Process for recovering materials from used rechargeable lithium batteries

Abstract

A method for recovering values ​​from energy storage devices (e.g., spent rechargeable lithium batteries, particularly those using nickel-based or nickel- and cobalt-containing cathode materials) is described. In particular, the proposed method uses carbonyl technology, also known as steam metallurgy, to regenerate pure materials that can be reused as feedstock for making active cathode materials for new lithium batteries.

Description

[Technical field]

[0001] [CROSS REFERENCE TO RELATED APPLICATIONS] All applications in which a foreign or domestic priority claim is identified in an Application Data Sheet or Request filed along with this application, such as U.S. Provisional Application No. 63 / 130,196, filed December 23, 2020, are incorporated by reference herein under 37 CFR 1.57 and Rules 4.18 and 20.6.

[0002] The present invention relates to a method for recovering values ​​from used rechargeable lithium batteries, particularly batteries having nickel-based cathodes. In particular, the method provided relates to the recovery of essentially pure materials that can be reused as raw materials in the manufacture of active cathode material for new rechargeable lithium batteries. [Background technology]

[0003] Since their commercialization, rechargeable lithium batteries have been used as energy storage components in a variety of devices and equipment, including mobile phones, portable computers, wireless power tools, hybrid and pure electric vehicles, etc. In recent years, the demand for high-power rechargeable lithium batteries has increased dramatically, especially with the rapid market growth of electric vehicles (EVs).

[0004] The main components of a rechargeable lithium battery include an anode, a cathode, and an electrolyte. During charge-discharge cycles, lithium ions shuttle between the anode and cathode active materials through the electrolyte. Due to its limited specific capacity, high manufacturing cost, and the use of expensive raw materials including lithium, nickel, and cobalt, the cathode active material is usually the most expensive component in a rechargeable lithium battery. In recent years, nickel-rich high-capacity cathode materials have been gaining market share in batteries for the EV market. This trend is expected to continue for the next decade. Considering the expected tremendous growth of the EV market, and thus the huge demand for the above cathode materials, the production of rechargeable lithium batteries may be limited in the future by the global supply shortage of critical elements (e.g., Ni, Co, and Li), especially in unstable geopolitical situations. Therefore, recycling used rechargeable lithium batteries to recover some or all of these critical elements may help alleviate the demand for raw materials and protect the supply chain of the electric vehicle industry. Furthermore, used rechargeable lithium batteries are considered to be environmentally harmful and a fire hazard, and it is important that they are recycled and reprocessed to sustain the large EV market.

[0005] Most research and development in the recycling and regeneration of rechargeable lithium batteries has focused on acid leaching technology. In general, the process involves several major steps: (a) discharging the used batteries; (b) dismantling the batteries and separating the battery components; (c) leaching out the desired metals using acid leaching and isolating them using a hydrometallurgical approach; and (d) using these metals to regenerate the cathode material using conventional existing industrial methods, i.e., co-precipitation of the metals to produce precursors and calcination with lithium compounds to obtain the final cathode material. Typically, such acid processes use sulfuric acid and other chemicals (e.g., Na) to leach out the metals in step (c). 2 SO 5 and Na 2 SO 3) is applied. A solvent extraction process can then be used to separate the different metals with organic extractants such as di-2-ethylhexyl phosphoric acid ("P204") and 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester ("P507"). However, this is a complex process with large amounts of liquid effluent generated, which must be treated to minimize environmental impact. The process can perform a solvent-free extraction step for metal separation, but such solvent-free processes can typically only be used on spent batteries with the same composition, and the purity of the cathode material regenerated without solvent extraction is significantly lower, since the metal separation step is also considered as a purification step.

[0006] Furthermore, since the valuable metals recovered from spent batteries using the above-mentioned acid leaching process must be in the form of metal salts such as nickel sulfate and cobalt sulfate, a co-precipitation process to make precursors is usually used to regenerate the cathode material. Such co-precipitation processes typically contain significant amounts of Na after removing the solid portion in a filtration process. 2 SO 4 A solution containing Na 2 SO 4 Since the collected solution contains 1,0 ... the collected solution cannot be reused in the reaction system and must therefore be treated as effluent. Furthermore, ammonia is usually added to the reaction system as a chelating agent to help provide the desired physical properties of the precursor material. Thus, in addition to salts (such as sodium sulfate), the effluent may also contain ammonia, ammonium, dissolved heavy metals, small solid particles, and the like. As required by regulations worldwide, the effluent must undergo treatment to remove ammonia and sodium sulfate before it can be discharged to the environment or recycled into the reaction system. Such effluent treatment involves a huge amount of energy consumption and is costly. Furthermore, sodium sulfate is generally considered a solid waste after effluent treatment, with little or no added value, due to its limited industrial use and demand.

[0007] Thus, current methods of acid leaching and hydrometallurgy processes for recycling rechargeable lithium batteries not only generate large amounts of liquid effluent themselves, but also lead to the use of traditional cathode material manufacturing techniques that generate more liquid effluent in the process, which creates a large environmental footprint in the life cycle of an EV battery.

[0008] Although several environmentally friendly processes are known for producing rechargeable lithium battery cathode materials that attempt to minimize environmental impact and cost by avoiding the generation of effluents, such processes typically require nickel and cobalt in metallic powder form as starting materials, however, the majority of the nickel and cobalt from spent lithium is not in metallic powder form.

[0009] It would be advantageous to provide a process for recycling cathode material elements from spent batteries (e.g., spent rechargeable lithium batteries) that could provide a more environmentally friendly and cost-effective process for recovering key elements. Summary of the Invention

[0010] For purposes of summarizing the disclosure and the advantages achieved over the prior art, certain objects and advantages of the disclosure are described herein. Not all such objects or advantages may be achieved in any particular embodiment. Thus, for example, one skilled in the art will understand that the invention may be embodied or implemented to achieve or optimize one or more advantages as taught herein, without necessarily achieving other objects or advantages as may be taught or suggested herein.

[0011] All of these embodiments are intended to be within the scope of the invention disclosed herein. These and other embodiments will become readily apparent to those of ordinary skill in the art from the following detailed description of the preferred embodiments, taken in conjunction with the accompanying drawings, and the invention is not limited to any particular preferred embodiment disclosed.

[0012] Thus, in a first aspect, a process is disclosed for recovering values ​​from spent rechargeable lithium batteries, particularly those using nickel-based and nickel- and cobalt-containing cathode materials, and for regenerating them into pure materials suitable, but not limited to, for a zero-emission process in the manufacture of cathode materials for new rechargeable lithium batteries.

[0013] In particular, one embodiment of the process preferably comprises the following main steps: discharging a used rechargeable lithium battery in an aqueous solution (e.g., saline solution); Dismantling the battery and separating the battery components; crushing the collected electrodes and separating the electrode material from other components; reducing the collected cathode electrode material together with the anode electrode material; and recovering valuable nickel and cobalt using carbonyl technology. Optionally, performing a carbonyl distillation step if the collected electrode material contains iron; recovering valuable lithium from the remaining electrode material after removal of nickel, iron (if present) and cobalt by water or acid leaching; Includes.

[0014] Thus, the present disclosure provides a process for recovering valuable elements from spent rechargeable lithium batteries and regenerating them into a form suitable for a zero-emission process in the remanufacturing of cathode materials for new rechargeable lithium batteries.

[0015] However, it should be noted that the use and applications of the elements recovered from the process of the present disclosure are not limited to the production of cathode materials for new rechargeable lithium batteries, as they may be used in other applications as well.

[0016] In one aspect, a process for recovering materials from an energy storage device electrode is described, the process including reducing an electrode active material mixture to form a reduced mixture, the electrode active material mixture including nickel oxide, cobalt oxide, and a lithium material selected from the group consisting of lithium salts, lithium oxides, and combinations thereof, performing a first carbonylation and subsequent first decomposition on the reduced mixture to isolate a nickel product comprising nickel metal and form a first carbonylation material, and performing a second decomposition on the first carbonylation material to isolate a cobalt product comprising cobalt metal and form a residue material.

[0017] In some embodiments, the reducing comprises reacting the electrode active material mixture with a compound selected from the group consisting of hydrogen, a carbonaceous material, a hydrocarbon material, a partially reformed product thereof, and combinations thereof. In some embodiments, the reducing is performed at a temperature of about 300-1200° C. In some embodiments, the first carbonylation comprises reacting the reduced mixture with a gas selected from the group consisting of carbon monoxide, nitric oxide, hydrogen, and combinations thereof. In some embodiments, the first carbonylation is performed at a temperature of about 40-120° C. In some embodiments, the first carbonylation is performed at a pressure of about 15-2000 PSIG.

[0018] In some embodiments, the process further comprises distilling the reduced mixture after the first carbonylation and before the first decomposition, thereby removing iron products comprising iron carbonyl from the reduced mixture. In some embodiments, the process further comprises mixing an additive with the reduced mixture. In some embodiments, the additive is a sulfur material, a tellurium material, Cl 2 , LiCl, NaCl, KCl, CaCl 2 , MgCl 2 and combinations thereof. In some embodiments, the additive is mixed with the reconstituted mixture at about 1-10% by weight of the reconstituted mixture.

[0019] In some embodiments, the process further comprises performing sublimation on the first carbonylation material prior to the second decomposition. In some embodiments, the process further comprises performing a second carbonylation on the first carbonylation material prior to the second decomposition. In some embodiments, the second carbonylation comprises reacting the reduced mixture with a gas comprising carbon monoxide. In some embodiments, the second carbonylation is performed at a temperature of about 40-120° C. In some embodiments, the second carbonylation is performed at a pressure of about 800-2500 PSIG. In some embodiments, the process further comprises performing a distillation on the first decarboxylated material after the second carbonylation and prior to the second decomposition.

[0020] In some embodiments, the process further includes discharging the energy storage device in an aqueous solution, dismantling the discharged energy storage device to separate the electrode material, and destructuring the electrode material to form an active material mixture. In some embodiments, the aqueous solution has a conductivity of at least about 1000 mS / m. In some embodiments, the aqueous solution has a Na 2 SO 4 , NaCl, and combinations thereof. In some embodiments, the destructuring forms an active material mixture including particles having an average particle size of up to about 5 mm. In some embodiments, the process further includes washing the destructured electrode material and separating the active material mixture from the current collector material. In some embodiments, the washing includes applying an organic solvent selected from the group consisting of N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide, N,N-dimethylacetamide, and combinations thereof. In some embodiments, the energy storage device is a spent lithium ion battery.

[0021] In some embodiments, the process further comprises performing a leach extraction to isolate the lithium product. In some embodiments, the leach extraction comprises dissolving the residual material in an aqueous solution to form a slurry, performing a solid-liquid separation on the slurry to isolate a lithium-rich solution from the solid residue, and performing an isolation process on the lithium-rich solution to form the lithium product. In some embodiments, the aqueous solution comprises an acid. In some embodiments, the lithium product is selected from the group consisting of lithium hydroxide, lithium carbonate, and combinations thereof. [Brief description of the drawings]

[0022] [Figure 1] FIG. 2 is a block diagram illustrating general process steps for recovering elements from spent batteries, according to one embodiment.

[0023] [Diagram 2] FIG. 1 is a block diagram illustrating carbonyl purification process steps, according to one embodiment.

[0024] [Diagram 3] FIG. 1 is a block diagram illustrating percolation extraction process steps, according to one embodiment.

[0025] [Figure 4] FIG. 2 is a block diagram illustrating certain process steps for recovering elements from spent batteries, according to one embodiment.

[0026] [Figure 5A] 1 is a Thermogravimetric Analyzer (TGA) result showing a plot of exhaust gas Ni(CO)4 concentration versus time.

[0027] [Figure 5B] 1 is a Thermogravimetric Analyzer (TGA) result showing a plot of the normalized weight of Ni(CO)4 in the exhaust gas versus elapsed time.

[0028] [Figure 6] 1 is a Thermogravimetric Analyzer (TGA) result showing the yield of total extractable metals versus time under various hydrogenation process conditions.

[0029] [Figure 7] 1 is a plot showing weight loss profile as a function of reduction temperature according to some embodiments.

[0030] [Figure 8A] 1 shows a powder X-ray diffraction (XRD) profile of a black mass material before reduction, according to some embodiments.

[0031] [Figure 8B] 1 shows a powder X-ray diffraction (XRD) profile of a reduced black mass material according to some embodiments.

[0032] [Figure 9A] 1 is a scanning electron microscope (SEM) image of nickel powder collected from the process of the present disclosure, according to some embodiments.

[0033] [Figure 9B] 1 is a scanning electron microscope (SEM) image of nickel powder collected from the process of the present disclosure, according to some embodiments.

[0034] [Figure 9C] 1 illustrates qualitative search / match results from powder X-ray diffraction (XRD) data of nickel powder collected from the process of the present disclosure, according to some embodiments. The major phase exhibits diffraction peaks consistent with face-centered cubic nickel (Fm-3m). The minor phase exhibits diffraction peaks consistent with hexagonal nickel (P63 / mmc).

[0035] [Figure 10A] 1 is a scanning electron microscope (SEM) image of nickel powder collected from the process of the present disclosure, according to some embodiments.

[0036] [Figure 10B] 1 is a scanning electron microscope (SEM) image of nickel powder collected from the process of the present disclosure, according to some embodiments.

[0037] [Figure 10C] FIG. 1 illustrates qualitative search / match results from powder X-ray diffraction (XRD) data of nickel powder collected from the process of the present disclosure, according to some embodiments.

[0038] [Figure 11A] 1 is a photographic image of a black mass, according to some embodiments.

[0039] [Figure 11B] 1 is a photographic image of reduced material according to some embodiments.

[0040] [Figure 11C] 1 is a photographic image of a refined nickel powder according to some embodiments.

[0041] [Figure 12] 1 is a graph showing the weight percent of control and additive materials over time when exposed to a process of the present disclosure, according to some embodiments.

[0042] Other embodiments of the invention are provided throughout this application. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0043] Various embodiments of processes are provided herein for recovering elements and compounds from energy storage devices (e.g., lithium ion batteries and used lithium ion batteries), their electrodes and intermediates (e.g., black mass, fines) of recycling processes. The chemical processes of the present disclosure can help overcome the environmental and cost-effective limitations of conventional recycling processes such as acid extraction processes, conventional solventless processes and conventional processes that do not produce effluents. In some embodiments, the process can be performed on wet or dry materials. In some embodiments, the process can be used to enrich metal (e.g., nickel cobalt, and / or iron)-containing powders by carbonyl treatment.

[0044] As part of the process, the disclosure includes a carbonyl refining method, also known as vapor metallurgical refining, for recovering valuable elements from spent lithium batteries. This refining technique is based on a chemical reaction in which the gaseous compound nickel tetracarbonyl is formed when pure or impure nickel metal is contacted with carbon monoxide at atmospheric pressure at a temperature of 50-60°C. The reaction is shown below: Ni(s)+4CO(g)→Ni(CO) 4 (g)

[0045] However, when nickel carbonyl is heated above about 220° C. (eg, about 220 to 250° C., about 400 to 500° C., about 220 to 900° C.), it decomposes to produce nickel metal and carbon monoxide. Ni(CO) 4 (g) → Ni(s) + 4CO(g) (In the formula, "g" and "s" represent "gas" and "solid," respectively.)

[0046] In materials including rechargeable lithium batteries and under the process conditions of the present disclosure, metal elements (e.g., nickel, cobalt and / or iron metals) can form carbonyl compounds, and carbonyl compounds formed from different metals have different formation and volatilization characteristics. Thus, this carbonyl purification method can be used to extract metals (e.g., nickel, cobalt and iron) from the mixture formed from the electrode and separate the individual metals from each other to form individual high purity metals. In some embodiments, using a specially designed decomposer, the purified nickel and cobalt elements can be recovered in their powder or solid form during the decomposition of the corresponding carbonyl. In some embodiments, the operation or conditions of the decomposer can be changed to allow for different forms and types of powders to be recovered.

[0047] The overall process of the present disclosure preferably includes the following main steps: discharging used rechargeable lithium batteries in an aqueous solution, dismantling the batteries and separating the battery components, reducing the collected cathode electrode material together with the anode electrode material, and recovering valuable nickel and cobalt by water leaching using carbonyl technology and lithium. For example, FIG. 1 shows a process 100 for recovering elements from used batteries according to one embodiment. The process 100 begins with discharging 102 the used batteries. In some embodiments, the discharging may be performed in an aqueous solution (e.g., saline). The discharged batteries are then dismantled (104) to separate the various battery components from the electrode material. For example, the electrodes (e.g., anode and cathode) may be separated and the electrode material (e.g., electrode film) may be isolated from the electrode foil. The electrode material is then destructured (e.g., crushed and / or reduced in size) (106) and the destructured electrode material is collected. In some embodiments, the cathode and anode electrode materials are destructured and collected together. The destructured electrode materials are subjected to a carbonyl refining process 108 to recover nickel and cobalt (110) and a leaching extraction (e.g., water leaching or acid leaching) 112 to recover lithium (114).

[0048] In some embodiments, the recovered nickel and cobalt are in their metallic form (e.g., powder). In some embodiments, the recovered lithium is in hydroxide or carbonate form. Such hydroxide, carbonate and / or metal materials may be used directly as feedstocks for manufacturing lithium battery cathode materials using the disclosed processes that do not generate effluents. In some embodiments, such recovered metals may also be used in other industries, such as powder metallurgy.

[0049] As mentioned above, used rechargeable lithium batteries are preferably discharged with an aqueous solution (e.g., saline) to reduce the potential risk of short circuit or battery explosion. In some embodiments, the solution may be an aqueous solution having a conductivity of about, at least, or at least about 800 mS / m, 1000 mS / m, 1500 mS / m, 2000 mS / m, 2500 mS / m, 3000 mS / m, 3500 mS / m, 4000 mS / m, 45000 mS / m, 5000 mS / m, 6000 mS / m, 8000 mS / m, or 10000 mS / m, or any value range therebetween. In some embodiments, the aqueous solution may be Na 2 SO 4 , NaCl or a combination thereof.

[0050] After discharge, the used rechargeable lithium battery is mechanically disassembled to remove the housing. After removing the housing, the electrode is destructured (such as by crushing or shredding) to form particles. In some embodiments, the destructured particles have an average particle size of about, at most, or at most about 0.1 mm, 0.5 mm, 0.8 mm, 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 8 mm, or 10 mm, or any range of values ​​therebetween. In some embodiments, a solvent (e.g., an organic solvent) can be used to wash the destructured particles. In some embodiments, the washing serves to remove the electrode active material from the current collector and remove the electrode binder material (e.g., polyvinylidene fluoride (PVDF)). In some embodiments, the solvent comprises N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide, N,N-dimethylacetamide, or a combination thereof. In some embodiments, a filtration process can be used to separate the solvent from the destructured electrode material (i.e., the electrode active material and the current collector). The solvent can be reused after binder removal by evaporation of the solvent. In some embodiments, a screening operation is then used to remove current collector materials, binders, and / or battery electrolyte to form an electrode active material mixture, resulting in a mixture of electrode active materials (i.e., anode active materials and cathode active materials (e.g., transition metal oxides)). The electrode active material mixture may include lithium salts, transition metal oxides (e.g., nickel, cobalt, and lithium oxides), carbon materials (e.g., graphite, activated carbon), and other organic and / or inorganic impurities.

[0051] After the electrode active material mixture is obtained, a carbonyl process is performed to recover nickel and cobalt in their metallic forms. For example, FIG. 2 shows a carbonyl purification process 200 for recovering metallic nickel and cobalt from the electrode active material mixture. The electrode active material mixture is reduced (202), followed by a first carbonylation 204. Decomposition 206 is performed on the first carbonylation material to obtain recovered nickel metal (208), and the first carbonylation 204 and decomposition 206 may be repeated to obtain additional recovered nickel metal (208). In some embodiments, an optional distillation 205 is performed after the first carbonylation 204 and before the decomposition 206 to separate nickel materials (e.g., nickel carbonyl) from iron materials (e.g., iron carbonyl) (209). If the feedstock contains Fe or a significant amount of Fe, the optional distillation 205 may be performed. In some embodiments, if the feedstock is free (or substantially free) of Fe, or contains negligible or very low amounts of Fe, optional distillation 205 is not performed. The isolated iron material 209 may be decomposed to obtain recovered iron metal. A second carbonylation 210 is performed on the remaining first carbonylation material, absent recovered nickel metal. Distillation 212 and subsequent decomposition 214 are performed on the second carbonylation material to obtain recovered cobalt metal (216), and the second carbonylation 210, distillation 212 and decomposition 214 may be repeated to obtain additional recovered cobalt metal (216). A residue material 218 remains after performing the carbonyl purification process 200 and includes lithium and carbon materials (e.g., graphite, activated carbon).

[0052] In some embodiments, the reduction of the electrode active material mixture is performed using hydrogen, carbonaceous materials, hydrocarbon materials (e.g., coke, pitch, or combinations thereof), partially reformed gaseous forms thereof, and combinations thereof. In some embodiments, the reduction is performed in a reducing atmosphere. In some embodiments, the reducing atmosphere comprises hydrogen gas. In some embodiments, carbon-containing materials remaining in the electrode active material mixture (e.g., activated carbon and graphite) are utilized as the reducing agent. In some embodiments, the reduction process is performed under mild conditions such that the carbon-containing materials are not consumed, are not substantially consumed, or are not completely consumed during the reduction process.

[0053] In some embodiments, the reduction is carried out at a temperature of about, at least, or at least about 200° C., 250° C., 300° C., 350° C., 400° C., 450° C., 500° C., 550° C., 600° C., 650° C., 700° C., 800° C., 900° C., 1000° C., 1100° C., 1200° C., 1300° C., 1500° C., or 1800° C., or any range of values ​​therebetween. For example, in some embodiments, the reduction temperature ranges between 300-1200° C., 450-600° C., or 500-1000° C. In some embodiments, the atmosphere during reduction includes nitrogen, hydrogen, carbon monoxide, or a combination thereof. In some embodiments, the reduction atmosphere contains nitrogen and hydrogen, or carbon monoxide and hydrogen.

[0054] An exemplary mechanism for the reduction reaction is as follows: 4LiNiO 2 +3C→2Li 2 O+3CO 2 +4Ni, 4LiCoO 2 +3C→2Li 2 O+3CO 2 +4Co and / or 2LiNiO 2 +3H 2 →Li 2 O+3H 2 O+2Ni, 2LiCoO2 +3H 2 →Li 2 O+3H 2 O+2Co and / or 2LiNiO 2 +3CO→Li 2 O+3CO 2 +2Ni, 2LiCoO 2 +3CO→Li 2 O+3CO 2 +2Co and / or 2Li(M)O 2 +3H 2 →Li 2 O+3H 2 O+2M In some embodiments, the lithium mixed metal dioxide (i.e., 2Li(M)O) shown in the above scheme is 2 In some embodiments, "M" comprises a metal element. In some embodiments, the metal element comprises Ni, Co, Fe, Mn, Al, Zr, Ca, or a combination thereof. For example, in some embodiments, M comprises at least Ni, Co, and / or Fe. In some embodiments, M comprises about, at least, or at least about 0.1 mol%, 0.5 mol%, 1 mol%, 5 mol%, 10 mol%, 20 mol%, 30 mol%, 40 mol%, 50 mol%, 60 mol%, 70 mol%, 80 mol%, 90 mol%, 95 mol%, or 100 mol%, or any range of values ​​therebetween, of each metal element M that it independently comprises. For example, in some embodiments, 2Li(M)O 2 is Li(Ni x Mn y Co z )O 2 , Li(Ni x )O 2 , or Li(Ni x Mn z Al z), where x, y, and z represent different mole % of each metal element present in M. In such embodiments, the reduction step involves a chemical reaction of nickel and cobalt from a valence of +3 to a valence of 0. In some embodiments, the results from the reduction of the lithium mixed metal dioxide may include metal oxide phases of individual metals (e.g., "M"; e.g., nickel, iron, and / or cobalt), metal alloys, and / or individual metals or metal alloys (e.g., nickel, cobalt, iron, manganese, aluminum, zirconium, and / or calcium). In some embodiments, the reduction conditions are configured to maximize the amount of nickel and cobalt produced in metallic form.

[0055] After reduction is complete, the reduced mixture is transferred under inert conditions (e.g., helium, nitrogen, and / or argon gas) to a carbonylation reactor (e.g., a first or second carbonylation reactor). In some embodiments, the first and second carbonylation reactors are the same or different reactors. In some embodiments, the reduced mixture is maintained at a temperature of about, at or up to about 20° C., 25° C., 30° C., 40° C., 50° C., 55° C., 60° C., 70° C., or 80° C., or any range of values ​​therebetween. The first carbonylation process is carried out by passing carbon monoxide gas through the reduced mixture to produce gaseous nickel carbonyl. In some embodiments, the first carbonylation is carried out at a pressure of about, at least, or at least about 14 PSIG, 15 PSIG, 20 PSIG, 50 PSIG, 100 PSIG, 150 PSIG, 200 PSIG, 250 PSIG, 300 PSIG, 400 PSIG, 500 PSIG, 600 PSIG, 700 PSIG, 800 PSIG, 900 PSIG, 1000 PSIG, 1100 PSIG, 1200 PSIG, 1300 PSIG, 1500 PSIG, 1800 PSIG, 2000 PSIG, 2200 PSIG, 2500 PSIG, 3000 PSIG, 3500 PSIG, or 4000 PSIG, or any range of values ​​therebetween. In some embodiments, the first carbonylation is carried out at a temperature of about, at most, or up to about 20° C., 30° C., 40° C., 50° C., 60° C., 70° C., 80° C., 90° C., 100° C., 120° C., 140° C., 150° C., 180° C., or 200° C., or any range of values ​​therebetween. In some embodiments, the first carbonylation is carried out at a pressure of 800-2000 PSIG and a temperature of 80-150° C.

[0056] Upon completion of the first carbonylation step, the nickel, iron and cobalt have been partially, substantially or completely converted to binary metal carbonyls. Nickel carbonyl and iron carbonyl, if present, are in their gaseous form and are removed from the remaining solid mixture in the carbonylation vessel. However, the cobalt carbonyl, Co, formed in the process 2 (CO) 8is in solid form due to its low volatility under such conditions. The separated nickel carbonyl and / or iron carbonyl can be heated and decomposed in a decomposition chamber to form pure metallic nickel and / or iron and carbon monoxide. In some embodiments, when a sufficient amount of iron carbonyl is present, Ni(CO) 4 and Fe(CO) 5 can be separated (e.g., by distillation) prior to decomposition. In some embodiments, nickel carbonyl is heated to form nickel metal at a temperature of about, at least, or at least about 200° C., 220° C., 250° C., 300° C., 350° C., 400° C., 450° C., 500° C., 600° C., 700° C., 800° C., 900° C., 1000° C., or 1200° C., or any range of values ​​therebetween. In some embodiments, iron carbonyl is heated to form iron metal at a temperature of about, at least, or at least about 200° C., 220° C., 250° C., 300° C., 350° C., 400° C., 450° C., 500° C., 600° C., 700° C., 800° C., 900° C., 1000° C., or 1200° C., or any range of values ​​therebetween.

[0057] After nickel and iron are removed by carbonylation, cobalt carbonyl (i.e., Co 2 (CO) 8) is converted to a volatile metal carbonyl in a second carbonylation process. In some embodiments, the second carbonylation is carried out at a pressure of about, at least, or at least about 14 PSIG, 15 PSIG, 20 PSIG, 50 PSIG, 100 PSIG, 150 PSIG, 200 PSIG, 250 PSIG, 300 PSIG, 400 PSIG, 500 PSIG, 600 PSIG, 700 PSIG, 800 PSIG, 900 PSIG, 1000 PSIG, 1100 PSIG, 1200 PSIG, 1300 PSIG, 1500 PSIG, 1800 PSIG, 2000 PSIG, 2200 PSIG, 2500 PSIG, 3000 PSIG, 3500 PSIG, or 4000 PSIG, or any range of values ​​therebetween. In some embodiments, the second carbonylation is carried out at a temperature of about, at most, or up to about 20° C., 30° C., 40° C., 50° C., 60° C., 70° C., 80° C., 90° C., 100° C., 120° C., 140° C., 150° C., 180° C., or 200° C., or any range of values ​​therebetween. For example, in some embodiments, the second carbonylation is carried out at about 2500 PSIG and about 40-120° C. (e.g., 90° C.).

[0058] In some embodiments, the second carbonylation process may be carried out by the following first method: 1) introducing a gaseous mixture of nitric oxide and carbon monoxide into the remaining first carbonylation mixture and adding Co 2 (CO) 8 is converted to the volatile and decomposable cobalt nitrosyltricarbonyl by the following chemical reaction: Co 2 (CO) 8 +NO→CoNO(CO) 3 +CO

[0059] In some embodiments, the second carbonylation process may be carried out by the following second method: 2A 1:1 (v / v) gas mixture of syngas, cobalt metal, cobalt salts, and carbon monoxide (i.e., synthesis gas) can be introduced into the reactor at a pressure of about, at least, or at least about 14 PSIG, 15 PSIG, 20 PSIG, 50 PSIG, 100 PSIG, 150 PSIG, 200 PSIG, 250 PSIG, 300 PSIG, 400 PSIG, 500 PSIG, 600 PSIG, 700 PSIG, 800 PSIG, 900 PSIG, 1000 PSIG, 1100 PSIG, 1200 PSIG, 1300 PSIG, 1500 PSIG, 1800 PSIG, 2000 PSIG, 2200 PSIG, 2500 PSIG, or 3000 PSIG, or any value therebetween. 2 (CO) 8 reacts to give cobalt tetracarbonyl hydride (i.e., HCo(CO) 4 This cobalt tetracarbonyl hydride compound is highly volatile and readily decomposes to cobalt metal in the absence of carbon monoxide.

[0060] Volatile cobalt carbonyls (e.g., cobalt nitrosyl tricarbonyl and / or cobalt tetracarbonyl hydride) can be separated from the solid mixture by distillation. In some embodiments, the second carbonylation process may be avoided or omitted, and instead, Co 2 (CO) 8 is separated from the first carbonylation residue by sublimation under mild vacuum. In some embodiments, the second carbonylation is 2 (CO) 8 and the cobalt carbonyl produced is about, at least, or at least about 50 wt%, 60 wt%, 70 wt%, 80 wt%, 90 wt%, 92 wt%, 95 wt%, 98 wt%, or 99 wt%, or any range of values ​​therebetween. 2 (CO) 8 Includes.

[0061] Isolated cobalt carbonyl (e.g., Co 2 (CO) 8 , CoNO(CO)3 and / or HCo(CO) 4 ) may be decomposed to pure metallic cobalt and a gas mixture (e.g., NO and / or CO). In some embodiments, the off-gas during decomposition may be recycled to the front process stream. In some embodiments, the carbonyl process (e.g., first and second carbonylation) may be carried out under closed loop conditions (i.e., introduced gases such as carbon monoxide and nitric oxide are collected and reused in the process without producing gaseous or liquid effluents). In some embodiments, the cobalt carbonyl is heated to form cobalt metal at a temperature of about, at least, or at least about 200° C., 220° C., 250° C., 300° C., 350° C., 400° C., 450° C., 500° C., 600° C., 700° C., 800° C., 900° C., 1000° C., or 1200° C., or any range of values ​​therebetween.

[0062] In some embodiments, the realized rate and / or extraction efficiency of the carbonylation reaction may be enhanced by the use of an additive. In some embodiments, the additive may be introduced just before or during the reduction step, the carbonylation (e.g., first and / or second carbonylation) step, or a combination thereof. In some embodiments, the additive is an elemental compound, a salt, a molecular compound, or a combination thereof. In some embodiments, the molecular compound is a chalcogenide (e.g., a sulfur or tellurium material), Cl, or a combination thereof. 2 , or a combination thereof. In some embodiments, the salt is a chloride salt. In some embodiments, a chloride salt can be added to the feedstock. In some embodiments, the additive is added to the feedstock at about, at least, or at least about 0.05%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 12%, or 15% by weight of the feedstock. In some embodiments, the chloride salt is LiCl, NaCl, KCl, CaCl 2 , MgCl 2or combinations thereof. Without being bound by theory, these salts can facilitate reduction at high temperatures and hydrogen pressures by in situ formation of HCl, which can react with metal halides that may be easier to reduce than existing oxides. Additionally, without being bound by theory, chalcogenides (e.g., sulfur or tellurium) can act as effective catalysts during carbonylation.

[0063] After removal of nickel, iron and / or cobalt, lithium (e.g., LiO 2 , LiOH and / or LiOH * (H 2 3 shows a leaching extraction process 300 for recovering lithium from the residual material. The residual material is dissolved 302 to form a slurry and subjected to solid-liquid separation 304 to isolate undissolved solid residue 306 from a lithium-rich solution 308. The lithium-rich solution 308 is subjected to evaporation, crystallization and / or precipitation 310 to isolate lithium product 312.

[0064] In some embodiments, water and / or a weak acid is introduced into the residual material to dissolve the residual material and form a slurry, and the lithium content of the residual material is dissolved in the liquid. In some embodiments, solid-liquid separation may occur in a dissolved air flotation unit or a separation tank. In some embodiments, the residual anode material (e.g., graphite) may float to the top of the slurry and is isolated by skimming. In some embodiments, the residual current collector material (e.g., Cu and Al) may precipitate to the bottom of the slurry and is collected. In some embodiments, the lithium product includes lithium hydroxide, lithium carbonate, or a combination thereof. In some embodiments, lithium hydroxide is obtained by evaporation / crystallization of the collected lithium-containing solution. In some embodiments, lithium carbonate is produced by a precipitation process by introducing carbon dioxide and / or carbonate into the collected lithium-containing solution.

[0065] FIG. 4 illustrates an example of a particular process 400 for recovering elemental nickel, cobalt, and lithium from spent batteries from start to finish. A spent lithium battery is provided (402), discharged (404), disassembled (406), and the housing is removed (408). The electrode material is crushed (410), and N-methyl-2-pyrrolidone (NMP) is added (412) to the crushed electrode material and mixed (414) to form a slurry. The slurry is subjected to solid-liquid separation 416, which may be repeated. The separated solid material is dried (418), the NMP solvent is returned (420), and reused in the mixing step 414, and the dried solid material is screened (422), and the current collector material 424, such as Al, Cu, etc., is separated from the electrode active material. The electrode active material in this example contains no Fe, or negligible and / or minimal amounts of Fe. The electrode active material is a carbon source (C) and / or a hydrogen source (H 2 ) 426 and undergoes reduction 428. The reduced material is combined with carbon monoxide (CO) 430 and undergoes first carbonylation 432 followed by decomposition 434 to produce nickel (Ni) metal 434. Because the electrode active material feedstock contained no Fe or negligible / minimal Fe, distillation was not required to separate Ni carbonyl from Fe carbonyl prior to decomposition 434. The decomposed carbon monoxide 438 can be reused in the first carbonylation 432. The remaining first carbonylation material is combined with nitric oxide (NO) and / or carbon monoxide (CO) 440 and undergoes second carbonylation 442 followed by distillation 444 and decomposition 446 of the distilled vapors to produce cobalt (Co) metal 448. The decomposed nitric oxide and / or carbon monoxide 449 can be reused in the second carbonylation 442. The residual material remaining from distillation 444 is combined with water (H 2 O) 450 is combined and mixed (452) to form a slurry, which is subjected to solid-liquid separation 454 to remove undissolved solid residue 456 from the lithium-rich solution. The lithium-rich solution is subjected to evaporation and / or crystallization 458 to produce lithium product 460. EXAMPLES

[0066] Exemplary embodiments of the present disclosure, including processes, materials and / or resulting products, are described in the following examples. General Methods and Equipment

[0067] All manipulations were carried out using standard laboratory handling techniques. Reduced materials were handled in a nitrogen-filled glove box or using standard inert handling techniques. Utilized gases (e.g., H 2 , CO, Ar, N 2 ) were all of high purity, equal or better.

[0068] Powder X-ray diffraction analysis was performed on a Bruker D8 Advance powder X-ray diffractometer equipped with a sealed tube copper source, a vertical goniometer, and a LYNXEYE XE-T detector in a 0 / 90° mount. Phase analysis was performed using Bruker Diffrac EVA software or Crystal impact Match! Software. Scanning electron microscopy was performed on a JEOL JSM-IT500HR / LA microscope. Particle size analysis was performed using ASTM certified test sieves or by laser diffraction on a Malvern Panalytical Mastersizer 3000 equipped with wet and dry measurement cells. Elemental analysis was performed using inductively coupled plasma optical emission spectroscopy (ICP-OES) on an Agilent series 5900 spectrometer. The surface area of ​​the materials was measured by gas adsorption using the Brunauer-Emmett-Teller (BET) surface analysis method. Measurements were performed using a Micrometrics Tristar II Plus 3030 surface area and porosity analyzer. Explanation of reduction furnace

[0069] Reduction tests were performed in a single-zone static pressure tube furnace equipped with a 100 mm diameter quartz tube and a hydrogen gas source (Across International STF 1200 series). The system was installed in a custom-configured glove box to allow handling of the reduced solids in the absence of oxygen or water. The black mass was placed in an alumina crucible and brought to the specified temperature at a specified ramp rate. Hydrogen gas was flowed through the tube at a specified flow rate to maintain the sample temperature for the specified residence time. After reduction, the material was cooled to ambient temperature (18-25 °C) and then collected under an inert atmosphere and stored for subsequent use or analysis. Carbonylation Unit Description

[0070] Carbonylation tests were conducted in a custom-built autoclave (Parr Instruments Company Series 4540 Horizontal / Vertical Reactor; 600 mL) configured with a vessel MAWP rating of 5000 PSI at 500 °C. The unit is equipped with a footless stirrer designed for solid agitation / fluidization, a gas manifold for argon, carbon monoxide or alternative gas delivery, and an HMI for process monitoring and data collection. The custom unit can be operated batchwise, at constant pressure, or with continuous gas flushing using mass flow controllers and back pressure regulators. Solid powder or slurry (50-500 g) was introduced into the reactor under an argon flush to exclude air and moisture. The reactor was then sealed and pressure tested under an inert atmosphere at 20-25 °C for 1 hour. The reactor was then brought to the target temperature (typically 100-150 °C) and allowed to stabilize (0.5-1 hour). Carbon monoxide gas was then introduced into the reactor. The reactor was operated in a constant pressure mode to supply make-up gas. After the designated reaction time, the supply of carbon monoxide to the reactor was shut off. The carbonyl gas was then sent to the powder decomposer system using a needle control valve and pressure regulator.

[0071] Powder Digestor System Description The powder decomposer system consists of two hot-wall decomposers connected in series with a powder collection bin. The unit works by injecting a stream of metal carbonyl vapor (Ni, Co or Fe) vertically downwards. The carbonyl stream can be pure or can be mixed with one or more carrier gases (e.g., CO, N 2 , Ar) or additives (e.g., NH 3 , O 2 The vapor stream enters a vertically oriented heated cylinder (1" diameter x 18" diameter) from the nozzle. The outside of the cylinder is resistively heated and insulated with fiberglass. The temperature of the heated section is monitored by a thermocouple. The system is cable that reaches a stable temperature up to 500°C. As the vapor stream exiting the nozzle passes through the heated section, the metal carbonyls dissociate to produce metal powder and carbon monoxide. The metal powder is isolated in a collection bin located below the heated section. Powder morphology can be varied by controlling the nozzle speed, carrier gas composition and decomposer temperature.

[0072] Example 1: Recycled batteries and black mass Black mass was generated from a lithium-ion battery pack (2170 cells, NMC cathode). The batteries were discharged, shredded, and washed. During washing, the intermediate material was sized to generate the "black mass" or "fines". The effect of these processing steps is to obtain a slurry or free-flowing powder (when dry) that is primarily free of the battery casing, electrolyte, separator film, and current collectors (i.e., copper and aluminum). This "black mass" is therefore composed of lithium, cathode (e.g., lithium metal oxide), and anode (e.g., graphite and activated carbon), which constitute the crude residue required for further concentration.

[0073] Representative physical and chemical properties of this material were characterized by optical microscopy, BET surface area, ICP-OES and tap density and are shown in Table 1. [Table 1]

[0074] Small scale samples of black mass (i.e., fine powder) were hydrogenated and then carbonylated in a thermogravimetric analyzer (TA Instruments HP75) capable of high pressure / high temperature operation. This allows the unit to function as a small reduction furnace and carbonylation reactor. Samples (50-100 mg) of black mass or mineralogical intermediates were placed in a crucible, which was then sealed in a reaction chamber. The material was then subjected to a specific set of reduction and carbonylation conditions using hydrogen gas and carbon monoxide gas, respectively. Gas pressure and flow rates are controlled using the instrument integration control. Hydrogenation conditions were 0-1000 PSIG H at 20-1000 °C with flow rates of 0-90 mL / min. 2 Carbonylation conditions can range from 0 to 1000 PSIG at temperatures between 20 and 200 °C. During unit operation, a magnetic levitation balance equipped on the instrument allows for the measurement and calculation of the change in mass and therefore the metal extraction efficiency. The exhaust of the apparatus was connected to a sampling line so that the gas composition of the effluent gas could be monitored by a mass spectrometer. This allows for the determination of the metal carbonyls (e.g., Ni(CO) 4 and Fe(CO) 5 The detection and quantification of ) was carried out using a Hidden Analytical real-time gas analyzer (RTGA) series HPR-20.

[0075] Example 2 (Control): Sequential hydrogenation / carbonylation of nickel powder Thermogravimetric analyzer (TGA) tests were performed on a commercial nickel powder (Vale grade 123) as a control and on black mass. Nickel powder (Vale 123, 10 μm D 50 ) was placed in a ceramic (alumina) crucible, placed in the instrument, and sealed. The sample was equilibrated at (50 °C) for 5 min under nitrogen purge (100 mL / min). The powder was then placed in a hydrogen atmosphere (50 PSIG, 90 mL / min H 2 ;N at 10 mL / min 2The sample was then cooled to 100° C. and flushed with nitrogen for 5 min, followed by carbon monoxide (800 PSIG or 150 PSIG, 90 mL / min CO; 10 mL / min N 2 The sample was heated to 150 °C under an atmosphere of 0.1% Ni(CO). During this time, the weight loss in the sample (corresponding to vaporized nickel) was monitored using a thermogravimetric analyzer (TGA). At the same time, the exhaust of the TGA was monitored using a real-time gas analyzer to obtain Ni(CO) 4 It was confirmed that the generation of Ni(CO) occurred simultaneously with mass loss. From the TGA plots shown in Figures 5A and 5B (concentration and normalized weight, respectively), Ni(CO) 4 It was confirmed that the occurrence of was simultaneous with the mass loss of the sample, and therefore the yield was calculated from the expected weight loss derived from the elemental composition of the sample. Table 2 summarizes the carbonylation results for the control nickel powder. [Table 2]

[0076] Example 3: Sequential hydrogenation / carbonylation of black mass The black mass (i.e., fine powder) obtained from the bulk processing of spent lithium ion batteries described in Example 1 was dried in air at 150°C for 4 hours to remove moisture and obtain a non-uniform black free-flowing powder. On average, the material was 83 wt% (+ / - 7 wt%) below 140 mesh (<106 μm). Optical microscopy and SEM imaging confirmed that the oversized material was mainly residual aluminum and copper conductors. This material was subjected to a series of sequential hydrogenation / carbonylation experiments under various conditions, and the results of these experiments are shown in Table 3 and Figure 6. T=0 is defined as the start of the carbonylation portion of the sequential hydrogenation / carbonylation experiments. The yields of all extractable metals were calculated based on the average Ni and Fe contents (wt%) in the feedstock. Calculated extraction efficiencies of up to 46 wt% were realized in small-scale trials. [Table 3]

[0077] Example 4: Tube furnace reduction of dried mass The dried black mass (i.e., fine powder) obtained from the treatment of used lithium ion batteries in Example 1 was pre-dried in air at 150°C for 4-12 hours in a muffle furnace to remove residual moisture from bulk washing and dehydration. On average, the moisture content in the black mass is about 40% by weight. The material was then subjected to reduction under various temperatures. Table 4 shows the reaction conditions and yields. For the reduction experiments summarized in Table 4, the specified amount of black mass sample was placed in an alumina crucible (about 25 g per crucible) and placed in a tube furnace. The furnace ramp rate, target temperature, and residence time were programmed and started. The gas flow was adjusted using a calibrated rotameter. At the end of the specified residence time, the furnace was turned off and cooled to room temperature. Once room temperature was reached, the process gas supply was stopped and the sample was removed under an inert atmosphere. [Table 4]

[0078] The weight loss profiles as a function of reduction temperature at various residence times (i.e., 4 h or 8 h) are summarized in Figure 7. Figures 8A and 8B show the powder X-ray diffraction (XRD) profiles of item 12 before and after reduction (450°C, 4 h), respectively, confirming the complete reduction of the cathode material and the formation of reduced metal.

[0079] Example 5: Tube furnace reduction of wet mass The wet black mass (i.e., fine powder) obtained from the treatment of used lithium ion batteries in Example 1 was directly reduced without a pre-drying step. Table 5 summarizes the reduction conditions and mass loss. In these experiments, the wet black mass was collected directly from the pre-battery treatment step, placed in alumina crucibles (approximately 25 g / crucible) and placed in a tube furnace. The furnace ramp rate, target temperature, and residence time were programmed and started. The gas flow was adjusted using a calibrated rotameter. At the end of the specified residence time, the furnace was turned off and cooled to room temperature. Once room temperature was reached, the process gas supply was stopped and the sample was removed under inert atmosphere. [Table 5]

[0080] Example 6: Carbonylation and powder production The reduced dry black mass (70 g) obtained according to Example 4, items 14, 16 or 17 was charged into a carbonylation reactor under argon flush. The reactor was sealed, placed in horizontal mode and pressure tested under argon at 282 PSIG for 1 hour. The reactor was then heated to 150° C. under argon and the reactor temperature was allowed to stabilize. The argon in the reactor was vented to 0 PSIG and then repressurized with carbon monoxide to a pressure of 1000 PSIG. The material was allowed to react for 13 hours. Ni(CO) 4 The reactor was slowly vented by passing rich carbon monoxide vapor through the powder decomposer. For this run, the wall temperature of the powder decomposer was maintained at about 350° C. After venting, the reactor and decomposer were flushed with carbon monoxide for 1 hour, argon for 10 minutes, and then air. The decomposer and reactor were opened and the resulting powder: nickel metal and residue were collected.

[0081] Further, reduced wet black mass (57 g) obtained according to item 21 or 22 of Example 5 was charged into the carbonylation reactor under argon flush. The reactor was sealed, placed in horizontal mode and pressure tested under argon at 200 PSIG for 1 hour. The reactor was then heated to 150° C. under argon and the reactor temperature was stabilized. The argon in the reactor was vented to 0 PSIG and then repressurized with carbon monoxide to a pressure of 800 PSIG. The material was allowed to react for 13 hours. Ni(CO) 4 The reactor was slowly vented by passing rich carbon monoxide vapor through the powder decomposer. For this run, the wall temperature of the powder decomposer was maintained at about 350° C. After venting, the reactor and decomposer were flushed with carbon monoxide for 1 hour, argon for 10 minutes, and then air. The decomposer and reactor were opened and the resulting powder: nickel metal and residue were collected.

[0082] Table 6 shows the reaction conditions and yields for the carbonylation of dry black mass (i.e., item 23) and the carbonylation of wet black mass (i.e., item 24). [Table 6] 1) Weight percent nickel and iron determined by ICP-OES analysis of reduced samples. Extraction performance is defined as: (actual mass loss) / (theoretical mass loss). * 100. 2) The theoretical mass loss is the sum of the nickel and iron contents in the starting material, calculated from the starting mass and the weight percentages of Ni and Fe determined by ICP-OES analysis. 3) The mass of metal powder was low due to the production of nano-nickel powder that was not captured in the powder decomposer trap.

[0083] Table 7 shows the physical and chemical properties of the dry black mass (i.e., item 23) and wet black mass (i.e., item 24) carbonylation materials as characterized by optical microscopy, BET surface area, and ICP-OES. [Table 7]

[0084] 9A and 9B are scanning electron microscope (SEM) images of nickel powder collected from item 23 (dry), the powder exhibiting a filamentary morphology. FIG. 9C shows the qualitative search / match results from the XRD data of nickel powder collected from item 23 (dry), which shows two phases of nickel: the major phase exhibits diffraction peaks consistent with face-centered cubic nickel (Fm-3m). The minor phase is hexagonal nickel (P6 3 / mmc) are shown.

[0085] Figures 10A and 10B are scanning electron microscope (SEM) images of nickel powder collected from item 24 (wet), the powder exhibiting an acicular morphology. Figure 10C shows the qualitative search / match results from the XRD data of nickel powder collected from item 24 (wet), which indicates a single phase: the major phase exhibits diffraction peaks consistent with face-centered cubic nickel (Fm-3m).

[0086] 11A-11C are photographic images of the black mass, reduced material, and purified nickel powder isolated from the process, respectively.

[0087] Example 7: Sulfur Additive The black mass (1.28 kg) obtained from the bulk processing of spent lithium ion batteries described in Example 1 was dried in air at 150° C. for 4 hours to remove moisture and obtain a non-uniform black free-flowing powder (0.75 kg, 41.3% mass loss). ICP-OES analysis of this material showed it to have a nickel content of about 26% by weight. The material was sieved to remove oversized (140 mesh) material. The oversized material consisted primarily of aluminum and copper electrode backing material that was missing during bulk processing. The undersized material was subjected to a carbonyl enrichment process in one of two ways: a control process without additional treatment or additional additives, and an additive process that included sulfur additive and mixed using a planetary mill grinding sequence.

[0088] Following the control process, a sample (approximately 50 mg) of the dry sieved control material was placed into the TGA-MS. The material was then subjected to sequential hydrogenation (50 PSI and 450° C. for 5 hours) and carbonylation (800 PSI and 150° C. for 19 hours) to produce the control final product (i.e., "PRM TRMB3 Dry U106"). The conversion (theoretical weight loss from extraction of nickel) was found to be <20 wt% in the control final product.

[0089] Following the additive process, a sample of the dry sieved material (98 g) was combined with 1 wt% sulfur (0.98 g) and placed in a high intensity planetary mill with ceramic jars and media (alumina). The material was ground at 300 rpm for 10 minutes. The resulting material was collected and a sample (approximately 50 mg) was placed in the TGA-MS. The material was then subjected to sequential hydrogenation (50 PSI and 450° C. for 5 hours) and carbonylation (800 PSI and 150° C. for 19 hours) to form the additive final product (i.e., “PRM TRMB3 Dry+1 wt% S”). The conversion (theoretical weight loss from the extraction of nickel) was found to be >90 wt%.

[0090] FIG. 12 shows the weight percent of the control and additive materials over time during the reduction and carbonylation steps, indicating that the sulfur additive improves nickel conversion and extraction.

[0091] Although specific embodiments have been described, these embodiments are presented as examples and are not intended to limit the scope of the present disclosure. Indeed, the novel methods and systems described herein may be embodied in a variety of other forms. In addition, various omissions, substitutions, and modifications of the systems and methods may be made without departing from the spirit of the present disclosure. The appended claims and their equivalents are intended to cover such forms or modifications as fall within the scope and spirit of the present disclosure.

[0092] It should be understood that features, materials, properties, or groups described in connection with a particular aspect, embodiment, or example are 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 the 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 in which at least some of such features and / or steps are mutually exclusive. Protection is not limited to the details of any of the foregoing embodiments. Protection extends to any novel, or any novel combination of features disclosed in this specification (including the accompanying claims, abstract, and drawings), or any novel, or any novel combination of steps of any method or process so disclosed.

[0093] Moreover, certain features described in this disclosure in the context of separate embodiments can also be implemented in combination in a single embodiment. Conversely, various features described in the context of a single embodiment can also be implemented in multiple embodiments separately or in any suitable subcombination. Furthermore, although features may be described above as acting in a particular combination, one or more features from a claimed combination can, in some cases, be deleted from the combination, and the combination can be claimed as a subcombination or a variation of the subcombination.

[0094] Furthermore, although operations may be shown in the figures or described herein in a particular order, such operations need not be performed in the particular order shown, or in sequential order, or all operations need not be performed to achieve desirable results. Other operations not shown or described may be incorporated into the exemplary methods and processes. For example, one or more additional operations may be performed before, after, simultaneously with, or between any of the described operations. Furthermore, operations may be rearranged or reordered in other implementations. Those skilled in the art will appreciate that in some embodiments, the actual steps performed in the illustrated and / or disclosed processes may differ from those shown in the figures. Depending on the embodiment, certain of the steps described above may be omitted and other steps may be added. Furthermore, the features and attributes of certain embodiments disclosed above may be combined in different ways to form additional embodiments, all of which are within the scope of the present disclosure. Also, it should be understood that the separation of various system components in the above implementations should not be understood to require such separation in all implementations, and the described components and systems may generally be integrated together in a single product or packaged in multiple products. For example, any of the components of the energy storage systems described herein may be provided separately or may be integrated (e.g., packaged together or attached together) to form an energy storage system.

[0095] For purposes of this disclosure, certain aspects, advantages, and novel features have been described herein. Not necessarily all such advantages may be achieved in accordance with any particular embodiment. Thus, for example, one skilled in the art will understand that the present disclosure may be embodied or implemented to achieve one or more advantages as taught herein, without necessarily achieving other advantages as may be taught or suggested herein.

[0096] Conditional language such as "can," "could," "might," or "may," unless otherwise specified or understood otherwise within the context in which it is used, is generally intended to convey that certain embodiments include certain features, elements, and / or steps, but other embodiments do not. Thus, such conditional language does not generally imply that the features, elements, and / or steps are in any way required by one or more embodiments, or that one or more embodiments necessarily include logic for determining whether those features, elements, and / or steps should be included in or performed in any particular embodiment, with or without user input or prompting.

[0097] Conjunctions such as the phrase "at least one of X, Y, and Z," unless otherwise noted, are understood in the context in which they are generally used to convey that an item, term, etc. can be either X, Y, or Z. Thus, such conjunctions are generally not intended to imply that a particular embodiment requires the presence of at least one of X, at least one of Y, and at least one of Z.

[0098] As used herein, language of degree, such as "approximately," "about," "generally," and "substantially," denotes a value, amount, or characteristic that approaches a stated value, amount, or characteristic that still performs a desired function or achieves a desired result.

[0099] The scope of the present disclosure is not intended to be limited by the specific disclosure of embodiments in this section or elsewhere herein, but may be defined by the claims, as presented in this section or elsewhere herein, or as presented in the future. The language of the claims should be interpreted broadly based on the language used in the claims, and not limited to the examples or during the prosecution of the application described herein, and the examples should be interpreted as non-exclusive.

[0100] Although specific embodiments have been described, these embodiments are presented as examples and are not intended to limit the scope of the present disclosure. Indeed, the novel methods and systems described herein may be embodied in various other forms. In addition, various omissions, substitutions, and modifications of the systems and methods may be made without departing from the spirit of the present disclosure. The appended claims and their equivalents are intended to cover such forms or modifications as fall within the scope and spirit of the present disclosure. Thus, the scope of the present invention is defined solely by reference to the appended claims.

Claims

1. 1. A process for recovering material from an electrode of an energy storage device, comprising: reducing the electrode active material mixture to form a reduced mixture, the electrode active material mixture comprising nickel oxide, cobalt oxide, and a lithium material selected from the group consisting of a lithium salt, a lithium oxide, and combinations thereof; performing a first carbonylation and subsequent first decomposition on the reduced mixture to isolate a nickel product comprising nickel metal and form a first carbonylation material; performing a second decomposition on the first carbonylation material to isolate a cobalt product comprising cobalt metal and form a residue material; The process includes:

2. 2. The process of claim 1, wherein the reducing step comprises reacting the electrode active material mixture with a compound selected from the group consisting of hydrogen, a carbonaceous material, a hydrocarbon material, partial reforming products thereof, and combinations thereof.

3. 3. The process according to claim 1 or 2, wherein the reduction is carried out at a temperature of from 300 to 1200°C.

4. 4. The process of claim 1, wherein the first carbonylation comprises reacting the reduced mixture with a gas selected from the group consisting of carbon monoxide, nitric oxide, hydrogen, and combinations thereof.

5. The process according to any one of claims 1 to 4, wherein the first carbonylation is carried out at a temperature of from 40 to 120°C.

6. 6. The process of any one of claims 1 to 5, wherein the first carbonylation is carried out at a pressure of from 15 to 2000 PSIG.

7. 7. The process of any one of claims 1 to 6, further comprising the step of distilling the reduced mixture after the first carbonylation and before the first decomposition, thereby removing iron products comprising iron carbonyl from the reduced mixture.

8. The process of any one of claims 1 to 7, further comprising the step of mixing an additive with the reduced mixture.

9. The additives include sulfur materials, tellurium materials, Cl ２ , LiCl, NaCl, KCl, CaCl ２ , MgCl ２ and combinations thereof.

10. 10. The process of claim 8 or 9, wherein the additive is mixed with the reduced mixture at 1 to 10% by weight of the reduced mixture.

11. The process of any one of claims 1 to 10, further comprising the step of performing sublimation on the first carbonylation material prior to the second decomposition.

12. 11. The process of any one of claims 1 to 10, further comprising the step of carrying out a second carbonylation on the first carbonylation material prior to the second decomposition.

13. 13. The process of claim 12, wherein the second carbonylation comprises reacting the first carbonylation material with a gas comprising carbon monoxide.

14. 14. The process of claim 12 or 13, wherein the second carbonylation is carried out at a temperature of from 40 to 120°C.

15. 15. The process of any one of claims 12 to 14, wherein the second carbonylation is carried out at a pressure of from 800 to 2500 PSIG.

16. 16. The process of any one of claims 12 to 15, further comprising the step of performing a distillation on the first carbonylation material after the second carbonylation and before the second decomposition.

17. 17. The process according to any one of claims 1 to 16, discharging the energy storage device in an aqueous solution; dismantling the discharged energy storage device to separate the electrode materials; destructuring the electrode material to form the electrode active material mixture; The process further comprises:

18. 20. The process of claim 17, wherein the aqueous solution has a conductivity of at least 1000 mS / m.

19. The aqueous solution contains Na ２ SO ４ 19. The process of claim 17 or 18, wherein the saline solution is a saline solution comprising a salt selected from the group consisting of NaCl, NaCl, and combinations thereof.

20. 20. The process of any one of claims 17 to 19, wherein destructuring forms the electrode active material mixture comprising particles having an average particle size of up to 5mm.

21. The process of any one of claims 17 to 20, further comprising washing the destructured electrode material and separating the electrode active material mixture from a current collector material.

22. 22. The process of claim 21, wherein the washing comprises applying an organic solvent selected from the group consisting of N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide, N,N-dimethylacetamide, and combinations thereof.

23. 23. The process of any one of claims 17 to 22, wherein the energy storage device is a spent lithium ion battery.

24. 24. The process of any one of claims 1 to 23, further comprising the step of performing a leach extraction to isolate the lithium product.

25. The leaching extraction is dissolving the residual material in an aqueous solution to form a slurry; subjecting the slurry to solid-liquid separation to isolate a lithium-rich solution from a solid residue; subjecting said lithium-rich solution to an isolation process to form said lithium product; 25. The process of claim 24, comprising:

26. 26. The process of claim 25, wherein the aqueous solution comprises an acid.

27. 27. The process of claim 25 or 26, wherein the lithium product is selected from the group consisting of lithium hydroxide, lithium carbonate, and combinations thereof.

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