Lithium Recovery

Abstract

The present invention provides a process for recovering lithium from end-of-life lithium-ion batteries and battery materials. A typical process for separating lithium from lithium-ion batteries prior to hydrometallurgical or pyrometallurgical processing includes providing black mass (BM) or shredded battery material (SBM) containing cation and anion components, mixing the BM or SBM with a mixture containing water and supercritical carbon dioxide, and separating the BM or SBM after lithium leaching from an aqueous leach solution containing lithium carbonate and / or bicarbonate.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This disclosure claims the benefit of priority to AU Patent Application No. 2022903247, filed November 1, 2022, the entire contents of which are incorporated herein.

[0002] The present invention relates to the recycling of battery materials and / or metals, such as lithium, from end-of-life batteries. [Background technology]

[0003] Precious metals are being mined from their constituent ores at an exponentially increasing rate. As their overall supply is strictly finite, some metals are already under supply and sustainability pressure. Without widespread recycling practices, the global supply of certain metals will inevitably be depleted sooner, long before consumer demand declines. One such metal is lithium.

[0004] At the industrial level, lithium is becoming increasingly popular due to its many applications, including, to name just a few, ceramics, glass, batteries, electronics, lubricating grease, metallurgy, fireworks manufacturing, air purification, optics, polymer chemistry, military, and medical applications. One of the primary uses of lithium is in batteries, and demand will continue to increase as new all-electric vehicles (among other emerging technologies) appear on the roads. Lithium is particularly well-suited for use in batteries due to its high electrode potential (the highest of all metals) and low atomic weight, which allows for high charge-to-weight and power-to-weight ratios. Lithium batteries have an advantage over other batteries due to their relatively high charge density (long life), but currently suffer from a relatively high cost per unit. Depending on the design and chemical compounds used, lithium cells can generate voltages ranging from 1.5 V (similar to zinc-carbon and alkaline batteries) to approximately 3.7 V.

[0005] With growing environmental awareness and the increasing demand for battery power as an alternative to fossil fuels, a new waste stream of used batteries is inevitable. However, as a result of the thinking that goes into working with such a waste stream, a proliferation of recycling technologies is even more inevitable, for example, where the valuable lithium contained within used batteries is recovered and recycled for future use.

[0006] It is estimated that approximately 1.2 million tonnes of lithium-ion batteries will reach the end of their life by 2030. This includes an estimated potential recovery of 125,000 tonnes of lithium, 35,000 tonnes of cobalt, and 86,000 tonnes of nickel that could be recovered for use in manufacturing new batteries. These figures must be considered in the context of the fact that the global supply of these elements is strictly finite, and without effective recycling practices, technological advances in lithium-ion batteries may be limited by supply rather than by the emergence of new and better battery technologies.

[0007] "Black mass" is an industry term for e-waste that includes crushed and shredded end-of-life battery cells. This contains a mixture of precious metals, including lithium, manganese, cobalt, and nickel, as well as graphite and other exterior or electrode materials. Initially, discarded batteries are collected, sorted, discharged, and disassembled. This is followed by mechanical crushing, drying, sorting and sieving, and thermal decomposition at temperatures up to 700°C to remove remaining electrolyte and potentially fluorine-containing components that are harmful to health. The resulting material is referred to as "black mass" in the battery recycling industry.

[0008] In traditional battery recycling, lithium is extracted in the final step or after significant processing. Examples include hydrometallurgy and pyrometallurgy. Hydrometallurgy refers to the extraction of metals by preparing an aqueous solution of the metal's salt and recovering the metal from the aqueous solution. Operations typically involve leaching or dissolving the metal or metal compound in water (usually with additional agents), waste separation and purification of the leachate, and precipitation of the metal or one of its pure compounds from the leachate by chemical or electrolytic means. Common leaching agents include, for example, sulfuric acid, hydrochloric acid, and / or hydrogen peroxide. Notably, multiple steps are required and large amounts of wastewater are generated.

[0009] Pyrometallurgy refers to the extraction and purification of metals by processes involving the application of heat. The most important operations are roasting, smelting, and refining. Such processes are very energy intensive, use many chemicals that are harmful to the environment, and result in the production of harmful gases.

[0010] The recovery of lithium is by traditional hydrometallurgical or pyrometallurgical methods and therefore involves significant environmental and consequent financial costs. Not surprisingly, several alternative technologies have recently emerged.

[0011] US Patent No. 2022 / 0149452 to Northvolt AB relates to a process for removing aluminum and iron in the recycling of rechargeable batteries, which process includes providing a leachate from black mass, adding phosphoric acid to the leachate and adjusting the pH to form iron (III) phosphate and aluminum phosphate, precipitating and removing the formed FePO4 and AlPO4, and forming a filtrate for further recovery of cathode metals, mainly NMC metals (nickel, manganese, cobalt) and lithium.

[0012] U.S. Patent No. 10,919,046 to Li-Cycle Corp. describes an apparatus for size reduction of battery material under immersion conditions, the apparatus having a battery inlet and at least a first comminution device disposed within a housing, the first comminution device configured to reduce the size of the battery material to form a reduced-size battery material and release black mass material, including electrolyte material and anode and cathode powders, from within the battery material. An immersion fluid can be present within the housing, and the first comminution device can be immersed such that the black mass material and reduced-size battery material are entrained within the immersion fluid to form a reduced-size feed stream. A feed outlet can be downstream of the first comminution device.

[0013] The COOL process (see, for example, Pavon, et al. The COOL-Process—A Selective Approach for Recycling Lithium Batteries. Metals, 11(2):259, 2021) is a process for recycling Li from black mass. Depending on the process parameters, lithium can be recovered almost quantitatively by utilizing the selective leaching properties of supercritical CO2 / water. The optimal reaction conditions are 230 °C, 4 h, and a water:black mass ratio of 90 mL / g, yielding 98.6 ± 0.19 wt% lithium. Mainly Li is solubilized, allowing the precipitation of Li2CO3 (>99.8 wt%). Furthermore, approximately 52% of the initial aluminum is co-extracted.

[0014] Another competing technology recently published by RWTH Aake University focuses on early-stage lithium recovery (see, for example, Schwich, et al., Early-Stage Recovery of Lithium from Tailored Thermally Conditioned Black Mass Part I: Mobilizing Lithium via Supercritical CO₂-Carbonation. Metals, 11(2):177, 2021). A complete NCM-based electric vehicle cell is heat-treated to recover the thermally conditioned black mass. The thermally conditioned black mass is then subjected to a HO leaching process to determine the proportion of aqueous lithium phases. This is compared to a supercritical CO₂ carbonation process, which allows for more lithium to be transferred from the thermally conditioned black mass into aqueous solution than HO leaching alone. Key factors affecting lithium yield include filter cake purification, lithium separation method, solid / liquid ratio, pyrolysis temperature and atmosphere, and autoclave carbonation setup, which can be performed in a HO environment or a dry autoclave environment. This approach achieves lithium yields of up to 79% through processing with supercritical CO2 in an autoclave reactor.

[0015] [Table 1]

[0016] Considering Table 1 above, it can be seen that the new wave of technologies described above still suffer from one or more of the following problems: energy intensity, chemical use, and pre-processing requirements. For these reasons, it is unexpected that black mass will be used in a process to directly extract lithium.

[0017] It is an object of the present invention to overcome or ameliorate at least one of the disadvantages of the prior art, or to provide a useful alternative. In particularly preferred forms of the present invention, it is an object to provide a relatively simple, convenient, and effective means for extracting lithium from used or end-of-life lithium-ion batteries. While the invention will be described with reference to specific embodiments, those skilled in the art will recognize that the invention can be embodied in many other forms. Summary of the Invention

[0018] A first embodiment is a process for separating lithium from a lithium-ion battery prior to hydrometallurgical or pyrometallurgical processing, the process comprising providing black mass (BM) or shredded battery material (SBM) comprising cation and anion components, mixing the BM or SBM with a mixture comprising water and supercritical carbon dioxide, and separating an aqueous leach solution comprising lithium carbonate and / or bicarbonate from the BM or SBM after lithium leaching.

[0019] A second embodiment is a process that includes grinding a plurality of lithium-ion cells in water to thereby provide a slurry comprising black mass (BM) or shredded battery material (SBM) and water, mixing the slurry with supercritical carbon dioxide, and separating an aqueous leach solution comprising lithium carbonate and / or bicarbonate from the lithium-leached BM or SBM.

[0020] A third embodiment is a process that includes grinding a plurality of lithium-ion cells in a solution of water and carbon dioxide, thereby providing a slurry including black mass (BM) or shredded battery material (SBM), lithium bicarbonate, water, and carbon dioxide, and separating an aqueous leachate including lithium bicarbonate from the BM or SBM.

[0021] A fourth embodiment is a method for extracting one or more materials from black mass (BM) end-of-life battery waste, the method including obtaining black mass containing the one or more materials, exposing the BM to an aqueous extraction medium defined by a reactor, a predetermined CO partial pressure, a predetermined extraction temperature, and a predetermined residence time, and obtaining at least one of the one or more materials in solution therefrom.

[0022] A fifth embodiment is an apparatus for extracting one or more materials from black mass (BM) end-of-life battery waste, the apparatus including a fluidized bed reactor, means for exposing the black mass to an aqueous extraction medium defined by a predetermined CO partial pressure, a predetermined extraction temperature, and a predetermined residence time, and means for obtaining at least one of the one or more materials in solution therefrom.

[0023] For a more complete understanding of the present disclosure, reference should be made to the following detailed description and accompanying drawings. [Brief explanation of the drawings]

[0024] [Figure 1] 1 is a schematic diagram of a hydrometallurgical recovery process known in the prior art. Hydrometallurgical processes are characterized by required pre-treatment, the use of hazardous chemicals, and the extraction of lithium as the final (or near-final) step in the process. [Figure 2] Schematic diagram of a cooling process known in the prior art. This is a selective process for recycling lithium from black mass. The optimal reaction conditions are 230°C, 4 hours, and a water:black mass ratio of 90 mL / g, yielding 98.6±0.19 wt% lithium. Mainly Li (>99.8 wt%) and Al (>52 wt%) are solubilized. [Figure 3]1 is a schematic diagram of a process according to the present invention, which comprises obtaining a black mass containing lithium, subjecting the black mass to an aqueous extraction medium defined by a fluidized bed reactor, a predetermined CO partial pressure, a predetermined extraction temperature, and a predetermined residence time, and obtaining therefrom technical grade lithium carbonate / bicarbonate in solution. In the process of the present invention, aluminum (and indeed other metals) is not removed from the black mass, nor is it co-extracted with lithium, as in, for example, a cooling process. [Figure 4] 1 is a photograph of a fluidized bed reactor employed at laboratory scale during testing of the present invention. [Figure 5] 1 is an image of a sample of lithium carbonate extracted from black mass through the process of the present invention. The slight green color in the product is due to small amounts of nickel impurities. [Figure 6] 1 is a plot of concentration versus time from a laboratory-scale run of the process of the present invention. It can be seen that lithium is most efficiently extracted between about 10 and 60 minutes, with the extraction efficiency decreasing between 60 and 150 minutes. Furthermore, relatively few impurities are extracted during the first 60 minutes, meaning that the extracted lithium is obtained in a relatively short time and with a relatively high purity. In contrast, beyond about 140 minutes, nickel is primarily extracted, with a ratio of about 2:1 with lithium and about 15:1 with cobalt. [Figure 7] 1 is a plot of extent of extraction versus time, comparing the extraction efficiency of lithium relative to nickel and cobalt. The data reveal that at approximately 140 minutes, 92 wt. % of lithium is selectively extracted compared to 5 wt. % and 1 wt. % of nickel and cobalt, respectively. [Figure 8]Figure 1 shows the FT-IR spectrum of standard lithium carbonate compared to the material extracted via the process of the present invention. The absorption peak at 477 cm-1 is attributed to the Li-O stretching vibration. The peaks in the range of 858, 1087, and 1411 cm-1 are identified as the stretching and bending vibrations of the CO3 2- group. FT-IR analysis shows that the spectrum of the extracted green material is in good agreement with the spectrum of standard lithium carbonate, confirming its chemical structure. [Figure 9] 1 shows the sieve size as a function of weight percentage for black mass samples processed according to the process of the present invention. As the data shows, the majority of the samples are in the size range of 75-425 μm. [Figure 10] The crystalline structure of the cathode material as determined by X-ray diffraction (XRD) analysis is shown. By referring to the XRD patterns of the standard samples listed in Table 3, all diffraction peaks can be assigned to four different phases. The high-intensity peaks are in good agreement with the standard data, suggesting that the two major phases are aluminum and lithium nickel cobalt oxide. [Figure 11] Scanning electron microscope (SEM) images and energy dispersive X-ray spectroscopy (EDS) analysis of untreated black mass before and after the extraction process are compared. The SEM and EDS results for the untreated black mass before extraction (Figures 11A and 11B) show that the aluminum is located in the center and is surrounded by Li-containing material on both sides. Figures 11C and 11D show the material after extraction as amorphous material with no particular shape. The SEM and EDS results confirm that the extraction process has transformed the layered structure of the untreated material and extracted the Li-containing material. DETAILED DESCRIPTION OF THE INVENTION

[0025] While specific examples are shown in the figures, it is understood that this disclosure is intended to be illustrative, and that these embodiments are not intended to limit the invention described and illustrated herein.

[0026] The objects, features, and advantages of the present invention will become apparent from the following detailed description. However, it should be understood that the detailed description and specific examples, while indicating specific embodiments of the present invention, are merely exemplary, and that various changes and modifications within the spirit and scope of the present invention will become apparent to those skilled in the art from this detailed description.

[0027] Herein, in the claims and / or specification, the use of the word "a" or "an" in conjunction with the term "comprising" can mean "one," but is also consistent with the meanings "one or more," "at least one," and "one or more than one." The term "about" generally means plus or minus 5% of the stated value. The use of the term "or" in the claims means "and / or" unless expressly stated to refer to alternatives only or that the alternatives are mutually exclusive; however, this disclosure supports the definition referring to alternatives only and "and / or."

[0028] As used herein, the term "shredded battery material" or SBM refers to material produced by shredding, crushing, or otherwise reducing lithium-ion battery cells into granular material. In some cases, the lithium-ion battery cells may be removed from the packaging, housing, or other material that contained the cell(s). SBM typically refers to lithium-ion battery cells that have been shredded, crushed, pulverized, pulverized, fragmented, crushed, split, or otherwise reduced to small granular material. SBM may be formed from end-of-life batteries or batteries that have failed testing / quality control. SBM may be formed from the same or different types of batteries, but all batteries must contain lithium.

[0029] The term "black mass" generally refers to granular material produced from recycled lithium-ion cathodes. As used herein, black mass is shredded, ground, or granular material produced primarily or entirely from lithium-ion battery cathodes. In preferred cases, the black mass is "raw" black mass of cathode material, which typically includes a binder, lithium metal oxide, and aluminum. While the terms black mass and raw black mass are sometimes used interchangeably, the invention presented herein is applicable to both materials containing aluminum and binder (typically raw black mass) and materials from which the aluminum and binder have been separated (refined black mass or simply black mass).

[0030] As used herein, the phrase "consisting of" excludes any element, step, or ingredient not specified in the claim. When the phrase "consists of" (or variations thereof) appears in a section of the body of a claim rather than immediately following the preamble, it limits only the elements recited in that section and does not exclude other elements from the claim as a whole. As used herein, the phrase "consisting essentially of" limits the claim to the specified elements or method steps plus elements that do not materially affect the essential and novel characteristics of the claimed subject matter.

[0031] When numerical ranges are recited using endpoints, all numbers subsumed within that range are included (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.).

[0032] The terms "preferred" and "preferably" refer to embodiments of the invention that may provide certain benefits in particular circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are unnecessary, or is not intended to exclude other embodiments from the scope of the invention.

[0033] A first embodiment is a process for separating lithium from a lithium-ion battery before hydrometallurgical or pyrometallurgical processing. The process can include providing a black mass (BM) or shredded battery material (SBM) containing cation and anion components, mixing the BM or SBM with a mixture containing water and supercritical carbon dioxide, and separating the BM or SBM after lithium leaching from an aqueous leachate containing lithium carbonate and / or bicarbonate. Here, hydrometallurgical and pyrometallurgical processes have a common meaning and are known to those skilled in the art. The BM or SBM is preferably a product of mechanically shredding one or more lithium-ion batteries. Thus, the process can include, for example, providing a lithium-ion battery, mechanically shredding the lithium-ion battery to produce the BM or SBM, and optionally mechanically separating the exterior material from the SBM to provide the BM or SBM. Here, the exterior material can include a plastic, metal, or metallized plastic containing an anode and a cathode.

[0034] In certain examples, the BM or SBM includes at least two of chopped cathode material, chopped anode material, electrolyte salt, and solid electrolyte interface (SEI) material. In certain examples, the BM includes chopped cathode material. In preferred embodiments, the SBM includes SEI material. The SEI is often composed of both organic and inorganic products from electrolyte decomposition. The SEI material can include amorphous layers of Li2CO3, LiF, Li2O, polyolefins, hemicarbonates, and mixtures thereof. In another preferred embodiment, the SBM includes chopped cathode material (SCM) and chopped anode material (SAM). The SCM can include iron, nickel, manganese, cobalt, or mixtures thereof. In particularly preferred cases, the SCM includes nickel. The SCM can further include aluminum from the cathode current collector. The SAM typically includes graphite, but if the cell is a lithium metal cell or an anodeless cell, the anode material can be graphite-free. The SAM can further include copper from the anode current collector. In rare instances of lithium metal cells, the SAM may be copper-free and consist essentially of lithium metal and its alloy components.

[0035] Notably, the BM or SBM contains a lithium mass that is the lithium content of the lithium-ion cells before shredding. In particularly preferred examples, the aqueous leachate separated from the combined BM or SBM and water / supercritical carbon dioxide mixture contains at least 75%, 80%, 85%, 90%, or 95% lithium mass.

[0036] In one particular example, the process uses an SBM in the process.

[0037] In one particular example, the process uses a BM in the process.

[0038] The process can further include crystallizing lithium carbonate from the aqueous leachate, followed by optional recrystallization. Crystallization of lithium carbonate is generally a process known in the art and is often driven by the inverse solubility of lithium carbonate in hot water compared to other water-soluble substances. Thus, lithium carbonate can be crystallized by heating the aqueous leachate to precipitate the lithium carbonate. Alternatively, crystallization can be driven by other processes known in the art, including the addition of an antisolvent.

[0039] The process may further include a concentration step to increase the concentration of lithium carbonate from the aqueous leachate. The concentration step typically involves removing a solvent, such as water, from the leachate containing lithium carbonate. Methods for removing the solvent and concentrating the solution are known to those skilled in the art, and may include, alone or in combination, concentrators, evaporation, reverse osmosis and / or electrodialysis, liquid-liquid extraction, selective adsorption, solid extraction, and / or membrane separation. Concentrating the leachate may be necessary to facilitate crystallization or recrystallization of lithium carbonate from the aqueous solvent.

[0040] Importantly, the process preferably provides a lithium-leached BM or SBM that is substantially free of lithium. In certain embodiments, the lithium-leached BM or SBM contains less than 25%, 20%, 15%, 10%, or 5% of the lithium contained within the SBM (by mass of lithium).

[0041] In another embodiment, the BM or SBM and water / supercritical carbon dioxide mixture are mixed at a temperature of about 80° C. to about 200° C. and a pressure of about 70 bar to about 250 bar. The temperature can be about 80° C. to about 150° C. and the pressure can be about 85 bar to about 150 bar, or the temperature can be about 100° C. to about 200° C. and the pressure can be about 85 bar to about 125 bar. Such temperatures may include 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, and about 200° C., including any temperature therebetween. Such pressures may include 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, and about 250 bar, including any pressure therebetween.

[0042] The process may further include hydrometallurgically separating the nickel from the lithium-leached SBM. Alternatively, the process may further include pyrometallurgically separating the nickel from the lithium-leached SBM. Both hydrometallurgical and pyrometallurgical processes are carried out according to standard practices in the art.

[0043] According to an exemplary process, shredded battery material (SBM) can be obtained by removing the outer packaging from multiple nickel-manganese-cobalt (NMC)-based lithium-ion batteries and crushing the cells. The SBM can then be mixed with supercritical CO and water in a fluidized-bed reactor, where the temperature and pressure of the system can be maintained at approximately 150°C and 100 bar. The temperature can range from 120 to 180°C, including 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180°C, and any temperature therebetween, such as 141, 142, 143, 144, 146, 147, 148, 149, 151, 152, 153, 154, 156, 157, 158, and 159°C. The pressure is in the range of 80-120 bar, including 80, 85, 90, 95, 100, 105, 110, 115, and about 120 bar, and any pressure therebetween, such as 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100 bar.

[0044] The extract can be removed from the system until the lithium concentration in the filtrate (extract) is less than about 10 ppm, e.g., about 9, 8, 7, 6, 5, 4, 3, 2, or 1 ppm. Therefore, approximately 90% of the lithium in the NMC-based lithium-ion battery can be recovered. Variations in system temperature and pressure (100°C to 200°C, 80 bar to 150 bar) provided similar results. In multiple experiments, ICP analysis of the residue from the fluidized-bed reactor showed less than 10% of the original lithium concentration.

[0045] A second embodiment is a process that includes grinding a plurality of lithium-ion cells in water to provide a slurry containing black mass (BM) or shredded battery material (SBM) and water. The process then includes mixing the slurry with supercritical carbon dioxide and separating the aqueous leachate from the lithium-leached BH or SBM. Preferably, the aqueous leachate contains lithium carbonate and / or bicarbonate. In a particularly preferred embodiment, the process is continuous.

[0046] The process can further include crystallizing lithium carbonate from the aqueous leachate (as described above) and separating the crystallized lithium carbonate from the aqueous leachate. Separation of the crystallized lithium carbonate can be achieved by filtration or centrifugation in a continuous or batch process. In one example, filtration is performed in a Natch filter press, and in another example, centrifugation is performed in a continuous centrifuge. Other processes and equipment are known to those skilled in the separation art. In a particularly preferred example, the aqueous leachate is recycled and used to grind lithium-ion cells. That is, multiple lithium-ion cells are ground in a mixture of the aqueous leachate and water. This recycling process (part of a continuous process) can reduce the water required for the overall process and improve lithium recovery.

[0047] In a preferred example, a supercritical carbon dioxide phase is separated from the slurry, the supercritical carbon dioxide phase comprising at least one of an organic electrolyte and an organic polymer (optionally a binder or separator). In one example, the supercritical carbon dioxide phase comprises an organic electrolyte (from a lithium-ion cell), which may comprise at least one of ethylene carbonate, fluoroethylene carbonate, propylene carbonate, and glycol. In another example, the supercritical carbon dioxide phase comprises an organic polymer comprising polyvinylidene fluoride (PVDF), polystyrene-butadiene rubber (SBR), carboxymethyl cellulose (CMC), a separator polymer, or a mixture thereof, e.g., CMC-SBR.

[0048] A plurality of lithium-ion cells can be ground in a mixture of water and carbon dioxide to provide a slurry containing black mass (BM) or shredded battery material (SBM), water, and carbon dioxide. Preferably, the mixture is water saturated with carbon dioxide (according to Beer's Law), although the concentration of carbon dioxide in the water can be below the saturation point. In one example, the lithium-ion cells can be ground at about 1 atm (standard pressure in an open vessel); alternatively, the cells can be ground at a positive pressure of up to about 15 bar. Notably, grinding under positive pressure can exclude oxygen and reduce the possibility of combustion during grinding.

[0049] A third embodiment is a process that includes milling a plurality of lithium-ion cells in a water and carbon dioxide solution to thereby provide a slurry containing black mass (BM) or shredded battery material (SBM), lithium bicarbonate, water, and carbon dioxide. The process further includes separating an aqueous leachate from the SBM, the aqueous leachate containing lithium bicarbonate. Here, milling the lithium-ion cells includes reacting lithium with water within the cells. That is, the process includes reacting lithium metal, lithium-carbon (LiC), or other chemical species common to charged lithium-ion cells with water and / or carbonate. The process can include reacting lithium with water to form lithium hydroxide, lithium with carbonate to form lithium bicarbonate, and / or lithium hydroxide with carbon dioxide or carbonate to form lithium bicarbonate. In a preferred example, the water and carbon dioxide solution is substantially free of oxygen, and even more preferably, the partial pressure of oxygen above the solution is too low to support combustion of hydrogen and / or organic components from the lithium-ion cells.

[0050] This process can include mixing the slurry with supercritical carbon dioxide and then separating the aqueous leachate containing lithium carbonate and / or bicarbonate and the post-lithium leached BM or SBM. That is, the lithium-ion cells are milled in a carbonated water solution (carbonated water), and then the resulting slurry is mixed with supercritical carbon dioxide. In one example, the organic and fluorinated materials in the slurry are solvent extracted (into the supercritical carbon dioxide) and recovered. In one embodiment, supercritical carbon dioxide is passed through the slurry to recover the organic and fluorinated materials, after which the aqueous leachate is separated from the post-lithium leached BM or SBM. Lithium carbonate is then preferably recovered from the aqueous leachate.

[0051] In another example, the process can further include mixing the BM or SBM with a second solution containing water and supercritical carbon dioxide, and then separating the aqueous leachate containing lithium carbonate and / or bicarbonate from the BM or SBM after lithium leaching. That is, the slurry obtained from the crushing of the lithium-ion cells can be added to a reactor (e.g., a fluidized bed reactor or a packed bed reactor) and passed through the reactor with the second solution. The passed solution can be separated into an aqueous leachate and a supercritical carbon dioxide leachate, or the passed solution can be subjected to a depressurization treatment (preferably with carbon dioxide recovery). Lithium carbonate can then be recovered from the aqueous leachate.

[0052] Another embodiment is a method for extracting one or more materials from black mass end-of-life battery waste, the method comprising: a) obtaining black mass containing one or more precious metals; b) exposing the black mass to an aqueous extraction medium defined by a reactor, a predetermined CO partial pressure, a predetermined extraction temperature, and a predetermined residence time; and c) obtaining one or more materials in solution therefrom. Preferably, the one or more materials comprise one or more precious metals. The one or more precious metals include Ag, Au, Li, Al, Ca, Cr, Co, Cu, Fe, Ga, K, Mg, Mn, Na, Ni, and V. Preferably, the one or more precious metals include Li, Co, and Ni, and more preferably, the one or more precious metals include lithium.

[0053] The black mass may further comprise one or more valuable materials, such as a binder or an electrolyte. Preferably, the electrolyte is lithium hexafluorophosphate (LiPF6) and the binder is selected from one or more of fluoroethylene carbonate (FEC), 1,3-propane sultone (PS), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), ethylene carbonate (EC), polyvinylidene fluoride (PVDF), or propylene carbonate (PC).

[0054] Step b) can further include the addition of one or more chelating agents. The chelating agents can be used to preferentially extract precious metals other than lithium, such as Ag, Au, Al, Ca, Cr, Co, Cu, Fe, Ga, K, Mg, Mn, Na, Ni, and V, preferably Ni and Co. The chelating agents can be selected from one or more of tri-n-butylphosphate (TBP), nitric acid, sodium hydroxide, hydrogen peroxide, diethanolamine (DEA), 2-ethylhexylphosphonic acid-mono-2-ethylhexyl ester, mono-2-ethylhexyl(2-ethylhexyl)phosphonate (PC88A), di-(2-ethylhexyl)phosphoric acid (DEHPA), bis(2,4,4-trimethylpentyl)phosphinic acid (Cyanex 272), or bis(2,4,4-trimethylpentyl)dithiophosphinic acid (Cyanex 301).

[0055] The processes described herein can be carried out continuously or semi-continuously. Semi-continuous operation can include a batch-type process in which each batch is run in a semi-continuous process. This can be achieved by operating multiple reactors independently of each other or in fluid communication with each other, such that each batch is run with increasing lithium concentration in solution as it passes through each reactor. The term "batch" should be understood to include fixed-bed, fluidized-bed, or moving-bed reactors. The process can employ multiple fluidized-bed reactors arranged in series or parallel.

[0056] In one particular example, a mixture comprising BM or SBM, water, and supercritical carbon dioxide is mixed at a predetermined extraction temperature and a predetermined partial pressure for a predetermined residence time.

[0057] The predetermined partial pressure of carbon dioxide can be about 0.1 to about 300 bar, about 1 to about 250 bar, about 5 to about 225 bar, about 10 to about 200 bar, about 25 to about 175 bar, about 50 to about 150 bar, about 75 to about 125 bar, about 80 to about 120 bar, about 85 to about 115 bar, about 90 to about 110 bar, or about 95 to about 105 bar. In another example, the predetermined partial pressure of carbon dioxide can be from about 0.1 to about 300 bar, from about 0.1 to about 250 bar, from about 0.1 to about 225 bar, from about 0.1 to about 200 bar, from about 0.1 to about 175 bar, from about 0.1 to about 150 bar, from about 0.1 to about 125 bar, from about 0.1 to about 120 bar, from about 0.1 to about 115 bar, from about 0.1 to about 110 bar, or from about 0.1 to about 105 bar. In yet another example, the predetermined partial pressure of carbon dioxide can be about 0.1 to about 300 bar, about 1 to about 300 bar, about 5 to about 300 bar, about 10 to about 300 bar, about 25 to about 300 bar, about 50 to about 300 bar, about 75 to about 300 bar, about 80 to about 300 bar, about 85 to about 300 bar, about 90 to about 300 bar, or about 95 to about 300 bar. In another preferred example, the predetermined partial pressure of CO2 is about 100 bar.

[0058] The predetermined extraction temperature can be from about 20° C. to about 350° C. This defined range includes the recited endpoints and all temperatures therebetween. Thus, the claimed ranges are: 20, 25, 30, 35, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220, 225, 230, 235, 240, 245 , 250, 255, 260, 265, 270, 275, 280, 285, 290, 295, 300, 305, 310, 315, 320, 325, 330, 335, 340, 345, 350°C, and any temperature in between such as 141, 142, 143, 144, 146, 147, 148, 149, 151, 152, 153, 154, 156, 157, 158, 159°C. In a preferred example, the predetermined extraction temperature is about 20°C to about 350°C, about 40°C to about 300°C, about 60°C to about 250°C, about 80°C to about 200°C, about 100°C to about 190°C, about 120°C to about 180°C, about 130°C to about 170°C, or about 140°C to about 160°C. In another preferred example, the predetermined extraction temperature is about 150°C. In another example, the predetermined extraction temperature is about 20°C to about 350°C, about 20°C to about 300°C, about 20°C to about 250°C, about 20°C to about 200°C, about 20°C to about 190°C, about 20°C to about 180°C, about 20°C to about 170°C, or about 20°C to about 160°C. In yet another example, the predetermined extraction temperature is about 20°C to about 350°C, about 40°C to about 350°C, about 60°C to about 350°C, about 80°C to about 350°C, about 100°C to about 350°C, about 120°C to about 350°C, about 130°C to about 350°C, or about 140°C to about 350°C.

[0059] The aqueous extraction medium can include a black mass concentration of about 0.1 to about 60% w / w. The black mass concentration corresponds to the weight / weight percent of solids in the aqueous (e.g., water) solution. The predetermined solids concentration is about 0.1% w / w to about 60% w / w. Thus, the claimed range includes 0.1, 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58, and 60% w / w, as well as any solids concentration therebetween, such as 21, 23, 25, 27, 29, 31, 33, 35, 37, and 39% w / w. The predetermined solids concentration can be about 0.1 to about 60% w / w, about 1 to about 55% w / w, about 5 to about 50% w / w, about 10 to about 40% w / w, about 20 to about 35% w / w, or about 30% w / w. In another example, the predetermined solids concentration is about 0.1 to about 60% w / w, about 0.1 to about 55% w / w, about 0.1 to about 50% w / w, about 0.1 to about 40% w / w, or about 0.1 to about 35% w / w. In yet another example, the predetermined solids concentration is about 0.1 to about 60% w / w, about 1 to about 60% w / w, about 5 to about 60% w / w, about 10 to about 60% w / w, or about 20 to about 60% w / w.

[0060] The BM or SBM can have an average particle size of about 0.1 μm to about 1000 μm. In a preferred example, the black mass has an average particle size of about 20 μm to about 425 μm. Without being bound by theory, it is believed that smaller particle sizes tend toward the extraction of lithium, cobalt, and nickel, or other precious metals of similar molecular size and / or chemical valence, while larger black mass particles provide selective extraction of other metals, such as aluminum.

[0061] Preferably, the average particle size of the BM or SBM is from about 0.1 μm to about 1000 μm, more preferably from about 20 μm to about 425 μm. The claimed ranges are: 0.1, 1, 20, 40, 60, 80, 100, 120, 140, 160, 180, 200, 220, 240, 260, 280, 300, 320, 340, 360, 380, 400, 420, 440, 460, 480, 500, 520, 540, 560, 580, 600, 620, 640, 660, 680, 700, 720, 740, 760, 780, 800, 820, 840, 860, 880, 890, 900, 910, 920, 930, 940, 950, 960, 970, 980, 990, 1000, 1010, 1020, 1030, 1040, 1050, 1060, 1070, 1080, 1090, 1100, 1110, 1120, 1130, 1140, 1150, 1160, 1180, 1190, 1200, 1220, 1240, 1260, 1280, 1290, 1300, 1310, 1320, 1330, 1 Included are average particle sizes of 0, 880, 900, 920, 940, 960, 980, and 1000 μm, as well as any average particle size therebetween such as 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, and 99 μm.

[0062] In one example, the average particle size of the BM or SBM is about 0.1 μm to about 1000 μm, about 1 μm to about 800 μm, about 5 μm to about 600 μm, about 10 μm to about 600 μm, about 20 μm to about 400 μm, about 30 μm to about 200 μm, about 40 μm to about 150 μm, or about 50 μm to about 100 μm. In another example, the predetermined average particle size is about 20 μm to about 425 μm. In yet another example, the average particle size of the black mass is from about 0.1 μm to about 1000 μm, from about 0.1 μm to about 800 μm, from about 0.1 μm to about 600 μm, from about 0.1 μm to about 600 μm, from about 0.1 μm to about 400 μm, from about 0.1 μm to about 200 μm, from about 0.1 μm to about 150 μm, or from about 0.1 μm to about 100 μm. In still another example, the average particle size of the black mass is about 0.1 μm to about 1000 μm, about 1 μm to about 1000 μm, about 5 μm to about 1000 μm, about 10 μm to about 1000 μm, about 20 μm to about 1000 μm, about 30 μm to about 1000 μm, about 40 μm to about 1000 μm, or about 50 μm to about 1000 μm.

[0063] The predetermined residence time can be from about 1 to about 1000 minutes. More preferably, the predetermined residence time is from about 60 to about 180 minutes. Even more preferably, the predetermined residence time is about 120 minutes. The predetermined time will, of course, depend on the combination of other parameters employed (CO2 partial pressure, temperature, pressure, and average particle size of the black mass). Thus, for a given combination of the four parameters, the predetermined time is the time until the reaction is complete or substantially complete (approximately 85% completion is observed for the exemplary extraction presented below). This defined range is intended to include the recited endpoints and all times therebetween.Therefore, the claimed ranges are: 1, 5, 10, 15, 20, 25, 30, 35, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220, 225, 230, 235, 240, 245, 250, 255, 260, 265, 270, 275, 280, 285, 290, 295, 300, 305, 310, 315 , 320, 325, 330, 335, 340, 345, 350, 355, 360, 365, 370, 375, 380, 385, 390, 395, 400, 405, 410, 415, 420, 425, 430, 435, 440, 445, 450, 455, 460, 465, 4 70, 475, 480, 485, 490, 495, 500, 505, 510, 515, 520, 525, 530, 535, 540, 545, 550, 555, 560, 565, 570, 575, 580, 585, 590, 595, 600, 605, 610, 620, 625, 630, 635, 640, 645, 650, 655, 660, 665, 670, 675, 680, 685, 690, 695, 700, 705, 710, 715, 720, 725, 730, 735, 740, 745, 750, 755, 760, 765, 770, 775, 78 0, 785, 790, 795, 800, 805, 810, 815, 820, 825, 830, 835, 840, 845, 850, 855, 860, 865, 870, 875, 880, 885, 890, 895, 900, 905, 910, 915, 920, 925, 930, 9 This includes 35, 940, 945, 950, 955, 960, 965, 970, 975, 980, 985, 990, 995, and 1000 minutes, as well as any time in between such as 452, 454, 456, 458, 462, 464, 466, 468, 472, 474, 476, 478, 482, 484, 486, 488, 492, 494, 496, 498, 502, 504, 506, 508, 512, 514, 516, 518, 522, 524, 526, 528, 532, 534, 536, 538, 542, 544, 546, and 548 minutes.

[0064] In a preferred example, the predetermined residence time is about 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, or about 180 minutes, and preferably about 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, or about 150 minutes. In another example, the predetermined time is about 1 to about 1,000 minutes, about 100 to about 900 minutes, about 150 to about 800 minutes, about 175 to about 700 minutes, about 200 to about 600 minutes, about 220 to about 500 minutes, about 240 to about 450 minutes, about 260 to about 400 minutes, about 280 to about 350 minutes, about 290 to about 320 minutes, or about 300 minutes. In yet another example, the predetermined time is about 1 to about 1,000 minutes, about 1 to about 950 minutes, about 1 to about 900 minutes, about 1 to about 850 minutes, about 1 to about 800 minutes, about 1 to about 750 minutes, about 1 to about 700 minutes, about 1 to about 650 minutes, about 1 to about 600 minutes, or about 1 to about 550 minutes. In yet another example, the predetermined time is about 1 to about 1,000 minutes, about 50 to about 1,000 minutes, about 100 to about 1,000 minutes, about 150 to about 1,000 minutes, about 200 to about 1,000 minutes, about 250 to about 1,000 minutes, about 300 to about 1,000 minutes, about 350 to about 1,000 minutes, about 400 to about 1,000 minutes, about 450 to about 1,000 minutes, or about 120 minutes. In a particularly preferred example, the predetermined time is about 90 to about 150 minutes, and more preferably, the predetermined time is about 120 minutes. Alternatively, the predetermined time can be about 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, or about 180 minutes.

[0065] The methods of the present invention result in yields of from about 1% to about 99% (based on extracted lithium), preferably greater than about 50%, 75%, 85%, 90%, or 95%.

[0066] In one example, the one or more impurities extracted from the BM or SBM include Ag, Au, Na, Co, Ni, K, Mg, Ca, Mn, Fe, Al, and Si. In one example, any one or more impurities are present at a concentration of about 0.5% to about 40% of the lithium concentration on a molar basis. In a preferred example, the one or more impurities extracted from the black mass, other than lithium, include cobalt, nickel, calcium, iron, magnesium, potassium, sodium, aluminum, silicon, and manganese. Preferably, the one or more impurities are present at a concentration of less than 0.5% of the lithium concentration on a molar basis.

[0067] In another example, the method or process can further comprise a concentration step d) in which the technical-grade lithium carbonate obtained in solution from step c) is concentrated. Preferably, the concentration step comprises standard concentration techniques in the art, including, but not limited to, the addition of a concentrator, evaporation, reverse osmosis and / or electrodialysis, liquid-liquid extraction, selective adsorption, solid-state extraction, and / or membrane separation. After concentration step c), the lithium carbonate can precipitate or crystallize from the solution. The method can further comprise a filtration step e) to separate the precipitated lithium carbonate from the mother liquor. Notably, the method is adaptable and / or scalable to continuous flow or batch-type scenarios.

[0068] In one example, the aqueous medium includes water, one or more mineral acids, one or more organic acids, one or more alkali salts, one or more ionic liquids, and combinations thereof. The one or more mineral acids can have a pH of about -1 to about 6. Preferably, the one or more mineral acids are optionally supplemented with a predetermined CO partial pressure of about 0.1 to about 300 bar, about 1 to about 250 bar, about 5 to about 225 bar, about 10 to about 200 bar, about 25 to about 175 bar, about 50 to about 150 bar, about 75 to about 125 bar, about 80 to about 120 bar, about 85 to about 115 bar, about 90 to about 110 bar, or about 95 to about 105 bar.

[0069] The one or more organic acids can be selected from acetic acid, formic acid, citric acid, lactic acid, oxalic acid, mixtures thereof, and the like. Preferably, the lithium salt extracted from the organic acid reaction medium is purified to form substantially pure lithium oxide or lithium carbonate. The one or more mineral acids are optionally supplemented with a predetermined partial pressure of CO2 (as defined above) from about 0.1 to about 300 bar. In another example, the one or more alkali salts include alkali hydroxides, carbonates, bicarbonates, and combinations thereof. Preferably, the one or more alkali salts include lithium hydroxide, lithium carbonate, lithium bicarbonate, and combinations thereof. In yet another example, the one or more alkali salts are supplemented with a predetermined partial pressure of CO2 (as defined above) from about 0.1 to about 300 bar. In yet another example, the one or more ionic liquids include protic and / or aprotic liquids. Preferably, the protic and / or aprotic liquids can be miscible or immiscible with water in the aqueous extraction medium. In another preferred example, the one or more ionic liquids are optionally supplemented with a predetermined CO 2 partial pressure of about 0.1 to about 300 bar (as defined above).

[0070] In another preferred example, the lithium is obtained as lithium carbonate / bicarbonate with a purity of about 85% on a molar basis. In other examples, the purity is about 50, 55, 60, 65, 70, 75, or 80% on a molar basis. In another example, the impurities include nickel in an amount of about 5% and cobalt in an amount of about 1% on a molar basis. In another example, nickel can be present at about 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10%. In another example, cobalt can be present at about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, or 1.5%.

[0071] In a particularly preferred embodiment of the present invention, CO2 had a specific molar amount of about 3.7 mol / kg in water, the (predetermined) extraction temperature was about 150°C, the (predetermined) pressure was about 100 bar, and the (predetermined) time was about 300 minutes (5 hours), and the reaction was observed to have reached about 85% completion (i.e., complete extraction based on the measured amount of lithium in the black mass). Observed impurities included K, Na, Ca, Mg, Mn, Fe, Al, Si, Ni, and Co. In some examples, lithium constituted about 85% of the metals extracted from the sample on a molar basis. In other examples, lithium constituted about 60% of the metals extracted from the sample on a molar basis.

[0072] An additional purification step may be carried out, which comprises precipitating at least a portion of the impurities from the technical grade lithium carbonate solution obtained in solution from step c).

[0073] Another embodiment is an apparatus for carrying out any one of the above-described embodiments. The apparatus can include: a) means for exposing black mass to an aqueous extraction medium defined by a reactor, a predetermined CO partial pressure, a predetermined extraction temperature, and a predetermined residence time; and b) means for obtaining one or more materials in solution therefrom. In one example, the apparatus includes multiple fluidized-bed reactors arranged in series and in fluid communication. In another example, the apparatus includes multiple fluidized-bed reactors arranged in parallel and in fluid communication. Preferably, the apparatus further includes means for performing an initial granulation step, thereby granulating the black mass to a predetermined average particle size before providing it as an aqueous suspension. The apparatus can further include means for concentrating the technical-grade lithium carbonate obtained in solution after exposure to the extraction medium. The apparatus can further include filtration means for filtering any precipitated lithium carbonate after exposure to the condensing means. The predetermined CO partial pressure, predetermined extraction temperature, predetermined solids concentration, and predetermined time are as defined above for the fourth and fifth aspects of the present invention. [Example]

[0074] The products were prepared according to standard GLP procedures for handling each material and mixture. All commercial materials were used as received.

[0075] Exemplary process: The outer packaging was removed from multiple NMC-based lithium-ion batteries, and the cells were crushed to provide shredded battery material (SBM). The SBM was mixed with supercritical CO2 and water in a fluidized-bed reactor, and the system temperature and pressure were maintained at approximately 150°C and 100 bar. The extract was removed from the system until the lithium concentration in the filtrate (extract) was less than 10 ppm. Approximately 90% of the lithium in the NMC-based lithium-ion batteries was recovered. Similar results were obtained when the system temperature and pressure were varied (from 100°C to 200°C and from 80 bar to 150 bar). ICP analysis of the residue in the fluidized-bed reactor showed less than 10% of the original lithium concentration.

[0076] Additional Examples The use of carbonic acid to extract lithium from black mass was demonstrated on a laboratory scale. The black mass was not pre-treated or concentrated by chemical or physical means, and its original metal content, including aluminum, remained consistent with the "raw" black mass of the cathode material. A 1 kg sample of granulated black mass (sieved to a size range of about 20 to about 425 μm) was held in a fluidized-bed reactor. A water flow of 1 g / min was passed through the reactor at a temperature of 150 °C and a pressure of 100 bar. The aqueous effluent from the reactor was sampled periodically and analyzed for the presence of lithium and other metals extracted from the input black mass.

[0077] When only water was passed through the reactor, a moderate release of lithium was observed. However, when CO2 was fed to the reactor in a volume of 3.7 mol / kg of water, a surprisingly large proportion of lithium appeared in the product sample, with the lithium concentration in the product sample increasing by more than five-fold.

[0078] During optimization experiments, the inventors varied the temperature of the extraction medium from about 25 to about 200°C. Below about 100°C, the rate was low, and increasing the temperature to 150°C significantly increased the rate, but no further increase was observed when the temperature was increased to 200°C. Importantly, increasing the temperature from 150 to 200°C significantly decreased the purity of the extract.

[0079] Lithium extraction from the finely divided black mass samples was approximately 60% complete after 1 hour and approximately 90% complete after 2 hours. Other metal ions detected in the extract were Al, Ca, Cr, Cu, Fe, Ga, K, Mg, Mn, Na, Si, V, Ni, and Co. Overall, lithium accounted for over 92% of the metals extracted from the black mass samples on a molar basis. The primary impurity was nickel (approximately 5%), followed by cobalt (approximately 1%).

[0080] The reaction was also detectable in a CO2-sparged batch reactor at ambient temperature and atmospheric pressure.

[0081] [Table 2]

[0082] [Table 3]

[0083] The data presented in Table 3 above should be read in conjunction with Figure 10, which shows the crystalline structure of the cathode material as determined by X-ray diffraction (XRD) analysis. By referencing the XRD patterns listed for standard samples, all diffraction peaks could be assigned to four different phases. The high intensity peaks are in good agreement with the standard data, suggesting that the two major phases may be aluminum and lithium nickel cobalt oxide.

[0084] [Table 4]

[0085] An elemental analysis of the Li-bearing material processed according to the present invention is shown in Table 4. The data reveal high concentrations of aluminum, lithium, nickel, and cobalt, which are in good agreement with the phases identified by XRD analysis, thereby confirming that aluminum and lithium nickel cobalt oxide are likely the major components of the sample.

[0086] Table 4 further shows that in addition to the major elements not extracted through this process, other impurities remain, most likely calcium, copper, iron, gallium, magnesium, manganese, sodium, and vanadium.

[0087] The general methodology employed above amply demonstrates the surprisingly effective use of carbon dioxide as a medium for the extraction of lithium carbonate from black mass. As theoretically explained above, this finding is completely counterintuitive given that strong acids and pretreatments are the preferred industrial methods for lithium extraction from black mass.

[0088] This methodology further demonstrates the effectiveness of carbonic acid as an extraction medium for recycling other precious metals from black mass. These metals may include any one or more of Ag, Au, Al, Ca, Cr, Cu, Fe, Ga, K, Mg, Mn, Na, Si, and V. These can be selectively extracted using chelating agents selected from one or more of tri-n-butyl phosphoric acid (TBP), nitric acid, sodium hydroxide, hydrogen peroxide, diethanolamine (DEA), 2-ethylhexylphosphonic acid-mono-2-ethylhexyl ester, mono-2-ethylhexyl(2-ethylhexyl)phosphonate (PC88A), di-(2-ethylhexyl)phosphoric acid (DEHPA), bis(2,4,4-trimethylpentyl)phosphinic acid (Cyanex 272), or bis(2,4,4-trimethylpentyl)dithiophosphinic acid (Cyanex 301).

[0089] While the compositions and methods of the present invention have been described with reference to preferred examples, it will be apparent to those skilled in the art that changes may be made to the compositions and / or methods in the steps or in the sequence of steps of the methods described herein without departing from the concept, spirit, and scope of the invention. More specifically, it will be apparent that certain agents that are both chemically and physically related may be substituted for the agents described herein while the same or similar results would be achieved. All similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope, and concept of the invention as defined by the appended claims.

Claims

1. 1. A process for separating lithium from a lithium ion battery prior to hydrometallurgical or pyrometallurgical processing, comprising: providing a black mass (BM) or chopped battery material (SBM) comprising cationic and anionic components; mixing the BM or the SBM with a mixture comprising water and supercritical carbon dioxide; separating the aqueous leach solution containing lithium carbonate and / or bicarbonate from the BM or SBM after lithium leaching; A process involving:

2. Providing the BM or the SBM includes: providing the lithium ion battery; mechanically shredding the lithium-ion battery to produce a BM or SBM; Optionally, mechanically separating the sheath material from the BM or SBM; The process of claim 1 comprising:

3. 10. The process of claim 1, wherein the BM or the SBM comprises at least two of a chopped cathode material, a chopped anode material, an electrolyte salt, and a solid electrolyte interface (SEI) material.

4. The process of claim 3 , wherein the BM or the SBM comprises the SEI material.

5. The process of claim 3 , wherein the BM or the SBM comprises the diced cathode material and the diced anode material.

6. 2. The process of claim 1, wherein the BM or the SBM comprises lithium mass and the aqueous leach solution comprises at least 75% of the lithium mass.

7. The process of claim 1 wherein said SBM is used in said process.

8. The process of claim 1 wherein the BM is used in the process.

9. 10. The process of claim 1, further comprising crystallizing the lithium carbonate from the aqueous leachate.

10. 10. The process of claim 1, wherein the BM or SBM after lithium leaching is substantially free of lithium.

11. 2. The process of claim 1, wherein the BM or SBM after lithium leaching contains less than 25% of the lithium contained in the BM or SBM.

12. 2. The process of claim 1, wherein the mixture comprising the BM or SBM, the water, and the supercritical carbon dioxide is mixed at a predetermined extraction temperature and a predetermined partial pressure for a predetermined residence time.

13. 2. The process of claim 1, wherein the BM or SBM and the mixture comprising the water and the supercritical carbon dioxide are mixed at a temperature of about 80° C. to about 200° C. and a pressure of about 70 bar to about 250 bar.

14. 10. The process of claim 1, further comprising hydrometallurgically separating nickel from the lithium-leached BM or SBM.

15. 10. The process of claim 1, further comprising pyrometallurgically separating nickel from the lithium-leached BM or SBM.

16. grinding a plurality of lithium-ion cells in water, thereby providing a slurry comprising black mass (BM) or shredded battery material (SBM) and water; mixing the slurry with supercritical carbon dioxide; separating the aqueous leach solution containing lithium carbonate and / or bicarbonate from the BM or SBM after lithium leaching; A process involving:

17. 17. The process of claim 16, wherein the process is continuous.

18. crystallizing lithium carbonate from the aqueous leachate; separating the crystallized lithium carbonate from the aqueous leachate; The process of claim 13 further comprising:

19. 17. The process of claim 16, wherein the plurality of lithium-ion cells are crushed with the mixture of the aqueous solution and the water.

20. 17. The process of claim 16, wherein a supercritical carbon dioxide phase is separated from the slurry, the supercritical carbon dioxide phase comprising at least one of an organic electrolyte or an organic polymer.

21. 20. The process of claim 19, wherein the organic electrolyte comprises at least one of ethylene carbonate, fluoroethylene carbonate, propylene carbonate, and glycol.

22. 20. The process of claim 19, wherein the organic polymer comprises a separator polymer and / or a binder.

23. 17. The process of claim 16, wherein the plurality of lithium-ion cells are ground in a mixture of water and carbon dioxide, thereby providing a slurry comprising the shredded black mass (BM) or battery material (SBM), water, and carbon dioxide.

24. grinding a plurality of lithium-ion cells in a solution of water and carbon dioxide to provide a slurry comprising black mass (BM) or shredded battery material (SBM), lithium bicarbonate, water, and carbon dioxide; separating the aqueous leachate containing lithium bicarbonate from the BM or SBM; A process involving:

25. 25. The process of claim 24, wherein the solution of water and carbon dioxide is substantially free of oxygen.

26. mixing the slurry with supercritical carbon dioxide; separating the aqueous leach solution containing lithium carbonate and / or bicarbonate from the BM or SBM after lithium leaching; 25. The process of claim 24, further comprising:

27. mixing the BM or the SBM with a second solution comprising water and supercritical carbon dioxide; and then separating the BM or SBM after lithium leaching from an aqueous leach solution containing lithium carbonate and / or bicarbonate; 25. The process of claim 24, further comprising:

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