Lime assisted leaching of calcined metal concentrate for the recovery of lithium

Abstract

Set forth herein are slurries useful for extracting lithium, and other metals and materials, from both inert and live battery scrap, in which the slurries include calcium oxide, calcium hydroxide, hydrated-lime, carbon, or a combination thereof. Also set forth herein are processes and apparatuses for extracting lithium, and other metals and materials, from both inert and live battery scrap that is calcined, once or twice, and processed in a slurry that includes calcium oxide, calcium hydroxide, hydrated-lime, carbon, or a combination thereof.

Description

LIME ASSISTED LEACHING OF CALCINED METAL CONCENTRATEFOR THE RECOVERY OF LITHIUMCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to, and the benefit of, U.S. Provisional Patent Applications Nos. 63 / 573,342, filed April 2, 2024, and 63 / 740,213, filed December 30, 2024, the entire contents of each of which are herein incorporated by reference in their entirety for all purposes.FIELD

[0002] The present disclosure concerns the recycling of batteries, battery components, devices that include batteries, and other related electronic devices and materials.BACKGROUND OF THE INVENTION

[0003] The proliferation of rechargeable batteries for electronic devices, power tools, transportation vehicles, drones, robots, and more, has created a waste problem. The volume of batteries recycled annually has yet to meet or exceed the volume of batteries produced in the same period. This is partly the result of the technical challenges and expenses involved in the recycling of rechargeable batteries.

[0004] One reason battery recycling is challenging relates to the variety of materials that are used to make a battery. Rechargeable batteries include solid and liquid organic compounds, metals, and metal oxides. Each of these materials requires unique processing conditions to be recycled efficiently. One example is lithium recovery during battery recycling, in which certain forms of lithium are preferred for further downstream battery manufacturing.

[0005] For example, when battery scrap is mechanically separated and the components calcined, the majority of the lithium in the battery scrap is sequestered in the form of lithium carbonate. For certain types of batteries, such as high nickel cathode batteries, lithium carbonate (TUCOs) is not a suitable starting material from which to build a new battery. Instead, lithium hydroxide (LiOH) is the preferred starting material for making certain types of batteries and in particular battery cathode active materials. However, it is challenging to convert Li2CO3 into LiOH during battery recycling. Therefore, what is needed are battery recycling processes thatproduce LiOH from battery scrap, or that convert Li2COs into LiOH in one of the recycling process steps.

[0006] Set forth herein are compositions, processes, systems, and apparatus, that are useful for producing LiOH in battery recycling processes and that overcome other challenges in the field to which the instant invention pertains.SUMMARY OF THE INVENTION

[0007] In one embodiment, set forth herein is a process for recovering lithium (Li) from battery material, in which the process includes the following steps: (a) providing calcined metal concentrate in an aqueous slurry; (b) contacting the aqueous slurry with a hydrated lime slurry to form a third slurry; (c) forming lithium hydroxide; and (d) separating the lithium hydroxide from the third slurry.

[0008] In a second embodiment, set forth herein in an aqueous slurry that includes a combination of water; calcined metal concentrate; lithium carbonate; lithium oxide, graphite, an alkali material selected from calcium oxide, calcium hydroxide, hydrated- lime, or a combination thereof.

[0009] In a third embodiments, set forth herein is a process that includes reacting an aqueous slurry of calcined metal concentrate that includes lithium carbonate with an alkali material selected from calcium oxide, calcium hydroxide, hydrated-lime, or a combination thereof; and forming lithium hydroxide. This process forms lithium hydroxide, or a water-soluble form thereof, and calcium carbonate when the lithium carbonate reacts with the calcium oxide, calcium hydroxide, hydrated-lime, or a combination thereof, in water.

[0010] In a fourth embodiments, set forth herein is a process that includes (1) providing calcined metal concentrate that includes lithium carbonate by calcining inert or live battery scrap in a nonrefractory-lined rotary kiln; (2) reacting an aqueous slurry of the calcined metal concentrate that includes lithium carbonate with calcium oxide, calcium hydroxide, hydrated-lime, or a combination thereof; and (3) forming lithium hydroxide. This process forms lithium hydroxide, or a water-soluble form thereof, and calcium carbonate when the lithium carbonate reacts with the calcium oxide, calcium hydroxide, hydrated-lime, or a combination thereof, in water.

[0011] In a fifth embodiment, set forth herein is a cathode active material made using the lithium hydroxide made by a process herein.

[0012] In a sixth embodiment, set forth herein is a process for making a cathode active material using the lithium hydroxide made by a process herein.

[0013] In a seventh embodiment, set forth herein is lithium metal made using the lithium hydroxide made by a process herein.

[0014] Also set forth herein are apparatus configured to implement one or more processes disclosed herein.

[0015] Also set forth herein are apparatus, systems, and processes, for storing lithium hydroxide produced by a process herein.

[0016] Also set forth herein are processes for electroplating lithium metal using lithium hydroxide produced by a process herein.

[0017] Also set forth herein are batteries and electrochemical electrodes made using the lithium hydroxide or lithium metal produced by a process herein.

[0018] Also set forth herein is a process for purifying a lithium-containing brine, that includes (a) providing a brine that includes lithium hydroxide (LiOH); (b) adding lime (Ca(OH)2) to the brine; (c) optionally filtering the brine to remove precipitates; and (d) purifying the brine using nanofiltration.BRIEF DESCRIPTION OF DRAWINGS

[0019] FIG. 1 shows an aliquot of dried lithium hydroxide made from Example 4.

[0020] FIG. 2 shows an aliquot of dried lithium hydroxide made from Example 4.

[0021] FIG. 3 shows an x-ray diffraction pattern for the product of Example 4.

[0022] FIG. 4 shows an embodiment of a leaching and nanofiltration process. InFIG. 4, RNHC refers to reduced high nickel concentrate.

[0023] FIG. 5 shows an embodiment of a Multistage Nanofiltration and Impurity Precipitation Loop process for purifying crude lithium hydroxide brine. FIG. 5 details the Multistage Nanofiltration and Impurity Precipitation Loop process illustrated in FIG. 4

[0024] FIG. 6 shows an embodiment of a Multistage Nanofiltration process for purifying crude lithium hydroxide brine. FIG. 6 details the Multistage Nanofiltration process illustrated in FIG. 4.DETAILED DESCRIPTION OF THE INVENTION

[0025] Set forth herein are compositions, such as, but not limited to slurries, as well as processes, systems, and apparatus, for recycling batteries and battery scrap and recovering lithium hydroxide. These compositions, processes, systems, and apparatus, uniquely produce lithium hydroxide in high volume, high purity, and with high efficiency.

[0026] In the processes described herein, live batteries can be calcined to create inert batteries. The inert batteries as well as inert battery components, such as cathode active materials, battery production scrap, or other related scrap can be mechanically processed to separate metals, such as those in the current collectors, from the battery scrap that is later calcined to make calcined metal concentrate.

[0027] Live batteries are described herein as undergoing a first calcination, at 300 °C to 500 °C, to deactivate them and then a secondary calcination, at, in certain embodiments, 800 °C to 950 °C, to provide calcined metal concentrate. Other secondary calcination temperatures are contemplated herein. Following a secondary calcination of live battery materials, the produced material behaves in the alkaline leach, described below, similar to calcined material produced from inert production scrap. Calcining inert production scrap under reducing conditions in a rotary kiln at temperatures between 800 °C to950 °C in the presence of a sufficient amount of carbon produces a calcined metal concentrate with a portion of the lithium existing as lithium oxide and another portion existing as lithium carbonate. A sufficient amount of carbon is, but is not limited to, graphite at 30% by mass.

[0028] Aluminum and iron are metals that are often mechanically separated so as to avoid forming lithium aluminate or lithium ferrous compounds during the subsequent processes described herein. In certain embodiments, the mechanical separation of aluminum, iron, copper, or a combination thereof, occurs between each calcination step, meaning after the calcination step to deactivate the battery and before the secondary calcination. During calcination, the lithium present in cathode activematerials may be converted to lithium carbonate or lithium oxide. For example, Li in spinel lithium nickel manganese cobalt oxides may form lithium oxide during calcination processes. In subsequent processes, the lithium oxide can react with water to form lithium hydroxide. The lithium carbonate can be converted to lithium hydroxide by reacting the lithium carbonate with hydrated lime or other alkaline reagents.

[0029] In some examples, carbon in the form of graphite is present when the calcined metal concentrate is made by calcination. This carbon may come from anode active materials. Or the carbon may be recycled back into a calcination process herein after it has been separated from battery materials in another process. The carbon, e.g. graphite, is useful for forming carbon monoxide (CO). Mixed metal oxides, when calcined, will release oxygen (O2). The O2 reacts with carbon to form carbon dioxide (CO2) or carbon monoxide (CO). At higher temperatures, the reaction equilibrium shifts towards CO and produces less CO2. This shift in the equilibrium has the benefit of forming less lithium carbonate (Li2COs). This is because CO2 will react with Li to form Li2COs but CO won’t react with Li to form the same Li2COs. By shifting the equilibrium from CO2 to CO, less lithium carbonate is formed. CO will react with Li to form Li2O. And Li2O can react with water to form LiOH. Working at higher temperatures also accelerates the decomposition of mixed metal oxides such as cathode active materials.

[0030] By calcining at high temperatures, such as but not limited to 800 °C to 950 °C, the amount of CO2 decrease and the amount of CO increases. This is beneficial for avoiding, or at least minimizing, the formation of lithium carbonate, and also for accelerating the decomposition of the battery materials.

[0031] The processes described herein show it is possible to recover 70% to 90%, or 80% to 95%, or even higher percents, of the available lithium in battery materials. In certain processes, between 8 g / L to 15 g / L lithium are recovered from battery materials using the processes described herein.

[0032] The processes herein show that Li2COs can be converted to LiOH using hydrated lime as well as other alkaline reagents.DEFINITIONS

[0033] As used herein, the phrase “battery scrap,” refers to used batteries, such as but not limited to lithium-ion batteries, devices that include used batteries, as well as the components of used batteries such as the cathode active materials in a battery and / or the current collectors. Battery scrap also includes battery production scrap, which is scrap material used to make a battery but before a battery is actually made. For example, waste material produced during the making of a battery would be a type of battery production scrap. A used battery includes, but is not limited to, a battery that has been charged, discharged, or both, at least once. A used battery includes, but is not limited to, a battery that has been sold. Inert battery scrap includes battery scrap that cannot be charged or has been discharged, for example by calcining the battery scrap at about 300 °C or higher. Live battery scrap includes batteries that could still be charged or that still carry a charge. Live battery scrap necessarily includes both a cathode and an anode configured together as a battery. Inert battery scrap may include a cathode and an anode or may just include cathode active materials optionally with the current collector.

[0034] As used herein, the phrase “lithium-ion battery scrap,” refers to battery scrap as defined above that is, originates from, or includes a lithium-ion battery or a component thereof. Lithium-ion battery scrap includes, but is not limited to, cathode active materials, anode active materials, current collector materials, and other battery parts and components, such as but not limited to electrolytes.

[0035] As used herein, “calcining” or “calcination” refers to the process by which material is heated to a high temperature, e.g., a temperature over 80 °C, in order to decompose the material, removing volatile materials, discharge the materials, and / or change the physical or chemical structure of the material. A chemical structure change may include, but is not limited to, a carbonate converting into an oxide or vice versa. Herein, calcining typically occurs under reducing conditions such that oxidation reactions are limited.

[0036] As used herein, the phrase “calcined metal concentrate,” refers to battery scrap calcination products. Calcined metal concentrate refers to the combination of metals present in battery scrap after the battery scrap has been calcined in a reducing atmosphere. Calcined metal concentrate typically includes copper, aluminum, nickel,nickel oxides, cobalt oxides, lithium, lithium hydroxide, lithium carbonate, graphite, or combinations thereof.

[0037] As used herein, the “hydrated-lime,” refers to the solid hydration products resulting from contacting calcium oxide (z.e., lime, or CaO) with water. When calcium oxide reacts with water, a variety of species are formed, including on the surface of CaO particles. Hydrated-lime contains mostly Ca(OH)2 and may also include some CaO.

[0038] As used herein, a “nonrefractory -lined rotary kiln,” refers to a kiln that rotates and that is not lined with refractory materials. A rotary kiln is configured to raise the temperature of materials inside the kiln. A rotary kiln rotates along its longitudinal axis. As material moves into and out of the rotary kiln, the material is heated and mixed while being moved. “Refractory,” refers to the property of a non-metallic material to be resistant to heat and chemical degradation. Refractory materials also tend to maintain strength and rigidity at elevated temperatures. Certain ceramics are considered refractory materials but metals are not considered refractory materials. For example, certain ceramics may be heated to high temperatures in air without undergoing any chemical or physical changes. Metals, by contrast, tend to liquify if not also oxidize when heated to high temperatures in air. Metals conduct heat well whereas ceramics tend not to conduct heat well. Because of their resistance to heat, refractory materials are often used in certain kilns, furnaces, reactors, and vessels that transport molten metal.

[0039] As used herein, the phrase “reducing atmosphere” refers to reaction conditions that have less oxygen present than is present in the atmosphere on planet Earth. A reducing atmosphere may also include N2, H2, CO2, Ar, or a combination thereof. A reducing atmosphere has less than 10% by volume oxygen, and typically less than 4% by volume oxygen with the remainder being N2, CO2, Ar, hydrocarbons, or a combination thereof. A reducing atmosphere may also include hydrocarbons produced from battery reactions (e.g., decomposition, calcination, evaporation), N2, H2, CO2, Ar, or a combination thereof. A reducing atmosphere may include hydrocarbons evaporated or released from a battery or a device housing a battery.

[0040] As used herein, the phrase “steady-state condition,” or “steady-state reaction,” refers to a reaction, or set of reactions, in which all state variables are constant in spiteof ongoing processes that strive to change them. For example, in a rotary kiln, material exits while other material enters. Despite this change in material in and out, the temperature in the kiln remains constant due to the reactions occurring inside the rotary kiln, when steady-state conditions are achieved. In some examples, external energy may be applied to activate and achieve a steady-state condition, and then the heat may be removed or reduced as the steady-state is achieved and maintained. In a steady state reaction, the rate of product formation and reactant consumption are approximately equal. In certain embodiments, minimal to no heat (e.g., external, indirect heat) is required when the rotary kiln is operating at a steady-state. During a steady-state process, some nitrogen may be introduced into the rotary kiln to cool the system if too much heat is building up in the rotary kiln or if the rotary kiln exceeds a certain set-point temperature.

[0041] As used herein, the phrase “stoichiometric amount,” refers to the amount of one chemical relative to the amount of another chemical such that the amounts are the same. For example, a stoichiometric amount of calcium oxide relative to the amount of lithium carbonate, means that there are equal number of moles of calcium oxide and lithium carbonate. In certain processes disclosed herein, lithium carbonate (Li2CO3), calcium oxide (CaO), and water (H2O) react to form CaCO3and Li(OH)2 according to the following reaction:Li2CO3+ CaO + H2O 2LiOH+ CaCO3In the above equation, one mole of CaO is used for every mole of Li2CO3. In this example, if there was 5 moles of Li2CO3, the stoichiometric amount of CaO would also be 5 moles. As another example, in certain processes disclosed herein, lithium carbonate (Li2CO3) and calcium hydroxide (Ca(OH)2 react in water (H2O) to form CaCO3and Li(OH)2 according to the following reaction:Li2CO3+ Ca(OH)22LiOH+ CaCO3In the above equation, one mole of Ca(OH)2 is used for every mole of Li2CO3. Similarly, in this second example, if there was 5 moles of Li2CO3, the stoichiometric amount of Ca(OH)2 would also be 5 moles.

[0042] As used herein, the phrase “stoichiometric excess,” refers to the amount of one chemical relative to the amount of another chemical such that one amount is greaterthan its stoichiometric amount relative to the other chemical. For example, in the above examples, a stoichiometric excess of calcium oxide relative to lithium carbonate would include a molar amount of calcium oxide that exceeds the molar amount of lithium carbonate. Similarly, a stoichiometric excess of calcium hydroxide relative to lithium carbonate would include a molar amount of calcium hydroxide that exceeds the molar amount of lithium carbonate.

[0043] As used herein, the phrase “aqueous slurry,” refers to a slurry that is mixture of water and solids such as, but not limited to, calcined metal concentrate, CaO, Ca(OH)2, hydrated lime, and combinations thereof. Solid to water ratios are, unless specified otherwise, about 2% by weight to about 30% by weight. Solid to water ratios of 40% or higher may be difficult to stir and are not included herein as aqueous slurries, unless specified as such. The water portion of an aqueous slurry is referred to as the aqueous phase.SLURRIES

[0044] In an embodiment, set forth herein in an aqueous slurry that includes: water; calcined metal concentrate; lithium carbonate; and an alkali material selected from calcium oxide, calcium hydroxide, hydrated-lime, or a combination thereof. In certain embodiments, the alkali material is calcium oxide. In certain embodiments, the alkali material is calcium hydroxide. In certain embodiments, the alkali material is hydrated- lime. In certain of these embodiments, the aqueous slurry also includes lithium oxide. In certain of these embodiments, the aqueous slurry also includes lithium oxide and carbon. In certain of these embodiments, the aqueous slurry also includes lithium oxide and graphite. In certain of these embodiments, the aqueous slurry also includes graphite.

[0045] In some embodiments, including any of the foregoing, the calcined metal concentrate and lithium carbonate is provided by calcining battery scrap in a nonrefractory -lined rotary kiln. The battery scrap may be live batteries or may be inert batteries. The live batteries are often calcined once to deactivate them and then calcined again at a higher temperature to provide the calcined metal concentrate. Live batteries include both cathode and anode active materials. Inert batteries may include both cathode and anode active materials but also only include just cathode active materials. The lithium carbonate originates from lithium in the battery scrap.

[0046] In some embodiments, including any of the foregoing, the rotary kiln is lined with a metal such as, but not limited to, stainless steel, iron, copper, alloys thereof, or a combination thereof.

[0047] In some embodiments, including any of the foregoing, the calcining is in a reducing atmosphere. In some of these embodiments, the reducing atmosphere is inside a rotary kiln. The reducing atmosphere is useful to evaporate volatile compounds without combusting or oxidizing those compounds or other components in the battery scrap. In certain of these embodiments, the rotary kiln has an atmosphere that has less than 10% by volume oxygen. In some embodiments, the amount of oxygen is between 1% by volume and 10% by volume. In some embodiments, the amount of oxygen is 0% by volume. In some embodiments, the amount of oxygen is 1% by volume. In some embodiments, the amount of oxygen is 2% by volume. In some embodiments, the amount of oxygen is 3% by volume. In some embodiments, the amount of oxygen is 4% by volume. In some embodiments, the amount of oxygen is 5% by volume. In some embodiments, the amount of oxygen is 6% by volume. In some embodiments, the amount of oxygen is 7% by volume. In some embodiments, the amount of oxygen is 8% by volume. In some embodiments, the amount of oxygen is 9% by volume. In some embodiments, the amount of oxygen is 10% by volume.

[0048] In some embodiments, including any of the foregoing, the calcining is under steady-state conditions.

[0049] In some embodiments, including any of the foregoing, the aqueous slurry includes, or is mixed with a second slurry to include, a stoichiometric amount of calcium oxide, calcium hydroxide, hydrated-lime, or a combination thereof; relative to the amount of lithium carbonate. In some of these examples, the molar amount of calcium oxide used equals the molar amount of lithium carbonate in the slurry. In some of these examples, the molar amount of hydrated-lime used equals the molar amount of lithium carbonate in the slurry. In some of these examples, the molar amount of calcium hydroxide used equals the molar amount of lithium carbonate in the slurry. In these particular embodiments, the amount of CaO, Ca(OH)2, and hydrated-lime refers to the amount when the slurry is initially batched with the CaO,Ca(OH)2, and / or hydrated-lime. As time progresses, the CaO, Ca(OH)2, and hydrated- lime react with the Li2COs and therefore their amounts will change.

[0050] In some embodiments, including any of the foregoing, the aqueous slurry includes a stoichiometric excess of calcium oxide, calcium hydroxide, hydrated-lime, or a combination thereof; relative to the amount of lithium carbonate. In some of these examples, the molar amount of calcium oxide exceeds the molar amount of lithium carbonate in the slurry. Since calcium oxide will react in the slurry to form calcium carbonate and lithium hydroxide, the stoichiometric amounts are those amounts initially when the slurry is batched. In some of these examples, the molar amount of hydrated-lime used exceeds the molar amount of lithium carbonate in the slurry. In some of these examples, the molar amount of calcium hydroxide used exceeds the molar amount of lithium carbonate in the slurry. In some embodiments, the amount of excess is 100% of the amount needed to react with the lithium carbonate present in the slurry. In some embodiments, the amount of excess is 125% of the amount needed to react with the lithium carbonate present in the slurry. In some embodiments, the amount of excess is 150% of the amount needed to react with the lithium carbonate present in the slurry. In some embodiments, the amount of excess is 200% of the amount needed to react with the lithium carbonate present in the slurry. In some embodiments, the amount of excess is 250% of the amount needed to react with the lithium carbonate present in the slurry. In some embodiments, the amount of excess is 300% of the amount needed to react with the lithium carbonate present in the slurry. In some embodiments, the amount of excess is 350% of the amount needed to react with the lithium carbonate present in the slurry. In some embodiments, the amount of excess is 400% of the amount needed to react with the lithium carbonate present in the slurry. In some embodiments, the amount of excess is 450% of the amount needed to react with the lithium carbonate present in the slurry. Since hydrated-lime and / or calcium hydroxide will react in the slurry to form calcium carbonate and lithium hydroxide, the stoichiometric amounts are those amounts initially when the slurry is batched.

[0051] In some embodiments, including any of the foregoing, the calcined metal concentrate is sourced from non-live battery production scrap.

[0052] In some other embodiments, including any of the foregoing, the calcined metal concentrate is sourced from live battery production scrap that is calcined twice: once to deactivate the live battery production scrap and form inert scrap, and then again to form calcined metal concentrate.

[0053] In some embodiments, including any of the foregoing, the calcined metal concentrate includes Ni, Co, Mn, Cu, Al, Li, or combinations thereof. In certain embodiments, the calcined metal concentrate includes Ni, Co, Mn, or combinations thereof. In certain embodiments, the calcined metal concentrate includes Ni, Co, Al, or combinations thereof. In certain embodiments, the calcined metal concentrate includes Ni, Co, or combinations thereof.

[0054] In some embodiments, including any of the foregoing, the aqueous slurry includes 10 % to 30 % by weight solids. In some embodiments, the slurry further includes 4% to 8% by weight lime. In certain embodiments, the aqueous slurry includes 4% by weight solids. In certain other embodiments, the aqueous slurry includes 5% by weight solids. In some embodiments, the aqueous slurry includes 6% by weight solids. In some other embodiments, the aqueous slurry includes 7% by weight solids. In other embodiments, the aqueous slurry includes 8% by weight solids. In yet other embodiments, the aqueous slurry includes 9% by weight solids. In certain embodiments, the aqueous slurry includes 10% by weight solids. In certain other embodiments, the aqueous slurry includes 11% by weight solids. In some embodiments, the aqueous slurry includes 12% by weight solids. In certain embodiments, the aqueous slurry includes 13% by weight solids. In some other embodiments, the aqueous slurry includes 14% by weight solids. In other embodiments, the aqueous slurry includes 15% by weight solids. In yet other embodiments, the aqueous slurry includes 16% by weight solids. In certain embodiments, the aqueous slurry includes 17% by weight solids. In certain other embodiments, the aqueous slurry includes 18% by weight solids. In some embodiments, the aqueous slurry includes 19% by weight solids. In some other embodiments, the aqueous slurry includes 20% by weight solids. In yet other embodiments, the aqueous slurry includes 21% by weight solids. In certain embodiments, the aqueous slurry includes 22% by weight solids. In certain other embodiments, the aqueous slurry includes 23% by weight solids. In some embodiments, the aqueous slurry includes 24% by weight solids. In some otherembodiments, the aqueous slurry includes 25% by weight solids. In yet other embodiments, the aqueous slurry includes 26% by weight solids. In certain embodiments, the aqueous slurry includes 27% by weight solids. In certain other embodiments, the aqueous slurry includes 28% by weight solids. In yet other embodiments, the aqueous slurry includes 29% by weight solids. In some other embodiments, the aqueous slurry includes 30% by weight solids.

[0055] In some embodiments, including any of the foregoing, the CMC includes lithium carbonate and lithium hydroxide.

[0056] In some embodiments, including any of the foregoing, the aqueous slurry has a pH of 11 to 10.5. In some embodiments, including any of the foregoing, the aqueous slurry has a pH of 12 or lower. In certain embodiments, the aqueous slurry has a pH of 11 or lower. In certain embodiments, the aqueous slurry has a pH of 11. In certain embodiments, the aqueous slurry has a pH of 9.5. In certain embodiments, the pH of the aqueous slurry is buffered. In certain embodiments, the aqueous slurry has a buffered pH of 9.5.

[0057] In some embodiments, including any of the foregoing, the third slurry has a pH of about 13 to about 14.

[0058] In some embodiments, including any of the foregoing, the third slurry has a pH of 13, 13.5, or 15, optionally wherein the pH is buffered.

[0059] In some embodiments, including any of the foregoing, the lithium concentration in the aqueous slurry is 5 grams per liter or greater.

[0060] In some embodiments, including any of the foregoing, the lithium concentration in the aqueous slurry is 6.8 grams per liter or greater at 30% by mass solids.

[0061] In some embodiments, including any of the foregoing, the lithium concentration in the aqueous slurry is 4.7 grams per liter or greater at 10% by mass solids.

[0062] In some embodiments, including any of the foregoing, the lithium concentration in the aqueous slurry is 10 grams per liter or greater.PROCESSES

[0063] In an embodiment, set forth herein is a process for recovering lithium (Li) from battery material, in which the process includes the following steps: (a) providing calcined metal concentrate in an aqueous slurry; (b) contacting the aqueous slurry with a hydrated lime slurry to form a third slurry; (c) forming lithium hydroxide; and (d) separating the lithium hydroxide from the third slurry.

[0064] In the processes herein, carbon must be present during the calcination process. However, carbon may be introduced externally, for example, as added graphite. In other embodiments, carbon may be introduced as a component of the battery scrap. For example, if the battery scrap includes anode materials that include carbon, the carbon in the anode may be sufficient such that no additional carbon is necessary.

[0065] In some embodiments, including any of the foregoing, the calcined metal concentrate is formed by first calcining battery material that includes live battery scrap at a temperature of about 300 °C to about 500 °C to form a calcined material and then calcining the calcined material at a temperature of about 800 °C to 900 °C. In other embodiments, the calcined metal concentrate is formed by calcining battery material that includes inert battery scrap at a temperature of about 300 °C to 900 °C, wherein the inert battery scrap includes: (1) cathode material; or (2) both cathode material and anode material. In certain embodiments, the calcined metal concentrate is formed by first calcining battery material that includes live battery scrap at 300 °C. In certain other embodiments, the calcined metal concentrate is formed by first calcining battery material that includes live battery scrap at 400 °C. In certain embodiments, the calcined metal concentrate is formed by first calcining battery material that includes live battery scrap at 500 °C. In some of these embodiments, the calcined metal concentrate is formed by calcining battery material that includes inert battery scrap at a temperature of about 300 °C. In some other embodiments, the calcined metal concentrate is formed by calcining battery material that includes inert battery scrap at a temperature of about 400 °C. In certain embodiments, the calcined metal concentrate is formed by calcining battery material that includes inert battery scrap at a temperature of about 500 °C. In certain other embodiments, the calcined metal concentrate is formed by calcining battery material that includes inert battery scrap at a temperature of about 600 °C. In some of these embodiments, the calcined metal concentrate is formed by calcining battery material that includes inert batteryscrap at a temperature of about 700 °C. In some other embodiments, the calcined metal concentrate is formed by calcining battery material that includes inert battery scrap at a temperature of about 800 °C. In certain embodiments, the calcined metal concentrate is formed by calcining battery material that includes inert battery scrap at a temperature of about 900 °C.

[0066] In some embodiments, including any of the foregoing, the process includes mechanically separating metals selected from aluminum, iron, copper, or combinations thereof, from the battery material prior to calcining the battery material. In certain embodiments, the mechanical separation of aluminum, iron, copper, or a combination thereof, occurs between each calcination step, meaning after the calcination step to deactivate the battery and before the secondary calcination.

[0067] In some embodiments, including any of the foregoing, the cathode material includes nickel (Ni), cobalt (Co), manganese (Mn), aluminum (Al), or a combination thereof.

[0068] In some embodiments, including any of the foregoing, the aqueous slurry includes lithium oxide, graphite, or a combination thereof.

[0069] In some embodiments, including any of the foregoing, the aqueous slurry includes 20% by weight to 40% by weight carbon, optionally wherein the carbon is graphite. In certain embodiments, the aqueous slurry includes 20% by weight to 40% by weight carbon, optionally wherein the carbon is graphite. In certain embodiments, the aqueous slurry includes 20% by weight carbon, optionally wherein the carbon is graphite. In certain embodiments, the aqueous slurry includes 21% by weight carbon, optionally wherein the carbon is graphite. In certain embodiments, the aqueous slurry includes 22% by weight carbon, optionally wherein the carbon is graphite. In certain embodiments, the aqueous slurry includes 23% by weight carbon, optionally wherein the carbon is graphite. In certain embodiments, the aqueous slurry includes 24% by weight carbon, optionally wherein the carbon is graphite. In certain embodiments, the aqueous slurry includes 25% by weight carbon, optionally wherein the carbon is graphite. In certain embodiments, the aqueous slurry includes 26% by weight carbon, optionally wherein the carbon is graphite. In certain embodiments, the aqueous slurry includes 27% by weight carbon, optionally wherein the carbon is graphite. In certain embodiments, the aqueous slurry includes 28% by weight carbon, optionally whereinthe carbon is graphite. In certain embodiments, the aqueous slurry includes 29% by weight carbon, optionally wherein the carbon is graphite. In certain embodiments, the aqueous slurry includes 30% by weight carbon, optionally wherein the carbon is graphite. In certain embodiments, the aqueous slurry includes 31% by weight carbon, optionally wherein the carbon is graphite. In certain embodiments, the aqueous slurry includes 32% by weight carbon, optionally wherein the carbon is graphite. In certain embodiments, the aqueous slurry includes 33% by weight carbon, optionally wherein the carbon is graphite. In certain embodiments, the aqueous slurry includes 34% by weight carbon, optionally wherein the carbon is graphite. In certain embodiments, the aqueous slurry includes 35% by weight carbon, optionally wherein the carbon is graphite. In certain embodiments, the aqueous slurry includes 36% by weight carbon, optionally wherein the carbon is graphite. In certain embodiments, the aqueous slurry includes 37% by weight carbon, optionally wherein the carbon is graphite. In certain embodiments, the aqueous slurry includes 38% by weight carbon, optionally wherein the carbon is graphite. In certain embodiments, the aqueous slurry includes 39% by weight carbon, optionally wherein the carbon is graphite. In certain embodiments, the aqueous slurry includes 40% by weight carbon, optionally wherein the carbon is graphite.

[0070] In some embodiments, including any of the foregoing, the aqueous slurry includes 30% by weight carbon, optionally wherein the carbon is graphite.

[0071] In some embodiments, including any of the foregoing, the aqueous slurry includes 10% by weight solids to 30% by weight solids.

[0072] In some embodiments, including any of the foregoing, the aqueous slurry includes 15% by weight solids to 20% by weight solids.

[0073] In some embodiments, including any of the foregoing, the aqueous slurry includes 4% by weight solids to 8% by weight solids.

[0074] In some embodiments, including any of the foregoing, the aqueous slurry includes 13% by weight solids; 15% by weight solids; 20% by weight solids, 30% by weight solids; 44% by weight solids; or 45% by weight solids.

[0075] In some embodiments, including any of the foregoing, the aqueous slurry is heated to about 50 °C to about 90 °C before, while, or after, contacting the aqueous slurry with the hydrated lime slurry.

[0076] In some embodiments, including any of the foregoing, the aqueous slurry is heated to about 50 °C before, while, or after, contacting the aqueous slurry with the hydrated lime slurry.

[0077] In some embodiments, including any of the foregoing, the aqueous slurry is heated to about 60 °C before, while, or after, contacting the aqueous slurry with the hydrated lime slurry.

[0078] In some embodiments, including any of the foregoing, the aqueous slurry is heated to about 70 °C before, while, or after, contacting the aqueous slurry with the hydrated lime slurry.

[0079] In some embodiments, including any of the foregoing, the aqueous slurry is heated to about 80 °C before, while, or after, contacting the aqueous slurry with the hydrated lime slurry.

[0080] In some embodiments, including any of the foregoing, the aqueous slurry is heated to about 90 °C before, while, or after, contacting the aqueous slurry with the hydrated lime slurry.

[0081] In some embodiments, including any of the foregoing, the hydrated lime slurry includes about 5% by weight hydrated lime to about 20% by weight hydrated lime.

[0082] In some embodiments, including any of the foregoing, the hydrated lime slurry includes about 8% by weight hydrated lime or about 15% by weight hydrated lime.

[0083] In some embodiments, including any of the foregoing, the amount of hydrated lime in the hydrated lime slurry is equal to or greater than the molar amount required to react with lithium carbonate in the aqueous slurry.

[0084] In some embodiments, including any of the foregoing, the amount of hydrated lime in the hydrated lime slurry is about 125% the molar amount required to react with lithium carbonate in the aqueous slurry.

[0085] In some embodiments, including any of the foregoing, the hydrated lime slurry includes calcium oxide, calcium hydroxide, hydrated-lime, water, or combinations thereof.

[0086] In some embodiments, including any of the foregoing, the process includes adding the hydrated lime slurry: (al) in equal aliquots; (bl) over a period of 30 minutes to 8 hours; (cl) in a cascading reactor; (dl) for a residence time of about 3 hours; (el) in which the hydrated lime slurry is heated to about 75 °C; or (fl) a combination selected from the group consisting of (al), (bl), (cl), (dl), and (el).

[0087] In some embodiments, including any of the foregoing, the process includes cooling the third slurry to 50 °C or less.

[0088] In some embodiments, including any of the foregoing, the process includes cooling the third slurry to about room temperature.

[0089] In some embodiments, including any of the foregoing, the separating the lithium hydroxide includes filtering graphite, calcium carbonate, unreacted lime, metals, or a combination thereof, optionally: (a2) wherein the filter is a 2.5 pm filter; (b2) using pressure filtration; (c2) using vacuum filtration; or (d2) a combination selected from the group consisting of (a2), (b2), and (c2).

[0090] In some embodiments, including any of the foregoing, the process includes crystallizing the lithium hydroxide by evaporation under vacuum.

[0091] In some embodiments, including any of the foregoing, the process includes recovering at least 70% by weight of the lithium originally present in the battery material.

[0092] In some embodiments, including any of the foregoing, the process increases the concentration of LiOH and lithium ions (Li+) in the third slurry without increasing the concentration of aluminum ions (Al3+).

[0093] In some embodiments, including any of the foregoing, the process converts lithium carbonate into lithium hydroxide and forms calcium carbonate.

[0094] In some embodiments, including any of the foregoing, the third slurry has a pH of about 9 to about 12.

[0095] In some embodiments, including any of the foregoing, the third slurry has a pH of 9, 9.5, 10, 10.5, 11, 11.5, or 12, optionally wherein the pH is buffered.

[0096] In some embodiments, including any of the foregoing, the process includes removing impurities selected from the group consisting of fluorine, aluminum, calcium, silica, ions thereof, and combinations thereof, from the third slurry phase.

[0097] In some embodiments, including any of the foregoing, the process includes reducing the concentration of fluorine, aluminum, calcium, silica, ions thereof, and combinations thereof, in the third slurry to: (a3) less than 1 mg / L; (b3) less than 1% by mass; (c3) less than 0.01% by mass; or (d3) less than 0.001% by mass.

[0098] In some embodiments, including any of the foregoing, the process includes reducing the concentration of impurities in the third slurry to: (a4) aluminum (Al) at 800 ppm to 1000 ppm; (b4) fluorine (F) at 150 ppm to 250 ppm; (c4) calcium (Ca) at 5 ppm to 10 ppm; (d4) silicon (Si) at 500 ppm to 1000 ppm; or (e4) a combination selected from the group consisting of (a4), (b4), (c4), and (d4).

[0099] In some embodiments, including any of the foregoing, the process includes reducing the concentration of impurities in the third slurry to: (a5) Al at 100 ppm to 200 ppm; (b5) Si at 50 ppm to 150 ppm; or (c5) a combination of (a5) and (b5).

[0100] In some embodiments, including any of the foregoing, the calcined metal concentrate is formed by calcining battery material that includes inert battery scrap that includes cathode material or both cathode material and anode material at a temperature of about 300 °C to 900 °C; and the process further includes separating carbon, optionally as graphite, and recycling the carbon back into the aqueous slurry.

[0101] In some embodiments, set forth herein is a process that includes reacting an aqueous slurry of calcined metal concentrate that includes lithium carbonate with an alkali material selected from calcium oxide, calcium hydroxide, hydrated-lime, or a combination thereof, in water; and forming lithium hydroxide. In some embodiments, the lithium hydroxide is dissolved partially or completely in the slurry until later steps during which the lithium hydroxide is concentrated and optionally crystallized. In some of these embodiments, the process further includes recovering unreacted reagents. In some of these embodiments, the recovering unreacted reagents is accomplished by gravimetric separation. In some other embodiments, the recoveringunreacted reagents is accomplished by a method other than gravimetric separation. In certain embodiments, the unreacted reagent is unreacted lime.

[0102] In some embodiments, set forth herein is a process that includes reacting an aqueous slurry of calcined metal concentrate that includes lithium carbonate with an excess amount of an alkali material selected from calcium oxide, calcium hydroxide, hydrated-lime, or a combination thereof, in water; and forming lithium hydroxide; and then recovering unreacted reagents.

[0103] In some embodiments, including any of the foregoing, the calcined metal concentrate is provided by calcining battery scrap in a nonrefractory -lined rotary kiln.

[0104] In some embodiments, set forth herein is a process that includes, first, (1) providing calcined metal concentrate that includes lithium carbonate by calcining battery scrap in a nonrefractory-lined rotary kiln; then, (2) reacting an aqueous slurry of the calcined metal concentrate that includes lithium carbonate with calcium oxide, calcium hydroxide, hydrated-lime, or a combination thereof, in water; and thirdly, (3) forming lithium hydroxide.

[0105] The aforementioned process forms lithium hydroxide, or a water-soluble form thereof, and calcium carbonate when the lithium carbonate in the calcined metal concentrate reacts with the calcium oxide, calcium hydroxide, hydrated-lime, or a combination thereof, in water.

[0106] In certain embodiments, including any of the foregoing, the process occurs in the order in which the steps are recited.

[0107] In some embodiments, including any of the foregoing, the process includes reacting an aqueous slurry of the calcined metal concentrate that includes lithium carbonate with calcium oxide, calcium hydroxide, hydrated-lime, or a combination thereof, in water,

[0108] In some embodiments, including any of the foregoing, the process includes increasing the concentration of LiOH and lithium ions (Li+) in water but not increasing the concentration of aluminum ions (Al3+). This is because the CaO, Ca(OH)2, and hydrated lime selectively react with Li2COs to extract lithium.However, the CaO, Ca(OH)2, and hydrated lime do not react materially with the compounds in which aluminum is present.

[0109] In some embodiments, including any of the foregoing, the process further includes converting lithium carbonate into lithium hydroxide.

[0110] In some embodiments, including any of the foregoing, the amount of calcium oxide, calcium hydroxide, hydrated-lime, or a combination thereof, is a stoichiometric amount relative to the amount of lithium carbonate in the calcined metal concentrate.

[0111] In some embodiments, including any of the foregoing, the amount of calcium oxide, calcium hydroxide, hydrated-lime, or a combination thereof, is a stoichiometric excess amount relative to the amount of lithium carbonate in the calcined metal concentrate. The presence of lime in the slurries results in less soluble Al and Al compounds due to the pH of the slurry and the kinetics of reaction with Al.

[0112] In some embodiments, including any of the foregoing, the aqueous slurry has a pH of 12 or lower.

[0113] In some embodiments, including any of the foregoing, the aqueous slurry has a pH of 11 or lower.

[0114] In some embodiments, including any of the foregoing, the aqueous slurry has a pH of 11.

[0115] In some embodiments, including any of the foregoing, the aqueous slurry has a buffered pH of 9.5.

[0116] In some embodiments, including any of the foregoing, the process forms calcium carbonate (CaCCh).

[0117] In some embodiments, including any of the foregoing, the process includes removing or separating calcium carbonate (CaCCh) from the aqueous slurry.

[0118] In some embodiments, including any of the foregoing, the process occurs above room temperature.

[0119] In some embodiments, including any of the foregoing, the process occurs at less than 150°C.

[0120] In some embodiments, including any of the foregoing, the process occurs at less than 50°C.

[0121] In some embodiments, including any of the foregoing, the process occurs between 50°C and 90°C.

[0122] In some embodiments, including any of the foregoing, the process occurs above 150°C.

[0123] In some embodiments, including any of the foregoing, the process occurs above 150°C and at greater than atmospheric pressure.

[0124] In some embodiments, including any of the foregoing, the process occurs above 150°C and at a pressure less than 200 kPa.

[0125] In some embodiments, including any of the foregoing, the process occurs above 150°C and at a pressure less than 100 kPa.

[0126] In some embodiments, including any of the foregoing, the process further includes concentrating the lithium hydroxide. In certain embodiments, the concentrating occurs by evaporating water from the slurry.

[0127] In some embodiments, including any of the foregoing, the process further includes crystallizing the lithium hydroxide. In certain embodiments, the crystallizing occurs by evaporating water from the slurry.

[0128] In some embodiments, including any of the foregoing, the process includes separating graphite from the slurry.

[0129] In some embodiments, including any of the foregoing, the process includes removing fluorine, aluminum, ions thereof, and combinations thereof from the aqueous slurry. In some embodiments, this is accomplished by selective precipitation. In some embodiments, this is accomplished by ion exchange. In some embodiments, this is accomplished by extracting Li out of solution. In some embodiments, this is accomplished by adsorption resins.

[0130] In some embodiments, including any of the foregoing, the process includes removing fluorine, aluminum, ions thereof, and combinations thereof, to less than 1 mg / L water.

[0131] In some embodiments, including any of the foregoing, the process includes removing fluorine, aluminum, ions thereof, and combinations thereof, to less than 1% by mass from the aqueous phase.

[0132] In some embodiments, including any of the foregoing, the process includes removing fluorine, aluminum, ions thereof, and combinations thereof, to less than 0.01% by mass from the aqueous phase.

[0133] In some embodiments, including any of the foregoing, the process includes removing fluorine, aluminum, ions thereof, and combinations thereof, to less than 0.001% by mass from the aqueous phase.

[0134] In some embodiments, including any of the foregoing, the process includes removing fluorine, aluminum, ions thereof, and combinations thereof, to less than 0.001% by mass from the aqueous phase.

[0135] In some embodiments, including any of the foregoing, the process recovers greater than 40% by mass of the lithium content in the calcined metal concentrate.

[0136] In some embodiments, including any of the foregoing, the process recovers greater than 50% by mass of the lithium content in the calcined metal concentrate.

[0137] In some embodiments, including any of the foregoing, the process recovers greater than 60% by mass of the lithium content in the calcined metal concentrate.

[0138] In some embodiments, including any of the foregoing, the process recovers greater than 70% by mass of the lithium content in the calcined metal concentrate.

[0139] In some embodiments, including any of the foregoing, the process recovers 40% to 65% by mass of the lithium content in the calcined metal concentrate.

[0140] In some embodiments, including any of the foregoing, the process recovers 44% to 63% by mass of the lithium content in the calcined metal concentrate.

[0141] In some embodiments, including any of the foregoing, the process recovers greater than 80% by mass of the lithium content in the calcined metal concentrate.

[0142] In some embodiments, including any of the foregoing, the lithium concentration in the aqueous slurry is 5 grams per liter or greater. This is a concentration after the slurry is contacted with CaO, Ca(OH)2, hydrated lime, or a combination thereof, and has had time to react.

[0143] In some embodiments, including any of the foregoing, the lithium concentration in the aqueous slurry is 6.8 grams per liter or greater at 30% by masssolids. At 30% by mass solids means that 30% of the slurry is solid material, e.g., 30 g of solids in 100 g slurry. Percent (%) by mass in a slurry is also referred to as pulp density. This is a concentration after the slurry is contacted with CaO, Ca(OH)2, hydrated lime, or a combination thereof, and has had time to react.

[0144] In some embodiments, including any of the foregoing, the lithium concentration in the aqueous slurry is 4.7 grams per liter or greater at 10% by mass solids. This is a concentration after the slurry is contacted with CaO, Ca(OH)2, hydrated lime, or a combination thereof, and has had time to react.

[0145] In some embodiments, including any of the foregoing, the lithium concentration in the aqueous slurry is 10 grams per liter or greater. This is a concentration after the slurry is contacted with CaO, Ca(OH)2, hydrated lime, or a combination thereof, and has had time to react.

[0146] In some embodiments, including any of the foregoing, the process recovers greater than 40% by mass of the lithium content in the calcined metal concentrate.

[0147] In some embodiments, including any of the foregoing, the process recovers greater than 50% by mass of the lithium content in the calcined metal concentrate.

[0148] In some embodiments, including any of the foregoing, the process recovers 40% to 65% by mass of the lithium content in the calcined metal concentrate.

[0149] In some embodiments, including any of the foregoing, the process recovers 44% to 63% by mass of the lithium content in the calcined metal concentrate.

[0150] In some embodiments, including any of the foregoing, the process recovers greater than 80% by mass of the lithium content in the calcined metal concentrate.

[0151] Also disclosed herein is lithium hydroxide made by a process herein.USES OF LITHIUM HYDROXIDE

[0152] Also set forth herein are processes for making cathode active materials using lithium hydroxide made by a process herein.

[0153] In some embodiments, set forth herein is a process for making a cathode active material that includes using the lithium hydroxide made by a process herein to lithiate a cathode active material.

[0154] In some embodiments, the cathode active material is selected from the group consisting of lithium nickel manganese cobalt oxide, lithium nickel cobalt aluminum oxide, lithium cobalt oxide, lithium manganese oxide, lithium iron phosphate, lithium manganese iron phosphate, lithium titanate, and combinations thereof.

[0155] In some embodiments, the cathode active material is LiNixMnyCozO2 (NMC), wherein x+y+z =1 and 0<x<l, 0<y<l, and 0<z<l.

[0156] In some embodiments, the cathode active material is LiNixAlyCozO2 (NCA), wherein x+y+z =1 and 0<x<l, 0<y<l, and 0<z<l.

[0157] In some embodiments, the cathode active material is LiMPCk (M=Fe, Ni, Co, Mn).

[0158] In some embodiments, the cathode active material is LiMn2XNixO4, wherein x is from 0 to 2.

[0159] In some embodiments, the cathode active material is LixTiyOz, wherein x is from 0 to 8, y is from 1 to 12, z is from 1 to 24.

[0160] Also set forth herein are processes for reducing lithium hydroxide to lithium metal.

[0161] Also set forth herein are processes for contacting lithium hydroxide with liquid electrolytes.

[0162] Also set forth herein are processes for contacting lithium hydroxide with active materials.

[0163] Also set forth herein are processes for reacting lithium hydroxide with active materials, such as, but not limited to, lithium iron phosphate active materials, nickel manganese cobalt oxide active materials, manganese oxides, nickel oxides, cobalt oxides, and combinations thereof.APPARATUS

[0164] Also set forth herein are apparatus configured to implement a process disclosed herein.BATTERIES

[0165] Also set forth herein are batteries and cathode active materials made using the recycled lithium hydroxide produced by a process herein. In certain of these embodiments, the batteries do not include lithium iron phosphate in the cathode. In certain of these embodiments, the batteries do include cathode active materials with high nickel amounts. Cathode active materials with high nickel amounts include, but are not limited to, nickel manganese cobalt oxides such as NMC622 (LiNio.eMno.2Coo.2O2) or NMC811 (LiNio.8Mno.1Coo.1O2).

[0166] Also set forth herein is lithium hydroxide made by a process herein. Also set forth herein are cathode active material made using this lithium hydroxide. Also set forth herein is lithium metal made using this lithium hydroxide. In certain embodiments, the lithium metal is made by electroplating the lithium hydroxide.

[0167] Also set forth herein are processes for making a cathode active material that includes using the lithium hydroxide to lithiate a cathode active material selected from the group consisting of lithium nickel manganese cobalt oxide, lithium cobalt oxide, lithium manganese oxide, lithium iron phosphate, lithium manganese iron phosphate, lithium titanate, and combinations thereof.

[0168] Also set forth herein are processes for making an electrochemical cell that includes using the lithium hydroxide provided herein, the cathode active material provided herein, the lithium metal provided herein, or a combination thereof.NANOFILTRATION

[0169] FIG. 4 shows a process flow sheet. Cathode scrap powder and / or jelly roll powder are provided depending on the feedstock of battery materials being recycled. These powders are down-sized and / or milled products of battery materials that are to be recycled. These materials are sent to a feed blending step. In the feed blending step, the cathode scrap powder and / or jelly roll powder are mixed and optionally combined with other materials such as, but not limited to, carbon, metals, and combinations thereof. In some embodiments, the carbon and metals that are mixed with the cathode scrap powder and / or jelly roll powder originate from upstream process steps in which the carbon and metals are separated from other battery materials. Next, the materials are thermally reduced in a calcination step that typically occurs in a reducing atmosphere and a rotating kiln. In some embodiments, thisthermal reduction converts active battery material into inactive battery material. In some embodiments, this thermal reduction breaks down battery materials by vaporizing organic material and / or reducing metal oxides to metals. Gases and dust that are produced during thermal reduction are extracted, sent to an off gas treatment step, and eventually vented to the atmosphere. After being thermally reduced (z.e., calcined), the resulting calcined material is milled and screened to separate material by size and / or by magnetization. This occurs in the Milling / Screening step in FIG. 4. Magnetic material such as iron is separated. The material mixture that results from this separation step includes base metals, base metal oxides, and lithium salts such as lithium carbonate and lithium hydroxide. This material mixture is then sent to a leaching and filtration step where water is added to form a slurry. As shown in FIG.4, during the leaching and filtration step no acid nor lime is added to the slurry. Only water is added to initiate the leaching process. However, in certain other embodiments, lime may be added at this process step in order to result in high lithium extractions in the leach. During leaching, lithium is dissolved into the water along with certain metals and impurities. As lithium dissolves so too does hydroxide and carbonate ions that are associated with lithium. Some metals, metal oxides, and nonsoluble materials are suspended in the water and form a slurry. This slurry is pressed and / or filtered to separate the liquid portion having dissolved lithium from the solid portion. The filtrate or aqueous portion contains leached lithium. The precipitate or solid portion separated from the filtrate forms a reduced high nickel concentration (RHNC) cake.

[0170] After separating the filtrate from the RHNC cake, the liquid filtrate is referred to as a crude lithium hydroxide (LiOH) brine. The crude LiOH brine, in certain embodiments, includes about 10 g / L to 25 g / L of LiOH and has a pH of about 14. The crude LiOH brine is sent to the Lime Causticization / Filtration step in which lime (Ca(OH)2) is added. The lime reacts with carbonate ions (CO32) in the brine and forms CaCOs. In some embodiments, this calcium carbonate is separated by filtration and added to the RHNC cake prior to drying the RHNC cake.

[0171] After reacting with lime to form CaCOs and remove COs2', the crude LiOH brine is transferred to a Multi-Stage Nanofiltration process that includes an Impurity Precipitation Loop, both of which are further detailed in FIGs. 5 - 6. This Multi-Stage Nanofiltration and Impurity Precipitation Loop process purifies the crude LiOH brine- T1 -and forms a LiOH brine suitable for making battery grade lithium hydroxide monohydrate (LiOH H2O). This Multi-Stage Nanofiltration and Impurity Precipitation Loop process also forms a lime / impurity cake bleed as a by-product. The purified LiOH brine is then transformed into battery grade lithium hydroxide monohydrate (LiOH H2O) using a Multi-stage Crystallization and Drying process. The process include crystallizing, recrystallizing, washing, and drying the LiOH to exclude impurities like potassium (K) and sodium (Na) from crystalline LiOH H2O. The Impurity Precipitation Loop is further detailed below in FIG. 5. The Multi-stage Nanofiltration process is further detailed below in FIG. 6.

[0172] In some embodiments, the lime / impurity cake bleed is added to the RHNC cake prior to drying the RHNC cake. Eventually the RHNC cake, optionally with CaCOs, lime, and / or impurities rejected from the Multi-stage Nanofiltration and Impurity Precipitation Loop is dried in a RHNC dryer. This drying process removes water and results in an RHNC powder.

[0173] FIG. 5 shows details of the Impurity Precipitation Loop. This Impurity Precipitation Loop shows the processes occurring when brine and impurities are rejected from the Multi-stage Nanofiltration process. As shown in FIG. 5, lithium brine rejected from the Multi-Stage Nanofiltration is first sent to an Impurity Precipitation step where lime (Ca(OH)2 is added. The lime precipitates certain solids, such as metal hydroxides, metal oxides, and calcium carbonate. The solids are sent to a Hydrocyclone that separates solids from liquids. Typically, the solid loading of a liquid containing these solids is about 5% by weight when it is sent to the Hydrocyclone. In some embodiments, these solids include LiF, CaCCL, and / or calcium-silicon-aluminates (Ca-Si-Al containing compounds). Because many impurities are fed to the nanofilter during nanofiltration at saturation, Pass 1 (z.e., brine from the Ultrafiltration Elements or from the Pass 1 Nanofiltration Elements in FIG. 6 below) of Nanofiltration has a high reject flow. About 75 % of the volume sent to the filter is rejected by the nanofilter. The high reject flow sends more water to the reject mixture and limits the amount of super saturation. This prevents precipitation of impurities in the filter itself, creates scaling. This results in a large recirculating flow that passes through the impurity precipitation loop. This large recirculating flow is difficult to feed through a conventional filter, so the Hydrocyclone acts as an initial solids / liquid separation step. Greater than 90% bymass of the solids are sent to the underflow. The yield is not 100% so there will be some solid fines that carryover to the overflow. These fines are removed through a filter. This is easier to manage at a much lower solids loading rate. The underflow is directly recycled back to the impurity precipitation tank. In the impurity precipitation tank, there is a filter that pulls off a small amount of the underflow volume. After the Hydrocyclone, the low (small size or less dense) solids are processed in a fines filter that removes these solids from the liquid. The liquid recirculates back to the impurity precipitation step. The high (large size or denser) solids are sent by way of the bleed line to another filter where liquid is separated from these high solids. The liquid separated from these solids often has a sufficient amount of lithium and is therefore circulated back to the Multi-Stage Nanofiltration process, detailed in FIG. 6, to extract that lithium. The separated solids are sent back to the product blend in the process in FIG. 4 or sent for disposal.

[0174] FIG. 6 shows a nanofiltration process. The process starts with Crude LiOH Brine sent to and stored in a Crude LiOH Storage Tank. In some embodiments, the Crude LiOH Brine originates from the Leaching / Filtration step illustrated in FIG. 4. Deionized water may be used to flush the crude lithium brine through an ultrafiltration pump that then pumps the brine at 801 through an Ultrafiltration Elements (z.e., ultrafiltration filtration). However, in some embodiments, water that is not deionized may be used. In certain embodiments, deionized water is useful for cleaning a membrane that is fouled and reducing the rate of permeate flow. In certain embodiments, the Crude LiOH Brine is sent directly through the Ultrafiltration Feed Pump and then through 801 to an Ultrafiltration Elements (z.e., ultrafiltration filtration) The Ultrafiltration Elements uses micron-sized filters to separate solids and impurities. Impurities separated from the Crude LiOH Brine exit the Ultrafiltration Elements at 802 and are sent to the Impurity Precipitation Reactor described in FIG. 5. This ultrafiltration step is important to remove very fine particles that are left following the standard filtration steps that may foul the nanofiltration membranes. The purified crude lithium brine is then sent at 803 to a Nanofiltration Pass 1 Feed Tank. Lithium brine (z.e., Crude LiOH Brine permeate that passed through the ultrafiltration) in the Nanofiltration Pass 1 Feed Tank is sent through line 805 to a Pass 1 Heat Exchanger and through line 806 to a Pass 1 Nanofiltration Feed Pump and then through line 807 to a Pass 1 Nanofiltration Elements (z.e., nanofiltration).The heat exchangers in FIG. 6 either heat or cool the brine. The Pass 1 Nanofiltration Elements uses an ion-selective polymer, spiral-wound membrane to purify the lithium brine. The ion-selective polymer, spiral-wound membrane separates certain ions and particles from the lithium brine. For example, highly charged ions such Ca2+and CO32’, as well as other charged species such as F’, and fluoride complexes, and large complexes such as A1(OH)T, are removed by the ion-selective polymer, spiral-wound membranes. The purified lithium brine is moved through 808 to another storage tank, the Nanofiltration Pass X Feed Tank. At this point in the process, the resulting brine in the Nanofiltration Pass X Feed Tank is repeatedly circulated from line 809, through Pass X Nanofiltration Heat Exchanger, Pass X Nanofiltration Feed Pump, and through line 811 to another nanofiltration device - labeled the Pass X Nanofiltration Elements. The Pass X Nanofiltration Elements also uses an ion-selective polymer, spiral-wound membrane to purify the lithium brine. Lithium brine is recirculated at line 812 back into the Nanofiltration Pass 1 Feed Tank, where the lithium brine again circulates at 805 through Pass 1 Nanofiltration Heat Exchanger, then at 806 to the Pass 1 Nanofiltration Feed Pump, and through line 807 to the pass 1 Nanofiltration Elements and back to Nanofiltration Pass X Feed Tank by way of 808. This recirculation from Nanofiltration Pass X Feed Tank to Nanofiltration Pass 1 Feed Tank and back to Nanofiltration Pass X Feed Tank is repeated at least two times. In some embodiments, the recirculation from Nanofiltration Pass X Feed Tank to Nanofiltration Pass 1 Feed Tank and back to Nanofiltration Pass X Feed Tank is repeated three times, four times. In some embodiments, the recirculation from Nanofiltration Pass X Feed Tank to Nanofiltration Pass 1 Feed Tank and back to Nanofiltration Pass X Feed Tank is repeated more than four times. The purified brine that exits the Pass X Nanofiltration Elements is then sent by way of line 813 to Nanofiltration Pass 5 Feed Tank. From Nanofiltration Pass 5 Feed Tank, the resulting lithium brine is filtered once more by way of line 814, Pass 5 Nanofiltration Heat Exchanger, line 815, Pass 5 Nanofiltration Feed Pump, line 816, and Pass 5 Nanofiltration Elements. If the lithium brine that exits the Pass 5 Nanofiltration Elements is not sufficiently pure, the brine will be recirculated back to Nanofiltration Pass X Feed Tank by way of line 817. Lithium brine that is sufficiently pure exits at line 818. Line 818 is then sent to the Multi-stage Crystallization / Drying step as shown in FIG. 4 so that lithium hydroxide monohydrate can be prepared by crystallizing and drying lithium hydroxide. The number of stages of recirculation through the Pass X Nanofiltration Elements dependson the purity of lithium, such as the ratio of F / Li. Fluoride has the lowest rejection rate. The number of passes is thus determined by the number of passes to get a sufficient Li / F ratio, such that the fluoride content in the corresponding crystal product is at or below the fluoride specification for battery grade LiOH.

[0175] As detailed in Example 7, below, the ion-selective polymer, spiral-wound membranes used in the nanofiltration at Pass 1 Nanofiltration Elements, Pass X Nanofiltration Elements, or Pass 5 Nanofiltration Elements, use size selection to exclude certain elements from the lithium brine. For example, the ion-selective polymer, spiral-wound membranes are capable of removing Al, Ca, Si, F, and CCE2' ions. Na and K are more difficult to remove from the lithium brine using ion-selective polymer, spiral-wound membranes. Na and K are eventually removed after Al, Ca, Si, F, and CCE2' ions are removed and the lithium brine is sent to a multi-stage crystallization / drying step.

[0176] In some embodiments, set forth herein is a process for purifying a lithium - containing brine, wherein the process includes: (a) providing a brine that includes lithium hydroxide (LiOH); (b) adding lime (Ca(OH)2) to the brine; (c) optionally filtering the brine to remove precipitates; and (d) purifying the brine using nanofiltration.

[0177] In some embodiments, including any of the foregoing, the providing a brine including lithium hydroxide (LiOH) includes thermally reducing inert or live battery materials to provide calcined metal concentrate; contacting the calcined metal concentrate with water to leach lithium from the calcined metal concentrate; and separating the water with leached lithium from unleached material (e.g., undissolved or not suspended solids).

[0178] In some embodiments, including any of the foregoing, the brine in step (a) includes at least 1 g / L LiOH; at least 10 g / L LiOH, or at least 25 g / L LiOH. In certain embodiments, the brine in step (a) includes at least 1 g / L LiOH. In certain embodiments, the brine in step (a) includes at least 10 g / L LiOH. In certain embodiments, the brine in step (a) includes at least 25 g / L LiOH. In certain embodiments, the brine in step (a) includes less than 100 g / L LiOH.

[0179] In some embodiments, including any of the foregoing, the brine in step (a) includes 1 g / L LiOH to 25 g / L LiOH.

[0180] In some embodiments, including any of the foregoing, the brine in step (a) includes: Al3+, optionally at 100 part per million (ppm) -1000 ppm; Ca2+, optionally at 10 ppm - 50 ppm; Si (e.g., (SiC )2’ and / or [SiO2(OH)2]2), optionally at 100 ppm - 1000 ppm; F’, optionally at 100 ppm - 300 ppm; Na+, optionally at 50 ppm - 200 ppm; K+, optionally at 10 ppm -50 ppm; (CCh)2', optionally at 1 g / L - 5 g / L; or a combination thereof.

[0181] In some embodiments, including any of the foregoing, the amount of lime added is at or above lime’s saturation limit in the brine.

[0182] In some embodiments, including any of the foregoing, the pH of the brine at step (a) is greater than 7.

[0183] In some embodiments, including any of the foregoing, the pH of the brine at step (a) is greater than 7 and less than or equal to 14.

[0184] In some embodiments, including any of the foregoing, the pH of the brine at step (a) is at least 13.

[0185] In some embodiments, including any of the foregoing, the pH of the brine at step (a) is about 14.

[0186] In some embodiments, including any of the foregoing, step (b) produces precipitates selected from CaCCL, calcium-aluminum-silica complexes, or a combination thereof.

[0187] In some embodiments, including any of the foregoing, the brine after step (c) includes: Al3+, optionally at 100 ppm - 400 ppm; Ca2+, optionally at about 50 ppm; Si (e.g., (SiCU)2' and / or [SiO2(OH)2]2), optionally at about 50 ppm; F’, optionally at 100 ppm - 300 ppm; Na+, optionally at 50 ppm - 200 ppm; K+, optionally at 10 ppm - 50 ppm; (CCh)2', optionally at less than 500 ppm; or a combination thereof.

[0188] In some embodiments, including any of the foregoing, the purifying the brine using nanofiltration includes removing aluminum (Al), calcium (Ca), silicon (Si), fluorine (F), sodium (Na), potassium (K), carbonate (CO32), ions thereof, complexes thereof, or combinations thereof.

[0189] In some embodiments, including any of the foregoing, step (b) occurs above room temperature.

[0190] In some embodiments, including any of the foregoing, step (b) occurs at about 80 °C.

[0191] In some embodiments, including any of the foregoing, the nanofiltration uses ion selective and polymer, spiral-wound membranes.

[0192] In some embodiments, including any of the foregoing, the polymer, spiralwound membranes have a molecular weight cut-off of 120 Daltons (Da) to 200 Da.

[0193] In some embodiments, including any of the foregoing, the purifying the brine using nanofiltration includes using lime to precipitate impurities from the bring before or after passing the brine through a nanofiltration filter.

[0194] In some embodiments, including any of the foregoing, the purifying the brine using nanofiltration includes repeatedly passing the brine through at least one nanofiltration filter. In certain embodiments, the brine passes through a nanofiltration filter or through nanofiltration elements at least once. In certain embodiments, the brine passes through a nanofiltration filter or through nanofiltration elements twice. In certain embodiments, the brine passes through a nanofiltration filter or through nanofiltration elements three times. In certain embodiments, the brine passes through a nanofiltration filter or through nanofiltration elements four times. In certain embodiments, the brine passes through a nanofiltration filter or through nanofiltration elements five times. In certain embodiments, the brine passes through a nanofiltration filter or through nanofiltration elements more than five times. In certain embodiments, the brine passes through a nanofiltration filter or through nanofiltration elements less than 10 times.

[0195] In some embodiments, including any of the foregoing, the purifying the brine using nanofiltration includes passing the brine through a polymer, spiral-wound membrane at 30 °C to 40 °C and a pressure of about 500 pounds-per-square-inch (PSI).

[0196] In some embodiments, including any of the foregoing, the process includes transferring nanofiltration rejected material to an impurity precipitation loop in which lime is used to precipitate impurities as solids that are filtered from the brine.

[0197] In some embodiments, including any of the foregoing, the purifying the brine using nanofiltration results in a brine that has lower concentrations of fluorine (F) than the brine did before the nanofiltration.

[0198] In some embodiments, including any of the foregoing, the purifying the brine using nanofiltration results in a brine that has lower concentrations of Al, Si, F, CCh2', or a combination thereof, than the brine did before the nanofiltration.

[0199] In some embodiments, including any of the foregoing, the purifying the brine using nanofiltration results in a brine that does not has lower concentrations of Na and / or K than the brine did before the nanofiltration.

[0200] In some embodiments, including any of the foregoing, after purifying the brine using nanofiltration, the brine includes 40 wt% to 60 wt% less F than the brine did before nanofiltration.

[0201] In some embodiments, including any of the foregoing, after purifying the brine using nanofiltration, the brine includes 90 wt% to 95 wt% less Si than the brine did before nanofiltration.

[0202] In some embodiments, including any of the foregoing, after purifying the brine using nanofiltration, the brine includes 90 wt% to 95 wt% less Ca than the brine did before nanofiltration.

[0203] In some embodiments, including any of the foregoing, after purifying the brine using nanofiltration, the brine includes 90 wt% to 95 wt% less Al than the brine did before nanofiltration.

[0204] In some embodiments, including any of the foregoing, the process includes crystallizing lithium hydroxide monohydrate (LiOH FfcO) from the brine.

[0205] In some embodiments, including any of the foregoing, the crystallizing lithium hydroxide monohydrate (LiOH FhO) includes recrystallization and washing to remove Na+and K+.

[0206] Also set forth herein is a purified lithium hydroxide brine, made by any one process set forth herein.

[0207] Also set forth herein is a lithium hydroxide made by any one of the processes herein. In certain embodiments, the lithium hydroxide is crystalline lithium hydroxide monohydrate.

[0208] Also set forth herein is a cathode active material made using lithium hydroxide made by a process herein.

[0209] Also set forth herein is lithium metal made using lithium hydroxide made by a process herein. In certain embodiments, the lithium is made by electroplating the lithium hydroxide.EXAMPLESEXAMPLE 1 - LITHIUM RECOVERY FROM LITHIUM-ION BATTERIES

[0210] This Example shows a high percent (%) lithium (Li) recovery from battery materials.

[0211] Step one: Calcined metal concentrate was provided from a rotary kiln coupled with mechanical treatment that processed spent Lithium-Ion Batteries (LIBs, also referenced herein as battery materials) with predominantly Nickel-Manganese-Cobalt cathode compositions.

[0212] Step two: A slurry was made by adding 60 g of the calcined metal concentrate to 395 g of de-ionized water and heated to 90 °C.

[0213] Step three: 544.3g of 8 weight percent (wt%) hydrated lime slurry was added to the slurry in equal aliquots every thirty minutes over a six-hour period.

[0214] Step four: The reaction was cooled to 50 °C.

[0215] Step five: Graphite, calcium carbonate, unreacted lime, and other metals were separated from the aqueous phase of the slurry via vacuum filtration with a 2.5 pm filter. The aqueous phase of slurry also included the product lithium hydroxide. The liquid lithium hydroxide product contained 1.8 grams-per-liter (gpL) Li, or 6.1 grams- per-liter (gpL) LiOH, resulting in a recovery yield of 1.4 g of Li or 4.8g of LiOH from 60 g of spent Lithium-Ion Batteries (LIBs).EXAMPLE 2- LITHIUM RECOVERY FROM LITHIUM-ION BATTERIES

[0216] This Example shows a high Li concentration (gpL) recovered from spent LIBs.

[0217] Step one: Calcined metal concentrate was provided from a rotary kiln coupled with mechanical treatment that processed spent Lithium-Ion Batteries (LIBs) with predominantly Nickel-Cobalt-Aluminum cathode compositions.

[0218] Step two: A slurry was made by adding 175 g of metal concentrate to 225 g of de-ionized water and heated to 80 °C.

[0219] Step three: 353g of 15 weight percent (wt%) hydrated lime slurry was added to the slurry in equal aliquots every thirty minutes over a six-hour period.

[0220] Step four: The reaction was cooled to 50 °C.

[0221] Step five: Graphite, calcium carbonate, unreacted lime, and other metals were separated from the aqueous phase of the slurry via vacuum filtration with a 2.5 pm filter. The aqueous phase of slurry also included liquid lithium hydroxide product. The liquid lithium hydroxide product contained 6.8 gram-per-liter Li or 11.7 gram- per-liter LiOH, resulting in a recovery yield of 3.4g Li or 11.7g Li OH from 175g of battery material.

[0222] This Example shows the achievement of a high concentration of 6.8 gpl Li at 30% by weight solids. The average recovery was 4.71 gpl. The minimum recovery was 1.7 gpl at 10% by weight solids.EXAMPLE 3- LITHIUM RECOVERY FROM LITHIUM-ION BATTERIES

[0223] This Example shows a high percent (%) lithium (Li) recovery from LIBs.

[0224] Step one: Calcined metal concentrate was provided from a rotary kiln coupled with mechanical treatment that processed spent Lithium-Ion Batteries (LIBs).

[0225] Step two: A slurry was made by adding 130 g of metal concentrate to 500 g of de-ionized water and heated to 80 °C.

[0226] Step three: 257 g of 15 weight percent (wt%) hydrated lime slurry was added to the slurry in equal aliquots every thirty minutes over a six-hour period.

[0227] Step four: The reaction was cooled to 50 °C.

[0228] Step five: Graphite, calcium carbonate, unreacted lime, and other metals were separated from the aqueous phase of the slurry via vacuum filtration with a 2.5 pm filter. The aqueous phase of the slurry also included the product lithium hydroxide. The liquid lithium hydroxide product contained 3.6 gpL Li or 12.4 gpL Li, which was a recovery yield of 2 g of Li or 6.9g of LiOH from 130 g of battery material.EXAMPLE 4- LITHIUM RECOVERY FROM LITHIUM-ION BATTERIES

[0229] This Example shows lithium (Li) extraction coupled with lithium hydroxide (LiOH) crystallization.

[0230] Step one: Calcined metal concentrate was provided from a rotary kiln coupled with mechanical treatment that processed spent Lithium-Ion Batteries (LIBs) with predominantly Nickel-Manganese-Cobalt cathode compositions.

[0231] Step two: 10 kilograms of slurry was made of 30 weight percent (wt%) calcined metal concentrate and heated to 50 °C.

[0232] Step three: 4 kilograms slurry was made of 15 wt% hydrated lime.

[0233] Step four: Peristaltic pumps were used to simultaneously dose the calcined metal concentrate slurry and the hydrated lime slurry into a cascading reactor so that the residence time of the combined slurries in the reactor was three hours and that the stoichiometric amount of hydrated lime added was 125% of the required amount for lithium carbonate conversion to lithium hydroxide. The reactor holding the combined slurries was heated to 75 °C.

[0234] Step five: The continuous leach was performed for eight hours.

[0235] Step six: All slurry was collected and cooled to room temperature.

[0236] Step seven: Graphite, calcium carbonate, unreacted lime, and other metals were separated from the aqueous phase of the slurry via pressurized filtration with a 2.5 pm filter. The aqueous phase of the slurry also included the product lithium hydroxide. The liquid lithium hydroxide product contained 5.3 gpL Li or 18.5 gpL, which was a recovery yield of 18.5g of Li or 137.2g of LiOH from 3 kilograms of battery material.

[0237] The recovered aqueous solution was evaporated under vacuum at 70 °C until the amount of distillate (evaporated water from the aqueous solution) recovered was 80% by weight of the original aqueous solution.

[0238] The solid lithium hydroxide product was separated from the aqueous lithium hydroxide product via vacuum filtration with a 2.5 pm filter.

[0239] The recovered solid lithium hydroxide product was then dried under vacuum at 30 °C to yield 94 g of lithium hydroxide monohydrate product.

[0240] The product was analyzed by x-ray diffraction.

[0241] The sample was milled in an agate mortar and pestle before analysis. Analysis performed using a Bruker D8 Advance XRD with Davinci design and a Lynxeye detector utilizing cobalt radiation produced at 35 kV and 40 mA. The scan range is 5°-85° 2-theta, with a step of 0.02° 2-theta and a time per step of 0.4 s. Mineral quantification completed using the Rietveld refinement method with Bruker TOP AS version 4.2 software.

[0242] A summary of the results is shown in Table 1 and Table 2, below, and the diffraction pattern is presented in FIG. 3. The sample is dominated by a lithium hydroxide hydrate (82 mass %), with the bulk of remainder made up by zabuy elite (18 mass%). Zabuyelite is a form of lithium carbonate. Trace amounts of hanjiangite and a sodium calcium vanadium oxide were tentatively identified, using the best fit method. The minor XRD peaks in this sample, not belonging to the two main phases, are too small to identify any matching phases with a high degree of confidence. The identification and related quantification of the minor to trace phases are not reported. A small bump between 18 and 24° 2-theta also indicates that some amorphous material is present. This amorphous component may be related to the two main phases and / or to the minor peaks detected.Table 1 - XRD Results Without Highly Tentative Phases* All mineral constitutes are normalized to 100%.Table 2 - XRD Results With Highly Tentative Phases* All mineral constitutes are normalized to 100%.EXAMPLE 5- LITHIUM RECOVERY FROM LITHIUM-ION BATTERIES

[0243] This Example shows lithium recovery from inert battery production scrap using high temperature calcination and alkaline leaching.

[0244] Step one: scrap cathode material was mechanically separated from aluminum foil and well blended with graphite (70 wt. % cathode, 30 wt. % graphite).

[0245] Step two: Battery material was calcined in a rotary tube furnace under reducing conditions at 850 °C for 2.25 hours.

[0246] Step three: A slurry was made with 150 g of the calcined material and 850 g of water (15% solids) in a well mixed container.

[0247] Step four: 45 g of hydrated lime was added to the slurry and the slurry volume was heated to 90 °C for 2 hours.

[0248] Step five: The reaction was cooled to 50 °C.

[0249] Step six: Graphite, calcium carbonate, unreacted lime, and other metals were separated from the aqueous phase of the slurry via vacuum filtration with a 2.5 pm filter. The aqueous phase of the slurry also included the product lithium hydroxide. The liquid lithium hydroxide product contained 11 gpL Li or 39 gpL LiOH resulting in a recovery yield of 5.5 g of Li or 19g of LiOH from 150 g of battery material.

[0250] Without calcination of the inert battery production scrap, lower yields of Li would have resulted. Furthermore, without controlling the alkalinity of the slurry thatincluded the calcined material, lower yields of Li would have resulted. The concentration of hydroxide, and thereby lithium hydroxide, was much higher on account of these calcination and alkalinity controlling process steps. The amount of Li recovered in this Example was unexpectedly high.EXAMPLE 6 - LITHIUM RECOVERY FROM LITHIUM-ION BATTERIES

[0251] This Example shows lithium recovery from calcined metal concentrate after secondary high temperature calcination and alkaline leaching. Calcined metal concentrate secondary means that live battery scrap was first calcined at around 300 °C to deactivate the live battery scrap. And then the resulting calcined material was calcined a second time at a higher temperature of about 800 °C to about 900 °C in a reducing atmosphere for about two to three hours to produce the calcined metal concentrate secondary. This Example showed that if only one calcination step was employed, only about 30 wt. % by weight of the available Li would have been recovered. However, by calcining the material twice, 78 wt. % to 80 % by weight (wt. %) of the available Li from the battery material was recovered from the solution.

[0252] Step one: Calcined metal concentrate was provided from a rotary kiln coupled with mechanical treatment that processed spent Lithium-Ion Batteries (LIBs).

[0253] Step two: Material was calcined in a rotary tube furnace under reducing conditions at 850 °C for 2.25 hours.

[0254] Step three: A slurry was made with 150 g of the calcined material and 600 g of water (20% by mass solids) in a well mixed container.

[0255] Step four: 35 g of hydrated lime was added to the slurry and the slurry volume was heated to 90 °C for 2 hours.

[0256] Step five: The reaction was cooled to 50 °C.

[0257] Step six: Graphite, calcium carbonate, unreacted lime, and other metals were separated from the aqueous phase of the slurry via vacuum filtration with a 2.5 pm filter. The aqueous phase of the slurry also included the product lithium hydroxide. The liquid lithium hydroxide product contained 17 gpL Li or 58 gpL LiOH, which was a recovery yield of 5.1 g of Li or 17g of LiOH from 150 g of battery material.EXAMPLE 7 - PROCESS FOR PURIFICATION OF LIOH BRINE USING NANOFILTRATION

[0258] A lithium hydroxide brine was made by leaching lithium (Li2CO3and LiOH) from calcined metal concentrate in water. The calcined metal concentrate was provided by thermally reducing spent lithium-ion batteries (LIBs) with predominantly nickel-manganese-cobalt cathode compositions in a rotary kiln after mechanical treatment. The brine was filtered to remove solids and undissolved material. This produced a crude lithium hydroxide brine.

[0259] A slurry of hydrated lime was added to the crude lithium hydroxide brine.

[0260] This caused calcium carbonate (CaCO3) to form. The CaCO3was separated from the lithium hydroxide brine via pressurized filtration with a 2.5 pm filter. This produced a crude LiOH brine that was further processed as detailed below.

[0261] The crude LiOH brine contained the following impurities: a. Al3+: 100 part per million (ppm) -1000 ppm; b. Ca2+: 10 ppm - 50 ppm; c. Si (e.g., (SiO4)2' and / or [SiO2(OH)2]2'): 100 ppm - 1000 ppm; d. F’: 100 ppm - 300 ppm; e. Na+: 50 ppm - 200 ppm; f. K+: 10 ppm - 50 ppm; and g. (CO3)2-: 1 g / L - 5 g / L.

[0262] The brine was mixed with a slurry of Ca(OH)2 (lime) at a temperature of about 80 °C. This step is referred to herein as causticization. Causticization had at least two effect. Causticization converted about 90 - 95% of the (CO3)2' to (OH)1' and precipitated many of the impurities as calcium-aluminum-silica complexes (z.e., Ca- Al-Si complexes).

[0263] The impurity profile following causticization was the following: a. Al3+: 100 ppm - 400 ppm; b. Ca2+: about 50 ppm;c. Si (e.g., (SiC )2’ and / or [SiO2(OH)2]2): about 50 ppm; d. F’: 100 ppm - 300 ppm; e. Na+: 50 ppm - 200 ppm; f. K+: 10 ppm - 50 ppm; and g. (CCh)2': less than 500 ppm.

[0264] Further purification and subsequent crystallization was performed as follows in order to remove additional impurities and produce battery grade lithium hydroxide monohydrate (LiOH hO).

[0265] The purification included using ion-selective nanofiltration using polymer, spiral-wound membranes that met the below criteria. These membranes are commercially available as Kovalus SelRO membranes.

[0266] The polymer, spiral -wound membranes had a molecular weight cut-off of 120 Daltons (Da) to 200 Da. The polymer, spiral-wound membranes were continuously stable at high pH (z.e., pH 14).

[0267] The polymer, spiral -wound membranes rejected certain elements and their ions as a function of temperature, starting concentration, and feed pressure. Several runs were performed to study the effect of permeate flow, lithium recovery, and impurity rejection.

[0268] In one run, the brine was passed through the polymer, spiral-wound membrane at 30 °C to 40 °C and a pressure of about 500 pounds-per-square-inch (PSI).

[0269] This run resulted in the following impurity rejections from the polymer, spiralwound membranes: a. Li+: 10 % by mass - 20 % by mass; b. Na+: 10 % by mass - 20 % by mass; c. K+: 10 % by mass - 20 % by mass; d. Al3+: 90 % by mass - 95 % by mass; e. Ca2+: 90 % by mass - 95 % by mass;f. Si (e.g., (SiC )2’ and / or [SiO2(OH)2]2): 90 % by mass - 95 % by mass; g. F’: 40 % by mass - 60 % by mass; and h. (CCh)2': 90 % by mass - 95 % by mass.

[0270] These results showed that the nanofiltration was effective at rejecting Ca2+, Al3+, Si (e.g., (SiCU)2' and / or [SiO2(OH)2]2), and (CCh)2'. These ions are multivalent and / or large ions / complexes that were either repelled by the membrane’s surface charge or physically blocked from permeating the membrane. Nanofiltration was not as effective at repelling Na+and K+since they are monovalent ions like Li1+.

[0271] It was unexpected that nanofiltration was effective at rej ectingF’. F’ is a small monovalent ion and would be expected to permeate. However, the results herein showed that F’ did not permeate through the polymer, spiral-wound membrane under the conditions tested.

[0272] Without being bound to theory, the rejection of fluoride (F‘) may have been because it complexed with Al and / or Ca; or that the fluoride formed CaF nanoparticles that could not be removed with filtration; or that the fluoride was balanced with Li+and not completely ionized due to strong bond strength interactions with lithium in solution.

[0273] The results herein showed that nanofiltration could be used in multiple stages to reject enough of the fluoride such that the resulting Li OH brine produces battery grade lithium hydroxide monohydrate.

[0274] The next steps describe prophetically how the LiOH brine would be transformed into lithium hydroxide monohydrate (LiOH H2O).

[0275] Because the rejects from nanofiltration contained a significant portion of the lithium, the rejects would be recycled in order to capture this lithium. A portion of the volume would be recycled back to the feed of the same membrane and the remainder would be recycled to the previous membrane stage.

[0276] For example, the reject flow from the first filtration stage would be sent to a precipitation step to provide an exit for the impurities from the process. This precipitation step would consist of a precipitation reactor, hydrocyclone, and two filters. In this precipitation step, Ca(OH)2 would be mixed with the nanofiltrationreject flow until the discharge slurry includes about 5 wt. % solids. In this condition, Al and Si would react with the Ca(OH)2 and precipitate as Ca-Al-Si complexes.Because Ca and F supersaturate in the nanofilter, the Ca(OH)2 provides a nucleation point and Ca and F would precipitate back to saturation concentration. The resulting slurry would be passed through a hydrocyclone to separate out greater than 95 wt. % of the solids through the hydrocyclone underflow and recycle them back to the precipitation reaction. A bleed would be pulled from the hydrocyclone underflow to keep the solids from accumulating. The hydrocyclone overflow would be passed through a fine particle filter and sent back to the first stage of nanofiltration.

[0277] After the above precipitation step, the final LiOH brine from the final stage of nanofiltration would have impurity levels compatible with battery grade lithium hydroxide monohydrate for all impurities except Na and K. Na and K would be then removed using washing steps and multi-stage crystallization.

[0278] The embodiments and examples described above are intended to be merely illustrative and non-limiting. Those skilled in the art will recognize or will be able to ascertain using no more than routine experimentation, numerous equivalents of specific compounds, materials and procedures. All such equivalents are considered to be within the scope and are encompassed by the appended claims.

Claims

Claims1. A process for recovering lithium (Li) from battery material, the process comprising the following steps:(1) providing calcined metal concentrate in an aqueous slurry;(2) contacting the aqueous slurry with a hydrated lime slurry to form a third slurry;(3) forming lithium hydroxide; and(4) separating the lithium hydroxide from the third slurry.

2. The process of claim 1, wherein:(a) the calcined metal concentrate is formed by first calcining battery material that comprises live battery scrap at a temperature of about 300 °C to about 500 °C to form a calcined material and then calcining the calcined material at a temperature of about 800 °C to 900 °C; or(b) the calcined metal concentrate is formed by calcining battery material that comprises inert battery scrap at a temperature of about 300 °C to 900 °C, wherein the inert battery scrap comprises:(1) cathode material and optionally carbon; or(2) both cathode material and anode material that comprises carbon.

3. The process of claim 2, further comprising mechanically separating metals selected from aluminum, iron, copper, and combinations thereof, from the battery material prior to calcining the battery material.

4. The process of claim 2 or 3, wherein the cathode material comprises nickel (Ni), cobalt (Co), manganese (Mn), aluminum (Al), or a combination thereof.

5. The process of any one of claims 1-4, wherein the aqueous slurry comprises lithium oxide, graphite, or a combination thereof.

6. The process of any one of claims 1-4, wherein the aqueous slurry comprises 20% by weight to 40% by weight carbon, optionally wherein the carbon is graphite.

7. The process of claim 6, wherein the aqueous slurry comprises 30% by weight carbon, optionally wherein the carbon is graphite.

8. The process of any one of claims 1-7, wherein the aqueous slurry comprises 10% by weight solids to 30% by weight solids.

9. The process of claim 8, wherein the aqueous slurry comprises 15% by weight solids to 20% by weight solids.

10. The process of claim 8, wherein the aqueous slurry comprises 4% by weight solids to 8% by weight solids.

11. The process of claim 8, wherein the aqueous slurry comprises 13% by weight solids; 15% by weight solids; 20% by weight solids, 30% by weight solids; 44% by weight solids; or 45% by weight solids.

12. The process of any one of claims 1-11, wherein the aqueous slurry is heated to about 50 °C to about 90 °C before, while, or after, contacting the aqueous slurry with the hydrated lime slurry.

13. The process of claim 12, wherein the aqueous slurry is heated to about 80 °C before, while, or after, contacting the aqueous slurry with the hydrated lime slurry.

14. The process of any one of claims 1-13, wherein the hydrated lime slurry comprises about 5% by weight hydrated lime to about 20% by weight hydrated lime.

15. The process of claim 14, wherein the hydrated lime slurry comprises about 8% by weight hydrated lime or about 15% by weight hydrated lime.

16. The process of any one of claims 1-15, wherein the amount of hydrated lime in the hydrated lime slurry is equal to or greater than the molar amount required to react with lithium carbonate in the aqueous slurry.

17. The process of claim 16, wherein the amount of hydrated lime in the hydrated lime slurry is about 125% the molar amount required to react with lithium carbonate in the aqueous slurry.

18. The process of any one of claims 1-17, wherein the hydrated lime slurry comprises calcium oxide, calcium hydroxide, hydrated-lime, water, or combinations thereof.

19. The process of any one of claims 1-18, comprising adding the hydrated lime slurry: (al) in equal aliquots;(bl) over a period of 30 minutes to 8 hours;(cl) in a cascading reactor;(dl) for a residence time of about 3 hours;(el) in which the hydrated lime slurry is heated to about 75 °C; or(fl) a combination selected from the group consisting of (al), (bl), (cl), (dl), and (el).

20. The process of any one of claims 1-19, further comprising cooling the third slurry to 50 °C or less.

21. The process of claim 20, further comprising cooling the third slurry to about room temperature.

22. The process of any one of claims 1-21, wherein separating the lithium hydroxide comprises filtering graphite, calcium carbonate, unreacted lime, metals, or a combination thereof, optionally:(a2) wherein the filter is a 2.5 pm filter;(b2) using pressure filtration;(c2) using vacuum filtration; or(d2) a combination selected from the group consisting of (a2), (b2), and (c2).

23. The process of any one of claims 1-22, further comprising crystallizing the lithium hydroxide by evaporation under vacuum.

24. The process of any one of claims 1-23, comprising recovering at least 70% by weight of the lithium originally present in the battery material.

25. The process of any one of claims 1-24, wherein the process increases the concentration of LiOH and lithium ions (Li+) in the third slurry without increasing the concentration of aluminum ions (Al3+).

26. The process of any one of claims 1-25, wherein the process converts lithium carbonate into lithium hydroxide and forms calcium carbonate.

27. The process of any one of claims 1-26, wherein the third slurry has a pH of about 9 to about 12.

28. The process of claim 27, wherein the third slurry has a pH of 9, 9.5, 10, 10.5, 11, 11.5, or 12, optionally wherein the pH is buffered.

29. The process of any one of claims 1-26, wherein the third slurry has a pH of about 13 to about 14.

30. The process of claim 29, wherein the third slurry has a pH of 13, 13.5, or 15, optionally wherein the pH is buffered.

31. The process of any one of claims 1-30, further comprising removing impurities selected from the group consisting of fluorine, aluminum, calcium, silica, ions thereof, and combinations thereof, from the third slurry phase.

32. The process of claim 31, comprising reducing the concentration of fluorine, aluminum, calcium, silica, ions thereof, and combinations thereof, in the third slurry to:(a3) less than 1 mg / L;(b3) less than 1% by mass;(c3) less than 0.01% by mass; or(d3) less than 0.001% by mass.-M -33. The process of claim 31, comprising reducing the concentration of impurities in the third slurry to:(a4) aluminum (Al) at 800 ppm to 1000 ppm;(b4) fluorine (F) at 150 ppm to 250 ppm;(c4) calcium (Ca) at 5 ppm to 10 ppm;(d4) silicon (Si) at 500 ppm to 1000 ppm; or(e4) a combination selected from the group consisting of (a4), (b4), (c4), and (d4).

34. The process of claim 31, comprising reducing the concentration of impurities in the third slurry to:(a5) Al at 100 ppm to 200 ppm;(b5) Si at 50 ppm to 150 ppm; or(c5) a combination of (a5) and (b5).

35. The process of any one of claims 2-34, wherein when the calcined metal concentrate is formed by calcining battery material that comprises inert battery scrap comprising cathode material or both cathode material and anode material at a temperature of about 300 °C to 900 °C; further comprising separating carbon, optionally as graphite, and recycling the carbon back into the aqueous slurry36. A process for purifying a lithium-containing brine, comprising:(a) providing a brine comprising lithium hydroxide (LiOH);(b) adding lime (Ca(OH)2) to the brine;(c) optionally filtering the brine to remove precipitates; and(d) purifying the brine using nanofiltration.

37. The process of claim 36, wherein providing a brine comprising lithium hydroxide (LiOH) comprises thermally reducing inert or live battery materials to provide calcined metal concentrate; contacting the calcined metal concentrate with water to leach lithium from the calcined metal concentrate; and separating the water with leached lithium from unleached material.

38. The process of claim 36 or 37, wherein the brine in step (a) comprises at least 1 g / L LiOH; at least 10 g / L LiOH, or at least 25 g / L LiOH.

39. The process of claim 38, wherein the brine in step (a) comprises 1 g / L LiOH to 25 g / L LiOH.

40. The process of any one of claims 36-39, wherein the brine in step (a) comprises:Al3+, optionally at 100 part per million (ppm) -1000 ppm;Ca2+, optionally at 10 ppm - 50 ppm;Si e.g., (SiC )2’ and / or [SiO2(OH)2]2), optionally at 100 ppm - 1000 ppm;F’, optionally at 100 ppm - 300 ppm;Na+, optionally at 50 ppm - 200 ppm;K+, optionally at 10 ppm -50 ppm;(CCh)2', optionally at 1 g / L - 5 g / L; or a combination thereof.

41. The process any one of claims 36-40, wherein the amount of lime added is at or above lime’s saturation limit in the brine.

42. The process any one of claims 36-41, wherein the pH of the brine at step (a) is greater than 7.

43. The process any one of claims 36-42, wherein the pH of the brine at step (a) is at least13.

44. The process any one of claims 36-43, wherein the pH of the brine at step (a) is about14.

45. The process of any one of claims 36-44, wherein step (b) produces precipitates selected from CaCCh, calcium-aluminum-silica complexes, or a combination thereof.

46. The process of any one of claims 36-45, wherein the brine after step (c) or step (d) comprises:Al3+, optionally at 100 ppm - 400 ppm;Ca2+, optionally at about 50 ppm;Si (e.g., (SiC )2’ and / or [SiO2(OH)2]2), optionally at about 50 ppm;F’, optionally at 100 ppm - 300 ppm;Na+, optionally at 50 ppm - 200 ppm;K+, optionally at 10 ppm - 50 ppm;(CCh)2', optionally at less than 500 ppm; or a combination thereof.

47. The process of any one of claims 36-46, wherein purifying the brine using nanofiltration comprises removing aluminum (Al), calcium (Ca), silicon (Si), fluorine (F), sodium (Na), potassium (K), carbonate (CO32), ions thereof, complexes thereof, or combinations thereof.

48. The process of any one of claims 36-47, wherein step (b) occurs above room temperature.

49. The process of any one of claims 36-48, wherein step (b) occurs at about 80 °C.

50. The process of any one of claims 36-49, wherein the nanofiltration uses ion selective and polymer, spiral-wound membranes.

51. The process of claim 50, wherein polymer, spiral-wound membranes have a molecular weight cut-off of 120 Daltons (Da) to 200 Da.

52. The process of any one of claims 36-51, wherein purifying the brine using nanofiltration comprises using lime to precipitate impurities from the bring before or after passing the brine through a nanofiltration filter.

53. The process of any one of claims 36-52, wherein purifying the brine using nanofiltration comprises repeatedly passing the brine through at least one nanofiltration filter.

54. The process of any one of claims 36-53, wherein purifying the brine using nanofiltration comprises passing the brine through a polymer, spiral-wound membrane at 30 °C to 40 °C and a pressure of about 500 pounds-per-square-inch (PSI).

55. The process of claim 54, further comprising transferring nanofiltration rejected material to an impurity precipitation loop in which lime is used to precipitate impurities as solids that are filtered from the brine.

56. The process of any one of claims 36-55, wherein purifying the brine using nanofiltration results in a brine that has lower concentrations of fluorine (F) than the brine did before the nanofiltration.

57. The process of any one of claims 36-56, wherein purifying the brine using nanofiltration results in a brine that has lower concentrations of Al, Si, F, CCh2', or a combination thereof, than the brine did before the nanofiltration.

58. The process of any one of claims 36-57, wherein purifying the brine using nanofiltration results in a brine that does not has lower concentrations of Na and / or K than the brine did before the nanofiltration.

59. The process of any one of claims 36-58, wherein after purifying the brine using nanofiltration, the brine comprises 40 wt% to 60 wt% less F than the brine did before nanofiltration.

60. The process of any one of claims 36-58, wherein after purifying the brine using nanofiltration, the brine comprises 90 wt% to 95 wt% less Si than the brine did before nanofiltration.

61. The process of any one of claims 36-58, wherein after purifying the brine using nanofiltration, the brine comprises 90 wt% to 95 wt% less Ca than the brine did before nanofiltration.

62. The process of any one of claims 36-58, wherein after purifying the brine using nanofiltration, the brine comprises 90 wt% to 95 wt% less Al than the brine did before nanofiltration.

63. The process of any one of claims 36-62, further comprising crystallizing lithium hydroxide monohydrate (LiOH FfcO) from the brine.

64. The process of claim 61, wherein crystallizing lithium hydroxide monohydrate (LiOH FhO) comprises recrystallization and washing to remove Na+and K+.

65. A purified lithium hydroxide brine, made by any one of the processes of claims 1-63.

66. Lithium hydroxide made by any one of the processes of claims 1-64 or from the lithium hydroxide brine of claim 65.

67. A cathode active material made using the lithium hydroxide of claim 66.

68. Lithium metal made using the lithium hydroxide of claim 66.

69. The lithium of claim 68, wherein the lithium is made by electroplating the lithium hydroxide.

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