Synthesizing sorbent compositions for direct metal extraction

Abstract

Methods and systems are provided for synthesizing high-capacity lithium manganese oxide (LMO) sorbents for direct metal extraction applications. The process includes forming a precursor blend comprising lithium and manganese compounds, optionally doped with transition metal or alkali additives. The blend undergoes a controlled multi-stage calcination, milling, and activation sequence to form LMO spinels with tailored crystallinity and surface properties. Acid activation further transforms LMO into hydrogen manganese oxide (HMO), enhancing ion-exchange capabilities. Optimized conditions yield sorbents with lithium loading capacities exceeding 18 mg / g, and in some cases over 24 mg / g for doped variants. These sorbents exhibit high surface area, structural stability, and selectivity for lithium ions in metal-containing fluids such as brines or produced water. The disclosure outlines protocols for the scalable production of LMO-based materials with tunable capacity and performance, improving the efficiency and economics of systems like direct lithium extraction (DLE) systems.

Description

[0001] Attorney Docket No.22782.008WO1 / Element3-005-PCT SYNTHESIZING SORBENT COMPOSITIONS FOR DIRECT METAL EXTRACTION PRIORITY CLAIM [1] This international application claims the benefit of priority under Article 8 of the Patent Cooperation Treaty to U.S. Provisional Patent Application No.63 / 570,771, entitled "SYNTHESIZING SORBENT", filed on March 27, 2024, in the name of the applicant(s), and directed to COMPOSITIONS, the disclosure of which is incorporated herein by reference in its entirety. TECHNICAL FIELD [2] The subject matter herein relates, generally, to spinel sorbents for extracting metals from metal-containing fluids, including produced water, and, more particularly, to manufacturing techniques for Lithium Manganese Oxide (LMO) spinels, including those with and without doping agents, and to biasing techniques for synthesizing such compositions in target volumes and with specific loading capacities for targeted metals. BRIEF SUMMARY [3] Embodiments of the present disclosure relate to methods for manufacturing a spinel sorbent for reducing the concentration of at least one metal from a volume of fluid. In some embodiments, the method comprises mixing reactants to form a precursor blend, reacting the blend to form an intermediate-state sorbent, cooling and milling the intermediate-state sorbent, reacting the intermediate-state sorbent to form a final sorbent, cooling the sorbent, and activating it. [4] In some embodiments, the reactants may include lithium hydroxide, lithium carbonate, or both, and optionally manganese compounds such as Mn₃O₄, MnCO₃, or Mn₂O₃. The precursor blend may be a 3:4 molar ratio of lithium to manganese and may be doped with various agents such as Al(OH)₃, Co₃O₄, Cr₂O₃, Cr(OH)₃, Fe₂O₃, Fe₃O₄, Ni₂O₃, or Ni(OH)₂, including aluminum-based compounds. The blend may be in the form of an aqueous slurry. [5] In some embodiments, the precursor blend is reacted at a temperature between 425℃ and 625℃ for approximately five hours, optionally involving calcining, or between 350℃ and 425℃ for at least three hours. The reaction may oxidize manganese-based reactants, and the resulting intermediate-state sorbent may appear black, especially if Mn₂O₃ is present Attorney Docket No.22782.008WO1 / Element3-005-PCT or if the blend transitions from tan or white to black. The reaction may partially agglomerate the precursor into a spinel structure. Cooling may involve heat removal for at least one hour. [6] In some embodiments, the intermediate and final sorbents are formed using sintering, with or without milling. In some variations, the method concludes after forming and cooling the intermediate-state sorbent. [7] In some embodiments, the sorbent is formed by calcining a precursor blend of lithium and manganese reactants, including high-grade compounds such as Mn₃O₄, MnCO₃, Mn₂O₃, LiOH monohydrate, or Li₂CO₃. Calcining at 525℃ for about five hours may yield an intermediate-state sorbent with at least 89% LMO and 4.5% Mn₂O₃. A second calcining step between 500℃ and 550℃ for approximately ten hours may yield a final blend with at least 70% LMO and 5.0% Mn₂O₃. [8] In some embodiments, a 3:4 lithium to manganese precursor blend is used in a two- step calcining process to produce LMO and Mn₂O₃. The initial calcining step may last at least two hours at a temperature of at least 500℃. The intermediate product may include less than 2% Mn₃O₄, less than 23% Mn₂O₃, and at least 75% LMO. The second step, conducted at 525℃ for at least two hours, may yield a sorbent with at least 70% LMO and a lithium loading capacity of at least 9.0 mg / g. [9] In other embodiments, an initial five-hour calcining at 650℃ forms a blend with at least 70% LMO and 4.5% Mn₂O₃. A subsequent ten-hour calcining at 525℃ may yield a final sorbent with less than 0.5% Mn₃O₄, under 9% Mn₂O₃, over 90% LMO, and a lithium loading capacity of at least 6.0 mg / g.

[0010] In some embodiments, activation involves mixing the sorbent with acid, agitating the mixture, and achieving at least 20% activation to form the activated sorbent.

[0011] In some embodiments, an undoped activated LMO sorbent is formed from a precursor blend of Li₂CO₃ and Mn₃O₄ with a lithium to manganese ratio between 0.70 and 0.85. The blend is calcined at 525℃, cooled, then calcined again at a minimum of 500℃ for five hours. Activation with acid forms at least one species of HMO sorbent spinel. The intermediate-state sorbent may have a lithium loading capacity of at least 18.0 mg / g, and the final sorbent may achieve at least 13.0 mg / g. Attorney Docket No.22782.008WO1 / Element3-005-PCT

[0012] In some embodiments, a doped sorbent spinel is manufactured by preparing a doped precursor blend with manganese sources such as MnCO₃ and lithium sources such as LiOH monohydrate, along with doping agents including Al(OH)₃, LiAlH₄, Co₃O₄, Cr₂O₃, Cr(OH)₃, Fe₂O₃, Fe₃O₄, Ni₂O₃, Ni(OH)₂, NaCl, AlCl₃, MgCO₃, Na₂CO₃, NaOH, or NaHCO₃. The precursor is calcined, cooled, and milled, forming a doped intermediate-state sorbent with a lithium loading capacity of at least 16.0 mg / g.

[0013] In some embodiments, a doped precursor blend with a 3:4 lithium to manganese ratio and 0.01–1.0% molar doping agent is calcined at 500℃, forming a doped LMO and Mn₂O₃. A second calcining step completes the formation of the doped sorbent. The first step may last 0.5 hours at 525℃, forming a sorbent with over 70% LMO, less than 2% Mn₂O₃, and under 27% Mn₃O₄. A second calcining of 30 minutes at 525℃ may produce a final blend with at least 85% LMO and a lithium loading capacity of at least 13.3 mg / g.

[0014] In other embodiments, the second calcining step may last at least two hours at 525℃, yielding a sorbent with less than 3% Mn₃O₄, less than 15% Mn₂O₃, and at least 80% LMO, with a lithium loading capacity of at least 12.0 mg / g. Alternatively, a five-hour first calcining at 525℃ followed by a five-hour second calcining at the same temperature may produce a doped sorbent with over 90% LMO, less than 3% Mn₃O₄, less than 7% Mn₂O₃, and a lithium loading of at least 16.0 mg / g.

[0015] In some embodiments, activation of the doped sorbent involves acid mixing and agitation to reach at least 20% activation.

[0016] In some embodiments, a doped activated LMO sorbent is made from a precursor with a 0.70 to 0.85 lithium to manganese ratio, calcined at 525℃, cooled, then calcined again at 500℃ for five hours. The intermediate-state blend may include less than 18% Mn₂O₃ and at least 65% LMO, with a lithium loading capacity of at least 7.0 mg / g. The final doped sorbent may include at least one doped HMO species after acid activation.

[0017] In some embodiments, a precursor aqueous slurry of 70–85% lithium to manganese is prepared using LiOH^H₂O and MnCO₃. The slurry is calcined at 350℃, forming an intermediate-state sorbent blend comprising at least 80% LMO and less than 1% MnCO₃. The LMO may exhibit a lithium loading capacity of at least 16.0 mg / g. In other embodiments, calcining at 350℃ for five hours may yield over 90% LMO with a loading capacity of at least 16.0 mg / g. Attorney Docket No.22782.008WO1 / Element3-005-PCT

[0018] In some embodiments, the slurry is prepared by mixing MnCO₃ and LiOH^H₂O in water before calcining. When calcined at 400℃, the intermediate-state sorbent may contain at least 75% LMO and less than 1% MnCO₃, with no detectable Mn₃O₄ or Mn₂O₃. The LMO may have a lithium loading capacity of at least 12.0 mg / g.

[0019] In some embodiments, calcining the slurry at 400℃ for five hours yields an intermediate-state sorbent with over 90% LMO and a lithium loading capacity of at least 12.0 mg / g.

[0020] In some embodiments, a 70–85% lithium to manganese slurry is calcined for five hours between 350℃ and 425℃ and cooled to yield LMO with at least 90% purity and a lithium loading of at least 15.0 mg / g. The resulting LMO may exhibit a lithium loading capacity of at least 15.0 mg / g after activation. BRIEF DESCRIPTION OF THE FIGURES

[0021] FIG. 1 is a flowchart illustrating a method for manufacturing a spinel sorbent, according to some embodiments of the present disclosure.

[0022] FIG. 2 is a flowchart further illustrating the method for activating the synthesized spinel sorbent from FIG.1, according to some embodiments of the present disclosure.

[0023] FIG. 3 is a flowchart further illustrating the method for manufacturing a spinel sorbent from FIG.1, according to some embodiments of the present disclosure.

[0024] FIG.4A-D are XRD graphs illustrating the Al-doped LMO at 425⁰C, 525⁰C, LMO at 525⁰C and 425⁰C, respectively.

[0025] FIG.5 is a flowchart illustrating the method for manufacturing Lithium Manganese oxide (LMO), according to some embodiments of the present disclosure.

[0026] FIG. 6 is a flowchart illustrating the method for manufacturing a doped Lithium Manganese oxide (LMO), according to some embodiments of the present disclosure.

[0027] FIG.7 is a table illustrating the effect of air, temperature, temperature duration, and crucible on Al-doped LMO Vs LMO, according to some embodiments of the present disclosure. Attorney Docket No.22782.008WO1 / Element3-005-PCT

[0028] FIG.8 is a flowchart illustrating a method, according to some embodiments of the present disclosure.

[0029] FIG.9 is a flowchart illustrating a method for manufacturing a LMO sorbent spinel, according to some embodiments of the present disclosure.

[0030] FIG.10 is a flowchart further illustrating the method for manufacturing a LMO sorbent spinel from FIG.9, according to some embodiments of the present disclosure.

[0031] FIG.11 is a flowchart further illustrating the method for manufacturing a LMO sorbent spinel from FIG.9, according to some embodiments of the present disclosure.

[0032] FIG.12 is a flowchart illustrating a method for manufacturing an activated LMO sorbent spinel, according to some embodiments of the present disclosure.

[0033] FIG.13 is a table illustrating the respective quantities of intermediate-state sorbent blend obtained at different calcining temperatures during the first calcining duration as described in the method for manufacturing an LMO sorbent spinel from FIG.9, according to some embodiments of the present disclosure.

[0034] FIG.14 is a table illustrating the respective compound compositions of intermediate-state sorbent blend obtained at a calcining temperature of 525℃ at different time intervals during the first calcining duration as described in the method for manufacturing an LMO sorbent spinel from FIG.9, according to some embodiments of the present disclosure.

[0035] FIG.15 is a table illustrating the respective quantities of intermediate-state sorbent blend as described in the method for manufacturing an LMO sorbent spinel from FIG.9, according to some embodiments of the present disclosure. The initial reacting was performed at different first durations at a few select first temperatures. The table also includes the compound compositions of the LMO sorbent spinel after the second calcination where calcining temperatures of 525℃ were performed at various second durations.

[0036] FIG.16 is a table illustrating the respective quantities of sorbent blend obtained at a first calcining temperature of 525℃ at different time intervals, while the duration of the second calcining is held constant for approximately ten (10) hours as described in the method for manufacturing a LMO sorbent spinel from FIG.5, according to some embodiments of the present disclosure. Attorney Docket No.22782.008WO1 / Element3-005-PCT

[0037] FIG.17 is a table illustrating the loading capacity of LMO sorbent spinel obtained at different calcining temperatures for different durations during the first and second calcining duration when activated as described in the method for manufacturing an LMO sorbent spinel from FIG.12, according to some embodiments of the present disclosure.

[0038] FIG.18 is a table illustrating the compound composition percentages of intermediate sorbents, loading capacities and iron percentages of undoped sorbent spinel after initial and second calcination temperatures and durations, when activated as described in the method for manufacturing an LMO sorbent spinel from FIG.12, according to some embodiments of the present disclosure.

[0039] FIG.19 is a flowchart illustrating a method according to some embodiments of the present disclosure.

[0040] FIG.20 is a flowchart illustrating a method for manufacturing a doped LMO sorbent spinel according to some embodiments of the present disclosure.

[0041] FIG. 21 is a flowchart further illustrating the method for manufacturing a doped LMO sorbent spinel from FIG.20, according to some embodiments of the present disclosure.

[0042] FIG. 22 is a flowchart further illustrating the method for manufacturing a doped LMO sorbent spinel from FIG.20, according to some embodiments of the present disclosure.

[0043] FIG. 23 is a flowchart illustrating a method for manufacturing a doped activated LMO sorbent spinel, according to some embodiments of the present disclosure.

[0044] FIG.24 is a table illustrating the compound percentages present within the intermediate-state sorbent blends of doped and undoped precursor blend at different initial calcination temperatures for five (5) hours as described in the method for manufacturing a doped LMO sorbent spinel from FIG. 20, according to some embodiments of the present disclosure.

[0045] FIG.25 is a table illustrating the compound percentages present within the intermediate-state sorbents of calcined doped and undoped precursor blend obtained at a different calcination duration at 525°C as described in the method for manufacturing a doped LMO sorbent spinel from FIG.20, according to some embodiments of the present disclosure. Attorney Docket No.22782.008WO1 / Element3-005-PCT

[0046] FIG.26 is a table illustrating the compound percentages present within the sorbents synthesized using calcined doped and undoped precursor blends at various second calcination temperatures and durations as described in the method for manufacturing a doped LMO sorbent spinel from FIG.23, according to some embodiments of the present disclosure.

[0047] FIG. 27 is a table illustrating the comparison of loading capacities of doped and undoped sorbent blend after initial and second calcination temperatures and durations as described in the method for manufacturing a doped LMO sorbent spinel from FIG. 23, according to some embodiments of the present disclosure.

[0048] FIG. 28 is a table illustrating the lithium manganese oxide (LMO) formation from a precursor blend comprising a slurry of MnCO₃ and LiOH at a 3:4 molar ratio, subjected to various calcination durations and firing temperatures, as described in the method for manufacturing an LMO sorbent spinel according to some embodiments of the present disclosure.

[0049] FIG. 29 is a table illustrating the compound percentages present within the intermediate-state sorbent blend resulting from calcination of a MnCO₃ and LiOH slurry-based precursor blend, as described in the method for manufacturing an LMO sorbent spinel according to some embodiments of the present disclosure. DETAILED DESCRIPTION

[0050] FIG.1 is a flowchart that describes a method for manufacturing a sorbent, according to some embodiments of the present disclosure. In some embodiments, at 110, the method may include mixing reactants to form a precursor blend. In some embodiments, it may be desirable to manufacture a high percentage of lithium manganese oxide (LMO) sorbent from the reactants. In order to produce an LMO, the reactants may include at least one lithium compound. In some embodiments, the at least one lithium compound may include at least one of lithium hydroxide, and lithium carbonate. In some embodiments, mixing of the precursor materials is required to form the precursor blend. If LiCO3is used as a precursor, then milling of the reactant can be desirable due to the propensity for LiCO3 to agglomerate. In some embodiments, the reactants may include at least one manganese compound. In some embodiments, the reactants may include at least one of Mn₃O₄, MnCO3, and Mn₂O₃. In some embodiments, the reactants may further comprise at least one of lithium hydroxide, lithium Attorney Docket No.22782.008WO1 / Element3-005-PCT carbonate, and at least one of Mn₃O₄, MnCO3, and Mn₂O₃. In some embodiments, the precursor blend may be a 3:4 lithium to manganese blend.

[0051] In some embodiments, the 3:4 lithium to manganese blend may be doped with a doping agent. In some embodiments, the doping agent may be at least one of Al(OH)3, Co3O4, Cr2O3, Cr(OH)3, Fe2O3, Fe3O4, Ni2,O3, and Ni(OH)2. In some embodiments, the doping agent may be at least one of Al(OH)3, Co3O4, Cr(OH)3, Fe3O4, and Ni(OH)2. In some embodiments, the doping agent may be at least one of NaCl, AlCl3, and MgCO3. If a doping agent is used, the doping agent is milled with the other reactants.

[0052] At 120, the method may include reacting the precursor blend forming an intermediate-state sorbent. In the foregoing description, ‘intermediate-state sorbent’ refers to the term that some portion of the reactants remain unreacted depending on the conditions of the “reacting” exercise (conditions may include temperature, air flow, time, pressure, mass of reactants). In this way, an intermediate-state sorbent has at least some sorbent, and some percentage of reactants from the precursor blend.

[0053] In some embodiments, the reacting the precursor blend further comprises reacting the precursor blend at a high temperature and pressure to produce the intermediate-state sorbent as part of a hydrothermal reaction. In some embodiments, the intermediate-state sorbent may be an aqueous slurry. In some embodiments, the reacting the precursor blend further comprises reacting the precursor blend at a temperature and an exposure time.

[0054] In some embodiments, the doping agent may be at least one of Na2CO3, NaOH, NaHCO3. In some embodiments, the doping agent may be aluminum hydroxide. In some embodiments, the doping agent may be an aluminum-based compound. In some embodiments, the precursor blend may be a 4:5 lithium to manganese blend. In some embodiments, the 4:5 lithium to manganese blend may be doped with a doping agent. In some embodiments, the doping agent may be at least one of Al(OH)3, Co3O4, Cr2O3, Cr(OH)3, Fe2O3, Fe3O4, Ni2,O3, and Ni(OH)2.

[0055] In some embodiments, the doping agent may be at least one of Al(OH)3, Co3O4, Cr2O3, Cr(OH)3, Fe2O3, Fe3O4, Ni2,O3, and Ni(OH)2.. In some embodiments, the doping agent may be at least one of NaCl, AlCl3, and MgCO3. In some embodiments, the doping agent may be at least one of Na2CO3, NaOH, NaHCO3. In some embodiments, the doping agent may be Attorney Docket No.22782.008WO1 / Element3-005-PCT aluminum hydroxide. In some embodiments, the doping agent may be an aluminum-based compound.

[0056] In some embodiments, the precursor blend may be a 0.70 to 0.85 ratio of lithium to manganese blend. In some embodiments, the 0.70 to 0.85 ratio of lithium to manganese blend may be doped with a doping agent. The doping agent may be an aluminum-based compound. In some embodiments, the doping agent may be at least one of Al(OH)3, Co3O4, Cr2O3, Cr(OH)3, Fe2O3, Fe3O4, Ni2,O3, and Ni(OH)2, or other transition metal oxides or hydroxides selected to enhance structural stability or ion-exchange performance.

[0057] In some embodiments, the doping agent may be at least one of Al(OH)3, Co3O4, Cr(OH)3, Fe3O4, and Ni(OH)2. In some embodiments, the doping agent may be at least one of NaCl, AlCl3, and MgCO3. In some embodiments, the doping agent may be at least one of Na2CO3, NaOH, NaHCO3. In some embodiments, the doping agent may be aluminum hydroxide. In some embodiments, the doping agent may be an aluminum-based compound.

[0058] In some embodiments, the reacting the precursor blend further comprises reacting the precursor blend at a high temperature and pressure to produce the intermediate-state sorbent. In some embodiments, the high temperature is between 500⁰C and 550⁰C. In some embodiments, the intermediate-state sorbent may be an aqueous slurry. In some embodiments, the reacting the precursor blend further comprises reacting the precursor blend at a temperature and an exposure time.

[0059] In some embodiments, the temperature may be between 425℃ and 625℃ and the exposure time may be approximately 5 hours. (can we get the literature Bill referenced for his temp range). In some embodiments, the reacting the precursor blend may be at least one of calcining, roasting, sintering, microwaving, and annealing. In some embodiments, the temperature may be between 300 ℃and 625 ℃and the exposure time may be at least 5 hours.

[0060] In some embodiments, the temperature may be between 300℃ and 625℃ and the exposure time may be at least 3 hours. In some embodiments, the reacting the precursor blend may further comprise a duration of approximately 5 hours at approximately 525℃ under an excess of pumped atmosphere (6L / min). In some embodiments, the reacting the precursor blend may be a heating method performed in a kiln. In some embodiments, the heating further comprises using kiln furniture. The kiln furniture may be aluminum-containing furniture. Attorney Docket No.22782.008WO1 / Element3-005-PCT

[0061] In some embodiments, the kiln furniture may be made up of aluminum oxide or aluminum-based compound. In some embodiments, the kiln furniture may be flat, and the reacting further comprises administering an airflow rate of at least 5L per minute per 100g of precursor blend. In some embodiments, the reacting the precursor blend further comprises administering a pumped air flow rate of at least 2L per minute per 100g of precursor blend.

[0062] In some embodiments, the pumped air may further comprise a reducing gas to reduce a partial pressure of oxygen content from the air. In some embodiments, the method may include administering a pumped gas flow rate of at least 2L per minute per 100g of precursor blend. In some embodiments, the pumped gas may further comprise a reducing gas, a reactive gas, or a combination thereof. In some embodiments, the pumped gas may further comprise a reducing gas. In an embodiment of the present invention, reducing gas is used to facilitate “pyrolysis” and “reduction”. The aforesaid steps can facilitate pyrometallurgy process by using less energy to reduce gases and solvents. Reducing gases such as H2 and O2 and the combination of CO / CO2 lowers the temperature needed to reduce metal oxides for final metal separation. In some embodiments, the precursor blend may be layered at a thickness of up to 1 cm. In some embodiments, the precursor blend may be layered at a thickness of between 1 cm and 3 cm. In some embodiments, the reacting the precursor blend at least partially agglomerates the precursor blend into a spinel structure. In some embodiments, the agglomerate may be at least 25% by weight.

[0063] At 130, the method may include cooling the intermediate-state sorbent. In some embodiments, cooling the intermediate-state sorbent further comprises removing a source of heat from the intermediate-state sorbent for at least one hour.

[0064] At 140, the method may include milling the intermediate-state sorbent. In some embodiments, milling the intermediate-state sorbent further comprises milling with the doping agent. In some embodiments, milling the intermediate-state sorbent further comprises milling at least 95%of intermediate-state sorbent by weight to less than a 3.0 mm particle size.In some embodiments, milling the intermediate-state sorbent further comprises milling at least 95%of intermediate-state sorbent by weight to less than 1.0 mm particle size. In some embodiments, milling further comprises milling the intermediate-state sorbent using at least any one of a hammer mill, rod mill, vibratory mill, ball mill, and attrition mill. Attorney Docket No.22782.008WO1 / Element3-005-PCT

[0065] At 150, the method may include reacting the intermediate-state sorbent forming a sorbent. In some embodiments, reacting the intermediate-state sorbent may further comprise the weight of LMO and volume of the kiln. In some embodiments, the reacting the intermediate-state sorbent further comprises reacting less than a 50% precursor blend by weight.

[0066] In some embodiments, the intermediate-state sorbent may have a minimum loading capacity of 2.0 mg / g. In some embodiments, the intermediate-state sorbent results in the synthesis of Mn₂O₃ from an Mn₃O₄ reactant. In some embodiments, the intermediate-state sorbent may have a color. For example, when manganese (III) oxide (Mn₂O₃) is used as the precursor in combination with lithium hydroxide (LiOH), the resulting lithium manganese oxide (LMO) may appear black or may darken upon sintering. In contrast, when manganese carbonate is used as the precursor, the material may initially appear white or brown and transition to a darker color, such as brown or black, during the reaction process. The observed color may correspond to differences in the absorption of electromagnetic radiation within the visible spectrum, which may increase as the spinel phase becomes more crystalline or as the oxidation state of manganese changes during thermal treatment. In some embodiments, the observed color change may be indicative of phase progression during thermal treatment, providing a qualitative measure of the development of crystallinity and changes in manganese oxidation state consistent with spinel formation.

[0067] In some embodiments, reacting the intermediate-state sorbent forming a sorbent further comprises reacting the intermediate-state sorbent at a high temperature and pressure to produce the intermediate-state sorbent. In another embodiment, the temperature is between 425℃ and 625℃, and the exposure time is approximately 5 hours. In some embodiments, reacting to the intermediate-state sorbent is at least one of calcining, roasting, sintering, microwaving, and annealing.

[0068] In some embodiments, the temperature is between 300℃ and 625℃, and the exposure time is at least 5 hours. In other embodiment, the temperature is between 300℃ and 625℃, and the exposure time is at least 3 hours. In yet another embodiment, the reacting the intermediate-state sorbent further comprises a duration of approximately 5 hours at approximately 525℃ under an excess of pumped atmosphere (6L / min). In some embodiments, the reaction of the intermediate-state sorbent is a heating method performed in a kiln. In some embodiments, the heating further comprises using kiln furniture, wherein the kiln furniture is Attorney Docket No.22782.008WO1 / Element3-005-PCT aluminum-containing furniture. In some embodiments, the kiln furniture is made up of aluminum oxide or aluminum. In some embodiments, the kiln furniture is flat, and the reacting further comprises administering an airflow rate of at least 5L per minute per 100g of intermediate-state sorbent.

[0069] In some embodiments, the reacting the intermediate-state sorbent further comprises administering a pumped air flow rate of at least 2L per minute per 100g of intermediate-state sorbent. In some embodiments, the pumped air further comprises a reducing gas to reduce a partial pressure of oxygen content from the air. In some embodiments, a pumped gas flow rate of at least 2L per minute per 100g of intermediate-state absorbent is administered.

[0070] In some embodiments the pumped gas further comprises a reducing gas, a reactive gas, or a combination thereof. In another embodiment, the pumped gas further comprises a reducing gas. In some embodiments, the intermediate-state sorbent is layered at a thickness of at least 1 cm. In some embodiments, the intermediate-state sorbent is layered at a thickness of between 1 cm and 3 cm.

[0071] At 160, the method may include cooling the sorbent. In some embodiments, cooling of the intermediate-state sorbent further comprises removing a source of heat from the intermediate-state sorbent for at least one hour.

[0072] At 170, the method may include activating the sorbent. In some embodiments, the acid further comprises mixing for a duration of less than 16 hours. In some embodiments, the acid further comprises mixing for a duration that may be less than or equal to 48 hours.

[0073] FIG. 2 is a flowchart that further describes the method for manufacturing a spinel sorbent from FIG. 1, according to some embodiments of the present disclosure. In some embodiments, activating the sorbent further comprises, the method may include 210. The acid may be an acid like HCl and / or Sulfuric acid. In some embodiments, the acid further comprises, the method may include 220 to 230. At 220, the acid is at least one of 1 N hydrochloric acid or 1N sulfuric acid. At 230, mixing the sorbent and the acid is in a ratio sufficient to activate the volume of the spinel sorbent within a desired period of time and at a minimum amount of activation. The mixing may be facilitated or augmented using mechanical means. Mechanical means may include the use of pumps to flow fluids, mixers, V-Blender, Double Cone blender, Screw Mixer, and / or a Ribbon Blender. Attorney Docket No.22782.008WO1 / Element3-005-PCT

[0074] In some embodiments, the agitating the sorbent and the acid is carried out in an agitator. In some embodiments, the agitator used is at least one of a cone bottom flask and a hydraulic mixer. In some embodiments, the agitating the sorbent and the acid is carried out for a duration that is less than or equal to 48 hours. In some embodiments, the agitating of the sorbent and the acid is carried out for a duration that is less than or equal to 16 hours.

[0075] In some embodiments, the method for manufacturing a spinel sorbent for reducing a concentration of at least one metal from a volume of fluid includes steps 110 to 160. In some embodiments, the method for manufacturing a spinel sorbent for reducing a concentration of at least one metal from a volume of fluid includes steps 110 to 130. The steps involved in manufacturing, in some embodiments, can be stopped at the intermediate step 130. In such a scenario, the activation step of the intermediate-state sorbent is necessary to obtain the sorbent's desired adsorbent capacity.

[0076] FIG. 3 is a flowchart that further describes the method for manufacturing a spinel sorbent from FIG. 1, according to some embodiments of the present disclosure. In some embodiments, activating the sorbent further comprises, the method may include 210. The acid may be at least one of HCl and Sulfuric acid. In some embodiments, the acid further comprises mixing using at least one agitator, cycling in a cone bottom tank, and hydraulic mixing. In some embodiments, mixing technologies can be used to optimize the activation process, such as those described in CSIRO "Swirl Flow: Increase production and reduce tank maintenance costs," https: / / www.csiro.au / en / work-with-us / industries / mining-resources / Processing / Swirl-flow. In some embodiments, the activated HMO may be used in a Direct Lithium Extraction (DLE) system. The timing of exposure of the LMO to an acid may vary based on the amount of activated sorbent needed to adsorb lithium from a lithium-containing fluid. For many systems, an example of the minimum amount of acid exposure may be goal-dependent, such as achieving an activated sorbent loading capacity of at least 2 mg / g at Standard Temperature and Pressure (STP). While higher loading capacities are preferable, 2 mg / g loading capacity at STP is often the minimum activation needed for commercial DLE systems. The loading capacity and therefore the activation period may be altered based on the pressure and temperature of the DLE system. In some embodiments, activation may not be performed where the sorbent is manufactured. For example, in some DLE systems, activation may be performed in the field.

[0077] The crystal structure of the adsorbent was characterized with XRD. Fig.4A shows the XRD patterns of the Al-doped LMO sorbent at 425OC. (Intensity (a.u) Vs 2 Theta(degree)) Attorney Docket No.22782.008WO1 / Element3-005-PCT Al Doped LMO, 425 ⁰C peaked at 18= 78000, 34=135000, 45=57000 and 55=58000. At 425 ⁰C with an airflow, and firing temperature of 5 hours, Al-doped LMO shift left compared t⁰Control, indicating larger lattice constant. The percentage of LMO is observed to be greater than 61% whereas the percentage of Mn₂O₃ is observed to be less than 39 %.

[0078] Fig. 4B shows the XRD patterns of the Al-doped LMO sorbent at 525 ⁰C sorbent. Al Doped LMO, 525 C peaked at 18= 65000; 36=48000;45=67000; 66=45000. At 525 ⁰C, with an airflow, and a firing temperature of 10 hours, Al-doped LMO shift right compared t⁰Control, indicating smaller lattice constant. The percentage of pure LMO is observed to be greater than 99.8% whereas the percentage of Mn₂O₃ is observed to be less than 1.2 %.

[0079] Fig. 4C shows the XRD patterns of the LMO sorbent at 425⁰C. LMO at 425⁰C at 19=62000; 33=115000; 45=45000; 56=48000. At 425 ⁰C with an airflow, and firing temperature of 5 hours, the percentage of LMO is observed to be greater than 61% whereas the percentage of Mn₂O₃ is observed to be less than 39%.

[0080] Fig. 4D shows the XRD patterns of the LMO sorbent at 525⁰C. LMO at 525⁰C at 18= 49000; 36=32000; 45=42000 AND 65=26000. From the above graph, Al-doped LMO attained the greatest intensity peak at 34 (135000). At 525⁰C, with an airflow, and a firing temperature of 10 hours, the percentage of pure LMO is observed to be 97.7% whereas the percentage of Mn₂O₃ is observed to be 2.3%.

[0081] FIG. 5 is a flowchart illustrating the method for manufacturing a Lithium Manganese oxide (LMO), according to some embodiments of the present disclosure. At step 510, the method includes mixing lithium-based and manganese-based reactants to form a precursor blend. At step 520, the method includes calcinating the precursor blend forming an intermediate-state sorbent. At step, 530, the method includes cooling the intermediate sorbent followed by milling the sorbent at step 540 and calcinating the intermediate sorbent forming a sorbent at step 550, and cooling the sorbent obtained at step 560. In an embodiment of the present invention, at 425 ⁰C with an airflow, and firing temperature of 5 hours, the loading capacity of Li ions is found to be 7.23%. At 525⁰C, with an airflow, and a firing temperature of 10 hours, the loading capacity of Li ions is found to be 17.56%. At 425⁰C with an airflow, and firing time of 5 hours, the loading capacity of Li ions is found to be 6.80%. At 525⁰C, with an airflow, and a firing temperature of 10 hours, the loading capacity of Li ions is found to be 14.79% when Nickel is used as a crucible. The percentage of pure LMO is observed to be 97.7 Attorney Docket No.22782.008WO1 / Element3-005-PCT % whereas the percentage of Mn₂O₃ is observed to be 2.3%. At 525⁰C, with an airflow, and a firing temperature of 10 hours, the loading capacity of Li ions is found to be 13.94% when Aluminum is used as a crucible. The percentage of pure LMO is observed to be 97.7 % whereas the percentage of Mn₂O₃ is observed to be 2.3%.

[0082] FIG. 6 is a flowchart illustrating the method for manufacturing a doped Lithium Manganese oxide (LMO), according to some embodiments of the present disclosure. At step 610, the method includes mixing a doped lithium-based and a manganese-based reactants to form a precursor blend. At step 620, the method includes calcinating the precursor blend forming an intermediate-state sorbent. At step, 630, the method includes cooling the intermediate sorbent following by milling the sorbent at step 640 and calcining the intermediate sorbent forming a sorbent at step 650 and cooling and activating the sorbent using IN sulfuric acid or Hydrochloric acid to reach an activation percentage of 90% to form an activated sorbent at step 660. It is observed that at 425⁰C with an airflow, and firing time of 5 hours, the loading capacity of Li ions is found to be 7.23%. The percentage of LMO is observed to be greater than 61% whereas the percentage of Mn₂O₃ is observed to be less than 39%. At 525⁰C, with an airflow, and a firing time of 10 hours, the loading capacity of Li ions is found to be 17.56%. The percentage of pure LMO is observed to be greater than 99.8% whereas the percentage of Mn₂O₃ is observed to be less than 1.2%. At 425⁰C with an airflow, and firing temperature of 5 hours, the loading capacity of Li ions is found to be 6.80%. The percentage of LMO is observed to be greater than 61% whereas the percentage of Mn₂O₃ is observed to be less than 39%.

[0083] At 525⁰C, with an airflow, and a firing time of 10 hours, the loading capacity of Li ions is found to be 14.79% when Nickel is used as a crucible. At 525⁰C, with an airflow, and a firing temperature of 10 hours, the loading capacity of Li ions is found to be 13.94% when Aluminum is used as a crucible.

[0084] FIG.7 is a table illustrating the effect of air, temperature, temperature duration and crucible on Al-doped LMO Vs LMO, according to some embodiments of the present disclosure. The XRD data at 425⁰C describes that the Al-doped LMO shifted towards the left compared to the undoped LMO, indicating a larger lattice constant. At 525⁰C, the Al-doped shifted towards right compared to undoped LMO indicating a smaller lattice constant. Also, at 425⁰C the yield of Al-doped LMO is 61.79%, and the yield of Mn₂O₃ is 38.21%. As the temperature is increased to 525⁰C, the yield of Al-doped LMO drastically increased to 99.84% and the Mn₂O₃ obtained as impurity is reduced to 0.16%. XRD data demonstrates that the Attorney Docket No.22782.008WO1 / Element3-005-PCT sorbent material consists of two phases, Li1.333Mn1.667O4and Mn₂O₃. Samples that were calcined at 425 ⁰C show a significant presence of an Mn₂O₃ phase, characterized by strong absorbance at 23, 33, while samples calcined at 525⁰C show minimal presence of this phase. At 425 ⁰C, a slight decrease in the diffraction angle was observed for peaks related to the Li1.333Mn1.667 O4 phase, indicating an increase in the lattice constant of the sorbent. At 525⁰C, a slight increase in the diffraction angle was observed for peaks related to the Li1.333Mn1.667O4phase, indicating a decrease in the lattice constant of the sorbent.

[0085] Practical Secondary Treatment Opportunities

[0086] Sorbent spinels can be doped during the synthesis process to improve the loading capacity of the sorbent for direct lithium extraction processes. The process of doping involves substituting small amounts of elements (e.g., Al, Ni, or other elements) for Mn, Co, or Ni in the LMO structure. Doping aids in improving the structural stability and performance of LMO particularly during phase transitions. The process is attributed to strong Al-O bonds, that facilitate adsorption or desorption thereby enhancing the structural stability of LMO.

[0087] The synthesis process can be aided by using an initial reactant that is converted to an intermediate-state product before ultimately reacting with lithium to form a sorbent spinel. For example, when an initial reactant is Mn₃O₄, the duration and temperature of the reaction, for example a calcination, can convert the Mn₃O₄ to Mn₂O₃. The Mn₂O₃ when in contact with a lithium reactant, such as lithium carbontate Li₂CO₃, forms an LMO. The duration of calcination and temperature when the reactants are doped is not significantly impacted between temperatures of 500 Celsius and 650 Celsius. Within these temperature ranges, when the duration of the calcination is increased, nearly 100% LMO is formed and loading capacities increase. The methods of the present disclosure may unlock the ability to do secondary treatments with temperature to the sorbent spinel.

[0088] Sorbent spinels are often agglomerated or bound in binding agents to make the sorbent spinels less vulnerable to breaking in direct metal extraction processes. Given the present disclosure as it relates to methods of synthesizing a spinel sorbent, the discussed LMO is only marginally impacted by elevated temperatures within a range of between 500 ⁰C and 650⁰C, and demonstrates enhanced loading capacity as durations are extended. Methods disclosed in relation to FIG. 1, demonstrate a commercially viable LMO may be produced using a first and second calcination of 30 minutes in duration each calcination. Given the ability Attorney Docket No.22782.008WO1 / Element3-005-PCT of doped LMOs produced using these methods may be enhanced in-terms loading capacity from extended calcination at temperature, the present doped LMOs may be well adapted to secondary processes where temperature exposure is necessary.

[0089] Undoped Sorbents that benefit from biasing techniques

[0090] Direct Lithium Extraction (DLE) often uses an activated Lithium Manganese Oxide (LMO) sorbent to remove lithium from produced water. While much research has been done exploring the use of LMOs to adsorb lithium at lab scale, improvements in manufacturing LMOs at the scale required to process tens of thousands of gallons of water per hour are needed. An example of a DLE system that may be used to continuously or batch process a produced water at scale is described in US provisional application number 63 / 489,645, titled SYSTEM AND METHOD FOR REDUCING A CONCENTRATION OF A METAL FROM PRODUCED WATER USING A LARGE FORMAT COMPOSITION, filed on March 10, 2023, the contents of which are incorporated in their entirety by reference to the extent not inconsistent herewith. A critical factor in scaling up DLE systems to meet commercial demand is producing LMOs in bulk with the reactants that are presently available.

[0091] Conventional techniques for producing lab-scale quantities of LMO are described in Paulsen, J. M.; Dahn, J. R.; "Phase Diagram of Li-Mn-O Spinel in Air"; published by the American Chemical Society on October 27, 1999 https: / / cdn.bc- pf.org / olympiads / chemistry / rus_sbory / 2010-Oct / thermo.pdf, the contents of which are incorporated by reference herein in their entirety to the extent not inconsistent herewith. Further, optimizing (or at least improving relative to other synthesis techniques) synthesis techniques of a spinel sorbent, reacting durations, and temperatures may be altered to enhance the purity and / or loading capacity of lithium manganese oxide (LMO) for various applications, including lithium-ion batteries, catalysis, and sorbents. For illustrative purposes, the initial calcining duration generally refers to the time under temperature and does not necessarily account for the ramp-up period to achieve temperature or the ramp-down period to achieve a cool-down temperature.

[0092] Spinel sorbents, such as LMOs, are an important group of compounds in direct lithium extraction (DLE) systems. Some techniques for manufacturing these spinel sorbents are often described with respect to laboratory scale. When synthesizing larger volumes of sorbent spinels, such as a 15 to 20 kg batch size of LMO sorbent for treating 500 gallons of 30 Attorney Docket No.22782.008WO1 / Element3-005-PCT PPM lithium produced water, it may be necessary to use a lower grade of the precursor blend. Lower-grade reactants may greatly impact the loading capacity of the sorbent, often reducing the loading capacity of the sorbent and impacting the fragility of the spinel structure and lattice integrities. Commercially available Mn₃O₄ may include several compounds that impact the formation of an LMO, which contributes to the ultimate loading capacity of the activated LMO and the quantity of LMO produced. Undesired compounds, such as iron (e.g., Fe2O3), vary in the amount present from a lower grade commercially available Mn₃O₄ source (e.g., percent by weight of iron more than 1.0) while higher grade Mn₃O₄ sources will have a lower volume of iron (e.g., percent by weight of less than 0.7). Similarly, the availability of Mn may vary by grade, such that higher grades of Mn₃O₄ may be available in %Mn by weight more than or equal to 71% of overall weight. The percentage of Mn and quality often must be factored in, as in some DLE systems, it may be necessary to use between 12 kg and 20 kg of LMO or more with at least a 13 mg / g loading capacity to process 500 gallons of produced water containing a concentration of 30 mg / L of lithium to economically perform DLE at industrial scale in a commercial DLE operation.

[0093] Conventional batch-processing techniques benefit from higher-purity reactants that can be sourced in sufficient quantities and purities to synthesize a spinel sorbent at the lab scale. As batch sizes increase to accommodate industrial-scale direct metal extraction systems, and costs of reactants and reaction time and the associated costs of reacting the reactants increase, techniques typically must be developed for synthesizing spinel sorbents that reflect the realities of today’s supply chains, variation in reactant grade from lot to lot, and limited availability of ideal reactants of relatively higher-grade reactants. For example, while Mn sources in Mn₂O₃ and / or Mn₃O₄ are desired in some embodiments, alternative sources of Mn, such as a manganese carbonate, might need to be used to synthesize the spinel sorbent due to lack of availability of the preferred grade of the Mn source. In such instances, biasing the compound composition of an intermediate sorbent to create desired compounds may be desirable before converting the intermediate state to a sorbent blend.

[0094] The present disclosure includes techniques for using commercially available reactants within a range of temperatures to manufacture a high-loading-capacity LMO at scale. Such techniques may include transitioning a commercially available precursor to an intermediate state or an intermediate-state sorbent blend at a higher range of temperatures before converting the intermediate state to a sorbent blend. In some embodiments, the Attorney Docket No.22782.008WO1 / Element3-005-PCT intermediates, Mn₃O₄ and Mn₂O₃ particles, were synthesized by calcination for a specific duration, and the desired LMO spinel is obtained through an economical route. Transitioning a commercially available precursor to an intermediate state or an intermediate state sorbent blend may be biased to produce a higher LMO product or a higher-intermediate-state compound-rich sorbent blend. Biasing the formation of specific constituents of the ultimate sorbent blend may be accomplished by varying the reactants within the precursor blend, varying the reaction modality (e.g., using different spinel sorbent synthesis techniques such as by calcining), varying the reaction duration, varying the reaction conditions (such as the temperature or temperatures of the reaction), and increasing the number of reactions. In some embodiments, a reaction period is used to calculate the number of reactions. For example, a reaction period may begin with an initial reaction time, followed by a cooling duration and milling. A second reaction period may signify a second reaction period has been initiated.

[0095] In some embodiments, an intermediate state is beneficial when a reactant, such as an economical form of manganese oxide like Mn₃O₄, is converted to an intermediate-state reactant, like Mn₂O₃ before a large amount of LMO may be synthesized. Some experimental results in which the reaction time was varied suggest that when calcining is stopped at defined intervals while the calcination temperature is held constant, the intermediate-state Mn₂O₃ increases in quantity until the initial-reactant Mn₃O₄ is no longer detectable using XRD. The evidence suggests that for a large amount of LMO to be synthesized from a relatively high- grade Mn source, an intermediate state compound may be a necessary precursor reactant for reaction with a lithium reactant, such as LiOH monohydrate, before a LMO may be formed. By adopting the techniques described in the present disclosure, manufacturers may be incentivized to bias reactions involved in synthesizing sorbent spinels to first produce intermediate reactants, such as Mn₂O₃. By altering reaction conditions, like temperature, pressure, and reaction duration, to first convert at least one reactant within a precursor blend to form an intermediate state compound, the reaction conditions can be optimized to produce sorbent spinels at volumes necessary for industrial scale.

[0096] In some embodiments, a commercially available manganese oxide reactant may be included as one constituent of a precursor blend. As some manganese oxides may be converted to a necessary precursor reactant at temperatures described in the present disclosure, it can be advantageous to react a commercially available manganese oxide with a lithium donor to form a precursor blend. Turning now to FIG. 8, a flowchart 800 describes a method, according to Attorney Docket No.22782.008WO1 / Element3-005-PCT some embodiments of the present disclosure. In some embodiments, at 810, the method may include obtaining reactants, such as Mn₂O₃ and LiOH monohydrate, to form a precursor blend. When seeking to produce an LMO spinel at scale, a precursor blend may include at least one reactant that typically must be chemically changed before an LMO spinel may be formed. Such a chemical transformation may occur by reacting the precursor blend. In some embodiments, the reacting the precursor blend may include reacting the precursor blend at a high temperature and pressure to produce the intermediate-state sorbent. In some instances, reacting may include firing, a solid-state reaction such as calcination or calcining, microwave-assisted synthesis, mechanochemical synthesis, and combustion synthesis.

[0097] At 820, the method may include reacting, or calcining, the precursor blend for an initial calcining duration and at a first temperature, forming an intermediate-state sorbent blend. In some embodiments, the initial calcining duration is the time spent holding the defined temperature and does not necessarily account for the ramp-up period to achieve temperature, or the cool-down period after the defined duration is complete. An intermediate-state sorbent blend may be a desirable intermediate-state between a pure precursor blend of reactants and an end state of substantially pure sorbent blend. For example, when the precursor blend is a mix of lithium and manganese-oxide blend, wherein the manganese-oxide blend is an initial chemical formula, the intermediate-state sorbent may include a reduced volume of at least one reactant, a reactant at a second state, and some LMO. For illustrative purposes, a precursor blend may include a 3:4 ratio of lithium to manganese blend, the manganese reactant being Mn₃O₄ as the first state. Upon calcining the 3:4 ratio of lithium to manganese blend for an initial duration of five (5) hours at 525°C, an intermediate-state sorbent blend may include at least 89% by weight LMO and at least 4.5% by weight Mn₂O₃ (a second state reactant of the Mn₃O₄ first reactant state). Testing the volumes of the chemical constituents of the intermediate-state sorbent blend may be accomplished using X-ray Diffractometer (XRD) equipment, such as the Rigaku Benchtop X-ray Diffractometer MiniFlex600.

[0098] At 830, the method may include cooling the intermediate-state sorbent blend. Cooling may be beneficial in some commercial settings to safely handle the intermediate-state sorbent blend. At 840, the method may include milling the intermediate-state sorbent blend. In some embodiments, the reacting, such as when calcining techniques are used, results in the agglomeration of the intermediate-state sorbent blend. In such instances, it may be beneficial to cool the intermediate-state sorbent blend and mill the blend to a size that is readily retained Attorney Docket No.22782.008WO1 / Element3-005-PCT within a batch- or continuous-processing DLE system. For example, the intermediate-state sorbent may be milled such that the size of the intermediate-state sorbent exceeds the pore size of membrane-based DLE systems such that the intermediate-state sorbent may be retained within the DLE system.

[0099] In some embodiments, the reactants may include at least one manganese compound. For example, the reactants may include at least one of MnO2, Mn₃O₄, Mn(NO3)2, MnCO3, or Mn₂O₃. In some embodiments, the reactants may include at least one lithium hydroxide, lithium carbonate, or at least one of Mn₃O₄, MnCO3, or Mn₂O₃. The manganese compound may have a chemical formula of Mn₃O₄. In some embodiments, the intermediate-state sorbent blend further comprises at least 4.5% by weight Mn₃O₄ and less than 40% by weight Mn₂O₃ after a first calcination. In some embodiments, the reactants may include Mn₂O₃ and LiOH. In some embodiments, the initial calcining duration may be at least five (5) hours, and the first temperature may be at least 525℃.

[0100] In some embodiments, the initial calcining duration may be at least five (5) hours, and the first temperature may be at least 500℃. In some embodiments, the intermediate-state sorbent blend further comprises approximately 1% by weight Mn₃O₄, 9% by weight Mn₂O₃, and 90.0% by weight an LMO. Approximately generally refers to measurements that are within the tolerance of the measuring equipment, or the measurement is within a + / - 5% of the stated value, whichever is greater. In some embodiments, the initial calcining duration may be at least five (5) hours, and the first temperature is approximately 600℃. In some embodiments, the intermediate-state sorbent blend further comprises less than 3.5% by weight Mn₃O₄, less than 26.0% by weight Mn₂O₃, less than 3.0% by weight of LiOH monohydrate, and at least 68% by weight an LMO when higher-grade reactants are used in the precursor blend. In some embodiments, the initial calcining duration may be approximately five (5) hours, and the first temperature may be at least 525℃. In some embodiments, the intermediate-state sorbent blend further comprises greater than 4.0% by weight Mn₂O₃, and greater than 90% by weight an LMO. The LMO may have a lithium loading capacity of at least 13.0 mg / g of LMO.

[0101] FIG. 9 is a flowchart that describes a method for manufacturing an LMO sorbent spinel, according to some embodiments of the present disclosure. In some embodiments, at 910, the method may include obtaining a precursor blend. A precursor blend may include reactants that are necessary for producing one or more reactions that have taken place. While the present disclosure describes the formation of lithium-manganese-oxides (LMOs), the Attorney Docket No.22782.008WO1 / Element3-005-PCT present techniques also apply to other metal-oxide sorbents, such as lithium-ion sieve (LIS) and uncoated sorbents like titanate sorbents. In some embodiments, the precursor blend may be one of a 3:4, a 4:5, or a 0.70 to 0.85 molar ratio of lithium to manganese blend.

[0102] At step 920, the method may include calcining as a means for reacting the precursor blend. In some embodiments, the step may include calcining the precursor blend for an initial calcining duration and at a first temperature of, e.g., at least 500°C. Calcining durations may be altered to bias the production of specific constituents within specific quantity ranges. In one embodiment, the calcining duration may be biased to produce an LMO of at least 85% phase composition as measured with XRD data, at least 7% intermediate-state product (e.g., Mn₂O₃), and ideally, an undetectable amount of reactant from the precursor blend. To synthesize the intermediate-state sorbent blend with the biased intermediate sorbent constituents, a calcining temperature of at least 500℃ and a minimum reaction duration of approximately five (5) hours is performed.

[0103] In some embodiments, at 930, the method may include cooling the intermediate- state sorbent blend. Cooling the sorbent may be useful when handling the intermediate sorbent blend at the reaction temperature is impractical or does not comply with manufacturing-safety protocols. Cooling the intermediate-state sorbent blend at 940 may include additional steps. In some embodiments, for example, the synthesis of an LMO may involve performing additional steps like milling an agglomerated intermediate-state sorbent blend. When additional refinement to the precursor blend is not desired, milling may be performed to support the measuring of the sorbent-blend for packaging and sale or for activation prior to use in a DLE system. In some embodiments, the milling step, as described in FIG.9 during LMO synthesis, can help remove impurities and enhance the material's purity, which in turn improves loading capacity. Additionally, optimization (or at least improvement relative to other synthesis techniques) of synthesis parameters such as temperature, calcination duration, or precursor ratios can influence the crystal structure and morphology of LMO spinel obtained, thereby affecting loading capacity.

[0104] In some embodiments, it may be desirable to further purify or otherwise increase the percent phase composition of a desired product, such as the LMO. When a precursor blend of relatively high quality is used in the first reaction, a second reaction event can be performed to reduce an intermediate-state product, like Mn₂O₃, and bias the reaction to produce a higher percentage of LMO. At 950, the method may include calcining the intermediate-state sorbent Attorney Docket No.22782.008WO1 / Element3-005-PCT blend for a second duration and the second temperature, thus forming a sorbent blend. The calcining may form an intermediate-state sorbent blend of at least Mn₂O₃ and an LMO. The lithium loading capacity of the LMO may vary based on the temperature used during the first and second reactions. When calcining is performed, generally lower calcining temperatures of approximately 425°C tend to produce LMOs with a lower loading capacity. In some embodiments, air may be pumped into a kiln during the calcination. When the air is not pre- heated to the kiln temperature, the added air may result in a lower-loading-capacity LMO.

[0105] Turning now to Table 1, multiple two-step reactions were conducted consistent with the process of FIG.9. A precursor blend of LiOH.H₂O and Mn₃O₄ were mixed in a 3:4 ratio of Li:Mn. In each reaction (i.e., React.1 and React.2), the reaction duration was held constant at five (5) hours, while the temperatures of each reaction were held at approximately 425 ⁰C and 525⁰C. In some instances, unheated air was pumped into the kiln. The intermediate-state sorbent blend was analyzed using XRD, with the results and loading capacity of the isolated LMO provided below. No. Air React.1 React.2 React 2 Loading Mn₂O LMO Duration (mg / g) ₃ TA gher-grade precursor blend.

[0106] As seen in Table 1, varying the reaction parameters of temperature and duration can bias the constituents present and the percentage of the constituents within the synthesized- sorbent blend. When the grade of the reactants forming the precursor blend is higher, the constituents of the sorbent blend are more reliably predicted. Overall, higher-quality reactants tend to comprise approximately 70% composition by weight of manganese. Lower-quality reactant sources often include compounds containing P, Fe, and CaO in percent by mass as high as 0.71%, 2.70%, and 0.46%, respectively. Consistently higher percentages of desired intermediate-state compounds, like LMO and Mn₂O₃, are produced when compounds like Fe Attorney Docket No.22782.008WO1 / Element3-005-PCT are reduced to approximately 0.20% or even eliminated. One such technique for reducing or removing iron content is magnetic separation. In some embodiments, the initial calcining duration may be set to at least five (5) hours. In some embodiments, the initial calcining duration may be at least five (5) hours and the first temperature may be at least 500℃. In some embodiments, the intermediate-state sorbent blend further comprises approximately 1% by weight Mn₃O₄, 9% by weight Mn₂O₃, and 90% by weight an LMO. In some embodiments, the initial calcining duration may be at least five (5) hours and the first temperature may be at least 600℃. In some embodiments, the intermediate-state sorbent blend further comprises approximately 2.01% by weight Mn₃O₄ 24% by weight Mn₂O₃, 2.0% by weight of LiOH monohydrate, and at least 72% by weight an LMO. In some embodiments, the initial calcining duration may be at least five (5) hours and the first temperature may be at least 525℃. In some embodiments, the intermediate-state sorbent blend further comprises approximately 5.0% by weight Mn₂O₃, and 94% by weight an LMO. The LMO may have a lithium loading capacity of at least 14.6 mg / g of LMO.

[0107] Additionally, Table 1 characterizes the impact of temperature, airflow, and reaction duration for biasing the synthesis of LMO and Mn₂O₃ of desired percentages of purity. To obtain an LMO of at least 60% by weight with a loading capacity of at least 6 mg / g using higher-grade reactants, the precursor blend should be calcined for an initial calcining temperature of at least 425℃ and a second calcining temperature of 500℃ for a duration of at least five (5) hours in the presence of air. To obtain an LMO of approximately 99% purity with a loading capacity of at least 17 mg / g, the precursor blend should be calcined for an initial calcining temperature of 525℃ and duration of five (5) hours, followed by a second calcining temperature of 525℃ and a duration of at least ten (10) hours, without forced air pumped into the kiln.

[0108] In order to bias the synthesis of an LMO to approximately 97% purity with a loading capacity of at least 14 mg / g within the intermediate-state sorbent, the precursor blend should be calcined for an initial calcining temperature of approximately 525℃ and duration of at least five (5) hours, followed by a second calcining temperature of at least 525℃ for a duration of at least ten (10) hours in the presence of forced unheated air. In some embodiments, forced air may be preheated to the temperature of a heating apparatus, for example a kiln. Preheating forced air, for example, to the desired temperature of the kiln for biasing purposes, offers Attorney Docket No.22782.008WO1 / Element3-005-PCT additional control over the effective temperature of the calcination temperature and marginally greater mass of LMO and improved loading capacity.

[0109] FIG.10 is a flowchart that further describes the method for manufacturing an LMO sorbent spinel based on principles described in relation to FIG. 9, according to some embodiments of the present disclosure. In some embodiments, the calcining of the intermediate-state sorbent blend for a second duration and a second temperature may include steps 1010 to 1020. In some embodiments, the calcination duration of step 950 (FIG. 9) may be set to a period of between three (3) hours, as in 1010, to as many as ten (10) hours. To demonstrate the variability of the process to bias the formation of specific compound constituents and their quantities within the sorbent blend, step 950 may be modified by selecting a temperature that is the same or different from the initial reaction temperature used in the first calcination. In some embodiments, a second calcination temperature of at least 500°C but less than 550°C may be desired. The sorbent may calcinate further, increasing the weight of LMO in the sorbent blend compared with the weight of LMO present in the intermediate sorbent blend. In some embodiments, the second calcination event may result in an LMO having an increased lithium loading capacity when activated.

[0110] FIG.11 is a flowchart that further describes the method for manufacturing an LMO sorbent spinel from FIG.9, according to some embodiments of the present disclosure. In some embodiments, at 1140, the method may include activating the sorbent blend. Activating the LMO often involves preparing an LMO, by displacing the lithium within the LMO structure with an alternative ionic element, such as hydrogen. In general, an activated LMO may be an HMO. In some embodiments, at 1110, the activating may include mixing the spinel sorbent with an acid. In some embodiments, the acid may be a single proton donor, such as HCl, or maybe a multiphoton donor, such as H2SO4. In some embodiments, the spinel sorbent, such as an LMO, may be activated using a ratio of 1g of LMO per 45 mL of an acid. At 1120, the activating may include agitating the sorbent. Agitating the sorbent may accelerate the activation step, and the mechanism for agitating the mix may be selected to reduce the damage done to the spinel structure. The spinel sorbent and the acid may be placed in contact for between sixteen to forty-eight (16 to 48) hours, although shorter durations may be possible. In some embodiments, spinel sorbent and the acid may be agitated during the contact time, allowing the contact time to be reduced to less than 16 hours. Since rough handling of the sorbent may degrade the spinel structure of the LMO, careful management of the process coupled with Attorney Docket No.22782.008WO1 / Element3-005-PCT active monitoring of the turbidity may be factored in to optimize (or at least to improve relative to other formation techniques) the contact time duration while minimizing (or at least to improve relative to other formation techniques) spinel-structure degradation. In some embodiments, the mixture of acid and spinel sorbent may be allowed to reach equilibrium without an agitation mechanism. The duration may be altered to achieve a certain amount of activation for the given reactant used. Factors that influence the duration in which the desired activation of the spinel structure is achieved vary based on the nature of the spinel sorbent (e.g., a titanate, an LMO, an aluminate sorbent), the reactant used to activate the spinel sorbent (e.g., when an acid is used, the molality of the acid, the strength of the acid), the volume of a fluid the spinel structure is immersed within, the chemical constituents of the fluid containing the spinel structure, and other variables like pressure, temperature, and mixing or agitation mechanisms used. For example, in some embodiments, at 1130, the activation may include activating the sorbent for a duration necessary to reach an activation percentage of at least 65% activation to form an activated sorbent at standard temperature and pressure (STP).

[0111] FIG. 12 is a flowchart that describes a method for manufacturing an undoped activated LMO sorbent spinel, according to some embodiments of the present disclosure. In some embodiments, at 1210, the method may include obtaining a precursor blend. When working with a sorbent spinel at an industrial scale, reactants critical to manufacturing the sorbent spinel are often accompanied by impurities introduced into the precursor blend. Purity, in the context of the sorbent blend comprising lithium manganese oxide (LMO), is a parameter that denotes the percentage of the desired reactants, along with other constituents. This concept of purity is particularly important when aiming for a specific biased yield of LMO to be synthesized within a specific reaction duration and, in certain embodiments, at predetermined temperatures. Achieving the desired level of purity in the sorbent blend ensures that the subsequent reactions and processes yield LMO with the intended structural and chemical properties, optimizing (or at least improving relative to other formation techniques) the LMO’s performance as a sorbent.

[0112] At 1220, the method may include calcining the precursor blend for an initial calcining duration and at a first temperature of at least 525℃. At 1230, the method may include milling the intermediate-state sorbent blend. At 1240, the method may include calcining the milled intermediate-state sorbent blend for a second duration and at a second temperature, the Attorney Docket No.22782.008WO1 / Element3-005-PCT result being forming a sorbent blend. At 1250, the method may include activating the sorbent blend with an acid.

[0113] In some embodiments, the purity and loading capacity of lithium manganese oxide (LMO) can be influenced by various factors, including the synthesis techniques, durations, and temperatures employed during its preparation. Different synthesis techniques known in the art, such as solid-state synthesis, sol-gel method, co-precipitation, hydrothermal synthesis, and combustion synthesis, can impact the purity and properties of LMO. For example, sol-gel methods typically involve the hydrolysis and condensation of precursor solutions to form a gel, followed by drying and calcination. Co-precipitation techniques involve the simultaneous precipitation of metal ions from solution, which can result in homogeneous mixing and fine particle size distribution, potentially increasing the loading capacity of LMO.

[0114] In some embodiments of the present disclosure, the duration of the reaction, including time at temperature and variations in temperature, may affect the purity and potentially the spinel structure of the LMO. In some commercial applications, it may be advantageous to produce a higher purity of LMO in relation to the initial reactants in a shorter duration using more readily available Manganese compound sources, such as Mn₃O₄. Referring to FIG.13, a table of reaction temperatures used during a constant reaction duration of five (5) hours is provided. Within the table, a precursor blend mass of twenty-five (25) grams composed of the reactants LiOH.H₂O and Mn₃O₄ mixed in a 3:4 molar ratio of lithium to manganese blend is utilized.

[0115] FIG. 13 is a table that describes the quantities of intermediate-state sorbent blend obtained at different calcining temperatures during the first calcining duration as described in the method for manufacturing an LMO sorbent spinel from FIG.9, according to some embodiments of the present disclosure. The values within FIG.13 represent the weight percent phase composition of each compound as determined by Rietveld refinement of XRD data. At 400oC, for a calcining duration of five (5) hours, 11.51% of LMO, 6.98% of Mn₂O₃, 77.41% of Mn₃O₄ and 4.11% of LiOH monohydrate are obtained. At 450⁰C, for a calcining duration of five (5) hours, 7.08% of LMO, 12.81% of Mn₂O₃, 78.07% of Mn₃O₄,and 2.04% of LiOH monohydrate are obtained. At 500⁰C, for a calcining duration of five (5) hours, 90.62 g of LMO, 9.04 g of Mn₂O₃, and 0.34% of Mn₃O₄ are obtained (little or no (0%) LiOH.H₂O is obtained). At 525⁰C, for a calcining duration of five (5) hours, 94.42% of LMO and 5.58% Mn₂O₃ are obtained (little or no (0%) Mn₃O₄ and little or no (0%) LiOH.H₂O are obtained). At Attorney Docket No.22782.008WO1 / Element3-005-PCT 550°C, for a calcining duration of five (5) hours, 82.6 g of LMO and 17.40 g of Mn₂O₃ are obtained (little or no (0%) Mn₃O₄ and little or no (0%) LiOH.H₂O are obtained). At 600oC, for a calcining duration of five (5) hours, 72.2% by weight of LMO, 23.98% by weight of Mn₂O₃, 2.21% of Mn₃O₄, and 1.62% of LiOH monohydrate (LiOH.H₂O) are obtained. At 650oC, for a calcining duration of five (5) hours, 74.34% by weight of LMO and 25.66% by weight of Mn₂O₃ are obtained (little or no (0%) Mn₃O₄ and little or no (0%) LiOH.H₂O are obtained).

[0116] A reaction, with regard to FIG.13, such as calcination of a fixed five-hour duration on the precursor blend, may be performed at various temperatures, for example, a temperature between 400⁰C and 650⁰C. At the end of each five-hour period, the calcining results in the formation of an intermediate-state sorbent blend of at least Mn₂O₃ and an LMO. The table suggests that as the calcination temperature increases, the reactants present in the precursor blend found within the intermediate-state sorbent decrease from their initial mass weights. In some embodiments, the presence of lithium hydroxide monohydrate (LiOH^H2O) facilitates the conversion of manganese (II, III) oxide (Mn₃O₄) to manganese (III) oxide (Mn₂O₃) and a lithium manganese oxide (LMO) through a reaction. Manganese (III) oxide (Mn₂O₃) may be produced as a byproduct of the reaction between lithium oxide and manganese (II, III) oxide. Mn₂O₃ may form as a separate phase or coexist with LMO depending on the synthesis conditions.

[0117] Optimization (or at least improvement relative to other formation techniques) of the formation of an LMO and reduction of the reactants within a limited time frame may be optimized (or at least improved relative to other formation techniques) within a window of calcination temperatures of approximately 500⁰C and 525⁰C. The data suggests that when 100 grams of reactants are mixed in a 3:4 ratio, and at least 90 grams of LMO are desired, the formation of LMO may be optimized (or at least improved relative to other formation techniques) by calcining at approximately 500⁰C and 525⁰C. In some embodiments, it may be desired to produce an intermediate-state sorbent blend with negligible or unmeasurable amounts of reactants. When the purity of the LMO requires at least 80 grams of LMO and negligible or unmeasurable amounts of reactants, a five-hour calcination period from approximately 525⁰C to approximately 550°C may be preferred. In some embodiments, lithium manganese oxide (e.g., a compound best match of Li1.33Mn1.67O4 as determined using XRD, LiMn2O4, or LMO) is the desired product of the reaction. LMO forms as a spinel phase by incorporating lithium ions into the manganese-oxide lattice. Attorney Docket No.22782.008WO1 / Element3-005-PCT

[0118] FIG.14 is a table illustrating the respective quantities of intermediate-state sorbent blend obtained at a calcining temperature of 525°C at different time intervals during the first calcining duration as described in the method for manufacturing an LMO sorbent spinel from FIG.9, according to some embodiments of the present disclosure. At 525°C, for 0.5 hours, 55.5% by weight of LMO, 7.04% by weight of Mn₂O₃, 37.19% of Mn₃O₄, and 0.26% of LiOH monohydrate (LiOH.H₂O) are obtained. At 525°C, for 1 hour, 69.02% by weight of LMO, 15.69% by weight of Mn₂O₃, 11.0% of Mn₃O₄, and 4.3% of LiOH monohydrate are obtained. At 525⁰C, for 1.5 hours, 84.36% by weight of LMO and 15.64% by weight of Mn₂O₃ are obtained (little or no (0%) Mn₃O₄ and little or no (0%) LiOH.H₂O are obtained). At 525°C, for five (5) hours, 94.42% by weight of LMO and 5.58% by weight of Mn₂O₃ are obtained (little or no (0%) Mn₃O₄ and little or no (0%) LiOH.H₂O are obtained). At 525°C, for eight (8) hours, 78.79% by weight of LMO, 20.66% by weight of Mn₂O₃, 0.08% of Mn₃O₄, and 0.47% of LiOH monohydrate (LiOH.H₂O) are obtained. At 525°C, for fifteen (15) hours, 83.54% by weight of LMO and 16.46% by weight of Mn₂O₃ are obtained (little or no (0%) Mn₃O₄ and little or no (0%) LiOH.H₂O are obtained). The calcination duration for Mn₂O₃ is about five (5) hours at 525°C to ensure conversion to 95% of LMO (e.g., a compound best match of Li₁.₃₃Mn₁.₆₇O₄ as determined using XRD, LiMn2O4) through dehydration while minimizing impurities and phase transformations. An extended calcination duration beyond five (5) hours results in the compound composition of LMO into secondary phases or the conversion of LMO to Mn₃O₄, inducing the formation of either any one of the phase impurities or particle growth / agglomeration or morphological changes or loss of lithium and manganese.

[0119] FIG. 15 is a table illustrating the compound composition percentages of the intermediate sorbents of calcined undoped precursor blend during second calcination temperatures and durations, as described in the method for manufacturing a doped LMO sorbent spinel from FIG. 12, according to some embodiments of the present disclosure. At 400⁰C, for an initial calcining duration of 5 hours and a second calcining duration of 10 hours at 525°C, the compound composition percentages of undoped intermediate-state sorbents are 76.59% by weight of LMO and 23.41% by weight of Mn₂O₃. At 525°C, for an initial calcining duration of 0.5 hours and a second calcining duration of 0.5 hours at the same temperature, the compound composition percentages of undoped intermediate-state sorbents obtained are 63.32% by weight of LMO, 25.68% by weight of Mn₂O₃, 10.37% by weight of Mn₃O₄, and 0.64% by weight of LiOH monohydrate. At 525°C, for an initial calcining duration of 0.5 hours and a second calcining duration of 10 hours at the same temperature, the compound Attorney Docket No.22782.008WO1 / Element3-005-PCT composition percentages of undoped intermediate-state sorbents obtained are 83.24% by weight of LMO, 16.67% by weight of Mn₂O₃, 0.06% by weight of Mn₃O₄, and 0.02% by weight of LiOH monohydrate obtained. At 525°C, for an initial calcining duration of 2 hours and a second calcining duration of 2 hours at the same temperature, the compound composition percentages of undoped intermediate-state sorbents obtained are 79.89% by weight of LMO, 19.42% by weight of Mn₂O₃, 0.49% by weight of Mn₃O₄, and 0.21% by weight of LiOH monohydrate. At 525°C, for an initial calcining duration of 2 hours and a second calcining duration of 10 hours at the same temperature, the compound composition percentages of undoped intermediate-state sorbents obtained are 89.82% by weight of LMO, 8.92% by weight of Mn₂O₃ and 1.26% by weight of Mn₃O₄. At 525°C, for an initial calcining duration of 5 hours and a second calcining duration of 10.0 hours at the same temperature, the compound composition percentages of undoped intermediate-state sorbents obtained are 91.38% by weight of LMO, 8.09% by weight of Mn₂O₃ and 0.53% by weight of LiOH monohydrate. At 525°C, for an initial calcining duration of 15 hours and a second calcining duration of 10 hours at the same temperature, the compound composition percentages of undoped intermediate-state sorbents obtained are 92.23% by weight of LMO, 7.16% by weight of Mn₂O₃, 0.33% by weight of Mn₃O₄, and 0.28% by weight of LiOH. At 650°C, for an initial calcining duration of 5 hours and a second calcining duration of 10 hours for the same temperature, the compound composition percentages of undoped intermediate-state sorbents obtained are 92.09% by weight of LMO, 7.76% by weight of Mn₂O₃ and 0.15% by weight of LiOH monohydrate.

[0120] In some embodiments, the first calcining step may not synthesize a pure LMO. By varying the duration of the reaction and / or temperature, some or all the reactants may be eliminated from the blend. The presence of the reactants in the precursor blend, and some intermediate products, such as Mn₂O₃, are formed during synthesis. A second calcination step may be performed to further reduce the presence of the constituents of the intermediate-state sorbent other than the LMO spinel, leading to higher-purity LMO. In some embodiments, LMO spinel formation may involve multiple reaction steps forming an intermediate-state sorbent blend of intermediates not present in the precursor blend, for example, Mn₂O₃ when a Mn₃O₄ reactant is present in the precursor blend. In some embodiments, the first calcination at 525°C for five (5) hours may not result in the desired phase-formation or crystal-structure optimization (or at least improvement relative to LMOs formed by other techniques) of the LMO. A second calcination step at 525°C for ten (10) hours allows for further phase transformation and Attorney Docket No.22782.008WO1 / Element3-005-PCT crystallization, leading to the formation of the desired LMO spinel phase with the optimal (or at least an improved relative to other LMO spinel phases) crystal structure and loading capacity.

[0121] In yet another embodiment, the second calcination step can promote better mixing and homogenization of the precursor materials, ensuring uniform distribution of lithium, manganese, and oxygen throughout the LMO particles.

[0122] FIG.16 is a table illustrating the respective quantities of intermediate-state sorbent blend obtained at a calcining temperature of 525oC at different time intervals during the second calcining duration as described in the method for manufacturing a LMO sorbent spinel from FIG.9, according to some embodiments of the present disclosure. At 525⁰C, for 0.5 hours, 83.24% by weight of LMO, 16.67% by weight of Mn₂O₃, 0.06% of Mn₃O₄, and 0.02% of LiOH monohydrate are obtained. At 525⁰C, for two (2) hours, 89.82% by weight of LMO, 8.92% by weight of Mn₂O₃, and 1.26% of Mn₃O₄ are obtained (little or no (0%) LiOH.H₂O is obtained). At 525⁰C, for five (5) hours, 91.38% by weight of LMO and 8.09% by weight of Mn₂O₃ and 0.53% of LiOH monohydrate are obtained (little or no (0%) Mn₃O₄ is obtained). At 525⁰C, for fifteen (15) hours, 92.23% by weight of LMO and 7.16% by weight of Mn₂O₃, 0.33% of Mn₃O₄, and 0.28% of LiOH monohydrate are obtained.

[0123] The purity of the reactants within the precursor blend can influence the crystal structure and morphology of LMO spinel. Purity, in the context of chemical reactants, refers to the proportion of the desired substance within a sample, free from any undesired contaminants or substances. Impurities, therefore, constitute any trace to substantial volumes of compounds, ions, or elements that are not the intended reactants or products within the precursor blend. These can originate from various sources during the manufacturing, handling, or storage processes and may include other chemicals used in production, environmental contaminants, or residues from the synthesis process itself. Most often, these impurities are found along with the necessary reactants intended for the precursor blend. The presence of these impurities, even in small quantities, can significantly influence the chemical reactions, leading to the formation of secondary phases, altering the stoichiometry of the LMO lattice structure, and ultimately affecting the spinel sorbent's properties such as the accessibility of lithium ions.

[0124] Purity, in the context of the sorbent blend comprising lithium manganese oxide (LMO), typically is a critical parameter that denotes the percentage of the desired sorbent spinel, along with other constituents, within the intermediate-sorbent blend. This concept of Attorney Docket No.22782.008WO1 / Element3-005-PCT purity is particularly pivotal when aiming for a biased yield of LMO to be synthesized within a specific reaction duration and, in certain embodiments, at predetermined temperatures. Achieving the desired level of purity in the sorbent blend typically ensures that the subsequent reactions and processes yield LMO with the intended structural and chemical properties, optimizing (or at least improving relative to other formation techniques) its performance as a sorbent. FIG.16 data suggests that the purity of the LMO spinel was maximized between five (5) and fifteen (15) hours at 525oC during the second calcination.

[0125] Upon activation of the sorbent, such as LMO, any intermediate-sorbent constituents that are extraneous to the desired outcome are often removed, enhancing the purity of the resultant product. For activated sorbents, purity thus can be defined as the percentage of LMO that has undergone conversion to hydrogen manganese oxide (HMO), reflecting the efficiency of the activation process. In essence, a high-purity activated LMO is indicative of a substantial conversion to HMO, quantified by the percentage of HMO by weight within the blend. This measure of purity can be crucial, as it can directly impact the spinel sorbent’s efficacy and suitability for its intended applications, particularly where specific sorbent characteristics are required for optimal (or at least for improvement relative to other sorbents) performance. Therefore, controlling the purity of the sorbent blend not only dictates the quality of the LMO produced but also ensures (or at least significantly improves the chances of) the success of the targeted reactions and the functional integrity of the activated sorbent in its application context.

[0126] FIG. 17 is a table illustrating the loading capacity of LMO sorbent spinel as described in the method for manufacturing an LMO sorbent spinel from FIG.12, according to some embodiments of the present disclosure. The table contents represent the impact temperature, duration of the reacting step, reactants, and a second reacting step have on the loading capacity of the resulting LMO. By varying each of one or more of the duration, temperature, duration of the reacting step, reactants, or a second reacting step, different amounts of LMO, intermediate compound, or reactants present within the precursor blend can be biased to preferred amounts. In particular, in this exemplary instance calcining, the duration and temperature of the reacting can be modified in a second calcining event of duration and temperature to achieve a desired loading capacity.

[0127] The formation of LMO spinel at rather high purities, e.g., above 90% purity by weight, can be accomplished by calcining reactants like Mn₃O₄ and LiOH monohydrate at a lower temperature for relatively brief durations of five (5) hours. This synthesis technique Attorney Docket No.22782.008WO1 / Element3-005-PCT allows a commercially available manganese compound to be chemically converted to an intermediate compound, like Mn₂O₃. In some experiments, the formation of the intermediate Mn₂O₃ compound in the presence of a precursor blend of Mn₃O₄ and LiOH monohydrate may facilitate the formation of the LMO spinel. Converting Mn₃O₄ to a volume of Mn₂O₃ compound during the calcining process also produces a spinel sorbent within a relatively short duration of five (5) hours. This represents a reduction in total calcination duration by 66% over conventional sorbent synthesis techniques. The present technique suggests that this method of utilizing an available compound for converting the compound in the presence of a precursor blend is feasible and effective for synthesizing a spinel sorbent.

[0128] Returning to FIG.17 experiments No.1 – 6 were conducted using a precursor blend of LiOH monohydrate (LiOH.H₂O) and a high-grade Mn₃O₄ source, while experiment No. 7 was conducted using a precursor blend of lithium carbonate (Li₂CO₃) and a high-grade Mn₃O₄ source. Typical of a higher grade Mn₃O₄ source, the high-grade Mn₃O₄ source comprised a lower volume of iron (e.g., percent by weight of less than 0.7) and availability of Mn in % by weight equal to or greater than 71% of overall weight. In general, calcining temperatures of approximately 525⁰C synthesized an LMO (e.g., a spinel LMO compound chemical formula best match of Li1.33Mn1.66O4 as determined using XRD) yielding higher loading capacities, while a second calcination generally increased the loading capacity of the activated LMO (e.g., an HMO) at the end of the second calcination event. Milling was performed between the initial and second calcinations. Ion Li+ Na+ K+ Cl- HCO3- Concentration

[0129] Loading capacity was measured on the intermediate-state sorbent and again after a second calcining period. A loading test was performed on the sorbent using a synthetic brine. The brine solution is defined in Table 2. Loading tests were conducted with 200 mL of brine solution and approximately 0.1 g of activated sorbent. This ratio is intended to supply an excess of lithium, allowing an accurate determination of the loading capacity. Samples were mixed for approximately one hour before collecting the depleted brine samples. Various other methodologies for assessing the absorption of the sorbent can be used to assess the loading capacity of a sorbent. It is acknowledged that the loading capacities determined through these tests may be influenced by the constituents of the testing brine. Components such as competing Attorney Docket No.22782.008WO1 / Element3-005-PCT ions, pH levels, and the presence of organic compounds or other metals within the brine solution can impact, significantly, the sorbent's lithium uptake. These interactions may lead to reduced loading capacities, highlighting the importance of considering the specific composition of the brine when evaluating sorbent performance. Additionally, the testing conditions, such as the contact time between the sorbent and the brine, temperature, and sorbent-to-brine ratio, can be critical factors that can affect the outcome of the loading capacity tests. As such, optimizing (or at least improving relative to other formation techniques) these parameters based on the characteristics of both the sorbent and the brine solution can be important, even essential, for achieving an accurate determination of loading capacity, ensuring (or at least improving the odds) that the findings are representative of real-world applications.

[0130] Experiments No. 1 – 5 and 7 had an initial calcination and second calcination temperature of 525⁰C, while the duration of each experiment was varied. In experiment No.1, an initial calcining duration of 0.5 hours was conducted, followed by a second calcining duration of 0.5 hours, yielding an LMO with a lithium loading capacity of 10.2 mg / g of activated LMO. In experiment No.2, an initial calcining duration of two (2) hours followed by a second calcination duration of two (2) hours yielded an LMO with an activated lithium loading capacity of 13.2 mg / g of activated LMO. In experiment No. 3, an initial calcining duration of two (2) hours was followed by a second calcination duration of ten (10) hours, yielding an LMO with an activated lithium loading capacity of 9.2 mg / g of LMO. In experiment No.4, an initial five-hour calcination was followed by a second ten-hour (10-hour) calcination, yielding an activated LMO with a lithium loading capacity of 15.9 mg / g of activated LMO. In experiment No. 5, an initial fifteen-hour (15-hour) calcination followed by a second ten-hour (10-hour) calcination yielded an LMO with an activated lithium loading capacity of 14.5 mg / g of activated LMO. Experiment No. 7 was conducted with a lithium carbonate and Mn₃O₄ precursor blend. The experiment included an initial five-hour (5-hour) calcining duration followed by a second ten-hour (10-hour) calcination, yielding an activated LMO with a lithium loading capacity of 23.9 mg / g of activated LMO.

[0131] Experiment No. 6 was conducted at a higher calcination temperature of 650⁰C during the initial five-hour (5-hour) calcination, followed by a second calcination period of ten (10) hours, yielding an LMO with an activated lithium loading capacity of 6.7 mg / g of activated LMO. As described in FIG.17, the highest loading capacity of 23.9 mg / g lithium in activated LMO is achieved by calcining for five (5) hours during the first calcination, followed by a ten- Attorney Docket No.22782.008WO1 / Element3-005-PCT hour (10-hour) calcination during the second firing at 525°C. The data obtained in the table of FIG. 17 further signifies that none of the firing combinations using LiOH monohydrate achieved as high of a loading capacity of the activated LMO as when Li₂CO₃ was a reactant and constituent of the precursor blend.

[0132] In another embodiment, the method of calcining the precursor blend at 525°C for five (5) hours looks in ambient atmosphere may form LMO via a one step, cost-effective and scalable method of synthesis of an LMO spinel. Referring again to the flow chart of FIG. 12, at 1210, the precursor blend may be a 0.70 to 0.85 ratio of lithium to manganese blend. Step 1220 includes calcining the precursor blend of step 1210 for an initial calcining duration and at a first temperature to form an intermediate-state sorbent blend of at least Mn₂O₃ and an LMO. In the subsequent step 1230, the resultant intermediate sorbent is milled to achieve particle-size reduction and homogenization of the intermediate-sorbent format size. At step 1240, the milled intermediate sorbent of step 1230 is subjected to calcination for the second time for a second duration and temperature, thereby synthesizing a sorbent blend. The resultant sorbent blend of step 1240 undergoes activation with an acid at step 1250, wherein the sorbent is activated to reach an activation percentage of at least 65% activation to form an activated LMO sorbent (e.g., an HMO). The LMO may have a lithium loading capacity of at least 5.0 mg / g of activated LMO at standard temperature and pressure for an initial calcination of approximately two (2) hours at 525⁰C using a 3:4 ratio of lithium-to-manganese precursor blend. The activated sorbent blend comprises at least one species of HMO sorbent spinel.

[0133] In some embodiments, the intermediate-state sorbent blend of at least Mn₂O₃ and an LMO may further comprise 50% by weight Mn₂O₃, 10% by weight Mn₃O₄, and 25% by weight LMO. In some embodiments, the sorbent blend further comprises 96% by weight LMO. The activated sorbent blend comprises at least one species of HMO sorbent spinel, having a lithium loading capacity of at least 6.0 mg / g of HMO.

[0134] FIG.18 is a table illustrating the impact of three different grades of Mn₃O₄ products used in the method for manufacturing an LMO sorbent spinel from FIG.9, according to some embodiments of the present disclosure. In general, when reactants are purchased, these reactants often include additional impurities. Higher-grade reactant materials contain a high actual percentage by weight of the reactant, and as low as possible impurities, although not all impurities have the same impact on sorbent formation and / or loading capacity. For illustrative purposes, the content of iron (one of several impurities found within the purchased Mn₃O₄), Attorney Docket No.22782.008WO1 / Element3-005-PCT was assessed to understand how the percentage of iron by weight of Mn₃O₄ impacts the loading capacity of LMO sorbent spinel. Each of Grade 1, Grade 2, and Grade 3 was calcinated twice using the same calcination schedule. Each of the compounds within the intermediate-state sorbent blend were determined by Rietveld refinement of XRD data, and the loading capacity of the activated LMO was assessed. For all three grades of Mn₃O₄, a first calcination of five hours was conducted at 525°C followed by a second calcination of 10 hours at 525°C.

[0135] At 525°C for an initial calcination of 5 hours, Grade 1 precursor yielded, 53.2% by weight of LMO, 6.11% by weight of Mn₂O₃, 38.27% of by weight of Mn₃O₄, and 2.42% of LiOH monohydrate. At the same temperature and duration of initial calcination, grade 2 precursor yielded 46.31% by weight of LMO and 3.33% by weight of Mn₂O₃, 46.31% by weight of Mn₃O₄, and 1.39% by weight of LiOH monohydrate and grade 3 precursor yielded, 94.42% by weight of LMO and 5.58 % by weight of Mn₂O₃, during initial calcination. During the second calcination of 10 hours at 525°C, grade 1 precursor yielded, 78.92% by weight of LMO and 11.34% by weight of Mn₂O₃, 6.58% by weight of Mn₃O₄, and 3.17% of LiOH monohydrate while grade 2 yielded, 81.59% by weight of LMO and 6.87% by weight of Mn₂O₃, 6.73% by weight of Mn₃O₄, and 4.81% of LiOH monohydrate; and grade 3 yielded, 91.38% by weight of LMO and 8 / 09% by weight of Mn₂O₃ and 0.53% of LiOH monohydrate during the same experimental period.

[0136] FIG.18 further illustrates the loading capacities of different grades against the LMO spinel's respective iron content. Grade 1 precursor exhibited a loading capacity of 5.6 mg / g with 2.70% iron content within the Mn₃O₄ reactant. Grade 2 precursor exhibited a higher loading capacity of 6.9 mg / g with 1.7% of iron content within the Mn₃O₄ reactant, and Grade 3 precursor showed the highest lithium loading capacity among the 3 grades of precursor materials utilized for the experiment with a loading capacity of 15.9 mg / g and associated Fe content within the Mn₃O₄ reactant of 0.17% by weight of Grade 3 reactant. The data presented in FIG. 18 correlates lower iron content with a higher loading capacity of the activated LMO spinel. The presence of iron as an impurity can impact the performance of the spinel, including its absorption or loading capacity for lithium in direct lithium extraction processes. Of note, other trace metals and compounds may also play a role in reducing LMO formation and ultimate loading capacity. Therefore, minimizing all impurities within the reactant source used in the precursor blend brings some predictability to the LMO weight synthesized and loading capacity performance of the sorbent at an industrial scale lithium extraction process. Attorney Docket No.22782.008WO1 / Element3-005-PCT

[0137] DOPED SORBENT SPINEL

[0138] The subject matter herein relates, generally, to doped lithium manganese oxide (LMO) spinels for extracting a metal from a metal-containing fluid and, more particularly, to improvement and optimization techniques for manufacturing such compositions at commercial-scale volumes.

[0139] Direct Lithium Extraction (DLE) often uses an activated Lithium Manganese Oxide (LMO) sorbent to remove lithium from produced water. While much research has been done exploring the use of LMOs to adsorb lithium at a lab scale, improvements in manufacturing LMOs at the scale required to process tens of thousands of gallons of water per hour are needed. An example of a DLE system that may be used to continuously or batch process a produced water at scale is described in US provisional application number 63 / 489,645, titled SYSTEM AND METHOD FOR REDUCING A CONCENTRATION OF A METAL FROM PRODUCED WATER USING A LARGE FORMAT COMPOSITION, filed on March 10, 2023, the contents of which are incorporated in their entirety by reference, to the extent not inconsistent herewith. A factor in scaling up DLE systems to meet commercial demand is producing LMOs in bulk with the reactants that are presently available.

[0140] Conventional techniques for producing lab-scale quantities of LMO are described in Paulsen, J. M.; Dahn, J. R.; "Phase Diagram of Li-Mn-O Spinel in Air"; published by the American Chemical Society on October 27, 1999 https: / / cdn.bc- pf.org / olympiads / chemistry / rus_sbory / 2010-Oct / thermo.pdf, the contents of which are incorporated by reference in their entirety, to the extent not inconsistent herewith. Further, improving or optimizing synthesis techniques of a spinel sorbent, reacting durations and temperatures may be altered to enhance the purity and / or loading capacity of lithium manganese oxide (LMO) for various applications, including lithium-ion batteries, catalysis, and sorbents.

[0141] Spinel sorbents, such as LMOs, are important compounds in direct lithium extraction (DLE) systems. Some techniques for manufacturing these spinel sorbents are often described with respect to laboratory scale. When synthesizing larger volumes of sorbent spinels, such as a 15 to 20 kg batch size of LMO sorbent for treating 500 gallons of 30 PPM lithium produced water, using a lower grade of the doped precursor blend may be necessary. Lower-grade reactants may significantly impact the loading capacity of the sorbent, often Attorney Docket No.22782.008WO1 / Element3-005-PCT reducing the loading capacity of the doped sorbent and impacting the fragility of the spinel structure and lattice integrities. Commercially available Mn₃O₄ may include compounds that impact the formation of an LMO, contributing to the ultimate loading capacity of the activated LMO and the quantity of LMO produced. Undesired compounds, such as iron (e.g., Fe2O3), vary in the amount present - in commercially available Mn₃O₄ sources (e.g., more-than-70% Mn sources will have a lower volume of iron (e.g., percent by weight of less than 0.7)). Similarly, the availability of Mn may vary by grade, such that higher grades of Mn₃O₄ may be available in % by weight more than or equal to 71% Mn of overall weight. The percentage of Mn and quality typically must be factored in, as in some DLE systems, it may be necessary to use between 12 kg and 20 kg of LMO with a 13 mg / g loading capacity to process 500 gallons of produced water containing a concentration of 30 mg / L of lithium.

[0142] Industrial batch-processing techniques benefit from higher-purity reactants that can be sourced in sufficient quantities and purities to synthesize a spinel sorbent. As batch sizes increase, and costs of reactants and reaction time and the associated costs of reacting the reactants increase, techniques typically must be developed for synthesizing spinel sorbents given the uncertain realities of today’s supply chains and potentially limited availability of ideal reactants of relatively higher-grade reactants. For example, while sources of Mn from Mn₂O₃ and / or Mn₃O₄ are preferred, at times alternative forms, such as a manganese carbonate like Mn2CO3, may be used.

[0143] The present disclosure includes techniques for using commercially available reactants at higher temperatures to manufacture a high-loading-capacity LMO at scale. Such techniques may include transitioning a commercially available precursor to a doped precursor, and, in turn, to a doped intermediate state or a doped intermediate state, sorbent blend at higher range temperatures before converting the doped intermediate state to a doped sorbent blend. In some embodiments, the doped intermediates, Mn₃O₄ and Mn₂O₃ compounds, were synthesized by calcination for a duration. Transitioning a commercially available precursor to a doped intermediate-state sorbent blend may allow the reaction to be biased to produce a higher % composition of doped LMO product. Biasing the formation of specific constituents of the ultimate doped sorbent blend may be accomplished by varying the reactants within the doped precursor blend, varying the reaction modality (e.g., calcining), varying the reaction duration, varying the reaction conditions (such as the temperature or temperatures of the reaction), and increasing the number of reactions. In some embodiments, a reaction period is used to calculate Attorney Docket No.22782.008WO1 / Element3-005-PCT the number of reactions. For example, a reaction period may begin with an initial reaction time, followed by a cooling duration and milling. A second reaction period may signify a second reaction period has been initiated.

[0144] In some embodiments, a doped intermediate state is beneficial when a reactant, such as an economical form of manganese oxide, such as Mn₃O₄, is converted to a doped intermediate-state reactant, such as Mn₂O₃. Some experimental results in which the reaction time was varied suggest that when calcining is stopped at defined intervals while the calcination temperature is held constant, the intermediate state Mn₂O₃ increases in quantity until the initial reactant Mn₃O₄ is no longer detectable using XRD. The evidence suggests that for a large amount of doped LMO to be synthesized from a relatively high-grade Mn source, it may be necessary for the Mn to transition to an intermediate state before the reaction with a lithium reactant, such as LiOH monohydrate, can proceed to form an LMO spinel. By adopting the techniques described in the present disclosure, manufacturers may be incentivized to produce manganese intermediate reactants, such as Mn₂O₃, in an intermediate state at volumes necessary for commercial scale.

[0145] Doping refers to introducing foreign elements into a material to modify its properties. In the context of lithium-manganese-oxide (LMO) spinels, doping can significantly impact the material's loading capacity. During the synthesis process, doping may aid in biasing production of LMO within intermediate-state sorbent blends and sorbent blends. In contrast to undoped LMOs, doped LMOs produced from the same initial reactants tend to have an enhanced loading capacity compared to their undoped counterpart LMOs.

[0146] In some embodiments, a commercially available manganese-oxide reactant may be included as one constituent of a precursor blend. As some manganese oxides may be converted to a necessary precursor reactant at temperatures described in the present disclosure, reacting a commercially available manganese oxide with a lithium donor can be advantageous in forming a precursor blend. Referring to FIG.19, flowchart 1900 describes a method according to some embodiments of the present disclosure. In some embodiments, at 1910, the method may include obtaining reactants, such as Mn₂O₃ and LiOH monohydrate, to form a precursor blend, such as a doped precursor blend. To produce an LMO spinel at scale, a precursor blend may include at least one reactant that must be chemically changed before forming a doped LMO spinel. In some embodiments, reacting the doped precursor blend may include reacting the doped precursor blend at a high temperature and pressure to produce the doped Attorney Docket No.22782.008WO1 / Element3-005-PCT intermediate-state sorbent. In some instances, reacting may include firing, a solid-state reaction such as calcination or calcining, microwave-assisted synthesis, mechanochemical synthesis, combustion synthesis, or rotary calcination.

[0147] The method may include obtaining reactants with a doping agent to form a doped precursor blend. After this step, the doped precursor blend is calcined for an initial duration and a first temperature, forming a doped intermediate-state sorbent blend at step 1920. A doped intermediate-state sorbent blend may be reacted to form a desirable intermediate state between a pure precursor blend of reactants and an end state of a doped sorbent blend. The reaction may be biased to alter the compound constituents present, the relative quantities of the chemical constituents, the chemical properties of the chemical constituents, or any combination thereof. The doped precursor blend at 1920 is a mix of lithium and manganese oxide blended along with a doping agent, wherein the manganese-oxide blend is an initial chemical formula, the doped intermediate-state sorbent may include a reduced volume of at least one reactant, a reactant at a second state, and some doped LMO. For illustrative purposes, a doped precursor blend may include a 3:4 molar ratio of lithium to manganese blend and a doping agent with a 0.01-1.0% molar replacement of the doping agent for manganese, where the manganese reactant being Mn₃O₄ is the first state.

[0148] The doped precursor blend is reacted with a doping agent at step 1920 is any one of a 3:4, a 4:5, or a 0.70 - 0.85 molar ratio of lithium to manganese blend and a doping agent with a specified molar replacement of the doping agent for manganese. For example, the doping agent is at least one of Al(OH)3, Co3O4, Cr2O3, Cr(OH)3, Fe2O3, Fe3O4, Ni2O3, Ni(OH)2, NaCl, AlCl3, MgCO3, Na2CO3, NaOH, NaHCO3 or an aluminum-based compound. In some embodiments, the precursor blend may be doped with at least one cation. In some embodiments, the cation may be Na+, Mg2+, Sn2+, Zn2+, Al3+, Cr3+, Sn4+, Zr4+, Ru4+, V5+, Nb5+, or the like. In some embodiments, the precursor blend may be an aluminate sorbent such as a lithium−aluminum-layered double-hydroxide-chloride (LDH) sorbent such as Lix^Al2(OH)6ClxnH2O, where the variable x represents the Li and Cl stoichiometry, and n represents the moles of interlayer water. The aluminate sorbent may be a layered double hydroxide (LDH) in some embodiments. In some embodiments, the aluminate sorbent may be doped. In some embodiments, the doped aluminate sorbent may be LiCl: Al 1.25 Fe0.25(OH)3, referred to as "Fe Doped LDH,” and related compounds. In some embodiments, the initial Attorney Docket No.22782.008WO1 / Element3-005-PCT calcining duration is the time under temperature and does not necessarily account for the ramp- up period to achieve temperature or the ramp-down period to achieve a cool-down temperature.

[0149] In some embodiments, the doping agent used is a nickel-based compound. In other preferred embodiments, the doping agent used is an aluminum-based compound. The concentration of doping agents and their distribution within the LMO spinel can significantly influence crystal structure and, therefore, the loading capacity.

[0150] In some embodiments, step 1920 comprises a doping agent with a 0.3% specified molar replacement of the doping agent for manganese. The doped precursor blend may include any number of doping agents to achieve the desired molar replacement of the doping agent for manganese in the LMO. In some embodiments in which a 3:4, a 4:5, or a 0.70 - 0.85 molar ratio of lithium to manganese blend is used, and an aluminum compound serves as the basis for the doping agent, data indicates a 0.3% specified molar replacement of the doping agent for manganese may enhance the loading capacity of the doped LMO over the synthesis of an undoped LMO that otherwise uses the same reactants, calcination durations, and temperatures. While 0.3% specified molar replacement of the doping agent for manganese has been described, the specified molar replacement of aluminum for manganese may be varied to between 0.1% to approximately 1.0% molar replacement. While aluminum has been specified, non-limiting examples of doping agents may include one or more of Al(OH)3, Co3O4, Cr2O3, Cr(OH)3, Fe2O3, Fe3O4, Ni2O3, Ni(OH)2, NaCl, AlCl3, MgCO3, Na2CO3, NaOH, NaHCO3 or an aluminum-based compound. Varying the doping agent, varying the reactants, and varying the duration, temperature, and the number of calcination periods may suggest the use of a higher or lower specified molar replacement.

[0151] Subsequently, calcining any one of a 3:4, a 4:5 or a 0.70-0.85 molar ratio of lithium- and-manganese blend and the doping agent with a 0.01-1.0% molar replacement of the doping agent for manganese for an initial duration of five (5) hours at 525°C, a doped intermediate- state sorbent blend may include 88% by weight LMO, 10% by weight Mn₂O₃ (a second state reactant of the Mn₃O₄ first reactant state), and less than 1% of LiOH monohydrate. Testing the volumes of the chemical constituents of the doped intermediate-state sorbent blend may be accomplished using X-ray Diffractometer (XRD) equipment, such as the Rigaku Benchtop X- ray Diffractometer MiniFlex600. Attorney Docket No.22782.008WO1 / Element3-005-PCT

[0152] At 1930, the method may include cooling the doped intermediate-state sorbent blend. Cooling may be beneficial in some commercial settings to safely handle the intermediate-state sorbent blend. At 1940, the method may include milling the doped intermediate-state sorbent blend. In some embodiments, the reacting, such as when calcining techniques are used, results in the agglomeration of the doped intermediate-state sorbent blend. In such instances, it may be beneficial to cool the doped intermediate-state sorbent blend and mill the blend to a size that is readily retained within a batch or continuous processing DLE system. For example, the doped intermediate-state sorbent may be milled such that the size of the doped intermediate-state sorbent exceeds the pore size of membrane-based DLE systems such that the doped intermediate-state sorbent may be retained within the DLE system.

[0153] In some embodiments, the reactants may include at least one manganese compound. For example, the reactants may include at least one of MnO2, Mn₃O₄, Mn(NO3)2, MnCO3, or Mn₂O₃. In some embodiments, the reactants may include at least one of lithium hydroxide, lithium carbonate, and at least one of Mn₃O₄, MnCO3, and Mn₂O₃. The manganese compound may have a chemical formula of Mn₃O₄. In some embodiments, the intermediate-state sorbent blend further comprises at least 83% by weight LMO and 3% by weight Mn₂O₃. In some embodiments, the reactants may include Mn₂O₃ and LiOH. In some embodiments, the initial calcining duration may be at least five (5) hours, and the first temperature may be at least 500℃. The LMO may have a lithium loading capacity of at least 16.0 mg / g of LMO.

[0154] In some embodiments, the doped intermediate-state sorbent blend further comprises at least 26% by weight Mn₃O₄, 2.0% by weight Mn₂O₃, and 70% by weight a doped LMO. In some embodiments, the initial calcining duration may be at least five (5) hours, and the first temperature may be at least 600℃. In some embodiments, the intermediate-state sorbent blend further comprises less than 14.0% by weight Mn₂O₃, and 88% by weight a doped LMO. In some embodiments, the intermediate-state sorbent blend further comprises at least 10.0% by weight Mn₂O₃, and 89% by weight a doped LMO.

[0155] FIG. 20 is a flowchart that describes a method for manufacturing a doped LMO sorbent spinel, according to some embodiments of the present disclosure. In some embodiments, at 2010, the method may include obtaining a precursor blend. A doped precursor blend may include reactants that are necessary for producing one or more reactions that have taken place. While the present disclosure describes the formation of lithium manganese oxides (LMOs), the present techniques also apply to other metal-oxide sorbents, such as lithium-ion Attorney Docket No.22782.008WO1 / Element3-005-PCT sieve (LIS) and uncoated sorbents like titanate sorbents. In some embodiments, the doped precursor blend may be one of a 3:4, a 4:5, and a 0.70 to 0.85 molar ratio of lithium-to- manganese blend with a 0.01-1.0% molar replacement of the doping agent for manganese to form a doped precursor blend.

[0156] At step 2020, the method may include obtaining the doped precursor blend with a doping agent in any one of a 3:4, a 4:5 or a 0.70 - 0.85 molar ratio of lithium to manganese with a 0.3% molar replacement of the doping agent for manganese to form a doped precursor blend. Doping agents may help in stabilizing the crystal lattice of the LMO without altering the crystal structure. In preferred embodiments, the doping agent includes a nickel-based compound. In other preferred embodiments, the doping agent is an aluminum-based compound. At step 2030, the method may include calcining as a means for reacting the doped precursor blend. In some embodiments, the step may include calcining the doped precursor blend for an initial calcining duration and at a first temperature. Calcining durations may be altered to bias the production of specific constituents within specific quantity ranges. In one embodiment, the calcining duration may be biased to produce an LMO of at least 88% phase composition as measured with XRD data, at least 10% intermediate-state product (e.g., Mn₂O₃), and ideally, an undetectable amount of reactant from the doped precursor blend. To synthesize the intermediate-state sorbent blend with the biased-doped intermediate-sorbent constituents, a calcining temperature of at least 500℃ and a minimum reaction duration of approximately five (5) hours is performed.

[0157] In some embodiments, at 2040, the method may include cooling the doped intermediate-state sorbent blend. Cooling the doped sorbent may be useful when handling the doped intermediate-sorbent blend at the reaction temperature is impractical or does not comply with manufacturing safety protocols. The cooled or cooling doped intermediate-state sorbent blend at 2050, may include additional steps. In some embodiments, for example the synthesis of an LMO, may involve performing additional steps like milling an agglomerated intermediate-state sorbent blend. When additional refinement to the doped precursor blend is not desired, milling may be performed to support the measuring the doped sorbent-blend for packaging and sale or for activation prior to use in a DLE system.

[0158] In some embodiments, it may be desirable to further purify or otherwise increase the percent phase composition of a desired product, such as the LMO. When a doped precursor blend of relatively high quality is used in the first reaction, a second reaction event can be Attorney Docket No.22782.008WO1 / Element3-005-PCT performed to reduce an intermediate-state product like Mn₂O₃ and bias the reaction to produce a higher percentage of doped LMO. At 2060, the method may include calcining the doped intermediate-state sorbent blend for a second duration and the second temperature, forming a sorbent blend such as a doped sorbent blend. The calcining may form a doped intermediate- state sorbent blend of at least Mn₂O₃ and a doped LMO. The lithium loading capacity of the doped LMO may vary based on the temperature used during the first and second reaction. When calcining is performed, generally lower calcining temperatures of approximately 425°C tend to produce doped LMOs with a lower loading capacity. In some embodiments, air may be pumped into a kiln during the calcination. When the air is not pre-heated to the kiln temperature, the added air may result in a lower loading capacity LMO.

[0159] Referring to Table 1, two (2) multiple-step reactions were conducted consistent with the process of FIG.20. A doped precursor blend of LiOH.H₂O and Mn₃O₄ wase mixed in a 3:4 molar ratio of lithium to manganese blend and a doping agent with a 0.3% molar replacement of the doping agent for manganese. The doped precursor blend is subjected to doping with a doping agent, preferably a nickel-based compound or an aluminum-based compound, in any one of a 3:4, a 4:5 or a 0.70- 0.85 molar ratio in an approximately 0.3% molar equivalent substitution of the dopant ion for Mn. In each reaction (i.e., React.1 and React.2), the reaction duration was held constant at five (5) hours, while the temperatures of each reaction were held at approximately 425°C and 525°C. To elaborate on the temperature improved or optimized, it has been observed that once 525 °C is hit, higher temperatures do not appear to have a significant impact on the weight of LMO produced. For temperatures at 525°C, it appears that as duration of the first calcining increases, loading capacity increases for the activated sorbent.

[0160] In some instances, unheated air was pumped into the kiln. The doped intermediate- state sorbent blend was analyzed using XRD, with the results and loading capacity of the isolated doped LMO provided below. No. Air React. React. React 2 Loading Mn₂O₃ LMO rade doped precursor blend. Attorney Docket No.22782.008WO1 / Element3-005-PCT

[0161] As mentioned in Table 3 and seen in FIG. 20, varying the reaction parameters of temperature and duration can bias the constituents present within and the percentage of the constituents within the synthesized doped sorbent blend. When the grade of the reactants forming the doped precursor blend is of a higher grade, the constituents of the doped sorbent blend are more reliably predicted. Lower-quality reactant sources often include compounds containing P, Fe, and CaO in percent by mass as high as 0.71%, 2.70%, and 0.46%, respectively. When the presence of these undesired compounds are reduced (e.g. iron reduced to approximately 0.20%) or even eliminated, they may yield consistently higher percentages of desired doped intermediate-state compounds like doped LMO and Mn₂O₃. In some embodiments, the initial calcining duration may be set to at least five (5) hours. In some embodiments, the initial calcining duration may be at least five (5) hours, and the first temperature may be at least 500℃. In some embodiments, the doped intermediate-state sorbent blend further comprises at least 88% by weight of LMO, less than 1% of LiOH monohydrate, and at least 10% by weight Mn₂O₃. In some embodiments, the doped intermediate-state sorbent blend further comprises less than 1% by weight Mn₃O₄, at least 10% by weight Mn₂O₃, at least 85% by weight of LMO, and less than 1% of LiOH monohydrate. The doped LMO may have a lithium loading capacity of at least 16.0 mg / g of LMO. In some embodiments, the initial calcining duration may be at least fifteen (15) hours and the first temperature may be at least 525℃ and the doped intermediate-state sorbent blend further comprises at least 7.0% by weight Mn₂O₃, and 90% by weight of LMO.

[0162] Further, Table 3 characterizes the impact of temperature, air flow, and reaction duration for biasing the synthesis of doped LMO and Mn₂O₃ of desired percentages of purity. To obtain a doped LMO of at least 60% with a loading capacity of at least 7mg / g using higher quality reactants, the doped precursor blend typically should be doped with a doping agent and the resulting doped precursor blend is calcined for an initial calcining temperature of 425℃ and a second calcining temperature of 500℃ for a duration of at least five (5) hours in the presence of air. To obtain a doped LMO of approximately 99% purity with a loading capacity of at least 17mg / g, the doped precursor blend typically should be calcined for an initial calcining temperature of 525℃ and duration of 5 hours, followed by a second calcining temperature of 525℃ and a duration of at least ten (10) hours, with or without forced air pumped into the kiln. To bias the synthesis of an LMO to approximately 98% purity with a loading capacity of at least 15mg / g within the doped intermediate-state sorbent, the doped precursor blend should be doped and calcined for an initial calcining temperature of Attorney Docket No.22782.008WO1 / Element3-005-PCT approximately 525℃ and duration of five (5) hours, followed by a second calcining temperature of at least 525℃, for a duration of at least ten (10) hours in the presence of forced air.

[0163] FIG.21 is a flowchart that further describes the method for manufacturing a doped LMO sorbent spinel based on principles described in relation to FIG. 20, according to some embodiments of the present disclosure. In some embodiments, the calcining of the doped intermediate-state sorbent blend for a second duration and a second temperature may include steps 2110 to 2120. In some embodiments, the calcination duration may be set to a period of between two (2) hours, as in 2110, to as many as fifteen (15) hours. To demonstrate the variability of the process to bias the formation of specific compound constituents and their quantities within the doped sorbent blend, step 2120 may be modified by selecting a temperature that is the same or different from the initial reaction temperature used in the first calcination. For example, in some embodiments, the first five (5) hour calcination at 650⁰C is followed by a second ten (10) hour calcination at 525⁰C. The resultant doped sorbent may blend is biased to produce at least 75% by weight LMO. When activated, the resulting doped HMO may have a lithium loading capacity of at least 13.0 mg / g of activated LMO.

[0164] FIG.22 is a flowchart that further describes the method for manufacturing a doped LMO sorbent spinel from FIG. 20, according to some embodiments of the present disclosure. In some embodiments, at 2240, the method may include activating the doped sorbent blend. Activating the doped LMO often involves preparing an HMO by displacing the lithium within the LMO structure with an alternative ionic element, such as hydrogen. In general, an activated LMO may be an HMO. In some embodiments, at 2210, the activating may include mixing the doped spinel sorbent with an acid. In some embodiments, the acid may be a single-proton donor, such as HCl, or may be a multi-proton donor such as H2SO4. In some embodiments, the doped spinel sorbent, such as an LMO, may be activated using a ratio of 1g of LMO per 45 mL of an acid. At 2220, the activating may include agitating the doped sorbent. Agitating the doped sorbent may accelerate the activation step, and the mechanism for agitating the mix may be selected to reduce the damage done to the doped spinel structure. The doped spinel sorbent and the acid may be placed in contact for between sixteen (16) to forty-eight (48) hours. In some embodiments, doped spinel sorbent and the acid may be agitated during contact time, reducing contact time to less than sixteen (16) hours. Since rough handling of the doped sorbent may degrade the spinel structure of the LMO, careful management of the process coupled with Attorney Docket No.22782.008WO1 / Element3-005-PCT active monitoring of the turbidity may be factored in to improve or to optimize the contact time duration while reducing or minimizing doped-spinel-structure degradation. In some embodiments, the mixture of acid and doped spinel sorbent may be allowed to reach equilibrium without an agitation mechanism. The duration may be altered to achieve a certain amount of activation. For example, in some embodiments, at 2230, the activating may include activating the doped sorbent to reach an activation percentage of at least 65% activation to form an activated sorbent.

[0165] FIG.23 is a flowchart that describes a method for manufacturing a doped activated LMO sorbent spinel, according to some embodiments of the present disclosure. In some embodiments, at 2310, the method may include obtaining a precursor blend. At 2320, the method may include obtaining the precursor blend with a doping agent to form a doped precursor blend. At 2330, the method may include calcining the doped precursor blend for an initial calcining duration and at a first temperature of at least 525℃. At 2340, the method may include milling the doped intermediate-state sorbent blend. At 2350, the method may include calcining the milled doped intermediate-state sorbent blend for a second duration and the second temperature, forming a sorbent blend, for example a doped sorbent blend. At 2360, the method may include activating the sorbent blend (e.g., doped sorbent blend) with an acid.

[0166] In some embodiments, the purity and loading capacity of lithium manganese oxide (LMO) can be influenced by various factors, including the synthesis techniques, durations, and temperatures employed during its preparation. Different synthesis techniques known in the art, such as solid-state synthesis, sol-gel method, co-precipitation, hydrothermal synthesis, and combustion synthesis, can impact the purity and properties of LMO. For example, sol-gel methods typically involve the hydrolysis and condensation of precursor solutions to form a gel, followed by drying and calcination. Co-precipitation techniques involve the simultaneous precipitation of metal ions from solution, which can result in homogeneous mixing and fine particle-size distribution, potentially increasing the loading capacity of LMO.

[0167] In some embodiments of the present disclosure, the duration of the reaction, including time at temperature and variations in temperature, may affect the purity and potentially the spinel structure of the doped LMO. In some commercial applications, it may be advantageous to produce a higher purity of LMO in relation to the initial reactants in a shorter time period using more readily available Manganese compound sources, such as Mn₃O₄. Referring to FIG.24, a table of reaction temperatures used during a constant reaction duration Attorney Docket No.22782.008WO1 / Element3-005-PCT of five (5) hours is provided. Within the table, a precursor blend mass of twenty-five (25) grams composed of the reactants LiOH.H₂O and Mn₃O₄ mixed in a 3:4 molar ratio of lithium to manganese blend and an Al(OH)3 doping agent with a 0.3% molar replacement of the aluminum for manganese is utilized.

[0168] FIG. 24 is a table that lists the compound constituents and percentages of each compound present in each of the intermediate-state sorbent blends. The table includes constituents present when doped and undoped precursor blends are calcined at various initial calcination temperatures for a duration of five (5) hours as described in the method for manufacturing a doped LMO sorbent spinel from FIG.20, according to some embodiments of the present disclosure. The values for the compound constituents listed within FIG.24 represent the weight-percent phase composition of each compound as determined by Rietveld refinement of XRD data. At 400 °C, for a calcining duration of five (5) hours, 15.63% by weight of LMO, 0.76% by weight of Mn₂O₃, 81.66% by weight of Mn₃O₄, and 1.95% by weight of LiOH monohydrate as against the compound constituent percentages of undoped intermediate-state sorbents which are 11.51% by weight of LMO, 6.98% by weight of Mn₂O₃, 77.41% by weight of Mn₃O₄, and 4.11% by weight of LiOH monohydrate obtained under the same calcining temperature and duration. At 450°C, for a calcining duration of 5 hours, 11.26% of LMO, 14.2% of Mn₂O₃, and 74.54% of Mn₃O₄ are obtained (nearly or actually 0% LiOH.H₂O is obtained) as against the compound constituent percentages of undoped intermediate-state sorbents which are 7.08% by weight of LMO, 12.81% by weight of Mn₂O₃, 78.07% by weight of Mn₃O₄, and 2.04% by weight of LiOH monohydrate obtained under the same calcining temperature and duration. At 500⁰C, for a calcining duration of five (5) hours, 70.58g of LMO, 2.33g of Mn₂O₃, 26.41% of Mn₃O₄, and 0.68% of LiOH monohydrate are obtained as against the compound constituent percentages of undoped intermediate-state sorbents which are 90.62% by weight of LMO, 9.04% by weight of Mn₂O₃, and 0.34% by weight of Mn₃O₄ (nearly or actually 0% LiOH.H₂O is obtained), obtained under same calcining temperature and duration. At 525⁰C, for a calcining duration of five (5) hours, 88.79% of LMO, 10.78% Mn₂O₃ and 0.43% of LiOH monohydrate (nearly or actually 0% Mn304 is obtained) are obtained as against the compound constituent percentages of undoped intermediate-state sorbents which are 94.42% by weight of LMO and 5.58% by weight of Mn₂O₃ (nearly or actually 0% Mn₃O₄ and nearly or actually 0% LiOH.H₂O are obtained) obtained under same calcining temperature and duration. At 550⁰C, for a calcining duration of five (5) hours, 80.13g of LMO, 19.37g of Mn₂O₃ and 0.5% of LiOH monohydrate are obtained (nearly or actually 0% Mn₃O₄ is obtained) Attorney Docket No.22782.008WO1 / Element3-005-PCT as against the compound constituent percentages of undoped intermediate-state sorbents which are 82.6% by weight of LMO and 17.4% by weight of Mn₂O₃, obtained (nearly or actually 0% Mn₃O₄ and nearly or actually 0% LiOH.H₂O are obtained) under the same calcining temperature and duration. At 600⁰C, for a calcining duration of five (5) hours, 88.04% by weight of LMO and 11.96% by weight of Mn₂O₃ are obtained (nearly or actually 0% Mn₃O₄ and nearly or actually 0% LiOH.H₂O are obtained) as against the compound constituent percentages of undoped intermediate-state sorbents which are 72.2% by weight of LMO, 23.98% by weight of Mn₂O₃, 2.21% by weight of Mn₃O₄, and 1.62% by weight of LiOH monohydrate obtained under the same calcining temperature and duration. At 650⁰C, for a calcining duration of five (5) hours, 89.78% by weight of LMO and 10.22% by weight of Mn₂O₃ are obtained (nearly or actually 0% Mn₃O₄ and nearly or actually 0% LiOH.H₂O are obtained) as against the compound constituent percentages of undoped intermediate-state sorbents which are 74.34% by weight of LMO and 25.66% by weight of Mn₂O₃, obtained (nearly or actually 0% Mn₃O₄ and nearly or actually 0% LiOH.H₂O are obtained) under the same calcining temperature and duration.

[0169] A reaction, regarding FIG.24, is a calcination of a fixed five-hour (5-hour) duration on the doped precursor blend, that is performed at various temperatures between 400⁰C and 650⁰C. At the end of each five-hour (5-hour) period, the calcining results in the formation of an intermediate-state sorbent blend of at least Mn₂O₃ and an LMO. The table suggests that as the calcination temperature increases, the reactants present in the doped precursor blend found within the doped intermediate-state sorbent decrease from their initial mass weights. In some embodiments, the presence of lithium hydroxide monohydrate (LiOH^H2O) facilitates the conversion of manganese (II, III) oxide (Mn₃O₄) to manganese (III) oxide (Mn₂O₃) and a lithium manganese oxide (LMO) through a reaction. Manganese (III) oxide (Mn₂O₃) may be produced as a byproduct of the reaction between lithium hydroxide and manganese (II, III) oxide. Mn₂O₃ may form as a separate phase or coexist with LMO depending on the synthesis conditions.

[0170] Improvement or optimization of the formation of a doped LMO and reduction of the reactants within a limited time frame may be improved or optimized within a window of calcination temperatures of approximately 525⁰C and 650⁰C. The data suggests that when 100 grams of reactants are mixed in a 3:4 ratio, and at least 90 grams of LMO are desired, the doped precursor blend is doped with a doping agent in any one of a 3:4, a 4:5 or a 0.70-0.85 molar Attorney Docket No.22782.008WO1 / Element3-005-PCT ratio of lithium to manganese with a 0.3% molar replacement of the doping agent for manganese, the formation of LMO may be improved or optimized by calcining between approximately 525⁰C and 650⁰C. In some embodiments, it may be desired to produce a doped intermediate-state sorbent blend with negligible or unmeasurable amounts of reactants. When the purity of the LMO requires at least 80 grams of LMO and negligible or unmeasurable amounts of reactants, a five-hour (5-hour) calcination period from approximately 525⁰C to approximately 550⁰C may be preferred. In some embodiments, lithium manganese oxide (Li₁.₃₃Mn₁.₆₇O₄, LiMn2O4 or LMO) is the desired product of the reaction. LMO forms as a spinel phase by incorporating lithium ions into the manganese-oxide lattice.

[0171] FIG. 25 is a table illustrating the respective quantities of doped intermediate-state sorbent blend obtained at a calcining temperature of 525°C at different time intervals during the first calcining duration as described in the method for manufacturing a doped LMO sorbent spinel from FIG.20, according to some embodiments of the present disclosure. At 525°C, for 0.5 hours, 72.18% by weight of LMO, 1.42% by weight of Mn₂O₃ and 26.4% by weight of Mn₃O₄ are obtained (nearly or actually 0% by weight of LiOH.H₂O is obtained) in contrast to the compound constituent percentages of undoped intermediate-state sorbents which are 55.5% by weight of LMO, 7.04% by weight of Mn₂O₃, 37.19% by weight of Mn₃O₄, and 0.26% by weight of LiOH monohydrate obtained under the same calcining temperature and duration. At 525°C, for one (1) hour, 77.71% by weight of LMO, 13.27% by weight of Mn₂O₃, 7.87 % by weight of Mn₃O₄, and 1.14% by weight of LiOH monohydrate are obtained as against the compound constituent percentages of undoped intermediate-state sorbents which are 69.02% by weight of LMO, 15.69% by weight of Mn₂O₃, 11.0% by weight of Mn₃O₄, and 4.3% by weight of LiOH monohydrate obtained under the same calcining temperature and duration. At 525°C, for two (2) hours, 86.4% by weight of LMO, 12.84% by weight of Mn₂O₃, 0.08% by weight of Mn₃O₄, and 0.68% by weight of LiOH monohydrate are obtained as against the compound constituent percentages of undoped intermediate-state sorbents which are 84.36% by weight of LMO and 15.64% by weight of Mn₂O₃, obtained (nearly or actually 0% Mn₃O₄ and nearly or actually 0% LiOH.H₂O are obtained) under the same calcining temperature and duration. At 525°C, for five (5) hours, 88.79% by weight of LMO and 10.78% by weight of Mn₂O₃ and 0.43% by weight of LiOH monohydrate are obtained (nearly or actually 0% Mn₃O₄ is obtained) in contrast with the compound constituent percentages of undoped intermediate- state sorbents which are 94.42% by weight of LMO and 5.58% by weight of Mn₂O₃, obtained (nearly or actually 0% Mn₃O₄ and nearly or actually 0% LiOH.H₂O are obtained) under the Attorney Docket No.22782.008WO1 / Element3-005-PCT same calcining temperature and duration. At 525°C, for eight (8) hours, 83.75% by weight of LMO, 15.91% by weight of Mn₂O₃, 0.03% by weight of Mn₃O₄, and 0.31% by weight of LiOH monohydrate are obtained in contrast with the compound constituent percentages of undoped intermediate-state sorbents which are 78.79% by weight of LMO, 20.66% by weight of Mn₂O₃, 0.08% by weight of Mn₃O₄, and 0.47% by weight of LiOH monohydrate obtained under the same calcining temperature and duration. At 525°C, for fifteen (15) hours, 92.22% by weight of LMO and 7.78% by weight of Mn₂O₃ are obtained (nearly or actually 0% Mn₃O₄ and nearly or actually 0% LiOH.H₂O are obtained) in contrast with the compound constituent percentages of undoped intermediate-state sorbents which are 83.54% by weight of LMO and 16.46% by weight of Mn₂O₃, obtained (nearly or actually 0% Mn₃O₄ and nearly or actually 0% LiOH.H₂O are obtained) under the same calcining temperature and duration. The calcination duration for Mn₂O₃ is about fifteen (15) hours at 525°C to ensure conversion to 92% of LMO through dehydration while reducing or minimizing impurities and phase transformations.

[0172] FIG.26 is a table illustrating the compound constituent percentages of thesorbents of calcined doped and undoped precursor blend during second calcination temperatures and durations, as described in the method for manufacturing a doped LMO sorbent spinel from FIG. 23, according to some embodiments of the present disclosure. At 400⁰C, for an initial calcining duration of five (5) hours and a second calcining duration of ten (10) hours at 525°C, 52.66% by weight of LMO, 46.35% by weight of Mn₂O₃, 0.33% by weight of Mn₂O₃, and 0.66% by weight of LiOH monohydrate are obtained in contrast with the compound constituent percentages of undoped intermediate-state sorbents which are 76.59% by weight of LMO and 23.41% by weight of Mn₂O₃, obtained (nearly or actually 0% Mn₃O₄ and nearly or actually 0% LiOH.H₂O are obtained) under the same calcining temperature and duration. At 525°C, for an initial calcining duration of 0.5 hours and a second calcining duration of 0.5 hours at the same temperature, 85.39% by weight of LMO, 7.93% by weight of Mn₂O₃, 4.58% by weight of Mn₂O₃ and 2.09% by weight of LiOH monohydrate are obtained in contrast with the compound constituent percentages of undoped intermediate-state sorbents which are 63.32% by weight of LMO, 25.68% by weight of Mn₂O₃, 10.37% by weight of Mn₃O₄, and 0.64% by weight of LiOH monohydrate obtained under the same calcining temperature and duration. At 525°C, for an initial calcining duration of 0.5 hours and a second calcining duration of ten (10) hours at the same temperature, 100.0% by weight of LMO, is obtained (nearly or actually 0% Mn₂O₃, nearly or actually 0% Mn₃O₄, and nearly or actually 0% LiOH.H₂O are obtained) in contrast with the compound constituents of undoped intermediate-state sorbents which are Attorney Docket No.22782.008WO1 / Element3-005-PCT 83.24% by weight of LMO, 16.67% by weight of Mn₂O₃, 0.06% by weight of Mn₃O₄, and 0.02% by weight of LiOH monohydrate obtained under same calcining temperature and duration. At 525°C, for an initial calcining duration of two (2) hours and a second calcining duration of two (2) hours at the same temperature, 92.29% by weight of LMO, 7.04% by weight of Mn₂O₃, and 0.67% by weight of Mn₂O₃ is obtained (nearly or actually 0% LiOH.H₂O is obtained) in contrast with the compound constituents of undoped intermediate-state sorbents which are 79.89% by weight of LMO, 19.42% by weight of Mn₂O₃, 0.49% by weight of Mn₃O₄, and 0.21% by weight of LiOH monohydrate obtained under same calcining temperature and duration.

[0173] At 525°C, for an initial calcining duration of two (2) hours and a second calcining duration of ten (10) hours at the same temperature, 100.0% by weight of LMO is obtained (nearly or actually 0% Mn₂O₃, nearly or actually 0% Mn₃O₄, and nearly or actually 0% LiOH.H₂O are obtained) in contrast with the compound constituents of undoped intermediate- state sorbents which are 89.82% by weight of LMO, 8.92% by weight of Mn₂O₃ and 1.26% by weight of Mn₃O₄ are obtained (nearly or actually 0% LiOH.H₂O is obtained) under the same calcining temperature and duration. At 525°C, for an initial calcining duration of five (5) hours and a second calcining duration of ten (10) hours at the same temperature, 95.43% by weight of LMO, 3.31% by weight of Mn₂O₃, 0.94% by weight of Mn₂O₃ and 0.33% by weight of LiOH monohydrate are obtained in contrast with the compound constituents of undoped intermediate-state sorbents which are 91.38% by weight of LMO, 8.09% by weight of Mn₂O₃, and 0.53% by weight of LiOH monohydrate obtained (nearly or actually 0% Mn₃O₄ is obtained) under the same calcining temperature and duration. At 525°C, for an initial calcining duration of fifteen (15) hours and a second calcining duration of ten (10) hours at the same temperature, 99.48% by weight of LMO, 0.2% by weight of Mn₂O₃, and 0.31% by weight of LiOH monohydrate are obtained (nearly or actually 0% Mn₃O₄ is obtained) in contrast with the compound constituents of undoped intermediate-state sorbents which are 92.23% by weight of LMO, 7.16% by weight of Mn₂O₃, 0.33% by weight of Mn₃O₄, and 0.28% by weight of LiOH monohydrate obtained under the same calcining temperature and duration. At 650°C, for an initial calcining duration of five (5) hours and a second calcining duration of ten (10) hours for the same temperature, 99.33% by weight of LMO, 0.42% by weight of Mn₂O₃ and 0.25% by weight of LiOH monohydrate are obtained (nearly or actually 0% Mn₃O₄ is obtained) in contrast with the compound constituents of undoped intermediate-state sorbents which are Attorney Docket No.22782.008WO1 / Element3-005-PCT 92.09% by weight of LMO, 7.76% by weight of Mn₂O₃ and 0.15% by weight of LiOH monohydrate are obtained (nearly or actually 0% Mn₃O₄ is obtained).

[0174] In some embodiments, the first calcining step may not synthesize a pure LMO. By varying the duration of the reaction and / or temperature, some or all of the reactants may be eliminated from the doped blend. The presence of the reactants from the doped precursor blend, and some doped intermediate products, such as Mn₂O₃, are formed during synthesis. A second calcination step may be performed to further reduce the presence of the constituents of the doped intermediate-state sorbent other than the doped LMO spinel, leading to higher-purity doped LMO. In some embodiments, doped-LMO spinel formation may involve multiple reaction steps forming a doped intermediate-state sorbent blend of intermediates not present in the doped precursor blend, for example Mn₂O₃. In some embodiments, a first calcination at 525°C for five (5) hours may not result in the desired phase-formation or crystal-structure improvement or optimization of the LMO. A second calcination step at 525°C for ten (10) hours allows for further phase transformation and crystallization leading to the formation of the desired doped-LMO spinel phase with an improved or the optimal crystal structure and loading capacity.

[0175] In yet another embodiment, the second calcination step can promote better mixing and homogenization of the doped precursor materials, facilitating or ensuring uniform distribution of lithium, manganese, and oxygen throughout the doped LMO particles.

[0176] FIG. 27 is a table illustrating the comparison of loading capacities of doped and undoped sorbent blend after initial and second calcinations and durations as described in the method for manufacturing a doped LMO sorbent spinel from FIG. 23, according to some embodiments of the present disclosure. At 525⁰C, for 0.5 hours of an initial calcining duration and a second calcining duration of 0.5 hours, the loading capacity of doped sorbent obtained is 13.3 mg / g of activated LMO in contrast with an undoped sorbent with loading capacity of 10.2 mg / g of activated LMO when LiOH was used as a precursor and a high-grade Mn₃O₄ source was used. At 525⁰C, for two (2) hours of an initial calcining duration and a second calcining duration of two (2) hours, the loading capacity of doped sorbent obtained is 16.2 mg / g of activated LMO in contrast with an undoped sorbent with loading capacity of 13.2 mg / g of activated LMO when LiOH was used as a precursor and a high-grade Mn₃O₄ source was used. At 525⁰C, for five (5) hours of an initial calcining duration and a second calcining duration of ten (10) hours, the loading capacity of doped sorbent obtained is 18.6 mg / g of activated LMO Attorney Docket No.22782.008WO1 / Element3-005-PCT in contrast with an undoped sorbent with loading capacity of 15.9 mg / g of activated LMO when LiOH was used as a precursor and a high-grade Mn₃O₄ source as used. At 525⁰C, for fifteen (15) hours of an initial calcining duration and a second calcining duration of ten (10) hours, the loading capacity of doped sorbent obtained is 19.8 mg / g of activated LMO as against undoped sorbent with loading capacity of 14.5 mg / g of activated LMO when LiOH was used as a precursor and a high-grade Mn₃O₄ source was used. At 525⁰C, for five (5) hours of an initial calcining duration and a second calcining duration of ten (10) hours, the loading capacity of doped sorbent obtained is 24.1 mg / g of activated LMO as against undoped sorbent with loading capacity of 23.9 mg / g of activated LMO when Li₂CO₃ was used as a precursor and a high-grade Mn₃O₄ source was used.

[0177] Purity can influence the crystal structure and morphology of doped LMO spinel. Forming a doped intermediate-state sorbent blend may lead to the formation of secondary phases or alter the stoichiometry of the LMO lattice structure. Changes in crystal structure can affect the accessibility of lithium ions within the material, potentially impacting loading capacity. FIG.27 data suggests that the purity of the LMO spinel was maximized between five (5) and fifteen (15) hours at 525°C during the second calcination.

[0178] FIG.27 is a table illustrating the loading capacity of doped LMO sorbent spinel as described in the method of manufacturing a doped LMO spinel from FIG. 23, according to some embodiments of the present disclosure. The table contents represent the impact temperature, duration of the reacting step, reactants, and a second reacting step have on the loading capacity of the resulting LMO. By varying each of the duration temperatures, duration of the reacting step, reactants, and a second reacting step, different amounts of LMO, intermediate compound, and reactants present within the doped precursor blend can be biased to preferred amounts. In particular, the duration and temperature of the reacting, in this exemplary instance, calcining can be modified in a second calcining event of duration and temperature to achieve a desired loading capacity. It is also pertinent to note that doping the doped precursor blend enhances the loading capacity of the resultant sorbent blend.

[0179] Referring to FIG.27, experiments No.1 – 4 were conducted using a doped precursor blend of LiOH monohydrate and a high-grade Mn₃O₄ source, while experiment No.5 was conducted using a doped precursor blend of lithium carbonate (Li₂CO₃) and a high-grade Mn₃O₄ source. Typical of a higher-grade Mn₃O₄ source, the high-grade Mn₃O₄ source comprised a lower volume of iron (e.g., percent by weight of less than 0.7), an availability of Attorney Docket No.22782.008WO1 / Element3-005-PCT Mn in % by weight equal to or greater than 71% of overall weight. The process of doping involves substituting small amounts of elements (e.g., Al, Ni, or other elements) for Mn, Co, or Ni in the LMO structure. Doping aids in improving the structural stability and performance of LMO, particularly during phase transitions. The process is attributed to strong Al-O bonds that facilitate adsorption or desorption, thereby enhancing the structural stability of LMO. In general, calcining temperatures of approximately 525⁰C synthesized an LMO (e.g., a spinel LMO compound chemical formula best matches Li₁.₃₃Mn₁.₆₇O₄ as determined using XRD), yielding higher loading capacities, while a second calcination generally increases the loading capacity of the activated LMO (e.g., an HMO) at the end of the second calcination event. Milling was performed between the initial and second calcinations. Ion Li+ Na+ K+ Cl- HCO3- Concentration ation and again after an extended second calcination period of ten (10) hours. A loading test was performed on the activated sorbent (e.g., an HMO) using a synthetic brine. The brine solution is defined in Table 4. Loading tests were conducted with 200 mL of brine solution and approximately (or actually) 0.1 g of activated sorbent. Approximately generally refers to measurements that are within the tolerance of the measuring equipment, or the measurement is within a + / - 5% of the stated value, whichever is greater. This ratio is intended to supply an excess of lithium, allowing an accurate determination of the loading capacity. Samples were mixed for approximately one hour before collecting the depleted brine samples. Various other methodologies for assessing the absorption of the doped sorbent can be used to assess the loading capacity of a sorbent. It should be acknowledged that the constituents of the testing brine may influence the loading capacities determined through these tests. Components such as competing ions, pH levels, and the presence of organic compounds or other metals within the brine solution can significantly impact the sorbent's lithium uptake. These interactions may lead to reduced loading capacities, highlighting the importance of considering the specific composition of the brine when evaluating sorbent performance. Additionally, the testing conditions, such as the contact time between the doped sorbent and the brine, temperature, and sorbent-to-brine ratio, are critical factors that can affect the outcome of the loading capacity tests. As such, improving or optimizing these parameters based on the characteristics of the doped sorbent and the brine Attorney Docket No.22782.008WO1 / Element3-005-PCT solution can be essential for accurately determining loading capacity, increasing the likelihood, or ensuring that the findings are representative of real-world applications.

[0181] As described in FIG. 27, the highest loading capacity of 24.1 mg / g lithium in activated LMO is achieved by calcining for five (5) hours during the first calcination, followed by another ten-hour (10-hour) calcination during the second firing period at 525°C, when Li₂CO₃ was used as a precursor and a high-grade Mn₃O₄ source was used. The data presented in the table of FIG.27 further signifies that none of the other firing combinations yield a higher loading capacity of activated LMO.

[0182] The formation of doped LMO spinel at rather high purities, e.g., above 90% purity by weight, can be accomplished by calcining reactants like Mn₃O₄ and LiOH monohydrate at a lower temperature for relatively brief durations of five (5) hours. This synthesis technique increases the odds a commercially available manganese compound can be sourced and chemically converted to an intermediate compound, like Mn₂O₃. In some experiments, the formation of the intermediate Mn₂O₃ compound in the presence of a doped precursor blend of Mn₃O₄ and LiOH monohydrate may facilitate the formation of the doped LMO spinel. Achieving a volume of Mn₂O₃ compound, and calcining produces doped spinel sorbent within a relatively short duration of five (5) hours at purities that are achieved at lab quantities in one- third the time. The present technique suggests this method of utilizing an available compound, converting the compound in the presence of a doped precursor blends is feasible and effective for synthesizing a doped spinel sorbent.

[0183] In a preferred embodiment, calcining the doped precursor blend at 525°C for five (5) hours in an ambient atmosphere may form LMO via a one-step, cost-effective and scalable method of synthesis of a doped LMO spinel. Referring to FIG.23, in some embodiments, steps of the method may include 2310 to 2360. At 2310, the doped precursor blend may be a 0.70 to 0.85 ratio of lithium-to-manganese blend. Step 2320 comprises reacting the doped precursor blend with a doping agent in a 0.70 to 0.85 ratio of lithium-to-manganese blend with a 0.3% molar replacement of the doping agent for manganese. At step 2330, calcining the doped precursor blend of step 2320 for an initial doped intermediate-state sorbent blend of at least Mn₂O₃ and a doped LMO. In the subsequent step 2340, the resultant doped intermediate sorbent is milled to achieve particle-size reduction and homogenization. At step 2350, the milled intermediate sorbent of step 2340, is subjected to calcination for the second time for a second duration and temperature thereby forming a doped sorbent blend. The resultant sorbent Attorney Docket No.22782.008WO1 / Element3-005-PCT blend of step 2350 undergoes activation with an acid at step 2360, wherein the doped sorbent is activated to reach an activation percentage of at least 65% activation to form an activated LMO sorbent. The doped LMO may have a lithium loading capacity of at least 19.8 mg / g of activated doped LMO at standard temperature and pressure. The activated sorbent blend comprises at least one species of doped HMO sorbent spinel.

[0184] In some embodiments, the doped intermediate-state sorbent blend of at least Mn₂O₃ and an LMO may further comprise at least 7.0% by weight Mn₂O₃ at least 4.0% by weight Mn₃O₄, at least 2% by weight of LiOH monohydrate, and 85% by weight LMO. In some embodiments, the doped sorbent may blend further comprise 99% by weight LMO, less than 1% by weight of Mn₂O₃ and less than 1% by weight of LiOH monohydrate. The doped activated sorbent blend comprises at least one species of doped HMO sorbent spinel having a lithium loading capacity of at least 19.8 mg / g of HMO may sorbent spinel.

[0185] In some embodiments, the milling step as described in FIG. 20 during LMO synthesis can reduce the presence of undesired products and increase the weight percent of LMO in the sorbent blend, as well as improve loading capacity. Additionally, improvement or optimization of synthesis parameters such as temperature, calcination duration, and precursor ratios can influence the crystal structure and morphology of LMO spinel obtained, thereby affecting loading capacity.

[0186] Given the fluid nature of the reactant availability, cost, and supply timelines of precursor reactants, it is important to understand how different precursor blends perform under varying synthesis conditions. The present disclosure addresses this need by evaluating how temperature and firing duration impact the formation and purity of LMO from distinct precursor routes. FIG. 28 and FIG. 29 relate to the synthesis and characterization of lithium manganese oxide (LMO) sorbents, which are essential for extracting lithium and other metals from produced water, wastewater brines, and related streams.

[0187] Each precursor route presents its own process considerations. Different reactant combinations may necessitate adjustments to firing temperature, mix ratio, or preparation technique to achieve optimal LMO purity and sorbent loading capacity. The present disclosure includes systems and methods for the optimized industrial manufacturing of precursor blends, both in undoped and doped forms, and demonstrates how temperature and duration impact the quality and sorbent characteristics of the resulting LMO. These findings provide a baseline for Attorney Docket No.22782.008WO1 / Element3-005-PCT comparison against the performance of a 3:4 molar ratio MnCO₃:LiOH slurry-based precursor blend.

[0188] As shown in FIG. 28 and FIG. 29, the MnCO₃:LiOH slurry blend demonstrates a distinct and advantageous thermal profile, achieving high-purity LMO at firing temperatures as low as 350°C. In some embodiments, the MnCO₃:LiOH slurry is prepared by combining stoichiometric amounts of powder MnCO₃ and LiOH^H₂O reactants in deionized water and mixing the components to form a uniform aqueous suspension suitable for calcination. The solids loading may range from 3:1 reactant to water by weight, and the mixture may be stirred continuously for a duration of minutes to 2 hours to ensure homogeneous distribution.

[0189] In some embodiments, the precursor slurry is formulated by dispersing a 3:4 molar ratio of MnCO₃ and LiOH^H₂O in deionized water, wherein the solids loading ranges are approximately 3:1 by weight of powder reactants to weight of water or greater. In some embodiments, approximately 2:1 by weight of powder reactants to the weight of water. In some embodiments, the solids loading ranges of the solids are greater than or equal to a 1:2 by weight of reactants to weight of water. In some embodiments, the solids may be mixed, for example under continuous stirring for up to 2 hours to ensure uniformity. This slurry formulation supports improved precursor interaction and reactivity during calcination, contributing to high LMO purity and loading capacity at lower firing temperatures.

[0190] In certain embodiments, the slurry is subjected to mild heating or ultrasonic agitation to promote dispersion and eliminate agglomerates. This wet mixing approach enhances precursor contact and reaction uniformity during calcination and stands in contrast to conventional solid-state or dry powder mixing methods, which may result in incomplete reaction or require higher temperatures to achieve comparable purity. This contrasts with the temperature requirements and sorbent characteristics observed in Mn₃O₄-based systems disclosed herein. The ability to achieve economically viable LMO sorbents at lower temperatures has meaningful implications for large-scale production, energy efficiency, and process flexibility.

[0191] FIG. 28 provides a graphical overview of lithium manganese oxide (LMO) formation at varying firing durations and temperatures from a precursor blend comprising a 3:4 molar ratio of powdered manganese carbonate (MnCO₃) to powdered lithium hydroxide (LiOH), prepared in slurry form of approximately a 2:1 ratio of powdered reactants to water. Attorney Docket No.22782.008WO1 / Element3-005-PCT This precursor blend slurry is introduced into a kiln and subjected to thermal treatment at 400°C for durations ranging from 0.5 to 15 hours, and at 300°C, 350°C, and 375°C for a fixed duration of 5 hours. The figure illustrates the progression of reaction completion and intermediate phase formation, specifically highlighting the conversion to LMO as a function of thermal exposure.

[0192] Unexpectedly, economically significant LMO formation begins at temperatures as low as 350°C, with measurable loading capacity that supports the feasibility of producing LMO at these lower temperatures. This early onset of LMO formation is economically advantageous, as it reduces the thermal energy input required for the process. At 350°C for 5 hours, a near- complete conversion to LMO is observed. As temperature increases to 375°C, complete conversion is achieved, with approximately 100% LMO formation and no detectable unreacted precursors or intermediates. However, beyond this temperature, particularly as the temperature approaches 450°C, the loading capacity of the resulting LMO begins to decline, suggesting the onset of phase degradation or unwanted transformations. These findings support an optimal thermal window for efficient LMO synthesis with high product quality and energy efficiency in ranges lower than some alternative precursor blends..

[0193] FIG. 29 provides X-ray diffraction (XRD) data characterizing the phase composition of the fired samples shown in FIG. 28. The data confirms the progressive transformation of the precursor blend into LMO, with key intermediates and unreacted components—including MnCO₃, LiOH, Li₂CO₃, Mn₃O₄, and Mn₂O₃—quantified across the different temperature and duration conditions. At 400°C, the XRD profiles show a rapid decrease in MnCO₃ and formation of LMO within 0.5 hours, with nearly complete conversion achieved by the 2-hour mark. Notably, the presence of Li₂CO₃ diminishes significantly with longer firing times, and trace manganese oxide phases (Mn₃O₄, Mn₂O₃) are only detectable at specific durations. At lower firing temperatures (300–375°C), conversion is markedly slower, with substantial residual MnCO₃ and incomplete LMO formation observed at 300°C. In contrast, 375°C firing for 5 hours yields full conversion to LMO with no detectable intermediates.

[0194] FIG. 29 details the phase composition across a range of firing temperatures and durations, providing insights into the purity and completeness of LMO formation, as well as the presence of intermediate sorbent blend constituents such as Li₂CO₃, Mn₃O₄, and Mn₂O₃ that may be present in addition to LMO. Attorney Docket No.22782.008WO1 / Element3-005-PCT

[0195] At 350°C and a 5-hour firing duration, the LMO formed from the MnCO₃:LiOH slurry precursor blend reaches a purity of 99.22%, which is notable given the relatively low firing temperature. This result is especially significant when contrasted with undoped precursor blends that begin with Mn₃O₄ rather than MnCO₃. Undoped Mn₃O₄-based blends typically require higher temperatures to drive complete reaction with lithium sources and often produce LMO with lower crystallinity or purity when fired at similar or even moderately higher temperatures. Additionally, doped Mn₃O₄ precursor blends, benefit from elevated temperatures or in some embodiments from extended durations to achieve comparable purity levels.

[0196] The ability of the MnCO₃:LiOH slurry blend to achieve high-purity LMO at 350°C without the need for doping or high-temperature processing highlights a clear economic and performance advantage. This route reduces thermal load, simplifies process conditions, and eliminates reliance on expensive or specialty dopants, making it well-suited for scalable and cost-effective LMO production.

[0197] Table 5 presents the results of loading capacity tests for lithium manganese oxide (LMO) sorbents synthesized using a manganese source, MnCO₃, in combination with two different lithium reactants, LiOH and Li₂CO₃. Each reactant within the sorbent precursor blend maintained a 3:4 molar ratio of Li:Mn and was subjected to identical firing conditions: 400°C for 5 hours in both the first firing (F1) and second firing (F2). Table 5 also includes samples with and without 0.30% Al(OH)₃ doping agent as part of the sorbent precursor blend to assess the influence of dopants on LMO loading performance. F1 F1 Lithium Dopant Temp Duration F2 F2 Loading g) By including reactants in at least a 2:1 powder reactant to water slurry by mass, lithium loading capacity is expected to be much higher.

[0198] The results suggest that the lithium reactant plays a significant role in the resulting sorbent’s loading capacity. Blends using LiOH as the lithium source consistently achieved higher loading capacities, exceeding 13 mg Li / g sorbent, with or without the presence of Attorney Docket No.22782.008WO1 / Element3-005-PCT Al(OH)₃ doping. In contrast, blends prepared with Li₂CO₃ yielded noticeably lower loading capacities, ranging from approximately 8.13 to 8.35 mg Li / g sorbent, representing a roughly 40% reduction in performance under otherwise identical processing conditions.

[0199] These findings underscore the importance of lithium precursor selection in the synthesis of LMO sorbents. When paired with MnCO₃, LiOH results in enhanced sorbent performance in terms of lithium loading capacity. While dopant presence had a modest effect, the choice of lithium source appears to most strongly influence the loading capacity under these calcination conditions. From a practical standpoint, these results suggest that the use of LiOH may be preferable for manufacturing high-performance sorbent LMOs, assuming that supply, cost, and handling considerations for LiOH remain viable.

[0200] In one industrial-scale embodiment, a precursor slurry is prepared in a 500-liter mixing vessel equipped with a mechanical impeller for continuous agitation. The slurry precursor blend is a slurry comprising at least a 3:4 molar ratio of lithium to manganese, the lithium source being 58 kilograms of lithium hydroxide monohydrate (LiOH^H₂O), 241 kilograms of manganese carbonate (MnCO₃), and approximately 150 liters of deionized water. This results in a solid:liquid ratio of approximately 2:1. The solid components may be gradually added to the water under stirring to prevent agglomeration, and the mixture is stirred for 90 minutes at an ambient temperature until a uniform suspension is formed.

[0201] In some embodiments, the slurry is transferred to a controlled-atmosphere kiln, where it is subjected to a first calcination at 400°C for five (5) hours, followed by a second calcination at 400°C for five (5) hours. The resulting LMO sorbent blend demonstrates a lithium loading capacity of approximately 13.997 milligrams per gram (mg / g) using a dry precursor blend. This performance confirms the commercial viability of the MnCO₃ and LiOH precursor route for scalable, high-yield LMO sorbent production with efficient lithium exchange characteristics.

[0202] Those skilled in the art will appreciate that the foregoing specific exemplary processes and / or devices and / or technologies are representative of more general processes and / or devices and / or technologies taught elsewhere herein, such as in the claims filed herewith and / or elsewhere in the present application.

[0203] Those having ordinary skill in the art will recognize that the state of the art has progressed to the point where there is little distinction left between hardware, software, Attorney Docket No.22782.008WO1 / Element3-005-PCT and / or firmware implementations of aspects of systems; the use of hardware, software, and / or firmware is generally a design choice representing cost vs. efficiency tradeoffs (but not always, in that in certain contexts the choice between hardware and software can become significant). Those having ordinary skill in the art will appreciate that there are various vehicles by which processes and / or systems and / or other technologies described herein can be affected (e.g., hardware, software, and / or firmware), and that the preferred vehicle will vary with the context in which the processes and / or systems and / or other technologies are deployed. For example, if an implementer determines that speed and accuracy are paramount, the implementer may opt for a mainly hardware and / or firmware vehicle; alternatively, if flexibility is paramount, the implementer may opt for a mainly software implementation; or, yet again alternatively, the implementer may opt for some combination of hardware, software, and / or firmware. Hence, there are several possible vehicles by which the processes and / or devices and / or other technologies described herein may be affected, none of which is inherently superior to the other in that any vehicle to be utilized is a choice dependent upon the context in which the vehicle will be deployed and the specific concerns (e.g., speed, flexibility, or predictability) of the implementer, any of which may vary.

[0204] In some implementations described herein, logic and similar implementations may include software or other control structures suitable to operation. Electronic circuitry, for example, may manifest one or more paths of electrical current constructed and arranged to implement various logic functions as described herein. In some implementations, one or more medias are configured to bear a device-detectable implementation if such media hold or transmit a special-purpose device instruction set operable to perform as described herein. In some variants, for example, this may manifest as an update or other modification of existing software or firmware, or of gate arrays or other programmable hardware, such as by performing a reception of or a transmission of one or more instructions in relation to one or more operations described herein. Alternatively, or additionally, in some variants, an implementation may include special-purpose hardware, software, firmware components, and / or general-purpose components executing or otherwise controlling special-purpose components. Specifications or other implementations may be transmitted by one or more instances of tangible or transitory transmission media as described herein, optionally by packet transmission or otherwise by passing through distributed media at various times. Attorney Docket No.22782.008WO1 / Element3-005-PCT

[0205] Alternatively, or additionally, implementations may include executing a special- purpose instruction sequence or otherwise operating circuitry for enabling, triggering, coordinating, requesting, or otherwise causing one or more occurrences of any functional operations described above. In some variants, operational or other logical descriptions herein may be expressed directly as source code and compiled or otherwise expressed as an executable instruction sequence. In some contexts, for example, C++ or other code sequences can be compiled directly or otherwise implemented in high-level descriptor languages (e.g., a logic-synthesizable language, a hardware description language, a hardware design simulation, and / or other such similar modes of expression). Alternatively or additionally, some or all of the logical expression may be manifested as a Verilog-type hardware description or other circuitry model before physical implementation in hardware, especially for basic operations or timing-critical applications. Those skilled in the art will recognize how to obtain, configure, and optimize suitable transmission or computational elements, material supplies, actuators, or other common structures in light of these teachings.

[0206] The foregoing detailed description has set forth various embodiments of the devices and / or processes via the use of block diagrams, flowcharts, and / or examples. Insofar as such block diagrams, flowcharts, and / or examples contain one or more functions and / or operations, it will be understood by those having ordinary skill in the art that each function and / or operation within such block diagrams, flowcharts, or examples can be implemented, individually and / or collectively, by a wide range of hardware, software, firmware, or virtually any combination thereof. In one embodiment, several portions of the subject matter described herein may be implemented via Application Specific Integrated Circuits (ASICs), Field Programmable Gate Arrays (FPGAs), digital signal processors (DSPs), or other integrated formats. However, those skilled in the art will recognize that some aspects of the embodiments disclosed herein, in whole or in part, can be equivalently implemented in integrated circuits, as one or more computer programs running on one or more computers (e.g., as one or more programs running on one or more computer systems), as one or more programs running on one or more processors (e.g., as one or more programs running on one or more microprocessors), as firmware, or as virtually any combination thereof, and that designing the circuitry and / or writing the code for the software and or firmware would be well within the skill of one of skill in the art in light of this disclosure. In addition, those skilled in the art will appreciate that the mechanisms of the subject matter described herein are capable of being distributed as a program product in a variety of forms, and that an Attorney Docket No.22782.008WO1 / Element3-005-PCT illustrative embodiment of the subject matter described herein applies regardless of the particular type of signal bearing medium used to actually carry out the distribution. Examples of a signal bearing medium include, but are not limited to, the following: a recordable type medium such as a USB drive, a solid state memory device, a hard disk drive, a Compact Disc (CD), a Digital Video Disk (DVD), a digital tape, a computer memory, etc.; and a transmission type medium such as a digital and / or an analog communication medium (e.g., a fiber optic cable, a waveguide, a wired communications link, a wireless communication link (e.g., transmitter, receiver, transmission logic, reception logic), etc.).

[0207] In a general sense, those skilled in the art will recognize that the various aspects described herein which can be implemented, individually and / or collectively, by a wide range of hardware, software, firmware, and / or any combination thereof can be viewed as being composed of various types of “electrical circuitry.” Consequently, as used herein “electrical circuitry” includes, but is not limited to, electrical circuitry having at least one discrete electrical circuit, electrical circuitry having at least one integrated circuit, electrical circuitry having at least one application specific integrated circuit, electrical circuitry forming a general purpose computing device configured by a computer program (e.g., a general purpose computer configured by a computer program which at least partially carries out processes and / or devices described herein, or a microprocessor configured by a computer program which at least partially carries out processes and / or devices described herein), electrical circuitry forming a memory device (e.g., forms of memory (e.g., random access, flash, read- only)), and / or electrical circuitry forming a communications device (e.g., a modem, communications switch, optical-electrical equipment). Those having ordinary skill in the art will recognize that the subject matter described herein may be implemented in an analog or digital fashion or some combination thereof.

[0208] Those skilled in the art will recognize that at least a portion of the devices and / or processes described herein can be integrated into a data processing system. Those having ordinary skill in the art will recognize that a data processing system generally includes one or more of a system unit housing, a video display device, memory such as volatile or non- volatile memory, processors such as microprocessors or digital signal processors, computational entities such as operating systems, drivers, graphical user interfaces, and applications programs, one or more interaction devices (e.g., a touch pad, a touch screen, an antenna), and / or control systems including feedback loops and control motors (e.g., feedback Attorney Docket No.22782.008WO1 / Element3-005-PCT for sensing position and / or velocity; control motors for moving and / or adjusting components and / or quantities). A data processing system may be implemented utilizing suitable commercially available components, such as those typically found in data computing / communication and / or network computing / communication systems.

[0209] In certain cases, use of a system or method as disclosed and claimed herein may occur in a territory even if components are located outside the territory. For example, in a distributed computing context, use of a distributed computing system may occur in a territory even though parts of the system may be located outside of the territory (e.g., relay, server, processor, signal-bearing medium, transmitting computer, receiving computer, etc. located outside the territory).

[0210] A sale of a system or method may likewise occur in a territory even if components of the system or method are located and / or used outside the territory.

[0211] Further, implementation of at least part of a system for performing a method in one territory does not preclude use of the system in another territory.

[0212] All of thebove U.S. patents, U.S. patent application publications, U.S. patent applications, foreign patents, foreign patent applications and non-patent publications referred to in this specification and / or listed in any Application Data Sheet, are incorporated herein by reference, to the extent not inconsistent herewith.

[0213] One skilled in the art will recognize that the herein described components (e.g., operations), devices, objects, and the discussion accompanying them are used as examples for the sake of conceptual clarity and that various configuration modifications are contemplated. Consequently, as used herein, the specific examples set forth and the accompanying discussion are intended to be representative of their more general classes. In general, use of any specific example is intended to be representative of its class, and the non-inclusion of specific components (e.g., operations), devices, and objects should not be taken to be limiting.

[0214] With respect to the use of substantially any plural and / or singular terms herein, those having ordinary skill in the art can translate from the plural to the singular or from the singular to the plural as is appropriate to the context or application. The various singular / plural permutations are not expressly set forth herein for sake of clarity. Attorney Docket No.22782.008WO1 / Element3-005-PCT

[0215] The herein described subject matter sometimes illustrates different components contained within, or connected with, different other components. It is to be understood that such depicted architectures are presented merely as examples, and that in fact many other architectures may be implemented which achieve the same functionality. In a conceptual sense, any arrangement of components to achieve the same functionality is effectively “associated” such that the desired functionality is achieved. Therefore, any tw⁰Components herein combined to achieve a particular functionality can be seen as “associated with” each other such that the desired functionality is achieved, irrespective of architectures or intermedial components. Likewise, any tw⁰Components so associated can also be viewed as being “operably connected,” or “operably coupled,” to each other to achieve the desired functionality, and any tw⁰Components capable of being so associated can also be viewed as being “operably couplable,” to each other to achieve the desired functionality. Specific examples of “operably couplable” include but are not limited to physically mateable or physically interacting components, wirelessly interactable components, wirelessly interacting components, logically interacting components, or logically interactable components.

[0216] In some instances, one or more components may be referred to herein as “configured to,” “configurable to,” “operable / operative to,” “adapted / adaptable,” “able to,” “conformable / conformed to,” etc. Those skilled in the art will recognize that “configured to” can generally encompass active-state components, inactive-state components, or standby- state components, unless context requires otherwise.

[0217] While particular aspects of the present subject matter described herein have been shown and described, it will be apparent to those skilled in the art that, based upon the teachings herein, changes and modifications may be made without departing from the subject matter described herein and its broader aspects and, therefore, the appended claims are to encompass within their scope all such changes and modifications as are within the true spirit and scope of the subject matter described herein. It will be understood by those within the art that, in general, terms used herein, and especially in the appended claims (e.g., bodies of the appended claims) are generally intended as “open” terms (e.g., the term “including” should be interpreted as “including but not limited to,” the term “having” should be interpreted as “having at least,” the term “includes” should be interpreted as “includes but is not limited to,” etc.). It will be further understood by those within the art that if a specific number of an introduced claim recitation is intended, such an intent will be explicitly recited in the claim, Attorney Docket No.22782.008WO1 / Element3-005-PCT and in the absence of such recitation no such intent is present. For example, the following appended claims may contain usage of the introductory phrases “at least one” and “one or more” to introduce claim recitations. However, the use of such phrases should not be construed to imply that the introduction of a claim recitation by the indefinite articles “a” or “an” limits any particular claim containing such introduced claim recitation t⁰Claims containing only one such recitation, even when the same claim includes the introductory phrases “one or more” or “at least one” and indefinite articles such as “a” or “an” (e.g., “a” or “an” should typically be interpreted to mean “at least one” or “one or more”); the same holds true for the use of definite articles used to introduce claim recitations. In addition, even if a specific number of an introduced claim recitation is explicitly recited, those skilled in the art will recognize that such a recitation should typically be interpreted to mean at least the recited number (e.g., the bare recitation of “two recitations,” without other modifiers, typically means at least two recitations, or two or more recitations). Furthermore, in those instances where a convention analogous to “at least one of A, B, and C, etc.” is used, in general such a construction is intended in the sense one having ordinary skill in the art would understand the convention (e.g., “a system having at least one of A, B, and C” would include but not be limited to systems that have A alone, B alone, ℃ alone, A and B together, A and ℃ together, B and ℃ together, and / or A, B, and ℃ together). In those instances where a convention analogous to “at least one of A, B, or C, etc.” is used, in general such a construction is intended in the sense one having ordinary skill in the art would understand the convention (e.g., “a system having at least one of A, B, or C” would include but not be limited to systems that have A alone, B alone, ℃ alone, A and B together, A and ℃ together, B and ℃ together, and / or A, B, and ℃ together). It will be further understood by those within the art that typically a disjunctive word or phrase presenting two or more alternative terms, whether in the description, claims, or drawings, should be understood t⁰Contemplate the possibilities of including one of the terms, either of the terms, or both terms unless context dictates otherwise. For example, the phrase “A or B” will be typically understood to include the possibilities of “A” or “B” or “A and B.”

[0218] With respect to the appended claims, those skilled in the art will appreciate that recited operations therein may generally be performed in any order. Also, although various operational flows are presented as sequences of operations, it should be understood that the various operations may be performed in other orders than those which are illustrated or may be performed concurrently. Examples of such alternate orderings may include overlapping, Attorney Docket No.22782.008WO1 / Element3-005-PCT interleaved, interrupted, reordered, incremental, preparatory, supplemental, simultaneous, reverse, or other variant orderings, unless context dictates otherwise. Furthermore, terms like “responsive to,” “related to,” or other past-tense adjectives are generally not intended to exclude such variants, unless context dictates otherwise.

[0219] While various aspects and embodiments have been disclosed herein, other aspects and embodiments will be apparent to those skilled in the art. The various aspects and embodiments disclosed herein are for purposes of illustration and are not intended to be limiting, with the true scope and spirit being indicated by the following claims.

Claims

Attorney Docket No.22782.008WO1 / Element3-005-PCT CLAIMS What we claim is:

1. A method for manufacturing a spinel sorbent for reducing a concentration of at least one metal from a volume of fluid, the method for manufacturing comprising: a. mixing reactants to form a precursor blend; b. reacting the precursor blend forming an intermediate-state sorbent; c. cooling the intermediate-state sorbent; d. milling the intermediate-state sorbent; e. reacting the intermediate-state sorbent forming a sorbent; f. cooling the sorbent; and g. activating the sorbent.

2. The method of claim 2, wherein the reactants further comprise at least one of lithium hydroxide, and lithium carbonate.

3. The method of claim 1, wherein the reactants further comprise at least one of lithium hydroxide, lithium carbonate, and at least one of Mn₃O₄, MnCO3, and Mn₂O₃.

4. The method of claim 1, wherein the 3:4 lithium to manganese blend is doped with a doping agent and the doping agent is at least one of Al(OH)3, Co3O4, Cr2O3, Cr(OH)3, Fe2O3, Fe3O4, Ni2,O3, and Ni(OH)2.

5. The method of claim 1, wherein the 3:4 lithium to manganese blend is doped with a doping agent and the doping agent is an aluminum-based compound.

6. The method of claim 1, wherein the precursor blend is a 0.70 to 0.85 ratio of lithium to manganese blend.

7. The method of claim 1, wherein the precursor sorbent blend is an aqueous slurry.

8. The method of claim 1, wherein the reacting the precursor blend further comprises reacting the precursor blend at a temperature and an exposure time and wherein the temperature is between 425℃ and 625℃ and the exposure time is approximately 5 hours.

9. The method of claim 1, wherein the reacting the precursor blend further comprises calcining the precursor blend.

10. The method of claim 1, the reacting the precursor blend further comprises reacting the precursor blend at a temperature and an exposure time and wherein the temperature is between 350℃ and 425℃ and the exposure time is at least 3 hours.Attorney Docket No.22782.008WO1 / Element3-005-PCT 11. The method of claim 1, wherein the intermediate-state sorbent results in an oxidation of a manganese-based reactant.

12. The method of claim 1, wherein the intermediate-state sorbent is black when the precursor blend comprises Mn₂O₃ or the intermediate-state sorbent is black when the precursor blend is tan or white.

13. The method of claim 1, wherein the reacting the precursor blend at least partially agglomerates the precursor blend into a spinel structure.

14. The method of claim 1, wherein cooling the sorbent further comprises removing a source of heat from the intermediate-state sorbent for at least one hour.

15. A method for manufacturing a spinel sorbent for reducing a concentration of an at least one metal from a volume of fluid, the method for manufacturing comprising: a. mixing reactants to form a precursor blend; b. sintering the precursor blend forming an intermediate-state sorbent; c. cooling the intermediate-state sorbent; d. milling the intermediate-state sorbent; e. sintering the intermediate-state sorbent forming a sorbent; and f. cooling the sorbent.

16. A method for manufacturing a spinel sorbent for reducing a concentration of an at least one metal from a volume of fluid, the method for manufacturing comprising: a. mixing reactants to form a precursor blend; b. sintering the precursor blend forming an intermediate-state sorbent; and c. cooling the intermediate-state sorbent.

17. A sorbent spinel material obtained by a method comprising steps of: a. obtaining reactants to form a precursor blend; b. calcining the precursor blend for an initial calcining duration and first calcining temperature, forming an intermediate-state sorbent blend; c. cooling the intermediate-state sorbent blend; and d. milling the intermediate-state sorbent blend.

18. The method of claim 1, wherein the reactants include at least one high-grade manganese compound.

19. The method of claim 18, wherein the reactants comprise at least one of a high-grade Mn₃O₄, MnCO3, or Mn₂O₃ or LiOH monohydrate or Li₂CO₃.Attorney Docket No.22782.008WO1 / Element3-005-PCT 20. The method of claim 17, wherein the initial calcining duration is approximately five hours and the first calcining temperature is at approximately 525°C, wherein the formed intermediate-state sorbent blend further comprises at least 89% by weight LMO and at least 4.5% by weight Mn₂O₃.

21. The method of claim 17, further comprising a second calcining event comprising a second calcining temperature is between 500°C and 550°C.

22. The method of claim 21, wherein the second calcining duration is approximately ten hours, wherein the second calcining event synthesizes a sorbent blend comprising at least 70% by weight LMO and at least 5.0% by weight Mn₂O₃.

23. A method for manufacturing a LMO sorbent spinel, the method comprising steps of: a. obtaining a precursor blend, wherein the precursor blend is a 3:4 molar ratio of lithium to manganese blend of LiOH monohydrate or Li₂CO₃ and Mn₃O₄; b. calcining the precursor blend for an initial calcining duration and at a first temperature, wherein the calcining forms an intermediate-state sorbent blend of at least Mn₂O₃ and an LMO; and c. calcining the intermediate-state sorbent blend for a second calcining duration and second calcining temperature thereby forming a sorbent blend.

24. The method of claim 23, wherein the initial calcining duration is at least two (2) hours.

25. The method of claim 24, wherein the first temperature is at least 500℃.

26. The method of claim 23, wherein the intermediate-state sorbent blend further comprises less than 2% by weight Mn₃O₄, less than 23% by weight Mn₂O₃, and at least 75% by weight LMO.

27. The method of claim 23, wherein the second duration is at least two (2) hours and the second calcining temperature is approximately 525℃, wherein the sorbent blend further comprises less than 25% by weight Mn₂O₃, and at least 70% by weight LMO, wherein the LMO has a lithium loading capacity of at least 9.0 mg / g of activated LMO.

28. The method of claim 23, wherein the initial calcining duration is approximately five (5) hours, and the first temperature is approximately 650°C, wherein the formed intermediate- state sorbent blend further comprises at least 70% by weight LMO and at least 4.5% by weight Mn₂O₃; and the second duration is approximately ten (10) hours and the second calcining temperature is approximately 525℃, wherein the sorbent blend further comprises less than 0.5% by weight Mn₃O₄, less than 9% by weight Mn₂O₃, and at least 90% byAttorney Docket No.22782.008WO1 / Element3-005-PCT weight LMO, wherein the LMO has a lithium loading capacity of at least 6.0 mg / g of activated LMO.

29. The method of claim 23, further comprising activating the sorbent blend, the activating comprising: a. mixing the sorbent with an acid; b. agitating the sorbent and the acid; and c. activating the sorbent to reach an activation percentage of at least 20% activation to form an activated sorbent.

30. A method for manufacturing an undoped activated LMO sorbent spinel, the method comprising steps of: a. obtaining a precursor blend, wherein the precursor blend is a 0.70 to 0.85 molar ratio of lithium to manganese blend of Li₂CO₃ and Mn₃O₄; b. calcining the precursor blend for an initial calcining duration and at a first temperature of at least 525℃, wherein the calcining forms an intermediate-state sorbent blend of at least Mn₂O₃ and an LMO; c. cooling the intermediate-state sorbent blend; d. calcining the cooled intermediate-state sorbent blend for a second duration of five (5) hours and a second temperature of at least 500⁰C forming a sorbent blend; and e. activating the sorbent blend with an acid, wherein the activated sorbent blend comprises at least one species of HMO sorbent spinel.

31. The method of claim 30, wherein the intermediate-state sorbent blend has a lithium loading capacity of at least 18.0 mg / g of activated LMO.

32. The method of claim 30, wherein the LMO has a lithium loading capacity of at least 13.0 mg / g of activated LMO.

33. A doped sorbent spinel material obtained by a method comprising steps of: a. obtaining reactants and at least one doping agent to form a doped precursor blend; b. calcining the doped precursor blend for an initial calcining duration at a first calcining temperature, thereby forming an intermediate-state sorbent blend; c. cooling the doped intermediate-state sorbent blend; and d. milling the doped intermediate-state sorbent blend.

34. The method of claim 33, wherein the precursor blend comprises at least one MnCO3 and LiOH monohydrate.Attorney Docket No.22782.008WO1 / Element3-005-PCT 35. The method of claim 33, wherein the doping agent is at least one of Al(OH)3, LiAlH4 Co3O4, Cr2O3, Cr(OH)3, Fe2O3, Fe3O4, Ni2O3, Ni(OH)2, NaCl, AlCl3, MgCO3, Na2CO3, NaOH, or NaHCO3.

36. The method of claim 33, wherein the LMO of the doped sorbent blend has an activated lithium loading capacity of at least 16.0 mg / g of activated LMO.

37. A method for manufacturing a doped LMO sorbent spinel, the method comprising steps of: a. obtaining a doped precursor blend, wherein the doped precursor blend is a 3:4 molar ratio of lithium to manganese, wherein the lithium source is of LiOH monohydrate or Li₂CO₃ and the manganese source is a Mn₃O₄ blend with a 0.01-1.0% molar replacement of the doping agent for manganese; b. calcining the doped precursor blend for an initial calcining duration and at a first temperature of at least 500℃, wherein the calcining forms a doped intermediate- state sorbent blend of at least Mn₂O₃ and a doped LMO; and c. calcining the doped intermediate-state sorbent blend for a second calcining duration and a second calcining temperature thereby forming a doped sorbent blend.

38. The method of claim 37, wherein the initial calcining duration is at least 0.5 hours and the initial calcining temperature is at least 525°C, wherein the formed intermediate-state doped sorbent blend further comprises at least 70% by weight doped LMO, less than 2% by weight Mn₂O₃ and less than 27% of Mn₃O₄; and the second duration is approximately thirty (30) minutes and the second calcining temperature is approximately 525℃, wherein the doped sorbent blend further comprises at least 85% by weight of doped LMO, less than 8.0% by weight Mn₂O₃, less than 5.0 % by weight Mn₃O₄, and less than 3.0% of LiOH monohydrate, wherein the LMO has a lithium loading capacity of at least 13.3 mg / g of activated LMO.

39. The method of claim 37, wherein the second duration is at least two (2) hours, and the second calcining temperature is at least 525℃, wherein the doped sorbent blend further comprises less than 3% by weight Mn₃O₄, less than 15% by weight Mn₂O₃, and at least 80% by weight LMO, wherein the LMO has a lithium loading capacity of at least 12.0 mg / g of activated LMO.

40. The method of claim 37, wherein the initial calcining duration is at least five (5) hours and the initial calcining temperature is at least 525°C, wherein the formed intermediate- state sorbent blend further comprises at least 75% by weight LMO and at least 5.5% byAttorney Docket No.22782.008WO1 / Element3-005-PCT weight Mn₂O₃; and the second duration is at least five (5) hours and the second calcining temperature is approximately 525℃, wherein the doped sorbent blend further comprises less than 3.0% by weight Mn₃O₄, less than 7% by weight Mn₂O₃, and at least 90% by weight LMO, wherein the LMO has a lithium loading capacity of at least 16.0 mg / g of activated LMO.

41. The method of claim 39, further comprising activating the doped sorbent blend, the activating comprising: a. mixing the doped sorbent with an acid; b. agitating the doped sorbent and the acid; and c. activating the doped sorbent to reach an activation percentage of at least 20% activation to form an activated doped sorbent.

42. A method for manufacturing doped activated LMO sorbent spinel, the method comprising steps of: a. obtaining a doped precursor blend, wherein the doped precursor blend is a 0.70 to 0.85 molar ratio of lithium to manganese, wherein the lithium source is LiOH monohydrate or Li₂CO₃ and the manganese source is a Mn₃O₄ blend with a 0.01- 1.0% molar replacement of the doping agent for manganese; b. calcining the doped precursor blend for an initial calcining duration and at a first temperature of at least 525℃, wherein the calcining forms a doped intermediate- state sorbent blend of at least Mn₂O₃ and a doped LMO; c. cooling the doped intermediate-state sorbent blend; and d. calcining the cooled intermediate-state sorbent blend for a second duration of at least five (5) hours and a second temperature of at least 500⁰C forming a doped sorbent blend.

43. The method of claim 42, wherein the doped intermediate-state sorbent blend comprises less than 18% by weight Mn₂O₃, and at least 65% by weight LMO, wherein the LMO has a lithium loading capacity of at least 7.0 mg / g of activated doped LMO.

44. The method of claim 43, further comprising activating the doped sorbent blend with an acid, wherein the activated doped sorbent blend comprises at least one species of doped HMO sorbent spinel.

45. A method for manufacturing an LMO sorbent spinel, the method comprising steps of:Attorney Docket No.22782.008WO1 / Element3-005-PCT a. obtaining a precursor blend, wherein the precursor blend is an aqueous slurry containing within it a 70-85% molar ratio of lithium to manganese, the lithium source being LiOH.H2O and the manganese source being MnCO₃; b. calcining the precursor blend for an initial calcining duration at a first temperature wherein the calcining forms an intermediate-state sorbent blend comprising lithium manganese oxide (LMO); and c. cooling the intermediate-state sorbent blend.

46. The method of claim 45, wherein the first temperature is 350℃ and the intermediate-state sorbent blend comprises at least 80 weight percent (wt%) lithium manganese oxide (LMO), and less than 1.0 weight percent (wt%) manganese carbonate (MnCO₃)₃.

47. The method of claim 46, wherein the first temperature is 350℃ and the lithium manganese oxide (LMO) has a lithium loading capacity of at least 16.0 milligrams per gram (mg / g) of activated LMO.

48. The method of claim 47, wherein the first temperature is 350℃, the calcining duration is five (5) hours, and the resulting intermediate-state sorbent blend comprises at least 90 weight percent (wt%) lithium manganese oxide (LMO) and exhibits a lithium loading capacity of at least 16.0 milligrams per gram (mg / g) of activated LMO.

49. The method of claim 45, further comprises preparing the aqueous slurry by mixing solid MnCO₃ and LiOH^H₂O in water to achieve a uniform suspension prior to the calcining.

50. The method of claim 45, wherein the first temperature is 400℃ and the intermediate-state sorbent blend comprises at least 75 weight percent (wt%) lithium manganese oxide (LMO), and less than 1.0 weight percent (wt%) manganese carbonate (MnCO₃).

51. The method of claim 50, wherein the lithium manganese oxide (LMO) has a lithium loading capacity of at least 12.0 milligrams per gram (mg / g) of activated LMO.

52. The method of claim 45, wherein the first temperature is 400℃, the calcining duration is five (5) hours, and the resulting intermediate-state sorbent blend comprises at least 90 weight percent (wt%) lithium manganese oxide (LMO) and exhibits a lithium loading capacity of at least 12.0 milligrams per gram (mg / g) of activated LMO.

53. A method for manufacturing an LMO sorbent spinel, the method comprising steps of: a. obtaining a precursor blend, wherein the precursor blend is an aqueous slurry containing within it a 70-85% molar ratio of lithium to manganese, the lithium source being LiOH.H2O and the manganese source being MnCO₃;Attorney Docket No.22782.008WO1 / Element3-005-PCT b. calcining the precursor blend for an initial calcining duration of five (5) hours at a first temperature between 350℃ and 425℃, wherein the calcining forms an intermediate-state sorbent blend comprising lithium manganese oxide (LMO); and c. cooling the intermediate-state sorbent blend, wherein the lithium manganese oxide (LMO) comprises at least 90 weight percent (wt%) of the intermediate-state sorbent blend, and wherein the lithium manganese oxide (LMO) has a lithium loading capacity of at least 15.0 milligrams per gram (mg / g) of LMO.

54. The method of claim 53, wherein the lithium manganese oxide (LMO) has a lithium loading capacity of at least 15.0 milligrams per gram (mg / g) of activated LMO.

55. The method of claim 53, wherein the precursor blend further comprises a dopant selected from the group consisting of Al(OH)₃, TiO₂, MgO, and ZnO, and wherein the dopant is present at a concentration of less than 1.0 weight percent (wt%) of the total solids in the precursor blend.

56. The method of claim 53, wherein the precursor blend further comprises a dopant that replaces between 0.01% and 1% of the manganese sites in the lithium manganese oxide (LMO) structure.

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