Metal recovery for recycling by chloroaluminum chemistry

Abstract

An aluminometallurgy method for separating lithium and transition metals from lithium-ion batteries, including their components, derivatives, and recycling materials, which involves obtaining recycling products extracted from them by using chloroaluminum chemical species. The recycling products comprise of mixtures of lithium chloride, transition metal chlorides, and aluminum hydroxide or aluminum oxide. The method includes precipitating lithium-aluminum layered double hydroxide chloride ([LixAl2(OH)6]Clx·nH2O) from the recycling products by adding water with or without additional aluminum hydroxide. Lithium can be extracted from solid [LixAl2(OH)6]Clx·nH2O using water while metals can be extracted from the supernatant by precipitation with a base.

Description

PCT Patent Application136766.8027.WO00METAL RECOVERY FOR RECYCLING BY CHLOROALUMINUM CHEMISTRYCROSS REFERENCE TO RELATED APPLICATION

[0001] This application claims priority to and benefit from U.S. Provisional Application No.63 / 773,243, titled “Metal Recovery for Recycling by Chloroaluminum Chemistry,” filed March 17, 2025, the contents of which are incorporated herein by reference in their entirety.STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH

[0002] This invention was made with U.S. government support under Grant No. WP21-1071 awarded by the U.S. Department of Defense (DoD) Strategic Environmental Research and Development Program (SERDP) and Grant No. 1847552 awarded by the U.S. National Science Foundation (NSF). The U.S. government has certain rights in the invention.BACKGROUND

[0003] Recycling metals from lithium (Li)-ion batteries is a critical societal need, though existing technologies have limitations that hinder their use on a global scale. As society continues to rapidly electrify and demand for lithium-ion batteries soars, recycling lithium-ion batteries has become an urgent environmental, economic, and humanitarian need. Currently, pyrometallurgy and hydrometallurgy are the most commonly used lithium-ion battery recycling methods. Pyrometallurgy requires minimal pretreatment and benefits from straightforward smelting process, but the produced alloys require further hydrometallurgical processes to separate and purify lithium. Pyrometallurgical processes are also energy intensive and produce toxic and greenhouse gases. Hydrometallurgy requires sophisticated mechanical pretreatment and separation of used lithium-ion batteries to obtain the so-called "black mass" (e.g., “black mass” including mixed electrode active materials, such as lithium transition metal oxides and graphite, as well as conductive carbon, binder, electrolyte residues, and metal current collector scraps) from which Li and transition metals are extracted with aqueous, Bronsted acidic solutions. Management of acidic waste produced at an industrial scale raises costs and environmental challenges. In addition, to pyrometallurgy and hydrometallurgy, direct recycling of lithium-ion batteries has recently been developed, wherein degraded electrode materials can be replenished to their original chemical composition and crystal structure. However, direct-1- 136766.8027. WOOO\ 186140454.6PCT Patent Application136766.8027.WO00recycling requires the separation and purification of electrode materials from used batteries, challenges that may require systemic changes to battery production to address. Thus, new lithium-ion battery recycling methods are urgently needed that are safe, scalable, cost-effective, and environmentally benign.BRIEF DESCRIPTION OF THE DRAWINGS

[0004] Figures 1A-1 J. Reaction mechanism between LiCoO2 and chloroaluminate ionic liquid [EMIm]AICl4. (Figure 1A) Photos of pristine [EMIm]AICl4 and products at each step in the reaction between LiCoO2and [EMIm]AICI4(Co:AI molar ratio of 1:5). Liquid-state (Figure 1B)1H and (Figure 1C)27AI single-pulse nuclear magnetic resonance (NMR) spectra of pristine [EMImJAICL and the supernatant using different Co:AI ratios. (Figure 1 D) ultraviolet-visible (UV-Vis) spectrum of the supernatant and (Figure 1E) X-ray diffraction (XRD) pattern of the precipitate in IV. (Figure 1F) Photos of the products at various steps in the reaction between LiCoO2 and [EMIm]AICl4 (Co:AI molar ratio of 1:2). (Figure 1G) X-ray photoelectron spectroscopy (XPS) Co 2p spectra. (Figure 1H) XRD pattern and (Figure 11) solid-state27AI NMR spectrum of the blue paste in V. (Figure 1J) Elemental distribution of Co, Li, and Al in the supernatant and precipitate in VIII. Error bars represent one standard deviation from the mean from three different experiments.

[0005] Figures 2A-2D. Computational study of chemical delithiation of LiCoO2 by AICL-. (Figure 2A) Snapshots of ab-initio molecular dynamics (AIMD) simulation of interactions between AICLr and LiCoO2 (Li; Co; O; Al; Cl; C; N; H). (Figure 2B) AI-CI and Li-CI distance of the dissociated Cl atom overtime. (Figure 2C) density functional theory (DFT) reaction energy profile of the formation of the first Li+vacancy: [EMIm]AICl4 adsorption on LiCoO2(104) surface, AI-CI bond break, and LiCI desorption. (Figure 2D) Most stable structure of LiCoO2(104) surface with two Li+vacancies and two adsorbed AlCh. From left to right: optimized geometry, front view, top view ([EMIm]+cation omitted), top view (Al, Cl omitted).

[0006] Figures 3A-3E. Reaction mechanism between LiCoO2 and AICL-EtOH. (Figure 3A) Photos of products from the reaction between LiCoCh and AICh-EtOH using different Co:AI molar ratios. Corresponding liquid-state (Figure 3B)27AI and (Figure 3C)1H single-pulse NMR spectra. After EtOH evaluation, (Figure 3D) XRD pattern of the “blue mass,” revealing LiCI and CoCI2. (Figure 3E) Solid-state27AI single-pulse and27AI{1H} dipolar-mediated heteronuclear multiple-quantum correlation (D-HMQC) NMR spectra of the “blue mass,” compared to a27AI single-pulse NMR spectrum of amorphous AI(OH)3.-2- 136766.8027. WOOO\ 186140454.6PCT Patent Application136766.8027.WO00

[0007] Figures 4A-4F. Aqueous separation of metals after the reaction between LiCoC>2 and AICh-EtOH. (Figure 4A) Photos of the “blue mass” obtained from the reaction between LiCoC>2 and AICh-EtOH and the products from each separation step. (Figure 4B) XRD pattern of the dried precipitate in II. (Figure 4C) Solid-state27AI NMR spectrum of the dried sediment from II, compared to a [LiAh(OH)6]CI standard. (Figure 4D) XRD patterns of LiCI from the supernatant in III and IV, a-CO(OH)2 precipitate in III, and AI(OH)3 precipitate in IV. (Figure 4E) Elemental distribution of Co, Li, and Al in the final products. Li product is from the combination of the two LiCI powders. Error bars represent one standard deviation from the mean from three different experiments. (Figure 4F) Schematic of the dissolution reaction between LiCoO2 and AICh-EtOH and subsequent aqueous metal separation.

[0008] Figures 5A-5E. Recycling demonstration using spent lithium-ion batteries and AICh-EtOH. (Figure 5A) Photo of reaction between the shredded contents of spent Li-ion batteries and a 2 M AICh-EtOH solution in a 2-L reactor. (Figure 5B) Photos of components and products from each step of the reaction and separation processes. (Figure 5C) Extraction efficiencies of Co and Li. (Figure 5D) XRD pattern of the fine powder from the insoluble solid content of the reaction, revealing the presence of graphite. (Figure 5E) The composition of final products: o-Co(OH)2and LiCI. Error bars represent one standard deviation from the mean from three different experiments.

[0009] Figure 6. Li separation process from the “blue mass” recycling product using the addition of AI(OH)3in aqueous solution, which promotes the formation of lithium-aluminum layered double hydroxide chloride ([LiAh(OH)6]CI) for subsequent washing and lithium extraction.

[0010] Figures 7A and 7B. Variable-temperature liquid-state NMR measurements. Liquid-state (Figure 7A)1H (Figure 7B)27AI NMR spectra acquired at different temperatures (0, 25, 80, and 120 °C) of the supernatant after the reaction between LiCoCh and [EMIm]AICl4 using different Co: Al molar ratios of 1:5, 1:10, and 1:20. As the Co:AI molar ratio increases, the1H and27AI NMR signals of the EMInT cations and AICL-anions, respectively, shift to higher frequencies and broaden, a consequence of increasing bulk magnetic susceptibility (BMS) effects with increasing cobalt content in solution. The1H and27AI NMR shifts are the sum of their diamagnetic chemical shift and BMS shifts, where the latter results from changes in the local magnetic field around these species as a consequence of changes in the BMS of the medium. BMS effects arising from paramagnetic species are typically inversely related to the temperature, resulting in the smallest deviations from expected diamagnetic shifts at the highest temperatures. Note that all signals within a spectrum for a single-3- 136766.8027. WOOO\ 186140454.6PCT Patent Application136766.8027.WO00composition and temperature are equally shifted, and the BMS shifts experienced by the1H nuclei are equal in ppm as the shifts experienced by the27AI nuclei.

[0011] Figures 8A and 8B. 2D27AI{27AI} multiple-quantum (MQ) MAS NMR spectra of the reaction products. (Figure 8A) Reaction product between L1COO2 and [EMIm]AICl4 (1:2, Co:AI molar ratio), disordered, amorphous AI2O3. (Figure 8B) Reaction product between LiCoO2 and AICh-EtOH (1 :2, Co:AI molar ratio), amorphous AI(OH)3. The amorphous nature of the materials is evident in the MQ-MAS NMR experiments: crystalline materials would yield distinct,27AI quadrupolar lineshapes in the indirect dimension indicative of locally well-ordered27AI environments.

[0012] Figure 9. Solid-state7Li NMR spectrum of the reaction product between LiCoO2 and [EMIm]AICl4 with spectral deconvolutions of individual7Li environments. The sharp, well-defined7Li signal at 0.6 ppm and the broad7Li signal centered at -1.4 ppm comprise 59% and 41 % of the lithium on a molar basis, respectively, as determined by their total integrated signal intensities. The7Li signal at 0.6 ppm is associated with LiCI, while the7Li signal at -1.4 ppm can be due to LiAICU-

[0013] Figure 10. Gas chromatography-mass spectrometry (GC-MS) spectrum of the gas in the reactor headspace for the reaction between LiCoO2and [EMIm]AICI4. The GC-MS spectrum of the gas phase in the rector with molar ratio of Co:AI at 1 :5 is compared with the GC-MS spectra of the headspace gas in the reactor with pure [EMIm]AICl4 and the gas in the argon-filled glovebox.

[0014] Figures 11, 12A and 12B, 13A and 13B, 14, and 15A and 15B. DFT calculations of AICI3 adsorption on LiCoO2 (104) surface with two Li+vacancies.

[0015] Figure 16. Kinetic study of the reaction between LiCoO2 and AICh-EtOH with Co:AI ratio of 1:2. Top: Images of AICh-EtOH solution at different time during the reaction with IJCOO2; Bottom: the extraction yield of Li and Co as a function of time.

[0016] Figure 17. 2D1H{13C} heteronuclear single-quantum coherence (HSQC) NMR spectrum of the reaction product between LiCoO2 and EtOH-AICh. The molar ratio of Co / AI was at 4:5. CH3CHO is therefore confirmed, presumably by the following chemical reaction: CH3CH2OH + ^O2— ► CH3COH + H2O.

[0017] Figure 18. GC-MS spectra of the gas in the reactor headspace from the reaction between LiCoO2 and AICI3-EtOH. The molar ratio of Co / AI was at 4:5. Existence of ethyl ether and ethyl chloride is confirmed. Ethyl chloride is generated by the reaction between ethanol and AlCh: 3CH3CH2OH + AICI3^ 3CH3CH2CI + AI(OH)3.-4- 136766.8027. WOOO\ 186140454.6PCT Patent Application136766.8027.WO00

[0018] Figures 19A-19C. Solid-state NMR (Figure 19A)27AI{1H} D-HMQC, and single-pulse (Figure 19B)7Li, and (Figure 19C)1H NMR spectra of the [LiAI2(OH)6]CI product resulting from the aqueous separation of the reaction products from LiCoO2and AICI3-EtOH (bottom), and synthesized [LiAI2(OH)6]CI (top).

[0019] Figure 20. 2D27AI{1H} D-HMQC NMR spectrum of the [LiAI2(OH)6]CI product resulting from the aqueous separation of the reaction products from LiCoO2and AICh-EtOH. This experiment shows the through-space correlation between27AI and the solid1H species from hydroxide, lines are drawn to guide the eye.

[0020] Figures 21A-21D. Li separation using layered double hydroxide (LDH). (Figure 21 A) Schematic of the process. (Figure 21 B) Elemental distribution of Co, Li, Al and Na in the final products. Error bars represent one standard deviation from the mean from three different experiments. (Figure 21C) XRD pattern of the LDH product after LiCI adsorption and AI(OH)3after Li desorption by washing. (Figure 21 D) XRD pattern of Co(OH)2precipitate and the dried supernatant containing NaCI.

[0021] Figures 22A-22F. Reaction between LiNio.6Mno.2Coo.202 (NMC622) and AICI3-EtOH at the transition metal to Al molar ratio of 4:5. (Figure 22A) Image of the green-colored homogeneous solution at the completion of the reaction; (Figure 22B) Liquid-state27AI NMR spectra and (Figure 22C) liquid-state1H NMR spectra of the AICI3-EtOH solution before and after the reaction; (Figure 22D) UV-Vis spectrum of the solution after the reaction (diluted by 1000 times with pure EtOH); (Figure 22E) XRD pattern of the "green mass" obtained after EtOH evaporation from the reaction product; and (Figure 22F) the elemental distribution of Li and the transition metals (Co, Ni, and Mn) using the same sample separation process as LiCoO2. Error bars represent one standard deviation about the mean from three different experiments.

[0022] Figures 23A-23B. Reaction between LiNi0.80Co0.15AI0.05 (NCA) and AICI3-EtOH at the transition metal to Al molar ratio of 4:5. (Figure 23A) Image of the green-colored homogeneous solution at the completion of the reaction; (Figure 23B) UV-Vis spectrum of the solution after reaction (diluted by 1000 times with pure EtOH).

[0023] Figures 24A-24C. Recycling demonstration using shredded LiCoO2composite cathode and separator in AICI3-EtOH solution. (Figure 24A) Photo of reaction between the shredded cathode and separator from spent Li-ion batteries and a 2 M AICI3-EtOH solution in a 2-L reactor. (Figure 24B) Photos of components and products from each step of the reaction and aqueous-based metal-5- 136766.8027. WOOO\ 186140454.6PCT Patent Application136766.8027.WO00separation process. (Figure 24C) Composition of the recycling products: a-Co(OH)2and LiCI. Error bars represent one standard deviation from the mean from three different experiments.DETAILED DESCRIPTION

[0024] The present technology relates to processes for recycling materials from Li-ion batteries. Specifically, recycling processes using chloroaluminum chemical species to extract lithium and transition metals from Li-ion batteries, whether by processing the entire electrochemical cell (e g., including components such as electrodes, separator, binder, conducting carbon, and / or metal current collectors), the harvested electrodes, or Li-ion battery recycling materials (e.g., processed derivatives such as “black mass”, or scrap material derived from manufacturing processes), result in recycling products, including mixtures of lithium chloride, transition metal chlorides, and aluminum compounds (e.g., aluminum hydroxide or aluminum oxide). Such recycling processes and products can include those described in International Patent Publication WO 2023 / 091287, titled “Recycling methods for lithium-ion batteries,” by Guo et al., filed October 28, 2022, the content of which is incorporated herein by reference in its entirety. The present technology involves the further treatment of the recycling products to separate and purify lithium and transition metals, which can be performed using entirely aqueous-based processing under mild conditions. The technology includes producing solid lithium-aluminum layered double hydroxide chloride [LiAl2(OH)e]CI, or more generally LixAl2(OH)6]Clx nH2O, from the recycling products formed upon reaction of lithium-ion batteries, including their components, derivatives, and recycling materials, with chloroaluminum chemical species, which can then be further processed to recover lithium in different chemical forms (e.g., as LiCI, LiOH, LiOH nfW, or U2CO3). Further, transition metals can also be recovered from the recycling product (e.g., as hydroxides or carbonates). The technology provides for a significant recovery of Li from the recycling product (e.g., more than 95% of Li can be separated from the recycling product). The present technology thereby comprises of efficient, low-cost processes for separating Li and transition metals from Li-ion batteries and their recycling products. Unless otherwise indicated, percentages are in reference to mass percentages throughout this disclosure.

[0025] The present technology is a novel lithium-ion battery recycling approach, aluminometallurgy, based on chloroaluminum chemistry, in which chloroaluminate AICL-anions and chloroaluminous AICh+cations are shown to chemically delithiate and dissolve lithium transition metal oxide electrode materials. We elucidate the reaction mechanisms and products involved when lithium transition metal oxides react with either a chloroaluminate ionic liquid containing AICLr anions or a solution of aluminum chloride in ethanol (AICh-EtOH) containing AICl2+cations (for example, in-6- 136766.8027. WOOO\ 186140454.6PCT Patent Application136766.8027.WO00the molecular complex AICl2+(EtOH)4). We show that these chloroaluminum species can dissolve lithium-ion battery electrode materials such as LiCoC>2(LCO), LiNixCovMni-x-y02 (NMC), LiNixCo,Ali.x-yO2(NCA) using short reaction times at ambient pressure and moderate temperatures (e.g., <2 h at 150 °C for chloroaluminate ionic liquid and <3 h at 75 °C for AICh-EtOH). Lithium and transition metals can then be recovered from the dissolved products with high yield and purity using entirely aqueous separation processes with near-neutral discharge. Aluminometallurgical extraction using AICh-EtOH solutions also enables solvent recycling and reuse. Using AICh-EtOH as the extraction reagent, we further demonstrate the efficiency and scalability of aluminometallurgy for recycling spent lithium-ion batteries.

[0026] Aluminometallurgy is a novel chemical approach rooted in solution-based chloroaluminum chemistry and establishes a new paradigm in lithium-ion battery recycling. Traditional hydrometallurgical methods use Bnansted acids and rely on proton-mediated leaching, often in the presence of additional reducing agents (e.g., aqueous H2SO4 with H2O2), to dissolve lithium transition metal oxides. Many reported solvometallurgical methods using deep-eutectic-solvent systems likewise dissolve cathodes primarily through proton-assisted leaching and / or reductive complexation. In contrast, aluminometallurgy uses reactive chloroaluminum species (AICL-anions and AICI2+cations) to chemically delithiate and destabilize transition metal oxide frameworks, thereby enabling their rapid dissolution through a fundamentally distinct chemical mechanism.LiCoC>2 and [EMImlAICU: Reaction and Separation

[0027] Chloroaluminate complexes can dissolve layered lithium transition metal oxides, such as UCOO2. The reaction products and mechanism were studied between LiCoO2and a chloroaluminate ionic liquid composed of AICI3and 1-ethyl-3-methylimidazolium chloride in a 1:1 molar ratio ([EMIm]AICI4), which contains AICI4‘ anions. The reaction products at different steps between UCOO2 and [EMImJAICL using a Co:AI molar ratio of 1:5 are shown in Figure 1A. The LiCoO2 powder is completely dissolved in [EMImjAICL after reaction for2 h at 150 °C (III, Figure 1A). After centrifugation, the product is a supernatant with the characteristic blue color of anhydrous Co(ll) complexes and a white precipitate (IV, Figure 1A). Liquid-state1H and27AI single-pulse NMR spectra of the supernatant (Figures 1 B, 1C) reveal that the1H and27AI NMR signals of the [EMIm]+cations and Al CL-anions, respectively, shift to higher frequencies and broaden as the Co:AI ratio increases. These changes in NMR shifts and relaxation properties are due to bulk magnetic susceptibility (BMS) effects resulting from the paramagnetic Co2+ion complexes in solution, a result further elucidated by variable-temperature NMR measurements (Figures 7A and 7B). The UV-Vis spectrum of the-7- 136766.8027. WOOO\ 186140454.6PCT Patent Application136766.8027.WO00supernatant (Figure 1 D), diluted with pure [EMImjAICk to avoid signal saturation, reveals three peaks at 630, 667, and 696 nm associated with cobalt tetrachloride (CoCU2-) anions. The XRD pattern of the white precipitate (Figure 1E) indicates the present of crystalline lithium chloride (LiCI).

[0028] Accordingly, LiCoO2 and [EMImJAICU can react to completion at a Co:AI molar ratio of 1:2. Due to the high solid-to-liquid ratio at this molar ratio, the final reaction product (V, Figure 1F) is a blue paste. An XPS spectrum acquired on the blue paste (Figure 1G) establishes that the oxidization state of Co is Co(ll), as evidenced by the narrower binding energy gap between the XPS Co 2p peak and its satellite peak (5 eV, indicating Co2+) compared to pristine LiCoO2 (10 eV, indicating Co3+). The XRD pattern of the blue paste (Figure 1H) reveals multiple reflections, which can be due to [EMIm]2CoCl4. We synthesized solid [EMIm]2CoCl4 by reacting [EMIm]CI and C0CI2 at a 2:1 molar ratio at 120 °C, where it forms an ionic liquid. The matching XRD pattern of [EMIm]2CoCI4(Figure 1H) confirms it as a reaction product. A solid-state27AI NMR spectrum of the blue paste (Figure 11) reveals a narrow, intense27AI signal at 104 ppm associated with liquid-like AICI4". Broad27AI signals at 72 ppm, 34 ppm, and 7 ppm are due to four-, five-, and six-coordinate Al environments, respectively, consistent with amorphous aluminum oxide (AI2O3). In particular, the large relative populations of five-coordinate Al environments indicates that the AI2O3 product exhibits significant structural disorder, which is evident from 2D27AI{27AI} MQ-MAS NMR experiments (Figure 8A). The broad27AI signals do not preclude the existence of chemical disorder, such as Cl defects, within the AI2O3 structure. The solid-state7Li NMR spectrum of the blue paste reveals a sharp7Li signal at 0.6 ppm due to LiCI and a broad7Li signal centered at -1.4 ppm that can be associated with LiAICk Spectral deconvolutions indicate that LiCI and LiAICL compromise 59% and 41% of the lithium on a molar basis (Figure 9).

[0029] The reaction between L1COO2 and AICL-using a Co:AI molar ratio of 1 :2 produces LiCI, CoCL2-, and AI2O3. The reaction process can be started from chemical extraction of Li+cation, followed by a self-redox reaction of the CoC>2“ framework: Co(lll) is reduced to Co(ll), accompanied by oxygen (O2) evolution. Carbon dioxide (CO2) was detected in the headspace in the reactor with GC-MS (Figure 10, a consequence of evolved O2 oxidizing organic species in the solution at 150 °C). Therefore, at a Co: Al molar ratio of 1:2, the following reaction between LiCoCh and AICLrcan occur:LiCoO2(s)+2AICi;(l)+2EMIm+(l)^LiCI(s)+[EMIm]2CoCI4(s)+^AI2O3(s)+AICI3(s)+lo2(g)Eq. (1)

[0030] AICI3 subsequently can form AICI4“ by reacting with LiCI and [EMIm^CoCL, explaining the presence of AICI4“ and the paste-like consistency of the final product. DFT calculations reveal -8- 136766.8027. WOOO\ 186140454.6PCT Patent Application136766.8027.WO00that the total reaction energy of Eq 1 is -0.97 eV, establishing that the reaction is spontaneous and demonstrating its thermodynamic feasibility.

[0031] Elemental analysis indicated that 100% of the Co and 99.98% of Li were extracted from L1COO2. The blue paste readily dissolves in water {VI, Figure 1F), resulting in a deep pink color characteristic of the octahedrally coordinated Co2+(H2O)6 cation. We observed that a precipitate gradually appeared when the solution rested in ambient environment. To accelerate this process, the solution was stirred for 12 h at 75 °C to achieve complete sedimentation {VII in Figure 1 F). After centrifugal separation {VIII, Figure 1F), elemental distribution of Al, Li and Co in the supernatant and precipitate (Figure 1 J) demonstrated a high degree of separation of Co and Al: 99.86% of Co from LiCoO? resides in the supernatant and 99.61% of Al from [EMIm]AICI4resides in the precipitate, establishing that Co and Al are separated by the reaction. Elemental analysis indicates that 36.16% and 63.82% of Li was in the supernatant and precipitate, respectively, which would require further separation.

[0032] The reaction between LiCoO2and AICI4“ was probed computationally, revealing how AICI4" interacts with the surface and triggers Li+extraction and transition metal oxide dissolution. Four snapshots of the interaction between AICI4“ and LiCoO2 at the UC0O2 surface from ab initio molecular dynamics (AIMD) simulations (Figure 2A) reveals that the reaction begins when AICI4~ adsorbs and one of its Cl atoms forms a bond with a surface Li atom. The AI-CI bond elongates and breaks as a new Li-CI bond is concomitantly formed (Figure 2B), resulting in a Li+cation vacancy. DFT calculations were then performed to elucidate the extraction process (Figure 2C) and indicate that the adsorption energy of an AICI4~ anion on the LiCoO2 surface is -1.64 eV. Subsequent breaking of the AI-CI bond is endothermic by 0.67 eV, which is accessible under the experiment temperature (150 °C). Finally, the desorption energy of the newly formed LiCI molecule is -0.18 eV. Thus, the reaction energy profile demonstrates the thermodynamic feasibility of this reaction pathway. To study the formation of other products, we studied a system where two AICI3 molecules are adsorbed on a LiCoO2surface containing two Li+vacancies, i.e. , the surface after two LiCI form and desorb, with DFT calculations. Various adsorption sites on five possible Li+vacancy configurations were examined (Figures 11, 12A and 12B, 13A and 13B, 14, and 15A and 15B), and the most stable AlCh-adsorbed structure (Figure 2D) reveals that one AICI3 bonds with an O atom near a Li+vacancy while the other dissociates into AICI2+and CL. While the CF binds with a near Co atom, the AICI2+binds to two oxygen atoms of different layers, bridging them over a Li vacancy site. The formation of AI-0 bonds and Co-CI bonds are consistent with the subsequent formation of AI2O3and CoCI42, respectively.-9- 136766.8027. WOOO\ 186140454.6PCT Patent Application136766.8027.WO00Table 1 below includes a list of possible AlCh adsorption sites on LiCoO2 (104) surface with different Li+vacancy configurations and their relative energy with respect to the most stable structure (entry 4) Figure: Top view of the optimized structures of the possible AlCh adsorption sites. [EMIm]+cation and bottom 4 layers were omitted for better visualization.Table 1.Li+Vacancy Possible AlChErelative (eV)Configuration Adsorption Site1 - 2.57a 2.212b 2.29a 2.193b 1.394 - 0.00a 2.735b 2.56LiCoCh and AICh-EtOH: Reaction and Separation

[0033] The computational study of the reaction between LiCoC>2 and AICU anions suggests the reaction is initiated by chemical delithiation enabled by the strong bonding between the chloride anion of AICU-and a Li+cation on the LiCO? surface. Therefore, other chloroaluminum complexes, such as chloroaluminous AICh+cations, may also be able to initiate the reaction with LiCoO2 via a similar mechanism. Molecular six-coordinate [AICh(EtOH)4]+complexes are the primary cationic species in AICh-EtOH solutions. Note that any H2O present, whether as impurities or as an additive, may also coordinate with AICh+and participate in the formation of molecular six-coordinate AICh+-containing complexes (e.g., by substituting an H2O molecule for an ethanol molecule).

[0034] Reactions between UCOO2 and a solution of 0.75 M AlCh in ethanol (AICh-EtOH) were performed at 75 °C using different Co:AI molar ratios. The final products were homogenous solutions with the characteristic cobalt blue color of anhydrous Co2+cations (Figure 3A). Using a Co:AI molar ratio at 1 :2, complete dissolution of LiCoO2 was observed in less than 2 h (Figure 16). We determined experimentally that a Co:AI molar ratio of 4:5 is the highest ratio that enables complete dissolution of LiCoO2. Liquid-state27AI and1H NMR single-pulse spectra of the pristine AICh-EtOH and reaction-10- 136766.8027. WOOO\ 186140454.6PCT Patent Application136766.8027.WO00solutions using different Co:AI molar ratios are shown in Figures 3B and 3C, respectively. The27AI NMR signals at 9.8 and 12.8 ppm from the pristine AICh-EtOH are attributed to different configurational isomers of the [AICh(EtOH)4]+cations. After reacting with LiCoO?, the27AI resonances shift to higher frequencies and broaden with increasing Co:AI ratio due to the presence of dissolved paramagnetic Co2+cations. The1H NMR signals demonstrate the same trend of increasing frequency with higher Co:AI ratios. Small quantities of acetaldehyde (CH3CHO) and diethyl ether (C4H10O) are detected in the1H NMR spectra (left panel, Figure 3C). The existence of CH3CHO is confirmed by a 2D1H-13C through-bond NMR correlation experiment (Figure 17). C4H10O and ethyl chloride (CH3CH2CI) were also detected in the vial headspace by GC-MS (Figure 18).

[0035] A "blue mass" was obtained as a reaction product after evaporating and recovering the EtOH from the solution with a Co:AI ratio at 4:5. XRD indicates that it contains crystalline LiCI and C0CI2 (Figure 3D). Solid-state27AI single-pulse and27AI{1H} D-HQMC NMR spectra (Figure 3E) reveal that the Al-containing content in the blue mass is aluminum hydroxide (AI(OH)3, Figure 8B). Based on the reaction products, we propose the following reaction mechanism between AICh-EtOH and IJCOO2:2AICl2+2Cr+2LiCoO2+6C2H5OH^2LiCI+2CoCl2+2AI(OH)3+^O2+3C4H10O Eq. (2)

[0036] In the proposed reaction between AICh+and LiCoO2, the Co:AI molar ratio is 1:1, but the experimentally determined ratio that minimizes the Al content, relative to Co, is lower (4:5). The reason may be that some AICI3 is consumed by the reaction with EtOH, generating CH3CH2CI and AI(OH)3. Note that the reaction can proceed in the presence of excess Al, relative to Co, as demonstrated above (e.g., for a Co:AI of 3:4: or 1:2, as shown in Figures 3A, 3B, and 3C.)

[0037] Similar to the blue paste product from the reaction between UCOO2 and [EMIm]AICl4, the blue mass obtained from the reaction with AICh-EtOH ( / in Figure 4A) is soluble in water, producing a pink solution that gradually generates a white sediment under ambient conditions. The solution was stirred at 75 °C for 12 h to accelerate sedimentation ( / / in Figure 4A), and then centrifuged to produce a white precipitate and pink supernatant. The precipitate was identified as lithium-aluminum layered double hydroxide chloride ([LiAI2(OH)6]CI) by XRD (Figure 4B) and solid-state27AI (Figure 4C, Figures 19A-19C, 20),1H (Figures 19A-19C) and7Li (Figures 19A-19C) singlepulse NMR measurements, in comparison to a synthesized [LiAI2(OH)6]CI standard. More generally, the lithium-aluminum layered double hydroxide chloride product has a chemical composition of LixAl2(OH)6]ClxnH2O; herein, [LiAh(OH)6]CI may be used in reference to its more general composition. [LiAh(OH)6]CI is commonly formed by the insertion of LiCI into an aqueous suspension -11- 136766.8027. WOOO\ 186140454.6PCT Patent Application136766.8027.WO00of AI(OH)3. Therefore, the formation of [LiA (OH)6]CI is additional evidence of the existence of LiCI and AI(OH)3 in the blue mass.

[0038] The dissolved metals in the supernatant were separated by chemical precipitation by using a base. The Co2+content in the supernatant was precipitated as a-Co(OH)2 by adjusting the pH to neutral conditions using lithium hydroxide (LiOH) ( / / / , Figure 4A). As a result, the supernatant in / / / contains only LiCI, which was retrieved by water evaporation. The Li+content in the [LiAI2(OH)6]CI precipitate was extracted as LiCI by rinsing with hot water (e.g., 90 °C was used, though any temperature less than the boiling point of water can be used), leaving insoluble AI(OH)3 (IV in Figure 4A). The XRD patterns of the obtained LiCI (faint blue color due to Co impurities), a-CO(OH)2, and AI(OH)3are displayed in Figure 4D. The elemental distribution of the separated products was measured with inductively coupled plasma-optical emission spectroscopy (ICP-OES) (Figure 4E): 99.38% of Co from LiCoO2was recovered as a-Co(OH)2, 0.57% of Co existed in the separated AI(OH)3, and 0.05% of Co existed in the separated LiCI. 93.99% of Li from LiCoO2and the added LiOH was recovered as LiCI, 5.68% of Li remained as [LiAI2(OH)6]CI, and 0.33% of Li was in a-Co(OH)2as an LiCI impurity. As for Al, 98.63% of the Al in AICh-EtOH was collected as AI(OH)s while 1.37% of Al existed in the separated a-Co(OH)2. A schematic of the reaction process and subsequent aqueous separation steps are illustrated in Figure 4F. The AICb-EtOH solution is thus shown to be an effective reagent to extract Li and Co from LiCoC due to its high dissolution efficiency coupled with facile aqueous separation of metals from the reaction products.

[0039] In addition, Li and Co within the blue mass can also be separated using a modified separation method illustrated in Figures 21A-21D and Figure 6. In this modified method, AI(OH)s is added to the aqueous solution of the blue mass to achieve a Li:AI molar ratio of 1:2 (alternatively, it can also be added in stoichiometric excess, i.e., such that the molar ratio of Al to Li greater than 2). The resulting mixture is stirred and heated (e.g., at temperatures in the range of 35 - 75 °C, such as 35, 55, and 70, or 75 °C, though any temperature less than the boiling point of water can be used) until all the water evaporates, resulting in a solid product. This step, which includes the addition of AI(OH)3, promotes the formation of [LiAb(OH)6]CI due to the insertion of lithium chloride into the suspended AI(OH)3. The solid product was dried (e.g., 70 °C was used, though temperatures up to the thermal decomposition temperature of [LiAb(OH)6]CI can be used, which is approximately 300 °C). The resultant solid product is dispersed in deionized water, and the mixture is separated (e.g., by centrifugation or filtration) to a solid precipitate that contains [LiAI2(OH)6]CI and any excess AI(OH)3and a supernatant that contains CoCI2and any remaining LiCI. To further enhance lithium absorption from the liquid supernatant into the solid [LiAI2(OH)6]CI phase, fresh AI(OH)3is added to -12- 136766.8027. WOOO\ 186140454.6PCT Patent Application136766.8027.WO00the supernatant to achieve a Li : Al molar ratio of 1 :2 (or, as mentioned above, a stoichiometric excess of AI(OH)3 can also be added). The resultant dispersion is mixed and heated (e.g., at temperatures in the range of 35 - 75 °C, such as 35, 55, and 70, and 75 °C) until all the water evaporates. The resultant product is subsequently dispersed in deionized water and the solid and liquid phases are separated (e.g., by centrifugation or filtration). As shown in Figure 6, this process — which involves AI(OH)3addition to the supernatant, mixing, water evaporation, dispersion in water, separation of liquid and solid product — can be repeated multiple additional times (e.g., two more times) to yield the final products, which are a solid mixture of [LiAI2(OH)6]CI and any excess AI(OH)3as well as an aqueous solution of CoCI2. When this process was repeated an additional two times, from ICP analysis, more than 96% of the Li from the blue mass is recovered as solid [LiAI2(OH)6]CI. LiCI is subsequently extracted from [LiAI2(OH)6]CI through a washing process, using water as the solvent (e.g., 90 °C was used, though any temperature less than the boiling point of water can be used), achieving a recovery rate of elemental Li of 90.09%. 93.46% of elemental Co in the blue mass is recovered from the supernatant as Co(OH)2by precipitation using NaOH.

[0040] As described above, one of the recycling products is a powder containing lithium chloride, transition metal chlorides, and either aluminum oxide (AI2O3from chloroaluminate ionic liquid extraction reagent) or aluminum hydroxide (AI(OH)3from extraction reagent composed of aluminum chloride in alcohol solvents). The subsequent separation process includes forming lithiumaluminum layered double hydroxide chloride ([LiAI2(OH)6]CI) as a solid in the aqueous solution of the extraction product. Additional AI(OH)3can also be added to the solution of the extraction product to produce greater quantities of [LiAI2(OH)e]CI, as described above and shown in Figures 21 A-21 D and Figure 6, thus improving the Li content in the solid precipitate and the separation efficiency between Li and transition metals. Using this modified separation method, after four AI(OH)3-addition cycles, the majority of the Li in the extraction product is separated out as solid [LiAI2(OH)6]CI; the majority of the Co in the extraction product remains in the supernatant as a chloride salt. Li can be recovered from [LiAI2(OH)e]CI as LiCI via aqueous washing processes. The transition metals can be readily recovered as a hydroxide, or alternatively as a carbonate, via precipitation. The disclosed method can use AI(OH)3present in the recycling products and / or added AI(OH)3to separate Li from the transition metals by forming solid [LiAI2(OH)6]CI, while the transition metals remain in aqueous solution. This method is simple and low-cost compared to prior methods. The process can achieve Li separation efficiency of above 90 % (e.g., above 90 %, above 95 %, or above 96 %), Co separation efficiency of above 90 % (e.g., above 90 %, above 92 %, or above 94 %), and / or Al separation efficiency of above 95 % (e.g., above 95 %, above 97 % or above 99% (see, Table 1).-13- 136766.8027. WOOO\ 186140454.6PCT Patent Application136766.8027.WO00

[0041] These aqueous metal separation technologies enable Li separation efficiency of above 90 % (e.g., above 90 %, above 95 %, or above 96 %), Co separation efficiency of above 90 % (e.g., above 90 %, above 92 %, or above 94 %) and / or Al separation efficiency of above 95 % (e.g., above 95 %, above 97 % or above 99%). When subjected to our modified aqueous separation process (Figure 21A), exemplary elemental distributions of Li, Co and Al in the separated supernatant and the solid residue are achieved (Table 2), as determined using Inductively Coupled Plasma Optical Emission spectroscopy (ICP-OS).Table 2.Blue mass separation Al Co LiSupernatant 0.2% 94.1% 3.4%Precipitate 99.8% 5.9% 96.6%Generality and Scalability of Aluminometallurqy

[0042] Chloroaluminum chemistry can be used to dissolve other layered lithium transition metal oxides, including those containing mixed transition metals. For example, Li-ion batteries using lithium nickel manganese cobalt oxide (NMC) cathodes with the general formula UNixCoYMni.x-yO2, as well as compositions with a stoichiometric excess of lithium, can be extracted with the AICh-EtOH solution using identical reaction processes and conditions. The dried reaction product obtained after NMC dissolution is a “green mass,” due to its nickel content, while the transition metals can be separated from lithium and aluminum using the same aqueous separation methods. We demonstrated this reaction between LiNi0.6Mn0.2Co02O2 (NMC622) and AICh-EtOH (Figures 22A-22F), establishing the generality of aluminometallurgy for dissolving other layered lithium transition metal oxides. For NMC622, when subjected to our aqueous metal separation process described above in Figure 4F, more than 99.1% of Co, 99.99% of Mn and 96.48% of Ni were separated as a mixture of transition metal hydroxides. 91.31% of Li from NMC622 was recovered as LiCI, less than 0.1% of the transition metals existed as transition metal chloride impurities, 8.43% of Li remained as [LiAI2(OH)6]CI in Al discharge, and 0.26% of Li was in the transition metal hydroxides mixture as an LiCI impurity. In the Al discharge, 98% of the Al in AICh-EtOH was separated as AI(OH)3whereas 2% of Al existed in the separated transition metal hydroxides mixture. Note that the lithium and transition metals in the NMC-derived “green mass” can also be separated using the modified separation method described above in Figure 21A, which involves the use of additional AI(OH)3to promote the formation of solid LiAI2(OH)6]CI.-14- 136766.8027. WOOO\ 186140454.6PCT Patent Application136766.8027.WO00

[0043] Similarly, Li-ion batteries using lithium nickel cobalt aluminum oxide (NCA) cathodes with the general formula LiNixCoYAli.x.yO2, as well as compositions with a stoichiometric excess of lithium, can also be extracted with the AICI3-EtOH solution using identical reaction processes and conditions. We demonstrated this reaction between LiNio.sCooisAlo.os (NCA) and AICh-EtOH (Figure 23A-23B), revealing that the NCA framework dissolves to completion and further establishing how aluminometallurgical methods can be used to dissolve layered lithium transition metal oxides containing a variety of mixed transition metals.

[0044] The practical use and scalability of aluminometallurgy was further demonstrated using spent Li-ion 18650-type batteries using LiCoCh cathodes. In this context, and in this document, the battery “cathode” from a Li-ion battery or cell refers to a composite battery electrode, which in addition to containing the electroactive material (e.g., LiCoCh), contains other components such as carbon (e.g., carbon black), binder (e.g., polyvinylidene fluoride (PVDF)), and possibly other additives, coated onto a current collector (e.g., aluminum metal). Feedstocks were reacted in 2 M AICh-EtOH solutions for 3 h at 75 °C. We first used separated and shredded LiCoCh cathodes and separators from four batteries as the feed stock (Figures 24A-24C). Separately, four battery cores were retrieved from their stainless-steel casings and shredded as the feed stock (Figure 5A). The products at different steps of the reaction and separation process are displayed in Figure 5B. Elemental analysis of the liquid product ( / / / in Figure 5B) and the insoluble content ( / \ / and \ / in Figure 5B) demonstrates that the extraction efficiency of Co and Li was virtually 100% (Figure 5C). The XRD pattern of the separated fine black powder (V in Figure 5B) indicates that it contained graphite (Figure 5D) from the anode. Carbon black and binder are also likely present, indicated by broad XRD reflection at low angles. The solution was subjected to our aqueous metal separation process describe above in Figure 4F. The elemental analysis of the separated products (Figure 5E) showed that the final Co-rich product contained 97.14 wt.% of a-Co(OH)2, 2.34 wt.% of LiCI, 0.51 wt.% of AI(OH)3and 0.01 wt.% of Cu(OH)2 (from the anode current collector). The final Li-rich product contained 99.41 wt.% of LiCI, 0.33 wt.% of C0CI2, and 0.26 wt.% of AI(OH)3.

[0045] These experiments demonstrate the practicality, efficiency, and scalability of the method on spent Li-ion batteries. Note that spent Li-ion batteries using other layered lithium transition metal compounds as electroactive materials, such as NMC or NCA, can also be subjected to an identical recycling process. Similarly, the aqueous separation method used to recycle lithium and transition metals in this cell-level demonstration (Figure 4F) can also be substituted for the modified separation process (Figure 21A) that uses additional AI(OH)3 to promote the formation of [LiAl2(OH)6]CI. Likewise, feedstocks could also be lithium-ion battery recycling materials, such as -15- 136766.8027. WOOO\ 186140454.6PCT Patent Application136766.8027.WO00shredded, deactivated, and / or processed derivatives, including “black mass,” harvested electrodes, or any scrap or material derived from Li-ion battery manufacturing processes.

[0046] In summary, the present technology is a novel lithium-ion battery recycling method, aluminometallurgy, that uses chloroaluminum chemistry and aqueous separation to recover lithium and transition metals from spent batteries with high yields and purities. Complex chloroaluminum ions chemically extract lithium from the surface of lithium transition metal oxides, forming LiCI, while the remaining chloroaluminum complex causes spontaneous self-redox and dissolution of the transition metal oxide framework. Lithium and transition metals from the dissolved products can be recovered with high yields and purities using entirely aqueous separation processes. For example, when using AICh-EtOH solution as the extraction reagent, spent Li-ion batteries using LiCO? cathodes were recycled, where lithium and cobalt were recovered as LiCI and a-Co(OH)2with 99.41% and 97.14% purity, respectively. This new recycling strategy is technologically attractive: in particular, AICI3and ethanol are industrial commodity chemicals, while ethanol can be recovered and reused. Acidic waste streams and toxic gas evolution are minimal. Energy consumption is low due to high dissolution and separation efficiency under mild reaction conditions. All reactions between lithium transition metal oxides and AICh-EtOH solutions were completed under 3 h at 75 °C, which can also occur at lower temperatures over longer timescales. Aluminometallurgy may be an economically viable alternative to pyrometallurgical, hydrometallurgical, and direct recycling methods.Experimental Information

[0047] 1-ethyl-3-methylimidazolium chloride (>98%, HPLC) was purchased from TCI Chemicals. High-purity anhydrous aluminum chloride (99.99%) and LiCoC>2 powder (99.8%, trace metals basis) were purchased from Sigma-Aldrich. Anhydrous AICI3 with lower purity (98.5%) was purchased from Fisher Scientific. Anhydrous ethanol (>99.5%, 200 proof) was purchased from Sigma-Aldrich and KOPTEC. Lithium hydroxide (LiOH) was purchased from Sigma-Aldrich. LiNi0.6Mn0.2Co0.2O2 powder was purchased from Targray Technology International, Inc. Used Li-ion batteries were purchased from A&G Electronics Recycling Angel, Riverside, CA.Reaction of LiCoO2 with TEMImlAICL Ionic Liquid

[0048] The 1-ethyl-3-methylimidazolium tetrachloroaluminate ionic liquid ([EMImJAICL) was prepared by slowly mixing high-purity anhydrous AICI3 and 1-ethyl-3-methylimidazolium chloride ([EMIm]CI) (AICl3 / [EMIm]CI molar ratio = 1:1) in a glass reactor inside an argon-filled glovebox (H2O-16- 136766.8027. WOOO\ 186140454.6PCT Patent Application136766.8027.WO00and O2 content <0.1 ppm). 1.82 g of AlCh and 2 g of [EMIm]CI would be used in a typical preparation. Both reagents were dried under vacuum inside the glovebox at 60 °C for 24 h prior to use. The mixture was stirred at room temperature until a transparent homogenous liquid was obtained. The reaction between LiCoC and the [EMImjAICL ionic liquid was started by mixing LiCoO2 powder into the ionic liquid with different LiCoCk / AICU-molar ratio (1:20, 1:10, 1:5, and 1:2). 267 mg of LiCoCk would be used in a typical 1:5 molar ratio reaction. The mixture was stirred at 150 °C for 2 h in the argon-filled glovebox. The reaction flask was equipped with a condenser circulating water at 10 °C. For reactions with UCOO2 / AICI4- molar ratios at 1:20, 1:10, and 1:5, the solid and liquid phases after the reaction were separated through centrifugation (20,000 x g). The liquid phase from reaction at the 1:20, 1:10, and 1:5 ratio was analyzed with nuclear magnetic resonance (NMR) spectroscopy (1H NMR and27AI NMR) at different temperatures (0 °C, 25 °C, 80 °C, and 120 °C) alongside the pristine ionic liquid. The liquid phase from the 1:5 reaction was diluted with the [EMIm]AICI4ionic liquid by 1000 times and characterized with ultraviolet-visible spectrometry (UV-Vis). The solid phase from the 1:5 reaction was characterized with X-ray diffraction (XRD). The gas phase generated from the 1:5 reaction was characterized with gas chromatography-mass spectroscopy (GC-MS). The reaction with IJCOO2 / AICI4-molar ratio at 1:2 resulted in a paste-like product (i.e., liquid and solid phases cannot be separated). This paste-like product was characterized with XRD, solid-state27AI NMR, and X-ray photoelectron spectroscopy (XPS). Metal (Li, Co, and Al) extraction and separation from this product were performed as follows: The paste-like product (approximately 1 g) was dissolved in 5 mL of water with complete dissolution. The water solution was stirred at 75 °C for 12 h in open atmosphere and the generated precipitate was separated from the supernatant through centrifugation and filtration. The metal (Li, Co, and Al) contents in the precipitate and supernatant, respectively, were measured with inductively coupled plasma optical emission spectrometry (ICP-OES).Reaction of LiCoCh with AICh-EtOH

[0049] LiCoO2 powder was mixed into a solution of 0.75 M of AICI3(anhydrous, 98.5% pure, Fisher Scientific) in anhydrous ethanol (EtOH) with different Co / AI molar ratio (1 :2, 3:4 and 4:5) inside the argon-filled glovebox. 5 mL of AICI3-EtOH solution (0.5 g of AICI3) and 293 mg of LiCoO2would be used in a typical 4:5 molar ratio reaction. The mixture was stirred at 75 °C for 3 h in a roundbottom flask equipped with a condenser circulating water at 10 °C. After the reaction completed, the obtained homogenous liquid product was characterized with1H and27AI single-pulse NMR spectroscopy, and heteronuclear single quantum coherence (13C{1H) HSQC) NMR spectroscopy-17- 136766.8027. WOOO\ 186140454.6PCT Patent Application136766.8027.WO00experiments. The gas phase generated from the 1:2 reaction was characterized with GC-MS. The liquid product from the 1:2 reaction was diluted with pure anhydrous EtOH by 1000 times and characterized with UV-Vis. EtOH was evaporated and recollected with rotary evaporation (80 to 100 °C and 120 to 180 rpm rotation speed) from the liquid product from the 4:5 reaction, resulting to a powder product. This solid product was characterized with XRD and solid-state27AI NMR spectroscopy. The powder was completely dissolved in water (typically 1 g of powder in 5 mL of water) and stirred at 75 °C for 12 h in the open atmosphere. Off-white precipitate was generated from the solution. The precipitate was separated from the supernatant through centrifugation and membrane filtration (cellulose acetate membrane, 0.22 pm porosity followed by PES membrane, 0.1 pm porosity). XRD, solid-state27AI NMR spectroscopy, ICP-OES was performed on the dried precipitate. LiOH was added into the supernatant to precipitate Co(OH)2. After the Co(OH)2is separated from the solution, the liquid phase is dried to obtain LiCI. The Li content in the precipitate is extracted by rinsing in 5 mL of water at 90 °C, 3 times. XRD was performed on the washed and dried precipitate. The rinsing solution was also dried to obtain LiCI.

[0050] [LiAI2(OH)e]CI was synthesized by heating AI(OH)3 in an aqueous solution of LiCI in a 4-fold molar excess at 90 °C for 6 h.

[0051] The kinetic study of the reaction with Co / AI ratio at 1:2 was performed as follows: 5 mL of reaction mixture was drawn 10 s, 30 s, 1 min, 2 min, 5 min, 10 min, 20 min, 1 h, and 2 h after the reaction started. The samples were immediately immersed into ice to quench the reaction. The drawn samples were filtered through 0.22 pm syringeal filters to remove the unreacted LiCoO2particles. The Li and Co contents in the sample were measured with ICP-OES.

[0052] The reactions between LiNio.6Mno.2Coo2O2 (NMC) or LiNi080Co0.15AI0.05O2 (NCA) and the AICh-EtOH solution were both performed under identical conditions as the one described above between LiCoO2 and the AICh-EtOH solution, with similar characterization parameters where applicable.Direct Li Separation Using Layered Double Hydroxide (LDH)

[0053] Blue mass is completely dissolved in deionized water. Additional AI(OH)s is added to the solution to achieve a Li / AI molar ratio of 1:2. The mixture is stirred to ensure AI(OH)s is well dispersed in the solution. The solution is then heated in a convection oven set to 70 °C until all the water evaporates, leaving behind a solid product. This step promotes the formation of the lithiumaluminum layered double hydroxide chloride ([LiAI2(OH)6]CI) by the reaction between LiCI and-18- 136766.8027. WOOO\ 186140454.6PCT Patent Application136766.8027.WO00AI(OH)3. The resulting solid product is dispersed again in deionized water, and the mixture is centrifuged to separate the solid containing [LiAl2(OH)e]CI and excess of AI(OH)3 from the supernatant containing the dissolved C0CI2 and the remaining LiCI. Fresh AI(OH)3 is added to the supernatant. The dispersion is mixed and heated at 70 °C in the conventional oven until all the water evaporates then the resulting solid product is dispersed in deionized water and centrifuged to separate the solid and liquid phases. This process is repeated two more times. The final products are a solid mixture of [LiAl2(OH)e]CI and excess AI(OH)3 and an aqueous solution of C0CI2. Li is recovered from [LiAI2(OH)6]CI as LiCI by washing, and Co is recovered as Co(OH)2precipitate by adding NaOH in the aqueous solution.Demonstration of Recycling Used Li-ion Batteries Using AIC -EtOH

[0054] The stainless-steel casings of fully discharged used 18650-type Li-ion batteries with LiCoC>2 cathode were removed with a disassembling cutter (MTI Corporation). The anode was removed and the rest of the components were shredded with a heavy-duty shredder (Maanshan JiaHe Technology and Machinery Co., Ltd). The shreds were dried in vacuum oven at 80 °C for 12 h prior to being loaded inside a 2-L batch reactor (Shanghai Cankun Instrument Equipment Company). 130 g of shreds would be used in a typical reaction. 1 L of 2 M AICI3 (anhydrous, 98.5% pure, Fisher Scientific) solution in ethanol (anhydrous, 200 proof, KOPTEC) was subsequently added into the reactor. The mixture was stirred at 75 °C for 3 h before the mixture was completely discharged from the reactor. The mixture was first strained through a size-4 mesh screen to remove the large particles mainly containing separator shreds. The strained solution was further filtered through vacuum filtration with a fine filter (VWR, Grade 413 filter paper) to remove the small solid particles including carbon back, graphite, and binder. Ethanol was evaporated and collected through rotary evaporation from the filtered solution to obtain the solid product. The Li and Co content in the product was measured with ICP-OES. The dried product was dissolved in water (typically 20 g of powder in 100 mL of water) and stirred at 75 °C for 12 h in open atmosphere. Off-white precipitate was generated from the solution. The precipitate was separated from the supernatant through centrifugation and membrane filtration (cellulose acetate membrane, 0.22 pm porosity followed by PES membrane, 0.1 pm porosity). LiOH was added into the supernatant to precipitate Co(OH)2. After the CO(OH)2is separated from the solution, the liquid phase is dried to obtain LiCI. The Li content in the precipitate is extracted by rinsing in water at 90 °C for three washing cycles. The rinsing solution was also dried to recover LiCI.-19- 136766.8027. WOOO\ 186140454.6PCT Patent Application136766.8027.WO00Spectroscopic Characterization

[0055] Crystal structures were identified using XRD (Panalytical Empyrean Series 2, 45 kV / 40 mA with a Cu Ka source). All the samples were dried at 80 °C under vacuum for 12 h. The hygroscopic samples were sealed with Kapton tape to avoid contact with ambient air. The scan range was from 10 to 90 ° with a 0.013 ° step size and a time per step of 148.92 s.

[0056] Agilent Cary 60 UV / Vis spectrophotometer was used to characterize the liquid solution containing transition metals. 3 ml_ of diluted liquid samples were inserted into a 10 * 10 mm quartz cuvette and sealed with a cap. Baseline measurements were taken on the pure [EMImjAICL ionic liquid and AlCh solution in EtOH in the same cuvette in the range of 350 to 750 nm.

[0057] The amount of cobalt (Co), lithium (Li), and aluminum (Al) were measured by a Perkin-Elmer Optima 7300DV ICP-OES apparatus. Samples were prepared by dissolving 5 to 10 mg of solid sample in 3 mL of HNO3 (68 to 70 wt.%) and 9 mL of HCI solution (36.5 to 38 wt.%) in a glass vial, then bringing the volume to 100 mL by adding deionized water (Milli-Q IQ 7000) using a volumetric flask.

[0058] Gases generated from the reactions between LiCoO2and the ionic liquid and AICI3solution in EtOH, respectively, were identified with GC-MS.

[0059] Liquid-state1H and27AI NMR spectra were acquired on a Bruker Avance 600 spectrometer with a 14.1 T narrow-bore (54 mm) superconducting magnet operating at 599.759 MHz for1H nuclei and 156.276 MHz and for27AI nuclei. To avoid mixing samples with the standard solution, a double-tube assembly was used where the sample was sealed inside a 5-mm NMR tube and a separate standard (e.g., deuterated chloroform or 0.1 M AICI3 in D2O) was added to a 3-mm NMR tube inserted inside the 5-mm NMR tube (with a sample: standard volume ratio of 2:3). All liquid-state27AI and1H experiments were conducted with radio frequency field strengths of 20.8 kHz and 26 kHz, respectively and with a recycle delay of 12.0 s when all the spins relaxed back to the thermal equilibrium. Except for the variable-temperature experiments, all27AI and1H NMR spectra were obtained at room temperature.

[0060] Solid-state NMR spectra were acquired on a Bruker AVANCE III HD 600 NMR spectrometer with a 14.1 T narrow-bore (54 mm) superconducting magnet operating at 600.14 MHz for1H, 233.24 MHz for7Li, and 156.38 MHz for27AI nuclei. A Phoenix NMR 1.6-mm HXY magic-angle-spinning (MAS) probe-head was used to conduct experiments at a 40 kHz MAS rate. Air was pumped through the probe-head at 600 L / h and 298.1 K to mitigate MAS-induced sample heating.-20- 136766.8027. WOOO\ 186140454.6PCT Patent Application136766.8027.WO001H was referenced with respect to tetramethyl silane (TMS) at 0 ppm by using solid adamantane as a secondary chemical shift reference.7Li shifts were referenced with respect to aqueous LiCI at 0 ppm, using solid LiF as a secondary chemical shift reference.27AI shifts were referenced to a 1 M aqueous AI(NO3)3 solution at 0 ppm. Solid-state27AI single-pulse MAS NMR experiments were performed under quantitative conditions by using (i) short, TT / 12 rf pulses (0.31 ps) to ensure linear excitation of all solid and liquid signals and (ii) recycle delays of 0.25-0.40 s such that all27AI nuclear spins relax to thermal equilibrium (>5 Ti). A 1 M aqueous AI(NC>3)3 standard was used to calibrate27AI rf pulses, where all pulses were based on an rf field strength of 135 kHz (TT / 2 of 1.85 ps). 2D27AI{27AI} MQ-MAS experiments were performed using a three-pulse sequence with excitation and conversion rf pulses of 3.6 ps and 1.2 ps, a CT-selective TT / 2 readout pulse of 24 ps, and a z-filter delay of 25 ps. Triple-quantum to single-quantum coherence selection was obtained via phase cycling. 2D27AI{1H} D-HMQC experiments were performed using the SR42i symmetry-based recoupling scheme, which recouples27AI-1H dipolar interactions while simultaneously decoupling1H-1H homonuclear interactions. Central-transition (CT) selective pulses used a27AI rf field strength of 10.4 kHz (TT / 2 of 24 ps). SR42i recoupling pulses used a1H rf field strength of 80 kHz (2 X MAS frequency). Preparatory, diverging27AI double-frequency sweep (DFS) pulses were used to achieve up to three-fold signal enhancements. DFS pulses were swept from 50 kHz to 1 MHz prior to each scan. The27AI{1H} D-HMQC NMR experiment is a probe of27AI nuclei with dipolar interactions to1H nuclei. This experiment indicates through-space interactions between27AI and1H nuclei on the subnanometer length scale. This experiment is further evidence of AI(OH)3formation, due to the proximate Al-H atoms. Note: the27AI{1H} D-HMQC is not a quantitative experiment, the intensities of the resultant spectra come from a combination of factors, including species concentration, strength of the27AI-1H dipolar interaction, and the27AI-1H internuclear distances.

[0061] XPS data were collected using Kratos AXIS Supra (Al Ka=1486.7 eV) at the UC Irvine Materials Research Institute. The samples were transported to the XPS facility inside a stainless-steel tube with KF flange sealing filled with argon. The samples were loaded in the sample chamber in the glovebox integrated with Kratos AXIS Supra for XPS analysis. All peaks of XPS data were analyzed by Casa XPS software and calibrated with the reference peak of C 1s at 284.6 eV (the adventitious carbon).Theoretical Computation

[0062] Density functional theory (DFT) calculations were carried out using the Vienna Ab initio Simulation Package (VASP) with planewave basis sets and a kinetic energy cutoff of 520 eV.-21- 136766.8027. WOOO\ 186140454.6PCT Patent Application136766.8027.WO00Projector augmented wave (PAW) potentials were used to describe the electron-ion interaction. The Perdew- Burke- Ernzerhof (PBE) functional of the generalized-gradient approximation (GGA) was chosen for electron exchange correlation. The reaction energy AE was calculated according to the equation:2[EMIm][AICI4](g)+LiCoO2(s)^LiCI(s)+[EMIm]2[CoCl4](g)+lO2(g)+AICl3(s)+lAI2O3(s)Eq. 3 where the total energy per formula unit of the corresponding species was used. For bulk LiCoO2, LiCI, and AICI3, 12x12*2, 9x9x4, and 4x2x4, T-centered k-point grid was used to sample the Brillouin zone respectively. Both atomic coordinates and lattice constants were allowed to relax during the optimization. [EMIm][AICl4] and [EMIm]2[CoCl4] were modeled as a gas-phase ion pair. Gas phase energies were calculated using a big supercell and the F -point only. Spin-polarized calculations were performed for all Co-containing systems and O2. For the initial stage of the decomposition, 2x4 supercell-slab model of the LiCoO2 (104) surface with symmetric terminations separated by a vacuum of 20 A was used. The termination was chosen for its stability demonstrated by previous studies. The bottom three layers were fixed during the optimization. 2x2x1 F-centered k-point grid was used for sampling the Brillouin zone. Force tolerance for all calculations was set to 0.0001 eV / A. A Hubbard on-site Coulomb interaction term of Ueff = 4.91 for Co was used.

[0063] Ab initio molecular dynamics (AIMD) simulation was carried out using the CP2K package. The mixed Gaussian and plane wave (GPW) approach was employed using the PBE functional with the D3 dispersion correction and the MOLOPT DZVP basis set. The cutoff for the finest grid level and Gaussian waves were 300 and 40 Ry, respectively. The 3x4 supercell contains two AICI4“ anions above the LiCoO2(104) surface, with 2D periodic boundary condition applied to X and Y directions. The slab model was first optimized with force tolerance of 0.005 eV / A, followed by a 3-ps AIMD simulation in NVT ensemble. The temperature was controlled at 1500 K to speed up the reaction using the Nose-Hoover chain method.Exemplary Preferred Embodiments

[0064] In some embodiments, an aluminometallurgy method for separating lithium and metals (e.g., transition metals) from lithium-ion batteries and / or composite cathodes of lithium-ion batteries recycling materials includes: obtaining recycling products, including mixtures of lithium chloride, transition metal chlorides, and aluminum compounds (e.g., aluminum hydroxide or aluminum oxide) wherein the recycling product is extracted from lithium-ion batteries, electrodes, or recycling-22- 136766.8027. WOOO\ 186140454.6PCT Patent Application136766.8027.WO00materials using chloroaluminum-containing chemicals; precipitating lithium-aluminum layered double hydroxide chloride ([LixAl2(OH)6]ClxnH2O) from the recycling product by adding water (e.g., as described in Figure 4F) or water and aluminum hydroxide (AI(OH)3) (e.g., described in Figure 21A), to the recycling product; separating (e.g., centrifuging or filtrating) solid [LixAl2(OH)6]ClxnH2O from a supernatant; and extracting lithium from the solid [LixAl2(OH)6]ClxnH2O. See, for example, Figures 4F, 6, and 21A and related descriptions. In some embodiments, the lithium-aluminum layered double hydroxide chloride LixAl2(OH)6]ClxnH2O includes [LiAl2(OH)e]CI.

[0065] In some embodiments, the chloroaluminum-containing chemicals are present as solvated AICh+cations in solutions of AlCh in alcohols or as AIC anions in chloroaluminate ionic liquids.

[0066] In some embodiments, the amount of extracted lithium corresponds to more than 80%, more than 85 %, more than 90% or more than 95 % of the lithium included in the recycling product.

[0067] In some embodiments, extracting lithium from the solid [LixAl2(OH)6]ClxnH2O includes washing the solid [LixAI2(O H)S]C lx■ nH2O with water in a temperature of less than 100 °C. For example, the temperature can range from 20-100 °C, 50-100 °C, or 60-100 °C. In some embodiments, the temperature is about 90 °C.

[0068] In some embodiments, the techniques described herein relate to an aluminometallurgy method, where the transition metal chlorides in the recycling product include cobalt chlorides, or mixtures of nickel, cobalt, and manganese chlorides, and the supernatant includes aqueous cobalt chloride, or aqueous mixtures of nickel, cobalt, and manganese chlorides.

[0069] In some embodiments, the method further includes adding a base including sodium hydroxide or lithium hydroxide to the supernatant to form and separate (extract) solid transition metal hydroxides, such as Co(OH)2, or mixtures of Ni(OH)2, Co(OH)2, and Mn(OH)2, from the supernatant. An amount of sodium chloride in the supernatant subsequent to extracting the solid nickel, cobalt, and / or manganese hydroxide is above 80%, above 90 %, or above 95 % of the added sodium hydroxide.

[0070] In some embodiments, the amount of the extracted transition metal(s), such as cobalt, or mixtures of nickel, cobalt, and manganese, corresponds to more than 80 %, more than 85 %, or more than 90 % of the transition metal content, such as cobalt, or mixtures of nickel, cobalt, and manganese, included in the recycling product.-23- 136766.8027. WOOO\ 186140454.6PCT Patent Application136766.8027.WO00

[0071] In some embodiments, the method further includes prior to dispersing, drying the precipitated [LixAl2(OH)6]Clx nH2O at a temperature below 300 °C (e.g., below 300 °C, below °C, or below °C). In some embodiments, the drying can be done at a temperature range of 50-100 °C, 60-100 °C, or 70-90 °C (e.g., at 80 °C)

[0072] In some embodiments, the method further includes, prior to extracting the lithium, adding additional aluminum hydroxide to the supernatant to increase an amount of the [LixAI2(OH)s]Clx nH2O separated from the supernatant.

[0073] In some embodiments, the method further includes, prior to extracting the lithium, adding additional aluminum hydroxide to the supernatant to form [LixAl2(OH)6]ClxnH2O and subsequently separating the [LixAI2(OH)6]Clx nH2O from the supernatant. In some embodiments, the steps of adding additional aluminum oxide to the supernatant, forming [LixAl2(OH)6]Clx nH2O, and separating [LixAl2(OH)6]ClxnH2O from the supernatant can be repeated multiple times (e.g., two, three, or four times).

[0074] In some embodiments, the supernatant includes transition metal chlorides. In some embodiments, the supernatant includes lithium chloride and an amount of lithium chloride in the supernatant corresponds to less than 5 %, less than 10 % or less than 20 % of lithium included in the recycling product.

[0075] In some embodiments, precipitating solid [LixAI2(OH)6]Clx nH2O from the recycling product includes adding an amount of aluminum hydroxide that leads to a lithium to aluminum molar ratio of 1:2., or that leads to a stoichiometric excess of aluminum such that the aluminum to lithium molar ratio is greater than 2 (e.g., 2.5, 3, or 4).

[0076] In some embodiments, the recycling product includes material extracted from lithium-ion batteries, including LiCoC>2 (LCO) cathodes. In some embodiments, the recycling product includes material extracted from lithium-ion batteries including LiNixMnyCoi-x-yO2 (NMC) or LiNixCoYAli.x-yO2(NCA) cathodes. In some embodiments, the recycling product includes a combination of two or more of LCO, NMC, or NCA.

[0077] In some embodiments, the method further includes extracting the recycling product, which includes mixtures containing lithium chloride, complex transition metal chlorides (e.g., [EMImkCoCL), and aluminum oxide, from lithium-ion batteries by reacting the cathode material of the lithium-ion batteries with a liquid containing chloroaluminate AICI4_ions. In some embodiments, the recycling product extracted by reacting the cathode materials with the liquid containing-24- 136766.8027. WOOO\ 186140454.6PCT Patent Application136766.8027.WO00chloroaluminate AICL-ions comprises [EMIm^CoCk. In some embodiments, the method further includes extracting the recycling product from lithium-ion batteries by reacting cathode materials of the lithium-ion batteries with a liquid containing solvated AICI2+ions to extract recycling product from the cathode material.

[0078] In some embodiments, a recycled lithium and metal materials are extracted from lithium-ion battery recycling materials by the aluminometallurgy disclosed herein. The metal materials can include transition metals (e.g., Ni, Co, Mn) and other metals (e.g., Na).

[0079] In some embodiments, a system for separating lithium and metals from lithium-ion batteries and / or lithium-ion battery recycling materials includes: an input configured to receive lithium-ion batteries and / or recycling products, wherein the recycling product is extracted from them using chloroaluminum-containing chemicals; a processing system configured to receive the recycling product via the input and precipitating lithium-aluminum layered double hydroxide chloride ([LixAI2(OH)6]ClxnH2O) from the recycling product by addition of water and optionally aluminum hydroxide to the recycling product; a separation system (e.g., a centrifuge or filtration system) configured to receive the precipitated [LixAI2(OH)6]ClxnH2O and to separate solid [LixAI2(OH)6]ClxnH2O from a supernatant; and an output configured to provide the solid [LixAI2(OH)6]ClxnH2O from the separation system and configured to extract metals from the supernatant by the addition of a base. The metals can include transition metals (e.g., Ni, Co, Mn) and other metals (e.g., Li, Na).

[0080] In some embodiments, a method for separating lithium and transition metals from lithium-ion batteries and / or lithium-ion battery recycling materials includes obtaining recycling product, including mixtures of lithium chloride and transition metal chlorides, wherein the recycling product is extracted from lithium-ion batteries using chloroaluminum-containing chemicals; precipitating the [LixAI2(OH)6]ClxnH2O from the recycling product by reaction with water and aluminum hydroxide; separating (e.g., centrifuging or filtrating) the precipitated [LixAI2(OH)6]ClxnH2O from a supernatant including dissolved metal chlorides; and adding a base to the supernatant to extract metals from the supernatant (e.g., transition metals (e.g., Ni, Co, Mn) and other metals (e.g., Li, Na)).

[0081] In some embodiments, a method for separating lithium and transition metals from lithium-ion batteries and / or lithium-ion battery recycling materials includes obtaining recycling product, including mixtures of lithium chloride and transition metal chlorides, wherein the recycling product is extracted from lithium-ion batteries using chloroaluminum-containing chemicals;-25- 136766.8027. WOOO\ 186140454.6PCT Patent Application136766.8027.WO00precipitating a lithium compound from the recycling product; separating (e.g., centrifuging or filtrating) the precipitated lithium compound from a supernatant including dissolved metal chlorides; and adding a base to the supernatant to extract metals from the supernatant. The method can also include extracting lithium from the lithium compound.

[0082] The following enumerated examples are preferred features that may be incorporated into various preferred embodiments.

[0083] 1. An aluminometallurgy method for separating lithium and metals from lithium-ion batteries and / or lithium-ion battery recycling materials:obtaining recycling product comprising lithium chloride, transition metal chlorides, and aluminum compounds,wherein the recycling product is extracted from lithium-ion batteries, or their components, derivatives, and recycling materials, using chloroaluminum- containing chemicals;precipitating lithium-aluminum layered double hydroxide chloride ([LixAl2(OH)6]Clx nH2O) by adding water and aluminum hydroxide to the recycling product;separating [LixAl2(OH)6]ClxnH2O from a supernatant; andextracting lithium from the [LixAl2(OH)6]Clx nH2O.

[0084] 2. The aluminometallurgy method of example 1, wherein an amount of the extracted lithium corresponds to more than 90 % of the lithium included in the recycling material.

[0085] 3. The aluminometallurgy method of examples 1-2, wherein extracting lithium from the [LixAl2(OH)6]ClxnH2O comprises washing the [LixAI2(OH)6]ClxnH2O with water in a temperature less than 100 °C.

[0086] 4. The aluminometallurgy method of examples 1-3, wherein the transition metal chlorides in the recycling product comprise cobalt chlorides and the supernatant comprises aqueous cobalt chloride.

[0087] 5. The aluminometallurgy method of examples 1-4, wherein the transition metal chlorides in the recycling product comprise nickel, cobalt, and / or manganese chlorides and the supernatant comprises aqueous nickel chloride, aqueous cobalt chloride, and / or aqueous manganese chloride.-26- 136766.8027. WOOO\ 186140454.6PCT Patent Application136766.8027.WO00

[0088] 6. The aluminometallurgy method of examples 1-5, further comprising adding a base including sodium hydroxide to the supernatant to extract solid nickel, cobalt, and / or manganese hydroxide from the supernatant.

[0089] 7. The aluminometallurgy method of example 6, wherein an amount of the extracted nickel, cobalt, and / or manganese corresponds to more than 90 % of nickel, cobalt, and / or manganese included in the recycling material.

[0090] 8. The aluminometallurgy method of example 6, wherein an amount of sodium chloride in the supernatant subsequent to extracting the nickel, cobalt, and / or manganese hydroxide is above 95 % of the added sodium hydroxide.

[0091] 9. The aluminometallurgy method of examples 1-8, further comprising adding a base including lithium hydroxide to the supernatant to extract solid nickel, cobalt, and / or manganese hydroxide from the supernatant, wherein an amount of the extracted nickel, cobalt, and / or manganese corresponds to more than 90 % of nickel, cobalt, and / or manganese included in the recycling material.

[0092] 10. The aluminometallurgy method of examples 1-9, further comprising, after separating [LixAl2(OH)6]ClxnH2O from the supernatant, drying the precipitated [LixAl2(OH)6]ClxnH2O at a temperature below 300 °C.

[0093] 11. The aluminometallurgy method of examples 1-9, further comprising, prior to extracting the lithium, adding additional aluminum hydroxide to the supernatant to increase an amount of the [LixAl2(OH)6]ClxnH2O separated from the supernatant.

[0094] 12. The aluminometallurgy method of examples 1-11, wherein the supernatant comprises transition metal chlorides.

[0095] 13. The aluminometallurgy method of examples 1-12, wherein the supernatant comprises lithium chloride and an amount of lithium chloride in the supernatant corresponds to less than 10 % of lithium included in the recycling product.

[0096] 14. The aluminometallurgy method of examples 1-13, wherein precipitating [LixAl2(OH)6]ClxnH2O from the recycling product comprises adding an amount of aluminum hydroxide that leads to a lithium to aluminum molar ratio of 1:2, or that leads to a stoichiometric excess of aluminum such that the aluminum to lithium molar ratio is greater than 2.-27- 136766.8027. WOOO\ 186140454.6PCT Patent Application136766.8027.WO00

[0097] 15. The aluminometallurgy method of examples 1-14, wherein the recycling product comprises material extracted from lithium-ion batteries including LiCoO2 (LCO) cathodes.

[0098] 16. The aluminometallurgy method of examples 1-15, wherein the recycling product comprises material extracted from lithium-ion batteries including LiNixMnyCoi.x-yO2 (NMC) cathodes.

[0099] 17. The aluminometallurgy method of examples 1-16, wherein the recycling product comprises material extracted from lithium-ion batteries LiNixCoYAli.x-yO2(NCA) cathodes.

[0100] 18. The aluminometallurgy method of examples 1-17, further comprising extracting the recycling product from lithium-ion batteries by reacting cathode materials of the lithium-ion batteries with a liquid containing solvated AICl2+ions to extract recycling product from the cathode material.

[0101] 19. The aluminometallurgy method of examples 1-17, further comprising extracting the recycling product from lithium-ion batteries by reacting cathode materials of the lithium-ion batteries with a liquid containing chloroaluminate AICk-ions to extract recycling product from the cathode material.

[0102] 20. The aluminometallurgy method of examples 1-19, wherein recycling product extracted by reacting cathode materials with a liquid containing chloroaluminate AICI4 ions comprises [EMIm]2CoCl4 and aluminum oxide.

[0103] 21. Recycled lithium and transition metal materials extracted from lithium-ion battery recycling materials by the aluminometallurgy method of example 1.

[0104] 22. A system for separating lithium and metals from lithium-ion batteries and / or lithium-ion battery recycling materials, the system comprising:an input configured to receive recycling product, wherein the recycling product is extracted from lithium-ion batteries, or their components, derivatives, and recycling materials, using chloroaluminum-containing chemicals;a processing system configured to:receive the recycling product via the input,precipitate lithium-aluminum layered double hydroxide chloride ([LixAl2(OH)6]ClxnH2O) from the recycling product by addition of water to the recycling product, anda separation system configured to receive the precipitated [LixAl2(OH)6]ClxnH2O to separate solid [LixAI2(OH)6]Clx nH2O from a supernatant comprising dissolved metal chlorides; and-28- 136766.8027. WOOO\ 186140454.6PCT Patent Application136766.8027.WO00an output configured to provide the solid [LixAl2(OH)6]ClxnH2O from the separation system and configured to extract metals from the supernatant by an addition of a base.

[0105] The system of example 22, further implementing any of methods of examples 1 to 21.

[0106] 23. A method for separating lithium and metals from lithium-ion batteries and / or lithium-ion battery recycling materials:obtaining recycling product comprising lithium chloride, transition metal chlorides, and aluminum compounds,wherein the recycling product is extracted from lithium-ion batteries, or their components, derivatives, and recycling materials, using chloroaluminum- containing chemicals;precipitating lithium-aluminum layered double hydroxide chloride ([LixAl2(OH)6]ClxnH2O) from the recycling product by reaction with water and aluminum hydroxide; separating the precipitated [LixAI2(OH)6]ClxnH2O from a supernatant comprising dissolved metal chlorides; andextracting metals from the supernatant.

[0107] The method of example 23, further including features of any of examples 2 to 21.

[0108] 24. A method for separating lithium and metals from lithium-ion batteries and / or lithium-ion battery recycling materials:obtaining recycling product comprising lithium chloride, transition metal chlorides, and aluminum compounds,wherein the recycling product is extracted from lithium-ion batteries, or their components, derivatives, and recycling materials, using chloroaluminum- containing chemicals;precipitating a lithium compound from the recycling product;separating the precipitated lithium compound from a supernatant comprising dissolved metal chlorides;extracting lithium from the lithium compound; and extracting metals from the supernatant.

[0109] The method of example 24, further including features of any of examples 2 to 21.

[0110] From the foregoing, it will be appreciated that specific embodiments of the invention have been described herein for purposes of illustration, but that various modifications may be made-29- 136766.8027. WOOO\ 186140454.6PCT Patent Application136766.8027.WO00without deviating from the scope of the invention. Accordingly, the invention is not limited except as by the appended claims.-30- 136766.8027. WOOO\ 186140454.6

Claims

PCT Patent Application136766.8027.WO00CLAIMSl / We claim:

1. An aluminometallurgy method for separating lithium and metals from lithium-ion batteries and / or lithium-ion battery recycling materials:obtaining recycling product comprising lithium chloride, transition metal chlorides, and aluminum compounds,wherein the recycling product is extracted from lithium-ion batteries, or their components, derivatives, and recycling materials, using chloroaluminum- containing chemicals;precipitating lithium-aluminum layered double hydroxide chloride ([LixAI2(OH)6]ClxnH2O) by adding water and aluminum hydroxide to the recycling product;separating [LixAl2(OH)6]ClxnH2O from a supernatant; andextracting lithium from the [LixAI2(OH)6]ClxnH2O.

2. The aluminometallurgy method of claim 1 , wherein an amount of the extracted lithium corresponds to more than 90 % of the lithium included in the recycling material.

3. The aluminometallurgy method of claim 1, wherein extracting lithium from the [LixAl2(OH)6]ClxnH2O comprises washing the [LixAl2(OH)6]ClxnH2O with water in a temperature less than 100 °C.

4. The aluminometallurgy method of claim 1, wherein the transition metal chlorides in the recycling product comprise cobalt chlorides and the supernatant comprises aqueous cobalt chloride.

5. The aluminometallurgy method of claim 1, wherein the transition metal chlorides in the recycling product comprise nickel, cobalt, and / or manganese chlorides and the supernatant comprises aqueous nickel chloride, aqueous cobalt chloride, and / or aqueous manganese chloride.-31- 136766.8027. WOOO\ 186140454.6PCT Patent Application136766.8027.WO006. The aluminometallurgy method of claim 1 , further comprising adding a base including sodium hydroxide to the supernatant to extract solid nickel, cobalt, and / or manganese hydroxide from the supernatant.

7. The aluminometallurgy method of claim 6, wherein an amount of the extracted nickel, cobalt, and / or manganese corresponds to more than 90 % of nickel, cobalt, and / or manganese included in the recycling material.

8. The aluminometallurgy method of claim 6, wherein an amount of sodium chloride in the supernatant subsequent to extracting the nickel, cobalt, and / or manganese hydroxide is above 95 % of the added sodium hydroxide.

9. The aluminometallurgy method of claim 1 , further comprising adding a base including lithium hydroxide to the supernatant to extract solid nickel, cobalt, and / or manganese hydroxide from the supernatant, wherein an amount of the extracted nickel, cobalt, and / or manganese corresponds to more than 90 % of nickel, cobalt, and / or manganese included in the recycling material.

10. The aluminometallurgy method of claim 1, further comprising, after separating [LixAl2(OH)6]ClxnH2O from the supernatant, drying the precipitated [LixAI2(OH)6]ClxnH2O at a temperature below 300 °C.

11. The aluminometallurgy method of claim 1, further comprising, prior to extracting the lithium, adding additional aluminum hydroxide to the supernatant to increase an amount of the [LixAI2(OH)6]ClxnH2O separated from the supernatant.

12. The aluminometallurgy method of claim 1, wherein the supernatant comprises transition metal chlorides.

13. The aluminometallurgy method of claim 1 , wherein the supernatant comprises lithium chloride and an amount of lithium chloride in the supernatant corresponds to less than 10 % of lithium included in the recycling product.-32- 136766.8027. WOOO\ 186140454.6PCT Patent Application136766.8027.WO0014. The aluminometallurgy method of claim 1 , wherein precipitating [LixAl2(OH)6]ClxnH2O from the recycling product comprises adding an amount of aluminum hydroxide that leads to a lithium to aluminum molar ratio of 1:2, or that leads to a stoichiometric excess of aluminum such that the aluminum to lithium molar ratio is greater than 2.

15. The aluminometallurgy method of claim 1, wherein the recycling product comprises material extracted from lithium-ion batteries including LiCoC>2 (LCO) cathodes.

16. The aluminometallurgy method of claim 1, wherein the recycling product comprises material extracted from lithium-ion batteries including LiNixMnyCoi.x-yO2 (NMC) cathodes.

17. The aluminometallurgy method of claim 1, wherein the recycling product comprises material extracted from lithium-ion batteries LiNixCovAli.x.yO2(NCA) cathodes.

18. The aluminometallurgy method of claim 1, further comprising extracting the recycling product from lithium-ion batteries by reacting cathode materials of the lithium-ion batteries with a liquid containing solvated AICl2+ions to extract recycling product from the cathode material.

19. The aluminometallurgy method of claim 1, further comprising extracting the recycling product from lithium-ion batteries by reacting cathode materials of the lithium-ion batteries with a liquid containing chloroaluminate AICU-ions to extract recycling product from the cathode material.

20. The aluminometallurgy method of claim 1, wherein recycling product extracted by reacting cathode materials with a liquid containing chloroaluminate AICk-ions comprises [EMIm CoCU and aluminum oxide.

21. Recycled lithium and transition metal materials extracted from lithium-ion battery recycling materials by the aluminometallurgy method of claim 1.-33- 136766.8027. WOOO\ 186140454.6PCT Patent Application136766.8027.WO0022. A system for separating lithium and metals from lithium-ion batteries and / or lithium- ion battery recycling materials, the system comprising:an input configured to receive recycling product, wherein the recycling product is extracted from lithium-ion batteries, or their components, derivatives, and recycling materials, using chloroaluminum-containing chemicals;a processing system configured to:receive the recycling product via the input,precipitate lithium-aluminum layered double hydroxide chloride ([LixAI2(OH)6]ClxnH2O) from the recycling product by addition of water to the recycling product, anda separation system configured to receive the precipitated [LixAI2(OH)6]ClxnH2O to separate solid [LixAI2(OH)6]ClxnH2O from a supernatant comprising dissolved metal chlorides; andan output configured to provide the solid [LixAI2(OH)6]ClxnH2O from the separation system and configured to extract metals from the supernatant by an addition of a base.

23. A method for separating lithium and metals from lithium-ion batteries and / or lithium- ion battery recycling materials:obtaining recycling product comprising lithium chloride, transition metal chlorides, and aluminum compounds,wherein the recycling product is extracted from lithium-ion batteries, or their components, derivatives, and recycling materials, using chloroaluminum- containing chemicals;precipitating lithium-aluminum layered double hydroxide chloride ([LixAI2(OH)6]ClxnH2O) from the recycling product by reaction with water and aluminum hydroxide; separating the precipitated [LixAI2(OH)6]ClxnH2O from a supernatant comprising dissolved metal chlorides; andextracting metals from the supernatant.

24. A method for separating lithium and metals from lithium-ion batteries and / or lithium- ion battery recycling materials:obtaining recycling product comprising lithium chloride, transition metal chlorides, and aluminum compounds,-34- 136766.8027. WOOO\ 186140454.6PCT Patent Application136766.8027.WO00wherein the recycling product is extracted from lithium-ion batteries, or their components, derivatives, and recycling materials, using chloroaluminum- containing chemicals;precipitating a lithium compound from the recycling product;separating the precipitated lithium compound from a supernatant comprising dissolved metal chlorides;extracting lithium from the lithium compound; andextracting metals from the supernatant.-35- 136766.8027. WOOO\ 186140454.6

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