Methods and compositions for reducing overconsumption of peroxide in hydrometallurgical digesting and recycling processes

Abstract

A method of treating a metal-containing composition comprising one or more of Li, Co, Mn, Fe, Cu, Al, and / or Ni, and / or a salt and / or an oxide thereof by contacting the metal-containing composition with an aqueous composition comprising a peroxide, a metal scavenger, and / or a free radical scavenger for a time and at a temperature sufficient to dissolve at least a portion of the metal-containing composition to produce a metal leachate comprising a liquid metal leachate and a solid residue, isolating the liquid metal leachate from the solid residue, and optionally separating dissolved salts and / or oxides of the Li, Co, Mn, Fe, Cu, Al, and / or Ni from the liquid metal leachate and from each other. Also, an aqueous composition for treating a metal-containing composition, comprising a metal scavenger and / or a free radical scavenger.

Description

[0001] METHODS AND COMPOSITIONS FOR REDUCING OVERCONSUMPTION OF PEROXIDE IN HYDROMET ALLURGICAL DIGESTING AND RECYCLING PROCESSES

[0002] FIELD

[0003] This invention relates to compositions and methods for reducing consumption of peroxide during metal digestion or metal recycling processes. Examples of such processes include refining of metals or metal alloys (for example, nickel refining) and recovery of lithium or other desirable metals from “black mass” or cathode active materials (CAM) arising from lithium-ion battery (LIB) material recycling.

[0004] BACKGROUND

[0005] Lithium-ion batteries (LIBs) have gained widespread use in energy storage tools because of their excellent electrochemical attributes, such as long life, high energy, and power density. As the world has grown to depend on the power and convenience brought by LIBs, their manufacturing and disposal have increasingly become subject to environmental and economic concerns. Reserves of lithium, cobalt, and other metals are limited, while their mining is energy and labor intensive and creates considerable pollution. If a spent LIB is discarded without proper treatment, heavy metals such as Co, Ni, and Mn can contaminate soil and underground water. Therefore, effective recycling is critical to ensure sustainable development in this field.

[0006] It is challenging for a single methodology to be both cost effective and environmentally friendly due to the complexity of the raw materials and the unpredictable chemistry that ensues. A combination of physical and chemical approaches is widely adopted to recycle spent LIBs (such as NMC, LCO, LMO, LFP and other battery types). Generally, physical methods are used to enhance the efficiency of recycling and typically include dismantling, crushing, sieving, thermal and chemical treatments. Two methods for separating and recovering metals from LIB scraps and end-of-life batteries are hydrometallurgical and pyrometallurgical.

[0007] Hydrometallurgy is often referred to as a leaching or lixiviation process. Lixiviation is the process of separating soluble from insoluble substances by dissolving (“digesting”) the former in an aqueous solution or in acid. Peroxides, such as hydrogen peroxide, are often used with acids to digest mixed metal streams. Two examples of such processes are recycling of a mixed metal stream or black mass arising from recycling of lithium-ion batteries and purification of metal alloys and / or nickel pig iron.

[0008] Peroxides, especially hydrogen peroxide, used in the inorganic acid leaching process, may act both as an oxidant or reducing agent based on the oxidation level of the metal. For example, peroxide acts as an oxidizer for certain metals present in battery materials (e.g., copper, iron, and aluminum), but acts as a reducing agent for metal oxides, such as nickel oxide, manganese oxide, and cobalt oxide. Peroxides, such as hydrogen peroxide, are quickly degraded, especially at elevated temperatures, in the presence of iron and copper ions.

[0009] Hydrogen peroxide catalytically reacts with free radicals and degrades into water and oxygen gas. The production of oxygen gas presents a significant safety issue, so there is a need to minimize its formation.

[0010] Electronic waste is a generic term used to describe all types of old, end-of-life or discarded electrical and electronic equipment, such as household appliances, office information and communications equipment, entertainment and consumer electronic equipment, lighting equipment, electric and electronic tools, toys, and leisure, sports and recreational equipment that are powered by electricity. Electronic waste contains both valuable and hazardous materials that require special handling and recycling methods. Black mass describes a type of electronic waste (e-waste) comprising crushed and shredded battery cell obtained once a battery has been processed for recycling. This shiny, metallic mixture called black mass contains various valuable metals that make up battery anodes and cathodes. Notably, black mass typically contains mixtures of metals including but not limited to lithium, copper, manganese, cobalt, and nickel.

[0011] Waste battery materials are collected, sorted, discharged, and disassembled. This is followed by mechanical crushing, drying, sorting, sieving, and in some cases, pyrolysis or calcination to remove any remaining electrolyte and potentially hazardous components. The resulting material is black mass. The composition of black mass varies significantly according to the composition of the incoming waste battery materials as well as to the mechanical and / or heat treatments that may have been used to form the black mass. Minimizing or eliminating the overconsumption of hydrogen peroxide in the hydrometallurgical treatment of recycled battery materials, including but not limited to lithium batteries, is especially challenging because of the complexity and varying compositions of the incoming metal streams that are treated with peroxide, usually in conjunction with acid, in hydrometallurgical metal refining processes.

[0012] For example, there are at least five different types of lithium-ion batteries, each with a different anode, cathode, and electrolyte features. These battery types are commonly referred to as LCO, LFP, LMO, NCA, and NMC. The main component in the cathodes of each of these batteries generally is as follows: LCO: LiCoO?; LFP: LiFePO4; LMO: LiMn2O4; NCA: LiAlxCoyNii-x-yO2; and NCM: LiCoxMnyNii-x-yO2. Also present are graphite, silicon, LiTi4O4, Sb, and various organometallics as part of the anode framework. Al and Cu may be present from current collectors. The following lithium salts from the electrolyte may also be present in the black mass: LiPF6, LiBF4, LiCF3SO3, Li (SO2CF3)2.

[0013] Nickel pig iron (NPI), likewise may vary widely its composition. Nickel pig iron is made of low-grade nickel ore, coking coal, and a mixture of gravel and sand as an aggregate. Iron is the main other component in nickel pig iron besides the nickel, but other impurities are present in varying amounts.

[0014] A metal alloy is a substance that combines more than one metal. Metal alloys such as nickel alloys, also vary greatly in composition. In the case of nickel alloys, the concentration in nickel can range from 30% to 99% and the other metals used in the alloy can be present in substantial amounts or as impurities (i.e., less than 1%).

[0015] Another significant problem associated with the use of hydrogen peroxide to enhance the dissolution of metals in hydrometallurgical processes is that a greater than stoichiometric amount of peroxide is consumed in these processes. As used here, this greater than stochiometric amount of peroxide is referred to as an over-consumption of hydrogen peroxide. It should also be understood that the peroxide may be used as either an oxidizing agent or a reducing agent, depending on the particular chemical make-up of the metal-containing composition, and the desired metal(s) to be recovered. US 3,293,093 discloses etching copper from copper or copper alloy metals with an aqueous solution of acid, hydrogen peroxide, and a small quantity of one or more or a mixture of two or more of phenacetin, sulfathiazole, or silver ion.

[0016] US 3,556,883 and US 3,597,290 disclose methods of etching copper from copper metals or copper alloys with an aqueous solution of acid, hydrogen peroxide, and a saturated aliphatic alcohol.

[0017] WO 2022 / 053448 Al discloses a process for preparing battery grade metal sulfate solutions by subjecting electrolytically produced metal objects to an aqueous leaching solution at an elevated temperature and acid pH in a continuous process with mixing, the leaching solution comprising at least one acid leaching agent and an oxidizing agent in liquid form.

[0018] WO 2023 / 148174 discloses methods for leaching material comprising copper in a zerooxidation state and for recycling battery material from lithium-ion battery, battery waste, battery production scrap, and cathode active material.

[0019] X. Cheng, G. Guo, Y Cheng, M. Liu, and J. Ji, Effect of Hydrogen Peroxide on the Recovery of Valuable Metals from Spent LiNio.6Coo.2Mno.2O2 Batteries, Energy Technol. 10:2200039 (2022), discloses the use of DL-malic acid and hydrogen peroxide to leach and recycle metals from spent lithium-nickel-cobalt-manganese oxide batteries.

[0020] Zachary J. Baum, Robert E. Bird, Xiang Yu, and Jia Ma, Lithium-Ion Battery Recycling - Overview of Techniques and Trends, ACS Energy Lett. 7:712-19 (2022), is a review from the CAS Content Collection relating to lithium-ion battery recycling.

[0021] Weiguang Lv, Zhonghang Wang, Hongbin Cao, Yong Sun, Yi Zhang, and Zhi Sun, A Critical Review and Analysis on the Recycling of Spent Lithium-Ion Batteries, ACS Sustainable Chem. Eng. 6: 1504-21 (2018), is a summary of lithium-ion battery recycling.

[0022] Omar Velazquez-Martinez, Johanna Valio, Annukka Santasalo-Aamio, Markus Reuter and Rodrigo Serna-Guerrero, A Critical Review of Lithium-Ion Battery Recycling Processes from a Circular Economy Perspective, Batteries 5:68 (2019), provides an analysis of recycling technologies from a circular economy perspective. Subramanian Natarajan and Vanchiappan Aravindan, Recycling Strategies for Spent Li- Ion Battery Mixed Cathodes, ACS Energy Lett. 3:2101-03 (2018), discloses an organic / inorganic acid-lixiviation of dried cathode active material with hydrogen peroxide.

[0023] Fan E, Li L, Wang Z, Lin J, Huang Y, Yao Y, Chen R, Wu F, Sustainable Recycling Technology for Li-Ion Batteries and Beyond: Challenges and Future Prospects, Chem. Rev. 120:7020-63 (2020), provides an overview of rechargeable battery sustainability, focusing on electric vehicles.

[0024] Faiza Arshad, Li, Kamran Amin, Ersha Fan, Nagesh Manurkar, Ali Ahmad, Jingbo Yang, Feng Wu, and Renjie Chen, A Comprehensive Review of the Advancement in Recycling the Anode and Electrolyte from Spent Lithium-Ion Batteries, ACS Sustainable Chem. Eng. 8:13527- 54 (2020), is a summary of recycling cathode, anode, and electrolyte materials and techniques.

[0025] Nathalia Vieceli, Piamcheewa Benjamasutin, Raksina Promphan, Pia Hellstrom, Magnus Paulsson, and Martina Petranikova, Recycling of Lithium-Ion Batteries: Effect of Hydrogen Peroxide and a Dosing Method on the Leaching of LCO, NMC Oxides, and Industrial Black Mass, ACS Sustainable Chem. Eng. 11 :9662-73 (2023), investigates the effect of hydrogen peroxide on the leachability of cathode active and black mass materials using sulfuric acid.

[0026] Niels Verbaan and Roxanne Naidoo, A review of hydrometallurgical flowsheets considered for the treatment of black mass, SGS Natural Resources, Lakefield ON, Canada (2023), describes various flowsheet configurations for hydrometallurgical treatment of black mass from battery shredding operations.

[0027] Alexander Chemyaev, Yuanmin Zou, Benjamin P. Wilson, Mari Lundstrom, The interference of copper, iron and aluminum with hydrogen peroxide and its effects on reductive leaching of LiNii / 3Mni / sCoi / 3O2, Separation and Purification Tech. 281 : 119903 (2022), discloses the effect of added hydrogen peroxide on its overconsumption in oxidation side reactions with copper, iron, and aluminum in leaching of nickel-manganese-cobalt active material.

[0028] Leon Dorfman and Gerald Adams, Reactivity of the Hydroxyl Radical in Aqueous Solutions, U.S. Dept, of Commerce, Bureau of Standards, June 1973, discloses reaction rate data of the hydroxyl radical in aqueous solution, including rate constant data. Lei Wang, Boqiang Li, Dionysios D. Dionysiou, Baiyang Chen, Jie Yang, and Juan Li, Overlooked Formation of H2O2 during the Hydroxyl Radical-Scavenging Process When Using Alcohols as Scavengers, Environ. Sci. Technol. 56:3386-96 (2022), discloses the adverse effects of hydrogen peroxide formation on the detection of hydroxyl ion during the use of alcohols as hydroxyl ion scavengers.

[0029] Chapter 4 - Fenton Type Activation and Chemistry of Hydroxyl radical, pp. 97-151 by J. Edwards and R. Curci, Published in Catalytic Oxidations with Hydrogen Peroxide as Oxidant, edited by Giorgio Strukul, 1992, reviews the activation of hydrogen peroxide.

[0030] In the present application, the inventors discovered a process wherein peroxide is used to enhance the dissolution of the desirable metals Li, Ni, Mn, and / or Co in an aqueous composition, which usually is acidic, and which optimizes the use of hydrogen peroxide in hydrometallurgical processes.

[0031] SUMMARY

[0032] The present invention relates to a method for chemically leaching metals present in recycled lithium batteries, and more particularly to a method for enhancing the dissolution of metals with hydrogen peroxide optionally under acidic and / or basic conditions and at high temperatures. The inventors discovered a method of treating a metal -containing composition using an aqueous leaching composition comprising certain metal stabilizers and / or free radical scavengers that unexpectedly prevent the catalytic decomposition of hydrogen peroxide due to transition metal impurities without negatively impacting the recovery yield of the metals (e.g., lithium, nickel, manganese, and cobalt).

[0033] The present invention also relates to a method for preventing the over-consumption of peroxide when chemically leaching metals in hydrometallurgical metal refining processes, such as when recovering metals from black mass or cathode materials during lithium-ion battery recycling, or when refining metals or metal alloys. In these processes, one or more peroxides are used, optionally with an acid and / or a base.

[0034] The inventors surprisingly discovered a solution to the above mentioned problems which uses certain stabilizers to prevent the catalytic decomposition of hydrogen peroxide in side reactions due to transition metal impurities, especially iron and / or copper, without negatively impacting the recovery yield of the desirable metals such as lithium, nickel, manganese, and / or cobalt

[0035] In particular, the inventors discovered that incorporating at least one of or a combination of free radical and / or metal scavenging agents prevents hydrogen peroxide degradation resulting in reduced-consumption of hydrogen peroxide. When the over-consumption of peroxide has been reduced or eliminated, more peroxide becomes available for dissolution or digestion of the targeted metals. The net result is that a lower overall amount of peroxide is needed to affect the dissolution / digestion / leaching process, thus providing the simultaneous benefits of improved economics and safety, since less oxygen is generated in the digestion process. This scavenging approach can be used with a variety of reactions, including for example the dissolution of nickel metal contaminated with iron and / or copper.

[0036] Importantly, when these metal scavengers and / or free radical scavengers are added to complex metal -containing compositions, they reduce the over-consumption of the peroxide without interfering with the peroxide’s intended use in multiple other reactions either as a reducing or oxidizing agent. The result is that the yields of the desired metals are not reduced. Preventing undesired side reactions from occurring also limits the unwanted formation of oxygen gas.

[0037] What is also new and surprising in this invention is the selective and targeted nature of the scavenging effect of hydroxyl free radicals achieved without interfering with the quasi- simultaneous reducing reaction taking place between hydrogen peroxide and the metals of interest (Li, Ni, Mn, and Co) in this complex acidified system at high temperatures. Using the processes and compositions of this invention, the hydrogen peroxide is substantially or even totally consumed by the reduction reaction with the metals of interest present in the black mass, and not substantially decomposed, or not decomposed at all, by the undesirable side reactions. This invention therefor significantly reduces the initial amount of hydrogen peroxide needed for the digestion / dissolution / leaching process without negatively impacting the metal recovery yield, which is in contrast to current hydroprocesses, where it is customary to add an excess of hydrogen peroxide to compensate for this loss.

[0038] The present methods and compositions improve both continuous processes (requiring the constant addition of hydrogen peroxide) and batch processes (e.g. leaching) by preventing an excessive or over consumption of hydrogen peroxide by side reactions as described above. These processes and compositions of the invention are also applicable to cobalt, manganese, lithium, or other metals of interest as well, which are dissolved or leached with peroxide.

[0039] According to a first aspect, a method of treating a metal-containing composition is provided, where the metal-containing composition comprises, consists of, or consists essentially of: first amounts of one or more of Li, Co, Mn, Fe, Cu, Al, and / or Ni, and / or a salt and / or an oxide thereof. The method comprises, consists of, or consists essentially of the following steps: a step of contacting the metal-containing composition with an aqueous leaching composition comprising, consisting of, or consisting essentially of a first amount of a peroxide; and a metal scavenger, and / or a free radical scavenger for a time and at a temperature sufficient to dissolve at least a portion of the metal-containing composition to produce a metal leachate composition comprising a liquid metal leachate and optionally a solid residue, the liquid metal leachate comprising a second amount of dissolved salts and / or oxides of the Li, Co, Mn, Fe, Cu, Al, and / or Ni; and a second amount of the peroxide; a step of isolating the liquid metal leachate from the solid residue; and an optional step of separating dissolved salts and / or oxides of the Li, Co, Mn, Fe, Cu, Al, and / or Ni from the liquid metal leachate and / or from each other; wherein the second amount of peroxide in the liquid metal leachate is greater than would be present in an identical method not including the metal scavenger and / or the free radical scavenger.

[0040] According to another aspect of the invention, the present methods of treating a metalcontaining composition may also be used to treat amounts of one or more of Ca, Ba, Al, Ti, Zr, Zn, Fe, V, Mo and W (including or excluding amounts of one more of Li, Co, Mn, Fe, Cu, Al, and / or Ni).

[0041] According to another aspect of the invention, an aqueous composition for treating a metal-containing composition is provided, where the aqueous composition comprises, consists of, or consists essentially of: 0.1 to 35 wt.%, preferably 0.2-17.5 wt.%, and more preferably 0.3- 12% wt.% of the peroxide, and at least 0.01 wt.%, preferably at least about 0.05%, more preferably 0.05 wt.% to 10 wt.%, more preferably 0.05 wt.% to 5 wt.%, more preferably 0.1 wt.% to 5 wt.%, most preferably 1.0 wt.% to 2.0 wt.%, of each of the metal scavenger and / or the free radical scavenger, based on a total weight of the aqueous leaching composition and the metal-containing composition to be treated.

[0042] BRIEF DESCRIPTION OF THE DRAWINGS

[0043] The following figures represent exemplary embodiments of the invention and are not intended to otherwise limit the description of the invention as described herein.

[0044] Figure 1 shows elements present in a lithium-ion battery material a minimal impact on hydrogen peroxide degradation.

[0045] Figure 2 shows elements present in a lithium-ion battery material having a strong impact on hydrogen peroxide degradation.

[0046] Figure 3 shows the effect of Fe and Cu contaminants on hydrogen peroxide concentration for one hour at 50 C.

[0047] Figure 4 shows the time to reach a full degradation of hydrogen peroxide in the presence of iron contaminant.

[0048] Figure 5 shows the evolution of the degradation of hydrogen peroxide concentration for two different BM with and without a free radical scavenger

[0049] Figure 6 shows degradation of hydrogen peroxide in the presence of cathode material NMC 622.

[0050] DETAILED DESCRIPTION

[0051] “Electronic waste” or “E-waste” as used herein means all types of old, end-of-life or discarded electrical and electronic equipment, such as household appliances, office information and communications equipment, entertainment and consumer electronic equipment, lighting equipment, electric and electronic tools, toys, and leisure, sports and recreational equipment that are powered by electricity.

[0052] “Black mass” as used herein means waste obtained from a battery, battery waste, battery production scrap, cathode active material, lithium-ion battery, lithium ion battery waste, lithium ion battery production scrap, lithium ion cell production scrap, lithium ion cathode active material, and combinations thereof, which include at least one or more of the following metals: lithium, copper, manganese, cobalt, and nickel.

[0053] A free-radical scavenger prevents formation of, removes, or de-activates free radicals and unwanted free radicals and reaction products of free radicals. As used herein, “free radical scavenger” is based on hydrogen abstraction. A free radical scavenger as used herein is a substrate or compound Y capable of donating a hydrogen free radical (H-) to a free radical (X) to provide a relatively more stable (more stable than the X-) Y-.

[0054] As used herein, an “abstractable hydrogen” is a hydrogen atom that is capable of reacting with a free radical X- to form HX, thus deactivating the free radical X-.

[0055] As used herein, a “metal scavenger” is a functionalized molecule designed to react and bind excess metal ions or metal complexes or metals. Typically, a metal scavenger has a high affinity for the targeted metal ions and / or metals.

[0056] As used herein, “comprising” encompasses “consisting” or “consisting essentially of.” If “consisting essentially of’ is used, the basic and novel characteristics of the method or composition recited are that the amount of peroxide consumed is less than that which would be consumed in an identical method or composition not including the metal scavenger and / or the free radical scavenger.

[0057] As used herein, a “solution” is a combination of a fluid and one or more compounds. For example, each of the one or more compounds in the solution may or may not be dissolved in the fluid.

[0058] Metal -Containing Composition:

[0059] The metal-containing composition is the composition that is subjected to the hydrometallurgical digestion or lixiviation processes of the invention. The metal -containing composition comprises first amounts of one or more of Li, Co, Mn, Fe, Cu, Al, and / or Ni, and / or a salt and / or an oxide thereof.

[0060] According to an embodiment, the metal-containing composition comprises first amounts of: up to 15 wt.% of Li and / or a salt and / or an oxide thereof, up to 96 wt.% of Co and / or a salt and / or an oxide thereof, up to 95 wt.% of Mn and / or a salt and / or an oxide thereof, up to 99.9 wt.% of Ni and / or a salt and / or an oxide thereof, up to 5 wt.% of Al and / or a salt and / or an oxide thereof, up to 10 wt.% of Cu and / or a salt and / or an oxide thereof, and / or up to 90 wt.% of Fe and / or a salt and / or an oxide thereof.

[0061] These first amounts are based on the total first weight of the Li, Co, Mn, Ni, Al, Fe, and Cu; and any salt and any oxide thereof in the metal -containing composition. Importantly, in this embodiment, the metal -containing composition comprises of at least one of: at least 0.001wt.% of Cu and / or a salt and / or an oxide thereof and / or at least 0.003 wt.% of Fe and / or a salt and / or an oxide thereof.

[0062] In other words, the metal -containing composition includes at least one of Cu and / or a salt and / or an oxide thereof and Fe and / or a salt and / or an oxide thereof. The amounts of each of these metals in the metal-containing composition, the Li, Co, Mn, and / or Ni; and / or their salts and / or oxides may vary depending on the source of the metal -containing composition that is treated with the aqueous composition as disclosed herein.

[0063] According to an embodiment, prior to the contacting step, the metal-containing composition may comprise a first amount of at least 0.5 wt.%, preferably at least 2 wt.%, more preferably at least 20 wt.% of metallic Ni and at least 0.01 wt.%, preferably at least 10 wt.%, more preferably at least 60 wt.% of metallic Fe based on a total first weight of the Li, Co, Mn, Ni, Al, Fe, and Cu; and any salt and any oxide thereof in the metal -containing composition. According to this embodiment, the metal leachate composition may comprise at least 99.9 wt.% of a Ni salt and / or Ni oxide thereof based on a total weight of the Ni and / or a salt and / or an oxide thereof in the liquid metal leachate composition.

[0064] According to another embodiment, the metal-containing composition may be black mass from lithium ion battery recycling operations and prior to the contacting step, the first amounts of the one or more of Li, Mn, Co, Ni, Al, Fe, Cu and / or Ni; and / or a salt and / or an oxide thereof are: 5 to 20 wt.% Li and / or a salt and / or an oxide thereof; 5 to 20 wt.% Mn and / or a salt and / or an oxide thereof; 10 to 40 wt.% Ni and / or a salt and / or an oxide thereof; 2 to 8 wt.% Al and / or a salt and / or an oxide thereof; 0.05 to 2 wt.% Fe and / or a salt and / or an oxide thereof; 0.5 to 10 wt.% Cu and / or a salt and / or an oxide thereof; and 50 to 70 wt.% Co and / or a salt and / or an oxide thereof.

[0065] The above amounts are all based on a total first weight of the Li, Co, Mn, Ni, Al, Fe, and Cu; and any salt and any oxide thereof in the metal -containing composition.

[0066] According to an embodiment, the metal-containing composition is black mass from lithium-ion battery recycling operations and prior to the contacting step, the first amounts of the one or more of Li, Mn, Co, Ni, Al, Fe, Cu and / or Ni; and / or a salt and / or an oxide thereof are:

[0067] 5 to 20 wt.% Li and / or a salt and / or an oxide thereof;

[0068] 70 to 95 wt.% Mn and / or a salt and / or an oxide thereof;

[0069] 0.01 to 40 wt.% Ni and / or a salt and / or an oxide thereof;

[0070] 0 to 8 wt.% Al and / or a salt and / or an oxide thereof;

[0071] 0.01 to 2 wt.% Fe and / or a salt and / or an oxide thereof;

[0072] 0. 1 to 10 wt.% Cu and / or a salt and / or an oxide thereof; and

[0073] 0 to 15 wt.% Co and / or a salt and / or an oxide thereof.

[0074] The above amounts are all based on a total first weight of the Li, Co, Mn, Ni, Al, Fe, and Cu; and any salt and any oxide thereof in the metal -containing composition.

[0075] According to an embodiment, the metal-containing composition may be black mass from lithium-ion battery recycling operations and prior to the contacting step, may include the following, based on a total first weight of the Li, Co, Mn, Ni, Al, Fe, and Cu; and any salt and any oxide thereof in the metal -containing composition:

[0076] 5 to 20 wt.% Li and / or a salt and / or an oxide thereof;

[0077] 0 to 20 wt.% Mn and / or a salt and / or an oxide thereof;

[0078] 10 to 40 wt.% Ni and / or a salt and / or an oxide thereof; 0.1 to 1 wt.% Al and / or a salt and / or an oxide thereof;

[0079] 10 to 90 wt.% Fe and / or a salt and / or an oxide thereof;

[0080] 0 to 10 wt.% Cu and / or a salt and / or an oxide thereof; and

[0081] 0 to 20 wt.% Co and / or a salt and / or an oxide thereof.

[0082] According to an embodiment, the metal-containing composition may be black mass from lithium-ion battery recycling operations and prior to the contacting step, may include the following, based on a total first weight of the Li, Co, Mn, Ni, Al, Fe, and Cu; and any salt and any oxide thereof in the metal-containing composition:

[0083] 5 to 20 wt.% Li and / or a salt and / or an oxide thereof;

[0084] 5 to 20 wt.% Mn and / or a salt and / or an oxide thereof;

[0085] 40 to 70 wt.% Ni and / or a salt and / or an oxide thereof;

[0086] 1 to 7 wt.% Al and / or a salt and / or an oxide thereof;

[0087] 2 to 12 wt.% Cu and / or a salt and / or an oxide thereof;

[0088] 0.05 to 1 wt.% Fe and / or a salt and / or an oxide thereof; and

[0089] 10 to 30 wt.% Co and / or a salt and / or an oxide thereof.

[0090] According to an embodiment, the metal-containing composition may be black mass from lithium iron phosphate (LFP) battery recycling operations and prior to the contacting step, may include iron (III) phosphate (ferric phosphate).

[0091] According to an embodiment, the metal-containing composition prior to the contacting step comprises the Cu, Cu salt, and / or the Cu oxide and the metal scavenger comprises phenyl acetamides, phosphoric acid, disodium pyrophosphate (Na2H2P2O?), tetrasodium pyrophosphate (Na4P2O?), phosphonates, or combinations thereof, preferably phenacetin, phosphoric acid, phosphonic acid, disodium pyrophosphate (Na2H2P2O?), tetrasodium pyrophosphate (Na4P2O?), NTMP (nitrilotrimethyl-phosphonic acid), EDTMP (ethylene diamine tetra methylene phosphonic acid), DTPMP (diethylenetriaminepentakis methylphosphonic acid), hydroxyethylidine diphosphonic acid (HEDP), or combinations thereof. According to another embodiment, the metal-containing composition prior to the contacting step comprises the Fe, the Fe salt, and / or the Fe oxide and the metal scavenger comprises stannates, phenolic acids, phosphoric acid, disodium pyrophosphate tetrasodium pyrophosphate (Na4P2O?), phosphonates, or combinations thereof, preferably tannic acid, gallic acid, phosphoric acid, disodium pyrophosphate (Na2H2P2O?), tetrasodium pyrophosphate (Na4P2O?), phosphonic acid, NTMP (nitrilotrimethyl-phosphonic acid), EDTMP (ethylene diamine tetra methylene phosphonic acid), DTPMP (diethylenetriaminepentakis(methylphosphonic acid), hydroxyethylidine diphosphonic acid (HEDP), potassium stannate; sodium stannate; sodium hexahydroxystannate, phosphonic acid, or combinations thereof.

[0092] According to an embodiment, the metal-containing composition prior to the contacting step may comprise one or more metal alloys.

[0093] According to an embodiment, the metal-containing composition prior to the contacting step may comprise electronic waste (E -waste).

[0094] Aqueous Leaching Composition:

[0095] An aqueous leaching composition for treating a metal-containing composition is provided. According to an embodiment, the aqueous leaching composition may comprise the metal scavenger. According to an embodiment, the aqueous leaching composition may comprise the free radical scavenger. According to an embodiment, the aqueous leaching composition may comprise the metal scavenger and / or the free radical scavenger.

[0096] According to an embodiment, the aqueous leaching composition comprises:

[0097] 0.1 to 35 wt.%, preferably 0.2-17.5 wt.%, and more preferably 0.3- 12% wt.% of a peroxide, and at least 0.01 wt.%, preferably at least about 0.05 wt.%, more preferably 0.05 wt.% to 10 wt.%, more preferably 0.05 wt.% to 5 wt.%, more preferably 0.1 wt.% to 5 wt.%, and most preferably 1.0 wt.% to 2.0 wt.%, of each of the metal scavenger and / or the free radical scavenger, based on a total weight of the aqueous leaching composition and the metal-containing composition to be treated. According to an embodiment, the aqueous leaching composition may further comprise an acid or a base.

[0098] According to an embodiment, the aqueous leaching composition can comprise a dispersion or a solution, preferably a solution, and more preferably a homogeneous solution.

[0099] Peroxides:

[0100] Non-limiting examples of suitable peroxides are hydrogen peroxide, perborates, percarbonates, persulfates, organic peroxides, peroxyacids, hydroperoxides, or combinations thereof, preferably at least one of hydrogen peroxide, peracetic acid, peroxy octanoic acid, cumene peroxide, hydroperoxides, diacyl peroxides, peroxyesters, or combinations thereof, more preferably hydrogen peroxide.

[0101] Metal Scavenger:

[0102] Non-limiting examples of suitable metal scavengers are phenyl acetamides, phenacetin, stannates, potassium stannate, sodium stannate, sodium hexahydroxystannate, phenolic acids, phosphoric acid, disodium pyrophosphate tetrasodium pyrophosphate (Na4P2O?), phosphonates, or combinations thereof, more preferably tannic acid, gallic acid, phosphoric acid, di sodium pyrophosphate (Na2H2P2O?), tetrasodium pyrophosphate (Na4P2O?), phosphonic acid, NTMP (nitrilotrimethyl-phosphonic acid), EDTMP (ethylene diamine tetra methylene phosphonic acid), DTPMP (diethylenetriaminepentakis(methylphosphonic acid), hydroxyethylidine diphosphonic acid (HEDP), or combinations thereof, most preferably, phosphoric acid, phosphonic acid, disodium pyrophosphate, tetrasodium pyrophosphate, or combinations thereof.

[0103] According to an embodiment, the metal scavenger comprises phenyl acetamides, phosphoric acid, disodium pyrophosphate (Na2H2P2O?), tetrasodium pyrophosphate (Na4P2O?), phosphonates, or combinations thereof, preferably phenacetin, phosphoric acid, phosphonic acid, disodium pyrophosphate (Na2H2P2O?), tetrasodium pyrophosphate (Na4P2O?), NTMP (nitrilotrimethyl-phosphonic acid), EDTMP (ethylene diamine tetra methylene phosphonic acid), DTPMP (diethylenetriaminepentakis(methylphosphonic acid), hydroxy ethylidine diphosphonic acid (HEDP), or combinations thereof. According to an embodiment, the metal scavenger comprises stannates, phenolic acids, dipicolinic acid, phosphoric acid, disodium pyrophosphate (TSfeHiPzO?), tetrasodium pyrophosphate (Na4P2O?), phosphonates, or combinations thereof, preferably tannic acid, gallic acid, phosphoric acid, phosphonic acid, disodium pyrophosphate (Na2H2P2O?), tetrasodium pyrophosphate (Na4P2O?), NTMP (nitrilotrimethyl-phosphonic acid), EDTMP (ethylene diamine tetra methylene phosphonic acid), DTPMP (diethylenetriaminepentakis(methylphosphonic acid), hydroxyethylidine diphosphonic acid (HEDP), or combinations thereof, most preferably, sodium stannate, phosphoric acid, phosphonic acid, disodium pyrophosphate, tetrasodium pyrophosphate, or combinations thereof.

[0104] The aqueous composition may comprise at least 0.01 wt.%, preferably at least about 0.05 wt.%, more preferably 0.05 wt.% to 10 wt.%, more preferably 0.05 wt.% to 5 wt.%, more preferably 0.1 wt.% to 5 wt.%, and most preferably 1.0 wt.% to 2.0 wt.% of the metal scavenger, based on the total weight of the aqueous leaching composition and the metal-containing composition to be treated.

[0105] Free Radical Scavenger:

[0106] The free radical scavenger may include a compound bearing at least one abstractable hydrogen. Non-limiting examples of suitable free radical scavengers are compounds comprising at least one OH group bearing an abstractable hydrogen. Non-limiting examples of such compounds are selected from monohydric alcohols, C1-C12 primary non-cyclic alcohols, preferably C4 to Cs primary non-cyclic alcohols, polyhydric alcohols, unsaturated aliphatic alcohols, alicyclic alcohols, diols, preferably straight aliphatic C5 - Cs diols, branched Cs-Cs diols, C3- C 12 cyclic diols, straight chain, branched, star, or comb polyethylene glycols having a weight average molecular weight from 60 to 10,000,000 Daltons, preferably 200-8000 Daltons, poly(tetra methylene oxide) also called polytetrahydrofuran having weight average molecular weight from 250 to 40,000 Daltons, glycol ether solvents, preferably 2-methoxyethanol, 2- ethoxyethanol, 2 -propoxy ethanol, 2-isopropoxyethanol, 2-butoxyethanol, 2-phenoxyethanol, 2- benzyloxy ethanol, 1-m ethoxy -2-propanol, 2-(2-methoxy ethoxy )ethanol, 2-(2- ethoxyethoxy)ethanol, 2-(2-butoxyethoxy)ethanol, dipropylene glycol methyl ether, C12-15 pareth-12, dialkyl ethers, preferably dimethoxyethane, diethoxyethane, dibutoxyethane, esters, preferably 2-m ethoxy ethyl acetate, 2-ethoxy ethyl acetate, 2 -butoxy ethyl acetate, l-methoxy-2- propanol acetate, hydrophilic non-ionic surfactants bearing at least on one OH group having an abstractable hydrogen, preferably polyethylene sorbitol esters, alkaloids, (quinine), purines, (guanine), saccharides, carboxylic acids, dimethyl sulfoxide, piperidine nitroxides, preferably TEMPOL (4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl), or combinations thereof, more preferably methanol, ethanol, propanol, n-butanol, heptanol, hexanol isopropanol, tertiary butanol, hexane diol, heptane diol, octane diol, triols, piperidine nitroxide TEMPOL (4-hydroxy- 2,2,6,6-tetramethylpiperidine-N-oxyl), benzoic acid, ascorbic acid, or combinations, thereof, most preferably n-butanol, ascorbic acid, or a combination thereof.

[0107] The preferred free radical scavengers include, but are not limited to linear, branched, isomeric branched, secondary, tertiary, or polyhydric alcohols that may contain even- and / or odd-numbered hydrocarbon chains, ranging from about C4 to C15, preferably including but not limited to, for example, butanol, 1-pentanol, 2-propanol, 1-hexanol, 1-octanol, 2-ethyl-l- hexanol; diol molecules HO-R-OH wherein R is a linear or branched alkyl group ranging from C4 to C15, further including for example, but not limited to 1,6-hexanediol, 1,5-pentanediol, 1,8- octanediol, 1,7-hepanediol; polyhydric alcohol fatty acid esters, polyhydric alcohol fatty acid esters comprising a fatty acid mono and / or diester of polyethylene glycol and / or polypropylene glycol; compounds based on fatty alcohols including, for example, but not limited to CnHzO with n ranging from 4 to 34 and z from 10 to 70; thioethers, such as, for example, but not limited to, HO-CH(R7)-CH2-S-CH2-CH(OH)-CH2-O-R4wherein R4is C4-20 alkyl, and R7is selected from the group consisting of H and CH2OH (preferably R7is H); and epichlorohydrinmercaptoethanol alcohol. The free radical scavengers more preferably include but are not limited to tert-butanol, sucrose, ethylene glycol, isopropanol, pentanol, ethanol, butanol, and ascorbic acid, and most preferably include but are not limited to n-butanol and ascorbic acid.

[0108] The aqueous composition may comprise at least 0.01 wt.%, preferably at least about 0.05 wt.%, more preferably 0.05 wt.% to 10 wt.%, more preferably 0.05 wt.% to 5 wt.%, more preferably 0.1 wt.% to 5 wt.%, and most preferably 1 .0 wt.% to 2.0 wt.% of the free radical scavenger, based on the total weight of the aqueous leaching composition and the metalcontaining composition. Acid:

[0109] According to an embodiment, the acid, if present in the aqueous leaching composition, comprises at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid, acetic acid, citric acid, lactic acid, malic acid, methane sulfonic acid, gluconic acid, formic acid, acetoacetic acid, succinic acid, adipic acid, oxalic acid, aspartic acid, or combinations thereof, preferably nitric, hydrochloric or sulfuric acid.

[0110] Base

[0111] According to an embodiment, the base, if present in the aqueous leaching composition, may be chosen from any of the known chemical bases, and preferably comprises at least one of ammonia, ammonium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, ammonium chloride, sodium carbonate, potassium carbonate, ammonium carbonate, and more preferably ammonia or sodium hydroxide. pH

[0112] According to an embodiment, a sufficient amount of the acid and / or base is present in the aqueous leaching composition to render a pH of the metal leachate composition to be 8 or less, preferably 7 or less, more preferably 6 or less, more preferably 5 or less, more preferably 4 or less, more preferably 3 or less, most preferably 2 or less. According to another embodiment, a sufficient amount of the acid and / or base is present in the aqueous leaching composition to render a pH of the metal leachate composition to be 6 or more, preferably 7 or more, more preferably 8 or more, more preferably 9 or more, preferably 10 or more, more preferably 11 or more, most preferably 12 or more. pH may be measured with a pH meter as is known in the art, such as, for example, using a Fisherbrand™ accumet™ API 10 Portable pH Meter Kit, Catalog NO.13-636-AP110 (Fisher Scientific), equipped with a Fisherbrand™ accumet™ pH / ATC Electrode, Catalog No. 13-620-AP50A (Fisher Scientific).

[0113] Metal Leachate Composition:

[0114] The metal leachate composition is formed by contacting the metal-containing composition with the aqueous leaching composition and comprises a liquid metal leachate and optionally a solid residue. Liquid Metal Leachate:

[0115] The liquid metal leachate includes the dissolved desirable metals, i.e., the salts and / or oxides of the Li, Co, Mn, Fe, Cu, Al, and / or Ni.

[0116] Solid Residue:

[0117] The solid residue left after the metal components are dissolved or digested includes all of the materials that do not dissolve in the aqueous composition. At a minimum, when the metalcontaining composition is the black mass from battery recycling operations, the solid residue includes carbon black and / or graphite. It may also include other inorganic or organic materials that do not dissolve in the aqueous composition, such as polymers and silicon or silica.

[0118] If the metal-containing composition is a metal alloy, the potential solid residue may include metal oxides, metal sulfides or sulfates, silica and / or slag.

[0119] Methods:

[0120] A method of treating a metal-containing composition is provided. The metal-containing composition comprises, consists of or consists essentially of first amounts of one or more of Li, Co, Mn, Fe, Cu, Al, and / or Ni, and / or a salt and / or an oxide thereof as described above. The method comprises, consists of, or consists essentially of the following steps.

[0121] A step of contacting the metal-containing composition with an aqueous leaching composition comprising, consisting of, or consisting essentially of: a first amount of a peroxide; and a metal scavenger, and / or a free radical scavenger; for a time and at a temperature sufficient to dissolve at least a portion of the metal-containing composition to produce a metal leachate composition comprising a liquid metal leachate and optionally a solid residue, the liquid metal leachate comprising a second amount of dissolved salts and / or oxides of the Li, Co, Mn, Fe, Cu, Al, and / or Ni; and a second amount of the peroxide.

[0122] A step of isolating the liquid metal leachate from the solid residue.

[0123] An optional step of separating dissolved salts and / or oxides of the Li, Co, Mn, Fe, Cu, Al, and / or Ni from the liquid metal leachate and from each other. In the method, the second amount of peroxide in the liquid metal leachate is greater than would be present in an identical method not including the metal scavenger and / or the free radical scavenger.

[0124] According to an embodiment, the amount of peroxide consumed is less than 80 wt.%, less than 70wt.%, less than 60 wt.%, less than 50 wt.%, less than 25wt.%, less than 20 wt.%, less than 15 wt.%, less than 10 wt.%, or less than 5 wt.% of that which would be consumed in the identical method not including the metal scavenger and / or the free radical scavenger. In some embodiments, the amount of peroxide consumed does not exceed the amount required stoichiometrically by the element(s) of interest.

[0125] According to some embodiments the method is a batch process. According to some other embodiments, the method is a continuous process. According to some embodiments, the method is a semi-batch process. According to some embodiments, the method is a semi-continuous process.

[0126] Contacting step:

[0127] The contacting step may be done according to any of the methods as are known to the art. Typically, the aqueous leaching composition is combined with the metal- containing composition in an appropriate reaction vessel for a time and at a temperature sufficient to dissolve at least a portion of the metal-containing composition to produce a metal leachate composition, the metal leachate composition comprising a liquid metal leachate and optionally a solid residue, the liquid metal leachate comprising a second amount of dissolved salts and / or oxides of the Li, Co, Mn, Fe, Cu, Al, and / or Ni . Descriptions of various commercially operating hydrometallurgical processes may be found in, e.g., Baum et al., Lithium-Ion Battery Recycling - Overview of Techniques and Trends, ACS Energy Lett. 7:712-19 (2022), Lv et al., A Critical Review and Analysis on the Recycling of Spent Lithium-Ion Batteries, ACS Sustainable Chem. Eng. 6: 1504- 21 (2018), Arshad et al., A Comprehensive Review of the Advancement in Recycling the Anode and Electrolyte from Spent Lithium-Ion Batteries, ACS Sustainable Chem. Eng. 8: 13527-54 (2020), Fan et al., Sustainable Recycling Technology for Li-Ion Batteries and Beyond: Challenges and Future Prospects, Chem. Rev. 120:7020-63 (2020), and Verbaan et al., A review of hydrometallurgical flowsheets considered for the treatment of black mass, SGS Natural Resources, Lakefield ON, Canada (2023). According to an embodiment, the time for which the temperature is maintained sufficient to dissolve at least a portion of the metal-containing composition may be from 0.5 minute to 24 hours, preferably from about 10 minutes to 2 hours, and the temperature that is maintained may be from 10 to 100°C, preferably from 15 to 90°C, more preferably from 20 to 80°C. According to some embodiments, external heat may be applied to raise and maintain the temperature. According to some other embodiments, the exothermic reactions are sufficient to raise the temperature and the time at temperature needed to affect the process is met by allowing the composition to cool on its own.

[0128] Isolating step:

[0129] The liquid metal leachate may be separated from the potential solid residue by typical solid / liquid separation methods such as filtration, centrifugal separation, settling and pouring off, for example. According to some embodiments, flocculants may be added to speed up or enhance settling of the solid residue.

[0130] Separating step:

[0131] Separating the desired dissolved salts and / or oxides of the Li, Co, Mn, Fe, Cu, Al, and / or Ni from the liquid metal leachate and from each other may be done by any of the electrochemical methods, or chemical methods as are known to the art. Commercially operating hydrometallurgical processes are described in, e.g., Baum et al., Lithium-Ion Battery Recycling - Overview of Techniques and Trends, ACS Energy Lett. 7:712-19 (2022), Lv et al., A Critical Review and Analysis on the Recycling of Spent Lithium-Ion Batteries, ACS Sustainable Chem. Eng. 6: 1504-21 (2018), Arshad et al., A Comprehensive Review of the Advancement in Recycling the Anode and Electrolyte from Spent Lithium-Ion Batteries, ACS Sustainable Chem. Eng. 8: 13527-54 (2020), Fan et al., Sustainable Recycling Technology for Li-Ion Batteries and Beyond: Challenges and Future Prospects, Chem. Rev. 120:7020-63 (2020), and Verbaan et al., A review of hydrometallurgical flowsheets considered for the treatment of black mass, SGS Natural Resources, Lakefield ON, Canada (2023).

[0132] Non-limiting aspects of the invention are summarized as follows:

[0133] Aspect 1 : A method of treating a metal-containing composition with an aqueous leaching composition containing a peroxide, characterized in that: - a metal -containing composition comprising first amounts of one or more of Li, Co, Mn, Fe, Cu, Al, and / or Ni, and / or a salt and / or an oxide thereof is contacted with an aqueous leaching composition comprising: a first amount of a peroxide; and a metal scavenger and / or a free radical scavenger;

[0134] - for a time and at a temperature sufficient to dissolve at least a portion of the metalcontaining composition to produce a metal leachate composition comprising a liquid metal leachate and optionally a solid residue, the liquid metal leachate comprising a second amount of dissolved salts and / or oxides of the Li, Co, Mn, Fe, Cu, Al, and / or Ni; and a second amount of the peroxide;

[0135] - isolating the liquid metal leachate from the solid residue; and optionally separating dissolved salts and / or oxides of the Li, Co, Mn, Fe, Cu, Al, and / or Ni from the liquid metal leachate and / or from each other; wherein the second amount of peroxide in the liquid metal leachate is greater than would be present in an identical method not including the metal scavenger and / or the free radical scavenger.

[0136] Aspect 2: The method of Aspect 1, further characterized in that the aqueous leaching composition comprises 0.1 to 35 wt.%, preferably 0.2-17.5 wt.%, and more preferably 0.3- 12% wt.% of the first amount of peroxide, and at least 0.01 wt.%, preferably at least about 0.05 wt.%, more preferably 0.05 wt.% to 10 wt.%, more preferably 0.05 wt.% to 5 wt.%, more preferably 0.1 wt.% to 5 wt.%, and most preferably 1.0 wt.% to 2.0 wt.%, of each of the metal scavenger and / or the free radical scavenger, based on a total weight of the aqueous leaching composition and the metal-containing composition.

[0137] Aspect 3 : The method of Aspect 1 or Aspect 2, further characterized in that the aqueous leaching composition further comprises an acid, and / or further characterized in that the aqueous leaching composition further comprises a base.

[0138] Aspect 4: The method of any of Aspects 1-3, further characterized in that the second amount of dissolved Li, Co, Mn, Fe , Cu, Al, and / or Ni in the liquid metal leachate is substantially the same or greater compared to the same method not including the metal scavenger and / or the free radical scavenger.

[0139] Aspect 5: The method of any of Aspects 1-4, further characterized in that the metalcontaining composition comprises first amounts of: up to 15 wt.% of Li and / or a salt and / or an oxide thereof, up to 96 wt.% of Co and / or a salt and / or an oxide thereof, up to 95 wt.% of Mn and / or a salt and / or an oxide thereof, up to 99.9 wt.% of Ni and / or a salt and / or an oxide thereof, up to 5 wt.% of Al and / or a salt and / or an oxide thereof, up to 10 wt.% of Cu and / or a salt and / or an oxide thereof, and / or up to 90 wt.% of Fe and / or a salt and / or an oxide thereof; based on the total first weight of the Li, Co, Mn, Ni, Al, Fe, and Cu; and any salt and any oxide thereof in the metal-containing composition; and wherein the metal -containing composition comprises first amounts of at least one of at least 0.001wt.% of Cu and / or a salt and / or an oxide thereof and / or at least 0.003 wt.% of Fe and / or a salt and / or an oxide thereof.

[0140] Aspect 6: The method of Aspect 5, further characterized in that, prior to the contacting step, the metal-containing composition comprises a first amount of at least 0.5 wt.%, preferably at least 2 wt.%, more preferably at least at least 20 wt.% of metallic Ni and at least 0.01 wt.%, preferably at least 10 wt.%, more preferably at least 60 wt.% metallic Fe based on a total first weight of the Li, Co, Mn, Ni, Al, Fe, and Cu; and any salt and any oxide thereof in the metalcontaining composition and the liquid metal leachate composition comprises at least 99.9 wt.% of a Ni salt and / or Ni oxide thereof based on a total weight of the Ni and / or a salt and / or an oxide thereof in the liquid metal leachate composition.

[0141] Aspect 7: The method of Aspect 5, further characterized in that the metal-containing composition is black mass from lithium ion battery recycling operations and prior to the contacting step, the first amounts of the one or more of Li, Mn, Co, Ni, Al, Fe, Cu and / or Ni; and / or a salt and / or an oxide thereof are:

[0142] 5 to 20 wt.% Li and / or a salt and / or an oxide thereof;

[0143] 5 to 20 wt.% Mn and / or a salt and / or an oxide thereof;

[0144] 10 to 40 wt.% Ni and / or a salt and / or an oxide thereof;

[0145] 2 to 8 wt.% Al and / or a salt and / or an oxide thereof;

[0146] 0.05 to 2 wt.% Fe and / or a salt and / or an oxide thereof;

[0147] 0.5 to 10 wt.% Cu and / or a salt and / or an oxide thereof; and

[0148] 50 to 70 wt.% Co and / or a salt and / or an oxide thereof.

[0149] Aspect 8: The method of Aspect 5, further characterized in that the metal-containing composition is black mass from lithium ion battery recycling operations and prior to the contacting step, the first amounts of the one or more of Li, Mn, Co, Ni, Al, Fe, Cu and / or Ni; and / or a salt and / or an oxide thereof are:

[0150] 5 to 20 wt.% Li and / or a salt and / or an oxide thereof;

[0151] 70 to 95 wt.% Mn and / or a salt and / or an oxide thereof;

[0152] 0.01 to 40 wt.% Ni and / or a salt and / or an oxide thereof;

[0153] 0 to 8 wt.% Al and / or a salt and / or an oxide thereof;

[0154] 0.01 to 2 wt.% Fe and / or a salt and / or an oxide thereof;

[0155] 0.1 to 10 wt.% Cu and / or a salt and / or an oxide thereof; and

[0156] 0 to 15 wt.% Co and / or a salt and / or an oxide thereof.

[0157] Aspect 9: The method of Aspect 5, further characterized in that the metal -containing composition is black mass from lithium ion battery recycling operations and prior to the contacting step, the first amounts of the one or more of Li, Co, Mn, Co, Ni, Al, Fe, Cu, and / or Ni; and / or a salt and / or an oxide thereof are: 5 to 20 wt.% Li and / or a salt and / or an oxide thereof;

[0158] 0 to 20 wt.% Mn and / or a salt and / or an oxide thereof;

[0159] 10 to 40 wt.% Ni and / or a salt and / or an oxide thereof;

[0160] 0.1 to 1 wt.% Al and / or a salt and / or an oxide thereof;

[0161] 10 to 90 wt.% Fe and / or a salt and / or an oxide thereof;

[0162] 0 to 10 wt.% Cu and / or a salt and / or an oxide thereof; and

[0163] 0 to 20 wt.% Co and / or a salt and / or an oxide thereof.

[0164] Aspect 10: The method of Aspect 5, further characterized in that the metal-containing composition is black mass from lithium ion battery recycling operation and prior to the contacting step, the first amounts of the one or more of Li, Co, Mn, and / or Ni; and / or a salt and / or an oxide thereof are:

[0165] 5 to 20 wt.% Li and / or a salt and / or an oxide thereof;

[0166] 5 to 20 wt.% Mn and / or a salt and / or an oxide thereof;

[0167] 40 to 70 wt.% Ni and / or a salt and / or an oxide thereof;

[0168] 1 to 7 wt.% Al and / or a salt and / or an oxide thereof;

[0169] 2 to 12 wt.% Cu and / or a salt and / or an oxide thereof;

[0170] 0.05 to 1 wt.% Fe and / or a salt and / or an oxide thereof; and

[0171] 10 to 30 wt.% Co and / or a salt and / or an oxide thereof.

[0172] Aspect 11 : The method of any of Aspects 1-10, further characterized in that the aqueous leaching composition comprises the metal scavenger, preferably selected from acetamides, phenyl acetamides, phenacetin, stannates, potassium stannate, sodium stannate, sodium hexahydroxy stannate, phenolic acids, phosphoric acid, disodium pyrophosphate (Na2H2P2O?), tetrasodium pyrophosphate (Na4P2O?), phosphonates, and combinations thereof, more preferably tannic acid, gallic acid, phosphoric acid, disodium pyrophosphate (NaiHJ^O?), tetrasodium pyrophosphate (Na4P2O?), phosphonic acid, NTMP (nitrilotrimethyl-phosphonic acid), EDTMP (ethylene diamine tetra methylene phosphonic acid), DTPMP (diethylenetriaminepentakis(methylphosphonic acid), hydroxyethylidine diphosphonic acid (HEDP), and combinations thereof, most preferably phosphoric acid, phosphonic acid, disodium pyrophosphate, tetrasodium pyrophosphate, and combinations thereof.

[0173] Aspect 12: The method of Aspect 11, further characterized in that the metal-containing composition prior to the contacting step comprises the Cu, Cu salt, and / or the Cu oxide and the metal scavenger comprises phenyl acetamides, phosphoric acid, disodium pyrophosphate (Na2H2P2O?), tetrasodium pyrophosphate (Na4P2O?), phosphonates, or combinations thereof, preferably phenacetin, phosphoric acid, phosphonic acid, disodium pyrophosphate (Na2H2P2O?), tetrasodium pyrophosphate (Na4P2O?), NTMP (nitrilotrimethyl-phosphonic acid), EDTMP (ethylene diamine tetra methylene phosphonic acid), DTPMP (diethylenetriaminepentakis(methylphosphonic acid), hydroxyethylidine diphosphonic acid (HEDP), or combinations thereof.

[0174] Aspect 13: The method of Aspect 11 or Aspect 12, further characterized in that the metalcontaining composition prior to the contacting step comprises the Fe, the Fe salt, and / or the Fe oxide and the metal scavenger comprises stannates, phenolic acids, phosphoric acid, disodium pyrophosphate (Na2H2P2O?), tetrasodium pyrophosphate (Na4P2O?), phosphonates, or combinations thereof, preferably tannic acid, gallic acid, phosphoric acid, disodium pyrophosphate (Na2H2P2O?), tetrasodium pyrophosphate (Na4P2O?), phosphonic acid, NTMP (nitrilotrimethyl-phosphonic acid), EDTMP (ethylene diamine tetra methylene phosphonic acid), DTPMP (diethylenetriaminepentakis(methylphosphonic acid), hydroxy ethylidine diphosphonic acid (HEDP), potassium stannate; sodium stannate; sodium hexahydroxy stannate, phosphonic acid, or combinations thereof.

[0175] Aspect 14: The method of any of Aspects 1-13, further characterized in that the aqueous leaching composition comprises the free radical scavenger, preferably a compound selected from: linear, branched, isomeric branched, secondary, tertiary, or polyhydric alcohols that optionally include even- and / or odd-numbered hydrocarbon chains ranging from about C4 to C15, diol molecules HO-R-OH wherein R is a linear or branched alkyl group ranging from C4 to C15, polyhydric alcohol fatty acid esters, polyhydric alcohol fatty acid esters comprising a fatty acid mono and / or diester of polyethylene glycol and / or polypropylene glycol, compounds based on fatty alcohols, and thioethers, more preferably fatty alcohols of formula CnHzO with n ranging from 4 to 34 and z from 10 to 70 and thioethers of formula HO-CH(R7)-CH2-S-CH2-CH(OH)- CH2-O-R4wherein R4is C4-20 alkyl, and R7is H, more preferably butanol, 1 -pentanol, 2- propanol, 1 -hexanol, 1 -octanol, 2-ethyl-l -hexanol, 1,6-hexanediol, 1,5 -pentanediol, 1,8- octanediol, 1,7-hepanediol, and epichlorohydrin-mercaptoethanol alcohol, more preferably tertbutanol, sucrose, ethylene glycol, isopropanol, pentanol, ethanol, butanol, and ascorbic acid, and most preferably n-butanol, ascorbic acid, or a combination thereof.

[0176] Aspect 15: The method of Aspect 14 further characterized in that the free radical scavenger comprises a compound bearing an abstractable hydrogen.

[0177] Aspect 16: The method of Aspect 14 or Aspect 15, further characterized in that the free radical scavenger comprises a compound comprising at least one OH group bearing an abstractable hydrogen.

[0178] Aspect 17: The method of any of Aspects 1-16, further characterized in that the amount of peroxide consumed is less than 80 wt.%, less than 70wt.%, less than 60 wt.%, less than 50 wt.%, less than 25wt.%, less than 20 wt.%, less than 15 wt.%, less than 10 wt.%, or less than 5 wt.% of that which would be consumed in the identical method not including the metal scavenger and / or the free radical scavenger.

[0179] Aspect 18: The method of any of Aspects 1-17, further characterized in that the peroxide comprises at least one of hydrogen peroxide, perborates, percarbonates, persulfates, organic peroxides, peroxyacids, hydroperoxides, or combinations thereof, preferably at least one of hydrogen peroxide, peracetic acid, peroxy octanoic acid, cumene peroxide, hydroperoxides, diacyl peroxides, peroxyesters, or combinations thereof, more preferably hydrogen peroxide.

[0180] Aspect 19: The method of any of Aspects 1-18, further characterized in that the acid comprises at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid, acetic acid, citric acid, oxalic acid, lactic acid, malic acid, methane sulfonic acid, gluconic acid, formic acid, acetoacetic acid, succinic acid, adipic acid, oxalic acid, aspartic acid, or combinations thereof, preferably nitric, hydrochloric, or sulfuric acid, more preferably sulfuric acid. Aspect 20: The method of any of Aspects 1 -19, further characterized in that the aqueous leaching composition has a pH of 8 or less, preferably 7 or less, more preferably 6 or less, more preferably 5 or less, more preferably 4 or less, more preferably 3 or less, most preferably 2 or less.

[0181] Aspect 21 : The method of any of Aspects 1-20, further characterized in that the aqueous leaching composition has a pH of at least 6, preferably at least 7, more preferably at least 8, more preferably at least 9, more preferably at least 10, most preferably at least 11.

[0182] Aspect 22: The method of any Aspects 1-21, further characterized in that in the maintaining step, the time is from about 0.5 minute to 24 hours, preferably from about 1 to 2 hours, and the temperature is from 15 tolOO°C, preferably from 15 to 90°C, more preferably from 20 to 80°C.

[0183] Aspect 23: The method of any of Aspects 1-22, further characterized in that the reaction is taking place under pressure between 1 and 10 atm, preferably at ambient pressure.

[0184] Aspect 24: The method of any of Aspects 1-23, further characterized in that the first amount of peroxide is from 0.1 to 35 %, preferably 0.2-17.5% and more preferably 0.3-12% wt.% based on a total weight of the aqueous leaching composition and the metal -containing composition.

[0185] Aspect 25: An aqueous composition for treating a metal -containing composition, characterized in that the aqueous composition comprises: a peroxide; a metal scavenger and / or a free radical scavenger.

[0186] Aspect 26: The aqueous composition of Aspect 25, further characterized in that the aqueous composition comprises:

[0187] 0.1 to 35%, preferably 0.2-17.5% and more preferably 0.3- 12% wt.% of the peroxide, and at least 0.01 wt.%, preferably at least about 0.05%, more preferably 0.05 wt.% to 10 wt.%, more preferably 0.05 wt.% to 5 wt.%, more preferably 0.1 wt.% to 5 wt.%, most preferably 1 .0 wt.% to 2.0 wt.%, of each of the metal scavenger and / or the free radical scavenger, based on a total weight of the aqueous leaching composition and the metal -containing composition to be treated.

[0188] Aspect 27: The composition of Aspect 25 or Aspect 26, further characterized in that the aqueous composition comprises an acid and / or a base.

[0189] Aspect 28: The aqueous composition of any of Aspects 25-27, further characterized in that the aqueous composition comprises the metal scavenger, wherein the metal scavenger comprises acetamides, phenyl acetamides, phenacetin, stannates, potassium stannate, sodium stannate, sodium hexahydroxy stannate, phenolic acids, phosphoric acid, disodium pyrophosphate (NazHzPzO?), tetrasodium pyrophosphate (Na4PzO?), phosphonates, or combinations thereof, more preferably tannic acid, gallic acid, phosphoric acid, disodium pyrophosphate (NazHzPzO?), tetrasodium pyrophosphate (Na4PzO?), phosphonic acid, NTMP (nitrilotrimethyl-phosphonic acid), EDTMP (ethylene diamine tetra methylene phosphonic acid), DTPMP (diethylenetriaminepentakis(methylphosphonic acid), hydroxyethylidine diphosphonic acid (HEDP), or combinations thereof, most preferably, phosphoric acid, phosphonic acid, disodium pyrophosphate, tetrasodium pyrophosphate, or combinations thereof.

[0190] Aspect 29: The aqueous composition of any of Aspects 25-28, further characterized in that the aqueous composition comprises the metal scavenger, wherein the metal scavenger comprises stannates, phenolic acids, dipicolinic acid, phosphoric acid, disodium pyrophosphate (NazHzPzO?), tetrasodium pyrophosphate (Na4P2O?), phosphonates, or combinations thereof, preferably tannic acid, gallic acid, phosphoric acid, phosphonic acid, disodium pyrophosphate (NazHzPzO?), tetrasodium pyrophosphate (Na4P2O?), NTMP (nitrilotrimethyl-phosphonic acid), EDTMP (ethylene diamine tetra methylene phosphonic acid), DTPMP (diethylenetriaminepentakis(methylphosphonic acid), hydroxyethylidine diphosphonic acid (HEDP), or combinations thereof, most preferably, sodium stannate, phosphoric acid, phosphonic acid, disodium pyrophosphate, tetrasodium pyrophosphate, or combinations thereof.

[0191] Aspect 30: The aqueous composition of any of Aspects 25-29, further characterized in that the aqueous composition comprises the free radical scavenger, preferably a compound selected from: linear, branched, isomeric branched, secondary, tertiary, or polyhydric alcohols that optionally include even- and / or odd-numbered hydrocarbon chains ranging from about C4 to Cis, diol molecules HO-R-OH wherein R is a linear or branched alkyl group ranging from C4 to C15, polyhydric alcohol fatty acid esters, polyhydric alcohol fatty acid esters comprising a fatty acid mono and / or diester of polyethylene glycol and / or polypropylene glycol, compounds based on fatty alcohols, and thioethers, more preferably fatty alcohols of formula CnHzO with n ranging from 4 to 34 and z from 10 to 70 and thioethers of formula HO-CH(R7)-CH2-S-CH2-CH(OH)- CH2-O-R4wherein R4is C4-20 alkyl, and R7is H, more preferably butanol, 1 -pentanol, 2- propanol, 1 -hexanol, 1 -octanol, 2-ethyl-l -hexanol, 1,6-hexanediol, 1,5 -pentanediol, 1,8- octanediol, 1,7-hepanediol, and epichlorohydrin-mercaptoethanol alcohol, more preferably tertbutanol, sucrose, ethylene glycol, isopropanol, pentanol, ethanol, butanol, and ascorbic acid, and most preferably n-butanol, ascorbic acid, or a combination thereof.

[0192] Aspect 31 : The aqueous composition of Aspect 30, further characterized in that the free radical scavenger comprises a compound bearing an abstractable hydrogen.

[0193] Aspect 32: The aqueous composition of Aspect 30 or Aspect 31, further characterized in that the free radical scavenger comprises a compound comprising at least one OH group bearing an abstractable hydrogen.

[0194] Aspect 33: The aqueous composition of any of Aspects 25-32, further characterized in that the aqueous composition has a pH of 8 or less, preferably 7 or less, more preferably 6 or less, more preferably 5 or less, more preferably 4 or less, more preferably 3 or less, most preferably 2 or less.

[0195] Aspect 34: The aqueous composition of any of Aspects 25-32, further characterized in that the aqueous composition has a pH of at least 6, preferably at least 7, more preferably at least 8, more preferably at least 9, more preferably at least 10, most preferably at least 11.

[0196] Aspect 35: The aqueous composition of any of Aspects 25-34, further characterized in that the peroxide comprises at least one of hydrogen peroxide, perborates, percarbonates, persulfates, organic peroxides, peroxyacids, hydroperoxides, or combinations thereof, preferably at least one of hydrogen peroxide, peracetic acid, peroxy octanoic acid, cumene peroxide, hydroperoxides, diacyl peroxides, peroxyesters, or combinations thereof, more preferably hydrogen peroxide. Aspect 36: The method of any of Aspects 1-24, further characterized in that the metalcontaining composition comprising first amounts of one or more of Li, Co, Mn, Fe, Cu, Al, and / or Ni, and / or a salt and / or an oxide thereof is black mass from a lithium ion battery, lithium ion battery waste, lithium ion battery production scrap, lithium ion cell production scrap, lithium ion cathode active material and combinations thereof.

[0197] Aspect 37: Use of the method of any of Aspects 1-24 and 36 to treat a metal-containing composition comprising black mass from a lithium ion battery, lithium ion battery waste, lithium ion battery production scrap, lithium ion cell production scrap, lithium ion cathode active material and combinations thereof, to recover at least one metal selected from Li, Co, Mn, Fe, Cu, Al, and / or Ni.

[0198] Aspect 38: Use of the aqueous composition of any of Aspects 25-35 to treat a metalcontaining composition comprising black mass from a lithium containing battery, lithium ion battery waste, lithium ion battery production scrap, lithium ion cell production scrap, lithium ion cathode active material and combinations thereof, to recover at least one metal selected from Li, Co, Mn, Fe, Cu, Al, and / or Ni.

[0199] EXAMPLES

[0200] Methods:

[0201] Temperature:

[0202] The temperature was monitored using a thermocouple directly linked to the stirring / heating plate. Because a hydrogen peroxide degradation reaction is exothermic, it is important to monitor the temperature. If the temperature increases, it is a potential sign that hydrogen peroxide is being degraded. In some experiments, the temperature of the self-heated reaction went above 90°C.

[0203] Peroxide concentration over time:

[0204] A refractometer specifically calibrated for hydrogen peroxide (0-50 wt.% concentration range), was used. With the refractometer, hydrogen peroxide concentration is calculated by measuring the refractive angle of a light sent through the sample. Using the refractometer is very simple: using a pipette, a small amount of the sample was collected from the solution in the beaker and a few drops were placed on the designated window. Temperature is corrected, but waiting for the sample to reach ambient temperature is recommended to get results with more accuracy and precision. Readings are obtained within 3 seconds and rounded to 0.2%. While this measuring method is very fast, it is very dependent on the purity and composition of the solution. If large quantities of sulfuric acid are used, or if solids are present, the density of the solution will be changed, leading to erroneous results. Since the effect of density was considered to be small, the first point at time zero (which had a known H2O2 concentration, such as 10%) was used as a reference point. A simple correction was applied for all the following measurements of the same formulation to measure the concentration of the hydrogen peroxide over time.

[0205] Hydrogen peroxide concentration measurements

[0206] Hydrogen peroxide concentration is measured using an automated titrator. The titration is based on the reaction (23) and hydrogen peroxide concentration is calculated by measuring the amount of potassium permanganate needed to consume all hydrogen peroxide. The reaction is done in an acidic media (sulfuric acid) as shown below. Measurements were done in replicate for each sample and the mean value was reported.

[0207] 5H2O2 + 2KMY1O4 + 3H2SO4 — > 2MnSO4 + K2SO4 + 5O2 + 8H2O

[0208] Hydrogen peroxide was introduced for each experiment by volume percent, but since the value provided by the titrator is a weight percentage, a correction was used to keep the results in weight % as shown below. total in the reactor(g)

[0209] Metal recovery measurement and calculation

[0210] The quantification of metal sulfates was done by inductively coupled plasma with mass spectrometer detector (ICP-MS) and x-ray refraction (XRF). A wt.% was given for each metal present in the sample. The recovery was calculated using the following formulas. Here, formulas are provided for nickel recovery, but they are similar for the other metals. Yield Ni = measured Ni wt.% / theoretical Ni wt.%

[0211] Theoretical % Ni = Ni%batxmbat / mtot.

[0212] Measured Ni wt.% is the result given by ICP-MS or XRF, Ni%bat is the nickel content in the battery material, mbat is the mass of battery material introduced in the reactor and mtot is the total mass in the reactor.

[0213] For all runs where the amount of hydrogen peroxide consumed was calculated, the following table shows how the results were calculated. The column A corresponds to the hydrogen peroxide concentration that was used to convert the different metals (the yield used). pH measurement: pH was measured using a using a Fisherbrand™ accumet™ API 10 Portable pH Meter Kit, Catalog No.l3-636-APl 10 (Fisher Scientific), equipped with a Fisherbrand™ accumet™ pH / ATC Electrode, Catalog No. 13-620-AP50A (Fisher Scientific).

[0214] Within this specification embodiments have been described in a way which enables a clear and concise specification to be written, but it is intended and will be appreciated that embodiments may be variously combined or separated without departing from the invention. For example, it will be appreciated that all preferred features described herein are applicable to all aspects of the invention described herein. In some embodiments, the invention herein can be construed as excluding any element or process step that does not materially affect the basic and novel characteristics of the compositions and methods described herein. Additionally, in some embodiments, the invention can be construed as excluding any element or process step not specified herein.

[0215] The foregoing description of various forms of the invention has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise forms disclosed. Numerous modifications or variations are possible in light of the above teachings. The forms discussed were chosen and described to provide the best illustration of the principles of the invention and its practical application to thereby enable one of ordinary skill in the art to utilize the invention in various forms and with various modifications as are suited to the particular use contemplated. All such modifications and variations are within the scope of the invention as determined by the appended claims when interpreted in accordance with the breadth to which they are fairly, legally, and equitably entitled.

[0216] Example 1:

[0217] Impact of metal sulfate on hydrogen peroxide degradation

[0218] In this test, 1000 ppm of the different metallic salts were used in 300 ml of a hydrogen peroxide solution at 10% and acidified at pH 2 with sulfuric acid (15 drops of sulfuric acid at 98%). The reactions were carried in a beaker at ambient temperature and at 50°C. The hydrogen peroxide concentration was determined using a refractometer (Atago 4439 PAL-39S).

[0219] Table 1: List of compounds tested and concentrations.

[0220] A strong degradation of hydrogen peroxide is observed with the elements Cu and / or Fe (Fig. 2) but not with the other elements present in the battery (i.e., Ni, Mn, Co, Al and graphite)(Fig. 1). This is a clear demonstration of the catalytic degradation effect of the elements Cu and Fe on hydrogen peroxide (H2O2) in this system.

[0221] Example 2:

[0222] Metal chelating agent interaction with the elements iron and copper. This is an example of tests done at 50°C in 300 ml solution (beaker) containing copper or iron salt at a concentration of 1000 ppm. Chelating agents have specific metal targets as indicated in the Table 2 below. A selection of results reported in Fig. 3 are provided as the amount of hydrogen peroxide left in the solution after 1 hour when using metal scavengers at concentrations ranging from 0.5% to 1%. The reference indicates that no hydrogen peroxide is left when no metal scavenger is used. While some metal scavengers in very small amounts (ppm levels) are known to be used in the stabilization of hydrogen peroxide, this example clearly proves that specifically blocking copper and iron present will considerably limit the degradation of hydrogen peroxide even at elevated temperature and high level of contaminant metals.

[0223] Table 2: Metal targets of the chelating agents Example 3:

[0224] Effect of free radical scavengers on the degradation of hydrogen peroxide

[0225] This test was done in a beaker at 50°C using 300 ml of solution containing 1000 ppm of iron in the form of iron sulfate and 10% hydrogen peroxide as described in the example above. Fig. 4 shows the time it took in minutes for the concentration in hydrogen peroxide to reach 0%.

[0226] Table 3: List of free radical compounds tested and experimental observations.

[0227] Free radical scavengers do not prevent degradation but considerably delay the time it takes for hydrogen peroxide to be fully degraded. It is noteworthy that without free radical scavengers the time to fully degrade hydrogen peroxide in this experimental setup is approximately 3 minutes. Hence, the first four compounds in Fig. 4 showed no free radical scavenging effects while the last six compounds show an increase in scavenging activity.

[0228] Example 4

[0229] Black mass leaching process - impact of 1% n-butanol

[0230] In a one-liter jacketed reactor with a temperature set at 50°C, black mass (from end-of-life batteries from different sources noted BM 1 and BM 2) is added to an aqueous solution containing 2M of sulfuric acid and 5% of hydrogen peroxide. The black mass concentration in the solution is 40 g / L. The hydrogen peroxide concentration is determined by titration (Metrohm Titrando instrument).

[0231] Fig. 5 shows the evolution of the concentration of hydrogen peroxide consumed by the reaction over time. Table 4 summarizes the results of the amount of hydrogen left in the reactor in percentage for the end point at 2 hours.

[0232] Table 4: Amount of H2O2 left in the reactor after 2 hours.

[0233] This example emphasizes the protective effect of the free radical scavenger n-butanol on the degradation of hydrogen peroxide.

[0234] Example 5 Addition of n-butanol to NMC622 - H2O2 degradation and impact on the metal yield recovery.

[0235] In a one-liter jacketed reactor with a temperature set at 50°C, cathode material NMC622 is added to an aqueous solution containing 2M of sulfuric acid and 5% of hydrogen peroxide. The cathode material is used at a concentration in solution of 20 g / L. The free radical scavenger n-butanol is added at a concentration of 1% in the solution. Fig. 6 shows the amount of hydrogen peroxide remaining in the reactor over a period of 2 hours of reaction at 50°C. The metal of interest yield is reported in the table below.

[0236] Table 5: Metal recovery yield impact in the presence of the free radical scavenger n-butanol

[0237] It is apparent that while limiting the overconsumption of hydrogen peroxide, the yield is unaffected by the addition of a free radical scavenger, in this case, n-butanol.

Claims

What is claimed is:

1. A method of treating a metal-containing composition with an aqueous leaching composition containing a peroxide, characterized in that:- a metal -containing composition comprising first amounts of one or more of Li, Co, Mn, Fe, Cu, Al, and / or Ni, and / or a salt and / or an oxide thereof is contacted with an aqueous leaching composition comprising: a first amount of a peroxide; and a metal scavenger and / or a free radical scavenger;- for a time and at a temperature sufficient to dissolve at least a portion of the metalcontaining composition to produce a metal leachate composition comprising a liquid metal leachate and optionally a solid residue, the liquid metal leachate comprising a second amount of dissolved salts and / or oxides of the Li, Co, Mn, Fe, Cu, Al, and / or Ni and a second amount of the peroxide;- isolating the liquid metal leachate from the solid residue; and optionally separating dissolved salts and / or oxides of the Li, Co, Mn, Fe, Cu, Al, and / or Ni from the liquid metal leachate and / or from each other; wherein the second amount of peroxide in the liquid metal leachate is greater than would be present in an identical method not including the metal scavenger and / or the free radical scavenger.

2. The method of claim 1, further characterized in that the aqueous leaching composition comprises 0.1 to 35 wt.%, preferably 0.2-17.5 wt.%, and more preferably 0.3- 12% wt.% of the first amount of peroxide, and at least 0.01 wt.%, preferably at least about 0.05 wt.%, more preferably 0.05 wt.% to 10 wt.%, more preferably 0.05 wt.% to 5 wt.%, more preferably 0.1 wt.% to 5 wt.%, and most preferably 1.0 wt.% to 2.0 wt.%, of each of the metal scavenger and / or the free radical scavenger, based on a total weight of the aqueous leaching composition and the metal-containing composition.

3. The method of claim 1 or claim 2, further characterized in that the aqueous leaching composition further comprises an acid, and / or further characterized in that the aqueous leaching composition further comprises a base.

4. The method of any of claims 1-3, further characterized in that the second amount of dissolved Li, Co, Mn, Fe, Cu, Al, and / or Ni in the liquid metal leachate is substantially the same or greater compared to the same method not including the metal scavenger and / or the free radical scavenger.

5. The method of any of claims 1 to 4, further characterized in that the amount of peroxide consumed is less than 80 wt.%, less than 70 wt.%, less than 60 wt.%, less than 50 wt.%, less than 25 wt.%, less than 20 wt.%, less than 15 wt.%, less than 10 wt.%, or less than 5 wt.% of that which would be consumed in the identical method not including the metal scavenger and / or the free radical scavenger.

6. The method of any of claims 1 to 5, further characterized in that the aqueous leaching composition has a pH of 8 or less, preferably 7 or less, more preferably 6 or less, more preferably 5 or less, more preferably 4 or less, more preferably 3 or less, most preferably 2 or less.

7. The method of any claims 1 to 6, further characterized in that the metal-containing composition is contacted with the aqueous leaching composition for a time of from about 0.5 minute to 24 hours, preferably from about 1 to 2 hours, and at a temperature of from 15 to 100°C, preferably from 15 to 90°C, more preferably from 20 to 80°C.

8. The method of any of claims 1 to 7, further characterized in that the first amount of peroxide is from 0.1 to 35 wt.%, preferably 0.2-17.5 wt.%, and more preferably 0.3- 12% wt.% based on a total weight of the aqueous leaching composition and the metal -containing composition.

9. The method of any of claims 1 to 8, characterized in that the metal-containing composition comprising first amounts of one or more of Li, Co, Mn, Fe, Cu, Al, and / or Ni, and / or a salt and / or an oxide thereof comprises black mass from a lithium-ion battery, lithium-ion battery waste, lithium-ion battery production scrap, lithium-ion cell production scrap, lithium-ion cathode active material, nickel pig iron, or any combination thereof.

10. An aqueous composition for treating a metal -containing composition comprising a peroxide, characterized in that the aqueous composition comprises a metal scavenger and / or a free radical scavenger.

11. The aqueous composition of claim 10, further characterized in that the composition comprises:0.1 to 35%, preferably 0.2-17.5% and more preferably 0.3- 12% wt.% of the peroxide, and at least 0.01 wt.%, preferably at least about 0.05%, more preferably 0.05 wt.% to 10 wt.%, more preferably 0.05 wt.% to 5 wt.%, more preferably 0.1 wt.% to 5 wt.%, most preferably 1.0 wt.% to 2.0 wt.%, of each of the metal scavenger and / or the free radical scavenger, based on a total weight of the aqueous leaching composition and the metal -containing composition to be treated.

12. The aqueous composition of claim 10 or 11, further characterized in that the composition comprises an acid and / or a base.

13. The aqueous composition of any of claims 10 to 12, having a pH of 8 or less, preferably 7 or less, more preferably 6 or less, more preferably 5 or less, more preferably 4 or less, more preferably 3 or less, most preferably 2 or less.

14. Use of the method of any of claims 1 to 9 to treat a metal-containing composition comprising black mass from a lithium-ion battery, lithium-ion battery waste, lithium-ion battery production scrap, lithium-ion cell production scrap, lithium-ion cathode active material, nickel pig iron, metal alloys, electronic waste, or any combination thereof, to recover at least one metal selected from Li, Co, Mn, Fe, Cu, Al, and / or Ni.

15. Use of the aqueous composition of any of claims 10 to 13 to treat a metal-containing composition comprising black mass from a lithium containing battery, lithium-ion battery waste, lithium-ion battery production scrap, lithium-ion cell production scrap, lithium-ion cathode active material, nickel pig iron, metal alloys, electronic waste, or any combination thereof, to recover at least one metal selected from Li, Co, Mn, Fe, Cu, Al, and / or Ni.

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