Oxidative and reductive leaching methods

Abstract

Disclosed herein is a method for obtaining a composition comprising copper sulfide from a material, the method comprising contacting the material with an acidic aqueous solution having a pH of less than 6 in the presence of sulfur dioxide to form copper sulfide; the material comprises one or more copper compounds selected from copper in the zero oxidation state, copper oxide, and copper hydroxide, the material comprising a metal in the zero oxidation state in an amount having a standard redox potential of less than zero volts versus a standard hydrogen electrode. Also disclosed are methods for recycling at least one battery material, and compositions comprising copper sulfide.

Description

[Technical Field]

[0001] The project that led to this application has received funding from the Bundesministerium fuer Wirtschaft und Klimaschutz (DE;FKZ:16BZF101A) and the applicant is responsible for all disclosures herein.

[0002] Disclosed herein is a method for obtaining a composition comprising copper sulfide from a material, the method comprising contacting the material with an acidic aqueous solution having a pH of less than 6 in the presence of sulfur dioxide to form copper sulfide; the material comprises one or more copper compounds selected from copper in the zero oxidation state, copper oxide, and copper hydroxide, the material comprising a metal in the zero oxidation state in an amount having a standard redox potential of less than zero volts versus a standard hydrogen electrode. Also disclosed are methods for recycling at least one battery material, and compositions comprising copper sulfide. [Background technology]

[0003] Lithium-ion battery materials and valuable metal ores are complex mixtures of various elements and compounds. For example, many lithium-ion battery materials contain valuable metals such as lithium, aluminum, nickel, cobalt, copper, and / or manganese. It may be desirable to recover various elements and compounds from lithium-ion battery materials and valuable metal ores. For example, it may be advantageous to recover lithium, aluminum, nickel, cobalt, copper, and / or manganese.

[0004] High-purity lithium is a valuable resource. Many lithium sources, such as lithium-ion batteries, lithium-ion battery waste, lithium-containing water (e.g., groundwater), and lithium-containing raw ores, are complex mixtures of various elements and compounds. The extraction and purification of lithium from materials, such as lithium-ion battery materials, is an exemplary step in the recycling of lithium-ion batteries. Lithium-ion battery materials are complex mixtures of various elements and compounds, and it may be desirable to remove various non-lithium impurities. Such impurities may exist in various oxidation states, which may affect the efficiency of the leaching process. For example, in some leaching processes, metals in high oxidation states may be leached more efficiently than metals in low or zero oxidation states, or may not be leached at all. Non-lithium impurities are also valuable resources, and it may be desirable to separate and purify various elements and compounds from such materials.

[0005] CN 114 634 192 A discloses a method and apparatus for recovering black mass from waste lithium-ion batteries. This method uses black mass obtained from lithium iron phosphate batteries. The method for recovering black mass from waste lithium iron phosphate batteries includes the following steps: adding a solvent to the black mass and stirring to prepare a slurry; then adding oxygen, sulfur dioxide, and a second inorganic acid solution to the slurry to react; and filtering the reacted slurry to obtain a first recycled material and a first solution. The first recycled material contains iron phosphate, and the first solution contains Li. + By adding oxygen, sulfur dioxide, and a small amount of inorganic acid to the slurry containing the black lumps, the oxygen and sulfur dioxide convert the Fe in the lithium iron phosphate into the black lumps under acidic conditions. 2+ is oxidized to Fe 3+ and Fe 3+ is PO4 in lithium iron phosphate 3- The first solution reacts with the lithium carbonate salt to precipitate iron phosphate. A soluble carbonate salt is added to the first solution to precipitate lithium carbonate, which is then filtered to obtain the lithium carbonate and the second solution. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] CN 114 634 192 A Summary of the Invention [Problem to be solved by the invention]

[0007] Therefore, there is a need for processes for removing lithium from materials, such as battery materials, and for recycling lithium-ion battery materials. Additionally, there is a need for processes for extracting valuable metals, such as copper. There is a need for leaching methods that efficiently and effectively leach complex mixtures of elements and compounds, such as mixed metals coexisting in various oxidation states. For example, there is a need for economical processes with high lithium recovery rates and high lithium purity. There is also a need for economical processes with high recovery rates and high purity for removing valuable metals, such as nickel, copper, and cobalt, from materials. [Means for solving the problem]

[0008] Disclosed is a method for obtaining a composition comprising copper sulfide from a material, the method comprising contacting the material with an acidic aqueous solution having a pH of less than 6 in the presence of sulfur dioxide to form copper sulfide; no oxidizing agent is added during the contacting step; the material comprises one or more copper compounds selected from copper in the zero oxidation state, copper oxide, and copper hydroxide, the material comprising a metal in the zero oxidation state in an amount having a standard redox potential of less than zero volts versus a standard hydrogen electrode.

[0009] In some embodiments, the method further comprises separating the copper sulfide-containing composition from the aqueous solution by solid-liquid separation.

[0010] In some embodiments, the method further comprises purifying the composition comprising copper sulfide by solid-solid separation.

[0011] In some embodiments, the composition comprises 0.1% to 100% by weight, for example 1% to 100% by weight, of copper sulfide, based on the total weight of the composition.

[0012] In some embodiments, the acidic aqueous solution comprises H2SO4.

[0013] In some embodiments, the material is a lithium ion battery material comprising one or more selected from black mass, cathode active material, cathode, cathode current collector foil, cathode active material precursor, graphite, anode, anode current collector foil, and combinations thereof.

[0014] In some embodiments, the material comprises 0% to 10% by weight lithium, 0.1% to 60% by weight nickel, 0% to 20% by weight cobalt, 0.1% to 20% by weight aluminum, 0% to 20% by weight iron, 0% to 20% by weight manganese, and 0% to 20% by weight zinc, each relative to the total weight of the material; an amount of at least one of nickel, cobalt, aluminum, iron, manganese, and zinc is present as a zero oxidation state metal; and the material has a molar ratio of copper to an amount of a zero oxidation state metal having a standard redox potential of less than zero volts versus a standard hydrogen electrode in the range of 1:0.1 to 1:10.

[0015] In some embodiments, the material or a precursor thereof is pyrolyzed prior to the contacting step.

[0016] In some embodiments, hydrogen gas and hydrogen sulfide gas are formed by contacting the material with an acidic aqueous solution having a pH less than 6 in the presence of sulfur dioxide, and after the hydrogen gas and hydrogen sulfide gas are formed, the method includes adding an oxidizing agent selected from O2, NO, a mixture of 0.1-5% by volume of sulfur dioxide and air, a mixture of 0.1-5% by volume of sulfur dioxide and oxygen, and combinations thereof.

[0017] In some embodiments, the method further comprises adding air after the contacting step.

[0018] In some embodiments, the acidic aqueous solution has an acid concentration in the range of 18 mol / L to 0.0001 mol / L.

[0019] In some embodiments, sulfur dioxide is provided as a gas during the contacting step at a rate of 1 to 500 Nl per kg of material.

[0020] In some embodiments, following the contacting step, the method further comprises adding an additional material comprising one or more selected from a metal oxide, a metal hydroxide, a metal carbonate, a metal bicarbonate, and combinations thereof.

[0021] Also disclosed is a method for recycling at least one battery material selected from lithium ion batteries, lithium ion battery waste, lithium ion battery manufacturing scrap, lithium ion cell manufacturing scrap, lithium ion cathode active material, and combinations thereof, wherein the method optionally includes heat treating the at least one battery material at a temperature in the range of 350°C to 900°C; mechanically crushing the at least one battery material to obtain a crushed material; optionally screening the crushed material to obtain a fine fraction (e.g., black mass) and a coarse fraction; and subjecting the fine fraction, optionally the black mass, the coarse fraction, or the fine fraction and the coarse fraction, to a leaching method disclosed herein.

[0022] In some embodiments, the method further comprises smelting the composition comprising copper sulfide.

[0023] In some embodiments, the method further comprises roasting the composition comprising copper sulfide.

[0024] Also disclosed are compositions comprising copper sulfide prepared according to the methods disclosed herein. [Brief explanation of the drawings]

[0025] [Figure 1] FIG. 1 illustrates an exemplary batch process consistent with certain embodiments of the present disclosure. [Figure 2] FIG. 2 illustrates an exemplary continuous process consistent with some embodiments of the present disclosure. [Figure 3] FIG. 3 shows the XRD pattern of an exemplary black mass. DETAILED DESCRIPTION OF THE INVENTION

[0026] As used herein, "a" or "an" entity refers to one or more of that entity; for example, "a compound" refers to one or more compounds or at least one compound, unless otherwise specified. Thus, the terms "a" (or "an"), "one or more," and "at least one" are used interchangeably herein.

[0027] As used herein, the term "material" refers to elements, components, and / or substances that make up or can be made into something.

[0028] As used herein, a "reducing agent" is a compound that can reduce metal oxides and / or metal hydroxides. For example, some reducing agents can reduce some metal oxides and / or some metal hydroxides but cannot reduce others.

[0029] As used herein, an "oxidizing agent" is a compound that can oxidize a metal in the zero oxidation state. For example, some oxidizing agents can oxidize some metals in the zero oxidation state but not others.

[0030] As used herein, a "solution" is a combination of a fluid and one or more compounds, e.g., each of the one or more compounds in a solution may or may not be dissolved in the fluid.

[0031] As used herein, an "essentially pure metal ion solution" is a solution comprising metal ions, counterions, and a solvent; wherein the combined mass of the metal ions and counterions is at least 50% by mass, excluding the mass of the solvent.

[0032] As used herein, an "essentially pure solid metal ion salt" is a solid comprising a metal ion and a counterion; wherein the combined mass of the metal ion and counterion is at least 50% by weight of the solid, excluding the mass of the solvent.

[0033] As used herein, the term "sparging" refers to dispersing a gas through a liquid.

[0034] As used herein, the term "base" refers to a material that can react with hydronium ions to raise the pH value of an acidic solution.

[0035] The term "standard electrode potential" as used herein is commonly used in the field of electrochemistry and is the value of the electromotive force of an electrochemical cell in which molecular hydrogen is oxidized to solvated protons at a standard hydrogen electrode at 1 bar and 298.15 K. The potential of the standard hydrogen electrode is, by definition, zero volts. An exemplary reference is: Johnstone, AH, "CRC Handbook of Chemistry and Physics - 69th Edition, Editor-in-Chief RC West, CRC Press Inc., Boca Raton, Florida, 1988."

[0036] As used herein, the term "smelting" refers to heating a material to a temperature at which it solidifies above its melting point, optionally in the absence of oxygen.

[0037] As used herein, the term "roasting" refers to heating a material to a temperature below its melting temperature, optionally in the presence of oxygen.

[0038] The term "mixed hydroxide precipitate" as used herein refers to a material containing at least two metal hydroxides. An exemplary mixed hydroxide precipitate is a commercially available MHP produced at MCC's (Metallurgical Corporation of China) Lamu plant in PNG (Papua New Guinea) according to the following procedure: (1) HPAL (high-pressure acid leach) sulfuric acid leaching of limonite laterite ore, (2) neutralizing the residual acid and removing Fe / Al by precipitation with CaCO to increase the pH, (3) precipitating Ni and Co from the separated PLS as MHP with NaOH, and (4) a final precipitation step with CaO (this second-stage precipitate is recycled to neutralize the autoclave discharge slurry), where Ni and Co (and Mn) are re-leached.

[0039] Disclosed is a method for obtaining a composition comprising copper sulfide from a material, the method comprising contacting the material with an acidic aqueous solution having a pH of less than 6 in the presence of sulfur dioxide to form copper sulfide; the material comprising one or more copper compounds selected from copper in the zero oxidation state, copper oxide, and copper hydroxide, the material comprising a metal in the zero oxidation state in an amount having a standard redox potential of less than zero volts versus a standard hydrogen electrode.

[0040] material: The material comprises one or more copper compounds selected from copper in the zero oxidation state, copper oxide, and copper hydroxide, and the material comprises a metal in the zero oxidation state in an amount having a standard redox potential of less than zero volts relative to a standard hydrogen electrode.

[0041] In some embodiments, the material is a lithium ion battery material comprising one or more selected from black mass, cathode active material, cathode, cathode current collector foil (e.g., comprising aluminum), cathode active material precursor, graphite, anode, anode current collector foil (e.g., comprising copper), and combinations thereof.

[0042] In some embodiments, the material comprises 0% to 10% by weight lithium, 0.1% to 60% by weight nickel, 0% to 20% by weight cobalt, 0.1% to 20% by weight aluminum, 0% to 20% by weight iron, 0% to 20% by weight manganese, and 0% to 20% by weight zinc, each based on the total weight of the material; wherein each weight percent is by weight of the total weight of the material; an amount of at least one of nickel, cobalt, aluminum, iron, manganese, and zinc is present as a zero oxidation state metal; and the material has a molar ratio of copper to an amount of a zero oxidation state metal having a standard redox potential of less than zero volts versus a standard hydrogen electrode in the range of 1:0.1 to 1:10 (e.g., 1:1 to 1:5, e.g., 1:1.5 or 1:3).

[0043] In some embodiments, the material comprises one or more metals in the zero oxidation state and one or more selected from metal oxides, metal hydroxides, metal carbonates, and combinations thereof.

[0044] In some embodiments, the material is a lithium ion battery material comprising one or more selected from black mass, cathode active material, cathode, cathode active material precursor, and combinations thereof.

[0045] In some embodiments, the material comprises one or more selected from nickel, cobalt, manganese, and combinations thereof.

[0046] In some embodiments, the one or more metals in the zero oxidation state are selected from nickel, cobalt, copper, aluminum, iron, manganese, rare earth metals, and combinations thereof.

[0047] In some embodiments, the metal oxide is selected from nickel oxide, cobalt oxide, copper oxide, aluminum oxide, iron oxide, manganese oxide, rare earth oxides, and combinations thereof.

[0048] In some embodiments, the metal hydroxide is selected from nickel hydroxide, cobalt hydroxide, copper hydroxide, aluminum hydroxide, iron hydroxide, manganese hydroxide, rare earth hydroxides, and combinations thereof.

[0049] In some embodiments, the material comprises between 0.1% and 10% by weight lithium, between 0% and 60% by weight nickel, between 0% and 20% by weight cobalt, between 0% and 20% by weight copper, between 0% and 20% by weight aluminum, between 0% and 20% by weight iron, and between 0% and 20% by weight manganese, where each weight percentage is based on the total weight of the material.

[0050] In some embodiments, the material or precursor thereof is pyrolyzed prior to leaching, hi some embodiments, the pyrolysis is carried out under an inert atmosphere, an oxidizing atmosphere, a reducing atmosphere, or a combination thereof.

[0051] In some embodiments, the material is a lithium ion battery material comprising one or more selected from black mass, cathode active material, cathode, cathode active material precursor, and combinations thereof.

[0052] "Black mass" refers to lithium-containing materials obtained by mechanical processing, such as mechanical grinding, from, for example, lithium-ion batteries, lithium-ion battery waste, lithium-ion battery manufacturing scrap, lithium-ion cell manufacturing scrap, lithium-ion cathode active material, and / or combinations thereof. For example, black mass may be obtained from battery scrap by mechanically processing the battery scrap to obtain active components of the electrode, such as graphite and cathode active material, and may contain impurities from the casing, electrode foil, cable, separator, and electrolyte. In some examples, the battery scrap is subjected to a heat treatment to pyrolyze organic materials (e.g., electrolyte) and polymeric materials (e.g., separator and binder). Such heat treatment may occur before or after mechanical grinding of the battery materials. In some embodiments, the black mass is subjected to a heat treatment.

[0053] Lithium-ion batteries can be disassembled, punched, crushed, for example, in a hammer mill or rotor mill, and / or shredded, for example, in an industrial shredder. Such mechanical processing provides the active material for the battery electrodes. Light fractions, such as organic plastics and housing parts made from aluminum or copper foil, can be removed, for example, by forced airflow, air separation, or classification or sieving.

[0054] Battery scrap can be derived from, for example, manufacturing waste, such as used batteries or off-spec materials. In some embodiments, the material is obtained from mechanically processed battery scrap, such as battery scrap processed in a hammer mill, rotor mill, or industrial shredder. Such material can have an average particle size (D50) ranging from 1 μm to 1 cm, such as from 1 μm to 500 μm, and further such as from 3 μm to 250 μm.

[0055] Large portions of the battery scrap, such as housings, wiring, and electrode carrier films, can be mechanically separated so that the corresponding materials are excluded from the battery material employed in the process.

[0056] Mechanically treated battery scrap can be subjected to a solvent treatment to dissolve and separate polymer binders used to bind transition metal oxides to the current collector film or, for example, to bind graphite to the current collector film. Suitable solvents are N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N-ethylpyrrolidone, and dimethyl sulfoxide, used in pure form, as a mixture of at least two of the foregoing, or as a mixture with 1% to 99% by weight of water.

[0057] In some embodiments, the mechanically processed battery scrap can be subjected to heat treatment in different atmospheres over a wide range of temperatures. In some embodiments, the temperature ranges from 100°C to 900°C. In some embodiments, lower temperatures below 300°C serve to evaporate residual solvent from the battery electrolyte, higher temperatures decompose the binder polymer, and temperatures above 400°C may change the composition of the inorganic materials such that some transition metal oxides are reduced by carbon contained in the scrap material or by the introduction of a reducing gas. In some embodiments, reduction of lithium metal oxides can be avoided by maintaining the temperature below 400°C and / or removing the carbonaceous material before heat treatment.

[0058] In some embodiments, the heat treatment is performed at a temperature ranging from 350°C to 900°C. In some embodiments, the heat treatment is performed at a temperature ranging from 450°C to 800°C. In some embodiments, the heat treatment is performed under an inert atmosphere, an oxidizing atmosphere, or a reducing atmosphere. In some embodiments, the heat treatment is performed under an inert atmosphere or a reducing atmosphere. In some embodiments, a reducing agent is formed from the pyrolyzed organic (polymer) components under the conditions of the heat treatment. In some embodiments, the reducing agent is formed by adding a reducing gas such as H2 and / or CO.

[0059] In some embodiments, the material comprises at least one selected from lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, lithium metal phosphate, lithium ion battery scrap, black nugget, and combinations thereof.

[0060] In some embodiments, the material has the formula Li x The lithium metal phosphates include MPO4, where x is an integer equal to or greater than 1, and M is selected from metals, transition metals, rare earth metals, and combinations thereof.

[0061] In some embodiments, the material comprises a lithiated nickel cobalt manganese oxide of the formula Li 1+x (Ni a Co b Mn c M 1 d ) 1-x O2, where M 1 is selected from Mg, Ca, Ba, Al, Ti, Zr, Zn, Mo, V, and Fe, 0 ≦ x ≦ 0.2, 0.1 ≦ a ≦ 0.95, 0 ≦ b ≦ 0.9 (e.g., 0.05 < b ≦ 0.5), 0 ≦ c ≦ 0.6, 0 ≦ d ≦ 0.1, and a + b + c + d = 1. Exemplary lithiated nickel cobalt manganese oxides include Li (1+x) [Ni 0.33 Co 0.33 Mn 0.33 (1-x) O2, Li (1+x) [Ni 0.5 Co 0.2 Mn 0.3 (1-x) O2, Li (1+x) [Ni 0.6 Co 0.2 Mn 0.2 (1-x) O2, Li (1+x) [Ni 0.7 Co 0.2 Mn 0.3 [[ID=_{54}]] (1-x) O2, Li (1+x) [Ni 0.8 Co 0.1 Mn 0.1 (1-x) O2, and Li[Ni 0.85 Co 0.13 Al 0.02 O2, where x is as defined above.

[0062] In some embodiments, the material is of the formula Li[Ni h Co i Al j O 2+rwherein h is in the range of 0.8 to 0.95, i is in the range of 0.1 to 0.3, j is in the range of 0.01 to 0.10, and r is in the range of 0 to 0.4.

[0063] In some embodiments, the material has the formula Li (1+x) Mn 2-x-y-z M y M' z O4, where x is in the range of 0 to 0.2, y+z is in the range of 0 to 0.1, and M' is selected from Al, Mg, Fe, Ti, V, Zr, and Zn.

[0064] In some embodiments, the material has the formula xLi (1+1 / 3) M (2 / 3) O2·yLiMO2·zLiM'O2, where M is at least one metal selected from the group consisting of Mn, Ni, and Co in the oxidation state +4, and M' is at least one transition metal, and <x<1であり、0<y<1であり、0<z<1であり、x+y+z=1である。

[0065] In some embodiments, the material comprises nickel, cobalt, manganese, copper, aluminum, iron, phosphorous, or a combination thereof.

[0066] In some embodiments, the material has a mass ratio of lithium to the total mass of nickel, cobalt, manganese, copper, aluminum, iron, and phosphorus in the range of 0.01 to 10. In some embodiments, the material has a mass ratio of lithium to the total mass of nickel, cobalt, manganese, copper, aluminum, iron, and phosphorus in the range of 0.01 to 5. In some embodiments, the material has a mass ratio of lithium to the total mass of nickel, cobalt, manganese, copper, aluminum, iron, and phosphorus in the range of 0.01 to 2. In some embodiments, the material has a mass ratio of lithium to the total mass of nickel, cobalt, manganese, copper, aluminum, iron, and phosphorus in the range of 0.01 to 1.

[0067] In some embodiments, the material is Li x The compound includes MO2, wherein x is an integer greater than or equal to 1, and M is selected from metals, transition metals, rare earth metals, and combinations thereof.

[0068] In some embodiments, a method for recycling lithium ion battery materials includes mechanically crushing at least one selected from lithium ion batteries, lithium ion battery waste, lithium ion battery manufacturing scrap, lithium ion cell manufacturing scrap, lithium ion cathode active material, and combinations thereof to obtain black mass.

[0069] In some embodiments, the material has a standard electrode potential in the range of +1.1 V to −1.7 V. In some embodiments, 0.1% to 10% by weight of the material has a standard electrode potential in the range of +0.1 V to +0.8 V, and 0.1% to 60% by weight of the material has a standard electrode potential in the range of −1.7 V to −0.01 V, relative to the total weight of the material.

[0070] In some embodiments, the one or more metals in the zero oxidation state each have a standard electrode potential in the range of 1.1 V to −1.7 V. In some embodiments, the one or more metals in the zero oxidation state each have a standard electrode potential in the range of −1.7 V to +0.35 V. Standard electrode potentials of some exemplary metals in the zero oxidation state include: Al / Al 3+ (E(0)=-1.66V), Cu / Cu 2+ (E(0)=+0.35V), Co / Co 2+ (E(0)=-0.28V), Fe / Fe 2+ (E(0)=-0.44V), and Ni / Ni 2+ (E(0)=-0.23V).

[0071] In some embodiments, one or more selected from metal oxides, metal hydroxides, and combinations thereof each have a standard electrode potential in the range of +0.1 V to +1.9 V. In some embodiments, one or more selected from metal oxides, metal hydroxides, and combinations thereof each have a standard electrode potential in the range of +0.15 V to +1.83 V. Standard electrode potentials of some exemplary metal ions, such as, for example, oxides or hydroxides, and metal ions resulting from dissolution of metal oxides and / or metal hydroxides, include the following: Co 3+ / Co 2+ (E(0)=+1.83V), NiO2+4H + / Ni 2+ +2H2O (E(0) = +1.678V), Mn 3+ / Mn 2+ (E(0) = +1.5415 V), and Mn(OH)3 / Mn(OH)2 + OH- (E(0) = +0.15 V).

[0072] method: Disclosed is a method for obtaining a composition comprising copper sulfide from a material, the method comprising: contacting the material with an acidic aqueous solution having a pH of less than 6 in the presence of sulfur dioxide to form copper sulfide; no oxidizing agent is added during the contacting step; the material comprises one or more copper compounds selected from copper in the zero oxidation state, copper oxide, and copper hydroxide, the material comprising a metal in the zero oxidation state in an amount having a standard redox potential of less than zero volts versus a standard hydrogen electrode.

[0073] In some embodiments, the method further comprises separating the copper sulfide-containing composition from the aqueous solution by solid-liquid separation (e.g., filtration, sedimentation, and / or centrifugation).

[0074] In some embodiments, the method further comprises purifying the copper sulfide-containing composition by solid-solid separation (e.g., flotation, magnetic separation using magnetic carrier particles capable of forming magnetic aggregates with copper sulfide particles, gravity separation, and / or dense media separation).

[0075] No oxidizing agents are added during the contacting step. In particular, air, O2, and NO2 are not added during the contacting step. When the material is contacted with an acidic aqueous solution with a pH less than 6 in the presence of sulfur dioxide, hydrogen gas is formed by the reaction of the acid with metals in the material in a zero oxidation state, which have a standard redox potential less than zero volts relative to the standard hydrogen electrode. The hydrogen gas then reacts with sulfur dioxide to form hydrogen sulfide, which reacts with copper present in the material to form copper sulfide. Therefore, the presence of oxidizing agents that oxidize hydrogen or inhibit the reduction of sulfur dioxide to sulfide is harmful, and the addition of oxidizing agents during the contacting step should be avoided after hydrogen gas formation, i.e., until copper sulfide is formed.

[0076] In some embodiments of this method, the acidic aqueous solution is not sparged with an oxidizing agent (eg, air) prior to the contacting step.

[0077] Contacting the material with an acidic aqueous solution having a pH less than 6 involves first contacting the material with an acid in the presence of sulfur dioxide, causing the production of hydrogen gas and the production of hydrogen sulfide gas.

[0078] In some embodiments, hydrogen gas is formed by contacting the material with an acidic aqueous solution having a pH less than 6, and the acidic aqueous solution having a pH less than 6 is contacted with sulfur dioxide during hydrogen gas formation.

[0079] In some embodiments, SO2 is purged through the solution at a rate of up to 20% solution volume / minute for 1 to 3 hours. SO2 is not provided as a mixture with O2 or air. In some embodiments, SO2 is provided as a pure gas having a purity of at least 90%, e.g., 99%, or as a mixture with an inert gas, e.g., nitrogen and / or argon.

[0080] In some embodiments, excess sulfur dioxide is recycled from the off-gas back to the reactor.

[0081] In some embodiments, the contacting step is carried out at ambient temperature. In some embodiments, the contacting step is carried out at a temperature ranging from 50° C. to 110° C. In some embodiments, the contacting step is carried out for a duration ranging from 2 hours to 4 hours.

[0082] In some embodiments, the acidic aqueous solution has a pH in the range of -1.0 to 3.

[0083] In some embodiments, the method includes an oxidation step in which an oxidizing agent is added to the acidic aqueous solution, and the oxidation step follows the contacting step. In some embodiments, the acidic aqueous solution is not sparged with air before the contacting step. In some embodiments, no oxidizing agent other than sulfuric acid is added to the acidic aqueous solution before the contacting step.

[0084] In some embodiments, a mixture of SO and O, or air containing 5% or more SO, is used as the oxidizing agent. In some embodiments, excess oxidizing gases, O and / or N O, for example in air, are recycled from the off-gas back to the leaching reactor.

[0085] In some embodiments of this method, the oxidizing agent is not added until after hydrogen gas formation, hi some embodiments, the oxidizing agent is not added until at least 1 minute, at least 10 minutes, at least 30 minutes, at least 1 hour, or at least 2 hours after the start of the contacting step.

[0086] In some embodiments, the black mass is slurried in water with a weight percentage of black mass relative to the total weight of the slurry ranging from 5% to 30%. In some embodiments, the slurried black mass is contacted with an acidic aqueous solution having a pH of less than 6. In some embodiments, the acidic aqueous solution having a pH of less than 6 is formed from the slurried black mass by the addition of an acid and / or an oxidizing agent. In some embodiments, the weight ratio of H2SO4 to black mass in the acidic aqueous solution ranges from 1:1 to 2:1. In some embodiments, H2SO4 is added to adjust the pH during the contacting step.

[0087] In some embodiments, the black mass is provided as a slurry. In some embodiments, the black mass is provided as a slurry in water. In some embodiments, the black mass is provided as a slurry in an aqueous side stream from a subsequent processing step, such as washing liquid from a filter. In some embodiments, the black mass is provided as a solid. In some embodiments, the cathode active material is provided as a slurry. In some embodiments, the cathode active material is provided as a slurry in water. In some embodiments, the cathode active material is provided as a slurry in an aqueous side stream from a subsequent processing step, such as washing liquid from a filter. In some embodiments, the cathode active material is provided as a solid. In some embodiments, the mixed hydroxide precipitate is provided as a slurry. In some embodiments, the mixed hydroxide precipitate is provided as a slurry in water. In some embodiments, the mixed hydroxide precipitate is provided as a slurry in an aqueous side stream from a subsequent processing step, such as washing liquid from a filter. In some embodiments, the mixed hydroxide precipitate is provided as a solid.

[0088] In some embodiments, a metal in a zero oxidation state having a standard redox potential of less than zero volts versus a standard hydrogen electrode is added to the material before or during contacting the material with an acid. Such metals include, for example, nickel, cobalt, manganese, iron, zinc, and / or aluminum.

[0089] In some embodiments, nickel is added when the material comprises battery materials derived from nickel-containing batteries.

[0090] In some embodiments, cobalt is added when the material comprises battery materials derived from cobalt-containing batteries.

[0091] In some embodiments, manganese is added when the material comprises battery materials derived from manganese-containing batteries.

[0092] In some embodiments, iron is added when the material comprises battery materials derived from iron (eg, lithium iron phosphate)-containing batteries.

[0093] In some embodiments, following the contacting step, the method further comprises adding a base. In some embodiments, the base is selected from CaO, hydroxide salts, carbonate salts, and combinations thereof. In some embodiments, the hydroxide salt is selected from LiOH, NaOH, KOH, NH4OH, Ca(OH)2, CaCO3, Ni(OH)2, Co(OH)2, Mn(OH)2, and combinations thereof. In some embodiments, the hydroxide salt is a mixed hydroxide precipitate obtained from nickel laterite ore processing.

[0094] In some embodiments, the method is carried out batchwise.

[0095] In some embodiments, the method is carried out sequentially in at least two reaction vessels. In some embodiments, the method is carried out sequentially in, for example, three, four, five, six, seven, or more reaction vessels. In some embodiments, the black mass is added to a first reaction vessel, an oxidizing agent is added to a second and / or third reaction vessel, a cathode active material and / or mixed hydroxide precipitate is added to a fourth reaction vessel, and a reducing agent is added to a fourth, fifth, and / or sixth reaction vessel.

[0096] In some embodiments, a reflux condenser is attached to at least one reaction vessel.

[0097] In some embodiments, contacting the material with the acidic aqueous solution is carried out at ambient pressure. In some embodiments, contacting the material with the acidic aqueous solution is carried out at elevated pressure.

[0098] In some embodiments, the contacting step is carried out at a temperature ranging from 20°C to 100°C for a duration ranging from 10 minutes to 10 hours. In some embodiments, the contacting step is carried out at 100°C for a duration ranging from 3 hours to 5 hours. In some embodiments, the contacting step is carried out at 60°C for a duration ranging from 3 hours to 5 hours. In some embodiments, the contacting step is carried out at 25°C for a duration ranging from 3 hours to 5 hours.

[0099] In some embodiments, the disclosed methods include leaching a material according to a method disclosed herein to obtain an aqueous solution containing metal ions, and separating the metal ions to obtain at least one essentially pure metal ion solution and / or at least one essentially pure solid metal ion salt.

[0100] In some embodiments, an essentially pure solid metal ion salt is a solid comprising a metal ion and a counterion; wherein the combined mass of the metal ion and counterion is at least 50% by weight of the solid, excluding the mass of the solvent, such as total water. In some embodiments, an essentially pure solid metal ion salt is a solid comprising a metal ion and a counterion; wherein the combined mass of the metal ion and counterion is at least 70% by weight of the solid, excluding the mass of the solvent. In some embodiments, an essentially pure solid metal ion salt is a solid comprising a metal ion and a counterion; wherein the combined mass of the metal ion and counterion is at least 80% by weight of the solid, excluding the mass of the solvent. In some embodiments, an essentially pure solid metal ion salt is a solid comprising a metal ion and a counterion; wherein the combined mass of the metal ion and counterion is at least 90% by weight of the solid, excluding the mass of the solvent. In some embodiments, an essentially pure solid metal ion salt is a solid comprising a metal ion and a counterion; wherein the combined mass of the metal ion and counterion is at least 95% by weight of the solid, excluding the mass of the solvent. In some embodiments, an essentially pure solid metal ion salt is a solid comprising a metal ion and a counterion; wherein the combined mass of the metal ion and counterion is at least 99% by weight of the solid, excluding the mass of the solvent.

[0101] In some embodiments, an essentially pure metal ion solution is a solution comprising a metal ion, a counterion, and a solvent, wherein the combined mass of the metal ion and counterion is at least 50% by weight of the solution, excluding the mass of the solvent. In some embodiments, an essentially pure metal ion solution is a solution comprising a metal ion, a counterion, and a solvent, wherein the combined mass of the metal ion and counterion is at least 70% by weight of the solution, excluding the mass of the solvent. In some embodiments, an essentially pure metal ion solution is a solution comprising a metal ion, a counterion, and a solvent, wherein the combined mass of the metal ion and counterion is at least 80% by weight of the solution, excluding the mass of the solvent. In some embodiments, an essentially pure metal ion solution is a solution comprising a metal ion, a counterion, and a solvent, wherein the combined mass of the metal ion and counterion is at least 90% by weight of the solution, excluding the mass of the solvent. In some embodiments, an essentially pure metal ion solution is a solution comprising a metal ion, a counterion, and a solvent, wherein the combined mass of the metal ion and counterion is at least 95% by weight of the solution, excluding the mass of the solvent. In some embodiments, an essentially pure metal ion solution is a solution comprising metal ions, counterions, and a solvent, wherein the combined mass of the metal ions and counterions is at least 99% by weight of the solution, excluding the mass of the solvent.

[0102] In some embodiments, separating the metal ions to obtain at least one essentially pure metal ion solution and / or at least one essentially pure solid metal ion salt comprises one or more of solid-liquid separation, extraction, precipitation, crystallization, and combinations thereof.

[0103] In some embodiments, the method may be implemented in part or in whole as a continuous process controlled by sensors and actuators as part of a computer-based process control system.

[0104] In some embodiments, the method further comprises smelting the composition comprising copper sulfide.

[0105] In some embodiments, the method further comprises roasting the composition comprising copper sulfide.

[0106] Compositions containing copper sulfide: Disclosed herein are compositions comprising copper sulfide.

[0107] In some embodiments, a composition comprising copper sulfide is prepared according to the methods disclosed herein.

[0108] In some embodiments, the composition comprising copper sulfide comprises copper-(II)-sulfide, CuS, and / or copper-(I)-sulfide, Cu S. In some embodiments, the composition comprising copper sulfide also comprises copper metal and sulfur.

[0109] In some embodiments, the copper sulfide species are amorphous.

[0110] In some embodiments, the composition comprising copper sulfide comprises 2.5% to 100% by weight of copper sulfide, based on the total weight of the composition. In some embodiments, the composition comprising copper sulfide comprises 10% to 100% by weight of copper sulfide, based on the total weight of the composition. In some embodiments, the composition comprising copper sulfide comprises 25% to 100% by weight of copper sulfide, based on the total weight of the composition. In some embodiments, the composition comprising copper sulfide comprises 2.5% to 30% by weight of copper sulfide, based on the total weight of the composition. In some embodiments, the composition comprising copper sulfide comprises 10% to 30% by weight of copper sulfide, based on the total weight of the composition. In some embodiments, the composition comprising copper sulfide comprises 25% to 50% by weight of copper sulfide, based on the total weight of the composition.

[0111] In some embodiments, the composition comprising copper sulfide is separated from the aqueous solution by solid-liquid separation. In some embodiments, the composition comprising copper sulfide is separated from the aqueous solution by at least one solid-liquid separation selected from filtration, sedimentation, and centrifugation.

[0112] In some embodiments, one or more valuable metals are separated by solvent extraction, hi some embodiments, one or more of Ni, Co, Mn, Cu, and Li are extracted from the separated liquid by solvent extraction.

[0113] In some embodiments, the composition comprising copper sulfide is purified by solid-solid separation. In some embodiments, the composition comprising copper sulfide is purified by at least one solid-solid separation selected from flotation, magnetic separation, gravity separation, and dense media separation.

[0114] In some embodiments, copper sulfide in the leach residue is separated by flotation in the presence of xanthate, dithiophosphate, thionocarbamate, xanthogenformate, xanthate ester, and / or mercaptobenzothiazole collectors.

[0115] In some embodiments, the carbon contained in the leach residue is separated by flotation in the presence of a hydrophobic oil as a collector, such as an alkane having 7 or more carbon atoms.

[0116] In some embodiments, the carbon material is first flotated using hydrophobic oil as a collector, and then the copper sulfide is flotated using xanthate, dithiophosphate, thionocarbamate xanthogen formate, xanthate ester, and / or mercaptobenzothiazole collector.

[0117] In some embodiments, the copper sulfide is first floated using a xanthate, dithiophosphate, thionocarbamate xanthogen formate, xanthate ester, and / or mercaptobenzothiazole collector, and the carbon material is then floated using a hydrophobic oil as the collector.

[0118] An exemplary magnetic separation process is provided in PCT International Application No. PCT / EP2008 / 061503, filed September 1, 2008. The disclosure of PCT International Application No. PCT / EP2008 / 061503, filed September 1, 2008, is incorporated herein by reference in its entirety.

[0119] An exemplary process for separating and purifying compositions containing copper sulfide is described in Appl, M. "Ullmann's Encyclopedia of Industrial Chemistry 2011." DOI 10.1002(2012):14356007; which is incorporated herein by reference in its entirety.

[0120] Oxidizer: In some embodiments, the oxidant comprises O. In some embodiments, the oxidant is air.

[0121] In some embodiments, the oxidizing agent has a standard electrode potential in the range of +0.1 V to +1.8 V. In some embodiments, the oxidizing agent has a standard electrode potential in the range of +0.4 V to +1.3 V. In some embodiments, the oxidizing agent has a standard electrode potential in the range of +1 V to +1.5 V.

[0122] Reducing Agent: In some embodiments, the reducing agent has a standard electrode potential in the range of +1 V to −0.5 V. In some embodiments, the reducing agent has a standard electrode potential in the range of +0.2 V to −0.3 V.

[0123] Hydrogen peroxide can act as both a reducing agent and an oxidizing agent, depending on the reaction partner. The possible oxidation and reduction reactions are: H2O2 → O2 + 2e - +2H + , and H2O2 + 2e - +2H + → 2H2O. In some embodiments, the standard electrode potential of the reaction partners influences which reaction occurs. For example, under certain conditions, permanganate (MnO4 -) is reduced by hydrogen peroxide, while Fe 2+ In some embodiments, the highly acidic conditions include oxidizing H to form water. + The oxidation reaction is favored because less acidic conditions are required, and H + In some embodiments, the following reactions may or may not occur depending on the metal(s), M, and the conditions used: 2LiMO2 + H2O2 + 3H2SO4 → 2LiSO4 + 2MSO4 + 4H2O + O2, and M + H2O2 + H2SO4 → MSO4 + 2H2O.

[0124] Example batch process: FIG. 1 illustrates an exemplary batch process (100) consistent with some embodiments of the present disclosure. In some embodiments, material (102), such as a black mass containing nickel, cobalt, copper, and manganese species, is acid leached in a continuously stirred reaction vessel (101) containing an aqueous acidic solution with a pH less than 0. In some embodiments, hydrogen gas is generated (105), and SO2 is added (103) during hydrogen gas generation. In some embodiments, the pH is adjusted to a pH in the range of 1-2, for example, using a cathode active material and / or a mixed hydroxide precipitate, and an oxidizing agent, such as O2 and / or NO, is added (104). In some embodiments, the resulting liquid phase (106) and solid phase (105) are separated by solid-liquid separation, for example, filtration, centrifugation, and / or sedimentation.

[0125] Exemplary continuous processes: FIG. 2 illustrates an exemplary continuous process (200) consistent with some embodiments of the present disclosure. In some embodiments, material (202), such as black mass containing nickel, cobalt, copper, and manganese species, is acid leached in a continuously stirred reaction vessel (201) containing an acidic aqueous solution having a pH less than 0. In some embodiments, acid leaching is further carried out in one or more additional continuously stirred reaction vessels (203). In some embodiments, SO2 is added to the continuously stirred reaction vessel (204) (205). In some embodiments, acid leaching in the presence of added oxidant is further carried out in one or more additional continuously stirred reaction vessels (206). In some embodiments, the pH is adjusted to a pH in the range of 1-2, for example, using a cathode active material and / or a mixed hydroxide precipitate, and in some embodiments, an oxidant, such as O2 and / or NO, is introduced to the continuously stirred reaction vessel (207) (208). In some embodiments, leaching in the presence of added oxidizing agent is further carried out in one or more additional continuously stirred reaction vessels (209). In some embodiments, the resulting liquid phase (211) and solid phase (210) are separated by solid-liquid separation, such as filtration, centrifugation, and / or sedimentation.

[0126] In some embodiments of the method, at the start of the contacting step, the oxidizing agent other than sulfuric acid is present in the acidic aqueous solution at less than 50 mole % based on the total number of moles of copper in the zero oxidation state and zero oxidation state metal having a standard redox potential less than zero volts relative to a standard hydrogen electrode. In some embodiments, at the start of the contacting step, the oxidizing agent other than sulfuric acid is present in the acidic aqueous solution at less than 25 mole % based on the total number of moles of copper in the zero oxidation state and zero oxidation state metal having a standard redox potential less than zero volts relative to a standard hydrogen electrode. In some embodiments, at the start of the contacting step, the oxidizing agent other than sulfuric acid is present in the acidic aqueous solution at less than 10 mole % based on the total number of moles of copper in the zero oxidation state and zero oxidation state metal having a standard redox potential less than zero volts relative to a standard hydrogen electrode. In some embodiments, at the start of the contacting step, the oxidizing agent other than sulfuric acid is present in the acidic aqueous solution at less than 1 mole % based on the total number of moles of copper in the zero oxidation state and zero oxidation state metal having a standard redox potential less than zero volts relative to a standard hydrogen electrode.

[0127] In some embodiments of this method, no oxidizing agent is added during the contacting step.

[0128] In some embodiments of this method, the subsequent oxidation step, which includes the addition of air, begins at least 1 minute after the contacting step begins, at least 10 minutes after the contacting step begins, at least 30 minutes after the contacting step begins, or at least 1 hour after the contacting step begins. In some embodiments, the subsequent oxidation step begins between 0 minutes and 2 hours after the contacting step begins.

[0129] In some embodiments of this method, the composition comprising copper sulfide is separated by flotation in the presence of a xanthate, dithiophosphate, thionocarbamate xanthogen formate, xanthate ester, and / or mercaptobenzothiazole collector.

[0130] In some embodiments, the method includes leaching a material to obtain an aqueous solution containing metal ions, and separating the metal ions to obtain at least one essentially pure metal ion solution and / or at least one essentially pure solid metal ion salt.

[0131] In some embodiments of this method, hydrogen gas is formed by contacting the material with an acidic aqueous solution having a pH less than 6, and the acidic aqueous solution having a pH less than 6 is contacted with sulfur dioxide during the formation of hydrogen gas.

[0132] A claim or description including "or" or "and / or" between at least one member of a group is deemed to be satisfied if one, more than one, or all of the members of the group are present in, employed in, or otherwise relevant to a given product or process, unless indicated to the contrary or otherwise clear from the context. The present disclosure includes embodiments in which exactly one member of the group is present in, employed in, or otherwise relevant to a given product or process. The present disclosure includes embodiments in which two or more, or all, group members are present in, employed in, or otherwise relevant to a given product or process.

[0133] Furthermore, the present disclosure encompasses all variations, combinations, and permutations in which at least one limitation, element, clause, and descriptive term from at least one of the recited claims is introduced into another claim. For example, a claim that depends on another claim can be amended to include at least one limitation found in any other claim that depends from the same base claim. When elements are presented as a list, such as in Markush group format, each subgroup of elements is also disclosed, and any element(s) can be removed from the group. In general, when the present disclosure or aspects of the present disclosure are referred to as including particular elements and / or features, it should be understood that embodiments of the present disclosure or aspects of the present disclosure consist of, or consist essentially of, such elements and / or features. For simplicity, those embodiments are not specifically described herein. When ranges are given, endpoints are included. Furthermore, unless otherwise indicated or apparent from the context and the understanding of one of ordinary skill in the art, values expressed as ranges can assume any specific value or subrange within the stated range in different embodiments of the present disclosure, unless the context clearly dictates otherwise.

[0134] Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the disclosure described herein which equivalents are intended to be encompassed by the following claims. [Example]

[0135] The following examples are intended to be illustrative and not to limit the scope of the present disclosure in any way.

[0136] Abbreviation % percent g / t grams per ton K2CO3 Potassium Carbonate Na2CO3 Sodium Carbonate Na2B4O7 Sodium tetraborate PA Grade Professional Analysis Grade nd Undecided mass % mass percent NaOH Sodium hydroxide Lithium Ni Nickel Co Cobalt Mn Manganese Cu Copper Al Aluminum Fe Iron P. Lin F Fluorine Ca Calcium.

[0137] Exemplary elemental analysis Elemental analysis of solid samples was performed by digestion with nitric acid and hydrochloric acid (feed samples, Examples 1 and 2) or by digestion by K2CO3-Na2CO3 / Na2B4O7 fusion and dissolution of the fusion residue in hydrochloric acid (Examples 3 and 4).

[0138] The metals in the obtained sample solutions were determined by optical emission spectroscopy using inductively coupled plasma (ICP-OES).

[0139] Some element concentrations were measured by X-ray fluorescence using a Malvern Panalytical Epsilon 4 DY-6024 using Malvern Panalytical Omnian Software.

[0140] Elemental analysis of fluorine and fluoride was carried out according to DIN EN 14582:2016-12 for sample preparation (waste samples) for overall fluorine content determination; detection method was ion-selective electrode measurement according to DIN 38405-D4-2:1985-07 (water samples; digestion of inorganic solids followed by acid-assisted distillation and fluoride determination using an ion-selective electrode).

[0141] Total carbon was determined by gas chromatography using a thermal conductivity detector on the gas obtained after combustion of the sample.

[0142] Sulfur was determined by catalytic combustion of the samples in an inert gas / oxygen atmosphere, which converted sulfur to a mixture of SO2 and SO3. The SO3 produced was then reduced to SO2 with copper granules. After drying and separation of the combustion gases, sulfur was detected and quantified as SO2 by thermal conductivity or IR spectroscopy.

[0143] black lump In the examples below, black agglomerates were obtained by mechanically crushing lithium-ion batteries and then separating the black agglomerates as a fine powder from other components of the lithium-ion batteries. The black agglomerates were obtained through a process involving the pyrolysis of battery scrap. The material contains small amounts of sulfur. The analyzed metals are present as oxide compounds, e.g., MnO, CoO, NiO, salts, e.g., LiF, LiAlO2, Li2CO3, and / or metals in the zero oxidation state, e.g., nickel, cobalt, and copper. The carbon is primarily elemental carbon in the form of graphite, with some soot and coke.

[0144] The composition of the black mass used in Examples 1 and 2 is shown in Table 1.

[0145] [Table 1]

[0146] Figure 3 shows the XRD pattern of the black block, where "a" represents graphite, "b" represents nickel-cobalt-manganese, "c" represents NiO, "d" represents CoO, "e" represents MnO, and "f" represents Ni, and the remaining reflections correspond to lithium salts and impurities.

[0147] The composition of the black mass used in Example 3 is shown in Table 2.

[0148] [Table 2]

[0149] Cathode Active Material The cathode active material (CAM) used in Examples 1 and 2 was HED™, commercially available from BASF. TM The CAM was designated NCM and had the following composition: 49.8 wt% Ni, 5.9 wt% Co, 2.6 wt% Mn, and 7.3 wt% Li.

[0150] Example 1 In this example, the black mass of Table 1 was contacted with an oxidizing acidic aqueous solution having a pH of less than 6, and then reduced with a reducing agent.

[0151] In a 0.75 L baffled, jacketed reactor flushed with argon, 174.13 g of the black mass was suspended in 337.21 g of water. Next, 243.78 g of H2SO4 (96 wt%) was added slowly with stirring within 55 minutes. The slurry was heated to 90°C during the acid addition. After the acid addition was completed, the reactor contents were held at 90°C for an additional 110 minutes until hydrogen gas evolution ceased. Air was then sparged at 20 standard liters per hour (Nlph) for 2.5 hours while maintaining the slurry temperature at approximately 80°C. After an additional 30 minutes, 25 g of cathode active material was added. The reactor was held under air for an additional 234 minutes. SO2 was then sparged through the solution at 1.8 Nlph for 51 minutes. The composition of the leaching residue is shown in Table 4.

[0152] [Table 3]

[0153] The recovery rates for each element were 98.2% for Ni, 98.1% for Co, 99.2% for Mn, and 99.0% for Li. Analysis of the washed and dried leach residue showed that the recovery rate for Cu was 98.7%.

[0154] Example 2 In this example, a black mass having the composition shown in Table 1 was leached with sulfuric acid in the presence of sulfur dioxide without introducing air as an oxidant.

[0155] In a reactor, 205 g of the black mass and 25 g of the cathode active material were suspended in 563 g of deionized water under an argon atmosphere. To this mixture, 266 g of sulfuric acid (96% by weight) was slowly added over approximately 45 minutes while vigorously stirring with a Rushton turbine. Simultaneously, sulfur dioxide was fed into the reactor at a rate of 2.7 g / h. The gas exiting the reactor was fed to a scrubber filled with 1,779 g of a solution of 50 g of copper(II) sulfate pentahydrate dissolved in 1,729 g of water. After the acid addition, the reactor was heated to 96°C within 40 minutes. The reactor was held at this temperature for an additional 205 minutes. Then, sulfur dioxide addition was stopped, and the reactor was cooled to ambient temperature. The reactor contents were filtered, washed with water, and dried to yield 61.65 g of a black solid. Sixty-five minutes after the start of sulfuric acid and sulfur dioxide addition, the initially blue copper sulfate solution in the scrubber began to turn greenish and a dark precipitate formed. The scrubber precipitate was also filtered, washed with water, and dried to yield 0.116 g of a dark solid. Analysis of the solid residue is shown in Table 7.

[0156] [Table 4]

[0157] The data in Table 7 indicate that an insoluble sulfur-containing phase formed during the reaction; this phase was not present in the feed black mass (Table 2). The molar ratio of Cu:S in the reactor product was 3:2. The molar ratio of Cu:S in the scrubber product was approximately 12:5. Without wishing to be bound by theory, it is believed that under reducing conditions in the presence of sulfur dioxide, a mixture of copper(II) sulfide (CuS) and copper(I) sulfide (CuS) formed in the reactor. The scrubber product was CuS, which is believed to account for the excess copper because some of the copper sulfate was adsorbed. The amount of copper in the filter residue of the reaction mixture represented approximately 92% of the copper. In this filter residue, copper-(I) sulfide was identified by XRD analysis by reflections at 27.8°, 46.3°, and 54.6° 2θ. These reflections were slightly shifted higher compared to pure copper(I) sulfide, indicating a substoichiometric composition.

[0158] Example 3 In this example, Example 2 was repeated using 186 g of black mass and 21 g of cathode active material according to Table 2.

[0159] The black mass and NCM were suspended in 588 g of deionized water. The suspension was stirred at 700 rpm, and 228 g of sulfuric acid (96% by weight) was slowly added over 52 minutes. Concurrently with the acid addition, sulfur dioxide gas was introduced into the reactor at a rate of 3 g / h. During the acid addition, the reactor temperature rose to 52°C. After the acid addition was completed, the reactor temperature was heated to 100°C, which was reached 90 minutes after the acid addition was completed. The sulfur dioxide addition continued until the end of the test, 282 minutes after the start of the sulfuric acid / sulfur dioxide addition. The reactor was flushed with argon, and the suspension was diluted with 199.4 g of deionized water. The cooled suspension was filtered, and the filter residue was washed with deionized water. The composition of the dried filter cake is shown in Table 8.

[0160] [Table 5]

[0161] This residue was subjected to flotation to separate Cu-sulfides, although the recovery rates of Ni and Co were lower than in Example 2. The flotation proceeded as follows:

[0162] 80 g of the dried residue was dispersed in a 2 L DENVER flotation cell with 800 g of deionized water and stirred at 1200 rpm for 15 minutes. Next, 5000 g / t of solid Shellsol D40, a hydrogenated C11-C13 hydrocarbon, was added as a graphite collector and dispersed at 1200 rpm for another 5 minutes. 200 g / t of solid methyl isobutyl carbinol (MIBC) was then added and stirred for another 5 minutes. 270 g of water was then added, the gas inlet valve was opened, and flotation was initiated at an air flow rate of approximately 150 L / H. After 10 minutes, the gas inlet valve was closed again to stop flotation (first froth). 200 g / t of potassium ethylhexyl xanthate was added and stirred at 1200 rpm for 10 minutes. 200 g / t of MIBC was further added, and the gas inlet valve was then reopened. This was followed by another 10 minutes of flotation (second froth). The data in Table 9 summarizes the composition and yield of the two flotation stages.

[0163] [Table 6]

[0164] In Table 9, under the heading "% by mass of element relative to total mass of fraction," the number without parentheses is the grade of the element in the fraction, and the number in parentheses is the percent recovery of the element. For example, in the first froth obtained with Shellsol collector, the grade is 7.7% Cu and the recovery is 67%. For example, in the second froth obtained with xanthate collector, the Cu grade is 22.5% and the recovery is only 6%. Final tailings is the residual material remaining after two consecutive flotation stages (the first stage using Shellsol as a collector for carbon, which also captures Cu, and the second stage using xanthate, which is specific for sulfide minerals, to capture Cu sulfides). In Table 9, mass pull is the total mass of solids recovered in the fraction divided by the mass of the solids feed. This exemplary flotation experiment demonstrates that copper can be concentrated.

[0165] Comparing Example 1 with Examples 2 and 3, it is believed that copper-(II)-sulfide CuS and / or copper-(I)-sulfide CuS are formed by simultaneous reduction with SO in a contacting step, as opposed to, for example, an oxidation step (e.g., air added as an oxidant) followed by subsequent reduction with SO and / or a combined oxidation / reduction step involving simultaneous addition of air and SO. Such copper sulfide compositions may be separated from aqueous solutions by solid-liquid separation, for example, filtration, sedimentation, and / or centrifugation. Such copper sulfide compositions can be purified by solid-solid separation, for example, flotation, magnetic separation using magnetic carrier particles capable of forming magnetic agglomerates with copper sulfide particles, gravity separation, and / or dense media separation.

Claims

1. 1. A method for obtaining a composition comprising copper sulfide from a material, comprising: The method includes contacting the material with an acidic aqueous solution having a pH of less than 6 in the presence of sulfur dioxide to form copper sulfide; No oxidizing agent is added during the contacting step; the material comprises one or more copper compounds selected from copper in the zero oxidation state, copper oxide, and copper hydroxide; The method wherein the material comprises an amount of a metal in a zero oxidation state having a standard redox potential of less than zero volts relative to a standard hydrogen electrode.

2. 10. The method of claim 1, further comprising separating the composition comprising copper sulfide from the aqueous solution by solid-liquid separation.

3. 3. The method of claim 1 or 2, further comprising purifying the composition comprising copper sulfide by solid-solid separation.

4. 3. The method of claim 2, wherein the composition comprises 0.1% to 100% by weight of copper sulfide, based on the total weight of the composition.

5. The acidic aqueous solution is H ２ SO ４ 3. The method of claim 1 or 2, comprising:

6. 3. The method of claim 1 or 2, wherein the material is a lithium ion battery material comprising one or more selected from black mass, cathode active material, cathode, cathode current collector foil, cathode active material precursor, graphite, anode, anode current collector foil, and combinations thereof.

7. the material comprising, by weight, 0% to 10% lithium, 0.1% to 60% nickel, 0% to 20% cobalt, 0.1% to 20% aluminum, 0% to 20% iron, 0% to 20% manganese, and 0% to 20% zinc, each relative to the total weight of the material; an amount of at least one of nickel, cobalt, aluminum, iron, manganese, and zinc is present as a zero oxidation state metal; and 3. The method of claim 1 or 2, wherein the material has a molar ratio of copper to a metal in its zero oxidation state in an amount having a standard redox potential of less than zero volts versus a standard hydrogen electrode in the range of 1:0.1 to 1:

10.

8. 3. The method of claim 1 or 2, wherein the material or a precursor thereof is pyrolyzed prior to the contacting step.

9. contacting the material with an acidic aqueous solution having a pH less than 6 in the presence of sulfur dioxide to form hydrogen gas and hydrogen sulfide gas; After hydrogen gas and hydrogen sulfide gas are formed, the method ２ , N ２ 3. The method of claim 1 or 2, comprising adding an oxidizing agent selected from O, a mixture of 0.1 to 5 volume percent sulfur dioxide and air, a mixture of 0.1 to 5 volume percent sulfur dioxide and oxygen, and combinations thereof.

10. 3. The method of claim 1 or 2, further comprising adding air after the contacting step.

11. 3. The method according to claim 1, wherein the acidic aqueous solution has an acid concentration in the range of 18 mol / L to 0.0001 mol / L.

12. 3. The process of claim 1 or 2, wherein sulfur dioxide is supplied as a gas during the contacting step at a rate of 1 to 500 Nl per kg of said material.

13. 3. The method of claim 1 or 2, further comprising adding, following the contacting step, an additional material comprising one or more selected from metal oxides, metal hydroxides, metal carbonates, metal bicarbonates, and combinations thereof.

14. 1. A method for recycling at least one battery material selected from lithium ion batteries, lithium ion battery waste, lithium ion battery manufacturing scrap, lithium ion cell manufacturing scrap, lithium ion cathode active material, and combinations thereof, comprising: Optionally, heat treating the at least one battery material at a temperature in the range of 350°C to 900°C; mechanically pulverizing the at least one battery material to obtain a pulverized material; Optionally, screening the ground material to obtain a fine fraction and a coarse fraction; and 3. Subjecting the ground material, and optionally the fine fraction, the coarse fraction, or the fine fraction and the coarse fraction, to the method of claim 1 or 2. A method comprising:

15. 3. The method of claim 1 or 2, further comprising smelting the composition comprising copper sulfide.

16. 3. The method of claim 1 or 2, further comprising roasting the composition comprising copper sulfide.

17. 3. A composition comprising copper sulfide prepared according to the method of claim 1 or 2.

18. 3. The method of claim 2, wherein the solid-liquid separation is selected from filtration, sedimentation, centrifugation, and combinations thereof.

19. 4. The method of claim 3, wherein the solid-solid separation is selected from flotation, magnetic separation, gravity separation, dense media separation, and combinations thereof.

20. 3. The method of claim 1 or 2, wherein one or more metals in the zero oxidation state selected from Ni, Co, Mn, Fe, and combinations thereof are added to the material prior to and / or during the contacting step.

21. 10. The method of claim 9, wherein the oxidant is not added until after hydrogen gas formation.

22. 11. The method of claim 10, wherein air is not added until at least 1 minute, at least 10 minutes, at least 30 minutes, at least 1 hour, or at least 2 hours after the contacting step begins.

23. 3. The method of claim 1 or 2, wherein the acidic aqueous solution is not sparged with an oxidizing agent (e.g., air) prior to the contacting step.

24. 3. The method of claim 1 or 2, wherein no oxidizing agent other than sulfuric acid is added to the acidic aqueous solution prior to the contacting step.

25. 3. The method of claim 1 or 2, wherein at the start of the contacting step, the amount of oxidizing agent other than sulfuric acid present in the acidic aqueous solution is less than 50 mole % based on the total number of moles of zero oxidation state copper and zero oxidation state metals having a standard redox potential less than zero volts versus a standard hydrogen electrode.

26. 3. The method of claim 1 or 2, wherein at the start of the contacting step, the amount of oxidizing agent other than sulfuric acid present in the acidic aqueous solution is less than 25 mole % based on the total number of moles of zero oxidation state copper and zero oxidation state metals having a standard redox potential less than zero volts versus a standard hydrogen electrode.

27. 3. The method of claim 1 or 2, wherein at the start of the contacting step, the amount of oxidizing agent other than sulfuric acid present in the acidic aqueous solution is less than 10 mole % based on the total number of moles of zero oxidation state copper and zero oxidation state metals having a standard redox potential less than zero volts versus a standard hydrogen electrode.

28. 3. The method of claim 1 or 2, wherein at the start of the contacting step, the amount of oxidizing agent other than sulfuric acid present in the acidic aqueous solution is less than 1 mole % based on the total number of moles of zero oxidation state copper and zero oxidation state metals having a standard redox potential less than zero volts versus a standard hydrogen electrode.

29. 11. The method of claim 10, wherein the subsequent addition of air begins at least 1 minute after the contacting step begins, at least 10 minutes after the contacting step begins, at least 30 minutes after the contacting step begins, or at least 1 hour after the contacting step begins.

30. 11. The method of claim 10, wherein the subsequent addition of air begins 0 minutes to 2 hours after the start of the contacting step.

31. 3. The method of claim 1 or 2, wherein the composition comprising copper sulfide is separated by flotation in the presence of a xanthate, dithiophosphate, thionocarbamate xanthogen formate, xanthate ester, and / or mercaptobenzothiazole collector.

32. 3. A method comprising leaching a material according to the method of claim 1 or 2 to obtain an aqueous solution comprising metal ions, and separating the metal ions to obtain at least one essentially pure metal ion solution and / or at least one essentially pure solid metal ion salt.

33. 3. The method of claim 1 or 2, wherein hydrogen gas is produced by contacting the material with an acidic aqueous solution having a pH of less than 6, and the acidic aqueous solution having a pH of less than 6 is contacted with sulfur dioxide during the production of hydrogen gas.

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