AU2015287769A1 - Producing lithium - Google Patents

Producing lithium Download PDF

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AU2015287769A1
AU2015287769A1 AU2015287769A AU2015287769A AU2015287769A1 AU 2015287769 A1 AU2015287769 A1 AU 2015287769A1 AU 2015287769 A AU2015287769 A AU 2015287769A AU 2015287769 A AU2015287769 A AU 2015287769A AU 2015287769 A1 AU2015287769 A1 AU 2015287769A1
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lithium
cathode
solution
producing
composite layer
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Lawrence Ralph Swonger
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Alpha EN Corp
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/02Electrolytic production, recovery or refining of metals by electrolysis of solutions of light metals
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/007Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells comprising at least a movable electrode
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/04Diaphragms; Spacing elements
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
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Abstract

The present disclosure generally relates to an electrolytic process for continuous production of lithium metal from lithium carbonate or other lithium salts by use of an aqueous acid electrolyte and a lithium producing cell structure. The lithium producing cell structure includes: a cell body with a cathode within the cell body; a sulfuric acid solution within the cell body, the solution containing lithium ions; and a composite layer intercalated between the cathode and the electrolyte aqueous solution, the composite layer comprising a lithium ion conductive glass ceramic (LI-GC) and a lithium ion conductive barrier film (LI-BF) that isolates cathode-forming lithium from the electrolyte aqueous solution.

Description

PCT/US2015/039768 WO 2016/007761
TITLE
PRODUCING LITHIUM
BACKGROUND
[0001] The present disclosure generally relates to an improved process for obtaining lithium metal and a cell for carrying out the process.
[0002] Lithium is a soft, silver-white metal belonging to the alkali metal group of chemical elements. It is the lightest metal and the least dense solid element. Lithium is highly reactive and flammable. Because of its high reactivity, it does not occur freely in nature, and instead, only appears in compositions, usually ionic in nature. Like the other alkali metals, lithium has a single valence electron that is easily given up to form a cation. Because of this, it is a good conductor of heat and electricity as well as a highly reactive element. Because of its reactivity, lithium is usually stored under cover of a hydrocarbon, often mineral oil. In moist air, lithium rapidly tarnishes to form a black coating of lithium hydroxide (LiOH and LiOH.I^O).
[0003] Uses of lithium compounds include lithium oxide as a flux for processing silica to glazes of low coefficients of thermal expansion, lithium carbonate (L12CO3), as a component in ovenware and with lithium hydroxide, which is a strong base that can be heated with a fat to produce a lithium stearate soap. Lithium soap can be used to thicken oils and in the manufacture of lubricating greases. Metallic lithium can be used as a flux for welding or soldering to promote fusing of metals to eliminate oxide formation by absorbing impurities. Its fusing quality is important as a flux for producing ceramics, enamels and glass. Metallic lithium is used to manufacture primary lithium batteries.
[0004] Lithium carbonate is a common form of lithium produced from spodumene or lithium containing brine. Lithium metal can be can be extracted from lithium carbonate in phases:
Conversion of lithium carbonate into lithium chloride.
Electrolysis of lithium chloride.
[0005] To convert lithium carbonate to lithium chloride the lithium carbonate is heated and mixed with hydrochloric acid (typically 31% HC1) in an agitated reactor:
Li2C03(s) + 2HCl(aq) ->’2LiCl(aq) + H20(aq) + C02(g) (Eq-2) [0006] The formed carbon dioxide is vented from the reactant solution. A small amount of barium chloride can be added to precipitate any sulfate. After filtering, the 1 PCT/US2015/039768 WO 2016/007761 solution is evaporated to a saleable 40% LiCl liquid product. Potassium chloride can be added to provide a dry lithium chloride-potassium chloride (45% LiCl; 55% KC1) of decreased melting point (614° C to approximate 420° C). Then the lithium chloride-potassium chloride (45% LiCl; 55% KC1) in a molten pure and dry state can be utilized to produce lithium metal in a steel reaction cell.
[0007] One steel cell has exterior ceramic insulation and a steel rod on the bottom as a cathode. The anode is constructed of graphite, which slowly sloughs-off during processing. The cell can be heated by gas firing between ceramic insulation and a cell’s interior steel wall. Lithium metal accumulates at the surface of the cell wall and is then poured into ingots. Chloride gas generated by reaction is routed away. Typically, the electrolysis process is operated with a cell voltage of ~6.7-7.5V, and the typical cell current can be in the range of 30-60 kA. The processing consumes 30-35 kWh of electricity energy and 6.2-6.4 kg LiCl to produce one kilogram of lithium metal with 20-40% energy efficiency.
Li+ + e' -» Li metal Cathode
Cl' -» 1/2(¾ + e' Anode 2LiCl 2Li + Cl2 Total [0008] A low temperature technology involves electrolysis of brine to form chlorine at an anode and sodium hydroxide or potassium hydroxide via a series of cathode reactions. The formation of either of these hydroxides can involve the reduction of an alkali cation, e.g. Li+ to metal at a liquid mercury cathode, followed by reaction of the formed mercury amalgam with water. The process operates near room temperature with a lower voltage than required for the molten salt system.
[0009] Amendola et al. U.S. Pat. No. 8,715,482 provides a system and process that obviates a mercury electrode. The liquid metal alloy electrode system of U.S. Pat. No. 8,715,482 includes: an electrolytic cell comprising a liquid metal cathode and an aqueous solution wherein the aqueous solution containing lithium ion and at least an anion selected from sulfate, trifluoromethane sulfonate, fluorosulfonate, trifluoroborate, trifluoroacetate, trifluorosilicate and kinetically hindered acid anions and wherein the lithium ion is produced from lithium carbonate. A heating system maintains temperature of the cell and liquid metal circulating systems higher than the melting point of the liquid metal cathode but lower than the boiling point of the aqueous solution. The reduced lithium from the electrolytic cell is extracted from the liquid metal cathode using a suitable extraction solution and a distillation 2 PCT/US2015/039768 WO 2016/007761 system for isolating the lithium metal. This system is solid at room temperature and is less toxic than previous systems.
[0010] Putter et al. U.S. Pat. No. 6,770,187 discloses another process that overcomes some of the high energy consumption and high temperature requirements of prior art processes. The Putter et al. process enables recycling of alkali metals from aqueous alkali metal waste, in particular lithium from aqueous lithium waste. Putter et al. provides an electrolytic cell comprising an anode compartment which comprises an aqueous solution of at least one alkali metal salt, a cathode compartment and an ion conducting solid composite that separates the anode compartment and the cathode compartment from one another, wherein that part of the surface of the solid electrolyte composite that is in contact with the anode compartment and/or that part of the surface of the solid electrolyte that is in contact with the cathode compartment has/have at least one further ion-conducting layer. The electrolyte used in U.S. Pat. No. 6,770,187 is water or water with organic solvent.
[0011] Previous lithium producing systems have involved substantial capital and operating costs. There is a need for a direct and improved electrolysis process that requires reduced capital and operating costs in a system that effectively provides direct production of lithium metal. Additionally, Putter et al. points out that “[ajlkali metal ion conductors of this type are frequently not resistant to water and/or to alkali metals, and the experiment therefore leads to damage of the alkali metal ion conductors after only a short period. This damage can comprise either mechanical failure of the ion conductor or loss of its conductivity.” A further aim of the present disclosure is therefore to keep the ion conductors stable over a prolonged working life.
[0012] There is a need for a process that does not have the disadvantages described above (high energy consumption, high temperature, etc.). A further object is to provide an electrolytic cell suitable for carrying out this process.
SUMMARY
[0013] The present disclosure provides an electrolytic cell and process characterized by a selective permeable barrier composite that provides for direct recovery of lithium metal. The cell and process are reasonably energy consuming and the lithium ion conducting composite layer is stable even in a highly corrosive anode compartment acid environment. 3 PCT/US2015/039768 WO 2016/007761 [0014] In an embodiment, the present disclosure provides a lithium producing cell comprising a cathode; a sulfuric acid solution containing a lithium ion; and a composite layer between the cathode and the sulfuric acid solution. The composite layer comprises a lithium ion conductive glass ceramic material and a lithium ion conductive barrier film. In such an embodiment, the composite layer may have an ion conductivity of at least 10'7 S/cm and be nonreactive to both lithium metal and the lithium ion conductive glass ceramic material.
[0015] In an embodiment, the lithium ion conductive barrier film comprises a physical organogel electrolyte.
[0016] In an embodiment, the lithium ion conductive barrier film comprises an organogel product of an in situ thermo-irreversible gelation and single ion-predominant conduction.
[0017] In an embodiment, the lithium ion conductive glass ceramic material comprises a glass-ceramic active metal ion conductor.
[0018] In an embodiment, the lithium ion conductive glass ceramic material comprises an ion conductive glass-ceramic comprising 26 to 55 molar percent of P2O5, 0 to 15 molar percent of S1O2, 25 to 50 molar percent of GeC>2 + T1O2, in which a molar percent of GeC>2 ranges from 0 to 50% and a molar percent of T1O2 ranges from 0 to 50%, 0 to 10 molar percent of Zr02, 0 to 10 molar percent of M2O3, 0 to 15 molar percent of AI2O3, Ga203 ΟΙ 5%, and 3 to 25 molar percent of U2O 3-25%. In such an embodiment, the ion conductive glass-ceramic contains a predominant crystalline phase comprising at least one of Lii+X(M, Al, Ga)x(Gei.yTiy)2-x(P04)3, where X < 0.8, 0 < Y < 1.0, and M is an element selected from the group consisting of Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb; and Lii+x+yQxTi2.xSi3P3. yOi2, where 0 < X < 0.4, 0 < Y < 0.6, and Q is Al or Ga.
[0019] In an embodiment, the composite layer has an ion conductivity of at least 10-4 S/cm.
[0020] In an embodiment, the cathode comprises a non-aqueous catholyte. In such an embodiment, the catholyte may comprise an ionic liquid.
[0021] In an embodiment, the cathode comprises an active material selected from the group consisting of: a solid oxidizer, a liquid oxidizer and a gaseous oxidizer.
[0022] In an embodiment, the lithium ion conductive glass ceramic material comprises a substantially impervious protective ceramic composite.
[0023] In an embodiment, the cathode is movable along an axis of the lithium producing cell. 4 PCT/US2015/039768 WO 2016/007761 [0024] In an embodiment, the sulfuric acid solution is selected from the group consisting of: a sulfuric acid electrolyte and a sulfuric acid leaching solution.
[0025] In another embodiment, the present disclosure provides a process for producing lithium comprising: providing an electrolytic cell comprising: a solution, an anode in contact with the solution, a cathode, and a composite layer between the cathode and the solution; and providing an ionizing electric current to the electrolytic cell to produce lithium metal at the cathode. The solution comprises a sulfuric acid solvent and a lithium ion source. The composite layer comprises a lithium ion glass ceramic material and a lithium ion conductive barrier film. The composite layer isolates the lithium metal produced at the cathode from the solution as the lithium metal is formed.
[0026] In an embodiment, the composite layer has an ion conductivity of at least 10'7 S/cm and is nonreactive to both lithium metal and the lithium ion conductive glass ceramic material.
[0027] In an embodiment, the cathode is moveable along an axis of the electrolytic cell away from the anode as the lithium metal is produced at the cathode.
[0028] In an embodiment, the electrolytic cell comprises an upper portion containing the cathode and a lower portion containing the solution. The electrolytic cell is configured to drive the cathode away from the composite layer as the lithium metal is formed on the cathode.
[0029] In an embodiment, the lithium ion conductive barrier film comprises a physical organogel electrolyte. In this regard, the lithium ion conductive barrier film may comprise an organogel product of an in situ thermo-irreversible gelation and single ion-predominant conduction.
[0030] In an embodiment, the lithium ion source comprises at least one selected from the group consisting of: lithium carbonate, lithium chloride and spodumene.
[0031] In an embodiment, the lithium ion source comprises a lithium salt that dissociates in the sulfuric acid solvent. A non-lithium portion of the salt is released from the solution as a gas.
[0032] In an embodiment, the solution is selected from the group consisting of: a sulfuric acid electrolyte and a sulfuric acid leaching solution.
[0033] In an embodiment, the lithium metal produced at the cathode is drawn off as a pure metallic phase. 5 PCT/US2015/039768 WO 2016/007761 [0034] In yet another embodiment, a process for producing lithium is provided. The process comprises: providing a solution; providing a composite layer between a cathode and the solution; and generating a current across the solution to produce lithium metal at the cathode. The solution comprises a hydrated acid solvent and lithium ions dissolved in the hydrated acid solvent. The composite layer comprises a lithium ion glass ceramic material. The composite layer isolates the lithium metal produced at the cathode from the solution as the lithium metal is formed.
[0035] In an embodiment, the composite layer comprises a lithium ion conductive barrier film.
[0036] In an embodiment, the hydrated acid is sulfuric acid. In such an embodiment, the solution may be selected from the group consisting of: a sulfuric acid electrolyte and a sulfuric acid leaching solution.
[0037] In an embodiment, the lithium metal produced at the cathode is drawn off as a pure metallic phase.
[0038] In another embodiment, the present disclosure provides a lithium metal product. The lithium metal product comprises lithium metal produced by: providing a composite layer between a cathode and a solution; and generating a current across the solution to produce the lithium metal at the cathode. The solution comprises lithium ions dissolved in sulfuric acid. The composite layer comprises a lithium ion glass ceramic material.
[0039] In an embodiment, the composite layer comprises a lithium ion conductive barrier film.
[0040] In an embodiment, the composite layer isolates the lithium metal produced at the cathode from the solution as the lithium metal is formed.
[0041] In an embodiment, the lithium metal produced at the cathode is drawn off as a pure metallic phase.
[0042] In an embodiment, the solution is selected from the group consisting of: a sulfuric acid electrolyte and a sulfuric acid leaching solution.
[0043] An advantage of the present disclosure is to provide an improved process for producing lithium and an improved lithium producing electrolytic cell for producing lithium. The improved process and improved lithium producing electrolytic cell allow lithium metal to be produced at a lower cost and with reasonable energy consumption. 6 PCT/US2015/039768 WO 2016/007761 [0044] Another advantage of the present disclosure is to provide a lithium metal product formed by the improved process for producing lithium.
[0045] Additional features and advantages are described herein, and will be apparent from the following Detailed Description and the figures.
BRIEF DESCRIPTION OF THE DRAWINGS
[0046] The foregoing summary, as well as the following detailed description of the disclosure, will be better understood when read in conjunction with the appended figures. For the purpose of illustrating the disclosure, shown in the figures are embodiments that are presently preferred. It should be understood, however, that the disclosure is not limited to the precise arrangements, examples and instrumentalities shown.
[0047] FIG. 1 shows a schematic elevation view of a lithium producing cell structure used in an embodiment of the present disclosure; [0048] FIG. 2 shows a schematic detail of the lithium producing cell structure of FIG. 1; and [0049] FIG. 3 shows a schematic exploded detail of a lithium producing cell of Example 1.
DETAILED DESCRIPTION
[0050] The present disclosure is directed to an electrolytic cell and a process for producing lithium metal using a selective permeable barrier composite.
[0051] Because of lithium’s high electrochemical potential, it is an important component of electrolytes and electrodes in batteries. A typical lithium-ion battery can generate approximately 3 volts, compared with 2.1 volts for lead-acid or 1.5 volts for zinc-carbon cells. Because of its low atomic mass, it also has a high charge- and power-to-weight ratio. Lithium-ion batteries are high energy-density rechargeable batteries. Other rechargeable battery types include the lithium-ion polymer battery, lithium iron phosphate battery, and the nanowire battery.
[0052] The present disclosure is directed to a process for producing lithium metal from lithium carbonate feed stock (or other lithium salt such as lithium chloride which dissociates in an acid electrolyte and releases the non-lithium portion of the feed stock (i.e., the carbonate or chloride) as gas). The process can continuously process lithium carbonate into lithium metal. The process includes using a sulfuric acid electrolyte to disassociate 7 PCT/US2015/039768 WO 2016/007761 lithium carbonate, placing the lithium ions into solution for processing, and venting off the carbonate portion without it entering into solution.
[0053] The use of sulfuric acid for lithium carbonate processing is important for the reasons described below. Lithium carbonate is essentially insoluble in water and organic solvents. Lithium cannot be efficiently extracted from lithium carbonate salt using an aqueous electrolyte with or without organic solvent. Use of a sulfuric acid solution provides much higher solubility of lithium carbonate into solution allowing efficient production of lithium metal from lithium carbonate. By disassociating the lithium carbonate and only placing the lithium ions into solution, the electrolyte solution remains stable and does not build up a concentration of the non-lithium ion portion of the feed stock. Lithium carbonate can be continuously fed into a tank outside of the electrolytic cell, venting off the CO2 gas released by the sulfuric acid electrolyte. The acid electrolyte does not need to be disposed of or replenished, lithium carbonate can be continuously added to a feed tank, venting off C02 and harvesting lithium metal from a cathode. This can be continuously operated or conducted as a batch process.
[0054] The present disclosure provides a cathode separated from lithium ion rich solution by a selectively permeable barrier composite (LIC-GC-BF). The composite comprises a lithium ion conductive glass ceramic layer (LI-GC) and a lithium ion conductive barrier film (LI-BF). The LIC-GC-BF composite allows for direct production of lithium metal from solution and direct deposition of lithium metal onto a clean cathode, without need for an additional extraction process. The system for producing lithium metal can include: an electrolyte feed system that provides a lithium ion rich electrolyte to the electrolytic cell; an electrolytic cell to move lithium metal from a water-based lithium ion solution through the LIC-GC-BF composite; and a method to package lithium metal. The system can be used for a continuous lithium metal production process or for a batch process.
[0055] Features of the invention will become apparent from the drawings and following detailed discussion, which by way of example without limitation describe preferred embodiments of the invention.
[0056] FIGS. 1 and 2 illustrate a production process of the invention wherein lithium-rich electrolyte flows through an extraction cell. When potential is applied to the system, lithium metal builds up on a moving cathode below an intercalated composite layer. FIG. 1 of the drawings is a schematic elevation view of lithium producing cell structure and FIG. 2 is a schematic detail of the cell structure of FIG. 1. In FIG. 1, and FIG. 2, the electrolytic cell 8 PCT/US2015/039768 WO 2016/007761 10 according to an embodiment includes an upper section 12 and lower section 14. The cell 10 is characterized by a movable cathode 16 that transects a cross-section of the cell. The cathode 16 transposes an axis of cell 10, advancing as an electrolysis reaction takes place in electrolyte 18 above the cathode 16, through the LIC-GC-BF composite layer. Anode 20 is provided in the cell upper section 12. The cell section 12 above the cathode 10 is loaded with electrolyte 18 via inlet 22, electrolysis proceeds and spent electrolyte is discharged via outlet 24. The cathode 16 is in contact with the electrolyte 18 through a composite layer 28 intercalated between the cathode 16 and electrolyte 18. The composite layer 28 comprises a lithium ion conductive glass ceramic layer (LI-GC) 30 adjacent the electrolyte 18 and a lithium ion conductive barrier film (LI-BF) 32 interposed between the ceramic layer 30 and cathode 18. The barrier layer 32 and glass ceramic layer 30 composite 28 isolates forming lithium at cathode 16 from electrolyte 18. Shaft 26 advances the cathode 16 and composite 28 as lithium metal is formed and deposited through the composite layer 28 onto the advancing cathode 16. The lithium metal produced at the solid cathode 16 can be drawn off as a pure metallic phase.
[0057] Suitable feed to the cell includes water-soluble lithium salts including but not limited to L12CO3 and LiCl. To improve solubility, the lithium salt is dissolved in hydrated acid and used as electrolyte in the electrolytic cell. Lithium Carbonate (L12CO3) was used as feed stock for initial trials.
[0058] Some suitable cell components in the lithium producing cell structure are described in US20130004852, which is incorporated into this disclosure in its entirety by reference.
[0059] Suitable electrolyte 18 components include water-soluble lithium salts including but not limited to L12CO3 and LiCl. To improve solubility the lithium salt can be dissolved in hydrated acid to be used as electrolyte. Lithium carbonate (L12CO3) is the most readily available lithium salt, being relatively inexpensive, and is a preferred lithium source. Cathode 16 is characterized by the intercalated composite (Li-GC/Li-BF) 28, meaning the composite 28 is inserted or interposed between the cathode 16 and electrolyte 18. The cathode 16 can be characterized as “transpositioning,” meaning the cathode advances along an axis of the cell 10 to transpire produced lithium through the composite 28 and to isolate cathode-deposited lithium. The cathode comprises a suitable material that is non-reactive with lithium metal and the composite layer. The Li-GC/Li-BF composite layer is a stationary barrier between the anode compartment and the lithium metal forming on the cathode. The 9 PCT/U S2015/039768 WO 2016/007761 cathode moves to accommodate the continuously thickening layer of lithium metal on the cathode.
[0060] Composite layer (Li-GC/Li-BF) 28 includes lithium ion conductive glass ceramic layer (LI-GC) 30 and lithium ion conductive barrier film (LI-BF) 32. The substantially impervious layer (LI-GC) 30 can be an active metal ion conducting glass or glass-ceramic (e.g., a lithium ion conductive glass-ceramic that has high active metal ion conductivity and stability to aggressive acidic electrolytes). Suitable materials are substantially impervious, ionically conductive and chemically compatible with aqueous electrolytes or other electrolyte (catholyte) and/or cathode materials that would otherwise adversely react with lithium metal. Such glass or glass-ceramic materials are substantially gap-free, non-swellable and are inherently ionically conductive. That is, they do not depend on the presence of a liquid electrolyte or other agent for their ionically conductive properties. They also have high ionic conductivity, at least 10'7 S/cm, generally at least 10'6 S/cm, for example at least 10'5 S/cm to 10‘4 S/cm, and as high as 10"3 S/cm or higher so that the overall ionic conductivity of the multi-layer protective structure is at least 10"7 S/cm and as high as 10‘3 S/cm or higher. The thickness of the layer is preferably about 0.1 to 1000 microns, or, where the ionic conductivity of the layer is about 10'7 S/cm, about 0.25 to l micron, or, where the ionic conductivity of the layer is between about 10'4 about 10"3 S/cm, about 10 to 1000 microns, preferably between 1 and 500 microns, and more preferably between 50 and 250 microns, for example, about 150 microns.
[0061] Examples of glass ceramic layer (LI-GC) 30 include glassy or amorphous metal ion conductors, such as a phosphorus-based glass, oxide-based glass, phosphorus-oxynitride-based glass, sulfur-based glass, oxide/sulfide based glass, selenide based glass, gallium based glass, germanium-based glass or boracite glass (such as are described D. P. Button et al., Solid State Ionics, Vols. 9-10, Part 1, 585-592 (December 1983)); ceramic active metal ion conductors, such as lithium beta-alumina, sodium beta-alumina, Li superionic conductor (LIS1CON), Na superionic conductor (NASICON), and the like; or glass ceramic active metal ion conductors. Specific examples include LiPON, Li3PO4.Li2S.SiS2, Li2S.GeS2.Ga2S3, and L12O.
[0062] Suitable glass-ceramic materials (LI-GC) include a lithium ion conductive glass-ceramic having the following composition in mol percent: P2O5 26-55%; S1O2 0-15%; Ge02+Ti02 25-50%; in which Ge02 0-50%; Ti02 0-50%; Zr02 0-10%; M203 0-10%; A1203 0-15%; Ga203 0-15%; Li20 3-25% and containing a predominant crystalline phase 10 PCT/US2015/039768 WO 2016/007761 comprising Lii+X(M, Al, Ga)x(Gei.yTiy)2-x(P04)3 where X < 0.8 and 0 < Y < 1.0 and where M is an element selected from the group consisting of Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb, and/or Lii+x+yQxTi2-xSi3P3.yOi2 where 0 < X < 0.4 and 0 < Y < 0.6, and where Q is Al or Ga. Other examples include IIAI2O3, Na20.11A1203, (Na, Li)i+xTi2-xAlx(P04)3 (0.6 < x < 0.9) and crystallographically related structures, Na3Zr2Si2POi2, Li3Zr2Si2P04, Na5ZrP30i2, Na5TiP30i2, Na3Fe2P3Oi2, Na4NbP3Ol2, Li5ZrP3Ol2, Li5TiP3Ol2, Li5Fe2P3Ol2 and Li4NbP30,2 and combinations thereof, optionally sintered or melted. Suitable ceramic ion active metal ion conductors are described, for example, in U.S. Pat. No. 4,985,317 to Adachi et al., incorporated by reference herein in its entirety.
[0063] Suitable LI-GC material includes a product from Ohara, Inc. (Kanagawa, JP), trademarked LIC-GC™, LISICON, LisO-AhOs-SiOz-^Os-TiCfe (LATP). Suitable material with similarly high lithium metal ion conductivity and environmental/chemical resistance are manufactured by Ohara and others. See for example, Inda, DN20100113243, now U.S. Pat. No. 8,476,174, incorporated herein in their entirety by reference. U.S. Pat. No. 8,476,174 discloses a glass-ceramic comprising at least crystallines having a having a LiTi2P30]2 structure, the crystallines satisfying 1< Iaii3/Iaio4 < 2, wherein U104 is the peak intensity assigned to the plane index 104 (20=20 to 21°), and Iai 13 is the peak intensity assigned to the plane index 113 (20=24 to 25°) as determined by X-ray diffractometry.
[0064] The lithium ion conductive barrier film 32 (Li-BF) is typically a lithium metal ion conductive film or coating with high lithium metal ion conductivity. The lithium ion conductive barrier film 32 (LI-BF) is a lithium metal ion conductive film or coating with high lithium metal ion conductivity, typically 1.0 mS/cm to 100 mS/cm. A high lithium ion transference number (t+) is preferred. Low t+Li+ electrolytes will hinder performance by allowing ion concentration gradients within the cell, leading to high internal resistances that may limit cell lifetime and limit reduction rates. Transference numbers between t+=0.70 and t+ = 1.0 are preferred. The lithium ion conductive barrier film is non-reactive to both lithium metal and the LiC-GC material.
[0065] The LI-BF film 32 includes an active metal composite, where “active metals” are lithium, sodium, magnesium, calcium, and aluminum used as the active material of batteries. Suitable LI-BF materials include a composite reaction product of active metal with CU3N, active metal nitrides, active metal phosphides, active metal halides, active metal phosphorus sulfide glass and active metal phosphorous oxynitride glass (CU3N, L3N, Li3P, Lil, LiF, LiBr, LiCl and LiPON). The LI-BF material must also protect against dendrites 11 PCT/US2015/039768 WO 2016/007761 forming on the cathode from coming in contact with the LI-GC material. This may be accomplished by creating physical distance between the cathode and LI-GC and/or providing a physical barrier that the dendrites do not penetrate easily. One preferred LI-BF film is a physical organogel electrolyte produced by in situ thermo-irreversible gelation and single ion-predominant conduction as described by Kim et al. in “A physical organogel electrolyte: characterized by in situ thermo-irreversible gelation and single-ion-predominent conduction,” Scientific Reports 3, Article number: 1917 (doi:10.1038/srep01917) (May 29, 2013). This electrolyte has t+ = 0.84 and conductivity of 8.63 mS/cm at room temperature. This organogel electrolyte can be set up in a porous membrane to provide additional structure and resistance to dendrite penetration. Typical porous membrane thickness is 1 pm to 500 pm, for example 20 pm. An acceptable porous membrane includes HIPORE polyolefin flat-film membrane by Asahi Kasei E-materials Corporation.
[0066] The production process produces lithium metal that can be used as part of a continuous lithium metal production process. In particular, the present process can utilize inexpensive lithium carbonate or an equivalent source of lithium ions.
[0067] The process can be used to produce lithium metal directly from the acid solution used to leach lithium metal out of spodumene ore or other natural lithium sources. For example, the process for converting spodumene ore to lithium carbonate involves leaching minerals from the ore using sulfuric acid. Lithium is then precipitated out of the sulfuric acid solution using soda ash to form lithium carbonate. The present process can be used to directly process lithium out of the sulfuric acid leaching solution before it is precipitated to lithium carbonate. In that case, the electrolyte 18 in FIGS. 1 and 2 would be replaced with the sulfuric acid solution used to leach minerals from the spodumene.
[0068] By way of example and not limitation, the following Example is illustrative of a lithium production process in accordance with the present disclosure.
EXAMPLE
[0069] A cell used for producing lithium is shown schematically in FIG. 3. The cell 110 includes cell cover 116, retainer 118, Pt anode 112, cathode 124 and a LI-GC conductive glass 114 with lithium ion conductive barrier film 120 incorporated into a porous polyolefin flat-film membrane 122. The supported LI-GC-BF multilayer is intercalated between cathode 124 and a lithium ion-rich electrolyte 18 (in FIGS. 1 and 2). The cell further comprises supporting Teflon® sleeve structure 126 with gaskets 128. One gasket seals 12 PCT/US2015/039768 WO 2016/007761 between the LI-GC and the housing to prevent leakage of the electrolyte from the anode compartment into the cathode compartment. The other gasket allows for even compression of the LI-GC by the Teflon® Sleeve to prevent breakage of the LI-GC plate.
[0070] The cell 110 includes anode 112 that is a platinized titanium anode, 1”χ4” rhodium and palladium jewelry plating. The cathode is a palladium cathode disk fabricated in-house, 1.4 inch round. The LI-GC 114 material is LICGC® G71-3 N33: DIA 2 IN* 150 pm tape cast, 150 pm thick, 2 inch round from Ohara Corporation, 23141 Arroyo Vista, Rancho Santa Margarita, California 92688.
[0071] The lithium ion conducting gel electrolyte 120 is fabricated from: a PVA-CN polymer supplied by the Ulsan National Institute of Science and Technology in Ulsan South Korea, Dr. Hyun-Kon Song, procured from Alfa Aesar, stock number H61502; LiPF6 (lithium hexafluorophosphate), 98%; EMC (ethyl methyl carbonate), 99%, from Sigma Aldrich, product number 754935; EC (ethylene carbonate), anhydrous, from Sigma Aldrich, product number 676802; and a porous membrane, ND420 polyolefin flat-film membrane from Asahi Corp.
[0072] The LI-BF bather layer 120 is fabricated in an argon purged glove bag. The glove bag is loaded with all materials, precision scale, syringes, and other cell components, then filled and evacuated 4 times before the start of the electrolyte fabrication process.
[0073] The organogel electrolyte is mixed as follows: 4.0 ml of EMC is liquefied by heating to about 140° F and placed in a vial. 2.0 ml of the EMC is then added to the vial, 0.133 g (2% wt) PVA-CN polymer is added to the vial, and the mixture is agitated for 1 hour to dissolve the PVA-CN. Then 0.133 g (2% wt) FEC is added as SEI-forming additive, 0.972 g (1M) LiPF6 is then added and mixed to complete the organogel electrolyte mixture. The electrolytic cell is then assembled inside the glove bag. With the LI-GC and gaskets in place, the anode and cathode compartments are sealed from each other. The organogel electrolyte mixture is used to wet the cathode side of the LI-GC, the HIPORE membrane is placed on the cathode side of the LI-GC and wetted again with organogel electrolyte mixture. The cathode disk is then placed on top of the organogel mixture. The cell is placed in a Mylar® bag and sealed while still under argon purge. The sealed Mylar® bag with assembled cell is then placed in an oven at 60° C for 24 hours to gel the electrolyte.
[0074] The electrolytic cell 110 is removed from the oven and placed in the argon purged glove bag, and allowed to cool to room temperature. Clear polypro tape is used to seal the empty space above the cathode disk and secure the electrode wire. The electrolytic 13 PCT/US2015/039768 WO 2016/007761 cell 110 is now ready for use, is removed from the glove bag, and is connected to the electrolyte circulating system.
[0075] An electrolyte 18 is prepared with 120 g of lithium carbonated in 200 ml of deionized water and 500 ml of 20% wt sulfuric acid. The sulfuric acid is slowly added to the lithium carbonate suspension and mixed well. Undissolved lithium carbonate is allowed to settle. A supernatant is collected from the stock solution, an 18% wt lithium stock solution. The 18% wt lithium solution has a measured pH of 9. Solution pH is lowered by addition of 20% wt sulfuric acid. Again, the sulfuric acid is added slowly to minimize foaming. The 18% wt lithium stock solution is adjusted to a pH of 4.5. The preferred pH is between 3.0 and 4.5, most preferred is between a pH of 3 .0 and a pH of 4.0, but the process can be run at a pH of 7.0 or below. A pH above 7.0 will result in carbonate in solution.
[0076] The electrolyte mixture is then poured into the circulating system. The circulating pump is primed and solution circulated for 30 minutes to check for leaks.
[0077] The lithium ion-rich electrolyte 18 flows through the top half of cell 110 over the LI-GC-BF multilayer 114/120 and past anode 112. When potential is applied to the system, lithium metal builds up on the moving cathode below the LI-GC-BF multilayer 114/120 system.
[0078] A Gamry Reference 3000 Potentiostat/Galvanostat/ZRA is attached to the cell 110. At voltages of 3-6 volts there is no significant activity. When the voltage is raised to 10V, the system responds. Amperage draw increases when the voltage is raised to 11 vdc. No gassing on the anode side of the cell was noted at 11 vdc. The Gamry Reference 3000 would not go above 11 vdc. Since no gassing occurred at 11 vdc, the reduction rate could most likely be much higher if voltage were increased. An even higher voltage and reduction rate are preferable if achieved with negligible oxygen production at the anode. The pH of the electrolyte at time zero is 4.46. The pH of the solution decreases to 4.29 after 35 minutes, and is 4.05 at the end of the experiment. The lowering pH indicates lithium ion removal from the electrolyte solution.
[0079] An amperage draw of 20 mA is noted at the start of the experiment. The amperage draw slowly increases to 60 mA after 30 minutes. Amperage holds fairly steady at this value for another 30 minutes. Experiment timer and graph are paused for 30 minutes to extend experiment (voltage held at 11 vdc). After approximately 65 minutes of run time, a large amperage spike and sudden vigorous gassing is noted on the anode side of the cell. This is indicative of LI-GC-BF 114/120 membrane failure. 14 PCT/US2015/039768 WO 2016/007761 [0080] Rapid gassing and bright white flame is observed when the cell 110 is opened and cathode 124 side is exposed to electrolyte leaking through the Ll-GC-BF 114/120, evidencing that the cell produces lithium metal by electrolysis of lithium ions in a sulfuric acid aqueous solution, through a LI-GC-BF 114/120 membrane system. and without diminishing its intended advantages. It is therefore and modifications be covered by the appended claims.
[0100] It should be understood that various changes and modifications to the presently preferred embodiments described herein will be apparent to those skilled in the art. Such changes and modifications can be made without departing from the spirit and scope of the present subject matter intended that such changes 15

Claims (33)

  1. CLAIMS The invention is claimed as follows:
    1. A lithium producing cell comprising: a cathode; a sulfuric acid solution containing a lithium ion; and a composite layer between the cathode and the sulfuric acid solution, wherein the composite layer comprises a lithium ion conductive glass ceramic material and a lithium ion conductive barrier film.
  2. 2. The lithium producing cell of claim 1, wherein the composite layer has an ion conductivity of at least 10'7 S/cm and is nonreactive to both lithium metal and the lithium ion conductive glass ceramic material.
  3. 3. The lithium producing cell of claim 1, wherein the lithium ion conductive barrier film of the composite layer comprises a physical organogel electrolyte.
  4. 4. The lithium producing cell of claim 1, wherein the lithium ion conductive barrier film comprises an organogel product of an in situ thermo-irreversible gelation and single ion-predominant conduction.
  5. 5. The lithium producing cell of claim 1, wherein the lithium ion conductive glass ceramic material comprises a glass-ceramic active metal ion conductor.
  6. 6. The lithium producing cell of claim 1, wherein the lithium ion conductive glass ceramic material comprises an ion conductive glass-ceramic comprising 26 to 55 molar percent of P2O5, 0 to 15 molar percent of S1O2, 25 to 50 molar percent of Ge02 + Ti02, in which a molar percent of Ge02 ranges from 0 to 50% and a molar percent of T1O2 ranges from 0 to 50%, 0 to 10 molar percent of ZKD2, 0 to 10 molar percent of M2O3, 0 to 15 molar percent of AI2O3, Ga203 0-15%, and 3 to 25 molar percent of L12O 3-25%, and wherein the ion conductive glass-ceramic contains a predominant crystalline phase comprising at least one of Lii+X(M, Al, Ga)x(Gei.yTiy)2-x(P04)3, where X < 0.8, 0 < Y < 1.0, and M is an element selected from the group consisting of Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb; and Lii+x+yQxTi2-xSi3P3.yOi2, where 0 < X < 0.4, 0 < Y < 0.6, and Q is Al or Ga.
  7. 7. The lithium producing cell of claim 1, wherein the composite layer has an ion conductivity of at least 10-4 S/cm.
  8. 8. The lithium producing cell of claim 1, wherein the cathode comprises a non-aqueous catholyte.
  9. 9. The lithium producing cell of claim 8, wherein the catholyte comprises an ionic liquid.
  10. 10. The lithium producing cell of claim 1, wherein the cathode comprises an active material selected from the group consisting of: a solid oxidizer, a liquid oxidizer and a gaseous oxidizer.
  11. 11. The lithium producing cell of claim 1, wherein the lithium ion conductive glass ceramic material comprises a substantially impervious protective ceramic composite.
  12. 12. The lithium producing cell of claim 1, wherein the cathode is movable along an axis of the lithium producing cell.
  13. 13. The lithium producing cell of claim 1, wherein the sulfuric acid solution is selected from the group consisting of: a sulfuric acid electrolyte and a sulfuric acid leaching solution.
  14. 14. A process for producing lithium comprising: providing an electrolytic cell comprising: a solution comprising a sulfuric acid solvent and a lithium ion source; an anode in contact with the solution; a cathode; and a composite layer between the cathode and the solution, the composite layer comprising a lithium ion glass ceramic material and a lithium ion conductive barrier film; and providing an ionizing electric current to the electrolytic cell to produce lithium metal at the cathode, wherein the composite layer isolates the lithium metal produced at the cathode from the solution as the lithium metal is formed.
  15. 15. The process for producing lithium of claim 14, wherein the composite layer has an ion conductivity of at least 10'7 S/cm and is nonreactive to both lithium metal and the lithium ion conductive glass ceramic material.
  16. 16. The process for producing lithium of claim 14, wherein the cathode is moveable along an axis of the electrolytic cell away from the anode as the lithium metal is produced at the cathode.
  17. 17. The process for producing lithium of claim 14, wherein: the electrolytic cell comprises an upper portion containing the cathode and a lower portion containing the solution, and the electrolytic cell is configured to drive the cathode away from the composite layer as the lithium metal is formed on the cathode.
  18. 18. The process for producing lithium of claim 14, wherein the lithium ion conductive barrier film comprises a physical organogel electrolyte.
  19. 19. The process for producing lithium of claim 14, wherein the lithium ion conductive barrier film comprises an organogel product of an in situ thermo-irreversible gelation and single ion-predominant conduction.
  20. 20. The process for producing lithium of claim 14, where the lithium ion source comprises at least one selected from the group consisting of: lithium carbonate, lithium chloride and spodumene.
  21. 21. The process for producing lithium of claim 14, wherein: the lithium ion source comprises a lithium salt that dissociates in the sulfuric acid solvent, and a non-lithium portion of the salt is released from the solution as a gas.
  22. 22. The process for producing lithium of claim 14, wherein the lithium metal produced at the cathode is drawn off as a pure metallic phase.
  23. 23. The process for producing lithium of claim 14, wherein the solution is selected from the group consisting of: a sulfuric acid electrolyte and a sulfuric acid leaching solution.
  24. 24. A process for producing lithium comprising: providing a solution comprising a hydrated acid solvent and lithium ions dissolved in the hydrated acid solvent; providing a composite layer between a cathode and the solution, the composite layer comprising a lithium ion glass ceramic material; and generating a current across the solution to produce lithium metal at the cathode, wherein the composite layer isolates the lithium metal produced at the cathode from the solution as the lithium metal is formed.
  25. 25. The process for producing lithium of claim 24, wherein the composite layer comprises a lithium ion conductive barrier film.
  26. 26. The process for producing lithium of claim 24, wherein the hydrated acid is sulfuric acid.
  27. 27. The process for producing lithium of claim 26, wherein the solution is selected from the group consisting of: a sulfuric acid electrolyte and a sulfuric acid leaching solution.
  28. 28. The process for producing lithium of claim 24, wherein the lithium metal produced at the cathode is drawn off as a pure metallic phase.
  29. 29. A lithium metal product comprising: lithium metal produced by: providing a composite layer between a cathode and a solution comprising lithium ions dissolved in sulfuric acid; and generating a current across the solution to produce the lithium metal at the cathode, wherein the composite layer comprises a lithium ion glass ceramic material.
  30. 30. The lithium metal product of claim 29, wherein the composite layer comprises a lithium ion conductive barrier film.
  31. 31. The lithium metal product of claim 29, wherein the composite layer isolates the lithium metal produced at the cathode from the solution as the lithium metal is formed.
  32. 32. The lithium metal product of claim 29, wherein the lithium metal produced at the cathode is drawn off as a pure metallic phase.
  33. 33. The lithium metal product of claim 29, wherein the solution is selected from the group consisting of: a sulfuric acid electrolyte and a sulfuric acid leaching solution.
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