WO2019032670A1 - Producing lithium directly from lithium feed sources - Google Patents
Producing lithium directly from lithium feed sources Download PDFInfo
- Publication number
- WO2019032670A1 WO2019032670A1 PCT/US2018/045750 US2018045750W WO2019032670A1 WO 2019032670 A1 WO2019032670 A1 WO 2019032670A1 US 2018045750 W US2018045750 W US 2018045750W WO 2019032670 A1 WO2019032670 A1 WO 2019032670A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- lithium
- spodumene
- electrolysis cell
- providing
- feed solution
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/02—Electrolytic production, recovery or refining of metals by electrolysis of solutions of light metals
-
- 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
Definitions
- the present disclosure generally relates to producing lithium directly from feed sources. More specifically, for example, the present disclosure relates to producing lithium using a lithium feed solution selected from the group consisting of lithium chloride brine, lithium sulfate spodumene liquor, lithium hydroxide, and a combination thereof. Additionally the present disclosure also relates to continuous processes for obtaining lithium metal.
- Lithium is a soft, silver-white metal belonging to the alkali metal group of chemical elements. Lithium is highly reactive and flammable, though it is the least reactive of the alkali metals. Because of its high reactivity, lithium does not occur freely in nature. Instead, lithium only appears naturally in compositions, usually ionic in nature. Therefore, lithium metal can be obtained only by extraction of lithium from such compounds containing lithium.
- lithium carbonate is then obtained from the lithium carbonate in two phases: (1) conversion of lithium carbonate into lithium chloride, and (2) electrolysis of lithium chloride using a high-temperature molten salt such as LiCl.
- the present disclosure relates to a process for producing lithium directly from lithium containing brine or liquor.
- the process includes providing a lithium feed solution selected from the group consisting of lithium chloride brine, lithium sulfate spodumene liquor, and a combination thereof.
- the lithium feed solution is provided to an electrolysis cell comprising a cathode suitable for electrolysis of lithium, and an anode.
- An ionizing electric current is provided to the electrolysis cell, thereby providing lithium metal at the cathode.
- the lithium chloride brine contains 1.5-18% lithium.
- the lithium chloride brine contains 4-6% lithium
- the lithium chloride brine is prepared by evaporation in an evaporation pond.
- the evaporation pond is selected from the group consisting of a solar evaporation pond and an electric evaporation pond.
- the lithium chloride brine is returned from the electrolysis cell to the evaporation pond.
- the lithium sulfate spodumene liquor contains 1-18% lithium.
- the lithium sulfate spodumene liquor contains 1.5-18% lithium.
- the lithium sulfate spodumene liquor contains 16-18% lithium.
- the lithium sulfate spodumene liquor is provided from a reservoir, and the lithium sulfate spodumene liquor is returned from the electrolysis cell to the reservoir.
- the lithium feed solution is prepared without removing boron or magnesium.
- the lithium feed solution is continuously provided to the electrolysis cell, and the lithium metal is continuously produced at the cathode.
- the temperature in the electrolysis cell for providing lithium metal is 15 to 40°C.
- the temperature in the electrolysis cell for providing lithium metal is approximately 23°C.
- the lithium feed solution has a pH of 3-9.
- An advantage of the present disclosure is to produce lithium on-site directly from the spodumene or brine.
- a lithium feed solution selected from the group consisting of lithium chloride brine, lithium sulfate spodumene liquor, and a combination thereof
- the spodumene or brine can be directly used without converting to lithium carbonate or lithium chloride, and without transportation or delivery over a substantial distance as in conventional lithium producing processes, therefore desirably streamlining the lithium production process, reducing operating costs, and/or improving energy efficiency in production of lithium.
- the process for producing lithium eliminates all of the large scale production processes required to turn lithium containing brine or spodumene into lithium metal, instead depositing pure lithium metal directly from lithium containing brine or spodumene liquor.
- the present disclosure relates to a process for producing lithium directly from an aqueous lithium feed solution selected from the group consisting of a lithium hydroxide solution, a lithium hydroxide monohydrate solution, and a combination thereof.
- the lithium feed solution is provided in an electrolysis cell comprising a cathode suitable for electrolysis of lithium, and an anode.
- An ionizing electric current is provided to the electrolysis cell, thereby providing lithium metal at the cathode.
- the lithium hydroxide solution contains 1.5-18% lithium.
- the lithium feed solution is continuously provided to the electrolysis cell, and the lithium metal is continuously produced at the cathode.
- the temperature in the electrolysis cell for providing lithium metal is 15 to 40°C.
- the temperature in the electrolysis cell for providing lithium metal is approximately 23°C.
- the lithium feed solution has a pH of 7-14.
- An advantage of the present disclosure is to produce lithium metal directly from lithium hydroxide in a basic pH aqueous solution resulting in extended selective membrane life, and simplification of handling over the previously proposed acid solutions.
- Figure 1 is a flow diagram showing the process for producing lithium according to an embodiment of the present disclosure.
- Figure 2 is a perspective view of a first embodiment of a lithium producing cell structure used to produce lithium in the process of Figure 1.
- Figure 3 is an elevation view of the lithium producing cell of Figure 2.
- Figure 4 is a section view taken along A— A of Figure 3.
- Figure 5 is a perspective view of a lithium producing cell according to a second embodiment of the present disclosure.
- Figure 6 is an exploded view of the lithium producing cell of Figure 5.
- the present disclosure generally relates to producing lithium directly from a lithium feed solution selected from the group consisting of lithium chloride brine, lithium sulfate spodumene liquor, lithium hydroxide, and a combination thereof. Additionally the present disclosure also relates to continuous processes for obtaining lithium metal.
- Lithium can be extracted from the earth by either pumping of brine from the ground or mining spodumene, petalite or lepidolite ore from the earth.
- Salar brines can be described as underground reservoirs that contain high concentrations of dissolved salts, such as lithium, potassium, and sodium.
- the lithium-rich water is pumped to the surface into a series of evaporation ponds where solar evaporation occurs over a number of months.
- salts of sodium, potassium, magnesium, etc. can be harvested from the brine as byproducts.
- Lithium concentration reached in this first stage is raised to 1.5% lithium in the evaporation pond.
- the brine is then transported to a secondary evaporation pond where lithium concentration is raised further to approximately 4-6% lithium. Potassium is often first harvested from early ponds, while later ponds have increasingly high concentrations of lithium.
- the process for producing lithium uses the lithium chloride solution before boron and magnesium extraction, filtering, or before it is treated with soda ash and converted into lithium carbonate.
- the lithium chloride solution according to an embodiment could be pumped directly from the evaporating pond or evaporation process, through the electrolysis cell, and returned back into the evaporating pond or process.
- Lithium can be extracted from spodumene concentrates after roasting and acid roasting operations.
- a concentrate with at least 6% Li 2 0 (approximately 75% spodumene) is suitable for roasting.
- Roasting is performed at about 1050°C, during which spodumene will go through a phase transformation from a-spodumene to ⁇ -spodumene.
- the a-spodumene is virtually refractory to hot acids.
- the phase transformation the spodumene crystal structure expands by about 30% and becomes amenable to hot sulfuric acid attack.
- the specific gravity of the spodumene decreases from 3.1 g/cm 3 (natural ⁇ -spodumene) to around 2.4 g/ cm 3 ( ⁇ -spodumene).
- the material is cooled and then mixed with sulfuric acid (95-97%). The mixture is roasted again at about 200°C. An exothermic reaction starts at 170°C and lithium is extracted from ⁇ - spodumene to form lithium sulfate, which is soluble in water.
- this lithium sulfate solution after the roasting operations is used as feed stock for producing lithium.
- the lithium sulfate solution could be pumped directly from or provided from a reservoir, through the electrolysis cell, and then returned back into the reservoir.
- Lithium carbonate is a stable white powder, which is a key intermediary in the lithium market because it can be converted into specific industrial salts and chemicals, or processed into lithium metal.
- the present disclosure provides directly processing a lithium feed solution to the cell into lithium metal prior to processing into lithium carbonate.
- Suitable lithium feed solutions to the cell include but are not limited to concentrated lithium chloride brine from salar ponds, sulfuric acid liquor from ore operations, and a combination thereof.
- Lithium containing solutions obtained from spodumene or clay using alkaline, chlorination, or other leaching operations may also be acceptable feed stock.
- these lithium-containing solutions have a concentration of 1-18% lithium.
- these lithium-containing solutions have a concentration of 1.5-18% lithium.
- these lithium- containing solutions have a concentration of 16-18% lithium.
- lithium containing solutions obtained from concentrating seawater, seawater, or bitterns may also be acceptable and resulting feed have a concentration of 1-18% lithium
- lithium containing solutions obtained by leaching of lithium from recycled lithium batteries would also make acceptable feed stock and have a lithium concentration of 1-18% lithium.
- lithium carbonate may not be present in the lithium feed solution according to the present disclosure.
- a lithium metal according to an embodiment may be produced using a cell as shown in Figures 2-4.
- the electrolytic cell 9 includes a cathode 7, an anode 8, and the lithium feed solution, which is used as electrolyte in the electrolytic cell 9.
- the anode 8 is in contact with the lithium feed solution.
- a lithium ion conducting membrane 2 separates the anode and cathode compartments.
- the cathode 7 is immersed in non-aqueous catholyte 5, providing a path for lithium ion flow from the membrane 2 to the cathode 7.
- electrolysis proceeds and lithium metal builds up on the cathode 7.
- the cathode 7 is suitable for electrolysis of lithium, and comprises a suitable material that is non-reactive with lithium metal or the catholyte 5.
- the cathode 7 can be made from copper.
- the anode 8 can be made from titanium or niobium coated with platinum, gold, or ruthenium.
- the anode 8 can be made from any material that is compatible with the anolyte, such as concentrated lithium chloride brine from salar ponds, sulfuric acid liquor from ore operations, and a combination thereof.
- an anionic selective membrane 2 is inserted between the cathode 7 and the anode 8, and only lithium flows through the membrane 2.
- a lithium chloride brine containing 1.5-18% lithium or a lithium sulfate spodumene liquor containing 1.5-18% lithium can be utilized as the lithium feed solution 6 to directly produce lithium metal in an electrolysis cell using electrolysis as shown in the reactions below:
- the lithium chloride brine contains 4-6% lithium.
- lithium 1.5-18% lithium can be utilized as the lithium feed solution to directly produce lithium metal in an electrolysis cell using electrolysis as shown in the reactions below:
- electrolysis is performed at approximately 23°C to produce lithium (and oxygen or chlorine gas as a byproduct).
- the lithium feed solution is continuously fed or provided into the electrolytic cell 9, and the lithium metal is continuously produced at the cathode.
- the lithium feed solution is circulated through the electrolytic cell 9 via an inlet of the cell body, spent electrolyte is discharged via an outlet of the cell body, and the oxygen or chlorine gas released by the anode is vented off.
- lithium chloride brine is prepared by solar or electric evaporation in an evaporation pond, and the lithium chloride brine is returned from the electrolysis cell to the evaporation pond.
- lithium sulfate spodumene liquor is provided from a reservoir or feed tank, and the lithium sulfate spodumene liquor is returned from the electrolysis cell to the reservoir or feed tank.
- the lithium feed solution is selected from the group consisting of a lithium hydroxide solution, a lithium hydroxide monohydrate solution, and a combination thereof, and the lithium feed solution is circulated via a pump.
- the lithium producing process is conducted as a batch process.
- the cell body can be made of a suitably rigid material such as polypropylene.
- the lithium producing processes described herein are not limited in this regard.
- the membrane holder 1 shall be electrically insulating to prevent electron flow between the anode and cathode compartments, preventing electrolysis of the water based lithium feed solution when applying voltage above 2.5vdc.
- the membrane 2 is an electrical insulator which only allows lithium ion flow, not electron flow.
- Example 1 The cell used in Example 1 is shown schematically in Figures 5-6. 75mm x 50mm x 25 micron pieces of copper were washed in a concentrated sulfuric acid solution. The samples were then rinsed with deionized water three times, and dried with a wipe. The samples were then loaded into an argon atmosphere glove box, exchanging the atmosphere of the antechamber three times.
- the bench flow cell show in Figures 5-6 was set up with an 8M aqueous lithium chloride solution circulating through the anode side of the cell, and a 1M LiPF6 (lithium hexafluorophosphate) EC (ethylene carbonate)-DMC (dimethyl carbonate) organic electrolyte circulating through the cathode (plating) side of the cell.
- a 1M LiPF6 (lithium hexafluorophosphate) EC (ethylene carbonate)-DMC (dimethyl carbonate) organic electrolyte circulating through the cathode (plating) side of the cell.
- an anionic selective membrane 14 is inserted between the cathode 18 (copper film) and the anode 12, and only lithium flows through the membrane 14.
- the samples were then loaded into a sample holder where the copper was masked, allowing 16 square centimeters of copper to be exposed to the electrolyte on one side.
- the sample holder with substrate was then loaded in the bench flow
- the lithium plating on the samples demonstrated that pure lithium can be plated directly from a lithium chloride brine feed.
- the resultant lithium film exhibited a blue color, which is indicative of a nano-rod morphology within the lithium metal film.
- the blue appearance might be due to a structural coloration effect, whereby the fine microscopic surface produces a structural color by interference among light waves scattered by two or surfaces of the film.
- Example 2 The cell used in Example 2 is shown schematically in Figures 5-6. 75mm x 50mm x 25 micron pieces of copper were washed in a concentrated sulfuric acid solution. The samples were then rinsed with deionized water three times, and dried with a wipe. The samples were then loaded into an argon atmosphere glove box, exchanging the atmosphere of the antechamber three times.
- the bench flow cell show in Figures 5-6 was set up with an 8M aqueous lithium chloride solution circulating through the anode side of the cell, and a 1M LiPF6 EC-DMC organic electrolyte circulating through the cathode (plating) side of the cell.
- an anionic selective membrane 14 is inserted between the cathode 18 (copper film) and the anode 12, and only lithium flows through the membrane 14.
- the samples were then loaded into a sample holder where the copper was masked, allowing 16 square centimeters of copper to be exposed to the electrolyte on one side.
- the sample holder with substrate was then loaded in the bench flow cell.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR112020002717-0A BR112020002717A2 (en) | 2017-08-08 | 2018-08-08 | direct production of lithium from sources of lithium supply |
AU2018313162A AU2018313162A1 (en) | 2017-08-08 | 2018-08-08 | Producing lithium directly from lithium feed sources |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201762542413P | 2017-08-08 | 2017-08-08 | |
US62/542,413 | 2017-08-08 | ||
US201762581140P | 2017-11-03 | 2017-11-03 | |
US62/581,140 | 2017-11-03 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2019032670A1 true WO2019032670A1 (en) | 2019-02-14 |
Family
ID=65271749
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2018/045750 WO2019032670A1 (en) | 2017-08-08 | 2018-08-08 | Producing lithium directly from lithium feed sources |
Country Status (5)
Country | Link |
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US (1) | US20190048483A1 (en) |
AU (1) | AU2018313162A1 (en) |
BR (1) | BR112020002717A2 (en) |
CL (1) | CL2020000335A1 (en) |
WO (1) | WO2019032670A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019213736A1 (en) * | 2018-05-10 | 2019-11-14 | Liep Energy Ltd. | Process for production of lithium battery electrodes from brine |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11201324B2 (en) * | 2018-09-18 | 2021-12-14 | Uchicago Argonne, Llc | Production of lithium via electrodeposition |
KR20230156962A (en) | 2018-12-21 | 2023-11-15 | 맹그로브 워터 테크놀로지스 리미티드 | Li recovery processes and onsite chemical production for li recovery processes |
CA3036143A1 (en) * | 2019-03-08 | 2020-09-08 | Liep Energy Ltd. | Process for extraction and production of lithium salt products from brine |
US20230192503A1 (en) * | 2020-05-12 | 2023-06-22 | Energy Exploration Technologies, Inc. | Systems and Methods for Recovering Lithium from Brines |
US11588146B2 (en) | 2020-08-28 | 2023-02-21 | Pure Lithium Corporation | Lithium metal anode and battery |
WO2022155752A1 (en) * | 2021-01-21 | 2022-07-28 | Li-Metal Corp. | Electrorefining apparatus and process for refining lithium metal |
EP4263911A1 (en) * | 2021-01-21 | 2023-10-25 | Li-Metal Corp. | Process for production refined lithium metal |
WO2023173133A1 (en) * | 2022-03-11 | 2023-09-14 | Energy Exploration Technologies, Inc. | Methods for lithium metal production direct from lithium brine solutions |
US11976375B1 (en) | 2022-11-11 | 2024-05-07 | Li-Metal Corp. | Fracture resistant mounting for ceramic piping |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2516109A (en) * | 1948-09-16 | 1950-07-25 | Metalloy Corp | Method of extracting lithium values from spodumene ores |
US4271131A (en) * | 1979-04-11 | 1981-06-02 | Foote Mineral Company | Production of highly pure lithium chloride from impure brines |
US6770187B1 (en) * | 1999-08-24 | 2004-08-03 | Basf Aktiengesellschaft | Method for electrochemically producing an alkali metal from an aqueous solution |
US20050100793A1 (en) * | 2003-11-10 | 2005-05-12 | Polyplus Battery Company | Active metal electrolyzer |
US20120006690A1 (en) * | 2010-06-30 | 2012-01-12 | Amendola Steven C | Electrolytic production of lithium metal |
-
2018
- 2018-08-07 US US16/057,127 patent/US20190048483A1/en not_active Abandoned
- 2018-08-08 AU AU2018313162A patent/AU2018313162A1/en not_active Abandoned
- 2018-08-08 WO PCT/US2018/045750 patent/WO2019032670A1/en active Application Filing
- 2018-08-08 BR BR112020002717-0A patent/BR112020002717A2/en not_active Application Discontinuation
-
2020
- 2020-02-07 CL CL2020000335A patent/CL2020000335A1/en unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2516109A (en) * | 1948-09-16 | 1950-07-25 | Metalloy Corp | Method of extracting lithium values from spodumene ores |
US4271131A (en) * | 1979-04-11 | 1981-06-02 | Foote Mineral Company | Production of highly pure lithium chloride from impure brines |
US6770187B1 (en) * | 1999-08-24 | 2004-08-03 | Basf Aktiengesellschaft | Method for electrochemically producing an alkali metal from an aqueous solution |
US20050100793A1 (en) * | 2003-11-10 | 2005-05-12 | Polyplus Battery Company | Active metal electrolyzer |
US20120006690A1 (en) * | 2010-06-30 | 2012-01-12 | Amendola Steven C | Electrolytic production of lithium metal |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019213736A1 (en) * | 2018-05-10 | 2019-11-14 | Liep Energy Ltd. | Process for production of lithium battery electrodes from brine |
Also Published As
Publication number | Publication date |
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AU2018313162A1 (en) | 2020-03-26 |
CL2020000335A1 (en) | 2020-11-13 |
US20190048483A1 (en) | 2019-02-14 |
BR112020002717A2 (en) | 2020-07-28 |
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