Method of alkaline leaching of metals from lithium-ion batteries

Abstract

This disclosure provides processes for recovering one or more metals or metal compounds from black mass from lithium-ion batteries by alkaline leaching to form an alkaline leachate, and preparing a cathode active material precursor from the alkaline leachate.

Description

METHOD OF ALKALINE LEACHING OF METALS FROM LITHIUM-ION BATTERIES TECHNICAL FIELD

[0001] This disclosure relates to processes for recovery of one or more metals or metal compounds from black mass from lithium-ion batteries by alkaline leaching. BACKGROUND

[0002] Lithium-ion batteries are being used in an increasing number of applications. Leaching useful materials from black mass generated from lithium-ion batteries, especially spent (i.e., end-of-life) lithium-ion batteries, using inorganic acids has been found to require subsequent pH adjustment and precipitation to generate mixed hydroxide precipitates or other products from transition metals and lithium streams. During precipitation, these processes require a large number of alkaline reagents, e.g., CaO and NaOH, to elevate the pH from acidic (generally less than 4) to alkaline (generally more than 10). Additionally, due to the non‐selective leaching behaviors of various inorganic acids (e.g., HCl, H2SO4, and HNO3), impurities (e.g., Fe, Al, Zn) also consume alkaline reagents.

[0003] Thus, there is an ongoing need to develop new processes for more efficient and more cost-effective methods for recycling useful materials from lithium-ion batteries. SUMMARY OF THE DISCLOSURE

[0004] This disclosure provides processes for recovery of one or more metals or metal compounds found in black mass from lithium-ion batteries by alkaline leaching. Typically, the black mass is from the cathode material of a lithium-ion battery.

[0005] An aspect of this disclosure is a process for leaching metals from black mass. The process comprises: a) contacting, in an ambient pressure system, an ammonium composition having a pH of 7 or greater and a black mass comprising one or more metals or metal compounds, wherein the metals or metal compounds contain one or more metal elements selected from the group consisting of lithium, cobalt, nickel, iron, aluminum, and any combination of two or more of the foregoing; b) separating the combination mixture to obtain solid residues and an alkaline leachate in a resulting solution; andc) heating the resulting solution at one or more temperatures no higher than the boiling point of the resulting solution, and while heating, adding an alkaline reagent to the resulting solution with agitation, while, if necessary, adding a reagent to adjust and maintain a pH range or value in the resulting solution, so as to precipitate at least a portion of the alkaline leachate and form a solid cathode active material precursor, the solid cathode active material precursor being comprised of one or more metal hydroxides, wherein the metal is selected from the group consisting of cobalt, nickel, manganese, aluminum, and any combination of two or more of the foregoing, and wherein the heating is in the substantial absence of oxygen when manganese is present.

[0006] In another aspect, the process further comprises: d) separating the solid cathode active material precursor from the resulting solution, and optionally e) forming a final precursor mixture comprising the cathode active material precursor and one or more lithium-containing compounds, and f) calcining the final precursor mixture to form a calcined final mixture comprising a cathode active material.

[0007] In still other aspects, the process may comprise, after separating the combination mixture in b) and before heating the resulting solution in c): b-2) contacting the resulting solution with one or more metal salts of nickel, cobalt, manganese, and / or aluminum in amounts to provide a molar ratio of metal cations relative to one another within a pre-selected range in the resulting solution. These and other aspects and features of this disclosure will be still further apparent from the ensuing description and appended claims. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] The Figure shows a bar chart of the recovery of certain metals from three different types of lithium-ion battery cathode materials after contact with an ammonium composition as described in Example 1.

[0009] The Figure illustrates specific aspects of the disclosure, and is not intended to impose limitations on the scope of the disclosure. FURTHER DETAILED DESCRIPTION OF THE DISCLOSURE

[0010] As used throughout this document, the terms "room temperature" and "ambient temperature" are used herein to describe any temperature from 15° C to 35° C in which no external heat or cooling source is directly applied to the reaction vessel. Accordingly, the terms "room temperature" and "ambient temperature" encompass the individual temperatures and any and all ranges, subranges, and combinations of subranges of temperatures from 15°C to 35°C wherein no external heating or cooling source is directly applied to the reaction vessel.

[0011] As used throughout this document, the terms "atmospheric pressure" and "ambient pressure" are used herein to describe an earth air pressure wherein no external pressure modifying means is utilized. Generally, unless practiced at extreme earth altitudes, "atmospheric pressure" is about 1 atmosphere (alternatively, about 14.7 psi or about 101 kPa).

[0012] Throughout this document, the abbreviation NMC refers to (lithium) nickel manganese cobalt oxide batteries, NCA refers to (lithium) nickel cobalt aluminum oxide batteries, and the abbreviation LMO refers to lithium manganese oxide batteries. Further, as used throughout this document, a three-digit number after NMC, e.g., NMC 622, refers to the ratio of nickel to manganese to cobalt (e.g., 622 is a 6:2:2 ratio of Ni:Mn:Co).

[0013] As used throughout this document, unless otherwise specified, the terms "battery" and "lithium battery" refer to a lithium-ion battery; similarly, the terms "batteries" and "lithium batteries" refer to lithium-ion batteries.

[0014] The methods of this disclosure are typically applied to disused or end-of-life lithium-ion batteries, normally after discharging and dismantling the lithium-ion batteries. Battery black mass from lithium-ion batteries is typically formed from at least disused or end-of-life lithium-ion batteries. As part of the dismantling process, there is often a pretreatment to remove the electrolyte solution, typically by evaporation; then the lithium- ion battery is subjected to a process comprising shredding, crushing, and / or sieving, preferably shredding, crushing, and sieving, along with separations of metal casings, plastic components, aluminum foil, and / or copper foil, to form a lithium-ion battery black mass. The lithium-ion battery black mass is generally in the form of a powder, preferably a granular powder. The lithium-ion battery black mass is preferably a granular powder, and preferably has an average particle size of about 500 microns or less, more preferably about 300 microns or less. The lithium-ion battery black mass can be subjected to particle size reductions techniques such as grinding or milling to achieve the desired particle sizes.

[0015] Lithium-ion battery black mass comprises one or more metal-containing compounds, generally selected from the group consisting of lithium, nickel, cobalt, aluminum, manganese, and combinations of lithium and any one or more of the other foregoing metals.

[0016] Often, lithium-ion battery black mass contains graphite from the lithium-ion battery. In some preferred aspects of this disclosure, the lithium-ion battery black mass is subjected to an optional process to remove the graphite. The process for removal of graphite from the lithium-ion battery black mass is frequently a flotation process; the flotation process can have more than one stage. Typical flotation procedures for graphite removal from lithium-ion battery black mass include froth flotation; in froth flotation, the foaming agent can be 4-methyl-2-pentanol (methyl isobutyl carbinol), and the graphite collector can be kerosene. The product of the flotation procedure is a 'clean' lithium-ion battery black mass preferably containing little or no graphite.

[0017] In the processes of this disclosure, the contacting in step a) is performed in an ambient pressure system, such that if the reactions that occur produce heat or the combination is heated, the pressure does not increase significantly above ambient pressure. In a closed system, this can be accomplished by periodically relieving pressure increases, for example by briefly opening a valve to the atmosphere.

[0018] The black mass comprises one or more metals or metal compounds, wherein the metals or metal compounds contain one or more metal elements selected from the group consisting of lithium, cobalt, nickel, iron, aluminum, and any combination of two or more of the foregoing. Often, the black mass is derived from lithium nickel manganese cobalt oxide batteries, lithium nickel cobalt aluminum oxide batteries, and / or lithium manganese oxide batteries. Preferably, the black mass is derived from one type of battery, preferably lithium nickel manganese cobalt oxide batteries or lithium nickel cobalt aluminum oxide batteries, more preferably lithium nickel cobalt aluminum oxide batteries. When the black mass is derived from lithium nickel manganese cobalt oxide batteries, typical nickel to manganese to cobalt ratios in the black mass are 1:1:1, 5:3:2, 6:2:2, 8:1:1, and 9:0.5:0.5. In some aspects, it may be preferred that the black mass is not derived from lithium-ion batteries comprising a lithium manganese oxide cathode (LMO) material. In some aspects, it may be preferred that the black mass is not derived from lithium iron phosphate batteries.

[0019] The ammonium composition has a pH of 7 or greater and comprises an ammonia source, typically ammonium hydroxide, ammonium sulfate, ammonium chloride, or anycombination of two or more of the foregoing; ammonium hydroxide is a preferred ammonia source. The ammonium composition is usually an aqueous solution. A buffer and / or a reducing agent may be present in the ammonium composition. In some aspects, a buffer is present in the ammonium composition, in other aspects, a reducing agent is present in the ammonium composition, and in still other aspects, both a buffer and a reducing agent are present in the ammonium composition.

[0020] The amount of the ammonium source present in the ammonium composition, and the amount of buffer and / or reducing agent, if used, may vary. Typically, the amount of ammonium source is in the range of about 0.5 M to about 5 M, preferably about 0.75 M to about 3 M. The amount of buffer, when present, is typically in the range of about 0.05 M to about 5 M, preferably about 0.1 M to about 1 M. The amount of reducing agent, when present, is typically in the range of about 0.1 M to about 2.5 M, preferably about 0.3 M to about 1.5 M.

[0021] The buffer is selected from the group consisting of ammonium carbonate, ammonium bicarbonate, lithium carbonate, lithium bicarbonate, sodium carbonate, sodium bicarbonate, carbonic acid, and any combination of two or more of the foregoing.

[0022] The reducing agent comprises ammonium sulfite and / or hydrogen peroxide.

[0023] The relative amounts of black mass to ammonium composition in the practice of this disclosure is typically in the range of about 5g / L to about 1000g / L, preferably about 100g / L to about 750 g / L, more preferably about 125 g / L to about 500 g / L or about 300 g / L to about 700 g / L, where grams refer to the black mass and liters refer to the ammonium composition.

[0024] The contacting of the black mass and the ammonium composition typically occurs in a reaction vessel or reaction zone, typically under conditions that apply physical agitation, usually stirring, to the combination mixture of black mass and ammonium composition over a period of time. Agitation can be carried out by mixing or stirring in any conventional manner under a given reactor configuration to give the ammonium composition and black mass the opportunity to come into contact with one another for some period of time, and that period of time may vary widely depending upon the components and reaction conditions, but typically will be in the range of about 0.5 to about 8 hours, under super- ambient, ambient or sub-ambient temperature conditions. When the agitation comprises stirring, the stirring speed is in the range of about 100 to about 2000 rpm, preferably about 100 to about 1000 rpm, more preferably about 100 to about 500 rpm.

[0025] In some aspects, the combination mixture formed by the ammonium composition and the black mass is heated to and maintained at one or more temperatures in the range of about 25°C to about 85°C, preferably to one or more temperatures in the range of about 35°C to about 70°C, during the contacting.

[0026] An advantage of this step is that conducting the contacting of the ammonium composition and black mass under an inert atmosphere is not required. In other words, the exclusion of oxygen is not necessary during this step.

[0027] In step b), the separating can be carried out by methods known in the art, such as decantation, centrifugation, or filtration; filtration is often preferred. The solid residues are usually disposed of, but may be subjected to further treatment if a substance of interest is present therein. The alkaline leachate in the resulting solution usually contains the metals of interest.

[0028] The resulting solution is then subjected to the treatment of step c). The treatment in step c) typically occurs in a reaction vessel or reaction zone. In step c), the resulting solution is heated at one or more temperatures no higher than the boiling point of the resulting solution. The boiling point of the resulting solution depends on various factors, such as the components of the solution and their concentration.

[0029] When manganese is present, heating of the resulting solution is in the substantial absence of oxygen. A substantial absence of oxygen typically means that step c) is carried out in an atmosphere of nitrogen, argon, helium, carbon dioxide, or a mixture of any two or more of the foregoing. The phrase "in the substantial absence of oxygen," as used throughout this document, refers to an essentially oxygen-free gas or mixture of gases; adventitious amounts of oxygen may be present in the essentially oxygen-free gas or mixture of gases. The essentially oxygen-free gas or mixture of gases is typically carbon dioxide, argon, nitrogen, helium, or a mixture of any two or more of these; nitrogen and argon are preferred.

[0030] While heating, an alkaline reagent is added to the resulting solution with agitation, and, if necessary, a reagent is added to adjust and maintain a pH range or value in the resulting solution, so as to precipitate at least a portion of the alkaline leachate and form a solid cathode active material precursor. Agitation can be carried out by mixing or stirring in any conventional manner under a given reactor configuration for some period of time to give the resulting solution the opportunity to form the solid cathode precursor material. The period of time may vary widely depending upon the components and reaction conditions,but typically will be in the range of about 0.5 to about 8 hours, under super-ambient, ambient or sub-ambient temperature and pressure conditions. When the agitation comprises stirring, the stirring speed is in the range of about 100 to about 2000 rpm, preferably about 100 to about 1000 rpm, more preferably about 100 to about 500 rpm.

[0031] The alkaline reagent added to the resulting solution is typically an alkali metal base or an ammonium base, preferably a sodium base, a potassium base, or an ammonium base, and can be added to the resulting solution in solid form, as an aqueous slurry, or as an aqueous solution. The alkaline reagent may be a hydroxide, a carbonate, a bicarbonate, or an oxalate. Preferably, the alkaline reagent is selected from the group consisting of sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, potassium hydroxide, ammonium hydroxide, ammonium carbonate, ammonium bicarbonate, and a combination of any two or more of the foregoing.

[0032] Addition of the alkaline reagent to the resulting solution causes precipitation of at least a portion of the metals present in the alkaline leachate from the resulting solution as one or more metal-containing compounds, typically the metal compounds are hydroxides. The precipitate is the solid cathode precursor material. The metals of the metal-containing compounds are selected from the group consisting of, cobalt, nickel, manganese, aluminum, and any combination of two or more of the foregoing.

[0033] During the addition of the alkaline reagent and any subsequent heating, the pH in the resulting solution is in the range of about 10 to about 14. In some instances, to maintain the pH in this range, one or more reagents is added to the resulting solution. Typically, the reagent is additional alkaline reagent, and preferably, the additional alkaline reagent is the same alkaline reagent or reagents that are being added or have been added to the resulting solution.

[0034] The heating of the resulting solution is carried out at least until the solid cathode active material precursor has a targeted morphology and / or tap density, after which the solid cathode active material precursor is recovered. Morphology refers to an average particle size, typically with a minimum and / or maximum particle size, and varies with the components and relative amounts of the solid cathode active material precursor being formed. The particle sizes and average particle size generally increase as the reaction proceeds, and then stabilize; the stabilizing of the particle sizes and average particle size is an indication that the reaction is complete. Tap density (or tapped density) refers to the density of a material after mechanical tapping, and the tap density of the solid cathode activematerial precursor usually increases as the reaction proceeds. Preferably, both the morphology and the tap density are monitored to determine an endpoint for the heating.

[0035] The solid cathode active material precursor obtained in step c) is usually comprised of one or more metal hydroxides, in which the metal is selected from the group consisting of cobalt, nickel, manganese, aluminum, and any combination of two or more of the foregoing. Preferably, the metals are a combination of cobalt, nickel, and manganese or a combination of cobalt, nickel, and aluminum; more preferably, the metals are a combination of cobalt, nickel, and aluminum.

[0036] An optional step that can be performed at any point during steps b)-c) is the introducing of one or more dopants into the resulting solution, each dopant comprised of an element selected from the group consisting of Al, Ag, Mg, Ti, Zn, Ga, Cu, Mo, Nb, Zr, Hf, Ta, W, B, P and F.

[0037] After step c), an optional step d) may be performed. Step d) comprises separating the solid cathode active material precursor from the resulting solution. The separating can be carried out by methods known in the art, such as decantation, centrifugation, or filtration; filtration is often preferred.

[0038] After optional step d), optional steps e) and f) may be performed. Step e) comprises forming a final precursor mixture comprising the cathode active material precursor and one or more lithium-containing compounds, and step f) comprises calcining the final precursor mixture to form a calcined final mixture comprising a cathode active material.

[0039] The lithium-containing compound in step e) preferably is selected from the group consisting of lithium hydroxide, lithium carbonate, lithium oxide, lithium peroxide, lithium acetate, lithium nitrate, and any combination of two or more of the foregoing.

[0040] In step f), the calcining is typically performed at one or more temperatures in the range of about 500°C to about 1100°C.

[0041] In some aspects, after separating the combination mixture in step b) and before heating the resulting solution in step c), a step b-2) is performed. In step b-2), the resulting solution is contacted with one or more metal salts of nickel, cobalt, manganese, and / or aluminum in amounts to provide a molar ratio of metal cations relative to one another within a pre-selected range in the resulting solution. Preferably, the molar ratio of metal cations relative to one another corresponds to a molar ratio of metals in a cathode active material, so that the cathode active material precursor obtained at the end of step c) has a molar ratio of metals corresponding to those in a cathode active material. For example, in someinstances in which the metals are a combination of nickel, cobalt, and manganese, the amounts of metal salts are added in amounts to provide a 6:2:2 molar proportion of Ni:Mn:Co in the resulting solution.

[0042] Each of the one or more metal salts in step b-2) preferably has an anion selected from the group consisting of hydroxide, carbonate, nitrate, sulfate, acetate, oxalate, lactate, tartrate, stearate, oleate, and a combination of any two or more of the foregoing. Sulfate is a preferred anion. Preferably, the metal salts in step b-2) are metal salts of nickel, cobalt, and / or aluminum, or the metal salts are metal salts of nickel, cobalt, and / or manganese.

[0043] The processes of this disclosure comprise steps a), b), and c). In some aspects, the processes of this disclosure comprise steps a), b), c), and d). In other aspects, the processes of this disclosure comprise steps a), b), c), d), e) and f).

[0044] In still other aspects, the processes of this disclosure comprise steps a), b), b-2), and c). In still other aspects, the processes of this disclosure comprise steps a), b), b-2), c), and d). In yet other aspects, a), b), b-2), c), d), e), and f). On the laboratory scale, a process comprising steps) a), b), b-2), c), and d), takes about 4 to about 12 hours depending on the desired morphology and density for the solid cathode material precursor.

[0045] The following examples are presented for purposes of illustration, and are not intended to impose limitations on the scope of this disclosure.

[0046] Recovery rates (i.e., the amount of metal recovered) of the indicated metals in the Examples below were determined by inductively coupled plasma optical emission spectroscopy (ICP-OES) after microwave digestion and before leaching of the black mass, and by ICP-OES for the resulting liquid sample(s) that were generated.

[0047] Specifically, initial black mass characterization, for each of the lithium-ion battery types indicated in the examples, was carried out as follows: 1) Black mass sample was homogenized using an acoustic mixer (LabRAM II, Resodyn Corporation), in case of any sample heterogeneity. This acoustic mixer was a low- frequency acoustic mixer that provided uniform mixing across a broad range of materials and can be applied to powder-powder systems. 2) Some of the homogenized black mass powder (initial mass recorded as m0) prepared in step 1) was heated at 110 °C in an oven for 12 hours. The black mass powder sample was cooled to room temperature and weighed; the sample mass m1was recorded. The LOD% (Loss on Drying) = (m0 -m1) / m0 × 100. The LOD% was calculated and then used to estimate the volatile content in the initial black mass.3) Some of the homogenized black mass powder (initial mass recorded as m0) prepared in step 1) was heated at 850 °C in an oven for 5 hours. The sample was cooled to room temperature and weighed; the sample mass was recorded as m1. The LOI% (Loss on Ignition) = (m0- m1) / m0× 100. The LOI% was calculated and then used to estimate the carbon content in the initial black mass. 4) For each black mass sample taken after baking at 850 °C for 5 hours in step 3), an LOI% to be used in step 5) was determined. First, ~ 100 mg of a sample was weighed, and the actual sample mass was recorded. The weighed sample was placed in a mixture of HNO3: HCl = 3 : 1 v / v, and the combined mixture was placed in a microwave digestion instrument (Multiwave 7000, Anton Paar GmbH) to achieve complete digestion. Each sample was run in triplicate. 5) Each sample from step 4) after digestion was diluted to a concentration range appropriate for ICP-OES analysis, the dilution factor (DF) was recorded, and then the sample was introduced to an inductively coupled plasma optical emission spectrometer (Avio®500 ICP-OES, PerkinElmer, Inc.). A baffled cyclonic spray chamber, alumina injector, and a one-slot demountable quartz torch for the Avio®200 / 500 were used. For a given element, the directly measured concentration from ICP-OES is cm. The initial concentration in the liquid sample was c0 = cm × DF. 6) Final stream analysis of the liquid samples was carried out as follows: Each liquid sample was diluted to a concentration range appropriate for ICP-OES analysis, the dilution factor (DF) was recorded, and then the sample was introduced to an inductively coupled plasma optical emission spectrometer (Avio®500 ICP-OES, PerkinElmer, Inc.). The instrument set up was the same as step 5) above for initial characterization of black mass. For a given element, the directly measured concentration from ICP-OES is cm. The initial concentration in the liquid sample was c0= cm× DF.

[0048] Unless otherwise indicated in the examples, the experiments were carried out at ambient temperature and pressure conditions. EXAMPLE 1

[0049] Three runs were performed as follows. An aqueous solution having a volume of about 250 mL and containing ammonia hydroxide (1.0 M), ammonium sulfite (0.5 M), and ammonium carbonate (0.1 M) was prepared and transferred into 500 mL reaction flaskequipped with agitation and heating system. The solution was agitated at a speed of about 200 rpm, while the solution was heated to a temperature of about 60°C. While the solution was heating, about 5 grams of a cathode powder or black mass was added into the 500 mL flask. After maintaining the solution at 60°C for 4 hours, the mixture was cooled to room temperature, and filtered to obtain an alkaline leachate. In one run, the cathode powder was lithium nickel manganese cobalt oxide cathode powder (6:2:2 molar proportion of Ni:Mn:Co, or NMC 622); in another run, the black mass was lithium nickel cobalt aluminum oxide (NCA) black mass prepared as in steps 1), 3), and 4) above. In the third run, the cathode powder was lithium manganese oxide powder. The cathode powders are used as an approximation for how a black mass derived from lithium-ion batteries will perform.

[0050] The recovery rates for the NMC 622 cathode powder, the NCA based black mass, and LMO cathode powder are summarized in Table 1, and shown as a bar graph of the relative recoveries in the Figure. These recovery rates indicate that less favorable results are obtained when the process is carried out on a cathode powder or black mass derived from LMO cathodes. TABLE 1 Li-ion battery type Metal NMC 622 NCA LMO Li 91.5% 96.7% 10% Ni 92.7% 86.9% -- Co 96.2% 98.8% -- Mn < 1% -- < 1% EXAMPLE 2

[0051] For each run, water will be introduced to a reactor, and nitrogen or argon will be bubbled through the water for 30 minutes, after which ammonia water and a sodium hydroxide solution will be added to the water to make a deoxygenated solution having a pH above 10. A pH meter will be used to monitor the deoxygenated solution.

[0052] Separately, to each of the alkaline leachates obtained in Example 1 will be added metal sulfates to obtained desired ratios of the metal cations. To the alkaline leachate from the lithium nickel manganese cobalt oxide cathode powder, MnSO4 will be added; to the alkaline leachate from the lithium nickel cobalt aluminum oxide black mass, aluminumsulfate with or without nickel sulfate and / or cobalt sulfate, depending on the desired ratios of metal cations, will be added.

[0053] The temperature of the deoxygenated solution will be raised to 60°C, and the alkaline leachates to which the sulfate salts are added will be pumped at a rate of 0.5 to 5 mL / min into the deoxygenated solution, and precipitation will start when the alkaline leachate comes into contact with the deoxygenated solution. The pH meter will determine when to add additional sodium hydroxide solution into the reactor; the pH meter will be connected to the reactor and to a control that will automatically add NaOH to the solution to maintain the pH at the set value.

[0054] The above process will be run continuously for up to three days while periodically sampling to monitor the particle size and tap density of the solids. When the reaction is complete, the precipitates will be filtered and washed with deionized water. The filtrate will contain Na+, SO42-, and ammonia, which may be recycled if desired. The final solid portion from the filtration step of each run (solid cathode active material precursor) will be collected and dried at a temperature above 100°C for five hours or longer.

[0055] Further aspects of the disclosure include, without limitation:

[0056] A) A process comprising: a) contacting, in an ambient pressure system, an ammonium composition having a pH of 7 or greater and a black mass comprising one or more metals or metal compounds, wherein the metals or metal compounds contain one or more metal elements selected from the group consisting of lithium, cobalt, nickel, iron, aluminum, and any combination of two or more of the foregoing; b) separating the combination mixture to obtain solid residues and an alkaline leachate in a resulting solution; and c) heating the resulting solution at one or more temperatures no higher than the boiling point of the resulting solution, and while heating, adding an alkaline reagent to the resulting solution with agitation, while, if necessary, adding a reagent to adjust and maintain a pH range or value in the resulting solution, so as to precipitate at least a portion of the alkaline leachate and form a solid cathode active material precursor, the solid cathode active material precursor being comprised of one or more metal hydroxides, wherein the metal is selected from the group consisting of cobalt, nickel, manganese, aluminum, and any combination of two or more of the foregoing, andwherein the heating is in the substantial absence of oxygen when manganese is present.

[0057] B) The process of A), wherein in step a) the ammonium composition comprises ammonium hydroxide.

[0058] C) The process of A) or B), wherein in step a) a buffer is present and / or wherein a reducing agent is present in the ammonium composition.

[0059] D) The process of C), wherein in step a) a buffer and a reducing agent are present in the ammonium composition.

[0060] E) The process of C) or D), wherein: the buffer is selected from the group consisting of ammonium carbonate, ammonium bicarbonate, lithium carbonate, lithium bicarbonate, sodium carbonate, sodium bicarbonate, carbonic acid, and any combination of two or more of the foregoing; and / or the reducing agent comprises ammonium sulfite and / or hydrogen peroxide.

[0061] F) The process of any one of A)-E), wherein in step a) the combination mixture is heated to one or more temperatures in the range of about 25°C to about 85°C.

[0062] G) The process of any one of A)-F), further comprising, after separating the combination mixture in b) and before heating the resulting solution in c): b-2) contacting the resulting solution with one or more metal salts of nickel, cobalt, manganese, and / or aluminum in amounts to provide a molar ratio of metal cations relative to one another within a pre-selected range in the resulting solution.

[0063] H) The process of G), wherein: the metal salts are metal salts of nickel, cobalt, and / or aluminum, or wherein the metal salts are metal salts of nickel, cobalt, and / or manganese; and / or each of the metal salts has an anion selected from the group consisting of hydroxide, carbonate, nitrate, sulfate, acetate, oxalate, lactate, tartrate, stearate, oleate, and a combination of any two or more of the foregoing.

[0064] I) The process of A), wherein the alkaline reagent is selected from the group consisting of sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, potassium hydroxide, ammonium hydroxide, ammonium carbonate, ammonium bicarbonate, and a combination of any two or more of the foregoing.

[0065] J) The process of A) or I), wherein in step c) the pH in the resulting solution is in the range of about 10 to about 14.

[0066] K) The process of any one of A), I), or J), wherein the agitation comprises stirring, and the stirring speed is in the range of about 100 to about 2000 rpm.

[0067] L) The process of any one of A) or I)-K), wherein the heating of the resulting solution is carried out at least until the solid cathode active material precursor has a targeted morphology and / or tap density, after which the solid cathode active material precursor is recovered.

[0068] M) The process of A), further comprising introducing one or more dopants into the resulting solution, each dopant comprised of an element selected from the group consisting of Al, Ag, Mg, Ti, Zn, Ga, Cu, Mo, Nb, Zr, Hf, Ta, W, B, P and F.

[0069] N) The process of A), further comprising d) separating the solid cathode active material precursor from the resulting solution.

[0070] O) The process of N), further comprising: e) forming a final precursor mixture comprising the cathode active material precursor and one or more lithium-containing compounds, and f) calcining the final precursor mixture to form a calcined final mixture comprising a cathode active material.

[0071] P) The process of O), wherein the lithium-containing compound is selected from the group consisting of lithium hydroxide, lithium carbonate, lithium oxide, lithium peroxide, lithium acetate, lithium nitrate, and any combination of two or more of the foregoing.

[0072] Q) The process of O) or P), wherein the calcining is performed at one or more temperatures in the range of about 500°C to about 1100°C.

[0073] Components referred to by chemical name or formula anywhere in the specification or claims hereof, whether referred to in the singular or plural, are identified as they exist prior to coming into contact with another substance referred to by chemical name or chemical type (e.g., another component, a solvent, or etc.). It matters not what chemical changes, transformations and / or reactions, if any, take place in the resulting mixture or solution as such changes, transformations, and / or reactions are the natural result of bringing the specified components together under the conditions called for pursuant to this disclosure. Thus the components are identified as ingredients to be brought together in connection with performing a desired operation or in forming a desired composition. Also, even though the claims hereinafter may refer to substances, components and / or ingredients in the presenttense ("comprises", "is", etc.), the reference is to the substance, component or ingredient as it existed at the time just before it was first contacted, blended or mixed with one or more other substances, components and / or ingredients in accordance with the present disclosure. The fact that a substance, component or ingredient may have lost its original identity through a chemical reaction or transformation during the course of contacting, blending or mixing operations, if conducted in accordance with this disclosure and with ordinary skill of a chemist, is thus of no practical concern.

[0074] The disclosure may comprise, consist, or consist essentially of the materials and / or procedures recited herein.

[0075] As used herein, the term "about" modifying the quantity of an ingredient in the compositions of the disclosure or employed in the methods of the disclosure refers to variation in the numerical quantity that can occur, for example, through typical measuring and liquid handling procedures used for making concentrates or use solutions in the real world; through inadvertent error in these procedures; through differences in the manufacture, source, or purity of the ingredients employed to make the compositions or carry out the methods; and the like. The term about also encompasses amounts that differ due to different equilibrium conditions for a composition resulting from a particular initial mixture. Whether or not modified by the term "about", the claims include equivalents to the quantities.

[0076] Except as may be expressly otherwise indicated, the article "a" or "an" if and as used herein is not intended to limit, and should not be construed as limiting, the description or a claim to a single element to which the article refers. Rather, the article "a" or "an" if and as used herein is intended to cover one or more such elements, unless the text expressly indicates otherwise.

[0077] This disclosure is susceptible to considerable variation in its practice. Therefore the foregoing description is not intended to limit, and should not be construed as limiting, the disclosure to the particular exemplifications presented hereinabove.

Claims

THAT WHICH IS CLAIMED IS:

1. A process comprising: a) contacting, in an ambient pressure system, an ammonium composition having a pH of 7 or greater and a black mass comprising one or more metals or metal compounds, wherein the metals or metal compounds contain one or more metal elements selected from the group consisting of lithium, cobalt, nickel, iron, aluminum, and any combination of two or more of the foregoing; b) separating the combination mixture to obtain solid residues and an alkaline leachate in a resulting solution; and c) heating the resulting solution at one or more temperatures no higher than the boiling point of the resulting solution, and while heating, adding an alkaline reagent to the resulting solution with agitation, while, if necessary, adding a reagent to adjust and maintain a pH range or value in the resulting solution, so as to precipitate at least a portion of the alkaline leachate and form a solid cathode active material precursor, the solid cathode active material precursor being comprised of one or more metal hydroxides, wherein the metal is selected from the group consisting of cobalt, nickel, manganese, aluminum, and any combination of two or more of the foregoing, and wherein the heating is in the substantial absence of oxygen when manganese is present.

2. The process according to Claim 1, wherein the heating of the resulting solution is carried out at least until the solid cathode active material precursor has a targeted morphology and / or tap density, after which the solid cathode active material precursor is recovered.

3. The process of Claim 1, further comprising, after separating the combination mixture in b) and before heating the resulting solution in c): b-2) contacting the resulting solution with one or more metal salts of nickel, cobalt, manganese, and / or aluminum in amounts to provide a molar ratio of metal cations relative to one another within a pre-selected range in the resulting solution.

4. The process according to Claim 1, further comprising d) separating the solid cathode active material precursor from the resulting solution.

5. The process of claim 1, wherein in step a) the ammonium composition comprises ammonium hydroxide.

6. The process of claim 1, wherein in step a) a buffer is present and / or wherein a reducing agent is present in the ammonium composition.

7. The process of claim 6, wherein the buffer is selected from the group consisting of ammonium carbonate, ammonium bicarbonate, lithium carbonate, lithium bicarbonate, sodium carbonate, sodium bicarbonate, carbonic acid, and any combination of two or more of the foregoing.

8. The process of claim 6, wherein the reducing agent comprises ammonium sulfite and / or hydrogen peroxide.

9. The process of claim 1, wherein in step a) a buffer and a reducing agent are present in the ammonium composition.

10. The process of claim 9, wherein the buffer is selected from the group consisting of ammonium carbonate, ammonium bicarbonate, lithium carbonate, lithium bicarbonate, sodium carbonate, sodium bicarbonate, carbonic acid, and any combination of two or more of the foregoing, and wherein the reducing agent comprises ammonium sulfite and / or hydrogen peroxide.

11. The process of claim 1, wherein in step a) the combination mixture is heated to one or more temperatures in the range of about 25°C to about 85°C.

12. The process according to claim 3, wherein each of the metal salts has an anion selected from the group consisting of hydroxide, carbonate, nitrate, sulfate, acetate, oxalate, lactate, tartrate, stearate, oleate, and a combination of any two or more of the foregoing.

13. The process of claim 3, wherein the metal salts are metal salts of nickel, cobalt, and / or aluminum, or wherein the metal salts are metal salts of nickel, cobalt, and / or manganese.

14. The process according to claim 1, wherein the alkaline reagent is selected from the group consisting of sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, potassium hydroxide, ammonium hydroxide, ammonium carbonate, ammonium bicarbonate, and a combination of any two or more of the foregoing.

15. The process according to claim 1, wherein in step c) the pH in the resulting solution is in the range of about 10 to about 14.

16. The process according to Claim 1, wherein the agitation comprises stirring, and the stirring speed is in the range of about 100 to about 2000 rpm.

17. The process of claim 4, further comprising: e) forming a final precursor mixture comprising the cathode active material precursor and one or more lithium-containing compounds, and f) calcining the final precursor mixture to form a calcined final mixture comprising a cathode active material.

18. The process of claim 17, wherein the lithium-containing compound is selected from the group consisting of lithium hydroxide, lithium carbonate, lithium oxide, lithium peroxide, lithium acetate, lithium nitrate, and any combination of two or more of the foregoing.

19. The process of claim 17, wherein the calcining is performed at one or more temperatures in the range of about 500°C to about 1100°C.

20. The process of claim 1, further comprising introducing one or more dopants into the resulting solution, each dopant comprised of an element selected from the group consisting of Al, Ag, Mg, Ti, Zn, Ga, Cu, Mo, Nb, Zr, Hf, Ta, W, B, P and F.

Images