Combined foam formation control and peroxide overconsumption prevention in battery recycling metal leaching processes

Abstract

A method of controlling foam formation in a process of treating a metal -containing composition with an aqueous composition that comprises a peroxide, wherein the aqueous composition comprises a free-radical scavenging and antifoaming and / or defoaming and / or wetting compound. Also, an aqueous composition comprising the free-radical scavenging and antifoaming and / or defoaming and / or wetting compound. Also, use of the method and aqueous composition 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, electronic waste, one or more metal alloys, nickel pig iron, or any combination thereof, to recover at least one metal selected from Li, Co, Mn, Fe, Cu, Al, and / or Ni.

Description

[0001] COMBINED FOAM FORMATION CONTROL AND PEROXIDE OVERCONSUMPTION PREVENTION IN BATTERY RECYCLING METAL LEACHING PROCESSES

[0002] FIELD

[0003] This invention relates to methods for chemically reducing and / or minimizing consumption of peroxide while at the same time inhibiting and / or reducing the foam generated during peroxidic metal digestion or metal recycling processes. Examples of such processes include 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 of LIBs, their manufacturing and disposal have increasingly become subject to environmental and economic concerns. The global push for environmental responsibility has prompted a growing focus on the recycling of lithium-ion batteries. With the escalating demand for clean energy solutions, the recycling of these batteries presents a dual advantage. Not only does it prevent the environmental hazards associated with improper disposal, but it also addresses the growing demand for the critical raw materials present in these batteries, promoting a more circular and sustainable approach to energy storage.

[0006] 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) that comprises crushed and shredded battery cell material obtained when a battery has been processed for recycling. This shiny, metallic mixture contains various valuable metals that make up battery anodes and cathodes. Black mass typically contains mixtures of valuable and recoverable metals, including but not limited to lithium, copper, manganese, cobalt, and nickel.

[0007] A combination of physical and chemical approaches has been adopted to recycle spent and waste battery materials. Generally, physical methods are used to enhance the efficiency of recycling and typically include dismantling, crushing, sieving, followed by thermal and / or chemical treatments. The resulting material is black mass.

[0008] The composition of black mass varies significantly according to the composition of the incoming waste battery materials as well as to the mechanical, thermal, or other treatments that may have been used to form the black mass. For example, there are at least five different types of lithium-ion batteries, each with different combinations of 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: LiCoO2; 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: LiPFe, LiBF4, LiCF3SO3, LiN(SO2CF3)2.

[0009] One method for separating and recovering metals from LIB scraps and end-of-life batteries is hydrometallurgical. 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 of acid and / or base. Peroxides, such as hydrogen peroxide, are often used with acids and / or bases to digest mixed metal streams. Peroxides 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.

[0010] The presence of iron or copper in the peroxidic leaching solution of the hydrometallurgical process can lead to an unwanted overconsumption of peroxide, because peroxides, such as hydrogen peroxide, are quickly degraded, especially at elevated temperatures, in the presence of iron and copper ions in the leaching solution. Hydrogen peroxide also catalytically degrades in the presence of free radicals. The degradation of peroxide and resulting production of oxygen gas also present a significant safety issue, so there is a need to minimize the formation of oxygen gas through unwanted degradation of the peroxide.

[0011] The presence of black mass in the leaching solution also leads to another unwanted problem, which is the formation of foam during the leaching process. When black mass is added to an acidic leaching solution, foam is quickly generated. Foaming is even more abundant when hydrogen peroxide also is present in the leaching solution. The inventors have found that this generation of foam is very detrimental to the metal extraction yield, because foaming leads to the deposit of significant quantities of black mass material on reactor sidewalls as the foam recedes. Black mass material deposited on the reactor sidewalls is not in contact with the acidic leaching solution and thus cannot be treated, leading to a noticeable loss of metals recovered for recycling. This yield loss is not acceptable from either an economical or an environmental point of view.

[0012] Broughton et al., Mechanism of Decomposition of Hydrogen Peroxide Solutions with Manganese Dioxide. I, J. Am. Chem. Soc. 69(4): 744-47 (1947), sought to clarify the mechanism by which manganese dioxide catalyzes the decomposition of aqueous hydrogen peroxide.

[0013] Kehua Dai, et al., The transformation of graphite electrode materials in lithium-ion batteries after cycling, Journal of Power Sources 298:349-54 (2015), investigated the stability of binder and graphite particles in the negative electrodes in a group of commercial LFP / graphite lithium-ion rechargeable cells.

[0014] Anne-Laure Fameau, et al., Effect of particles and aggregated structures on the foam stability and aging, C. R. Physique 15:748-60 (2-14), reviews foaming properties of particles and self-assembled and aggregated structures.

[0015] Pouria Amani, et al., Pickering foams and parameters influencing their characteristics, Advances in Colloid and Interface Science 301 :102606 (2022), presents a review of the behavior of particle-stabilized foams.

[0016] Nathalia Vieceli, et al ., 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. 1 1 :9662-73 (2023), investigates the effect of hydrogen peroxide on the leachability of cathode active and black mass materials using sulfuric acid.

[0017] SUMMARY

[0018] In the present application, the inventors discovered a method of improving a hydrometallurgical process wherein peroxide is used to enhance the dissolution of the desirable metals such as Li, Ni, Mn, and / or Co in an aqueous composition, usually acidic, which method optimizes the use of peroxide and the yield of recovered metals. The invention is a new method to chemically minimize the amount of peroxide (such as hydrogen peroxide) overconsumed by unwanted side reactions during the lixiviation process and, at the same time, to prevent or reduce the foam generated during the process. This chemistry is implemented without negatively impacting the leaching yield of the targeted metals, such as lithium, nickel, manganese, and cobalt, recovered from scrap or end-of-life battery black mass.

[0019] Using the methods and compositions of this invention, the 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 undesirable side reactions catalyzed by copper, iron, or free radicals. At the same time, using the methods and compositions of this invention, foaming in the hydrometallurgical treatment of black mass is reduced or prevented. This invention therefore significantly reduces the amount of peroxide needed for the digestion / dissolution / leaching process while maintaining or increasing metal recovery yield.

[0020] The present methods and compositions improve both continuous processes (requiring the constant addition of peroxide) and batch processes (e g., leaching) by preventing an excessive or over consumption of peroxide by side reactions and by reducing or preventing foam, 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.

[0021] According to a first aspect, a method of controlling foam formation in a process of treating a metal -containing composition with an aqueous composition that comprises a peroxide is provided, wherein the metal -containing composition comprises one or more of Li, Co, Mn, Fe, Cu, Al, and / or Ni, and / or a salt and / or an oxide thereof, characterized in that the aqueous composition comprises a free-radical scavenging and antifoaming and / or defoaming and / or wetting compound and optionally at least one additional free-radical scavenger and / or metal scavenger.

[0022] According to another aspect, a method is provided, further characterized in that the aqueous composition comprises 0.001% to 10%, preferably 0.01% to 5% by weight of the free- radical scavenging and antifoaming and / or defoaming and / or wetting compound, based on the combined weight of the metal containing composition and the aqueous composition.

[0023] According to another aspect, a method is provided, further characterized in that the metal-containing composition comprises e-waste, 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, one or more metal alloys, nickel pig iron, or any combination thereof.

[0024] According to another aspect, a method is provided, further characterized in that the aqueous composition comprises at least one additional metal -scavenging and / or free-radical scavenging compound.

[0025] According to another aspect, a method is provided, further characterized in that the aqueous composition further comprises an acid and / or a base.

[0026] According to another aspect, a method is provided, 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.

[0027] According to another aspect, a method is provided, further characterized in that the aqueous composition further comprises an acid and the acid comprises at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid, acetic acid, citric acid, lactic acid, malic acid, methanesulfonic 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. According to another aspect, a method is provided, 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.

[0028] According to another aspect, a method is provided, 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.

[0029] According to another aspect, a method is provided, further characterized in that the metal-containing composition is contacted with the aqueous composition for a time of from about 1 minute to 24 hours, preferably from about 10 minutes to 2 hours, more preferably from about 0.5 to 2 hours, and at a temperature of from 10 to 100°C, preferably from 15 to 90°C, more preferably from 20 to 80°C.

[0030] According to another aspect, a method is provided, wherein the aqueous composition is under a pressure between 1 and 10 atm, preferably at ambient pressure.

[0031] According to another aspect, a method is provided, further characterized in that the free- radical scavenging and antifoaming and / or defoaming and / or wetting compound is selected from linear, branched, isomeric branched, secondary, tertiary, or polyhydric alcohols, that optionally include even- and / or odd-numbered hydrocarbon chains ranging from about Ci to Cis, diol molecules HO-R-OH wherein R is a linear or branched alkyl group ranging from Ci to Cis, 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 (in particular thioethers of formula HO-CH(R1)-CH2-S-CH2- CH(OH)-CH2-O-R2wherein R1is H and R2is C4-C20 alkyl), or from butanol, 1-pentanol, 2- propanol, 1-hexanol, 1-octanol, 2-ethyl-l -hexanol, butanediol, 1,6-hexan ediol, 1,5-pentanediol, 1,8 -octanediol, 1,7-hepanediol, and epichlorohydrin-mercaptoethanol alcohol, or from tertbutanol, ethylene glycol, isopropanol, pentanol, 2-ethyl-l -hexanol, ethanol, hexanol and butanol, or from C4-C8 alcohols, or any combination thereof; and / or the free-radical scavenging and antifoaming and / or defoaming and / or wetting compound comprises one or more of a linear, branched or polyhydric alcohol, a polyether, a polyhydric alcohol fatty acid ester, a fatty alcohol, a diol, a thioether, a polyvinyl copolymer, a gemini surfactant, or a combination thereof. According to another aspect, the free-radical scavenging and antifoaming and / or defoaming and / or wetting compound does not include polyvinyl alcohol (PVA).

[0032] According to another aspect, an aqueous composition for treating a metal containing composition is provided, the aqueous composition comprising a peroxide and an acid and / or a base, characterized in that the aqueous composition further comprises a free-radical scavenging and antifoaming and / or defoaming and / or wetting compound and optionally at least one additional free-radical scavenger and / or metal scavenger.

[0033] According to another aspect, an aqueous composition for treating a metal containing composition is provided, further characterized in that the free-radical scavenging and antifoaming and / or defoaming and / or wetting compound is selected from linear, branched, isomeric branched, secondary, tertiary, or polyhydric alcohols, that optionally include even- and / or odd-numbered hydrocarbon chains ranging from about Ci to C15, diol molecules HO-R- OH wherein R is a linear or branched alkyl group ranging from Ci 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 (in particular thioethers of formula HO-CH(R1)-CH2-S-CH2-CH(OH)-CH2-O-R2wherein R1is H and R2is C4-C20 alkyl), or from butanol, 1-pentanol, 2-propanol, 1-hexanol, 1- octanol, 2-ethyl-l -hexanol, butanediol, 1,6-hexanediol, 1,5-pentanediol, 1,8-octanediol, 1,7- hepanediol, and epichlorohydrin-mercaptoethanol alcohol, or from tert-butanol, ethylene glycol, isopropanol, pentanol, 2-ethyl-l -hexanol, ethanol, hexanol and butanol, or from C4-C8 alcohols, or any combination thereof; and / or the free-radical scavenging and antifoaming and / or defoaming and / or wetting compound comprises one or more of a linear, branched or polyhydric alcohol, polyether, a polyhydric alcohol fatty acid ester, a fatty alcohol, a diol, a thioether, a polyvinyl copolymer, a gemini surfactant, or a combination thereof.

[0034] According to another aspect, the invention provides for the use of the inventive method or methods 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, electronic waste, one or more metal alloys, nickel pig iron, or any combination thereof, to recover at least one metal selected from Li, Co, Mn, Fe, Cu, Al, and / or Ni. According to another aspect, the invention provides for the use of the inventive aqueous composition or compositions 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, electronic waste, one or more metal alloys, nickel pig iron, or any combination thereof, to recover at least one metal selected from Li, Co, Mn, Fe, Cu, Al, and / or Ni.

[0035] BRIEF DESCRIPTION OF THE DRAWINGS

[0036] The following figures represent exemplary embodiments of the invention and are not intended to otherwise limit the description of the invention as described herein.

[0037] Figure 1 shows time for total consumption of hydrogen peroxide;

[0038] Figure 2 shows a correlation between the number of carbons (alkane chain length) and the efficacy in free radical scavenging;

[0039] Figure 3 shows the amount of hydrogen peroxide consumed during reactor runs; and

[0040] Figure 4 shows metal extraction yields after 2 hours of reaction in a reactor.

[0041] Figure 5 shows the time to reach a full degradation of hydrogen peroxide in the presence of iron contaminant.

[0042] Figure 6 shows the evolution of the degradation of hydrogen peroxide concentration for two different BM with and without a free radical scavenger

[0043] Figure 7 shows degradation of hydrogen peroxide in the presence of cathode material NMC 622.

[0044] DETAILED DESCRIPTION

[0045] “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. “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.

[0046] As used herein, “a free-radical scavenging and antifoaming and / or defoaming and / or wetting compound” and “a free-radical scavenging and antifoaming compound” are used interchangeably and denote a compound that has both free-radical scavenging properties and one or more of defoaming, antifoaming, and / or wetting properties.

[0047] As used herein, “controlling foam formation” includes defoaming, antifoaming, and / or wetting and which results in reduction or elimination of foam formation in liquid media.

[0048] 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-.

[0049] 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-.

[0050] 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.

[0051] As used herein, “comprising” encompasses “consisting of’ or “consisting essentially of.”

[0052] 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.

[0053] Method of Controlling Foam Formation

[0054] The present invention relates to a method of controlling foam formation in a process of treating a metal -containing composition, wherein the metal-containing composition may comprise one or more of Li, Co, Mn, Fe, Cu, Al, and / or Ni, and / or a salt and / or an oxide thereof, with an aqueous composition that comprises a peroxide. The method of the present invention is characterized in that the aqueous composition comprises a free-radical scavenging and antifoaming and / or defoaming and / or wetting compound and optionally at least one additional free-radical scavenger and / or metal scavenger.

[0055] In the process of treating the metal-containing composition, the metal -containing composition is contacted with an aqueous composition comprising, consisting of, or consisting essentially of a peroxide, a free-radical scavenging and antifoaming and / or defoaming and / or wetting compound, and optionally at least one additional free-radical scavenger and / or metal scavenger, preferably 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 dissolved salts and / or oxides of the Li, Co, Mn, Fe, Cu, Al, and / or Ni. Typically, the metal-containing composition is mixed with sulfuric acid in water to dissolve the metals into sulfates. A peroxide, preferably hydrogen peroxide, is used as a reducing agent to speed the dissolution process.

[0056] The contacting step may be done according to any of the methods as are known to the art. Typically, the aqueous 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 an 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). Two further examples of such processes are purifications of metal alloys and / or nickel pig iron.

[0057] 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 1 minute to 24 hours, preferably from about 10 minutes to 2 hours, more preferably from about 0.5 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. The aqueous composition may be under a pressure between 1 and 10 atm, preferably at ambient pressure (i.e., about 1 atm).

[0058] 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.

[0059] The liquid metal leachate may then be further treated to isolate the liquid metal leachate from the solid residue. The isolated liquid metal leach may then be further treated to separate the 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. 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. 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, physical, and / or chemical methods as are known to the art.

[0060] 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.

[0061] The method or methods of the present invention may be used 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, electronic waste, one or more metal alloys, nickel pig iron, or any combination thereof, to recover at least one metal selected from Li, Co, Mn, Fe, Cu, Al, and / or Ni.

[0062] Metal -Containing Composition:

[0063] The metal-containing composition is the composition that is subjected to the hydrometallurgical digestion or lixiviation processes of the invention. The metal-containing composition may comprise one or more of Li, Co, Mn, Fe, Cu, Al, and / or Ni, and / or a salt and / or an oxide and / or an alloy thereof.

[0064] According to an embodiment, the metal-containing composition may include at least one of Cu and / or a salt and / or an oxide and / or an alloy thereof and Fe and / or a salt and / or an oxide and / or an alloy 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 and / or alloys may vary depending on the source of the metal-containing composition that is treated with the aqueous composition as disclosed herein.

[0065] According to an embodiment, the metal-containing composition may comprise e-waste, 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, one or more metal alloys, nickel pig iron, or any combination thereof.

[0066] According to an embodiment, the metal-containing composition may comprise recycled lithium-ion battery materials derived from end-of-life batteries and / or from battery scrap materials. Battery material-derived black mass is composed mostly of metal oxide(s) and graphite. Typically, the graphite content of black mass is 15% to 20% by weight, but the amount of graphite may vary considerably with the processing used to generate the product, so graphite content as low as 5% by weight or less and up to 30% or more by weight is possible.

[0067] According to an embodiment, the metal-containing composition may be black mass from lithium iron phosphate (LFP) battery recycling operations and may include iron (III) phosphate (ferric phosphate).

[0068] According to an embodiment, the metal-containing composition may comprise one or more metal alloys. 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%).

[0069] According to an embodiment, the metal-containing composition may comprise electronic waste (E- waste).

[0070] According to an embodiment, the metal-containing composition may comprise nickel pig iron. Nickel pig iron is made of low-grade nickel ore, coking coal, and a mixture of gravel and sand as an aggregate, and its composition may vary widely. Iron is the main other component in nickel pig iron besides the nickel, but other impurities are present in varying amounts.

[0071] Aqueous Composition:

[0072] An aqueous composition for treating a metal-containing composition is provided. According to an embodiment, the aqueous leaching composition may comprise the free-radical scavenging and antifoaming and / or defoaming and / or wetting compound and optionally at least one additional free-radical scavenger and / or metal scavenger.

[0073] Preferably, the aqueous composition is an aqueous leaching composition.

[0074] According to an embodiment, the aqueous leaching composition may comprise 0.001% to 10%, preferably 0.01% to 5% by weight of the free-radical scavenging and antifoaming and / or defoaming and / or wetting compound, based on the combined weight of the metal containing composition and the aqueous leaching composition.

[0075] According to an embodiment, the aqueous leaching composition may further comprise an acid and / or a base.

[0076] According to an embodiment, the aqueous leaching composition can comprise a dispersion or a solution, preferably a solution, and more preferably a homogeneous solution.

[0077] The aqueous leaching composition or compositions of the invention may be used 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, electronic waste, one or more metal alloys, nickel pig iron, or any combination thereof, to recover at least one metal selected from Li, Co, Mn, Fe, Cu, Al, and / or Ni.

[0078] Free-Radical Scavenging and Antifoaming and / or Defoaming and / or Wetting Compound

[0079] The aqueous leaching composition comprises one or more free-radical scavenging and antifoaming and / or defoaming and / or wetting compounds. As used herein, a free-radical scavenging and antifoaming and / or defoaming and / or wetting compound is a single compound having both free-radical scavenging properties or activity and at least one of antifoaming and / or defoaming and / or wetting properties or activity.

[0080] The free-radical scavenging and antifoaming and / or defoaming and / or wetting compound for use in the present invention may be selected from linear, branched, isomeric branched, secondary, tertiary, or polyhydric alcohols, that optionally include even- and / or odd-numbered hydrocarbon chains ranging from about Ci to C15, diol molecules HO-R-OH wherein R is a linear or branched alkyl group ranging from Ci 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.

[0081] In preferred embodiments, the free-radical scavenging and antifoaming and / or defoaming and / or wetting compound for use in the present invention may be selected from thioethers of formula HO-CH(R' )-CH2-S-CH2-CWOH)-CH2-O-R2wherein R1is H and R2is C4-C20alkyl.

[0082] Even more preferably, the free-radical scavenging and antifoaming and / or defoaming and / or wetting compound for use in the present invention may be selected from butanol, 1- pentanol, 2-propanol, 1-hexanol, 1-octanol, 2-ethyl-l -hexanol, butanediol, 1,6-hexanediol, 1,5- pentanediol, 1,8-octanediol, 1,7-hepanediol, and epichlorohydrin-mercaptoethanol alcohol, or, more preferably, from tert-butanol, ethylene glycol, isopropanol, pentanol, 2-ethyl-l -hexanol, ethanol, hexanol and butanol, or, most preferably, from C4-C8 alcohols, or any combination thereof. In another aspect, the free-radical scavenging and antifoaming and / or defoaming and / or wetting compound may comprise at least one of a linear, branched or polyhydric alcohol, a polyether, a polyhydric alcohol fatty acid ester, a fatty alcohol, a diol, a thioether, a polyvinyl copolymer, a gemini surfactant, or a combination thereof, preferably in an amount of 0.01 to 2% by weight, preferably 0.01 to 1% by weight, based on the combined weight of the metal containing composition and the aqueous leaching composition.

[0083] In another aspect, the free-radical scavenging and antifoaming and / or defoaming and / or wetting compound may comprise polyoxyalkylated glycerol, polyoxyalkylated sorbitol, poly oxy alkylated sorbitan, poly oxy alkylated sucrose, and isomers thereof, wherein the polyoxyalkylated glycerol, sorbitol, sorbitan, or sucrose contains ethylene oxide in the range between about 0-60 weight % and has a molecular weight in the range between about 200- 10,000.

[0084] In another aspect, the free-radical scavenging and antifoaming and / or defoaming and / or wetting compound may comprise: 10-90% by weight of a polyether surfactant, said polyether surfactant comprising at least one compound selected from the group consisting of polyoxyalkylated glycerol, polyoxyalkylated sorbitol or sorbitan, polyoxyalkylated sucrose, and isomers thereof; wherein said polyoxyalkylated glycerol, sorbitol, sorbitan, or sucrose contains ethylene oxide in the range between about 0-60 weight % and has a molecular weight in the range between about 200-10,000; and 10-90% by weight of a polyhydric alcohol fatty acid ester, said polyhydric alcohol fatty acid ester comprising: a fatty acid mono and / or diester of polyethylene glycol and / or polypropylene glycol.

[0085] Suitable free-radical scavenging and antifoaming and / or defoaming and / or wetting compounds for use in the present invention include: Dynol™ 360 thioether [CAS No.928768-73- 4]; ZetaSperse® 3100 polyvinyl copolymer (Evonik); and Surfynol® AD-01 gemini surfactant (Evonik).

[0086] Peroxides:

[0087] The aqueous leaching composition comprises one or more peroxides. 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, peroxyoctanoic acid, cumene peroxide, hydroperoxides, diacyl peroxides, peroxyesters, or combinations thereof, more preferably hydrogen peroxide. Optional Free-Radical Scavenger and / or Metal Scavenger

[0088] The aqueous leaching composition optionally may comprise at least one additional free- radical scavenger and / or metal scavenger, which is preferably different from the free-radical scavenging and antifoaming compound.

[0089] Metal Scavenger

[0090] Non-limiting examples of suitable optional metal scavengers are phenyl acetamides, phenacetin, stannates, potassium stannate, sodium stannate, sodium hexahydroxystannate, phenolic acids, phosphoric acid, disodium pyrophosphate (Na2H2P2O?), tetrasodium pyrophosphate (Na4P2O?), phosphonates, or combinations thereof, more 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), or combinations thereof, most preferably, phosphoric acid, phosphonic acid, disodium pyrophosphate, tetrasodium pyrophosphate, or combinations thereof.

[0091] According to an embodiment, the metal scavenger may comprise phenyl acetamides, phosphoric acid, disodium pyrophosphate (NfeH^O?), 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.

[0092] According to an embodiment, the metal scavenger may comprise stannates, phenolic acids, dipicolinic acid, phosphoric acid, disodium pyrophosphate (Na2H2P2O?), 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 (EfEDP), or combinations thereof, most preferably, sodium stannate, phosphoric acid, phosphonic acid, disodium pyrophosphate, tetrasodium pyrophosphate, or combinations thereof.

[0093] According to an embodiment, the at least one additional metal-scavenging compound may comprise phenyl acetamides, phenacetin, stannates, potassium stannate; sodium stannate; sodium hexahydroxystannate, phenolic acids, phosphoric acid, disodium pyrophosphate, tetrasodium pyrophosphate, phosphonates, or combinations thereof, preferably tannic acid, gallic acid, phosphoric acid, disodium pyrophosphate, tetrasodium pyrophosphate, phosphonic acid, nitrilotrimethyl-phosphonic acid, ethylene diamine tetra methylene phosphonic acid, diethylenetriaminepentakis(methylphosphonic acid), hydroxyethylidine diphosphonic acid, or combinations thereof.

[0094] The aqueous leaching 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 metalcontaining composition to be treated.

[0095] Free Radical Scavenger

[0096] The optional 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-C15 primary non-cyclic alcohols, preferably C4 to Cs primary non-cyclic alcohols, polyhydric alcohols, unsaturated aliphatic alcohols, alicyclic alcohols, diols, preferably straight aliphatic C5 - Cx diols, branched C5-C8 diols, C3 - C12 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 poiytetrahydrofuran having weight average molecular weight from 250 to 40,000 Daltons, glycol ether solvents, preferably 2- methoxy ethanol, 2-ethoxyethanol, 2 -propoxy ethanol, 2-isopropoxy ethanol, 2-butoxy ethanol, 2- phenoxy ethanol, 2 -benzyloxy ethanol, l-methoxy-2-propanol, 2-(2-m ethoxy ethoxy)ethanol, 2-(2- ethoxyethoxy)ethanol, 2-(2-butoxyethoxy)ethanol, dipropylene glycol methyl ether, C12-15 pareth-12, dialkyl ethers, preferably dimethoxy ethane, di ethoxy ethane, dibutoxy ethane, esters, preferably 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, I -methoxylpropanol 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, 2-ethyl-l -hexanol, 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, hexanol, ascorbic acid, or a combination thereof.

[0097] 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 Ci 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 C2to 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; thioethers, such as, for example, but not limited to, HO-CH(R7)-CH2-S-CH2-CH(OH)-CH2-O-R4wherein R4is C4-2o 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, 2-ethyl-l -hexanol, ethanol, hexanol, butanol, and ascorbic acid, and most preferably include but are not limited to n- butanol, hexanol and ascorbic acid.

[0098] The aqueous leaching 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. Acids

[0099] According to an embodiment, the acid, if present in the aqueous leaching composition, may comprise at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid, acetic acid, citric acid, lactic acid, malic acid, methanesulfonic acid, gluconic acid, formic acid, acetoacetic acid, succinic acid, adipic acid, oxalic acid, aspartic acid, or combinations thereof, preferably nitric, hydrochloric, or sulfuric acid.

[0100] Bases

[0101] 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 may comprise 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

[0102] 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.

[0103] 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).

[0104] Non-limiting aspects of the invention are summarized as follows:

[0105] Aspect 1 : A method of controlling foam formation in a process of treating a metalcontaining composition with an aqueous leaching composition that comprises a peroxide, wherein the metal -containing composition comprises one or more of Li, Co, Mn, Fe, Cu, Al, and / or Ni, and / or a salt and / or an oxide thereof, characterized in that the aqueous leaching composition comprises a free-radical scavenging and antifoaming and / or defoaming and / or wetting compound and optionally at least one additional free-radical scavenger and / or metal scavenger.

[0106] Aspect 2: The method according to Aspect 1, further characterized in that the aqueous leaching composition comprises 0.001% to 10%, preferably 0.01% to 5% by weight of the free- radical scavenging and antifoaming and / or defoaming and / or wetting compound, based on the combined weight of the metal containing composition and the aqueous leaching composition.

[0107] Aspect 3: The method of Aspect 1 or 2, further characterized in that the metal -containing composition comprises e-waste, 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, one or more metal alloys, nickel pig iron, or any combination thereof.

[0108] Aspect 4: The method of any of Aspects 1 to 3, further characterized in that the aqueous leaching composition comprises at least one additional metal-scavenging and / or a free-radical scavenging compound.

[0109] Aspect 5 : The method of any of Aspects 1 to 4, further characterized in that the aqueous leaching composition further comprises an acid and / or a base.

[0110] Aspect 6: The method of any of Aspects 1 to 5, 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, peroxyoctanoic acid, cumene peroxide, hydroperoxides, diacyl peroxides, peroxyesters, or combinations thereof, more preferably hydrogen peroxide.

[0111] Aspect 7: The method of any of Aspects 5 to 6, 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, lactic acid, malic acid, methanesulfonic 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 8: The method of any of Aspects 1 to 7, 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.

[0112] Aspect 9: The method of any of Aspects 1 to 8, 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.

[0113] Aspect 10: The method of any Aspects 1 to 9, further characterized in that the metal - containing composition is contacted with the aqueous leaching composition for a time of from about 1 minute to 24 hours, preferably from about 10 minutes to 2 hours, more preferably from about 0.5 to 2 hours, and at a temperature of from 10 to 100°C, preferably from 15 to 90°C, more preferably from 20 to 80°C.

[0114] Aspect 11 : The method of any of Aspects 1 to 10, further characterized in that the aqueous leaching composition is under a pressure between 1 and 10 atm, preferably at ambient pressure.

[0115] Aspect 12: The method of any of Aspects 1 to 11, further characterized in that the free- radical scavenging and antifoaming and / or defoaming and / or wetting compound is selected from linear, branched, isomeric branched, secondary, tertiary, or polyhydric alcohols, that optionally include even- and / or odd-numbered hydrocarbon chains ranging from about Ci to Cis, diol molecules HO-R-OH wherein R is a linear or branched alkyl group ranging from Ci to Cis, 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 (in particular thioethers of formula HO-CH(R1)-CH2-S-CH2- CH(OH)-CH2-O-R2wherein R1is H and R2is C4-C20 alkyl), or, more preferably, from butanol, 1-pentanol, 2-propanol, 1-hexanol, 1-octanol, 2-ethyl-l -hexanol, butanediol, 1,6-hexanediol, 1,5- pentanediol, 1,8-octanediol, 1,7-hepanediol, and epichlorohydrin-mercaptoethanol alcohol, or, more preferably, from tert-butanol, ethylene glycol, isopropanol, pentanol, 2-ethyl-l -hexanol, ethanol, hexanol and butanol, or, most preferably, from C4-C8 alcohols, or any combination thereof. Aspect 13: The method of any of Aspects 1 to 12, further characterized in that the free- radical scavenging and antifoaming and / or defoaming and / or wetting compound comprises at least one of a linear, branched, or polyhydric alcohols, a polyether, a polyhydric alcohol fatty acid ester, a fatty alcohol, a diol, a thioether, a polyvinyl copolymer, a gemini surfactant, or a combination thereof, preferably in an amount of 0.01 to 2% by weight, preferably 0.01 to 1% by weight, based on the combined weight of the metal containing composition and the aqueous leaching composition.

[0116] Aspect 14: The method of any of Aspects 1 to 13, further characterized in that the free- radical scavenging and antifoaming and / or defoaming and / or wetting compound comprises polyoxyalkylated glycerol, polyoxyalkylated sorbitol, polyoxyalkylated sorbitan, polyoxyalkylated sucrose, and isomers thereof, wherein the polyoxyalkylated glycerol, sorbitol, sorbitan, or sucrose contains ethylene oxide in the range between about 0-60 weight % and has a molecular weight in the range between about 200-10,000.

[0117] Aspect 15: The method of any of Aspects 4 to 14, further characterized in that the at least one additional free-radical scavenging compound comprises at least one of monohydric alcohols, Ci to C15 primary non-cyclic alcohols, preferably C4 to Cs primary non-cyclic alcohols, polyhydric alcohols, unsaturated aliphatic alcohols, alicyclic alcohols, diols, preferably straight aliphatic C5 to Cs diols, branched C5 to Cs diols, C3 to C12 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) having weight average molecular weight from 250 to 40,000, glycol ether solvents, preferably 2- methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-isopropoxy ethanol, 2-butoxyethanol, 2- phenoxy ethanol, 2-benzyloxy ethanol, l-methoxy-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 dimethoxy ethane, di ethoxy ethane, dibutoxy ethane, esters, preferably 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, I -methoxylpropanol 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, 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, more preferably n-butanol, hexanol, ascorbic acid, or a combination thereof.

[0118] Aspect 16: The method of any of Aspects 4 to 15, further characterized in that the at least one additional metal-scavenging compound comprises phenyl acetamides, phenacetin, stannates, potassium stannate; sodium stannate; sodium hexahydroxystannate, phenolic acids, phosphoric acid, disodium pyrophosphate, tetrasodium pyrophosphate, phosphonates, or combinations thereof, preferably tannic acid, gallic acid, phosphoric acid, disodium pyrophosphate, tetrasodium pyrophosphate, phosphonic acid, nitrilotrimethyl-phosphonic acid, ethylene diamine tetra methylene phosphonic acid, diethylenetriaminepentakis(methylphosphonic acid), hydroxyethylidine diphosphonic acid, or combinations thereof.

[0119] Aspect 17: The method of any of Aspects 1 to 16, further characterized in that the metalcontaining composition comprises recycled lithium-ion battery materials derived from end-of- life batteries and / or from battery scrap materials.

[0120] Aspect 18: An aqueous leaching composition for treating a metal containing composition, the aqueous leaching composition comprising a peroxide, characterized in that the aqueous leaching composition further comprises a free-radical scavenging and antifoaming and / or defoaming and / or wetting compound and optionally at least one additional free-radical scavenger and / or metal scavenger.

[0121] Aspect 19: The aqueous leaching composition of Aspect 18, further characterized in that the aqueous leaching composition comprises 0.001% to 10%, preferably 0.01% to 5% by weight of the free-radical scavenging and antifoaming and / or defoaming and / or wetting compound, based on the combined weight of the metal containing composition and the aqueous leaching composition.

[0122] Aspect 20: The aqueous leaching composition of Aspect 18 or 19, further characterized in that the aqueous leaching composition comprises at least one additional metal-scavenging and / or a free-radical scavenging compound. Aspect 21 : The aqueous leaching composition of any of Aspects 18 to 20, further characterized in that the aqueous leaching composition further comprises an acid and / or a base.

[0123] Aspect 22: The aqueous leaching composition of any of Aspects 18 to 21, 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, lactic acid, malic acid, methanesulfonic 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.

[0124] Aspect 23: The aqueous leaching composition of any of Aspects 18 to 22, 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, peroxyoctanoic acid, cumene peroxide, hydroperoxides, diacyl peroxides, peroxyesters, or combinations thereof, more preferably hydrogen peroxide.

[0125] Aspect 24: The aqueous leaching composition of any of Aspects 18 to 23, 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.

[0126] Aspect 25: The aqueous leaching composition of any of Aspects 18 to 24, 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.

[0127] Aspect 26: The aqueous leaching composition of any of Aspects 18 to 25, further characterized in that the free-radical scavenging and antifoaming and / or defoaming and / or wetting compound is selected from linear, branched, isomeric branched, secondary, tertiary, or polyhydric alcohols, that optionally include even- and / or odd-numbered hydrocarbon chains ranging from about Ci to C15, diol molecules HO-R-OH wherein R is a linear or branched alkyl group ranging from Ci 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 (in particular thioethers of formula HO-CH(R1)-CH2-S-CH2-CH(OH)-CH2-O-R2wherein R1is H and R2is C4-C20 alkyl), or, more preferably, from butanol, 1-pentanol, 2-propanol, 1-hexanol, 1-octanol, 2-ethyl-l -hexanol, butanediol, 1,6-hexanediol, 1,5-pentanediol, 1,8-octanediol, 1,7-hepanediol, and epichlorohydrin-mercaptoethanol alcohol, or, more preferably, tert-butanol, ethylene glycol, isopropanol, pentanol, 2-ethyl-l -hexanol, hexanol, ethanol, and butanol, or, most preferably, from C4-C8 alcohols, or any combination thereof.

[0128] Aspect 27: The aqueous leaching composition of any of Aspects 18 to 26, further characterized in that the free-radical scavenging and antifoaming and / or defoaming and / or wetting compound comprises at least one of a polyether, a polyhydric alcohol fatty acid ester, a fatty alcohol, a diol, a thioether, a polyvinyl copolymer, a gemini surfactant, or a combination thereof, preferably in an amount of 0.01 to 2% by weight, preferably 0.01 to 1% by weight, based on the combined weight of the metal containing composition and the aqueous leaching composition.

[0129] Aspect 28: The aqueous leaching composition any of Aspects 18 to 27, further characterized in that the free-radical scavenging and antifoaming and / or defoaming and / or wetting compound comprises polyoxyalkylated glycerol, polyoxyalkylated sorbitol, polyoxyalkylated sorbitan, polyoxyalkylated sucrose, and isomers thereof, wherein the polyoxyalkylated glycerol, sorbitol, sorbitan, or sucrose contains ethylene oxide in the range between about 0-60 weight % and has a molecular weight in the range between about 200- 10,000.

[0130] Aspect 29: The aqueous leaching composition of any of Aspects 20 to 28, further characterized in that the at least one additional free-radical scavenging compound comprises at least one of monohydric alcohols, Ci to C15 primary non-cyclic alcohols, preferably C4 to Cs primary non-cyclic alcohols, polyhydric alcohols, unsaturated aliphatic alcohols, alicyclic alcohols, diols, preferably straight aliphatic C5 to diols, branched C5 to Cs diols, C3 to C12 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) having weight average molecular weight from 250 to 40,000, glycol ether solvents, preferably 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2- isopropoxy ethanol, 2 -butoxy ethanol, 2-phenoxyethanol, 2-benzyloxyethanol, 1 -methoxylpropanol, 2-(2 -methoxyethoxy )ethanol, 2-(2-ethoxy ethoxy )ethanol, 2-(2-butoxyethoxy)ethanol, dipropylene glycol methyl ether, C 12-15 pareth-12, dialkyl ethers, preferably dimethoxy ethane, di ethoxy ethane, dibutoxy ethane, esters, preferably 2-methoxy 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, preferably methanol, ethanol, propanol, n-butanol, heptanol, hexanol, isopropanol, 2-ethyl-l -hexanol, 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, more preferably n-butanol, hexanol, ascorbic acid, or a combination thereof.

[0131] Aspect 30: The aqueous leaching composition of any of Aspects 20 to 29, further characterized in that the at least one additional metal-scavenging compound comprises phenyl acetamides, phenacetin, stannates, potassium stannate, sodium stannate, sodium hexahydroxy stannate, phenolic acids, phosphoric acid, disodium pyrophosphate, tetrasodium pyrophosphate, phosphonates, or combinations thereof, preferably tannic acid, gallic acid, phosphoric acid, disodium pyrophosphate, tetrasodium pyrophosphate, phosphonic acid, nitrilotrimethyl-phosphonic acid, ethylene diamine tetra methylene phosphonic acid, diethylenetriaminepentakis(methylphosphonic acid), hydroxy ethylidine diphosphonic acid, or combinations thereof.

[0132] Aspect 31 : Use of the method of any of Aspects 1 to 17 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, electronic waste, one or more metal alloys, nickel pig iron, or any combination thereof, to recover at least one metal selected from Li, Co, Mn, Fe, Cu, Al, and / or Ni.

[0133] Aspect 32: Use of the aqueous leaching composition of any of Aspects 18 to 30 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, electronic waste, one or more metal alloys, nickel pig iron, or any combination thereof, to recover at least one metal selected from Li, Co, Mn, Fe, Cu, Al, and / or Ni.

[0134] EXAMPLES

[0135] EXPERIMENTAL

[0136] Methods:

[0137] Temperature:

[0138] 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.

[0139] Peroxide concentration over time:

[0140] 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 a pipette, a small amount of sample was collected from the solution in the beaker and a few drops were placed on a designated window. Temperature is corrected, and readings are obtained within 3 seconds and rounded to 0.2%. 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 measurements of the same formulation to measure the concentration of the hydrogen peroxide over time.

[0141] 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).

[0142] T1

[0143] Hydrogen peroxide concentration measurements

[0144] Hydrogen peroxide concentration was measured using an automated titrator. The titration is based on the reaction (below) 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.

[0145] 5H2O2 + 2KMnO4 + 3H2SO4 — > 2MnSO4 + K2SO4 + 5O2 + 8H2O

[0146] 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 %. total in the reactor(g)

[0147] Metal recovery measurement and calculation

[0148] 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.

[0149] Yield Ni = measured Ni wt.% / theoretical Ni wt.%

[0150] Theoretical % Ni = Ni%batxmbat / mtot. Measured Ni wt.% is the result given by TCP-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. pH measurement: pH was measured using a 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).

[0151] Small Scale Experiment: Beaker Test

[0152] Anti-foam preliminary test

[0153] Preliminary tests (test 1 and test 2) were conducted on graphite (same type as used in batteries) in the presence of iron and copper impurities added to simulate a black mass composition. A second series of tests was conducted on black mass scrap materials, which generate less foam than the black mass from end-of-life EV batteries.

[0154] • Test 1 (low sulfuric acid - high surfactant - 20°C)

[0155] In a beaker of 1000 mL, to 250 g of ultra-pure water (MilliQ), 0.2805g (250 ppm) of FeSO4,5H2O and 0.2950 g (250 ppm) of CuSO4,5H2O were added and stirred to homogenize. Then, 15 drops of H2SO4 were added to lower the pH to around 1. The resulting solution was stirred until a light clear blue color was observed. 3 g (which represent approximately 1% of the formulation weight) of inventive additive (free radical scavenging and antifoaming compound) were added, and then finally 7.5 g of graphite. The beaker contents were mixed with a stir bar until the graphite was mostly in suspension, and then 60 g of H2O2 (cone. 50%) were added to initiate the reaction.

[0156] • Test 2 (high sulfuric acid - low surfactant - 20°C)

[0157] In a beaker of 1000 mL, to 250 g of ultra-pure water, 0.2805 g (250 ppm) of FeSO4,5H2O and 0.2950 g (250 ppm) of CuSC>4,5H2O were added and stirred to homogenize. Then 30 g of H2SO4 were added under mixing until the solution showed a light clear blue color. 0.35 g (which represent 0.1% of the formulation weight) of inventive additive (free radical scavenging and antifoaming compound) were added, and then finally 7.50 g of graphite (Actilion GHDR 15-4 DR2-221214-2). The beaker contents were stirred until the graphite was mostly in suspension, and then 60 g of H2O2 (cone. 50%) were added to initiate the reaction.

[0158] • Test 3 (high sulfuric acid - very low surfactant - high temperature 50°C)

[0159] In a beaker of 1000 mL, 30.0 g of H2SO4 were added to 200 g of ultra-pure water (MilliQ) and stirred at 300 RPM for a few minutes. 0.030 g (0.01%) of inventive additive (free radical scavenging and antifoaming compound) were added and mixed, followed by 10 g of black mass scrap materials. The contents were stirred until the black mass was mostly in suspension. When the suspension temperature reached 50°C, 50 g of H2O2 (cone. 50%) were added to initiate the reaction.

[0160] Scavenger test

[0161] In a beaker of 1000 mL 240 g of ultra-pure water (MilliQ) were mixed with 1.1220g (1000 ppm) of FeSO4,5H2O and stirred, followed by the addition of 15 drops of FLSCLto drop the pH to about 1. The solution was stirred until a light clear orange color was observed. 3 g of inventive additive (1%) were added. When the solution reached a temperature of 50°C, 60 g of H2O2 (cone. 50%) were added to initiate the reaction.

[0162] Reactor Run

[0163] In a 1 -liter jacketed reactor, 403.02 g of ultra-pure water (MilliQ) were added and agitation was started at 100 RPM. 103.24 g (2M) of H2SO4 were added, followed by 3 g of inventive additive (1 % (w / v)). The agitation rate was increased to 300 RPM, and when the temperature of the solution reached 50°C, 20.0 g (ratio of 40g / L) of black mass were added to the reactor, and the reaction was initiated by the addition of 50 g of H2O2 (cone. 50%).

[0164] RESULTS AND DISCUSSION

[0165] Beaker tests

[0166] Foam

[0167] The goal of these experiments was to assess if wetting agents help prevent the formation of foam in the system. The system is particularly aggressive with high concentrations of sulfuric acid (2M in reactor), an elevated temperature of at least 50°C, and the presence of hydrogen peroxide. It was unknown whether antifoam molecules would survive these harsh conditions.

[0168] The beaker test was initiated as an initial test and especially as a safety precaution to ensure that no hazardous reaction is taking place before moving to the larger size jacketed reactor.

[0169] The initial concentration of the additives was chosen at 1% (w / v). Lower antifoam concentrations were tested as well. Results of the foam height (rough measurement reported in cm) generated in the beaker are listed in Table 1 below.

[0170] Table 1: Height of foam (cm) as a function of the additives

[0171] Test #1 and Test #2 were done with a typical graphite similar to what is found in the anode of lithium batteries (e.g., graphite Actilion GHDR 15). Test #3 were made with black mass (end-of-life battery).

[0172] In the first column of Table 1, the results show that Dynol™ 360 is the most effective compound to prevent or, at least, limit the formation of foam. The products 1 -octanol and 2- ethyl-1 -hexanol are less effective but their effect on foam is still very noticeable.

[0173] For Test #3, the goal was to reduce the concentration of the antifoam additives since wetting agents are usually used in low concentrations. In these experiments, alcohols were not evaluated because they are not typically used in the same concentration range as the wetting agents. In test #3, Dynol™ 360 appeared to be the most effective compound. Scavenging tests

[0174] The compounds that showed the best antifoam results were evaluated for their scavenging properties in the scavenger tests. Results with 1% additives are presented below. This test was designed to simulate the presence of metal impurities in the black mass. The goal was to get the longest hydrogen peroxide persistence time compared to a reference (i.e., when no additive is present). The times reported in Figure 1 correspond to the time it takes for the hydrogen peroxide to be fully consumed (started at the addition of hydrogen peroxide until total consumption of hydrogen peroxide, or maximum exotherm). The result in Figure 1 showed that all the wetting agents evaluated had a positive action in slowing down the consumption of hydrogen peroxide.

[0175] One additional important parameter to consider is solubility, as efficient antifoams are often not water soluble and, by design, are supposed to float on the surface of the liquid where the foam is generated. The solubilities of the additives are reported in Table 2. The other important parameter in a scavenger is the number of attack sites, which in this case, are usually carbons (methylene group in the alpha, beta, etc. position). The number of carbons (-CH2-) present within a compound and their proximity to other molecules (e.g., oxygen, sulfur) is plotted against hydrogen peroxide consumption time in Figure 2.

[0176] Table 2: solubility of compound

[0177] Figure 2 shows a correlation between the number of carbon (alkane chain length) and the efficacy in free radical scavenging. An optimal scavenging effect is observed for molecules containing 6 carbons. This was confirmed for linear alcohols and diol molecules. Reactor Runs

[0178] Following the foam tests and the scavenger tests in beaker conditions, black mass in the 1 L reactor was investigated. The initial black mass tested was an end-of-life recycled material from EV. Table 3 below summarizes the foam levels observed and Table 4 the hydrogen peroxide consumption results.

[0179] Table 3: Foam high (in cm) during reactor runs, 40g I, BM, 2M H2SO4, 5% H2O2 + additives

[0180] The reference corresponded to the amount of hydrogen peroxide consumed by black mass (without any free radical or antifoam additives) with an initial concentration of approximately 4.5% in hydrogen peroxide. These data are reported in graph form in Figure 3.

[0181] As shown in Table 3, 1 -hexanol and 1 -octanol are efficient antifoam compounds. The ring of solids observed on the glass edge with 1 -hexanol was minimal and not a concern. In most cases, it can be prevented with modification of the agitation speed.

[0182] Regarding the scavenging effect (see Figure 3), there was a clear impact from the molecules 1 -octanol and 1 -hexanol on the amount of hydrogen peroxide consumed, compared to the reference Dynol™ 360.

[0183] To investigate whether the antifoam interferes with the metal leaching yield, the concentrations of nickel, cobalt and manganese in the leachate were analyzed and compared to theoretical initial concentrations in the solution. The results are reported in Figure 4. The presence of antifoams and free radical scavengers did not appear to affect the metal leaching yield.

[0184] Testing with additional free-radical scavenger and antifoaming compounds, i.e., compounds that have both free-radical scavenging properties and one or more of defoaming, antifoaming, and / or wetting properties was carried out on three different black mass samples - BM-1, BM-2 and BM-3. The composition of the black mass samples are shown in Table 4. Table 4: Composition of Black Mass Samples

[0185] Samples BM-1, BM-2 and BM-3 were each leached with sulfuric acid at 50°C, using 5% hydrogen peroxide and 1% additive (the free-radical scavenger and antifoaming compound). The results are shown in Table 5. The results were recorded right after the addition of hydrogen peroxide when foaming is the most intense.

[0186] Table 5: Foam height (in cm) during reactor runs, 100 g L BM, 2MH2SO4, 5% H2O2 + 1% additives The results in Table 5 show that the addition of alcohol, or a combination of alcohols, significantly reduces the amount of foam generated during lixiviation and in some cases makes the foam less persistent. The addition of alcohol not only reduces the amount of foam but also considerably reduces the undesirable degradation of hydrogen peroxide, as shown in the following examples.

[0187] The Effect of free radical scavengers on the degradation of hydrogen peroxide was tested 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. 5 shows the time it took in minutes for the concentration in hydrogen peroxide to reach 0%.

[0188] Table 6: List of free radical compounds tested and experimental observations.

[0189] 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. 5 showed no free radical scavenging effects while the last six compounds show an increase in scavenging activity.

[0190] The impact of 1% n-butanol on the black mass leaching process was tested as follows. In a one-liter jacketed reactor with a temperature set at 50°C, black mass (from end-of-life batteries from different sources BM-4 and BM-5, as noted in Table 4 above) 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). Fig. 6 shows the evolution of the concentration of hydrogen peroxide consumed by the reaction over time. Table 7 summarizes the results of the amount of hydrogen left in the reactor in percentage for the end point at 2 hours.

[0191] Table 7: Amount ofE C left in the reactor after 2 hours.

[0192] In a separate test, 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. 7 shows the amount of hydrogen peroxide remaining in the reactor over a period of 2 hours of reaction at 50°C.

[0193] These examples emphasize the protective effect of the free radical scavenger n-butanol on the degradation of hydrogen peroxide.

[0194] The combined foam prevention and reduction in hydrogen peroxide consumption when using alcohols with hydrogen peroxide in the treatment of black mass is novel and inventive over known leaching techniques. The results in Table 5 also confirm the universal applicability of the free-radical scavenger and antifoaming compounds in combination with hydrogen peroxide in the leaching of black mass irrespective of the origin of the black mass.

[0195] 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. 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.

Claims

CLAIMSWhat is claimed is:

1. A method of controlling foam formation in a process of treating a metal -containing composition with an aqueous composition that comprises a peroxide, wherein the method comprises contacting the metal -containing composition with the aqueous composition, wherein the metal -containing composition comprises one or more of Li, Co, Mn, Fe, Cu, Al, and / or Ni, and / or a salt and / or an oxide thereof, characterized in that the aqueous composition comprises a free-radical scavenging and antifoaming compound and optionally at least one additional free- radical scavenger and / or metal scavenger that is different from the free-radical scavenging and antifoaming compound.

2. The method of claim 1, further characterized in that the aqueous composition comprises 0.001% to 10%, preferably 0.01% to 5% by weight of the free-radical scavenging and antifoaming compound, based on the combined weight of the metal containing composition and the aqueous composition.

3. The method of claim 1 or 2, further characterized in that the metal-containing composition comprises e-waste, 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, one or more metal alloys, nickel pig iron, or any combination thereof.

4. The method of any of claims 1 to 3, further characterized in that the aqueous composition comprises at least one additional metal-scavenging and / or a free-radical scavenging compound.

5. The method of any of claims 1 to 4, further characterized in that the aqueous composition further comprises an acid and / or a base.

6. The method of any of claims 1 to 5, 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, peroxyoctanoic acid, cumene peroxide, hydroperoxides, diacyl peroxides, peroxyesters, or combinations thereof, more preferably hydrogen peroxide.

7. The method of any of claims 1 to 6, further characterized in that the aqueous composition further comprises an acid and the acid comprises at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid, acetic acid, citric acid, lactic acid, malic acid, methanesulfonic 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.

8. The method of any of claims 1 to 7, 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.

9. The method of any of claims 1 to 7, 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.

10. The method of any claims 1 to 9, further characterized in that the metal-containing composition is contacted with the aqueous composition for a time of from about 1 minute to 24 hours, preferably from about 10 minutes to 2 hours, more preferably from about 0.5 to 2 hours, and at a temperature of from 10 to 100°C, preferably from 15 to 90°C, more preferably from 20 to 80°C.

11. The method of any of claims 1 to 10, wherein the aqueous composition is under a pressure between 1 and 10 atm, preferably at ambient pressure.

12. An aqueous composition for treating a metal containing composition, the aqueous composition comprising a peroxide and an acid and / or a base, characterized in that the aqueous composition further comprises a free-radical scavenging and antifoaming compound and optionally at least one additional free-radical scavenger and / or metal scavenger that is different from the free-radical scavenging and antifoaming compound.

13. The aqueous composition of claim 12 or the method of any of claims 1 to 11, further characterized in that the free-radical scavenging and antifoaming compound is selected from linear, branched, isomeric branched, secondary, tertiary, or polyhydric alcohols, that optionally include even- and / or odd-numbered hydrocarbon chains ranging from about Ci to Cis, diol molecules HO-R-OH wherein R is a linear or branched alkyl group ranging from Ci to Cis,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, in particular thioethers of formula HO-CH(R1)-CH2-S-CH2- CH(OH)-CH2-O-R2wherein R1is H and R2is C4-C20 alkyl, or from butanol, 1-pentanol, 2- propanol, 1-hexanol, 1-octanol, 2-ethyl-l -hexanol, butanediol, 1,6-hexan ediol, 1,5-pentanediol, 1,8-octanediol, 1,7-hepanediol, and epichlorohydrin-mercaptoethanol alcohol, or from tertbutanol, ethylene glycol, 2-ethyl-l -hexanol, isopropanol, pentanol, ethanol, hexanol and butanol, or from C4-C8 alcohols, or any combination thereof; and / or the free-radical scavenging and antifoaming compound comprises one or more of a linear, branched, or polyhydric alcohols, a polyether, a polyhydric alcohol fatty acid ester, a fatty alcohol, a diol, a thioether, a polyvinyl copolymer, a gemini surfactant, or a combination thereof.

14. Use of the method of any of claims 1 to 11 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, electronic waste, one or more metal alloys, nickel pig iron, 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 claim 12 or 13 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, electronic waste, one or more metal alloys, nickel pig iron, 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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