Industrial process to recover critical minerals from battery, electronic waste, and derived materials

Abstract

The present disclosure relates to methods for recovering metals from used lithium ion batteries. The methods employ free-standing or unhoused metal-extraction membranes, where at least a portion of the membranes are submerged in a feed solution containing metals of interest. The methods reduce viscous transport between feed and the strip solutions, as compared to conventional orthogonally-flowing feed and strip solution extraction methods.

Description

INDUSTRIAL PROCESS TO RECOVER CRITICAL MINERALS FROM BATTERY, ELECTRONIC WASTE, AND DERIVED MATERIALSBACKGROUND

[0001] This application claims priority to U.S. Provisional Application No. 63 / 725,642 filed November 27, 2024, which is incorporated by reference herein in it entirety.FIELD OF THE DISCLOSURE

[0002] The disclosure relates generally to methods for the extraction and enrichment of metals from batteries and other forms of electronic waste.BACKGROUND

[0003] The production of lithium-ion batteries (LIBs) is constantly increasing due to the ubiquity of portable consumer electronic devices and the increasing prevalence of hybrid and fully electric vehicles. LIB service life is limited and these batteries must be replaced after a certain period, resulting in large quantities of disposed LIB material that can pose health and environmental hazards. As the demand for lithium-ion batteries rises, the growing quantity of waste produced from lithium-ion battery electrode materials becomes an issue of concern. Developing efficient methods for recycling LIBs can considerably reduce their negative impact as well as the dependence on raw materials in the battery supply chain.

[0004] Many current LIB recycling methods employ cartridge-encased or housed membrane modules for recovering metals from used LIB material. In a conventional cartridgebased or housed membrane system, the membrane cartridge is subjected to bi-directional current flows. Typically, a strip solution flows through the lumen of cartridge-encased membranes in a direction that is parallel to the lumen surface. A separate feed solution flows in a direction that is orthogonal to the lumen surface and to the direction of strip solution flow. The orthogonal-flowing feed and strip solutions cause viscous transport between the feed and the strip solutions, which results in diffusive transport of ions through membrane pores. This bi-directional flow mechanism requires distinct pumping machinery and associated fluid conduits for the feed and strip solutions. This type of arrangement also requires that the feed solution pressure be higher than the strip solution pressure, which leads to contamination of the highly pure metal-bearing strip solutions due to the viscous crossover of the feed solution to the strip side, as the liquid membrane undergoes per-force degradation under continuous duty industrial service.MOMT.P0003 WO / 1001367625 1

[0005] Conventional cartridge-encased or housed membrane modules also impart limitations on metal extraction system design. The pre-assembled cartridges with pre-defined shapes, dimensions, arrangements, and feed inlets and outlets limit the degrees of freedom when one is designing and constructing a metal extraction system. Given the numerous shortcomings of conventional cartridge-encased membranes, there exists a need for improved metal extraction membranes and techniques to recycle battery components.SUMMARY

[0006] The present inventors have devised novel methods for the recovery of valuable metals including cobalt, nickel, and lithium from used, refuse, and waste LIBs. The methods involve the use of free-standing or unhoused metal-extraction membranes that can be arranged in a variety of configurations. The modular free-standing, unhoused membrane designs disclosed herein operate through a distinct housing-free mechanism that increases metal-extraction capacity by increasing the membrane surface area exposed to and in contact with a metal-containing feed solution. Forgoing the membrane cartridge housing allows the engineer to design and construct the metal extraction membranes in a number of different configurations, including various shapes, sizes, arrangements, groupings, and layouts. Forgoing the membrane cartridge housing also allows for the use of membranes made of flexible materials that permit dynamic changing of membrane position, which is favorable for wetting and maintenance.

[0007] The use of free-standing, unhoused membranes submerged in a feed solution reduces viscous transport between feed and the strip solutions, as compared to conventional orthogonally-flowing feed and strip solution extraction methods. The reduced viscous transport between feed and strip solutions, in turn, reduces diffusive transport of ions through membrane pores. Diffusive transport of ions refers to ion flux through membrane pores that is not mediated by an extractant. Reduced viscous transport also reduces extractant loss by diffusion into feed and strip solutions, and reduces attrition of membrane material.

[0008] Some aspects of the present disclosure are directed to a method for recovering metals. In some aspects, the method comprises passing a strip solution through a membrane lumen of an unhoused porous membrane having an extractant immobilized on least a portion of the porous membrane, wherein at least a portion of the membrane is submerged in a feed solution comprising at least one metal cation; collecting the strip solution after at least a portion of the strip solutionMOMT.P0003 WO / 1001367625 2has traversed the membrane lumen, wherein the collected strip solution comprises at least a portion of at least one metal cation; and recovering the at least one metal cation from the collected strip solution. In some aspects, the at least one metal cation is at least one metal cation from a used lithium-ion battery. In some aspects, the at least one metal is selected from the group consisting of lithium, manganese, cobalt, nickel, copper, zinc, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. The metal(s) to be extracted can vary based on the input used, refuse, and / or waste material, and the user can select the extractant or extractants that are selective for the metal(s) to be extracted.

[0009] In some aspects, the feed solution is in a tank, and a net flux of feed solution through the tank volume is zero. In some aspects, feed solution in the tank is replenished such that there is a net flux of feed solution through the tank volume. In some aspects, an exterior portion of the unhoused porous membrane submerged in the feed solution is in direct contact with the feed solution. In some aspects, at least 50 % of an exterior surface area of the membrane submerged in the feed solution is in contact with the feed solution. In some aspects, a strip solution pressure is greater than a feed solution pressure. In some aspects, the feed solution is at atmospheric pressure. In some aspects, the method further comprises passing a solution of extractant in an organic solvent through the membrane lumen to increase a concentration of immobilized extractant in the membrane pores. Prior to passing the extractant solvent through the membrane lumen, the strip solution can be drained from the membrane.

[0010] In some aspects, a solution of an extractant in an organic solvent is fed to the membrane and passed through the membrane lumen to immobilize the extractant within the membrane pores. Passing a solution of an extractant in an organic solvent through the membrane lumen can be performed to “wet” the membrane by immobilizing extractant within the membrane pores. Passing a solution of an extractant in an organic solvent through the membrane lumen can be performed to “rewet” the membrane by replacing extractant that has been lost through regular use. An organic solvent can be passed through the membrane lumen to de-foul the membrane after use, or to rinse the lumen. In some aspects, the membrane is not removed from the reservoir or tank containing a strip solution prior to draining, de-fouling, and / or rewetting. During draining, de-fouling, and / or rewetting, the membrane can remain within the reservoir or tank containing a strip solution. Alternatively, the membrane can be removed from the reservoir or tank containingMOMT.P0003 WO / 1001367625 3a strip solution prior to draining, de-fouling, and / or rewetting. Tn some aspects, an inert gas is passed through the membrane lumen prior to rewetting. In some aspects, a pump is used to pump organic solvent or a solution of extractant in an organic solvent through the membrane lumen. In some aspects, an organic solvent or a solution of extractant in an organic solvent that is fed through a membrane lumen is provided at a temperature that is any one of, less than, greater than, or between 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, and 60 °F. By employing an organic solvent or a solution of extractant in an organic solvent at a temperature that is higher than ambient temperature, the viscosity of the organic solvent or solution of extractant in an organic solvent is reduced. Employing an organic solvent or a solution of extractant in an organic solvent at a temperature that is higher than ambient temperature can reduce the time required to de-foul or rewet the membrane. By employing an organic solvent or a solution of extractant in an organic solvent at a temperature that is higher than ambient temperature, the pressure required to pump the organic solvent through the membrane lumen can be reduced.

[0011] Non-limiting examples of organic solvents that can be used to immobilize extractant within membrane pores, to rewet membranes, and to de-foul membranes include chlorinated hydrocarbon solvents such as dichloromethane, carbon tetrachloride, and chloroform, aromatic solvents such as benzene, toluene, and xylene, ketones such as methylethylketone, ethyl acetate, and methyl isobutyl ketone, ether solvents such as diethyl ether, di-isopropyl ether, and methyl / -butyl ether, naphthenic solvents such as cyclohexane, methylcyclopentane, and 1-ethyl- 2-methylcyclopentane, isoparaffinic solvents such as any solvent from the Isopar line of synthetic isoparaffinic solvents, heterocyclic solvents such as tetrahydrofuran, paraffinic solvents such as pentane, hexane, and heptane, kerosene, silicone oil, their equivalents, and any combination thereof. In some aspects, the synthetic C11-C13 isoparaffinic hydrocarbon solvent, Isopar L, is used as the organic solvent. In some aspects, a diluent is used to adjust viscosity, wettability, and / or stability of the extractant in order to improve the extractant's useful life and increase the extractant's extraction capacity. The diluent can be included with the extractant in the organic solvent used to immobilize the extractant within the membrane pores. In some aspects, an extractant and a diluent can be used in an extractant to diluent mass:mass ratio ranging from 1 :4 to 3:2. In some aspects, an external magnetic field is created to inhibit or enhance the transport of ferromagnetic ions such as cobalt and nickel to control and enhance the cation exchange process.MOMT.P0003 WO / 1001367625 4

[0012] Upon submerging a membrane comprising an extractant immobilized in the membrane pores into a feed solution, metal ions present in the feed solution are extracted into the membrane pores by way of the immobilized extractant. In some aspects, the feed and strip solutions have different pH values, and the difference in pH values favors the complexation of metals from feed solution with extractant, and freeing of metals within strip solution. The extractant can be selected based upon the desired metal to be extracted, as many extractants exhibit higher affinity for a specific metal or metals. In some aspects, the pH of the strip solution and the pH of the feed solution can independently be varied from 1.5 and 12. In some aspects, the pH of the strip solution is lower than the pH of the feed solution. The pH of the strip solution can be any one of, less than, greater than, or between 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7,2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9,5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1,7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3,9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10.0, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8, 10.9, 11.0, 11.1, 11.2,11.3, 11.4, 11.5, 11.6, 11.7, 11.8, 11.9, and 12.0, or any value derivable therein. The pH of the feed solution can be any one of, less than, greater than, or between 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1,2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3,4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5,6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7,8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10.0, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7,10.8, 10.9, 11.0, 11.1, 11.2, 11.3, 11.4, 11.5, 11.6, 11.7, 11.8, 11.9, and 12.0, or any value derivable therein. In some aspects, the temperature of the feed solution and the temperature of the strip solution can independently be varied from 10 to 70 C. The temperature of the feed solution can be any one of, less than, greater than, or between 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, and 70 °C, or any value derivable therein. The temperature of the strip solution can be any one of, less than, greater than, or between 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, and 70 °C, or any value derivable therein. In some aspects, a strip solution pressure may be any one of, less than, greater than, or between 0, 1, 2, 3,MOMT.P0003 WO / 1001367625 54, 5, 6, 7, 8, 9, 10, 1 1, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 , 32, 33, 34, and 35 pounds per square inch (psi), or any value derivable therein. In some aspects, a feed solution pressure may be any one of, less than, greater than, or between 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, and 35 pounds per square inch (psi), or any value derivable therein. In some aspects, a strip solution pressure is higher than a feed solution pressure. In some aspects, a feed solution contained in a feed solution tank is at atmospheric pressure.

[0013] In some aspects, the feed solution within the feed solution tank is agitated. The feed solution within the feed solution tank can be agitated using a static mixer, ultrasonic head, an impeller, a recirculation loop, or a combination thereof.

[0014] The methods disclosed herein employ free-standing membranes in various forms, including hollow fiber membranes, tubular membranes, spiral-wound membranes, and flat sheet membranes, combinations thereof, and any other membrane geometries. Dimensions and related aspects of membranes, including length, height, width, diameter, circumference, number of spiralwinds per unit length, total number of spiral-winds, distance between flat sheets, total number of flat sheets, and pore size can be adjusted based on the scale of the metal extraction operation. The number of membranes employed in a metal extraction method can be adjusted based on the scale of the metal extraction operation. Multiple membranes and / or bundles of membranes can be arranged in series, parallel, or a combination of series and parallel. Individual membranes within a multi-membrane system can include the same, different, or a combination of extractants immobilized within the pores of each individual membrane.

[0015] In some embodiments, a metal extraction system as disclosed herein can include 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690, 700, 710, 720, 730, 740, 750, 760, 770, 780, 790, 800, 810, 820, 830, 840, 850, 860, 870, 880, 890, 900, 910, 920,MOMT.P0003 WO / 1001367625 6930, 940, 950, 960, 970, 980, 990, or 1,000 membranes or bundles of membranes arranged in series, parallel, or a combination of series and parallel, or any number derivable therein. Membranes or membrane bundles can be oriented vertically, horizontally, or at an angle that is any one of, less than, greater than, or between 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17,18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43,44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69,70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, and 90° within a feed solution containing at least one metal of interest, with respect to a horizontal surface.

[0016] In some aspects, the methods disclosed herein include one or more pre-processing steps that are employed to generate a feed solution comprising at least one metal of interest. The pre-processing steps can include all of, any one of, or any combination of the steps outlined below. In some aspects, the methods disclosed herein comprise a leaching step where a material containing at least one metal of interest is contacted with an aqueous solution of acid in order to leach the at least one metal of interest from the material to the aqueous solution of acid. In some aspects, a leaching step is employed to leach at least one metal of interest from a material containing the at least one metal of interest into an acid solution. In some aspects, the acid solution comprising the at least one metal of interest can serve as a feed solution in a subsequent metal extraction step. In some aspects, the acid can be an organic or a mineral acid. Non-limiting examples of acids include citric acid, ascorbic acid, tartaric acid, sulfuric acid, nitric acid, hydrochloric acid, sulfuric acid, or any combination thereof. When a material containing at least one metal of interest is contacted with an aqueous solution of acid, the aqueous acid solution becomes enriched with metal ions leached from the metal-containing material. In some aspects, the extent to which a metal is leached from a material containing at least one metal of interest is controlled to maximize leaching yield. In some aspects, a material containing at least one metal of interest is contacted with an aqueous solution of acid by means of a metal-extracting technique selected from the group consisting of continuous counter-current, vat, heap, and tank leaching techniques. In some aspects, any of the metal-extracting techniques disclosed herein can be employed in conjunction with a mixing technique that includes, but it not limited to impeller mixing, static mixing, sonic mixing, and any combination thereof In some aspects, spent solids derived from material containing at least one metal of interest are filtered to obtain filtrate with reduced solids content or substantially no solids content. In some aspects, filtered solids areMOMT.P0003 WO / 1001367625 7washed with fresh, unused acid solution to improve extracted metal yields. In some aspects, filtering spent solids can be performed using a filter press. In some aspects, a filter aid, such as diatomaceous earth and / or a coagulant can be used during filtration to obtain filtrate with reduced solids content or substantially no solids content. Spent solids can be batch filtered, continuously filtered, or preferentially filtered in a semi-continuous manner.

[0017] Metal-containing solutions can include metals of interest and additional, unwanted or low-value metals, including but not limited to iron, zinc, aluminum, and copper. At least a portion of unwanted metals can be removed from a solution comprising at least one metal of interest in order to reduce unwanted metal burden on extractant and extraction membranes. In some aspects, low-value metals or impurities, such as iron, zinc, aluminum, and other non-target metals can be removed from a feed solution by adjusting the pH of the feed solution to precipitate unwanted metals. In some aspects, low-value metals or impurities, such as iron, zinc, aluminum, and other non-target metals can be removed from a feed solution by adjusting the pH of the feed solution to a pH in the range of 4 to 6.5. In some aspects, the pH of a feed solution is adjusted to a pH value that is any one of, less than, greater than, or between 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, and 6.5, or any pH value derivable therein. In some aspects, the pH is adjusted using a lime slurry, or an aqueous solution of sodium hydroxide, potassium hydroxide, ammonium hydroxide, magnesium oxide, or other alkali solution, for example. In some aspects, the pH is adjusted using a saturated aqueous solution of sodium hydroxide or potassium hydroxide. In some aspects, the pH of the feed solution is adjusted to a pH level that maximizes removal of non-target metals and minimizes precipitation of metals of interest. Adjustment of the pH of the feed solution can be performed by controlled addition of an alkali solution to a mixed feed solution. Precipitated impurities can be removed from the pH-adjusted solution after pH-adjustment, continuously as precipitated impurities are generated, or continuously as the pH is increased. In some aspects, the pH is adjusted using an acidic solution. A basic or acidic solution can be used to adjust the pH of a feed based on a starting pH of the feed and a target pH of the feed.

[0018] A reducing agent can be used to reduce unwanted metal ion concentration prior to a metal extraction process. Treating metal ions with a reducing agent can increase the degree to which metal ions of interest are extracted from a solution comprising metal ions. In some aspects, a solution comprising metal ions is treated with a reducing agent. Non-limiting examples ofMOMT.P0003 WO / 1001367625 8reducing agents include hydrogen peroxide and sodium metabisulfite. In some aspects, the solution is contacted with a reducing agent using a recirculation loop equipped with a static mixer, ultrasonic head, or a combination thereof. In some aspects, the reducing agent is added downstream of the static mixer in the recirculation loop to economize the use of the reducing agent. The solution comprising metal ions can be recirculated into the recirculation loop to increase the grade of the feed solution and decrease the amount of free acid.

[0019] In some aspects, an oxidizing agent can be used to reduce unwanted metal ion concentration prior to a metal extraction process. For example, gaseous oxygen or air containing oxygen can be bubbled through a metal-containing solution to oxidize at least one metal. In some aspects, gaseous oxygen or air containing oxygen can be bubbled through a metal-containing solution to oxidize iron ions into iron oxide.

[0020] In some aspects, a membrane can be de-fouled by disconnecting a strip solution feed line from the membrane and draining the membrane of any solution or solvent contained therein. In some aspects, an organic solvent is fed through the membrane lumen. The organic solvent can clean the membrane lumen by removing contaminants that have fouled the membrane lumen and / or pores. In some aspects, the organic solvent used to remove contaminants includes no solute. In other aspects, the organic solvent used to remove contaminants includes one or more components, e.g., a surfactant or detergent, to aid in removal of contaminants. In some aspects, water or an aqueous solution is fed through the membrane lumen. The water or aqueous solution can clean the membrane lumen by removing contaminants that have fouled the membrane lumen and / or pores. In some aspects, the aqueous solution is a solution of an acid in water. In some aspects, the aqueous solution is a solution of a surfactant or a detergent.

[0021] After extended usage, the concentration of extractant immobilized in membrane pores can decrease, which reduces transport kinetics of target metal ions from the feed side to the strip side. The extractant immobilized in the membrane pores can be replenished by rewetting the membrane with a solution of extractant in an organic solvent.

[0022] As used herein, “black mass” refers to a type of waste material comprising used and / or unwanted lithium ion batteries. After removing structural and other non-functional components from end-of-life batteries, a black mass mixture is left. Black mass comprises batteryfunctional metals, including lithium, manganese, cobalt, nickel, copper, and zinc typically in theMOMT.P0003 WO / 1001367625 9form of oxides and / or salts, and can include additional battery materials, including anode separators, binders, additives and battery packaging. As used herein “e-waste” refers to discarded electrical or electronic devices. E-waste comprises metals used in electronic devices, including lithium, manganese, cobalt, nickel, copper, zinc, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. The foregoing metals can be included in e-waste as ground state metals, or in the form of oxides and / or salts.

[0023] As used herein, an “extractant” refers to a compound or group of compounds that is used to extract a substance from a material. In some aspects, the substance is a metal ion. In some aspects, the affinity of an extractant for a particular metal ion is pH-dependent. In some aspects, the affinity of an extractant for a particular metal ion is temperature-dependent. In some aspects, the extractant is an organic extractant that can extract at least one metal from an aqueous solution.

[0024] As used herein, the term "leaching" refers to the removal or extraction of a metal from a metal-containing composition. In some aspects, the metal-containing composition is a solution or mixture comprising the metal.

[0025] The terms “membrane” and “membrane bundle” and “bundle of membranes” are used interchangeably herein. A “membrane bundle” and a “bundle of membranes” are defined as a plurality of membranes or membrane fibers grouped together. A terminal portion of a membrane bundle can include an apparatus, e g., a cap with an inlet, to deliver a feed from a single feed source to the plurality of membranes or membrane fibers within the membrane bundle.

[0026] As used herein, the term "metal" includes metal salts, metal oxides, ground state metals, and metal ions. Examples of metals include lithium, cobalt, nickel, manganese, and copper. As used herein, the term "lithium" includes lithium metal, lithium salts, and oxides of lithium. As used herein, the term "cobalt" includes cobalt metal, cobalt salts, and oxides of cobalt. As used herein, the term "nickel" includes nickel metal, nickel salts, and oxides of nickel. As used herein, the term "manganese" includes manganese metal, manganese salts, and oxides of manganese. As used herein, the term "copper" includes copper metal, copper salts, and oxides of copper.MOMT.P0003 WO / 1001367625 10

[0027] The use of the word “a” or “an,” when used in conjunction with the term “comprising” in the claims and / or the specification may mean “one,” but it is also consistent with the meaning of “one or more,” “at least one,” and “one or more than one.”

[0028] Throughout this application, the term “about” is used to indicate that a value includes the inherent variation of error for the device, the method being employed to determine the value, or the variation that exists among the study subjects.

[0029] The terms “comprise,” “have” and “include” are open-ended linking verbs. Any forms or tenses of one or more of these verbs, such as “comprises,” “comprising,” “has,” “having,” “includes” and “including,” are also open-ended. For example, any method that “comprises,” “has” or “includes” one or more steps is not limited to possessing only those one or more steps and also covers other unlisted steps.

[0030] The above definitions supersede any conflicting definition in any reference that is incorporated by reference herein. The fact that certain terms are defined, however, should not be considered as indicative that any term that is undefined is indefinite. Rather, all terms used are believed to describe the disclosure in terms such that one of ordinary skill can appreciate the scope and practice the present disclosure.

[0031] It is specifically contemplated that any limitation discussed with respect to one embodiment of the disclosure may apply to any other embodiment of the disclosure. Furthermore, any composition of the disclosure may be used in any method of the disclosure, and any method of the disclosure may be used to produce or to utilize any composition of the disclosure.

[0032] Other objects, features and advantages of the present disclosure will become apparent from the following detailed description. It should be understood, however, that the detailed description and the specific examples, while indicating preferred embodiments of the disclosure, are given by way of illustration only, since various changes and modifications within the spirit and scope of the disclosure will become apparent to those skilled in the art from this detailed description.BRIEF DESCRIPTION OF THE DRAWINGS

[0033] FIG. l is a schematic that depicts steps involved in extraction of metals from a feed solution into a strip solution. A bundle of hollow fiber membranes is placed into a tank containingMOMT.P0003 WO / 1001367625 11the feed solution, and a strip solution is passed through the membrane lumen. An extractant immobilized in the membrane lumen facilitates transfer of the metals from the feed solution into the mobile strip solution.

[0034] FIG. 2 is a schematic that depicts a method for leaching metals from used lithium- ion batteries. The metals are leached from black mass obtained from used lithium-ion batteries The metal-enriched solution can be used as a feed solution for a metal extraction process.

[0035] FIG. 3 is a schematic that depicts a method for precipitating low-value metals.

[0036] FIGS. 4A-4C. FIG. 4A depicts a plate that includes a flat sheet membrane coupled to a frame. FIG. 4B depicts a spacer frame to which no membrane is coupled; the frame includes holes which can be used to secure spacer frame to other plates or frames. FIG. 4C depicts a plate and frame membrane metal extraction system that includes a series of plates and spacer frames arranged in an alternating relationship.

[0037] FIGS. 5A-5C. FIG 5A depicts a hollow fiber membrane plate. FIG. 5B depicts a spacer frame that includes a frame, a mesh or grate, and a plurality of holes through which a feed solution can be plumbed. FIG. 5C depicts plate-supported hollow fiber membrane metal recovery system that employs a series of hollow fiber membrane plates and spacer frames arranged in an alternating relationship.DETAILED DESCRIPTION

[0038] Embodiments of the disclosure include modular, energy-efficient, and relatively inexpensive methods for extraction and enrichment of metals from scrap materials, including, but not limited to, waste batteries, electronic waste (i.e., e-waste), ‘black mass’ and materials such as mixed hydroxide precipitates at an industrial scale. The methods are premised on the use of freestanding or unhoused metal-extraction membranes that can be arranged in a variety of configurations. The methods enable a metal-extraction engineer to design and build customized metal extraction systems that are not limited by design constraints associated with traditional cartridge-based extraction membranes. The methods disclosed herein can be used to recover up to 99.9% pure lithium, nickel, cobalt, manganese, copper, etc., in the form of various oxides, hydroxides, or salts, including but not limited to sulfate, chloride, and nitrate salts.MOMT.P0003 WO / 1001367625 12

[0039] During an extraction process, a membrane as disclosed herein is placed in tank containing a feed solution that contains at least one metal of interest such that at least a portion of the membrane is submerged in the feed solution. A strip solution is then pumped through the lumen of the membrane residing in the feed solution. The use of a single mobile phase, e.g., the mobile strip solution, reduces viscous or diffusive transport between the mobile strip solution and the feed solution, as compared to a conventional extraction system where both the strip solution and feed solution are induced to flow orthogonally through an extraction membrane. The methods disclosed herein employ membranes that do not require a pressurized outer shell or housing, and this allows the feed solution to be maintained at lower pressures than conventional extraction systems where both the feed and strip solutions are pressurized. The strip solution is pumped through the lumen of the unhoused membrane at a higher pressure than the feed solution, which reduces the degree to which unwanted metals and other contaminants in the feed solution traverse the membrane pores through viscous or diffusive transport and contaminate the strip solution.

[0040] The methods disclosed herein employ relatively small amounts of chemicals, energy, and labor, and the solvent and extractant requirements, in particular, are relatively low compared to traditional methods. This reduces the need for large inventories and use of expensive reagents and associated losses. The methods disclosed herein also significantly improve the safety profile of conventional metal extraction processes by reducing the bulk handling and storage of dangerous and flammable substances. This system allows for a fully continuous operation and allows for faster scale-up at lower costs.BLACK MASS

[0041] “Black mass” refers to a powder made from processed lithium batteries. Black mass can include electrode active materials, polymeric binder, residual aluminum and copper current collection material, and other residual particulates. The chemical composition of black mass depends upon the components and chemical nature of the lithium ion batteries processed into black mass. Black mass can comprise any material, or combination of materials, selected from the group consisting of lithium, lithium compounds, aluminum, aluminum compounds, nickel, nickel compounds, zinc, zinc compounds, cadmium, cadmium compounds, copper, copper compounds, lead, lead compounds, graphite, and polymeric binder.MOMT.P0003 WO / 1001367625 13

[0042] In some aspects, a slurry is made from the black mass. The term “slurry” as used herein refers to any fluidized suspension or dispersion of black mass, including, for example, aqueous liquid slurries, non-aqueous liquid slurries, and mixed-solvent liquid slurries. Additional processing steps can be performed prior to or after formation of a black mass slurry, including but not limited to solvent wash treatment, water rinse treatment, froth flotation treatment, mechanical dispersion, and / or ultrasonic dispersion.

[0043] In some aspects, black mass is treated with a wash solvent to dissolve and remove polymeric electrode binder, such as, for example, polyvinylidene fluoride, from the electrode active materials (e.g., graphite, lithium metal compounds, nickel oxyhydroxide, and the like). Suitable wash solvents include, for example, N-methyl-2-pyrrolidone, tetrahydrofuran, ethanol, dimethyl carbonate , diethyl carbonate, dimethyl acetamide, diethyl formamide, methyl isobutyl ketone, and combinations of any thereof. Alternatively, or in addition, black mass may be treated with a water rinse before, after, or instead of a solvent wash treatment. Alternatively, or in addition, black mass may be heat treated or subject to a pyrolysis treatment. For example, black mass may be exposed to elevated temperatures in air or other oxidizing environments. Heat or pyrolysis treatments may be performed at environmental temperatures of at least 300 °C, for example.

[0044] In some aspects, black mass may be subjected to a froth floatation treatment to remove lead and lead compounds from the black mass, which may be inadvertently or intentionally present due to the presence of lead-acid batteries in scrap battery input to the processes and systems. In some aspects, black mass comprising Pb (II) and Pb (IV) compounds may be suspended in water in a froth flotation vessel with a froth flotation agent and sparged with air to entrain hydrophobically-modified lead compound materials and float the lead-based materials out of the vessel, thereby removing the lead-based materials from the black mass.

[0045] The production of a black mass slurry can include the dispersion or suspension of black mass in a carrier fluid. Carrier fluids include liquids such as, for example, water, alcohols, hydrocarbons, condensed carbon dioxide, and the like, and gases such as, for example, air, nitrogen, carbon dioxide, and the like. In some aspects, a slurry can include a black mass content that is any one of, less than, greater than, or between 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, and 60 percent by mass of black massMOMT.P0003 WO / 1001367625 14content, or any value derivable therein. In some aspects, a black mass slurry may be subjected to an ultrasonic dispersion operation to break-up particle agglomerates and reduce particle size. In some aspects, the production of an aqueous liquid slurry comprising black mass may use distilled and / or deionized, pH-neutral water to maintain the chemistry of the constituent electrode active material particles. In some aspects, the dispersion or suspension of the black mass in a carrier fluid employs mixing equipment to maintain particles in dispersion or suspension and avoid accumulation of non-dispersed or non-suspended particles.ELECTRONIC WASTE

[0046] As used herein, electronic waste or e-waste refers to discarded electrical or electronic devices. Examples of different classes of e-waste include discarded large household appliances, small household appliances, industrial technology equipment, lamps and luminaries, toys, tools, medical devices, monitoring and control instruments, and automatic dispensers. Nonlimiting examples of specific e-waste products include discarded refrigerators, washing machines, microwaves, heaters, fans, air fryers, cell phones, desktop computers, laptop computers, electronic tablets, circuit boards, hard drives, video disc players, televisions, fax machines, video game systems, copiers, printers, remote controls, electrical cords, treadmills, smart watches, heart monitors, electronic diabetes testing equipment, dialysis machines, imaging machines, power strips, power distribution systems, and defibrillators.LITHIUM ION BATTERIES

[0047] As used herein, a lithium ion cell refers to the single or basic electrochemical unit that contains the base components of electrodes (cathode and anode), separator, and electrolyte. The cathode can include a metal oxide and can include an aluminum foil as a cathode plate covered with cobalt nickel alloy, lithium cobalt oxide (LCO), lithium iron phosphate, lithium manganese oxides, lithium fluoride phosphate (LFP), lithium moly oxide (LMO), nickel cobalt oxide (NCO) or other metal oxides. The anode can include a copper foil as the anode plate covered with graphite or some other carbon-based material, such as graphene. The electrolyte can include a mixture of organic solvents, organic polymers, phosphates, fluorides and lithium salts. A common electrolyte component is lithium phosphate fluoride (LiPFe). The cathode and anode are commonly separated by a polymeric separator, such as a polypropylene or polyethylene.MOMT.P0003 WO / 1001367625 15

[0048] In the case of a common lithium-ion cell, this basic unit may employed in any form. Non-limiting lithium-ion cell arrangements include cylindrical, prismatic, and pouch units. A lithium ion battery is a collection of lithium ion cells within an appropriate housing. The lithium ion batteries that can be used in the methods disclosed herein include simple batteries, such as a single-cell phone battery, and complex batteries, such as an electric vehicle battery that includes thousands of cells in a collection of separate modules. In some aspects, essentially the entire lithium ion battery or lithium ion battery cell can be processed in order to extract and recover metals of interest. The terms “cell” and “battery” are used interchangeably herein. The terms “cells” and “batteries” are used interchangeably herein.EXTRACTION EQUIPMENT

[0049] The methods disclosed herein can employ different types of membranes for metal extraction. Membrane configurations used for the membrane extraction processes disclosed herein include hollow fiber membranes, tubular membranes, spiral-wound membranes, plate and frame membranes, and any other membrane geometry. Materials employed in extraction membranes include any material that is compatible with feed and strip solutions, and organic extractant-diluent immobilized in the porous membrane structure. Non-limiting examples of materials employed in extraction membranes include porous plastic membranes including but not limited to polyethylene, polypropylene, polytetrafluoroethylene, porous metal membranes, glass filter, ceramic filter, paper filter, fibrous filters, and porous membranes obtained by expanding a thermoplastic crystalline polymer. In some aspects, material used for the construction of the membrane is selected such that the constructed membrane allows surface tension-mediated adhesion between the organic extractant-diluent solution and the vast majority of membrane pores. Membrane pore size and membrane material of the membrane can be varied to allow for optimized immobilization of extractant within the membrane pores.

[0050] With respect to membrane housing, the free-standing and unhoused membranes disclosed herein are configured such that at least 50 % of an exterior surface area of the membrane is exposed, where the exposed surface is in contact with a liquid in which it is submerged. Thus, it is contemplated that an amount of exterior surface area of a membrane that is exposed such that this membrane surface contacts a liquid in which it is submerged may be any one of, less than, greater than, or between 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68,MOMT.P0003 WO / 1001367625 1669, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, and 100 %, or any range derivable therein.

[0051] Membrane pore sizes can range from 1 nm to 1 micrometer. Thus it is contemplated that the membrane pore size may be any one of, less than, greater than, or between 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33,34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59,60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85,86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 110, 120, 130, 140, 150, 160, 170, 180,190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370,380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560,570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690, 700, 710, 720, 730, 740, 750,760, 770, 780, 790, 800, 810, 820, 830, 840, 850, 860, 870, 880, 890, 900, 910, 920, 930, 940,950, 960, 970, 980, 990, and 1,000 nm (1 pm), or any range derivable therein.

[0052] The membranes disclosed herein can be arranged as single membranes, or bundles of membranes. In some embodiments, a bundle of membrane includes a plurality of membrane fibers. In other embodiments, a bundle of membranes includes a plurality of individual membranes. Thus it is contemplated that a membrane bundle can include a number of individual membranes or membrane fibers that is any one of, less than, or greater than 1, 2, 3, 4, 5, 6, 7, 8, 9,10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61,62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87,88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380,390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570,580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690, 700, 710, 720, 730, 740, 750, 760,770, 780, 790, 800, 810, 820, 830, 840, 850, 860, 870, 880, 890, 900, 910, 920, 930, 940, 950,960, 970, 980, 990, 1,000, 1,500, 2,000, 2,500, 3,000, 3,500, 4,000, 4,500, 5,000, 5,500, 6,000, 6,500, 7,000, 7,500, 8,000, 8,500, 9,000, 9,500, 10,000, 11,000, 12,000, 13,000, 14,000, 15,000, 20,000, 25,000, 30,000, 35,000, 40,000, 45,000, and 50,000, or any integer value therein.MOMT.P0003 WO / 1001367625 17

[0053] The membranes or membrane fibers disclosed herein can have a length ranging from 1 inch to 15 feet. Thus it is contemplated that membrane length may be any one of, less than, greater than, or between 1 inch, 2 inches, 3 inches, 4 inches, 5 inches, 6 inches, 7 inches, 8 inches,9 inches, 10 inches, 11 inches, 12 inches, 2 feet, 3 feet, 4 feet, 5 feet, 6 feet, 7 feet, 8 feet, 9 feet,10 feet, 11 feet, 12 feet, 13 feet, 14 feet, and 15 feet in length, or any range derivable therein.A. HOLLOW FIBER MEMBRANES

[0054] Hollow fiber membranes are membranes that comprise a porous tube or hollow fiber. Hollow fiber membranes work through tangential cross-flow, and can be provided as a bundled group of parallel plurality of porous tubes or hollow fibers. The hollow fiber membranes disclosed herein typically do not include a housing or shell, and are therefore unhoused hollow fiber membranes. Hollow fiber membranes may comprise different membrane materials, membrane thicknesses, membrane pore sizes, lengths, and diameters to adapt the hollow fiber membrane to different applications.

[0055] Prior to use in a metal extraction process and an extractant is immobilized within the porous wall(s) of a hollow fiber membrane. At least a portion of the unhoused hollow fiber membrane is placed into a feed solution comprising at least one metal of interest. A strip solution passes through the lumen(s) unhoused hollow fiber membrane tube(s) or fiber(s), and metals of interest are transferred from the feed solution to the strip solution, a process that is facilitated by the extractant within the porous wall.

[0056] In some aspects, the hollow fiber membranes disclosed herein do not comprise a housing or a shell such that at least 50% of an exterior surface area of the tube or hollow fiber wall is exposed. In some aspects, at least 50% of an exterior surface area of the unhoused tube or hollow fiber wall come into direct contact with a liquid in which at least a portion of the unhoused tubular membrane is submerged. In some aspects, a plurality of tubes or hollow fibers are bundled together such that at least 50% of an exterior surface area of the plurality of tube or hollow fiber walls are exposed. In some aspects, at least 50% of an exterior surface area of the plurality of tubular walls will come into direct contact with a liquid in which an unhoused tubular membrane comprising a plurality of tubes or hollow fibers is submerged.MOMT.P0003 WO / 1001367625 18B. TUBULAR MEMBRANES

[0057] Tubular membranes are tube-like structures with porous walls with diameters that are typically larger than that of hollow fiber membranes. In some aspects, tubular membranes are used to process feed streams with high dissolved solids and / or high suspended solids. Tubular membranes may comprise different membrane materials, membrane thicknesses, membrane pore sizes, lengths, and diameters to adapt the tubular membrane to different applications.

[0058] Prior to use in a metal extraction process and an extractant is immobilized within the porous wall. At least a portion of the unhoused tubular membrane is placed into a feed solution comprising at least one metal of interest. A strip solution is pumped through the unhoused tubular membrane lumen, and metals of interest are transferred from the feed solution to the strip solution within the tubular membrane lumen, a process that is facilitated by the extractant within the porous wall.

[0059] In some aspects, the unhoused tubular membranes disclosed herein do not comprise a housing or a shell such that at least 50% of an exterior surface area of the tubular wall is exposed. In some aspects, at least 50% of an exterior surface area of the unhoused tubular wall comes into direct contact with a liquid in which at least a portion of the unhoused tubular membrane is submerged. In some aspects, a plurality of tubular membranes are bundled together such that at least 50% of an exterior surface area of the plurality of tubular membrane walls are exposed. In some aspects, at least 50% of an exterior surface area of the plurality of tubular walls will come into direct contact with a liquid in which at least a portion of the unhoused tubular membranes are submerged.C. SPIRAL-WOUND MEMBRANES

[0060] Spiral-wound filtration membranes are porous membranes that can include a feed spacers, permeate spacer, and a permeate tube. An exemplary method for assembly of a spiralwound membrane can include the following steps. First, a membrane is laid out and folded in half. A feed spacer is then put in between the folded membrane portions, forming a membrane sandwich. The feed spacer provides a space for a fluid to flow between the membrane surfaces, and allows for uniform flow between the membrane leaves. A permeate spacer is attached to a permeate tube, and the membrane sandwich is attached to the permeate spacer. A subsequent permeate layer is laid down and sealed, and the process is repeated until all of the requiredMOMT.P0003 WO / 1001367625 19permeate spacers have been attached to the membranes. The finished membrane layers then are wrapped around the tube creating a spiral shape. The resulting spiral-wound membrane does not include a housing or shell. Spiral-wound membranes may comprise different spacers, permeate tubes, membrane materials, membrane thicknesses, membrane pore sizes, lengths, and diameters to adapt the spiral-wound membrane to different applications.

[0061] Prior to use in a metal extraction process and an extractant is immobilized within the porous membrane walls of the spiral-wound membrane. At least a portion of the unhoused spiral-wound membrane is placed into a feed solution comprising at least one metal of interest. A strip solution travels through the flow channels between the membrane leaves along the length of the spiral-wound membrane. The extractant within the porous membrane walls facilitates transport of metal ions of interest between the feed solution and the mobile strip solution.D. FLAT SHEET MEMBRANES

[0062] Flat sheet membranes coupled with plate and frame separators are referred to as plate and frame membranes, and can be employed in the methods disclosed herein. A series of flat sheet membranes coupled with plate and frame separators can be employed by passing a strip solution through a membrane lumen that exists between adjacent parallel membranes. Flat sheet membranes may comprise different frames with different mesh sizes, feed line cavities, tubes connecting feed line cavities, membrane materials, membrane thicknesses, membrane numbers, membrane pore sizes, and membrane lengths and widths to adapt the plate and frame membrane to different applications.

[0063] Prior to use in a metal extraction process and an extractant is immobilized within the flat sheet membrane material. At least a portion of the flat sheet membrane is submerged within a feed solution comprising at least one metal of interest. One face of the flat sheet membrane is contacted with a feed solution comprising at least one metal of interest, and a strip solution contacts an opposite face of the flat sheet membrane. The extractant within the porous membrane walls facilitates transport of metal ions of interest from the feed solution on one face of the flat sheet membrane to the strip solution on the opposite face of the flat sheet membrane.MOMT.P0003 WO / 1001367625 20EXTRACTANTS

[0064] The extractants employed herein can be temperature-dependent or temperatureindependent extractants. The extractants employed herein can be pH-dependent or pH-independent extractants. Non-limiting examples of extractants useful in the present disclosure include, for example, aldoxime and ketoxime extractants such as the Acorga® series of extractants, phosphinic acid-based extractants such as the Cyanex® series of extractants, P-di ketones such as acetyl acetone, trifluoroacetylacetone, dibenzoylmethane, thenoyltrifluoroacetone (TTA or HTTA), quinolines such as 8-hydroxyquinoline (oxine), oximes and dioximes such as N- nitrosophenylhydroxylamine ammonium (cupferron), N-benzoyl-N-pheynlhydroxylamine (NBPHA), and N-furoylphenylhydroxylamine, dithizones, di-(2-ethylhexyl)phosphoric acid (D2EHPA), and any combination thereof.A. Examples

[0065] Referring to FIG. 1, a method 100 for recovering metals can include the following steps. At step 110, an organic extractant-diluent solution is fed through a bundled plurality of hollow fiber membranes in order to immobilize dissolved extractant in the pores of the membranes. At step 120, the bundled plurality of hollow fiber membranes is placed in a tank containing a feed solution containing at least one dissolved metal of interest. The external surfaces of the hollow fibers are exposed to the feed solution, which contains a mixture of dissolved metal ions. At step 130, extractants immobilized within the membrane pores coordinates to metals dissolved in the feed solution and extracts the metals from the feed solution. At step 140, an acidic strip solution is passed through the lumen of the hollow fibers. The mobile strip solution passes through the membrane lumen and comes into contact with extractant-metal complexes immobilized in the membrane pores. At step 150, the metals are then transferred from the extractant-metal complexes to the mobile strip solution, and this metal transfer driven by the increased solubility of the dissolved metals in the acidic strip solution. At step 160, the metal-enriched strip solution exits the membrane bundle lumen after having passed through the length of the membranes, and is collected.

[0066] Referring to FIG. 2, a method 200 for leaching metals from used lithium-ion batteries is described. At step 210, used lithium-ion batteries are ground into a black mass. At step 220, the black mass is placed into an acidic solution. The aqueous acid solution becomes enrichedMOMT.P0003 WO / 1001367625 21with metal ions leached from the black mass. The extent of leaching is controlled to maximize leaching yield. At step 230, the acid solution is mixed in order to maximize the leaching yield of metals. At step 240, the metal-enriched acid solution is collected. At step 250, remaining solids are filtered to additional metals remaining in the solids. The spent solids are washed with fresh acid solution to extract remaining metals within the spent solids. At step 260, filtrate is combined with the metal-enriched acid solution previously obtained. The combined metal -enriched solutions can be used as a feed solution in a metal extraction process.

[0067] Referring to FIG. 3, a method 300 for precipitating low-value metals, including iron, zinc, and aluminum, is described. At step 310, used lithium-ion batteries are ground into a black mass. At step 320, a black mass slurry is prepared by mixing the black mass in water. At step 330, the pH of the black mass slurry is increased using a solution of sodium hydroxide and low-value metals are precipitated. At step 340, precipitated impurities are removed from the pH- adjusted slurry by fdtration. At step 350, the filtrate is collected. The filtrate includes significantly- reduced concentration of low -value metals, in comparison to the lack mass slurry.

[0068] Referring to FIGS. 4A-4C, an embodiment of a series of flat sheet membranes, and a method for recovering metals using a series of flat sheet membranes are described. Depicted in FIG. 4A includes a plate 400 that includes a flat sheet membrane 401 coupled to a frame 402. Plate 400 includes holes 403 which can be used to secure plate 400 to other plates and / or frames. FIG. 4B includes a spacer frame 410 to which no membrane is coupled. Frame 410 includes holes 413 which can be used to secure spacer frame 410 to other plates or frames. Referring to FIG. 4C, a series of plates 400 and spacer frames 410 are arranged in an alternating relationship within plate and frame membrane metal extraction system 420. Spacer frames 410 create a space or volume between membranes of adjacent plates 400 such that an inter-membrane lumen is created between adjacent plates 400. End plate 424 includes holes 423 that can be used to secure end plate 424 to a spacer frame 410 or a plate 400. In operation, a feed solution 421 and a strip solution 422 are provided through alternating inter-membrane lumens. This creates an alternating arrangement of feed and strip solution volumes residing within alternating inter-membrane lumens. When feed and strip solutions are provided to metal extraction system 420, at least a portion of each membrane is submerged in a feed solution comprising at least one metal cation. Extractant immobilized within flat sheet membranes 401 facilitates transfer of metals of interest from feed solution to strip solution. Metal-enriched strip solution is collected after at least a portion off the strip solution hasMOMT.P0003 WO / 1001367625 22traversed the membrane lumen, and at least one metal of interest is recovered from the metal- enriched strip solution.

[0069] Referring to FIGS. 5A-5C, an embodiment of a hollow fiber membrane metal recovery system using plate-supported hollow fiber membranes is described. FIG. 5A depicts a hollow fiber membrane plate 500. Hollow fiber membrane plate 500 includes frame 502 and an array of hollow fiber membranes 504 coupled to hollow fiber membrane array inlet 505 and hollow fiber membrane array outlet 506. Frame 502 includes a plurality of holes 503 through which a feed solution can be plumbed. FIG. 5B depicts a spacer frame 510 that includes frame 511, mesh or grate 512, and a plurality of holes 513 through which a feed solution can be plumbed. Referring to FIG. 5C, a series of hollow fiber membrane plates 500 and spacer frames 510 are arranged in an alternating relationship within plate-supported hollow fiber membrane metal recovery system 520. End plate 524 includes a hole 521 at each comer through which a feed solution can be plumbed. End plate holes 521 are coupled to hollow fiber membrane plate holes 503 and spacer frame holes 513 such that a feed solution can be plumbed through the holes and into an interior space of plate- supported hollow fiber membrane metal recovery system 520. Strip inlet line 522 is coupled to hollow fiber membrane array inlets 505 of each hollow fiber membrane plate 500. The hollow fiber membranes of hollow fiber membrane plates 500 are submerged in feed solution. Extractant immobilized within the hollow fiber membranes facilitates transfer of metals of interest from feed solution to strip solution. Metal-enriched strip solution exits fiber membrane array outlet 506, and outlets 506 are couples to strip outlet line 523. Metal-enriched strip solution is collected from strip outlet line 523, and at least one metal of interest is recovered from the metal -enriched strip solution.MOMT.P0003 WO / 1001367625 23

Claims

CLAIMS1. A method comprising: passing a strip solution through a membrane lumen of an unhoused porous membrane having an extractant immobilized on least a portion of the porous membrane, wherein at least a portion of the membrane is submerged in a feed solution comprising at least one metal cation; collecting the strip solution after at least a portion of the strip solution has traversed the membrane lumen, wherein the collected strip solution comprises at least a portion of at least one metal cation; and recovering the at least one metal cation from the collected strip solution.

2. The method of claim 1 , wherein an exterior portion of the unhoused porous membrane submerged in the feed solution is in direct contact with the feed solution.

3. The method of claim 1, wherein at least 50 % of an exterior surface area of the membrane submerged in the feed solution is in contact with the feed solution.

4. The method of claim 1, wherein the at least one metal cation is at least one metal cation from a used lithium-ion battery.

5. The method of claim 1, wherein a strip solution pressure is greater than a feed solution pressure.

6. The method of claim 5, wherein the feed solution is at atmospheric pressure.

7. The method of claim 1, further comprising passing a solution of extractant in an organic solvent through the membrane lumen to increase a concentration of immobilized extractant in the membrane pores.

8. The method of claim 1, wherein the feed solution is in a tank, wherein a net flux of feed solution through the tank volume is zero.MOMT.P0003 WO / 1001367625 249. The method of claim 8, wherein the feed solution in the tank is agitated.

10. The method of claim 1, wherein the at least one metal is selected from the group consisting of lithium, manganese, cobalt, nickel, copper, zinc, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.

11. The method of claim 1 , wherein the feed solution is treated to remove at least one unwanted metal prior to passing the strip solution through the membrane lumen.

12. The method of claim 11, wherein the at least one unwanted metal is selected from the group consisting of iron, zinc, aluminum, and copper.

13. The method of claim 11, wherein a pH of the feed solution is increased with an alkali to remove at least one unwanted metal.

14. The method of claim 13, wherein the alkali is selected from the group consisting of a lime slurry, a solution of sodium hydroxide, a solution of ammonium hydroxide, a solution of potassium hydroxide, a solution of magnesium oxide, and any combination thereof.

15. The method of claim 1, wherein a pH of the strip solution is lower than a pH of the feed solution.MOMT.P0003 WO / 1001367625 25

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