines a first passage between the interior of the second container and the first container.
  • the first metal comprises aluminum, magnesium, lithium, beryllium, silicon, strontium, potassium, sodium, barium, scandium, titanium, silicon or calcium. In some embodiments, the first metal comprises aluminum or magnesium.
  • the first metal comprises aluminum.
  • an apparatus comprising a conduit having a first end and a second end; a first container disposed at the second end of the conduit, and configured to contain at least a portion of a liquid first metal within the conduit and a liquid second metal within the conduit, the liquid second metal having higher density than the liquid first metal; and a solid conductor portion in electrical contact with the second liquid metal; wherein the solid conductor is disposed to provide electrical contact between the second liquid metal and an electrical source outside the conduit.
  • the apparatus further comprises a second container disposed at the first end of the conduit, and configured to hold a molten electrolyte, the second container having an interior surface; a cooling mechanism disposed around at least a portion of the first container; an anode disposed in ion-conducting contact with the molten electrolyte; and a power source for generating an electric potential between the anode and the first liquid metal; wherein the conduit comprises a ledge extending from the interior of the second container to the first container.
  • the apparatus further comprises a solid conductor portion in electrical contact with the liquid second metal, and wherein at least a portion of the liquid first metal and the liquid second metal are in electrical contact, the liquid second metal disposed to provide electrical contact between the liquid first metal and an electrical source outside the conduit.
  • the conduit does not dissolve into the first metal more than about 5% by weight.
  • the conduit comprises carbon, silicon carbide, titanium diboride, boron nitride, aluminum nitride, silicon nitride, aluminum oxide or an aluminum-bearing compound with an element that does not dissolve into the first metal more than about 5% by weight.
  • the liquid second metal does not dissolve into the first metal more than about 5% by weight.
  • a method for electrically connecting a liquid first metal cathode to a current source of an electrolytic cell comprising: providing a conduit having a first end and a second end; providing a liquid first metal disposed at the first end of the conduit and within the conduit; providing a solid first metal disposed at the second end of the conduit and within the conduit; providing a solid conductor portion in electrical contact with the solid first metal; and providing a cooling mechanism disposed at the second end of the conduit;
  • liquid first metal and the solid first metal are in electrical contact, and the solid conductor provides electrical contact between the solid first metal and an electrical source outside the conduit.
  • the conduit does not dissolve into the first metal more than about 5% by weight.
  • the conduit comprises carbon, silicon carbide, titanium diboride, boron nitride, silicon nitride, aluminum nitride, aluminum oxide or an aluminum- bearing compound with an element that does not dissolve into the first metal more than about 5% by weight.
  • the methods further comprise providing a conduit sheath disposed around at least a portion of the conduit.
  • the cooling mechanism comprises air, gas, and/or a cooling liquid.
  • the solid conductor comprises the first metal.
  • the methods further comprise providing a first container configured to contain at least a portion of the liquid first metal.
  • the first container comprises a well, tube, or ledge extending from a second container.
  • At least a portion of the liquid first metal is drawn into the conduit via vacuum.
  • the methods further comprise providing a second container holding a molten electrolyte, the second container having an interior surface; and providing a power source for generating an electric potential between the anode and the cathode.
  • the first metal collects on the floor of the second container. [0048] In some embodiments, during generation of the electric potential, the first metal collects on a top surface of the molten electrolyte when the electrolyte is disposed in the second container.
  • a temperature gradient develops along the first metal and extends to form the electrical contact with the solid metal portion of the current collector.
  • the temperature gradient exists between the operating temperature of the cell and the melting point of the first metal disposed in the conduit.
  • a method for electrically connecting a liquid first metal cathode to a current source of an electrolytic cell comprising: providing a conduit having a first end and a second end; providing the liquid first metal disposed at the first end of the conduit and within the conduit; providing a first container disposed at the second end of the conduit, the first container containing at least a portion of a liquid first metal and a liquid second metal, the liquid second metal having higher density than the liquid first metal; and providing a solid conductor portion in electrical contact with the liquid second metal; wherein at least a portion of the liquid first metal and the liquid second metal are in electrical contact, and the solid conductor provides electrical contact between the liquid second metal and an electrical source outside the conduit.
  • the conduit does not dissolve into the first metal more than about 5% by weight.
  • the conduit comprises carbon, titanium diboride, silicon carbide, boron nitride, silicon nitride, aluminum nitride, aluminum oxide or an aluminum- bearing compound with an element that does not dissolve into the first metal more than about 5% by weight.
  • the method further comprises providing a conduit sheath disposed around at least a portion of the conduit.
  • the first container comprises a well, tube, or ledge extending from a second container.
  • At least a portion of the liquid first metal is drawn into the conduit via vacuum.
  • the method further comprises providing a second container holding a molten electrolyte, the second container having an interior surface; and providing a power source for generating an electric potential between the anode and the cathode.
  • the first metal collects on a top surface of the molten electrolyte when the electrolyte is disposed in the second container.
  • the temperature gradient exists between the operating temperature of the cell and the melting point of the first metal disposed in the conduit.
  • the liquid first metal is drawn from the second container toward the liquid second metal.
  • the liner comprises carbon, boron nitride, titanium diboride, SiC, Si 3 N 4 , aluminum nitride, or fused alumina. In some embodiments, the liner comprises titanium diboride, boron nitride, Si 3 N 4 , or fused alumina. In some embodiments, the liner comprises boron nitride, Si 3 N 4 , or fused alumina. In some embodiments, the liner comprises titanium diboride. In some embodiments, the liner comprises boron nitride. In some embodiments, the liner comprises Si 3 N 4 . In some embodiments, the liner comprises fused alumina.
  • a portion of a side wall of the second container defines a first passage between the interior of the second container and the first container.
  • a sheath is disposed around at least a portion of the solid oxygen ion-conducting membrane, the sheath extending from a level below the first metal- molten electrolyte interface to a level above the top surface of the first metal, and the sheath preventing contact between the first metal being recovered and the solid oxygen ion-conducting membrane.
  • the sheath comprises boron nitride, Si 3 N 4 , aluminum nitride, or fused alumina.
  • the sheath comprises Si 3 N 4 , or fused alumina.
  • the sheath comprises boron nitride or Si 3 N 4 .
  • the sheath comprises boron nitride.
  • the sheath comprises Si 3 N 4 .
  • the sheath comprises fused alumina.
  • the solid oxygen ion-conducting membrane and sheath define an annular space between the membrane and sheath, the apparatus further comprising a gas inlet in communication with the annular space. In some embodiments, the solid oxygen ion- conducting membrane and sheath define an annular space between the membrane and sheath, the method further comprising providing a gas in the annular space.
  • the first metal comprises aluminum, magnesium, lithium, beryllium, silicon, strontium, potassium, sodium, barium, scandium, titanium, silicon or calcium. In some embodiments, the first metal comprises aluminum, magnesium, lithium, beryllium, silicon, strontium, potassium, or calcium. In some embodiments, the first metal comprises aluminum or magnesium. In some embodiments, the first metal comprises aluminum. In some embodiments, the first metal comprises magnesium.
  • the solid conductor comprises the first metal.
  • a tapping well is provided on the first container.
  • At least a portion of the second container is thermally insulated.
  • the first container comprises a well, tube or ledge extending from the second container. In some embodiments, the first container comprises a tube or ledge extending from the second container. In some embodiments, the first container comprises a well or ledge extending from the second container. In some embodiments, the first container comprises a well or tube extending from the second container. In some embodiments, the first container comprises a well extending from the second container. In some embodiments, the first container comprises a tube extending from the second container. In some embodiments, the first container comprises a ledge extending from the second container.
  • a liquid second metal is disposed in the first container, the liquid second metal having low miscibility in the liquid first metal.
  • liquid first metal is drawn from the second container toward the liquid second metal.
  • At least a portion of the first metal collects as a liquid on a top surface of the molten electrolyte and extends through the conduit to the first container.
  • a conduit sheath is disposed around at least a portion of the conduit.
  • the conduit sheath comprises steel.
  • a temperature gradient develops along the first metal and extends to form the electrical contact with the solid metal portion. In some embodiments, a temperature gradient exists between the operating temperature of the cell and the melting point of the first metal disposed in the conduit.
  • Figure 1 An illustrative embodiment of an electrolytic cell configuration and method according to an embodiment of the invention.
  • Figure 2. An illustrative embodiment of an electrolytic cell configuration and method according to an embodiment of the invention.
  • FIG. 3 An illustrative embodiment of an electrolytic cell configuration and method according to an embodiment of the invention.
  • FIG. 4 An illustrative embodiment of an electrolytic cell configuration and method according to an embodiment of the invention.
  • FIG. 5 An illustrative embodiment of an electrolytic cell configuration and method according to an embodiment of the invention.
  • FIG. 6 An illustrative embodiment of an electrolytic cell configuration and method according to an embodiment of the invention.
  • Figure 7 Shows voltage and current vs. time according to an illustrative embodiment of the invention.
  • Figure 8. Shows voltage and current vs. time according to an illustrative embodiment of the invention.
  • Figure 9 Shows voltage and current in a ramp from 0 to 2.0 V, according to an illustrative embodiment of the invention.
  • Figure 10 Calculated temperature distribution for a 0.8 m long aluminum lead with a 100 A/cm 2 current density.
  • Figure 11 Calculated energy loss through the current collector vs. length for current density 20-100 A/cm 2 .
  • the present invention provides designs and methods for a conduit that enables a solid metal to maintain electrical contact with a liquid metal to form a current collector.
  • the current collector comprises a non-carbon metallic electrical connection to a floating or submerged liquid metal pad in an metal reduction cell.
  • the non-carbon metallic electrical connection exhibits high-conductivity.
  • an apparatus comprising: (a) a conduit having a first end and a second end; (b) a conduit sheath disposed around at least a portion of the conduit; (c) a liquid first metal disposed at the first end of the conduit; (d) a solid first metal disposed at the second end of the conduit; (e) a solid conductor portion in electrical contact with the solid first metal; and (f) a cooling mechanism disposed at the second end of the conduit; wherein at least a portion of the liquid first metal and the solid first metal are in electrical contact, and the solid conductor disposed to provide electrical contact connects between the solid first metal and an electrical source outside the conduit.
  • the apparatus further comprises: a second container for holding a molten electrolyte, the second container having an interior surface; a liner disposed along at least a portion of the interior surface of the second container; a solid oxygen ion- conducting membrane disposed to be in ion-conducting contact with the electrolyte when the molten electrolyte is disposed in the second container; an anode in ion-conducting contact with the solid oxygen ion-conducting membrane, the solid oxygen ion-conducting membrane disposed between the anode and the molten electrolyte; and a power source for generating an electric potential between the anode and the liquid first metal.
  • an apparatus comprising: (a) a conduit having a first end and a second end; (b) a first container disposed at the second end of the conduit, and configured to contain at least a portion of a liquid first metal and a liquid second metal, the liquid second metal having higher density than the liquid first metal; (c) a second container disposed at the second end of the conduit, and configured to hold a molten electrolyte, the second container having an interior surface; (d) a solid conductor portion in electrical contact with the liquid first metal; (e) a cooling mechanism disposed around at least a portion of the first container; (f) a liner disposed along at least a portion of the interior surface of the second container; (g) an anode disposed in electrical contact with the molten electrolyte; and (h) a power source for generating an electric potential between the anode and the first liquid metal; wherein the conduit comprises a ledge extending from the interior of the second container to the first container,
  • an apparatus comprising: (a) a conduit having a first end and a second end; (b) a liquid first metal disposed at the first end of the conduit; and (c) a first container disposed at the second end of the conduit, the first container configured to contain at least a portion of the first liquid metal and a liquid second metal, the liquid second metal having higher density than the first liquid metal; wherein at least a portion of the liquid first metal and the liquid second metal are in electrical contact, the liquid second metal disposed to provide electrical contact between the liquid first metal and an electrical source outside the conduit.
  • a method for electrically connecting a liquid first metal cathode to a current source of an electrolytic cell comprising: (a) providing a conduit having a first end and a second end; (b) providing a conduit sheath disposed around at least a portion of the conduit; (c) providing a liquid first metal disposed at the first end of the conduit; (d) providing a solid first metal disposed at the second end of the conduit; (e) providing a solid conductor portion in electrical contact with the solid first metal; and (f) providing a cooling mechanism disposed at the second end of the conduit; wherein at least a portion of the liquid first metal and the solid first metal are in electrical contact, and the solid conductor provides electrical contact between the solid first metal and an electrical source outside the conduit.
  • the method further comprises; (g) providing a second container holding a molten electrolyte, the second container having an interior surface; (h) providing a liner disposed along at least a portion of the interior surface of the second container; (i) providing a solid oxygen ion-conducting membrane disposed in ion-conducting contact with the molten electrolyte; and j) a power source for generating an electric potential between the anode and the cathode.
  • a method for electrically connecting a liquid first metal cathode to a current source of an electrolytic cell comprising: (a) providing a conduit having a first end and a second end; (b) providing the liquid first metal disposed at the first end of the conduit; (c) providing a first container disposed at the second end of the conduit, the first container containing at least a portion of a liquid first metal and a liquid second metal, the liquid second metal having higher density than the liquid first metal; (d) providing a solid conductor portion in electrical contact with the solid first metal; and (e) providing a cooling mechanism disposed at the second end of the conduit; wherein at least a portion of the liquid first metal and the liquid second metal are in electrical contact, and the solid conductor provides electrical contact between the solid first metal and an electrical source outside the conduit.
  • the method further comprises; (f) providing a second container holding a molten electrolyte, the second container having an interior surface; (g) providing a liner disposed along at least a portion of the interior surface of the second container; (h) providing a solid oxygen ion-conducting membrane disposed in ion-conducting contact with the molten electrolyte; and (i) a power source for generating an electric potential between the anode and the cathode.
  • the conduit does not dissolve into the first metal.
  • the conduit comprises graphitic carbon, silicon carbide, boron nitride, aluminum oxide or an aluminum-bearing compound with an element that does not dissolve into the first metal.
  • a vacuum port is disposed along at least a portion of the conduit. In some embodiments, at least a portion of the liquid first metal is drawn into the conduit via vacuum.
  • At least a portion of the conduit and solid conductor portion comprise a mould for extraction of the solid first metal.
  • the apparatus and/or methods further comprise a first container configured to contain at least a portion of the liquid first metal.
  • the first container comprises a well, tube or ledge extending from a second container.
  • the apparatus and/or methods further comprise a cooling mechanism.
  • the cooling mechanism comprises air, gas, and/or a cooling liquid.
  • the cooling mechanism comprises an inert gas, and/or a cooling liquid.
  • the cooling mechanism comprises an inert gas.
  • the cooling mechanism comprises a cooling liquid.
  • the cooling liquid comprises oil.
  • the apparatus and/or methods further comprise a cathode conductor, at least a portion of which is disposed in electrical contact with the molten electrolyte. In some embodiments, the apparatus and/or methods further comprise a cathode conductor, at least a portion of which is disposed in electrical contact with the molten electrolyte and the liquid first metal.
  • the interior surface of the second container includes a floor and the floor comprises carbon.
  • the liner extends from the floor upward along the interior surface of the second container to a level that prevents contact between the liquid first metal and the interior surface of the second container.
  • the first metal is recovered from an oxide of the first metal dissolved in the molten electrolyte and the first metal collects on the floor of the second container.
  • the liner extends from a first level below the first metal-molten electrolyte interface to a second level above the first metal-molten electrolyte interface, and the liner prevents contact between the first metal-molten electrolyte interface and the interior surface of the second container.
  • the first metal is recovered from an oxide of the first metal dissolved in the molten electrolyte, the first metal collects on the floor of the second container, and the liner extends to a level that prevents contact between the first metal-molten electrolyte interface and the interior surface of the second container.
  • the solid conductor comprises the first metal.
  • the second container comprises steel. In some embodiments, the second container is electrically isolated from the cathode.
  • At least a portion of the metal floats on the molten electrolyte. In some embodiments, during generation of the electric potential at least a portion of the metal collects on the floor of the second container.
  • the first metal is recovered from an oxide of the first metal dissolved in the molten electrolyte, the first metal collects on the floor of the second container.
  • the first metal is recovered from an oxide of the first metal dissolved in the molten electrolyte and the first metal collects on a top surface of the molten electrolyte when the electrolyte is disposed in the second container, the liner extends from a first level below the first metal-molten electrolyte interface to a second level above the first metal-molten electrolyte interface, and the liner prevents contact between the first metal-molten electrolyte interface and the interior surface of the second container.
  • the liner comprises carbon, boron nitride, titanium diboride, SiC, S1 3 N 4 , or fused alumina.
  • the liner comprises titanium diboride, boron nitride, S1 3 N 4 , or fused alumina. In some embodiments, the liner comprises boron nitride, S1 3 N 4 , or fused alumina. In some embodiments, the liner comprises titanium diboride. In some embodiments, the liner comprises boron nitride. In some embodiments, the liner comprises S1 3 N 4 . In some embodiments, the liner comprises fused alumina.
  • a portion of a side wall of the second container defines a first passage between the interior of the second container and the first container.
  • a sheath is disposed around at least a portion of the solid oxygen ion-conducting membrane, the sheath extending from a level below the first metal- molten electrolyte interface to a level above the top surface of the first metal, and the sheath preventing contact between the first metal being recovered and the solid oxygen ion-conducting membrane.
  • the sheath comprises boron nitride, S1 3 N 4 , or fused alumina.
  • the sheath comprises S1 3 N 4 , or fused alumina.
  • the sheath comprises boron nitride or S1 3 N 4 .
  • the sheath comprises fused alumina.
  • the sheath comprises boron nitride.
  • the sheath comprises Si 3 N 4 .
  • the solid oxygen ion-conducting membrane and sheath define an annular space between the membrane and sheath, the apparatus further comprising a gas inlet in communication with the annular space. In some embodiments, the solid oxygen ion-conducting membrane and sheath define an annular space between the membrane and sheath, the method further comprising providing a gas in the annular space.
  • the first metal comprises aluminum, magnesium, lithium, beryllium, silicon, strontium, potassium, or calcium. In some embodiments, the first metal comprises aluminum or magnesium. In some embodiments, the first metal comprises aluminum. In some embodiments, the first metal comprises magnesium.
  • the solid conductor comprises the first metal.
  • a tapping well is provided on the first container.
  • At least a portion of the second container is thermally insulated.
  • the first container comprises a well, tube or ledge extending from the second container. In some embodiments, the first container comprises a tube or ledge extending from the second container. In some embodiments, the first container comprises a well or ledge extending from the second container. In some embodiments, the first container comprises a well or tube extending from the second container. In some embodiments, the first container comprises a well extending from the second container. In some embodiments, the first container comprises a tube extending from the second container. In some embodiments, the first container comprises a ledge extending from the second container.
  • a liquid second metal is disposed in the first container, the liquid second metal having low miscibility in the liquid first metal.
  • liquid first metal is drawn from the second container toward the liquid second metal.
  • At least a portion of the first metal collects as a liquid on a top surface of the molten electrolyte and extends through the conduit to the first container.
  • a conduit sheath is disposed around at least a portion of the conduit.
  • the conduit sheath comprises steel.
  • a temperature gradient develops along the first metal and extends to form the electrical contact with the solid metal portion. In some embodiments, a temperature gradient exists between the operating temperature of the cell and the melting point of the first metal disposed in the conduit.
  • an apparatus comprising: (a) a conduit having a first end and a second end; (b) optionally, a conduit sheath disposed around at least a portion of the conduit; (c) a liquid first metal disposed at the first end of the conduit; (d) a solid first metal disposed at the second end of the conduit; (e) a solid conductor portion in electrical contact with the solid first metal; and (f) a cooling mechanism disposed at the second end of the conduit; wherein at least a portion of the liquid first metal and the solid first metal are in electrical contact, and the solid conductor disposed to provide electrical contact connects between the solid first metal and an electrical source outside the conduit.
  • the apparatus further comprises: a second container for holding a molten electrolyte, the second container having an interior surface; a liner disposed along at least a portion of the interior surface of the second container; a solid oxygen ion-conducting membrane disposed to be in ion-conducting contact with the electrolyte when the molten electrolyte is disposed in the second container; an anode in ion-conducting contact with the solid oxygen ion-conducting membrane, the solid oxygen ion-conducting membrane disposed between the anode and the molten electrolyte; and a power source for generating an electric potential between the anode and the liquid first metal.
  • an apparatus comprising: (a) a conduit having a first end and a second end; (b) a first container disposed at the second end of the conduit, and configured to contain at least a portion of a liquid first metal and a liquid second metal, the liquid second metal having higher density than the liquid first metal; (c) a second container disposed at the second end of the conduit, and configured to hold a molten electrolyte, the second container having an interior surface; (d) optionally, a solid conductor portion in electrical contact with the liquid first metal; (e) a cooling mechanism disposed around at least a portion of the first container; (f) a liner disposed along at least a portion of the interior surface of the second container; (g) an anode disposed in electrical contact with the molten electrolyte; and (h) a power source for generating an electric potential between the anode and the first liquid metal; wherein the conduit comprises a ledge extending from the interior of the second container to the
  • an apparatus comprising: (a) a conduit having a first end and a second end; (b) a liquid first metal disposed at the first end of the conduit; and (c) a first container disposed at the second end of the conduit, the first container configured to contain at least a portion of the first liquid metal and a liquid second metal, the liquid second metal having higher density than the first liquid metal; wherein at least a portion of the liquid first metal and the liquid second metal are in electrical contact, the liquid second metal disposed to provide electrical contact between the liquid first metal and an electrical source outside the conduit.
  • a method for electrically connecting a liquid first metal cathode to a current source of an electrolytic cell comprising: (a) providing a conduit having a first end and a second end; (b) providing a conduit sheath disposed around at least a portion of the conduit; (c) providing a liquid first metal disposed at the first end of the conduit; (d) providing a solid first metal disposed at the second end of the conduit; (e) providing a solid conductor portion in electrical contact with the solid first metal; and (f) providing a cooling mechanism disposed at the second end of the conduit; wherein at least a portion of the liquid first metal and the solid first metal are in electrical contact, and the solid conductor provides electrical contact between the solid first metal and an electrical source outside the conduit.
  • the methods further comprise; providing a second container holding a molten electrolyte, the second container having an interior surface;
  • a method for electrically connecting a liquid first metal cathode to a current source of an electrolytic cell comprising: (a) providing a conduit having a first end and a second end; (b) providing the liquid first metal disposed at the first end of the conduit; (c) providing a first container disposed at the second end of the conduit, the first container containing at least a portion of a liquid first metal and a liquid second metal, the liquid second metal having higher density than the liquid first metal; (d) providing a solid conductor portion in electrical contact with the solid first metal; and (e) providing a cooling mechanism disposed at the second end of the conduit; wherein at least a portion of the liquid first metal and the liquid second metal are in electrical contact, and the solid conductor provides electrical contact between the solid first metal and an electrical source outside the conduit.
  • the methods further comprise; providing a second container holding a molten electrolyte, the second container having an interior surface;
  • One illustrative embodiment is an aluminum connection from the liquid first metal pad all the way to an external cathode bus near the environment temperature.
  • this aluminum connection will be liquid on the end of the aluminum pad in the cell, and solid on the end of the cathode bus connection.
  • the liquid first metal can be contained in a conduit comprising materials with low solubility in the liquid metal (e.g, wherein the liquid metal is aluminum), such as but not limited to carbon, e.g. graphitic carbon, or silicon carbide, or boron nitride, or aluminum oxide, or other aluminum-bearing compounds with elements having low solubility in aluminum. Any of these materials can be used as dense solids, powders, or coatings.
  • the conduit allows the first metal (e.g., aluminum) to maintain conductivity, and advantageously does not react appreciably with and/or does not dissolve into the first metal.
  • the conduit comprises materials with low solubility in the liquid first metal. In some embodiments the conduit does not dissolve into the liquid first metal.
  • the conduit does not dissolve into the liquid first metal more than about 5% by weight. In some embodiments the conduit does not dissolve into the liquid first metal more than about 4% by weight. In some embodiments the conduit does not dissolve into the liquid first metal more than about 3% by weight. In some embodiments the conduit does not dissolve into the liquid first metal more than about 2% by weight. In some embodiments the conduit does not dissolve into the liquid first metal more than about 1% by weight. In some embodiments the conduit does not dissolve into the liquid first metal more than about 0.5% by weight. In some embodiments the conduit comprises materials with low solubility in aluminum.
  • the conduit comprises carbon, silicon carbide, boron nitride, aluminum oxide, or aluminum-bearing compounds comprising elements having low solubility in the liquid first metal. In some embodiments the conduit comprises carbon, silicon carbide, boron nitride, aluminum oxide, or aluminum-bearing compounds comprising elements having low solubility in aluminum. In some embodiments the conduit comprises carbon, silicon carbide, boron nitride, or aluminum oxide. In some embodiments the conduit comprises carbon, silicon carbide, or boron nitride. In some embodiments the conduit comprises silicon carbide, boron nitride, aluminum oxide, aluminum nitride, or aluminum-bearing compounds comprising elements having low solubility in the liquid first metal.
  • the conduit comprises silicon carbide, boron nitride, or aluminum oxide. In some embodiments the conduit comprises boron nitride, or aluminum oxide. In some embodiments the conduit comprises carbon. In some embodiments the conduit comprises graphitic carbon. In some embodiments the conduit comprises silicon carbide. In some embodiments the conduit comprises boron nitride. In some embodiments the conduit comprises aluminum oxide. In some embodiments the conduit comprises aluminum- bearing compounds comprising elements having low solubility in aluminum.
  • conduit sheath e.g. a strong steel sheath
  • the conduit sheath advantageously is strong at operating temperature of the cell and resistant to heat and air.
  • the conduit sheath improves mechanical robustness and/or corrosion resistance.
  • the conduit sheath may be comprised of materials other than steel, such as titanium or its alloys, nickel or its alloys, or other materials with melting point above about 1400°C and creep strength above about 1 MPa throughout the device temperature range.
  • the conduit sheath comprises materials with a melting point above about 1400 °C and creep strength above about 1 MPa throughout the device temperature range.
  • the conduit sheath comprises steel, titanium, alloys of titanium, nickel, or alloys of nickel.
  • the conduit sheath comprises steel, titanium, or nickel.
  • the conduit sheath comprises steel.
  • the conduit sheath comprises titanium.
  • the conduit sheath comprises nickel.
  • FIG. 1 A schematic embodiment is shown in Figure 1 , with the current collector using aluminum as an exemplary first liquid metal.
  • Figure 1 shows an exemplary current collector and electrolytic cell configuration with high-density salt and floating aluminum pad, with a liquid aluminum ledge and an insulated solid aluminum plate or rod current collector.
  • An anode (100) is shown in contact with a solid oxygen ion-conducting electrolyte (105).
  • the molten salt (1 10) is contained within a second container that is thermally insulated (1 15) and further contains at least one cathode conductor (120) and a seal pot (125) on the side.
  • Metal oxide e.g., alumina
  • a liner (145) is disposed along the interior surface of the second container, and extends from a first level below the liquid aluminum-molten electrolyte interface to a second level above the liquid aluminum-molten electrolyte interface, and prevents contact between the liquid aluminum-molten electrolyte interface and the interior surface of the second container.
  • the current collector comprises liquid aluminum, a first container (150) (e.g., a ledge in this embodiment), and the solid first metal (155) and a conduit (160).
  • the first container (150) (e.g., horizontal tube and/or ledge) contains liquid aluminum and extends from the molten electrolyte bath with a temperature gradient between the cell temperature and aluminum melting point. Thus, a cooling gradient is provided along the tube and/or ledge.
  • the solid first metal (155) comprising aluminum plates or shafts connects at the end of the tube and/or ledge away from the bath and anode.
  • the solid aluminum connects directly to the external cathode bus.
  • a conduit (160) is disposed around at least a portion of the current collector, which maintains conductivity of the aluminum.
  • Optional embodiments further provide a steel sheath disposed around at least a portion of the conduit and/or a high-conductive metal (e.g., solid conductor portion) at the environment end of the current collector.
  • Figure 2 shows an exemplary electrolytic cell configuration with high-density salt and floating aluminum pad, with an insulating current collector tube or conduit drawing liquid aluminum into contact with solid aluminum.
  • An anode (200) is shown in contact with a solid oxygen ion-conducting electrolyte (205).
  • the molten salt (210) is contained within a second container that is thermally insulated (215) and further contains at least one cathode conductor (220) and a seal pot (225) on the side.
  • a gas inlet (230) for inert gas, e.g., argon, is disposed between the annulus of the SOM and an insulating sheath (235).
  • Metal oxide e.g., alumina
  • liquid aluminum metal (240) which settles on top of the molten electrolyte, and can be removed via a tap on the side of the second container.
  • a liner (245) is disposed along the interior surface of the second container, and extends from a first level below the liquid aluminum-molten electrolyte interface to a second level above the liquid aluminum-molten electrolyte interface, and prevents contact between the liquid aluminum-molten electrolyte interface and the interior surface of the second container.
  • Oxygen ions migrate from the molten salt (210) through the solid electrolyte (205) to the liquid metal anode (200), where they form dissolved oxygen atoms. The oxygen atoms diffuse through the liquid metal anode to the gas phase where they form oxygen gas that evolves from the anode (See, e.g., U.S. Patent No. 8,658,007; herein
  • the current collector comprising a conduit (260) (e.g., vertical tube) draws liquid aluminum upward from the cell toward a solid conductor .
  • the solid first metal (255) comprising solid aluminum plates or shafts connects at the aluminum conductor portion of the conduit away from the bath and anode. In this embodiment, the solid conductor portion is also the solid first metal.
  • the solid aluminum connects directly to the external cathode bus.
  • the conduit (260) is disposed around at least a portion of the liquid first metal (240), which maintains conductivity of the aluminum.
  • Optional embodiments further provide a steel sheath disposed around at least a portion of the conduit and/or a high-conductive metal at the environment end of the current collector.
  • liquid first metal e.g. aluminum
  • a liquid second metal that is saturated with the first metal that itself has low solubility in the liquid first metal, e.g. tin, bismuth, or lead.
  • the liquid second metal comprises tin, bismuth or lead.
  • the liquid second metal comprises tin.
  • the liquid second metal comprises bismuth.
  • the liquid second metal comprises lead. At least a portion of the liquid first metal and liquid second metal are contained in a first container comprising a liner with low solubility in both metals, such as but not limited to carbon, e.g.
  • the liquid second metal has low miscibility with the liquid first metal, e.g, aluminum, and, optionally is more dense than the liquid first metal, e.g., aluminum.
  • the denser second metal is at a lower temperature than the liquid first metal near it, thus liquid first metal above the denser second metal is stratified (colder second-metal-saturated higher-density liquid first metal is on the bottom) and resists convection, minimizing transport of the second metal through the liquid first metal and into the first metal product.
  • Cathode bus connection to the liquid second metal is via a solid conductor portion, e.g., immiscible solid metal, such as a steel connection to bismuth or lead, or carbon connection to tin.
  • Such embodiments have the advantage of eliminating melt interface instability during constant current operation; however aluminum product contamination by the liquid second metal may occur.
  • Figure 3 shows an exemplary electrolytic cell configuration with high-density salt and floating liquid first metal, e.g., aluminum, pad, with a current collector configured as a liquid aluminum ledge with a liquid second metal pool.
  • An anode (300) is shown in contact with a solid oxygen ion-conducting electrolyte (305).
  • the molten salt (310) is contained within a second container that is thermally insulated (315) and further contains at least one cathode conductor (320) and a seal pot (325) on the side.
  • a gas inlet (330) for inert gas, e.g., argon, is disposed between the annulus of the SOM and an insulating sheath (335).
  • Metal oxide e.g., alumina
  • liquid aluminum metal (340) which settles on top of the molten electrolyte, and can be removed via a tap on the side of the container.
  • a liner (345) is disposed along the interior surface of the second container, and extends from a first level below the liquid aluminum-molten electrolyte interface to a second level above the liquid aluminum-molten electrolyte interface, and prevents contact between the liquid aluminum-molten electrolyte interface and the interior surface of the second container.
  • Oxygen ions migrate from the molten salt (310) through the solid electrolyte (305) to the liquid metal anode (300), where they form dissolved oxygen atoms. The oxygen atoms diffuse through the liquid metal anode to the gas phase where they form oxygen gas that evolves from the anode (See, e.g., U.S. Patent No.
  • the current collector comprising a conduit (360) (e.g., horizontal tube and/or ledge) contains liquid aluminum (340) and extends from the molten electrolyte bath with a temperature gradient between the cell temperature to the first container (350), which contains the cooler second metal (365) in a pool below the ledge.
  • a conduit e.g., horizontal tube and/or ledge
  • Figure 4 shows an exemplary electrolytic cell configuration with high-density salt and floating liquid first metal, e.g., aluminum, pad, with a metal current collector configured as an insulating current collector bridge tube to a liquid second metal pool.
  • An anode (400) is shown in contact with a solid oxygen ion-conducting electrolyte (405).
  • the molten salt (410) is contained within a second container that is thermally insulated (415) and further contains at least one cathode conductor (420) and a seal pot (425) on the side.
  • a gas inlet (430) for inert gas, e.g., argon, is disposed between the annulus of the SOM and an insulating sheath (435).
  • Metal oxide e.g., alumina
  • liquid aluminum metal (440) which settles on top of the molten electrolyte, and can be removed via a tap on the side of the container.
  • a liner (445) is disposed along the interior surface of the second container, and extends from a first level below the liquid aluminum-molten electrolyte interface to a second level above the liquid aluminum-molten electrolyte interface, and prevents contact between the liquid aluminum- molten electrolyte interface and the interior surface of the second container.
  • Oxygen ions migrate from the molten salt (410) through the solid electrolyte (405) to the liquid metal anode (400), where they form dissolved oxygen atoms.
  • the oxygen atoms diffuse through the liquid metal anode to the gas phase where they form oxygen gas that evolves from the anode (See, e.g., U.S. Patent No. 8,658,007; herein incorporated by reference in its entirety).
  • U.S. Patent No. 8,658,007 herein incorporated by reference in its entirety.
  • a conduit (460) draws liquid aluminum from the cell toward a first container (450) containing an external pool of liquid second metal (465).
  • the aluminum can be drawn upward into the bridge tube by pulling a partial vacuum in it, e.g, from a vacuum port (470) at the top of the bridge.
  • Figure 5 shows an exemplary electrolytic cell configuration with low-density salt and submerged liquid first metal pad with an insulating current collector tube or conduit drawing liquid aluminum into contact with solid first metal.
  • An anode (500) is shown in contact with molten salt (510) with a submerged first metal (540).
  • a liner (545) is disposed along the bottom of the second container.
  • the current collector comprising a conduit (560) (e.g., vertical tube) draws liquid first metal upward from the cell.
  • the conduit configured with a cooling jacket, such that cooling fluid, e.g., heat transfer oil, can flow into (590) and through the jacket and exit (575), thereby inducing a cooling effect on the first metal.
  • a hydraulically driven oscillating liquid cooled mould (580) extracts the solid first metal (555) from the conduit via a continuous process to maintain metal inventory. The mould oscillates vertically and a billet cut off saw (585) is used to remove the solid first metal.
  • the device enables a continuous tapping and ingot casting as well as an electrical contact.
  • the solid first metal is vertically extracted from a pool of first metal through an oscillating, liquid cooled vertical mould.
  • the solid billet is continuously removed from the first metal pool in the cell via an oscillating, liquid cooled mould to maintain metal inventory.
  • Mould cooling utilizes, e.g, heat transfer oil to avoid the risks associated with water and aluminum.
  • the mould cooling method is not limited to heat transfer oil, but can also be performed via active liquid or gas cooling (e.g., via circulation through the conduit), or via exposure of the second container to an environment such that the first metal cools and solidifies. Exemplary exposure includes to temperatures less than the operating temperature of the cell.
  • the mould oscillates vertically and slowly creeps upward at the required rate via hydraulic actuators and clamps. At the required interval it resets to a lower position.
  • the billet comprising solid first metal is cut off at an appropriate interval, advantageously by a dedicated vehicle servicing many cells. Oscillation is optional, and prevents and/or minimizes sticking of the first metal to the second container.
  • the upper portion of the solid first metal is clamped.
  • the clamp is oscillating and moving upward slowly to withdraw the solid first metal out of the second container, then releases the solid first metal and re-clamps at a lower section.
  • the lower portion of the clamp remains fixed.
  • the metal will be extracted at a rate dependent on the production of the cell and the billet diameter, and can be calculated by those of ordinary skill in the art via, e.g., volumetric calculations.
  • the conduit, where the freeze line occurs is in motion as it continuously sticks for a short distance (both moving in same direction in the cycle), and then is broken by the
  • Another embodiment is to provide a tap to remove the solid first metal from the cell.
  • the flexible busbar is connected to the top and bottom of the mould sleeves to facilitate current connection and avoid voltage potentials between the two, which may cause over heating if there is a sub-optimal contact. It is advantageous not to use the hydraulic cylinders to carry current.
  • the cylinders are constructed with insulated connections to ensure no current path, even at lOx normal voltage or above.
  • the mould operates at a low oscillation frequency - of the order of a couple of Hertz or slower. Length of the freeze zone that attaches is between about 5 mm and 15 mm.
  • the solid first metal has a surface freeze thickness (or length) that can be easily broken by the sleeve motion.
  • the diameter of the solid first metal is about 1 cm to about 40 cm. In some embodiments, the diameter of the solid first metal is about 3 cm to about 30 cm. In some embodiments, the diameter of the solid first metal is about 5 cm to about 30 cm. In some embodiments, the diameter of the solid first metal is about 10 cm to about 30 cm.
  • the diameter of the solid first metal is about 15 cm to about 30 cm. In some embodiments, the diameter of the solid first metal is about 3 cm to about 25 cm. In some embodiments, the diameter of the solid first metal is about 5 cm to about 25 cm. In some embodiments, the diameter of the solid first metal is about 10 cm to about 25 cm. In some embodiments, the diameter of the solid first metal is about 15 cm to about 30 cm. In some embodiments, the diameter of the solid first metal is about 20 cm to about 30 cm.
  • the mould caster operates with a sinusoidal frequency, and it is advantageous to match the metal billet extraction velocity on the upstroke followed by a fast-shock shear on the down stroke to achieve shorter disconnection and improve electrical contact. Hydraulic activation would provide such flexibility, as would mechanical analogs. Thus, the caster can operate via variable frequency and amplitudes.
  • the apparatus and/or method can be applied to a
  • Hoopes cell U.S. Patent 1,534,320; herein incorporated by reference in its entirety
  • first metal/copper mix e.g., Al/Cu mix
  • the current collector will be in contact with the floating liquid metal above the molten salt, but would not extend to the liquid layer of first metal/copper mix.
  • the Hoopes Cell, or Hoopes Process named for its inventor William Hoopes, is a three-layer liquid metal electrorefining cell for aluminum metal. To create a dense molten metal anode at the bottom of the cell, impure aluminum feed metal is poured into the dense alloy via an underflow wier and mixes with a denser metal such as aluminum-copper alloy.
  • the molten salt bath in the middle layer typically comprises a fluoride of aluminum and barium.
  • the top layer is where the purified aluminum accumulates and acts as the cell cathode.
  • the anode connection on the bottom of the cell, connecting to the aluminum-copper anode, consists of a series of rectangular graphite blocks forming a large flat conductive electrode similar to the cathode connection at the bottom of a Hall-Heroult cell.
  • the cathode connection on the top of the cell, connecting to the high-purity liquid aluminum product layer, consists of graphite electrodes with current densities of 2-20 A/cm 2 . At such high current density, the voltage drop across those graphite electrodes is often as high as one volt, contributing about 3 kWh/kg to the energy consumption per unit aluminum product.
  • the remainder of the cell including the resistance in the molten salt bath, anode assembly and busbars, contributes about 1.3-2.0 V to the energy consumption, i.e. 4-6 kWh/kg, so the resistance of the graphite cathode connectors represents 30-40% of the total energy consumption of the cell.
  • the present invention would operate at a voltage drop of about 0.15-0.2 V in the current collector, at current density of 20-100 A/cm 2 . This would significantly reduce the energy consumption of the cell as a whole, and also allow all of the current to pass through a reduced number of smaller diameter current collectors.
  • the current collector tube is bent such that gas bubbles, if present, will accumulate at top and can be removed via suction, e.g., from a vacuum port at the top of the tube.
  • cooling techniques are contemplated and may be used within the scope of the invention.
  • active liquid and/or gas cooling e.g., via circulation through the jacket on the outside of the conduit
  • exemplary environments include temperatures less than the operating temperature of the cell, such as an environment that is not insulated or insulated to a lesser extent than that of the second container, thus cooling the first liquid metal to a temperature at which it solidifies.
  • the cathode conductor is advantageously stable at the bath/metal interface, e.g., between the cathode conductor, liquid first metal, and molten salt).
  • the cathode conductor material is advantageously compatible with liquid metal and molten salt and has high electronic conductivity.
  • the cathode conductor comprises TiB 2 , ZrB 2 or composites of TiB 2 /graphite. In some embodiments, the cathode conductor comprises TiB 2 or
  • the cathode conductor comprises TiB 2 or composites of TiB 2 /graphite. In some embodiments, the cathode conductor comprises TiB 2 . In some embodiments, the cathode conductor comprises ZrB 2 . In some embodiments, the cathode conductor comprises composites of TiB 2 /graphite.
  • the liquid aluminum product rests on a carbon floor to prevent it from contacting the steel of the second container.
  • a liner material prevents aluminum reaction with the steel vessel, and also salt catalysis of aluminum carbide (AI 4 C 3 ) formation. Because the interface level rises and falls with production and withdrawal of liquid aluminum, the liner extends vertically over the full extent of the rising and falling of the interface. In some embodiments, it is advantageous that the liner extend over the entire vertical interior surface of the vessel.
  • the liner can be one of several materials stable in contact with steel, not soluble in liquid metal, and either not soluble or slow-dissolving in the molten salt bath.
  • Exemplary materials include stabilized zirconia, such as yttria-stabilized zirconia similar to that used in the zirconia tubes, or low-cost calcia-stabilized zirconia; oxide materials such as alumina, e.g. fuse-cast alumina; other compounds such as boron nitride, cerium oxide, TiB 2 , SiC, and/or Si 3 N 4
  • the liner materials can be applied by several methods including: insertion of plates, tiles, or bricks; or thermal spray to create an adhering layer of material on the steel and carbon.
  • the liners need not create a perfect seal between the steel vessel and liquid metal or molten salt bath.
  • the inert environment makes the steel vessel stable in the molten salt, and the liner need only slow down metal-steel interaction kinetics sufficiently to prevent liquid first metal from breaking out of the second container, e.g., steel vessel, and to prevent steel from contaminating the liquid first metal beyond the product composition specification.
  • the floating liquid first metal configuration uses a dam, tube, or similar partition to create an opening through the floating liquid metal and permit direct feeding of first metal oxide into the molten salt bath.
  • This constraint material preferably has minimal reaction with the first metal and molten salt, such that zirconia, TiB 2 , boron nitride, or similar materials will have long lifetime in this function.
  • larger metal oxide (e.g., alumina) pellets are fed into the liquid first metal (e.g., aluminum), when the metal oxide has higher density than liquid first metal, such that as long as surface tension does not support the metal oxide, it will sink through the liquid first metal into the salt and dissolve therein.
  • Floating metal configurations enable simplified tapping using a separate chamber, or seal pot, holding liquid first metal, which is lined with carbon, boron nitride, TiB 2 or similar material not soluble in the metal. An opening in the vessel can allow liquid first metal to flow out of the vessel and into the seal pot.
  • the floating liquid first metal configuration adds greater flexibility in metal oxide feed morphology: pellets of sintered metal oxide fines which fall to the bottom slowly dissolve in the molten salt, where in the other configurations or the conventional Hall-Heroult cell they would sink through the liquid first metal and accumulate as sludge; less contamination of metal product if a zirconia tube breaks and releases the liquid metal anode, which will likely have higher density than the salt bath as the main candidates are silver, copper and tin; and opportunity for simplified tapping using the liquid metal seal pot with top tapping.
  • a sealed second container e.g. steel
  • the sealed container prevents ingress of air and/or gas that would react with the liquid first metal or corrode the interior of the container.
  • the non-oxidizing environment prevents or minimizes oxidation of the steel container catalyzed by the molten electrolyte.
  • the non-oxidizing environment exists because oxygen containing components (oxygen gas, carbon dioxide or water vapor) are positioned on the inside of the zirconia tube, and the applied electrical potential drives oxygen into the zirconia tube from the molten salt outside of it.
  • Such configurations enable insulation to reduce thermal energy loss and/or allow the process to run at high salt superheat (above its melting point), which avoids the complication of crust
  • feeding first metal oxide is simplified because there is no crust to break in order to mix the metal oxide into the molten electrolyte.
  • Embodiments where liquid first metal is disposed on top of the molten electrolyte salt are also enabled by the non-oxidizing environment, as the non-oxidizing environment prevents oxidation of the floating metal.
  • a non-oxidizing environment can be established by any number of ways including, e.g., providing an inert gas and, optionally, electrochemically pumping oxygen by establishing an anode-cathode potential, or by bubbling inert gas below the molten electrolyte and/or the liquid first metal. Bubbling inert gas below the molten electrolyte and/or liquid first metal may further advantageously provide mixing to assist the metal oxide reach the oxide-ion conducting membrane.
  • the inert gas may comprise a noble gas, e.g., argon, or nitrogen. Other inert gases include SF 6 and CF 4 .
  • the inert gas comprises a noble gas or nitrogen.
  • the inert gas comprises argon or nitrogen.
  • the inert gas comprises argon. In some embodiments, the inert gas comprises nitrogen.
  • Dry scrubbing the inert gas is also an optional process.
  • any HF present e.g., in the inert gas or otherwise
  • metal oxide e.g., alumina
  • metal fluoride e.g., aluminum trifluoride
  • an inert gas exit bleed is controlled and carries HF to the metal oxide to form metal fluoride.
  • a side tapping well is added on the first container. The well enables removal of metal from the apparatus.
  • a partition or dam is provided to separate the metal from a portion of the top surface of the molten salt electrolyte, such that the metal oxide can be fed directly into the salt.
  • the first metal produced is not limited to aluminum. In some embodiments,
  • the first metal is any metal that has a density less than the molten salt electrolyte at the operating temperature of the cell. Thus, in some embodiments, the first metal will float on top of the electrolyte.
  • the first metal comprises aluminum, magnesium, lithium, beryllium, silicon, strontium, potassium, sodium, barium, scandium, titanium, silicon or calcium.
  • the first metal comprises aluminum, magnesium, lithium, beryllium, silicon, strontium, potassium or calcium.
  • the first metal comprises aluminum, lithium, beryllium, silicon, strontium, or potassium. In some
  • the first metal comprises aluminum, lithium, beryllium, strontium, or potassium. In some embodiments, the first metal comprises aluminum, lithium, strontium, or potassium. In some embodiments, the first metal comprises aluminum, magnesium, lithium, beryllium, silicon, potassium or calcium. In some embodiments, the first metal comprises aluminum, magnesium, lithium, silicon, potassium or calcium. In some embodiments, the first metal comprises aluminum, magnesium, silicon, potassium or calcium. In some embodiments, the first metal comprises aluminum, magnesium, silicon, potassium or calcium. In some embodiments, the first metal comprises aluminum or magnesium. In some embodiments, the first metal comprises magnesium. In some embodiments, the first metal comprises aluminum. It is understood that the metal oxide comprises an oxide of the metal to be produced.
  • the solid electrolyte comprises zirconia doped with yttria, calcia, magnesia, scandia, other rare earth oxide, or other additives that stabilize its cubic phase and enhance its conductivity; or ceria doped with oxides to increase its ion, e.g oxygen, conductivity; or any other oxygen ion-conducting solid electrolyte.
  • the solid electrolyte comprises zirconia doped with yttria, calcia, magnesia, scandia, or other rare earth oxide; or ceria doped with oxides to increase its oxygen ion conductivity.
  • the solid electrolyte comprises zirconia doped with yttria, calcia, magnesia, scandia, or other rare earth oxide. In some embodiments, the solid electrolyte comprises zirconia doped with yttria, calcia, magnesia, or scandia. In some embodiments, the solid electrolyte comprises ceria doped with oxides.
  • the molten electrolyte composition may be comprised of several components. Preferred molten electrolyte systems are selected based on several criteria:
  • Cation oxide free energy All salt cation species ideally have oxide free energies of formation more negative than that of the metal, such that the process does not reduce spectator cations along with the product.
  • Representative cation species include magnesium, sodium, cerium, lanthanum, calcium, strontium, barium, lithium, potassium and ytterbium.
  • the molten electrolyte comprises cations of magnesium, sodium, cerium, lanthanum, calcium, strontium, barium, lithium, potassium or ytterbium.
  • the molten electrolyte comprises cations of magnesium, sodium, cerium, and lanthanum.
  • the salt exhibits very low vapor pressure and evaporation rate in the process temperature range.
  • TGA thermo-gravimetric analysis
  • DSC differential scanning calorimetry
  • DTA differential thermal analysis
  • fluoride salts are advantageous over chlorides. The volatility of lithium fluoride makes it less advantageous.
  • Low melting point A preferred range of about 900-1200° C provides balance between energy efficiency and material flexibility at low temperature, and good oxide ion conductivity in stabilized zirconia at high temperature.
  • the salt must be liquid at the operating temperature.
  • High ionic conductivity supports high current density without significant transport limitation.
  • a salt with low ionic conductivity inhibits mass transfer to the zirconia and the cathode; at the zirconia oxygen ions are depleted in the boundary layer, reducing the current, and at the cathode the target metal ions are depleted in the boundary layer, leading to reduction and co-deposition of salt cations, reducing purity.
  • Viscosity inhibits mass transport to electrodes. Salts with high fluoride/oxide ratio have had sufficiently high ionic conductivity and low viscosity to support up to about 2 A/cm 2 anode and cathode current density.
  • Target oxide solubility The salt must dissolve the metal oxide to at least about 3-5 wt % in order to achieve preferred ionic current densities. DSC or DTA experiments at various compositions can efficiently characterize oxide solubility.
  • Salt corrosion of the solid electrolyte is preferably very slow.
  • the salt preferably satisfies two criteria: salt optical basicity and yttria (or other stabilizing oxide) chemical potential are both close to those values in the solid electrolyte.
  • salt optical basicity and yttria (or other stabilizing oxide) chemical potential are both close to those values in the solid electrolyte.
  • Fluoride salts are particularly preferred as they offer advantageous combinations of properties due to their low volatility and viscosity, high oxide solubility and ionic conductivity, and low basicity.
  • Preferred molten salts comprise LiF, NaF, CaF 2 , MgF 2 , SrF 2 , and A1F 3 .
  • the optimal molten salt will have maximum metal oxide solubility and minimum metal solubility.
  • the apparatus In the case of multiple current collectors, if the apparatus is running at about constant current and a disturbance occurs such that some of the solid conductor portion is melted, the resistance is increased and more electrical energy flows through the other current collectors. However, it is about stable at constant voltage operation, e.g., about 1 volt.
  • constant voltage operation e.g., about 1 volt.
  • the overall current would increase by about 11% in the remaining connectors. Re-freezing would reduce resistance in the formerly melted current collector and bring it back to an equilibrium state. If the connectors are all connected to a common bus outside the cell, the interface is advantageously stabilized.
  • the apparatus is configured such that current density x lead length is about constant.
  • current density x length is between about 4 x 10 5 A/m and 7xl0 6 A/m. In some embodiments, current density x length is between about 5 x 10 5 A/m and 5x10 6 A/m. In some embodiments, current density x length is between about 8 x 10 5 A/m and 3x10 6 A/m. In some embodiments, current density x length is between about 8 x
  • current density x length is about 9 x 10 5 A/m.
  • the apparatus is configured such that aluminum current density is about 10 6 A/m 2 (about 100 A/cm 2 ). In some embodiments, current density is about
  • 10 6 A/m 2 and length of the aluminum lead is about 1 m. In some embodiments, current density is about 10 6 A/m 2 and length of the aluminum lead is about 0.85 m.
  • the apparatus is configured such that energy loss through the current collector is about 0.3V to about 1.8V. In some embodiments, energy loss through the current collector is about 0.3V to about 1.3V. In some embodiments, energy loss through the current collector is about 0.4V to about 1.8V. In some embodiments, energy loss through the current collector is about 0.4V to about 1.3V. In some embodiments, energy loss through the current collector is about 0.5V to about 0.8V. In some embodiments, energy loss through the current collector is about 0.5V to about 1.8V. In some embodiments, energy loss through the current collector is about 0.5V to about 1.3V. In some embodiments, energy loss through the current collector is about 0.5V to about 0.8V.
  • a sealed steel cell creates a controlled environment which can be made inert by injecting argon, helium, nitrogen, or other gas. This prevents rapid steel corrosion by molten salt catalysis of steel oxidation. It also prevents molten salt catalysis of TiB 2 corrosion, enabling that cathode material to protrude upward out of the salt.
  • the injection site for the inert gas is submerged in the bath, in order to create gas lift stirring and promote oxide circulation, thus minimizing and/or preventing localized oxide depletion.
  • the steel vessel further creates opportunities for thermal manipulation.
  • heating including fuel-fired heaters
  • Figure 6 shows a schematic of an exemplary current collector experiment.
  • Two 4.13 cm OD alumina tubes (691) act as electrical insulators between the graphite tubes and apparatus, and as thermal insulators between those tubes and the environment.
  • Additional magnesiosilicate blanket insulation (692) packs the annulus between the alumina and graphite tubes, minimizing lateral temperature difference in the graphite.
  • the alumina tubes and graphite tubes pass through openings in the top plate of the retort, which is purged with argon gas.
  • the tops of the graphite tubes have fittings (693) which seal to coaxial 0.63 cm diameter copper rods (694), which descend from the top into the graphite tubes to connect with the aluminum.
  • the apparatus is further configured with a furnace tube lid (695), radiation baffles (696), a furnace tube (697), and furnace heating elements (690).
  • optimal current density is around 150 A/cm 2 .
  • Current in the aluminum core with cross section area 0.71 cm 2 will be about 106 A.
  • current in the graphite tubes with cross section 4.35 cm 2 - over six times that of the aluminum - would be about 70 A.
  • This conductivity value is approximately that of room temperature graphite conductivity, so actual conductivity and resulting current will be lower.
  • thermocouples in each of the graphite tubes to measure temperature vs. height every 10 cm. Case is exercised so as not to submerge the thermocouple in the aluminum pool, as this would dissolve its end. Temperature distribution should be about the same in both tubes.
  • Figure 7 shows the voltage and current vs. time during steps 4-5 in the above procedure. Measured current is lower than predicted, due to poor electrical connection to the graphite tubes, and incomplete melting and consolidation of the aluminum in the bottom of the crucible. That said, current and voltage are roughly linearly related as predicted.
  • Figure 8 shows the voltage and current vs. time during a second set of experiments.
  • First voltage was increased to 4 V, resulting in about 150 A current across the graphite (voltage curve tracking above the current curve for about the first 0.4 hr).
  • Second, voltage was reduced to 0.4 V.
  • steps 7-9 were performed on one current collector, causing liquid aluminum to flow upward into it and partially solidify from the top. This increased the current from 14.5 A to a steady state value of 19.9 A (voltage curve tracking below the current curve from about 0.4 hr to about 1.7 hr).
  • steps 7-9 were performed on the second current collector, causing liquid aluminum to flow upward into it and partially solidify from the top. This increased the current to 25.6 A, about twice the original current. Thus about as much current flowed through the aluminum as through the graphite, despite having only about one-sixth the cross section area. This demonstrated the very high current density in this liquid-solid aluminum current collector with a graphite conduit. A subsequent increase in voltage to 2.9 V caused current to reach 184 A, indicating about one half the prior resistance. This also demonstrated the ability of this device to carry current at about 100 A/cm 2 in the aluminum core.
  • Figure 9 shows the voltage and current in a ramp from 0 to 2.0 V, resulting in current increase to a maximum of 165 A, again demonstrating very low resistance and high current density. Voltage curve in Fig. 9 tracks above the current curve from about 0.015 hr to about 0.145 hr.
  • AV pJL (J is current density, L is lead length), this bounds the product JL to be between about 6 l0 5 and 7 l0 6 A/m.
  • Typical maximum industrial aluminum bus bar current density is around 10 6 A/m 2 (i.e. 100 A/cm 2 ); using this current density would result in optimal aluminum lead length on the order of 1 m.
  • Optimal geometry with a second metal depends on its composition and temperature distribution.
  • a 1-D Finite Difference model of electrical and thermal conduction in the liquid and solid current collector helps to quantify the trade-off between electrical and thermal losses.
  • This analysis assumes constant cross-section area of the liquid and solid aluminum ledge or conduit, uniform current density J throughout it, and uniform temperature in any cross- section. It neglects effects of convection and radiation, assumes a single flat liquid-solid interface, and assumes that the outside of the conduit is perfectly insulated. The latter assumption is a design goal for the conduit, as it is most effective at retaining energy when thermal loss from its sides is as low as possible.
  • the slope at the environment end dT/dx times thermal conductivity k gives the total energy loss per unit cross-section area of the conductor q. Total thermal energy loss per unit metal product is proportional to q/J, which has units of volts.
  • Figure 11 shows the calculated total energy loss q/J as a function of total current collector length L for several values of current density J. It indicates that minimum total energy loss is approximately 0.34 V (1.0 kWh/kg) for values of J from 40 to 100 A/cm 2 . In addition, the product of current density times optimal length at that current density is roughly constant at approximately 90 m-A/cm 2 , i.e. 9 ⁇ 10 5 A/m. [00226] For this reason, an aluminum solid/liquid current collector operating at
  • 100 A/cm 2 should be approximately 0.85 m long. It loses approximately 16% more energy if it is 30% shorter, and 7% more energy if it is 30% longer, than this optimal length.

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Abstract

Selon certains aspects, l'invention concerne des appareils et des procédés destinés à connecter une première cathode métallique liquide à une source de courant d'une cellule électrolytique comprenant un conduit présentant une première extrémité et une seconde extrémité, un premier métal liquide disposé à la première extrémité du conduit, un premier métal solide disposé à la seconde extrémité du conduit, et une partie conductrice solide en contact électrique avec le premier métal solide.
PCT/US2015/056230 2014-10-17 2015-10-19 Procédé et appareil pour une connexion d'électrode métallique liquide dans la production ou le raffinage de métaux WO2016061577A1 (fr)

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CN110649240A (zh) * 2019-09-27 2020-01-03 东北大学 基于碳酸钙制备的硅基Si-B-C负极材料及其制法和应用

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CN110649239B (zh) * 2019-09-27 2020-10-23 东北大学 Si-B-C负极材料和制备方法、应用以及包含其的负极材料、电极极片和锂离子电池
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