Method of soda ash preparation for lithium mineral refining, and compositions thereof

Abstract

A process of extracting lithium from a lithium mineral using a soda ash leach process, wherein the soda ash is generated from byproducts from processing the lithium mineral is described. The soda ash utilized may be generated on-site using the CO2 generated during the calcination process.

Description

METHOD OF SODA ASH PREPARATION FOR LITHIUM MINERAL REFINING, AND COMPOSITIONS THEREOFINCORPORATION BY REFERENCE TO ANY PRIORITY APPLICATIONS

[0001] Any and all applications for which a foreign or domestic priority claim is identified in the Application Data Sheet or PCT Request as filed with the present application are hereby incorporated by reference under 37 CFR 1.57, and Rules 4.18 and 20.6. This application claims the benefit of priority to U.S. Prov. Patent App. No. 63 / 644,926, filed on May 9, 2024, which is incorporated herein by reference in its entirety for all purposes.BACKGROUNDField

[0002] This disclosure is generally related to extractions. More specifically, this disclosure is related to methods of extracting lithium from lithium minerals.Description of the Related Art

[0003] Lithium minerals, such as spodumene, may be refined to create lithium hydroxide monohydrate (“LHM” or LiOH’FEO). Lithium minerals may be refined using a sulfuric acid leach process or a soda ash leach process. However, the soda ash leach process requires large amounts of soda ash (i.e., Na2COs) to be purchased and shipped to the lithium mineral refining location, which produces additional costs and logistical bottlenecks.SUMMARY

[0004] For purposes of summarizing the invention and the advantages achieved over the prior art, certain objects and advantages of the invention are described herein. Not all such objects or advantages may be achieved in any particular embodiment of the invention. Thus, for example, those skilled in the art will recognize that the invention may be embodied or carried out in a manner that achieves or optimizes one advantage or group of advantages as taught herein without necessarily achieving other objects or advantages as may be taught or suggested herein.

[0005] In one aspect, a process for extracting lithium from a lithium mineral is described. The process includes: calcinating a lithium mineral with heat from combusting a carbon fuel source to form a calcinated lithium mineral and a combustion byproduct including CO2; reacting the CO2 of the combustion byproduct with a brine mixture comprising NaCl, NH3 and water to form a byproduct-brine mixture comprising NH4CI and NaHCCh; removing the NH4CI from the byproduct-brine mixture to form an intermediate reaction product including NaHCCh; processing the removed NH4CI to form NH3 and a byproduct HC1; recycling the NH3 into the brine mixture; decomposing the intermediate reaction product to form a regeneration CO2 and reaction product including Na2COs; recycling the regenerated CO2 into the byproduct-brine mixture; combining the reaction product with the calcinated lithium mineral to form a slurry comprising a depleted mineral and a leach solution; and processing the leach solution to form a lithium product including lithium hydroxide.

[0006] In another aspect, a process for extracting lithium from a lithium mineral is described. The process includes: calcinating a lithium mineral with heat from combusting a carbon fuel source to form a calcinated lithium mineral and a combustion byproduct comprising CO2; reacting the CO2 of the combustion byproduct with a brine mixture comprising NaCl and water to form a reaction product comprising Na2COs; and combining the reaction product with the calcinated lithium mineral to form a slurry comprising a depleted mineral and a leach solution, wherein the leach solution comprises lithium.

[0007] In some embodiments, the process further comprises combining NaCl and water to form the brine mixture. In some embodiments, the brine mixture further comprises NH3. In some embodiments, reacting the CO2 of the combustion byproduct with a brine mixture forms a byproduct-brine mixture comprising NH4CI. In some embodiments, the process further comprises removing the NH4CI from the byproduct-brine mixture to form an intermediate reaction product. In some embodiments, the process further comprises processing the removed NH4CI to form a regenerated NH3 and a byproduct HC1. In some embodiments, the process further comprises recycling the regenerated NH3 into the brine mixture. In some embodiments, the intermediate reaction product comprises NaHCCh, and the intermediate reaction product is decomposed to form the reaction product and a regenerated CO2. In some embodiments, the process further comprises combining the regenerated CO2 with the CO2 of the combustion byproduct.

[0008] In some embodiments, the lithium mineral is selected from spodumene, lepidolite, zinnwaldite, smectite, hectorite, muscovite, and combinations thereof. In some embodiments the lithium mineral comprises spodumene. In some embodiments, the lithium mineral comprises spodumene. In some embodiments, the process does not include combining an additional ISfeCCh different from the Na2COs of the reaction product with the calcinated lithium mineral. In some embodiments, the process further comprises processing the leach solution to form a lithium product comprising lithium hydroxide.

[0009] In some embodiments, the CO2 utilized in the process is sourced from the combustion byproduct, the regenerated CO2, or combinations thereof. In some embodiments the leach solution has a pH of at least about 4. In some embodiments, the leach solution has an extraction efficiency of at least about 20%. In some embodiments, the process further includes capturing CO2 of the combustion byproduct, the regenerated CO2, or combinations thereof. In some embodiments, the process further comprises isolating the lithium hydroxide.

[0010] In another aspect, a process of preparing a cathode active material is disclosed. The process includes: performing a process for extracting lithium from a lithium mineral; and reacting the lithium hydroxide with a cathode active material precursor to form a cathode active material.BRIEF DESCRIPTION OF THE DRAWINGS

[0011] These and other features, aspects, and advantages of the present disclosure are described with reference to the drawings of certain embodiments, which are intended to illustrate certain embodiments and not to limit the invention.

[0012] FIG. 1 is a flow chart of a process for extracting lithium from a lithium mineral using a recycled soda ash leach process, according to some embodiments.

[0013] FIG. 2 is a flow chart of a detailed process for extracting lithium from a lithium mineral using a recycled soda ash leach process, according to some embodiments.

[0014] FIG. 3 is a flow chart of an example process for extracting lithium from a lithium mineral using a recycled soda ash leach process, according to some embodiments.

[0015] It will be clearly understood though, that the examples and figures are for illustrative purpose only, and are not necessarily restrictive of the scope of the present invention.DETAILED DESCRIPTION

[0016] Although certain preferred embodiments and examples are disclosed below, the inventive subject matter extends beyond the specifically disclosed embodiments to other alternative embodiments and / or uses and to modifications and equivalents thereof. Thus, the scope of the claims appended hereto is not limited by any of the particular embodiments described below. For example, in any method or process disclosed herein, the acts or operations of the method or process may be performed in any suitable sequence and are not necessarily limited to any particular disclosed sequence. Various operations may be described as multiple discrete operations, in turn, in a manner that may be helpful in understanding certain embodiments; however, the order of description should not be construed to imply that these operations are order-dependent. Additionally, the structures, systems, and / or devices described herein may be embodied as integrated components or as separate components. For purposes of comparing various embodiments, certain aspects and advantages of these embodiments are described. Not necessarily all such aspects or advantages are achieved by any particular embodiment. Thus, for example, various embodiments may be carried out in a manner that achieves or optimizes one advantage or group of advantages as taught herein without necessarily achieving other aspects or advantages as may also be taught or suggested herein.

[0017] The present disclosure is directed at a process of extracting lithium from a lithium mineral using a soda ash leach process, wherein the soda ash is generated from byproducts from processing the lithium mineral. The soda ash leach process includes calcinating a lithium mineral (e.g., spodumene), and leaching the calcinated lithium mineral with water and soda ash (i.e., Na2COs). In some embodiments, the soda ash leach process forms Li2CC>3 that may then be converted to LiOH using a base (e.g., Ca(OH)2). In some embodiments, the LiOH may be crystallized to form a lithium hydroxide monohydrate (e.g., LHM) powder. In some embodiments, the lithium hydroxide or lithium hydroxide monohydrate obtained from the process may be utilized to form cathode active materials for energy storage devices (e.g., lithium-ion batteries).

[0018] The soda ash utilized may be generated on-site using the CO2 generated during the calcination process, as high temperature calcination is fueled by combustion of a carbon fuel source (e.g., natural gas) and generates CO2 emissions. Such CO2 emissions canbe captured and converted to Na2CO3, which can be utilized in the soda ash leach process. The disclosed process takes advantage of an existing “free” source of CO2. Furthermore, such onsite generation of soda ash eliminates logistics and transportation costs associated with shipping the soda ash, and allows for the use of wet soda ash that does not require a final drying step as opposed to purchased soda ash that is typically fully dried. In addition, the capture and utilization of CO2 may eliminate or reduce the greenhouse gas emissions of the lithium extraction process. Example reactions for converting CO2 into soda ash are shown below.

[0019] In some embodiments, the process produces at least a sufficient amount of soda ash for the soda ash leach process to proceed to completion, without the need to supplement with additional soda ash. For example, the spodumene refining process consumes about 0.2 tons of Na2CO3per ton of spodumene and the spodumene calcination process using natural gas generates about 0.12 tons of CO2 per ton of spodumene, which if converted to an equivalent amount of Na2CO3is about 0.28 tons of Na2CO3per ton of spodumene. As such, this example demonstrates that stoichiometrically all of the Na2CO3required for spodumene leaching can be generated using the CO2 from spodumene calcination.

[0020] FIG. 1 shows a process 100 for extracting lithium from a lithium mineral using a recycled soda ash leach process. In process 100, a lithium mineral is calcinated 102 to form a calcinated lithium mineral 104 and a combustion byproduct 106 including CO2. The combustion byproduct 106 is combined with a brine mixture 108 to form a reaction product 110 including Na2CO3. The calcinated lithium mineral 104 and the Na2CO3of the reaction product 110 are combined to form a slurry 112 including a depleted mineral and a leach solution (e.g., lithium rich leach solution). The leach solution may be further processed to produce a lithium product, such as Li2CO3and / or LiOH.

[0021] FIG. 2 shows a detailed process 200 for extracting lithium from a lithium mineral using a recycled soda ash leach process. In process 200, a lithium mineral 202 is combined with the heat from combusting a carbon fuel source 204 to calcinate the lithium mineral 206 and form a calcinated lithium mineral 208 and a combustion byproduct 210 including CO2. NaCl 212 and H2O 214 are combined with NH3230 to form a brine mixture216. The brine mixture 216 is combined with the CO2 of the combustion byproduct 210 to form a byproduct-brine mixture 218. The byproduct-brine mixture 218 is filtered 220 to form an intermediate reaction product 222 and aqueous NH4CI 224. The NH4CI 224 is processed 226 to form HC1 228 and NH3 230, wherein the NH3 230 is utilized to form the brine mixture 216 previously discussed. The intermediate reaction product 222 is dried 232 to produce regenerated CO2234 and a reaction product 236 including Na2CC>3. The regenerated CO2234 is combined with the combustion byproduct 210. The Na2CC>3 of the reaction product 236 is then combined with the calcinated lithium mineral 208 to form a slurry where the lithium leaching process can occur. The slurry 238 is filtered to separate a depleted mineral 242 and a leach solution 244. The leach solution 244 is processed 246 to form a lithium product 248 including U2CO3 and / or a lithium hydroxide (e.g., LiOH or LiOH’FfcO).

[0022] In some embodiments, the process, such as the process 200 of FIG. 2, may utilize the following chemical reaction steps in forming soda ash:7. 2NaHCO3(s) + heat Na2CO3(s) + CO2(g) + H2O(g)

[0023] In some embodiments, the soda ash leach process includes calcinating a lithium mineral to form a calcinated lithium mineral. In some embodiments, the lithium mineral is calcinated with heat from combusting a carbon fuel source, wherein the combustion of the carbon fuel source forms a combustion byproduct that includes CO2. In some embodiments, the CO2 of the combustion byproduct is reacted to form Na2CC>3, a reaction product including Na2CC>3, and / or an intermediate reaction product. In some embodiments, the reaction product further includes NH4CI. In some embodiments, the CO2 of the combustion byproduct is combined with a brine mixture. In some embodiments, the brine mixture includes compounds selected from a salt (e.g., NaCl), water, NH3, and combinations thereof. In some embodiments, a salt (e.g., NaCl), water, NH3, or a combination thereof are combined to formthe brine mixture. In some embodiments, the CO2 and the brine mixture react to form Na2COs, a reaction product including Na2COs, and / or an intermediate reaction product. In some embodiments, the reacted CO2 and the brine mixture form an intermediate reaction product and an aqueous solution. In some embodiments, the intermediate reaction product and an aqueous solution are separated (e.g., filtered). In some embodiments, the aqueous solution includes NH4CI. In some embodiments, the aqueous solution is processed. In some embodiments, processing of the aqueous solution including NH4CI produces NH3 and HC1. In some embodiments, the NH3 and HC1 are separated. In some embodiments, the NH3 produced may be added to the brine mixture. In some embodiments, the intermediate reaction product includes NaHCCh. In some embodiments, the NaHCCh of the intermediate product is decomposed (e.g., by heating and / or drying) to form a reaction product, regenerated CO2, Na2CC>3 and / or water. In some embodiments, the regenerated CO2 may be recaptured to be combined with the CO2 of the combustion byproduct and / or added to the brine mixture. In some embodiments, the reaction product includes Na2CO3. In some embodiments, the reaction product further comprises water. In some embodiments, the reaction product is not fully dried.

[0024] The produced Na2CO3 may be reacted with the calcinated lithium mineral to form a lithium product. In some embodiments, the lithium product is selected from Li2CO3, a lithium hydroxide (e.g., LiOH, LiOH’I O), or combinations thereof. In some embodiments, the Na2CC>3 and the calcinated lithium mineral are combined to form a slurry. In some embodiments, Na2CO3 and the calcinated lithium mineral are combined with or without additional water added. In some embodiments, the slurry includes a depleted mineral and a leach solution. In some embodiments, the depleted mineral includes a lower concentration of lithium relative to the lithium mineral and / or calcinated lithium mineral. In some embodiments, the leach solution is a lithium rich leach solution which contains the lithium leached out from the calcinated lithium mineral. In some embodiments, the lithium within the lithium leach solution is U2CO3. In some embodiments, the leach solution is processed to form a lithium product. In some embodiments, processing the leach solution may include adding a base, isolating (e.g., filtering, crystallization), or combinations thereof. In some embodiments, the base is a strong base (e.g., Ca(OH)2). In some embodiments, adding the base to the leach solution converts Li2CO3 to LiOH.

[0025] In some embodiments, the lithium is extracted from the calcinated lithium mineral by a liquid leach. In some embodiments, the liquid used in the liquid leach comprises water. In some embodiments, the liquid used in the liquid leach consists essentially of or consists of water. In some embodiments, the liquid leach is performed at a temperature of or of about 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 70°C, 80°C, 90°C, 100°C, 120°C, 140°C, 150°C, 160°C, 180°C, 200°C, 220°C, 240°C, 250°C, 260°C, 275°C or 300°C, or any range of values therebetween. In some embodiments, the liquid leach is performed for 0.25 hours, 0.5 hours, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 8 hours, 12 hours, 16 hours, 18 hours or 24 hours, or any range of values therebetween. In some embodiments, the liquid leach comprises agitation of the mixture. In some embodiments, agitation is performed at 100 RPM, 200 RPM, 300 RPM, 400 RPM, 500 RPM, 600 RPM, 700 RPM, 800 RPM, 900 RPM, 1000 RPM, 1200 RPM, 1400 RPM, 1500 RPM, 1600 RPM, 1800 RPM or 2000 RPM, or any range of values therebetween.

[0026] Once the liquid leach is complete, a composition comprising a depleted mineral and a leach solution (e.g., lithium rich leach solution) is formed. In some embodiments, the lithium rich leach solution is filtered to remove the depleted mineral and / or other solid materials. The depleted mineral comprises, comprises about, comprises at most, or comprises at most about, 10 g, 8 g, 7 g, 6 g, 5 g, 4 g, 3 g, 2 g, 1.5 g, 1.2 g, 1 g, 0.8 g, 0.5 g, 0.3 g, 0.2 g,0.1 g, 0.05 g or 0.01 g of Li / kg, or any range of values therebetween. In some embodiments, the leach solution comprises, comprises about, comprises at least, or comprises at least about 10 ppm, 20 ppm, 30 ppm, 40 ppm, 50 ppm, 60 ppm, 70 ppm, 80 ppm, 90 ppm, 100 ppm, 150 ppm, 200 ppm, 500 ppm, 1000 ppm, 1500 ppm, 2000 ppm, 3000 ppm, 4000 ppm, 5000 ppm, 6000 ppm, 7000 ppm, 7500 ppm, 7700 ppm, 8000 ppm, 9000 ppm or 10000 ppm of lithium, or any range of values therebetween.

[0027] In some embodiments, the relative amount of an element extracted from the lithium mineral and into the leach solution may be characterized as the elemental extraction efficiency of the process or the leach solution itself. In some embodiments, the lithium extraction efficiency is, is about, is at least, or is at least about, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 85% or 90%, or any range of values therebetween. In some embodiments, the relative amount of CO2 captured or recaptured from the CO2 of the combustion byproduct and or the regenerated CO2 is, is about, is at least, or is at least about 50 wt.%, 60 wt.%, 70 wt.%,80 wt.%, 85 wt.%, 90 wt.%, 95 wt.%, or 98 wt.% or any range of values therebetween. In some embodiments, the relative amount of CO2 captured or recaptured from the CO2 of the combustion byproduct and or the regenerated CO2 is, is about, is at least, or is at least about 50 mole %, 60 mole %, 70 mole %, 80 mole %, 85 mole %, 90 mole %, 95 mole %, or 98 mole % or any range of values therebetween. In some embodiments, CO2 may be captured from the combustion of carbon fuel for calcinating lithium mineral material, heating of the intermediate reaction product, drying of intermediate reaction product, the combustion of carbon fuel for drying intermediate reaction product, the combustion of carbon fuel for heating intermediate reaction product, and any combination of process steps.

[0028] In some embodiments, an acid is not utilized in the described process. In some embodiments, a strong acid is not utilized in the described process. In some embodiments, a strong acid includes HC1, HBr, HI, HNO3, HCIO4 and H2SO4. In some embodiments, the leach solution has a pH of, of about, of at least, or of at least about 4, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11 or 12, or any range of values therebetween. For example, in some embodiments the leach solution has a pH of about 5-10, about 8-10 or 8-9.5.

[0029] In some embodiments, a lithium mineral may be selected from spodumene, lepidolite, zinnwaldite, smectite, hectorite, muscovite, and combinations thereof. In some embodiments, the lithium mineral may be pulverized. In some embodiments, pulverization is performed by milling and / or grinding in a high-energy mill for desired time duration. In some embodiments, the high-energy mill comprises a ball mill. In some embodiments, the high- energy mill is selected from the group consisting of a planetary ball-mill, a Spex mill, a high shear high energy mill, an attritor mill, and a vibratory mill, or combinations thereof.

[0030] In some embodiments, the lithium hydroxide or lithium hydroxide hydrate formed by the process described may be utilized to form a cathode active material for an energy storage device. In some embodiments, the lithium hydroxide or lithium hydroxide hydrate is reacted with a cathode active material precursor to form a cathode active material. In some embodiments the cathode active material precursor is a metal oxide, a metal phosphate, or a combination thereof. In some embodiments, the cathode active material is a lithium metal oxide, a lithium metal phosphate, or a combination thereof. In some embodiments, the lithium metal oxide is selected from lithium cobalt oxide (LCO), lithium manganese oxide (LMO), lithium nickel manganese cobalt oxide (NMC), lithium nickel cobalt aluminum oxide (NCA),or combinations thereof. In some embodiments, the lithium metal phosphate is lithium iron phosphate.Processing the Solid Material

[0031] In some embodiments, solid intermediates and solid products may be further processed and / or extracted from aqueous solutions (e.g., to form one or more purified solid products and to remove impurities). In some embodiments, the processing of the solid product may include an acid leach, a solid liquid separation, a hydrometallurgical circuit, filtration, crystallization, and combinations thereof.Electrode Film Materials and Electrode Films

[0032] The lithium product of the present disclosure may be utilized in the formation of electrode films and energy storage devices. Electrode film mixtures and electrode films that may be found in energy storage device materials are described herein. In some embodiments, components of an active layer or electrode film may comprise particles. The particles for forming the active layer or electrode film may be combined with a material to provide an electrode film mixture. In some embodiments, the active layer or electrode film may be formed from the electrode film mixture such that weight percentages of the components of the active layer or electrode film and weight percentages of the components of the electrode film mixture are substantially the same.

[0033] An active material (e.g., cathode active material, anode active material) may be used in the preparation of an electrode film and / or electrode for an energy storage device.

[0034] In some embodiments, the active material is a cathode active material. In some embodiments, the cathode active material is selected from at least one of a metal oxide, metal sulfide, a sulfur-carbon composite, a lithium metal oxide, and a material including sulfur. In some embodiments, the cathode active material is selected from lithium iron phosphate (i.e., LiFePO4 or “LFP”), lithium manganese iron phosphate (e.g., LiMno.6Feo.4PO4 or “LMFP”), lithium nickel manganese cobalt oxide (i.e., LiNixMnyCoi-x-yO2 or “NMC”), lithium nickel cobalt aluminum oxide (i.e., LiNixCoyAlzO2 or “NCA”), lithium manganese oxide (“LMO”), lithium nickel manganese oxide (“LNMO”), lithium cobalt oxide (“LCO”), lithium titanate (“LTO”), or combinations thereof. In some embodiments, the cathode active material includesat least two of LFP, LMFP, NMC, NCA, LMO, LNMO, LCO, LTO, and combinations thereof. In some embodiments, the cathode active material is an iron phosphate-based active material. In some embodiments, iron phosphate-based active materials include LiFePO4 (i. e. , “lithium iron phosphate” and “LFP”) and LiMni-xFexP04 (i.e., “lithium manganese iron phosphate” and “LMFP”) (e.g., LiMno.eFeo.4PO4 or LiMno.8Feo.2PO4). In some embodiments, the iron phosphate-based active material includes LFP. In some embodiments, the iron phosphate- based active material includes an LMFP. In some embodiments, the iron phosphate-based active material includes an LFP and / or an LMFP.

[0035] In some embodiments, the active material is an anode active material. In some embodiments, anode active materials can include, for example, an insertion material (such as carbon, graphite, and / or graphene), an alloying / dealloying material (such as silicon, silicon oxide, tin, and / or tin oxide), a metal alloy or compound (such as Si- Al, and / or Si-Sn), and / or a conversion material (such as manganese oxide, molybdenum oxide, nickel oxide, and / or copper oxide). The anode active materials can be used alone or mixed together to form multi-phase materials (such as Si-C, Sn-C, SiOx-C, SnOx-C, Si-Sn, Si-SiOx, Sn-SnOx, Si- SiOx-C, Sn-SnOx-C, Si-Sn-C, SiOx-SnOx-C, Si-SiOx-Sn, or Sn-SiOx-SnOx.). Anode active materials include common natural graphite, synthetic or artificial graphite, surface modified graphite, spherical-shaped graphite, flake-shaped graphite and blends or combinations of these types of graphite, metallic elements and its compound as well as metal-C composite for anode.

[0036] In some embodiments, the electrode film comprises the active material in an amount of, of about, of at least, or at least about, 70 wt.%, 75 wt.%, 80 wt.%, 85 wt.%, 86 wt.%, 87 wt.%, 88 wt.%, 89 wt.%, 90 wt.%, 91 wt.%, 92 wt.%, 93 wt.%, 94 wt.%, 95 wt.%, 96 wt.%, 97 wt.%, 98 wt.%, 98.5 wt.%, 99 wt.%, 99.5 wt.%, 99.8 wt.% or 99.9 wt.%, or any range of values therebetween.

[0037] In some embodiments, an electrode film comprises a carbon material configured to reversibly intercalate lithium ions. In some embodiments, the lithium intercalating carbon is selected from a graphitic carbon, graphite, hard carbon, soft carbon and combinations thereof. For example, the electrode film of the electrode can include a binder material, one or more of graphitic carbon, graphite, graphene- containing carbon, hard carbon and soft carbon, and an electrical conductivity promoting material. In some embodiments, an electrode is mixed with lithium metal and / or lithium ions. In some embodiments, the electrodecomprises the carbon material in a total amount of, of about, of at most, or at most about, 20 wt.%, 15 wt.%, 10 wt.%, 9 wt.%, 8 wt.%, 7 wt.%, 6 wt.%, 5 wt.%, 4 wt.%, 3 wt.%, 2 wt.%, 1 wt.%, or any range of values therebetween.

[0038] In some embodiments, an electrode film includes a conductive additive. In some embodiments, the conductive additive may comprise a conductive carbon additive, such as a carbon black. In some embodiments, the conductive additive may comprise a conductive carbon additive. In some embodiments, the conductive carbon additive comprises carbon black, carbon nanotubes, such as single- walled carbon nanotubes (SWCNTs) and multi-walled carbon nanotubes (MWCNTs). In some embodiments, the electrode film comprises the conductive additive in a total amount of, of about, of at most, or at most about, 10 wt.%, 9 wt.%, 8 wt.%, 7 wt.%, 6 wt.%, 5 wt.%, 4 wt.%, 3 wt.%, 2 wt.%, 1 wt.%, 0.5 wt.%, 0.25 wt.%, 0.1 wt.%, or any range of values therebetween. In some embodiments, each of the conductive additive is in an amount of, of about, of at most, or at most about, 10 wt.%, 9 wt.%, 8 wt.%, 7 wt.%, 6 wt.%, 5 wt.%, 4 wt.%, 3 wt.%, 2 wt.%, 1 wt.%, 0.5 wt.%, 0.25 wt.%, 0.1 wt.%, of the electrode film, or any range of values therebetween. In some embodiments, the conductive additive is carbon black.

[0039] In some embodiments, the electrode film includes a binder or binder material. In some embodiments, binders can include polytetrafluoroethylene (PTFE), a polyolefin, polyalkylenes, polyethers, styrene-butadiene, co-polymers of polysiloxanes and polysiloxane, branched polyethers, polyvinylethers, a carboxymethylcellulose (CMC), copolymers thereof, and / or combinations thereof. In some embodiments, the polyolefin can include polyethylene (PE), polypropylene (PP), polyvinylidene fluoride (PVDF), acrylic, acrylamide, polyvinylpyrrolidone (PVP), co-polymers thereof, and / or combinations thereof. For example, the binder can include polyvinylene chloride, poly(phenylene oxide) (PPO), polyethylene-block-poly(ethylene glycol), poly(ethylene oxide) (PEO), poly(phenylene oxide) (PPO), polyethylene-block-poly(ethylene glycol), polydimethylsiloxane (PDMS), polydimethylsiloxane-coalkylmethylsiloxane, co-polymers thereof, and / or combinations thereof. In some embodiments, the binder may include a thermoplastic. In some embodiments, the binder comprises a fibrillizable and / or fibrillized polymer. In some embodiments, the binder comprises a cellulosic binder. In certain embodiments, the binder comprises, consists essentially, or consists of a single fibrillizable and / or fibrillized binder, such as PTFE. In someembodiments, the electrode film includes, includes about, includes at most, or includes at most about, 1 wt.%, 2 wt.%, 3 wt.%, 4 wt.%, 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, 10 wt.%, or any range of values therebetween, of a binder.

[0040] In some embodiments, the electrode film can be a wet processed electrode film. In some embodiments, the electrode film is prepared by a wet or slurry-based electrode fabrication process. In some embodiments, the electrode film of the present disclosure can be a dry processed electrode film. In some embodiments, the electrode film is prepared by a dry electrode fabrication process. As used herein, a dry electrode fabrication process can refer to a process in which no or substantially no solvents are used to form a dry electrode film. For example, components of the active layer or electrode film, including carbon materials and binders, may comprise, consist of, or consist essentially of dry particles. The dry particles for forming the active layer or electrode film may be combined to provide a dry particle active layer mixture. In some embodiments, the active layer or electrode film may be formed from the dry particle active layer mixture such that weight percentages of the components of the active layer or electrode film and weight percentages of the components of the dry particles active layer mixture are substantially the same. In some embodiments, the active layer or electrode film formed from the dry particle active layer mixture using the dry fabrication process may be free from, or substantially free from, any processing additives such as solvents and solvent residues resulting therefrom. In some embodiments, the resulting active layer or electrode films are self-supporting films formed using the dry process from the dry particle mixture. In some embodiments, the resulting active layer or electrode films are free-standing films formed using the dry process from the dry particle mixture. A process for forming an active layer or electrode film can include fibrillizing the fibrillizable binder component(s) such that the film comprises fibrillized binder. In further embodiments, a free-standing active layer or electrode film may be formed in the absence of a current collector. In still further embodiments, an active layer or electrode film may comprise a fibrillized polymer matrix such that the film is self-supporting. It is thought that a matrix, lattice, or web of fibrils can be formed to provide mechanical structure to the electrode film.

[0041] In some embodiments, an electrode film is disposed on a current collector to form an electrode. In some embodiments, a current collector can include a metallic material, such as a material comprising aluminum, nickel, copper, combinations of the foregoing. Insome embodiments, a current collector comprises a pure metal. In some embodiments, a current collector comprises a metallized polymer film or metal coated polymer film. In some embodiments, the polymer comprises polyethylene terephthalate (PET), biaxially oriented polypropylene (BOPP) or a combination thereof. In some embodiments, the metal coating comprises aluminum. In some embodiments, coating the final electrode film mixture comprises forming a uniform electrode film mixture coating. In some embodiments, the current collector comprises a thickness of, of about, of at most, or at most about, 200 pm, 100 pm, 50 pm, 40 pm, 30 pm, 20 pm, 15 pm, 10 pm, 5 pm, or any range of values therebetween.Electrodes and Energy Storage Devices

[0042] Energy storage systems or devices that may be formed by utilizing the lithium product, or materials processed from the lithium product, are described herein. An energy storage system or device includes a positive electrode (i.e., cathode), a negative electrode (i.e., anode), a separator and an electrolyte positioned within a housing. Each electrode includes an electrode film disposed over a current collector. The electrode includes an electrode film disposed over a current collector. In some embodiments, the current collector is a foil. In some embodiments, the current collector is aluminum foil, copper foil, or combinations thereof. In some embodiments, a current collector can include a metallic material, such as a material comprising aluminum, nickel, copper, or combinations of the foregoing. In some embodiments, a current collector comprises a pure metal. In some embodiments, a current collector comprises a metallized polymer film or metal coated polymer film. In some embodiments, the polymer comprises polyethylene terephthalate (PET), biaxially oriented polypropylene (BOPP), or a combination thereof. In some embodiments, the metal coating comprises aluminum. In some embodiments, coating the final electrode film mixture comprises forming a uniform electrode film mixture coating. In some embodiments, the current collector comprises a thickness of, of about, of at most, or at most about, 200 pm, 100 pm, 50 pm, 40 pm, 30 pm, 20 pm, 15 pm, 10 pm, 5 pm, or any range of values therebetween. In some embodiments, an active layer is disposed on each side of the current collector.

[0043] In some embodiments, an electrode is a double-sided electrode. In some embodiments, the double-sided electrode includes two electrode films. In some embodiments,the double-sided electrode may include a current collector, a top electrode film, and a bottom electrode film. In some embodiments, each of the two electrode films can have any suitable shape, size and thickness.

[0044] In some embodiments, the energy storage device comprises a separator, an anode electrode, the cathode electrode, an electrolyte, and a housing, wherein the electrolyte, separator, anode electrode and cathode electrode are disposed within the housing and the separator is positioned between the anode and cathode electrodes. In some embodiments, an energy storage device is formed by placing an electrolyte, a separator, an anode electrode and the cathode electrode described herein within a housing, wherein the separator is placed between the anode electrode and the cathode electrode.

[0045] An electrode assembly includes a cathode, an anode, and a separator between the anode and cathode. In some embodiments, the electrode assembly is a wound electrode (i.e., rolled electrode) assembly (e.g., a jelly roll). In some embodiments, the energy storage device is selected from the group consisting of a cylindrical energy storage device, a stacked prismatic energy storage device, and a spiral-wound prismatic energy storage device.

[0046] The electrode disclosed herein may be used for an energy storage device. In some embodiments, the energy storage device comprises a separator, an anode electrode, a cathode electrode, an electrolyte, and a housing, wherein the electrolyte, separator, anode electrode and cathode electrode are disposed within the housing and the separator is positioned between the anode and cathode electrodes. In some embodiments, an energy storage device is formed by placing an electrolyte, a separator, an anode electrode and the cathode electrode described herein within a housing, wherein the separator is placed between the anode electrode and the cathode electrode. In some embodiments, the energy storage device comprises an anode electrode positioned between two cathode electrodes. In some embodiments, the anode electrode and / or the cathode electrode comprises a shaped electrode film. In some embodiments, the energy storage device is a lithium-ion battery. In some embodiments, the energy storage devices may be a battery, capacitor, capacitor-battery hybrid, fuel cell, or combinations thereof. In some embodiments, the energy storage system or energy storage device may be used for electromobility. In some embodiments, the energy storage device may be used in motor vehicles, including hybrid electric vehicles (HEV), plug-in hybrid electric vehicles (PHEV), and / or electric vehicles (EV). In some embodiments, the energy storagedevice used in motor vehicles, including hybrid electric vehicles (HEV), plug-in hybrid electric vehicles (PHEV), and / or electric vehicles (EV) reduces greenhouse gas emissions.

[0047] In some embodiments, the energy storage device is charged with a suitable lithium-containing electrolyte. For example, the energy storage device can include a lithium salt, and a solvent, such as a non-aqueous or organic solvent. Generally, the lithium salt includes an anion that is redox stable. In some embodiments, the anion can be monovalent. In some embodiments, a lithium salt can be selected from lithium hexafluorophosphate (LiPFe), lithium bis(trifluoromethanesulfonyl)imide (LiFSI), lithium tetrafluoroborate (LiBF4), lithium perchlorate (LiC104), lithium bis(trifluoromethansulfonyl)imide (LiN / SChCF^ ), lithium trifluoromethansulfonate (L1SO3CF3), lithium bis(oxalato)borate (LiB(C2O4)2), lithium bis(fhrorosulfonyl)imide (LiN(SO2F)2, lithium difluoro(oxalato)borate (LiC2BF2O4) and combinations thereof. In some embodiments, the electrolyte can include a quaternary ammonium cation and an anion selected from the group consisting of hexafluorophosphate, tetrafluoroborate and iodide. In some embodiments, the salt concentration can be about 0.1 mol / L (M) to about 5 M, about 0.2 M to about 3 M, or about 0.3 M to about 2 M. In further embodiments, the salt concentration of the electrolyte can be about 0.7 M to about 2 M. In certain embodiments, the salt concentration of the electrolyte can be about 0.2 M, about 0.3 M, about 0.4 M, about 0.5 M, about 0.6 M, about 0.7 M, about 0.8 M. about 0.9 M, about 1 M, about 1.1 M, about 1.2 M, 1.3M, 1.4M, 1.5M or values therebetween.

[0048] In some embodiments, an energy storage device can include a liquid solvent. The solvent need not dissolve every component, and need not completely dissolve any component, of the electrolyte. In further embodiments, the solvent can be an organic solvent. In some embodiments, a solvent can include one or more functional groups selected from dioxathiolane (e.g., l,3,2-dioxathiolane-2,2-dioxide (i.e., “DTD”)), carbonates, ethers and / or esters. In some embodiments, the solvent can comprise a carbonate. In further embodiments, the carbonate can be selected from cyclic carbonates such as, for example, ethylene carbonate (EC), propylene carbonate (PC), vinyl ethylene carbonate (VEC), vinylene carbonate (VC), fluoroethylene carbonate (FEC), and combinations thereof, or acyclic carbonates such as, for example, dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), 1,3-propene sultone (PRS), and combinations thereof. In some embodiments, the solvent can comprise an ester. In some embodiments, the ester is selected from methyl acetate (MA),methyl propionate (MP), ethyl acetate (EA), methyl butyrate (MB), and combinations thereof. In some embodiments, the solvent may include EC, PC, VEC, VC, FEC, DMC, DEC, EMC, MA, MP, EA, MB, and combinations thereof. In some embodiments, the solvent may include EC, DMC, DEC, EMC, MA, and combinations thereof. In some embodiments, the solvent may include EC, DMC, EMC, and combinations thereof. In some embodiments, the solvent may include a ratio of EC:DMC:EMC of 10-30:0-90:0-70.

[0049] In some embodiments, one or more solvents can be used at a concentration of, of about, of at least, or at least about, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, 50 wt.%, 55 wt.%, 60 wt.%, 65 wt.%, 70 wt.%, 75 wt.%, 80 wt.%, 85 wt.% or 90 wt.%, or any range of values therebetween. In some embodiments, solvents are utilized as additives in the electrolyte system, and can be used at a concentration of, of about, of at most, or at most about, 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, 1 wt.%, 1.1 wt.%, 1.2 wt.%, 1.3 wt.%, 1.4 wt.%, 1.5 wt.%, 1.6 wt.%, 1.7 wt.%, 1.8 wt.%, 1.9 wt.%, 2 wt.%, 2.1 wt.%, 2.2 wt.%, 2.3 wt.%, 2.4 wt.%, 2.5 wt.%, 2.6 wt.%, 2.7 wt.%, 2.8 wt.%, 2.9 wt.%, 3 wt.%, 4 wt.%, 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.% or 10 wt.%, or any range of values therebetween. For example, in some embodiments, the amount of an additive in the electrolyte is or is about in any one of the following ranges: 0.1-10 wt.%, 1-6 wt.%, 2-5 wt.%, 0.1-6 wt.%, 2-8 wt.%, 2-3 wt.%, or 1-4 wt.%.

[0050] In some embodiments, an energy storage device is created such that one electrode (e.g., anode) is larger than and overhangs the other electrode (e.g., cathode). One electrode may overhang the other in the winding direction and / or non-winding direction of the electrode assembly. Such electrode overhangs may avoid yield losses. In some embodiments, where there is no, or is substantially no, overlap and / or intermingling of the separator and the shaped electrode film (e.g., cathode electrode film), the boundary of the shaped electrode film is easier to identify and therefore improves the ability to form a counter electrode (e.g., anode electrode) with an overhang.

[0051] A method of preparing a rolled electrode assembly may include preparing an electrode assembly and rolling the electrode assembly to form a rolled electrode assembly. The method of forming an energy storage device may include preparing the rolled electrode assembly and disposing the rolled electrode assembly and an electrolyte within a housing.EXAMPLES

[0052] FIG. 3 is an example process 300 for extracting lithium from a lithium mineral using a recycled soda ash leach process. In process 300, spodumene 302 (i.e., a- LiAlSi2Oe) is calcinated by heating with the heat generated by combusting a carbon fuel source to form a calcinated spodumene 306 (i.e., P-LiAlSi20e) and CO2 308. An NaCl salt 310 and H2O 312 are combined with NH3 328 to form an ammoniated brine 314, which is combined with the CO2 308 of the calcination process in a carbonating tower 316 to form solid NaHCCh 320 and aqueous NH4CI 322. A solid / liquid filtration 318 is performed to separate the solid NaHCCh 320 and aqueous NH4CI 322, wherein an ammonia recovery process 324 is performed to produce an aqueous HC1 byproduct and NH3 328 that is utilized to form the ammoniated brine 314 previously discussed. The solid NaHCCh 320 is processed in a soda ash dry 330 to produce regenerated CO2 332 and Na2CO3 334. The regenerated CO2 332 is combined with the CO2 308 of the calcination process prior to processing by the carbonating tower 316. The Na2CC>3 334 is then combined with the calcinated spodumene 306 and a spodumene leaching process 336 is performed to produce a depleted mineral (i.e., NaAlSi2Oe) and a leach solution comprising U2CO3. The Li2CCh is reacted with a base (e.g., Ca(OH)2) to produce LiOFFFEO.

[0053] While certain embodiments of the inventions have been described, these embodiments have been presented by way of example only, and are not intended to limit the scope of the disclosure. Indeed, the novel methods and systems described herein may be embodied in a variety of other forms. Furthermore, various omissions, substitutions and changes in the systems and methods described herein may be made without departing from the spirit of the disclosure. The accompanying claims and their equivalents are intended to cover such forms or modifications as would fall within the scope and spirit of the disclosure. Accordingly, the scope of the present inventions is defined only by reference to the appended claims.

[0054] Features, materials, characteristics, or groups described in conjunction with a particular aspect, embodiment, or example are to be understood to be applicable to any other aspect, embodiment or example described in this section or elsewhere in this specification unless incompatible therewith. All of the features disclosed in this specification (including any accompanying claims, abstract and drawings), and / or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations where at leastsome of such features and / or steps are mutually exclusive. The protection is not restricted to the details of any foregoing embodiments. The protection extends to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any novel one, or any novel combination, of the steps of any method or process so disclosed.

[0055] Furthermore, certain features that are described in this disclosure in the context of separate implementations can also be implemented in combination in a single implementation. Conversely, various features that are described in the context of a single implementation can also be implemented in multiple implementations separately or in any suitable subcombination. Moreover, although features may be described above as acting in certain combinations, one or more features from a claimed combination can, in some cases, be excised from the combination, and the combination may be claimed as a subcombination or variation of a subcombination.

[0056] Moreover, while operations may be depicted in the drawings or described in the specification in a particular order, such operations need not be performed in the particular order shown or in sequential order, or that all operations be performed, to achieve desirable results. Other operations that are not depicted or described can be incorporated in the example methods and processes. For example, one or more additional operations can be performed before, after, simultaneously, or between any of the described operations. Further, the operations may be rearranged or reordered in other implementations. Those skilled in the art will appreciate that in some embodiments, the actual steps taken in the processes illustrated and / or disclosed may differ from those shown in the figures. Depending on the embodiment, certain of the steps described above may be removed, others may be added. Furthermore, the features and attributes of the specific embodiments disclosed above may be combined in different ways to form additional embodiments, all of which fall within the scope of the present disclosure. Also, the separation of various system components in the implementations described above should not be understood as requiring such separation in all implementations, and it should be understood that the described components and systems can generally be integrated together in a single product or packaged into multiple products. For example, any of the components for an energy storage system described herein can be provided separately,or integrated together (e.g., packaged together, or attached together) to form an energy storage system.

[0057] For purposes of this disclosure, certain aspects, advantages, and novel features are described herein. Not necessarily all such advantages may be achieved in accordance with any particular embodiment. Thus, for example, those skilled in the art will recognize that the disclosure may be embodied or carried out in a manner that achieves one advantage or a group of advantages as taught herein without necessarily achieving other advantages as may be taught or suggested herein.

[0058] Conditional language, such as “can,” “could,” “might,” or “may,” unless specifically stated otherwise, or otherwise understood within the context as used, is generally intended to convey that certain embodiments include, while other embodiments do not include, certain features, elements, and / or steps. Thus, such conditional language is not generally intended to imply that features, elements, and / or steps are in any way required for one or more embodiments or that one or more embodiments necessarily include logic for deciding, with or without user input or prompting, whether these features, elements, and / or steps are included or are to be performed in any particular embodiment.

[0059] Conjunctive language such as the phrase “at least one of X, Y, and Z,” unless specifically stated otherwise, is otherwise understood with the context as used in general to convey that an item, term, etc. may be either X, Y, or Z. Thus, such conjunctive language is not generally intended to imply that certain embodiments require the presence of at least one of X, at least one of Y, and at least one of Z.

[0060] Language of degree used herein, such as the terms “approximately,” “about,” “generally,” and “substantially” as used herein represent a value, amount, or characteristic close to the stated value, amount, or characteristic that still performs a desired function or achieves a desired result. For example, the terms “approximately”, “about”, “generally,” and “substantially” may refer to an amount that is within less than 10% of, within less than 5% of, within less than 1% of, within less than 0.1% of, and within less than 0.01% of the stated amount, depending on the desired function or desired result.

[0061] The scope of the present disclosure is not intended to be limited by the specific disclosures of preferred embodiments in this section or elsewhere in this specification, and may be defined by claims as presented in this section or elsewhere in this specification oras presented in the future. The language of the claims is to be interpreted broadly based on the language employed in the claims and not limited to the examples described in the present specification or during the prosecution of the application, which examples are to be construed as non-exclusive.

Claims

WHAT IS CLAIMED IS:

1. A process for extracting lithium from a lithium mineral, comprising: calcinating a lithium mineral with heat from combusting a carbon fuel source to form a calcinated lithium mineral and a combustion byproduct comprising CO2; reacting the CO2 of the combustion byproduct with a brine mixture comprising NaCl, NH3 and water to form a byproduct-brine mixture comprising NH4CI and NaHCCh; removing the NH4CI from the byproduct-brine mixture to form an intermediate reaction product comprising NaHCCh; processing the removed NH4CI to form NH3 and a byproduct HC1; recycling the NH3 into the brine mixture; decomposing the intermediate reaction product to form a regenerated CO2 and a reaction product comprising Na2COs; recycling the regenerated CO2 into the byproduct-brine mixture; combining the reaction product with the calcinated lithium mineral to form a slurry comprising a depleted mineral and a leach solution; and processing the leach solution to form a lithium product comprising lithium hydroxide.

2. A process for extracting lithium from a lithium mineral, comprising: calcinating a lithium mineral with heat from combusting a carbon fuel source to form a calcinated lithium mineral and a combustion byproduct comprising CO2; reacting the CO2 of the combustion byproduct with a brine mixture comprising NaCl and water to form a reaction product comprising Na2COs; and combining the reaction product with the calcinated lithium mineral to form a slurry comprising a depleted mineral and a leach solution, wherein the leach solution comprises lithium.

3. The process of Claim 2, further comprising combining NaCl and water to form the brine mixture.

4. The process of Claim 2 or 3, wherein the brine mixture further comprises NH3.

5. The process of Claim 4, wherein reacting the CO2 of the combustion byproduct with a brine mixture forms a byproduct-brine mixture comprising NH4CI.

6. The process of Claim 5, further comprising removing the NH4CI from the byproduct-brine mixture to form an intermediate reaction product.

7. The process of Claim 6, further comprising processing the removed NH4CI to form a regenerated NH3 and a byproduct HC1.

8. The process of Claim 7, further comprising recycling the regenerated NH3 into the brine mixture.

9. The process of any one of Claims 6-8, wherein the intermediate reaction product comprises NaHCCh, and the intermediate reaction product is decomposed to form the reaction product and a regenerated CO2.

10. The process of Claim 9, further comprising combining the regenerated CO2 with the CO2 of the combustion byproduct.

11. The process of any one of Claims 2-10, wherein the lithium mineral is selected from spodumene, lepidolite, zinnwaldite, smectite, hectorite, muscovite, and combinations thereof.

12. The process of Claim 11, wherein the lithium mineral comprises spodumene.

13. The process of any one of Claims 2-11, wherein the process does not include combining an additional Na2CO3 different from the ISfeCCh of the reaction product with the calcinated lithium mineral.

14. The process of any one of Claims 2-12, further comprising processing the leach solution to form a lithium product comprising lithium hydroxide.

15. The process of Claim 9 or 10, wherein the CO2 utilized in the process is sourced from the combustion byproduct, the regenerated CO2, or combinations thereof.

16. The process of any one of Claims 2-12, wherein the leach solution has a pH of at least about 4.

17. The process of any one of Claims 2-12, wherein the leach solution has an extraction efficiency of at least about 20%.

18. The process of Claim 9 or 10, further comprising capturing CO2 of the combustion byproduct, the regenerated CO2, or combinations thereof.

19. The process of Claim 14, further comprising isolating the lithium hydroxide.

20. A process of preparing a cathode active material, comprising: performing the process of Claim 19; andreacting the lithium hydroxide with a cathode active material precursor to form a cathode active material.

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