METHOD OF ALKALINE LEACHING OF USEFUL METALS FROM LITHIUM- ION BATTERIES TECHNICAL FIELD [0001] The present disclosure relates generally to processes for recovering useful materials from used lithium-ion batteries. BACKGROUND [0002] This section introduces information that may be related to or provide context for some aspects of the compositions or processes described herein and/or claimed below. This information is background facilitating a better understanding of the disclosed subject matter. Such background may include a discussion of “related” art. That such art is related in no way implies that it is also “prior” art. The related art may or may not be prior art. The discussion is to be read in this light, and not as admissions of prior art. [0003] Leaching useful materials from black mass generated from spent (i.e., end-of-life) lithium-ion batteries using inorganic acid has been found to require subsequent pH adjustment and precipitation to generate mixed hydroxide precipitate (MHP) or other products from transition metals and lithium (Li) streams. During precipitation, the process requires a large number of alkaline reagents, e.g., CaO and NaOH, to elevate the pH from acid (generally less than 4) to alkaline (generally more than 10). Additionally, due to the non‐selective leaching behaviors of inorganic acids (e.g., HCl, H2SO4, and HNO3) impurities (e.g., Fe, Al, Zn) also consume alkaline reagents to be removed. [0004] Thus, there is an ongoing need to develop new processes for more effective and efficient recovery of useful materials from black mass formed from spent lithium-ion batteries. SUMMARY OF THE DISCLOSURE [0005] In general, the present disclosure provides a process comprising. (A) contacting, in an ambient pressure system, a mass with a liquid ammonium system comprising an ammonia source, so as to form a combination, wherein the mass was formed from at least secondary batteries (e.g., lithium-ion batteries) and comprises one or
Atty Docket No. ESS-L1-8131 WO more metal-containing compounds, wherein the metal is selected from the group consisting of lithium, cobalt, nickel, iron, aluminum, and any combination of two or more of the foregoing; (B) separating an alkaline leachate from the combination; (C) infusing one or more oxidizing agents into the alkaline leachate; (D) adjusting the pH of the alkaline leachate to enhance formation of a precipitate comprising one or more metal-containing compounds, wherein the metal is selected from the group consisting of lithium, cobalt, nickel, iron, aluminum, and any combination of two or more of the foregoing; and (E) infusing one or more of carbon dioxide, sodium carbonate, sodium bicarbonate, lithium carbonate, and lithium bicarbonate into the alkaline leachate to enhance formation of an additional precipitate comprising one or more metal-containing compounds, where in the metal is selected from the group consisting of cobalt, nickel, iron, aluminum, and any combination of two or more of the foregoing. [0006] In some aspects of the invention, the ammonium system comprises the ammonia source and a buffer. [0007] In some aspects of the invention, the buffer comprises ammonium carbonate, ammonium bicarbonate, lithium carbonate, lithium bicarbonate, sodium carbonate, sodium bicarbonate, carbonic acid, or a combination of any two or more of the foregoing. [0008] In some aspects of the invention, the ammonia source comprises ammonium hydroxide, ammonium sulfate, ammonium chloride, or any combination of two or more of the foregoing. [0009] In some aspects of the invention, the ammonium system further comprises a reducing agent. In other aspects of the invention, the reducing agent comprises ammonium sulfite, hydrogen peroxide, or a combination of the two. [0010] In other aspects of the invention, in step (A) of the process the pH of the ammonium system is in the range of about 7 to about 14. In other aspects of the invention the pH of the ammonium system is in the range of about 8 to about 11. [0011] While multiple embodiments and aspects of the invention are disclosed, still other embodiments will become apparent to those skilled in the art from the following detailed description. As will be apparent, certain embodiments and aspects, as disclosed herein, are capable of modifications in various aspects apparent to those of skill in the art in the light of this disclosure, all without departing from the spirit and scope of the claims as
Atty Docket No. ESS-L1-8131 WO presented below. Accordingly, the drawings and detailed description are to be regarded as illustrative in nature and not restrictive. BRIEF DESCRIPTION OF THE DRAWINGS [0012] For a detailed description of certain embodiments of the disclosed subject matter, reference will now be made to the accompanying drawing(s) in which: [0013] The Figure illustrates a bar graph showing the experimental results obtained in Example 1. [0014] While the claimed subject matter is susceptible to various modifications and alternative forms, the drawing(s) and examples illustrate specific embodiments herein described in detail by way of example. It should be understood, however, that the description herein of specific embodiments is not intended to limit the claimed subject matter to the particular embodiment(s) disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims. DESCRIPTION [0015] Following the Definitions provided below, illustrative aspects of the subject matter claimed further below will now be disclosed. In the interest of clarity, not all features of an actual implementation are described in this specification. It will be appreciated that in the development of any such actual embodiment, numerous implementation-specific decisions must be made to achieve the developers’ specific goals, such as compliance with system- related and business-related constraints, which will vary from one implementation to another. Moreover, it will be appreciated that such a development effort, even if complex and time-consuming, would be a routine undertaking for those of ordinary skill in the art having the benefit of this disclosure. [0016] In this disclosure, features of the subject matter are described such that, within particular aspects, a combination of different features can be envisioned. For each and every aspect and each and every feature disclosed herein, all combinations that do not detrimentally affect the processes or methods described herein are contemplated with or without explicit description of the particular combination. Additionally, unless explicitly recited otherwise, any aspect or feature disclosed herein can be combined to describe inventive processes or methods consistent with this disclosure.
Atty Docket No. ESS-L1-8131 WO Definitions [0017] Unless otherwise indicated, the following definitions are applicable to this disclosure. Terms that do not appear below have their ordinary and customary meaning understood in the context of this disclosure by a person of ordinary skill in the art relating to the technical field of this disclosure. To the extent that any definition or usage provided by any document incorporated here by reference conflicts with the definition or usage provided herein, the definition or usage provided in this disclosure controls. [0018] While processes or methods are often described in this disclosure in terms of “comprising” various components or steps, the methods can also “consist essentially of” or “consist of” the various components or steps, unless stated otherwise. For example, a process consistent with aspects of the disclosed subject matter can comprise; alternatively, can consist essentially of; or alternatively, can consist of, the process steps indicated. [0019] The terms “a,” “an,” and “the” are intended to include plural alternatives, e.g., at least one, one or more, and one or more than one, unless otherwise specified. [0020] The term “contacting” is used herein to describe systems, compositions, processes, and methods in which the components are contacted, combined, or brought together in any order, in any manner, and for any length of time, unless otherwise specified. For example, the components can be combined by blending or mixing, using any suitable technique. [0021] The terms “room temperature” or “ambient temperature” are used herein to describe any temperature from 15° C to 35° C wherein 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. [0022] The term “atmospheric pressure” or “ambient pressure” is 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). [0023] 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. [0024] The term “about” means that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but may be approximate including being larger or smaller, as desired, reflecting tolerances, conversion factors,
Atty Docket No. ESS-L1-8131 WO rounding off, measurement errors, and the like, and other factors known to those of skill in the art. In general, an amount, size, formulation, parameter or other quantity or characteristic is “about” or “approximate” whether or not expressly stated to be such. 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 stated quantities. [0025] Various numerical ranges are disclosed herein. When a range of any type is disclosed or claimed herein (e.g., “ranging from…”, “in a range of from…”, “in the range of from…”, “in a range of from”, “in a range of”) the intent is to disclose or claim individually each possible number that such a range could reasonably encompass, including end points of the range as well as any sub-ranges and combinations of sub- ranges encompassed therein, unless otherwise specified. Detailed Description [0026] The ammonium-based leaching aspect of the processes disclosed herein is an effective process feature enabling the processes to achieve selective extraction of valuable metals (e.g., Li, Co, Ni) from black mass. Such a process, in at least some aspects, employs an ammonium system for selective Li, cobalt (Co), and nickel (Ni) leaching where manganese (Mn) is eliminated from the leachate. The leaching efficiencies are remarkable, as will be noted from the examples below. [0027] Embodiments disclosed herein can provide the materials listed as suitable for satisfying a particular feature of the embodiment delimited by the term “or.” For example, a particular feature of the disclosed subject matter can be disclosed as follows: Feature X can be A, B, or C. It is also contemplated that for each feature the statement can also be phrased as a listing of alternatives such that the statement “Feature X is A, alternatively B, or alternatively C” is also an embodiment of the present disclosure whether or not the statement is explicitly recited. [0028] Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the subject matter described herein, the typical methods and materials are herein described. A. Leaching [0029] In aspects of the invention, a mass (e.g., black mass formed from shredded lithium- ion battery active material components, preferably separated from other non-active
Atty Docket No. ESS-L1-8131 WO lithium-ion battery components, such as plastic casings and the like) is contacted, in an ambient pressure system, with a liquid ammonium system comprising an ammonia source, so as to form a combination. The battery mass is one that has been formed from at least disused or end-of-life lithium-ion batteries. As part of the battery 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 and plastic components, to form a (lithium-ion battery) mass. The lithium- ion battery mass is generally in the form of a powder, preferably a granular powder. The lithium-ion battery 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. [0030] Often, the (lithium-ion battery) mass contains graphite from the lithium-ion battery. In some preferred embodiments of this disclosure, the mass is subjected to an optional process to remove the graphite. The process for removal of graphite from the mass is frequently a flotation process; the flotation process can have more than one stage. Typical flotation procedures for graphite removal from the 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' mass preferably containing little or no graphite. [0031] 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. [0032] The (lithium-ion battery) mass comprises one or more metal-containing compounds. The metal of the metal containing compounds is selected from the group consisting of lithium, cobalt, nickel, iron, aluminum, and any combination of two or more of the foregoing. Typical non-limiting examples of the metal-containing compounds are copper, manganese, zinc, calcium, silicon, and the like. Often, the mass is derived from lithium nickel manganese cobalt oxide batteries, lithium nickel cobalt aluminum oxide batteries, and/or lithium manganese oxide batteries. Preferably, the mass is derived from
Atty Docket No. ESS-L1-8131 WO one type of battery, preferably lithium nickel manganese cobalt oxide batteries or lithium nickel cobalt aluminum oxide batteries. [0033] In some aspects of the invention, the mass is formed from lithium-ion batteries that exclude those of the iron phosphate or Li iron phosphate (LFP) type. The mass in some aspects of the invention is also pre-treated to remove copper (Cu), unless known to be devoid of copper, so that copper is not present in any material amount in the leachate formed. It may also be preferred in some aspects of the invention that the mass is not derived from manganese-based lithium-ion batteries (e.g., those with lithium-ion manganese oxide cathode (LMO) material). [0034] The ammonium source of the liquid ammonium system in at least some aspects of the invention comprises either ammonium hydroxide, ammonium sulfate, ammonium chloride, or any combination of two or more of the foregoing. In some aspects of the invention, the liquid ammonium system optionally may comprise additional components, including a buffer or a reducing agent, or both. When present, the buffer in some aspects of the invention comprises ammonium carbonate, ammonium bicarbonate, lithium carbonate, lithium bicarbonate, sodium carbonate, sodium bicarbonate, carbonic acid, or a combination of the two or more of the foregoing. When present, the reducing agent in some aspects of the invention comprises ammonium sulfite, hydrogen peroxide, or a combination of the two. The liquid ammonium system’s components are typically in an aqueous solution. The amount of the ammonium source present in the liquid ammonium system, and the amount of buffer and/or reducing agent, if used, may vary, but typically the amount of ammonium source will be in the range of about 0.5 M to about 5M, the amount of buffer if present will be in the range of 0 to about 5M, and the amount of reducing agent if present will be in the range of about 0 to about 2.5M. [0035] The ammonium system employed in at least some aspects of the invention will just prior to contacting the mass have a pH in the range of about 7 to about 14. In yet other aspects of the invention, the pH of the ammonium system at that time will be in the range of about 8 to about 11. [0036] The relative amounts of mass to liquid ammonium system employed 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 liquid ammonium system. [0037] The contacting undertaken in this step will typically be in a reaction vessel or zone, typically under conditions that apply a physical agitation, usually stirring, to the
Atty Docket No. ESS-L1-8131 WO combination of mass and ammonium system, over a period of time. The agitation can be carried out by mixing or stirring in any conventional manner under a given reactor configuration to give the liquid ammonium system and particulate 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 ambient 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. In some aspects of the invention, the mixture is maintained at one or more temperatures in the range of about 26° C to about 60° C during this leaching period. B. Separation of Alkaline Leachate [0038] Following contacting of the mass and ammonium system, the resulting mixture is treated so that alkaline leachate can be recovered by separation from the remaining material in the mixture by methods known in the art, such as decantation, centrifugation, or filtration. The separation is carried out typically by filtration. The alkaline leachate usually contains the metals of interest. C. Infusion of Oxidizing Agent [0039] An oxidizing agent is then infused into the recovered alkaline leachate. In this step, the oxidizing agent is typically air or oxygen gas. The oxidizer is infused by means such as bubblers, aerators, porous membranes or the like, so as to infuse the oxidizing agent in gas form into the alkaline leachate. The infusion may be carried out at various temperature and pressure conditions over a varying time period, but typically is carried out at ambient pressure and temperature conditions and for a period of time in the range of 5 minutes to about 5 hours. The amount of oxidizing agent infused will also vary but is typically in the range of about 1 Nl/(min^L) to about 50 Nl/(min^L) at ambient pressure and temperature conditions. D. Adjustment of pH
Atty Docket No. ESS-L1-8131 WO [0040] Following infusion of the oxidizing agent, the pH of the alkaline leachate is adjusted to enhance formation of a precipitate comprising one or more metal-containing compounds, wherein the metal is selected from the group consisting of lithium, cobalt, nickel, iron, aluminum, and any combination of two or more of the foregoing. The pH typically is adjusted by the addition of sodium hydroxide or another base of a type and quantity that brings the alkaline leachate pH in the range of about 10 to about 13. E. Second Infusion to Enhance Precipitation [0041] After pH adjustment, one or more of carbon dioxide, sodium carbonate, sodium bicarbonate, lithium carbonate, and lithium bicarbonate are infused into the alkaline leachate to enhance formation of an additional precipitate comprising one or more metal- containing compounds, wherein the metal is selected from the group consisting of cobalt, nickel, iron, aluminum, and any combination of two or more of the foregoing. In this step, one or more lithium compounds may be present in the precipitate due to incomplete recovery of lithium into the liquid phase, and/or by formation of additional precipitate comprising lithium compounds. This infusion may be carried about by a variety of means such as bubblers, aerators and porous membranes, and the like. The temperature and pressure conditions under which the infusion is carried out may be under super-ambient, ambient, or sub-ambient temperature and pressure conditions, but most conveniently is carried out under ambient temperature and pressure conditions. Examples [0042] The subject matter having been generally described, the following examples are given as particular embodiments of the subject matter of this disclosure and to demonstrate the practice and advantages thereof. It is understood that the examples are given by way of illustration and are not intended to limit the claims to follow in any manner. [0043] Recovery rates (i.e., amount recovered from liquid phase/initial amount in black mass) of indicated metals in the various examples below were determined by microwave digestion and inductively coupled plasma optical emission spectroscopy (ICP-OES) for
Atty Docket No. ESS-L1-8131 WO the involved black mass, and by ICP-OES for the resulting liquid sample(s) that were generated and examined. [0044] 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 m1 was 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
Atty Docket No. ESS-L1-8131 WO 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. [0045] Unless otherwise indicated in the examples, the experiments were carried out at ambient temperature and pressure conditions. Example 1 (Ammonium leaching) [0046] Three runs were performed as follows. An aqueous solution having a volume of about 250 mL and containing ammonia hydroxide (about 1.0 M), ammonium sulfite (0.5 M), and ammonium carbonate (0.1 M) was prepared and transferred into 500 mL reaction flask equipped 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 filtered to obtain an alkaline leachate after cooling to room temperature. 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. In the third run, the cathode powder was lithium manganese oxide cathode powder. [0047] For NMC 622 cathode powder, recovery rates were 91.5% of Li, 96.2% of Co, and 92.7% of Ni. For NCA based black mass, recovery rates were 96.7% of Li, 98.8% of Co, and 86.9% of Ni. The Figure shows a bar graph of the relative recoveries. The latter result indicates less favorable results when the process is carried out using LMO cathode powder. Example 2 (Li carbonate/bicarbonate synthesis) [0048] The alkaline leachate collected from each run of Example 1 was used in a run of Example 2. The alkaline leachate was aerated with air for four (4) hours. Then, the pH was adjusted and controlled to about 12 by adding sodium hydroxide. The alkaline leachate thereafter was aerated with carbon dioxide for 8 hours. The slurry was generated from the reaction flask, and the solid was filtered and washed with water. For the run from the NCA based black mass, Li recovery rate in filtrate was 52.9%, with Co and Ni under the
Atty Docket No. ESS-L1-8131 WO detection limit in the filtrate; all of the Co and Ni and the remainder of the Li were in the solid. Example 3 (comparison) [0049] For comparison purposes, a second experiment using an NCA based black mass was conducted in which the reaction conditions were similar to those described in Example 1. The only significant difference was that the first-time aeration with air was not done. The recovery rates in filtrate were 85% of Li, 90% of Co, and 8.4% of Ni. In other words, the Co was not effectively removed without a first step aeration. Example 4 (alternative) [0050] An alkaline leachate collected after the procedure of Example 1 from NCA based black mass was used in a process according to that of Example 2, except the aeration of the alkaline leachate was carried out with carbon dioxide for 2 hours. Then, the pH of the leachate was adjusted and controlled to about 12 by adding sodium hydroxide. The alkaline leachate then was aerated with carbon dioxide for 2 hours. The slurry was generated from reaction flask, and the solid was filtered and washed with water. Li recovery rate in filtrate was 46.7%, with Co and Ni below the detection limit in the filtrate. Additional Aspects of the Invention [0051] The subject matter is described above with reference to various aspects and specific examples. Many variations will suggest themselves to those skilled in the art in light of the above detailed description. All such obvious variations are within the full intended scope of the appended claims. Other aspects of the subject matter disclosed herein can include, but are not limited to, the following (aspects are described as “comprising” but, alternatively, can “consist essentially of”, or “consist of”): 1. A process comprising (A) contacting, in an ambient pressure system, a mass with a liquid ammonium system comprising an ammonia source, so as to form a combination, wherein the mass was formed from at least lithium-ion batteries and comprises one or more metal-containing
Atty Docket No. ESS-L1-8131 WO compounds, wherein the metal is selected from the group consisting of lithium, cobalt, nickel, iron, aluminum, and any combination of two or more of the foregoing; (B) separating an alkaline leachate from the combination; (C) infusing one or more oxidizing agents into the alkaline leachate; (D) adjusting the pH of the alkaline leachate to enhance formation of a precipitate comprising one or more metal-containing compounds, wherein the metal is selected from the group consisting of lithium, cobalt, nickel, iron, aluminum, and any combination of two or more of the foregoing; and (E) infusing one or more of carbon dioxide, sodium carbonate, sodium bicarbonate, lithium carbonate, and lithium bicarbonate into the alkaline leachate to enhance formation of an additional precipitate comprising one or more metal-containing compounds, where in the metal is selected from the group consisting of cobalt, nickel, iron, aluminum, and any combination of two or more of the foregoing. 2. The process of Aspect 1, wherein the ammonium system comprises the ammonia source and a buffer. 3. The process of Aspect 2, wherein the buffer comprises either ammonium carbonate, ammonium bicarbonate, lithium carbonate, lithium bicarbonate, sodium carbonate, sodium bicarbonate, carbonic acid, or a combination of the two. 4. The process of any one of Aspects 1-3, wherein the ammonia source comprises either ammonium hydroxide, ammonium sulfate, ammonium chloride, or any combination of two or more of the foregoing. 5. The process of any of Aspects 1-4, wherein the ammonium system further comprises a reducing agent. 6. The process of Aspects 5, wherein the reducing agent comprises either ammonium sulfite, hydrogen peroxide, or a combination of the two. 7. The process of any one of Aspects 1-6, wherein in step (A) the pH of the ammonium system is in the range of about 7 to about 14. 8. The process of Aspects 7, wherein the pH of the ammonium system is in the range of about 8 to about 11.