Alkyl carbonates as reducing agents in hydrometallurgy.

Abstract

Disclosed herein is a method for extracting one or more metals from a material, the method comprising contacting the material with an acidic aqueous solution having a pH less than 7 and reducing one or more metal oxides selected from nickel oxide, cobalt oxide, and manganese oxide from the material using an alkyl carbonate; the material comprising one or more metal oxides. Also disclosed is a method comprising extracting one or more metals from the 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. Additionally, 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.

Description

[Technical Field]

[0001] The project that led to this application has received funding from the Bundesministerium fuer Wirtschaft und Klimaschutz (DE;FKZ:16BZF101A).

[0002] Disclosed herein is a method for extracting one or more metals from a material, the method comprising: contacting the material with an acidic aqueous solution having a pH less than 7; and reducing one or more metal oxides selected from nickel oxide, cobalt oxide, and manganese oxide with an alkyl carbonate, wherein the material comprises one or more metal oxides.

[0003] Also disclosed are methods that include extracting one or more metals from 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.

[0004] Further 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. [Background technology]

[0005] Lithium-ion battery materials and valuable metal ores (e.g., manganese ore) are complex mixtures of various elements and compounds. For example, many lithium-ion battery materials contain valuable metals such as lithium, aluminum, nickel, cobalt, 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, and / or manganese.

[0006] 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. Removal and purification of lithium from materials, such as lithium-ion battery materials, is an exemplary step in recycling 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. Some non-lithium impurities are also valuable resources, and it may be desirable to separate and purify various elements and compounds from such materials.

[0007] CN 113 363 609 A discloses a method for recycling cathode material from waste lithium batteries using a fluid gradual solidification process. The method includes the following steps: S1—adding the cathode material to a mixture of a salting agent and a fluidizing agent and stirring evenly; S2—heating and storing the mixture of the cathode material, salting agent, and fluidizing agent obtained in step S1 to allow the reaction to occur and obtain solid metal salts; S3—adding the resulting solid metal salt mixture to water to dissolve it, followed by filtering to obtain a salt solution of lithium, cobalt, nickel, and manganese. The salting agent is selected from the group consisting of perchloric acid, hydrochloric acid, sulfuric acid, nitric acid, hydrogen sulfate, and a mixture of disodium hydrogen sulfate, dipotassium hydrogen sulfate, sodium dihydrogen sulfate, and potassium dihydrogen sulfate. The water content of the salting agent is less than 10% by weight, and the dosage ratio is 0.5 to 2:1. The fluidizing agent is selected from the group consisting of propylene carbonate, diethyl carbonate, methyl ethyl carbonate, dimethyl carbonate ester, ethylene carbonate, methanol, ethanol, acetic acid, formic acid, propionic acid, malonic acid, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylethylamide, water, Tween 20, and Tween 80, and the ratio of the added mass of the fluidizing agent to the added mass of the positive electrode material is 0.005 to 0.1:1. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] CN 113 363 609 A Summary of the Invention [Problem to be solved by the invention]

[0009] Therefore, there is a need for processes for recovering lithium from materials, such as battery materials, and for recycling lithium-ion battery materials. There is also a need for processes for extracting and / or purifying valuable metals from ores. 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 recovering valuable metals, such as nickel, nickel, and cobalt, from materials. [Means for solving the problem]

[0010] Disclosed is a method for extracting one or more metals from a material, the method comprising: contacting the material with an acidic aqueous solution having a pH less than 7; and reducing one or more metal oxides selected from nickel oxide, cobalt oxide, and manganese oxide with an alkyl carbonate, wherein the material comprises one or more metal oxides. [Brief explanation of the drawings]

[0011] [Figure 1] FIG. 1 illustrates an exemplary process consistent with some embodiments of the present disclosure. [Figure 2] FIG. 2 illustrates an exemplary continuous process consistent with some embodiments of the present disclosure. [Figure 3] Figure 3 shows the XRD pattern of an exemplary black mass. Typically, the lithium metal oxide therein is characterized by a reflection at 2θ of 18.5°, and the reflection due to lithium nickel, cobalt, and manganese oxide is indicated by the letter b. DETAILED DESCRIPTION OF THE INVENTION

[0012] Disclosed is a method for extracting one or more metals from a material, the method comprising: contacting the material with an acidic aqueous solution having a pH less than 7; and reducing one or more metal oxides selected from nickel oxide, cobalt oxide, and manganese oxide with an alkyl carbonate, wherein the material comprises one or more metal oxides.

[0013] In some embodiments, the alkyl carbonate is a cyclic alkyl carbonate. In some embodiments, the cyclic alkyl carbonate is selected from ethylene carbonate, propylene carbonate, and butylene carbonate. In some embodiments, the alkyl carbonate is selected from diethyl carbonate, dimethyl carbonate, dipropyl carbonate, ethyl methyl carbonate, propyl methyl carbonate, ethyl propyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, and fluoroalkyl carbonate. In some embodiments, the alkyl carbonate comprises a lithium ion battery electrolyte condensate.

[0014] In some embodiments, the weight ratio of the material to the alkyl carbonate ranges from 1:1 to 1:0.001.

[0015] In some embodiments, the material has the formula Li p M q M' r O s wherein M comprises one or more metals selected from nickel, manganese, and cobalt; M' comprises one or more metals selected from Mg, Ca, Ba, Al, Ti, Zr, Zn, Fe, V, and Mo; p is in the range of 1 to 1.4; q is in the range of 0.6 to 2; r is in the range of 0 to 1; and s is in the range of 2 to 4.

[0016] In some embodiments, the material has the formula Li (1+x) (Ni a Co b Mn c M'd ) (1-x) O2 (where M’ 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 or 0.05 < b ≤ 0.5; 0 ≤ c ≤ 0.6; 0 ≤ d ≤ 0.1; and a + b + c + d = 1) and includes a cathode active material.

[0017] In some embodiments, the material includes a cathode active material of the formula Li h Co i Al j O 2+r (where h ranges from 0.8 to 0.95, i ranges from 0.1 to 0.3, j ranges from 0.01 to 0.10, and r ranges from 0 to 0.4).

[0018] In some embodiments, the material includes a cathode active material of the formula Li (1+x) Mn 2-x-z M’ z O4 (where x ranges from 0 to 0.2, z ranges from 0 to 0.1, and M’ is selected from Al, Mg, Ni, Co, Fe, Ti, V, Zr, and Zn).

[0019] In some embodiments, the material includes a cathode active material of the formula xLi (1+1 / 3) M (2 / 3) O2·yLiMO2·zLiM’O2 (where M includes at least one metal of Mn, Ni, Co in an oxidation state of +4, M’ is at least one transition metal, 0 < x < 1, 0 < y < 1, 0 < z < 1, and x + y + z = 1).

[0020] In some embodiments, the material includes at least one lithium-ion battery material selected from lithium-ion batteries, lithium-ion battery waste, lithium-ion battery manufacturing scraps, black masses, lithium-ion cell manufacturing scraps, lithium-ion cathode active materials, and combinations thereof.

[0021] In some embodiments, the material comprises 0.1% to 10% by weight lithium, 0% to 60% by weight nickel, 0% to 20% by weight cobalt, 0% to 20% by weight copper, 0% to 20% by weight aluminum, 0% to 20% by weight iron, and 0% to 20% by weight manganese, each based on the total weight of the material, and the sum of nickel, cobalt, and manganese is greater than 0% by weight.

[0022] In some embodiments, the acidic aqueous solution has an acid concentration in the range of 18 mol / L to 0.0001 mol / L.

[0023] In some embodiments, the acidic aqueous solution comprises H2SO4.

[0024] Also disclosed is a method that includes extracting one or more metals from a material according to the methods disclosed herein to obtain an aqueous solution containing the 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.

[0025] 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, the method comprising: optionally 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 black mass; optionally sorting the black mass to obtain a fine fraction and a coarse fraction; and subjecting the black mass, optionally the fine fraction, the coarse fraction, or the fine fraction and the coarse fraction, to a method for extracting one or more metals from materials disclosed herein.

[0026] Also disclosed is a method for leaching a material comprising one or more metals in the zero oxidation state and one or more selected from metal oxides, metal hydroxides, and combinations thereof, the method comprising: contacting the material with an oxidizing, acidic aqueous solution having a pH less than 6, and subsequently reducing the one or more selected from metal oxides, metal hydroxides, and combinations thereof with an alkyl carbonate.

[0027] In some embodiments, the material is from an extract from manganese ore.

[0028] Definition: 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.

[0029] As used herein, the term "material" refers to elements, components, and / or substances that make up or can be made into something.

[0030] 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.

[0031] As used herein, an "oxidizing acidic aqueous solution" is an aqueous solution having a pH less than 7 that is capable of oxidizing metals in the zero oxidation state. For example, some oxidizing acidic aqueous solutions are capable of oxidizing some metals in the zero oxidation state, but are unable to oxidize other metals. One example of an oxidizing acidic aqueous solution is an aqueous solution containing sulfuric acid. An additional example of an oxidizing acidic aqueous solution is an aqueous solution containing sulfuric acid and O2.

[0032] 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 cannot oxidize others. An example of an oxidizing agent is O2, such as in air.

[0033] 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.

[0034] 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.

[0035] 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.

[0036] As used herein, the term "sparging" refers to dispersing a gas through a liquid.

[0037] 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.

[0038] 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.

[0039] As used herein, the term "alkyl carbonate" refers to compounds and / or mixtures of compounds of the following form: [ka] wherein R1 and R2 may be the same, different, or linked to form a cyclic ring; R1 and R2 each independently represent an alkyl group, or R1 and R2 together represent a cyclic alkyl ring. In some embodiments, R1 and R2 are each independently selected from C1-C5 alkyl. In some embodiments, R1 and R2 are the same and are selected from C1-C5 alkyl. In some embodiments, R1 and R2 together represent a cyclic alkyl ring; wherein R1 and R2 contain 2 to 5 ring carbon atoms.

[0040] As used herein, "alkyl" or "alkyl group" includes straight-chain, branched, and cyclic hydrocarbons. As used herein, the term "lithium ion battery electrolyte solvent" refers to a composition derived from a lithium ion battery, wherein the composition comprises one or more alkyl carbonates.

[0041] As used herein, the term "cathode active material" refers to a material that can store and release electrical charge in the form of lithium ions.

[0042] As used herein, the term "ore" refers to a naturally occurring solid material from which metals can be extracted and the concentrates obtained therefrom, for example, by flotation.

[0043] Disclosed herein is a method for extracting one or more metals from a material, the method comprising: contacting the material with an acidic aqueous solution having a pH less than 7; and reducing one or more metal oxides selected from nickel oxide, cobalt oxide, and manganese oxide from the material with an alkyl carbonate. Also disclosed is a method comprising extracting one or more metals from 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. Additionally, 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.

[0044] material: The present disclosure provides methods for extracting one or more metals from a material, the material comprising one or more metal oxides. In some embodiments, the metal oxides comprise metals in a high-value oxidation state that cannot be fully leached by simple acid leaching without an electron transfer agent, resulting in lower-value metal species. An example is manganese(IV) oxide, which is sparingly soluble in sulfuric acid but dissolves as manganese(II) sulfate in the presence of an electron transfer agent or reducing agent, such as hydrogen peroxide and sulfur dioxide.

[0045] In some embodiments, the material has the formula Li p M q M' r O s wherein M comprises one or more metals selected from nickel, manganese, and cobalt; M' comprises one or more metals selected from Mg, Ca, Ba, Al, Ti, Zr, Zn, Fe, V, and Mo; p is in the range of 1 to 1.4; q is in the range of 0.6 to 2; r is in the range of 0 to 1; and s is in the range of 2 to 4.

[0046] In some embodiments, the material has the formula Li (1+x) (Nia Co b Mn c M’ d ) (1-x) O2 (where M’ 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, or 0.05 < b ≦ 0.5; 0 ≦ c ≦ 0.6, 0 ≦ d ≦ 0.1, and a + b + c + d = 1) and contains a cathode active material.

[0047] In some embodiments, the material has the formula Li[Ni h Co i Al j O 2+r (where h ranges from 0.8 to 0.95, i ranges from 0.1 to 0.3, j ranges from 0.01 to 0.10, and r ranges from 0 to 0.4) and contains a cathode active material.

[0048] In some embodiments, the material has the formula Li (1+x) Mn 2-x-z M’ z O4 (where x ranges from 0 to 0.2, z ranges from 0 to 0.1, and M’ is selected from Al, Mg, Ni, Co, Fe, Ti, V, Zr and Zn) and contains a cathode active material.

[0049] In some embodiments, the material has the formula xLi (1+1 / 3) M (2 / 3) O2·yLiMO2·zLiM’O2 (where M’ contains at least one metal in the +4 oxidation state). In some embodiments, the material has the formula xLi (1+1 / 3) M (2 / 3) O2·yLiMO2·zLiM’O2 (where M contains at least one metal of Mn, Ni, Co in the +4 oxidation state, M’ is at least one transition metal, 0 < x < 1, 0 < y < 1, 0 < z < 1, and x + y + z = 1) and contains a cathode active material.

[0050] In some embodiments, the material comprises at least one lithium ion battery material selected from lithium ion batteries, lithium ion battery waste, lithium ion battery manufacturing scrap, black mass, lithium ion cell manufacturing scrap, lithium ion cathode active material, and combinations thereof.

[0051] In some embodiments, the material comprises 0.1% to 10% by weight lithium, 0% to 60% by weight nickel, 0% to 20% by weight cobalt, 0% to 20% by weight copper, 0% to 20% by weight aluminum, 0% to 20% by weight iron, and 0% to 20% by weight manganese, each based on the total weight of the material, and the sum of nickel, cobalt, and manganese is greater than 0% by weight.

[0052] 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, and combinations thereof.

[0053] 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.

[0054] In some embodiments, the material comprises one or more selected from nickel, cobalt, manganese, and combinations thereof.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] In some embodiments, the material comprises 0.1% to 10% by weight lithium, 0% to 60% by weight nickel, 0% to 20% by weight cobalt, 0% to 20% by weight copper, 0% to 20% by weight aluminum, 0% to 20% by weight iron, and 0% to 20% by weight manganese, each based on the total weight of the material.

[0059] 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.

[0060] 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.

[0061] "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.

[0062] 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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] In some embodiments, the heat treatment is carried out at a temperature ranging from 350°C to 900°C. In some embodiments, the heat treatment is carried out at a temperature ranging from 450°C to 800°C. In some embodiments, the heat treatment is carried out under an inert atmosphere, an oxidizing atmosphere, or a reducing atmosphere. In some embodiments, the heat treatment is carried out 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, a reducing gas, such as H2 and / or CO, is added.

[0068] 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.

[0069] 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.

[0070] In some embodiments, the material has the formula Li1+x (Ni a Co b Mn c M1 d ) 1-x comprises lithium nickel cobalt manganese oxide of O2, wherein M1 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 (for example 0.05 < b ≦ 0.5), 0 ≦ c ≦ 0.6, 0 ≦ d ≦ 0.1, and a + b + c + d = 1. Exemplary lithium 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<00−00061>) (1-x) O2, Li (1+x) [Ni 0.7 Co 0.2 Mn 0.3 ) (1-x) O2, and Li[Ni (1+x) Co 0.8 Al 0.1 O2 are included, where x is as defined above.

[0071] In some embodiments, the material comprises lithium nickel-cobalt-aluminum oxide of the formula Li[Ni[[ID= / / ]] h Co<000−0077>Al j O 2+r where h ranges from 0.8 to 0.95, i ranges from 0.1 to 0.3, j ranges from 0.01 to 0.10, and r ranges from 0 to 0.4.

[0072] It should be noted that there seems to be a small formatting issue in the original text where some of the tags like ` (1+x) ` and ` (1+x) ` might be misformatted. I've translated it as accurately as possible based on the provided text. If you have any further clarifications or corrections regarding the original text, it would be helpful for a more precise translation.​​​​​​​​​In some embodiments, the material comprises nickel, cobalt, manganese, copper, aluminum, iron, phosphorous, or a combination thereof.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] 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).

[0078] 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) = +1.5415V), and Mn(OH)3 / Mn(OH)2 + OH - (E(0)=+0.15V).

[0079] In some embodiments, the material is an ore. In some embodiments, the material is an ore comprising at least 0.1% by weight manganese based on the total weight of the material. In some embodiments, the material is an ore comprising at least 1% by weight manganese based on the total weight of the material. In some embodiments, the material is an ore comprising at least 10% by weight manganese based on the total weight of the material.

[0080] In some embodiments, the material is an ore containing 0.1% to 65% manganese by weight, based on the total weight of the material. In some embodiments, the material is an ore containing 0.1% to 50% manganese by weight, based on the total weight of the material. In some embodiments, the material is an ore containing 0.1% to 25% manganese by weight, based on the total weight of the material. In some embodiments, the material is an ore containing 0.1% to 10% manganese by weight, based on the total weight of the material. In some embodiments, the material is an ore containing 1% to 65% manganese by weight, based on the total weight of the material. In some embodiments, the material is an ore containing 10% to 65% manganese by weight, based on the total weight of the material. In some embodiments, the material is an ore containing 25% to 65% manganese by weight, based on the total weight of the material. In some embodiments, the material is an ore containing 50% to 65% manganese by weight, based on the total weight of the material.

[0081] In some embodiments, the material comprises MnO2. In some embodiments, the material comprises pyrolusite.

[0082] In some embodiments, the material is from a manganese ore extract.

[0083] Alkyl carbonate: The present disclosure includes a process for reducing one or more metal oxides selected from nickel oxide, cobalt oxide, and manganese oxide from a material using an alkyl carbonate.

[0084] In some embodiments, the alkyl carbonate is a cyclic alkyl carbonate.

[0085] In some embodiments, the cyclic alkyl carbonate is selected from ethylene carbonate, propylene carbonate, and butylene carbonate.

[0086] In some embodiments, the alkyl carbonate is selected from diethyl carbonate, dimethyl carbonate, dipropyl carbonate, ethyl methyl carbonate, propyl methyl carbonate, ethyl propyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, and fluoroalkyl carbonate.

[0087] In some embodiments, the alkyl carbonate comprises a lithium ion battery electrolyte condensate.

[0088] This can be obtained from the pulverized battery cell material by a drying procedure, for example, at a temperature ranging from 25°C to 300°C and an absolute pressure ranging from 1013 mbar to 0.1 mbar. In some embodiments, the electrolyte condensate is obtained by washing the pulverized battery cell material with a suitable solvent, such as water or an organic solvent selected from alcohols, esters, carbonates, ketones, and ethers. Examples of such solvents include methanol, ethanol, propanol, isopropanol, methyl formate, methyl acetate, alkyl carbonates such as dimethyl carbonate and diethyl carbonate, acetone, tetrahydrofuran, and mixtures thereof. In some embodiments, the aqueous electrolyte condensate mixture is distilled, salted out, and / or phase separated to obtain the electrolyte condensate. In some embodiments, the aqueous electrolyte condensate mixture is added directly to the leaching reactor as a reducing agent.

[0089] In some embodiments, the molar ratio of nickel, cobalt, and manganese oxides to alkyl carbonate in the material ranges from 1:2 to 10:1. In some embodiments, the molar ratio of nickel, cobalt, and manganese oxides to alkyl carbonate in the material ranges from 1:2 to 8:1. In some embodiments, the molar ratio of nickel, cobalt, and manganese oxides to alkyl carbonate in the material ranges from 1:2 to 6:1. In some embodiments, the molar ratio of nickel, cobalt, and manganese oxides to alkyl carbonate in the material ranges from 1:2 to 4:1. In some embodiments, the molar ratio of nickel, cobalt, and manganese oxides to alkyl carbonate in the material ranges from 1:2 to 2:1. In some embodiments, the molar ratio of nickel, cobalt, and manganese oxides to alkyl carbonate in the material ranges from 1:2 to 1:1.

[0090] In some embodiments, the material is a cathode active material, the alkyl carbonate is dipropyl carbonate, and the weight ratio of the material to the alkyl carbonate ranges from 1:3 to 1:0.2.

[0091] In some embodiments, the material is a cathode active material, the alkyl carbonate is dimethyl carbonate, and the weight ratio of the material to the alkyl carbonate ranges from 1:2 to 1:0.1.

[0092] In some embodiments, the material is a cathode active material, the alkyl carbonate is a mixed ethyl / methyl carbonate, and the weight ratio of the material to the alkyl carbonate ranges from 1:2 to 1:0.1.

[0093] In some embodiments, the material is 1% to 20% Mn ore, the alkyl carbonate is ethylene carbonate, and the molar ratio of manganese to alkyl carbonate in the material ranges from 1:2 to 10:1.

[0094] method: Disclosed is a method for extracting one or more metals from a material, the method comprising: contacting the material with an acidic aqueous solution having a pH less than 7; and reducing one or more metal oxides selected from nickel oxide, cobalt oxide, and manganese oxide with an alkyl carbonate.

[0095] In some embodiments, the acidic aqueous solution has an acid concentration in the range of 18 mol / L to 0.0001 mol / L. In some embodiments, the acidic aqueous solution has an acid concentration in the range of 18 mol / L to 0.001 mol / L. In some embodiments, the acidic aqueous solution has an acid concentration in the range of 18 mol / L to 0.01 mol / L. In some embodiments, the acidic aqueous solution has an acid concentration in the range of 18 mol / L to 0.1 mol / L. In some embodiments, the acidic aqueous solution has an acid concentration in the range of 18 mol / L to 1 mol / L. In some embodiments, the acidic aqueous solution has an acid concentration in the range of 18 mol / L to 10 mol / L. In some embodiments, the acidic aqueous solution has an acid concentration in the range of 17 mol / L to 1 mol / L. In some embodiments, the acidic aqueous solution has an acid concentration in the range of 16 mol / L to 1 mol / L.

[0096] In some embodiments, the acidic aqueous solution comprises H2SO4.

[0097] In some embodiments, a method includes: extracting one or more metals from 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.

[0098] In some embodiments, the material or its precursor is pyrolyzed prior to leaching.

[0099] Some embodiments are methods of 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 includes: optionally 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 black mass; optionally sorting the black mass to obtain a fine fraction and a coarse fraction; and subjecting the black mass, optionally the fine fraction, the coarse fraction, or the fine fraction and the coarse fraction, to a method for extracting one or more metals from a material disclosed herein.

[0100] Some embodiments are methods for leaching a material comprising one or more metals in the zero oxidation state and one or more selected from metal oxides, metal hydroxides, and combinations thereof, the method comprising: contacting the material with an oxidizing, acidic aqueous solution having a pH less than 6, and subsequently reducing the one or more selected from metal oxides, metal hydroxides, and combinations thereof with an alkyl carbonate.

[0101] In some embodiments, the leaching method comprises: contacting the material with an oxidizing, acidic aqueous solution having a pH less than 6, and reducing one or more selected from metal oxides, metal hydroxides, and combinations thereof with an alkyl carbonate. 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, and combinations thereof.

[0102] In some embodiments, the oxidizing acidic aqueous solution comprises at least one selected from H2SO4, O2, N2O, and combinations thereof. In some embodiments, the oxidizing acidic aqueous solution comprises H2SO4. In some embodiments, the oxidizing acidic aqueous solution comprises one or more acids selected from H2SO4, CH3SO3H, HNO3, and combinations thereof. In some embodiments, the oxidizing acidic aqueous solution further comprises one or more selected from O2, N2O, and combinations thereof. In some embodiments, the oxidizing acidic aqueous solution comprises an acid that is also an oxidizing agent, such as, for example, H2SO4. In some embodiments, the oxidizing acidic aqueous solution comprises an oxidizing agent that is not an acid, such as, for example, O2, N2O, or combinations thereof. In some embodiments, the oxidizing acidic aqueous solution comprises an acid and an oxidizing agent. In some embodiments, the oxidizing acidic aqueous solution comprises an acid that is also an oxidizing agent and further comprises an oxidizing agent that is not an acid. In some embodiments, the oxidizer is a high valent metal oxide compound selected from potassium permanganate, potassium chromate, potassium dichromate, and lithium metal oxides (e.g., lithium cobalt dioxide, lithium manganese oxide, and mixed lithium nickel cobalt manganese oxide).

[0103] In some embodiments, the oxidizing acidic aqueous solution comprises H2SO4 and O2. In some embodiments, the oxidizing acidic aqueous solution comprises O2, where the O2 is provided as air.

[0104] In some embodiments, additional metal oxide and / or metal hydroxide is added after the contacting step and before the reducing step.

[0105] In some embodiments, the reducing agent, in addition to alkyl carbonate, further comprises one or more selected from SO2, metabisulfite, bisulfite, thiosulfate, dithionite, H2O2, H2, and combinations thereof.

[0106] 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.

[0107] 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.

[0108] In some embodiments, contacting the material with the oxidizing acidic aqueous solution is carried out at a temperature ranging from 50° C. to 110° C. In some embodiments, the time period for contacting the material with the oxidizing acidic aqueous solution is in the range of 2 hours to 4 hours. In some embodiments, contacting the material with the oxidizing acidic aqueous solution is carried out at a first temperature and the reduction step is carried out at a second temperature, the second temperature being in the range of 70% to 20% of the first temperature.

[0109] In some embodiments, the oxidizing acidic aqueous solution comprises air. In some embodiments, the air comprises 3% or less by volume of sulfur dioxide. In some embodiments, contacting the material with an oxidizing acidic aqueous solution having a pH less than 6 comprises sparging air through the oxidizing acidic aqueous solution. In some embodiments, air is sparged through the oxidizing acidic aqueous solution at a rate of up to 20% solution volume / minute.

[0110] In some embodiments, the oxidizing acidic aqueous solution has a pH in the range of -1.0 to 3.

[0111] In some embodiments, contacting a material with an oxidizing, acidic aqueous solution having a pH of less than 6 comprises first contacting the material with an acid, and subsequently adding an oxidizing agent selected from O2, NO, and combinations thereof. In some embodiments, contacting a material with an oxidizing, acidic aqueous solution having a pH of less than 6 comprises first contacting the material with an acid that causes the formation of hydrogen gas, and subsequently adding an oxidizing agent selected from O2, NO, a metal oxide having an oxidation state of +3 or higher, nickel manganese cobalt oxide, a cathode active material, and combinations, to form hydrogen gas. In some embodiments, contacting a material with an oxidizing, acidic aqueous solution having a pH of less than 6 comprises first contacting the material with an acid that causes the formation of hydrogen gas, monitoring the formation of hydrogen gas by gas chromatography and / or a hydrogen sensor, and subsequently adding an oxidizing agent selected from O2, NO, and combinations, to form hydrogen gas. In some embodiments, contacting the material with an oxidizing, acidic aqueous solution having a pH less than 6 comprises first contacting the material with an acid that causes the formation of hydrogen gas, monitoring the formation of hydrogen gas by gas chromatography and / or a hydrogen sensor, and when the concentration of hydrogen gas is less than 5% by volume, e.g., less than 1% by volume, e.g., less than 0.1% by volume, adding an oxidizing agent selected from O2, NO, and combinations.

[0112] In some embodiments, the subsequent reduction step begins immediately after the contacting step begins. In some embodiments, the subsequent reduction step begins at least 1 minute after the contacting step begins. In some embodiments, the subsequent reduction step begins at least 10 minutes after the contacting step begins. In some embodiments, the subsequent reduction step begins at least 30 minutes after the contacting step begins. In some embodiments, the subsequent reduction step begins at least 1 hour after the contacting step begins. In some embodiments, the subsequent reduction step begins 0 minutes to 2 hours after the contacting step begins.

[0113] In some embodiments, excess oxidizing gases, such as O2 and / or N2O, in air are recycled from the off-gas to the leaching reactor.

[0114] In some embodiments, the reducing agent further comprises SO2 in addition to the alkyl carbonate, and the SO2 is purged through the solution at a rate of up to 20% solution volume / minute for 1 to 3 hours. In some embodiments, the reducing agent further comprises SO2 in addition to the alkyl carbonate, and the SO2 is provided as a mixture with O2 or air containing 10% or more SO2. In some embodiments, the reducing agent further comprises SO2 in addition to the alkyl carbonate, and the SO2 is not provided as a mixture with O2 or air. In some embodiments, the reducing agent further comprises SO2 in addition to the alkyl carbonate, and the 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.

[0115] In some embodiments, the reduction step is carried out at ambient temperature.

[0116] 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), CaCO, Ni(OH), Co(OH), Mn(OH), and combinations thereof.

[0117] In some embodiments, the method is carried out batchwise.

[0118] 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.

[0119] In some embodiments, excess sulfur dioxide is recycled from the off-gas to the reactor.

[0120] In some embodiments, a reflux condenser is attached to at least one reaction vessel.

[0121] 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.

[0122] 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.

[0123] In some embodiments, the reduction 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 reduction step is carried out at 100°C for a duration ranging from 3 hours to 5 hours. In some embodiments, the reduction step is carried out at 60°C for a duration ranging from 3 hours to 5 hours. In some embodiments, the reduction step is carried out at 25°C for a duration ranging from 3 hours to 5 hours.

[0124] In some embodiments, methods are disclosed herein that include 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.

[0125] 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.

[0126] 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.

[0127] 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.

[0128] 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.

[0129] Oxidizer: In some embodiments, the oxidizing acidic aqueous solution includes an oxidizing agent. In some embodiments, the oxidizing agent is an acid, such as H2SO4, HNO3, and combinations thereof. In some embodiments, the oxidizing agent is not an acid, such as O2, N2O, and combinations thereof.

[0130] In some embodiments, metal oxides having an oxidation state of +3 or higher are used as oxidizing agents.

[0131] In some embodiments, the oxidizing acidic aqueous solution comprises an acid that is not an oxidizing agent and an oxidizing agent that is not an acid. In some embodiments, the oxidizing acidic aqueous solution comprises an acid that is an oxidizing agent and an oxidizing agent that is not an acid. In some embodiments, the oxidizing acidic aqueous solution comprises an acid that is not an oxidizing agent and an oxidizing agent that is an acid. In some embodiments, the oxidizing acidic aqueous solution comprises an acid that is an oxidizing agent and an oxidizing agent that is an acid. In some embodiments, the oxidizing acidic aqueous solution comprises an acid that is an oxidizing agent. In some embodiments, the acidic aqueous solution is an oxidizing acidic aqueous solution. In some embodiments, the acidic aqueous solution is not an oxidizing acidic aqueous solution.

[0132] In some embodiments, the oxidizing agent has a standard electrode potential in the range of +0.1 V to +1.5 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.

[0133] Reducing Agent: In some embodiments, the reducing agent is an alkyl carbonate.

[0134] Without wishing to be bound by theory, it is believed that alkyl carbonates can reduce metal oxides via the following reaction: 4MO2 + ethylene carbonate + 4H2SO4 ⇔ 4MSO4 + 5H2O + oxalic acid + CO2.

[0135] In some embodiments, the reducing agent further comprises one or more selected from SO2, metabisulfite, bisulfite, dithionite, thiosulfate, H2O2, H2, and combinations thereof.

[0136] 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 reactions occur. 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.

[0137] 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, and manganese species, is acid leached in a continuously stirred reaction vessel (101) containing an acidic aqueous solution with a pH less than 1. In some embodiments, hydrogen gas is evolved. In some embodiments, an oxidizing agent, such as O2 and / or N2O, is added (103). 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 a reducing agent, such as an alkyl carbonate, is introduced (104). In some embodiments, the resulting liquid phase (106) and solid phase (105) are separated by solid-liquid separation, such as filtration, centrifugation, and / or settling.

[0138] 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, and manganese species, is acid leached in a continuously stirred reaction vessel (201) containing an acidic aqueous solution having a pH less than 1. In some embodiments, the acid leaching is further carried out in one or more additional continuously stirred reaction vessels (203). In some embodiments, an oxidizing agent, such as O2 and / or NO, is added to the continuously stirred reaction vessel (204) (205). In some embodiments, the acid leaching in the presence of the added oxidizing agent 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 a reducing agent, such as an alkyl carbonate, is introduced to the continuously stirred reaction vessel (207) (208). In some embodiments, leaching in the presence of added reducing 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.

[0139] 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.

[0140] 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.

[0141] 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]

[0142] The following examples are intended to be illustrative and not to limit the scope of the present disclosure in any way.

[0143] Abbreviation % percent 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.

[0144] 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).

[0145] The metals in the obtained sample solutions were determined by optical emission spectroscopy using inductively coupled plasma (ICP-OES).

[0146] Some element concentrations were measured by X-ray fluorescence using a Malvern Panalytical Epsilon 4 DY-6024 calibrated with data from ICP-OES measurements.

[0147] Elemental analysis of fluorine and fluoride was carried out according to DIN EN 14582:2016-12 for sample preparation (solid samples) for total fluorine content determination; detection method was ion-selective electrode measurement. 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).

[0148] Total carbon was determined by gas chromatography using a thermal conductivity detector on the gas obtained after combustion of the sample.

[0149] 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.

[0150] Electrolyte solvent condensate The electrolyte solvent condensate used in Example 4 was obtained by drying crushed lithium-ion batteries at an average temperature of 87°C and an average pressure of 222 mbar, and contained approximately 53.8% ethyl methyl carbonate, 37.9% diethyl carbonate, 4.1% ethylene carbonate, and 2.8% biphenyl as measured by gas chromatography-mass spectrometry.

[0151] Cathode Active Material The cathode active material (CAM) used in Examples 1 and 2 was HED™, commercially available from BASF Corp. 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.

[0152] Example 1 In this example, the cathode active material was leached and no alkyl carbonate was used.

[0153] While stirring, 25.06 g of NCM111 was suspended in 145.5 g of deionized water. While stirring, 60 g of sulfuric acid (96% by weight) was slowly added to this suspension over 70 minutes. The temperature was observed to rise from room temperature to 50°C. The reaction mixture was then heated to 80°C. The mixture was held at this temperature for 30 minutes and then further heated to 100°C. The mixture was held at 100°C for an additional 80 minutes. The mixture was then cooled to room temperature and filtered to obtain a residue. The residue was dried, yielding 14.75 g of a dry solid residue. The solid residue was analyzed by ICP-OES, and the results are shown in Table 1.

[0154] Example 2 In this example, the cathode active material was leached and an alkyl carbonate was used.

[0155] Example 2 was carried out according to the procedure described in Example 1, except that 7.5 g of diethyl carbonate was added over 30 minutes at 80° C. and the resulting mixture was held at 100° C. for 60 minutes. Example 2 yielded 10.64 g of a dry solid residue. The solid residue was analyzed by ICP-OES, and the results are shown in Table 1.

[0156] Example 3 In this example, the cathode active material was leached and an alkyl carbonate was used.

[0157] Example 3 was carried out according to the procedure described in Example 1, except that 6.6 g of ethylene carbonate was added as a melt at 80° C. over 30 minutes and the resulting mixture was held at 100° C. for 60 minutes. At the end of the procedure, no solid residue was present. This solid residue was analyzed by ICP-OES, and the results are shown in Table 1.

[0158] Example 4 In this example, the cathode active material is leached and condensed with an electrolyte solvent containing alkyl carbonate.

[0159] Example 4 was carried out according to the procedure described in Example 1, except that 7.3 g of electrolyte solvent condensate was added at 80° C. over 30 minutes and the resulting mixture was held at 92° C. for 60 minutes. Example 4 yielded 4.51 g of a dry solid residue. This solid residue was analyzed by ICP-OES, and the results are shown in Table 1.

[0160] [Table 1]

[0161] Comparing Example 1 with Examples 2 to 4, it can be seen that the addition of one or more alkyl carbonates improves leaching efficiency. Without wishing to be bound by theory, it is believed that the alkyl carbonate acts as a reducing agent, improving leaching efficiency.

Claims

1. 1. A method for extracting one or more metals from a material, comprising: contacting the material with an acidic aqueous solution having a pH less than 7 at a temperature ranging from 20°C to 100°C for a duration ranging from 10 minutes to 10 hours; and reducing one or more metal oxides selected from nickel oxide, cobalt oxide and manganese oxide from said material using an alkyl carbonate at a temperature ranging from 20°C to 100°C for a duration ranging from 10 minutes to 10 hours; A method comprising:

2. The method of claim 1 wherein the alkyl carbonate is a cyclic alkyl carbonate.

3. 3. The method of claim 2, wherein the cyclic alkyl carbonate is selected from ethylene carbonate, propylene carbonate, and butylene carbonate.

4. 2. The method of claim 1, wherein the alkyl carbonate is selected from diethyl carbonate, dimethyl carbonate, dipropyl carbonate, ethyl methyl carbonate, propyl methyl carbonate, ethyl propyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, and fluoroalkyl carbonate.

5. 10. The method of claim 1, wherein the alkyl carbonate comprises a lithium ion battery electrolyte solvent.

6. 3. The method according to claim 1, wherein the molar ratio of the one or more metal oxides selected from nickel oxide, cobalt oxide and manganese oxide in the material to the alkyl carbonate is in the range of 1:2 to 10:

1.

7. The material has the formula Li ｐ M ｑ M' ｒ O ｓ a cathode active material of wherein M comprises one or more metals selected from nickel, manganese, and cobalt; M' comprises one or more metals selected from Mg, Ca, Ba, Al, Ti, Zr, Zn, Fe, V, and Mo; p is in the range of 1 to 1.4; q is in the range of 0.6 to 2; r ranges from 0 to 1; and 3. The method of claim 1, wherein s is in the range of 2 to 4.

8. The material has the formula Li （１＋ｘ） (Ni ａ Co ｂ Mn ｃ M' ｄ ) （１－ｘ） O ２ a cathode active material of wherein M′ 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, or 0.05<b≦0.5; 0≦c≦0.6; 0≦d≦0.1, and 3. The method of claim 1, wherein a+b+c+d=1.

9. The material has the formula Li[Ni ｈ Co ｉ Al ｊ ]O ２＋ｒ a cathode active material of where 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, 3. The method of claim 1, wherein r is in the range of 0 to 0.

4.

10. The material has the formula Li （１＋ｘ） Mn ２－ｘ－ｚ M' ｚ O ４ a cathode active material of wherein x ranges from 0 to 0.2; z is in the range of 0 to 0.1; 3. The method of claim 1 or 2, wherein M' is selected from Al, Mg, Ni, Co, Fe, Ti, V, Zr and Zn.

11. The material has the formula xLi （１＋１／３） M （２／３） O ２ ・yLiMO ２ ・zLiM'O ２ a cathode active material of 3. The method of claim 1, wherein M' comprises at least one metal in the oxidation state +4.

12. The material has the formula xLi （１＋１／３） M （２／３） O ２ ・yLiMO ２ ・zLiM'O ２ wherein M comprises at least one metal of Mn, Ni, Co in an oxidation state +4; M′ is at least one transition metal; 0<x<1; 0<y<1; 0<z<1; and x+y+z=1.

13. 3. The method of claim 1 or 2, wherein the material comprises at least one lithium ion battery material selected from lithium ion batteries, lithium ion battery waste, lithium ion battery manufacturing scrap, black chunk, lithium ion cell manufacturing scrap, lithium ion cathode active material, and combinations thereof.

14. The materials each comprise, based on the total mass of the material: 0.1% to 10% by weight of lithium, 0% to 60% by weight of nickel, 0% to 20% by weight of cobalt, 0% to 20% by weight of copper, 0% to 20% by weight of aluminum, 0% to 20% by weight of iron, and 0% to 20% by weight of manganese Including, 3. The method of claim 1 or 2, wherein the sum of nickel, cobalt and manganese is greater than 0% by mass.

15. 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.

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

17. 3. The method of claim 1, wherein the acidic aqueous solution has a pH in the range of -1.0 to 3.

18. Extracting one or more metals from a material according to the method of claim 1 or 2 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. A method comprising:

19. 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 crushing the at least one battery material to obtain black agglomerates; Optionally, sorting the black mass to obtain a fine fraction and a coarse fraction; and subjecting the black mass, 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:

20. the material comprises one or more metals in a zero oxidation state and one or more selected from metal oxides, metal hydroxides, and combinations thereof, and the method comprises: contacting the material with an oxidizing, acidic aqueous solution having a pH of less than 6 at a temperature ranging from 20°C to 100°C for a duration ranging from 10 minutes to 10 hours; and subsequently reducing one or more selected from metal oxides, metal hydroxides, and combinations thereof with an alkyl carbonate at a temperature ranging from 20°C to 100°C for a duration ranging from 10 minutes to 10 hours; The method of claim 1 , comprising:

21. 21. The method of claim 20, wherein the oxidizing acidic aqueous solution has a pH in the range of -1.0 to 3.

22. 21. The method of claim 1 or 20, wherein the material is an ore containing 0.1% to 65% by weight of manganese relative to the total weight of the material.

23. 23. The method of claim 22, wherein the material comprises pyrolusite.

24. 21. The method of claim 1 or 20, wherein the material is from a manganese ore extract.

25. The material is MnO ２ 23. The method of claim 22, comprising:

26. The oxidizing acidic aqueous solution is ２ SO ４ , O ２ , N ２ 21. The method of claim 20, comprising at least one selected from the group consisting of: , , , and combinations thereof.

27. The oxidizing acidic aqueous solution is H ２ SO ４ 21. The method of claim 20, comprising:

28. The oxidizing acidic aqueous solution contains HCl, H ２ SO ４ , C.H. ３ SO ３ H, HNO ３ 21. The method of claim 20, comprising at least one acid selected from:

29. The reduction step is ２ , metabisulfite, bisulfite, thiosulfate, H ２ O ２ , H ２ 3. The method of claim 1 or 2, further comprising contacting the material with one or more selected from:

30. 3. The method of claim 1 or 2, wherein the material or a precursor thereof is pyrolyzed prior to contacting the material with the acidic aqueous solution.

31. The oxidizing acidic aqueous solution is H ２ SO ４ and O ２ 21. The method of claim 20, comprising:

32. The oxidizing acidic aqueous solution is O ２ This O ２ 21. The method of claim 20, wherein the is supplied as air.

33. 3. The method of claim 1 or 2, further comprising adding additional metal oxide and / or metal hydroxide after the contacting step and before the reducing step.

34. Contacting the material with an oxidizing acidic aqueous solution having a pH less than 6 causes the formation of hydrogen gas, and after the formation of hydrogen gas, O ２ , N ２ 21. The method of claim 20, comprising adding an oxidizing agent selected from O and combinations thereof.

35. 21. The method of claim 20, wherein the subsequent reduction step begins immediately after the contacting step begins.

36. 21. The method of claim 20, wherein the subsequent reduction step 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.

37. 21. The method of claim 20, wherein the subsequent reduction step begins 0 minutes to 2 hours after the contacting step begins.

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