Alkyl carbonates as reducing agents in hydrometallurgy

Abstract

Disclosed herein are methods for extracting one or more metals from a material wherein the method comprises contacting the material with an acidic aqueous solution having a pH of less than 7 and reducing one or more metal oxides selected from the group consisting of nickel oxide, cobalt oxide and manganese oxide with an alkyl carbonate; wherein the material comprises the one or more metal oxides. Also disclosed are methods comprising extracting one or more metals from a material to obtain an aqueous solution comprising metal ions, and separating the metal ions to obtain at least one substantially pure metal ion solution and / or at least one substantially pure solid metal ion salt. Further disclosed are methods for recycling at least one battery material selected from the group consisting of lithium ion batteries, lithium ion battery waste, lithium ion battery production waste, lithium ion battery cell production waste, lithium ion cathode active materials, and combinations thereof.

Description

[0001] The project leading to this application has received funding from the Federal Ministry for Economic Affairs and Climate Action (Bundesministerium für Wirtschaft und Klimaschutz) (Germany; FKZ: 16BZF101A); the applicants are responsible for all disclosures in this article. Technical Field

[0002] Disclosed herein is a method for extracting one or more metals from a material, wherein the method comprises: contacting the material with an acidic aqueous solution having a pH of 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 the one or more metal oxides.

[0003] Also disclosed are methods comprising extracting one or more metals from a material to obtain an aqueous solution comprising metal ions, and separating the metal ions to obtain at least one substantially pure metal ion solution and / or at least one substantially pure solid metal ion salt.

[0004] Further disclosed is a method for recycling at least one battery material selected from the group consisting of lithium ion batteries, lithium ion battery waste, lithium ion battery production waste, lithium ion battery cell production waste, lithium ion cathode active material, and combinations thereof. Background Art

[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 raw lithium-containing ores, are complex mixtures of various elements and compounds. Removing and purifying lithium from materials such as lithium-ion battery materials is an exemplary step in lithium-ion battery recycling. 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, for example, the efficiency of a leaching method. For example, in some leaching methods, high oxidation state metals may be more efficiently or less efficiently leached than low or zero oxidation state metals. Some non-lithium impurities are also valuable resources, and it may be additionally desirable to separate and purify various elements and compounds from such materials.

[0007] Accordingly, there is a need for methods for removing lithium from materials such as battery materials and for recycling lithium-ion battery materials. There is also a need for methods for extracting and / or purifying valuable metals from ores. For example, there is a need for leaching methods for efficiently and effectively leaching complex mixtures of various elements and compounds such as mixed metals coexisting in various oxidation states. For example, there is a need for economical methods with high lithium recovery and high lithium purity. There is also a need for economical methods with high recovery and high purity for removing valuable metals such as nickel and cobalt from materials.

[0008] CN 113 363 609A discloses a method for recycling the positive electrode material of discarded lithium batteries by a fluid gradual solidification method. The method comprises the following steps: S1-adding the positive electrode material to a mixture of a salt agent and a fluidizing agent, and stirring it uniformly; S2-keeping the mixture of the positive electrode material, the salt agent and the fluidizing agent obtained in step S1 warm and reacting to obtain a solid metal salt; S3-adding the obtained solid metal salt mixture to water for dissolution, and then filtering to obtain a salt solution of lithium, cobalt, nickel and manganese. The salt agent is selected from the group consisting of a mixture of perchloric acid, hydrochloric acid, sulfuric acid, nitric acid, bisulfate, disodium hydrogen sulfate, dipotassium hydrogen sulfate, sodium dihydrogen sulfate and potassium dihydrogen sulfate, the water content in the salt agent is less than 10wt.%, and the dosage ratio is 0.5-2:1. The fluidizing agent is selected from the group consisting of propylene carbonate, diethyl carbonate and ethyl methyl carbonate, dimethyl carbonate, 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 0.005-0.1:1. Summary of the invention

[0009] A method for extracting one or more metals from a material is disclosed, wherein the method comprises: contacting the material with an acidic aqueous solution having a pH of 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 the one or more metal oxides. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] Figure 1 Exemplary methods consistent with some embodiments of the present disclosure are depicted.

[0011] Figure 2 An exemplary continuous process consistent with some embodiments of the present disclosure is depicted.

[0012] Figure 3Depicts the XRD pattern of an exemplary black material. Typically, the lithium metal oxide therein is characterized by a reflection at 2θ of 18.5°, and the reflections caused by lithium, nickel, cobalt, and manganese oxides are denoted by the letter b. Detailed Description

[0013] Discloses a method for extracting one or more metals from a material, wherein the method comprises: 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 contains the one or more metal oxides.

[0014] 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, methyl propyl carbonate, ethyl propyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, and fluoroalkyl carbonate. In some embodiments, the alkyl carbonate contains a lithium-ion battery electrolyte condensate.

[0015] In some embodiments, the mass ratio of the material to the alkyl carbonate ranges from 1:1 to 1:0.001.

[0016] In some embodiments, the material contains a cathode active material having the formula Li p M q M’ r O s ; wherein: M contains one or more metals selected from nickel, manganese, and cobalt; M’ contains one or more metals selected from Mg, Ca, Ba, Al, Ti, Zr, Zn, Fe, V, and Mo; p ranges from 1 to 1.4; q ranges from 0.6 to 2; r ranges from 0 to 1; and s ranges from 2 to 4.

[0017] In some embodiments, the material contains a cathode active material having the formula Li (1+x) (Ni a Co b Mn c M’ d ) (1-x) O2, 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 a + b + c + d = 1.

[0018] In some embodiments, the material contains a cathode active material having the formula Li[Ni h Co iAl j O 2+r The cathode active material, wherein: the range of h is 0.8 to 0.95; the range of i is 0.1 to 0.3; the range of j is 0.01 to 0.10; and the range of r is 0 to 0.4.

[0019] In some embodiments, the material comprises a cathode active material having the formula Li (1+x) Mn 2-x-z M’ z O4, wherein: the range of x is 0 to 0.2; the range of z is 0 to 0.1; and M’ is selected from Al, Mg, Ni, Co, Fe, Ti, V, Zr, and Zn.

[0020] In some embodiments, the material comprises a cathode active material having the formula xLi (1+1 / 3) M (2 / 3) O2·yLiMO2·zLiM’O2, wherein M comprises at least one metal among Mn, Ni, Co in an oxidation state of +4, M’ is at least one transition metal, and 0 < x < 1, 0 < y < 1, 0 < z < 1 and x + y + z = 1.

[0021] 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 production scrap, black substances, lithium-ion battery cell production scrap, lithium-ion cathode active materials, and combinations thereof.

[0022] In some embodiments, the material comprises: 0.1 wt% to 10 wt% of lithium, 0 wt% to 60 wt% of nickel, 0 wt% to 20 wt% of cobalt, 0 wt% to 20 wt% of copper, 0 wt% to 20 wt% of aluminum, 0 wt% to 20 wt% of iron, and 0 wt% to 20 wt% of manganese; wherein each wt% is based on the total weight of the material and the sum of nickel, cobalt, and manganese is greater than 0 wt%.

[0023] In some embodiments, the acidic aqueous solution has an acid concentration in the range of 18 mol / L to 0.0001 mol / L.

[0024] In some embodiments, the acidic aqueous solution comprises H2SO4.

[0025] Also disclosed is the following method, comprising: extracting one or more metals from the material according to the method disclosed herein to obtain an aqueous solution containing metal ions, and separating the metal ions to obtain at least one substantially pure metal ion solution and / or at least one substantially pure solid metal ion salt.

[0026] Also disclosed is a method for recycling at least one battery material selected from lithium-ion batteries, lithium-ion battery waste, lithium-ion battery production waste, lithium-ion battery cell production waste, lithium-ion cathode active materials, and combinations thereof, wherein the method comprises: optionally, heat treating the at least one battery material at a temperature ranging from 350°C to 900°C, mechanically crushing the at least one battery material to obtain a black substance, optionally, sorting the black substance to obtain a fine fraction and a coarse fraction, and subjecting the black substance, 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 the material disclosed herein.

[0027] Also disclosed is a method for leaching a material comprising one or more metals in a zero oxidation state and one or more selected from metal oxides, metal hydroxides, and combinations thereof, wherein the method comprises contacting the material with an oxidizing acidic aqueous solution having a pH of less than 6, and subsequently reducing the one or more selected from the metal oxides, metal hydroxides, and combinations thereof with an alkyl carbonate.

[0028] In some embodiments, the material is derived from manganese ore extraction.

[0029] definition:

[0030] As used herein, "a" or "an" entity refers to one or more of that entity, e.g., "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.

[0031] As used herein, the term "material" refers to an element, component, and / or substance that makes up or can be made into something.

[0032] As used herein, a "reducing agent" is a compound capable of reducing metal oxides and / or metal hydroxides. For example, some reducing agents can reduce some metal oxides and / or some metal hydroxides, but cannot reduce other metal oxides and / or metal hydroxides.

[0033] As used herein, an "oxidizing acidic aqueous solution" is an aqueous solution having a pH of less than 7 that is capable of oxidizing a metal in a zero oxidation state. For example, some oxidizing acidic aqueous solutions are capable of oxidizing some metals in a zero oxidation state, but are not capable of oxidizing other metals in a zero oxidation state. An example of an oxidizing acidic aqueous solution is an aqueous solution comprising sulfuric acid. Another example of an oxidizing acidic aqueous solution is an aqueous solution comprising sulfuric acid and O2.

[0034] As used herein, an "oxidant" is a compound that is capable of oxidizing a metal in a zero oxidation state. For example, some oxidants are capable of oxidizing some metals in a zero oxidation state, but not others. An example of an oxidant is O2, for example, in air.

[0035] As used herein, a "solution" is a combination of a fluid and one or more compounds. For example, each of the one or more compounds in the solution may or may not be dissolved in the fluid.

[0036] As used herein, a "substantially pure metal ion solution" is a solution comprising metal ions, counterions, and a solvent; wherein the total weight of the metal ions and counterions is at least 50% by weight excluding the weight of the solvent.

[0037] As used herein, a "substantially pure solid metal ion salt" is a solid comprising a metal ion and a counterion; wherein the combined weight of the metal ion and the counterion is at least 50% by weight of the solid excluding the weight of the solvent.

[0038] As used herein, the term "bubbling" refers to the dispersion of a gas through a liquid.

[0039] As used herein, the term "base" refers to a material that is capable of reacting with hydronium ions and increasing the pH of an acidic solution.

[0040] As used herein, the term "standard electrode potential" has its common usage 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. By definition, the potential of the standard hydrogen electrode is 0 volts. An exemplary reference is: Johnstone, AH "CRC Handbook of Chemistry and Physics" 69th edition, ed.: RC Weast, CRC Press, Boca Raton, Florida, 1988.

[0041] As used herein, the term "alkyl carbonate" is a compound and / or mixture of compounds having the form

[0042]

[0043] wherein R1 and R2 may be the same, different or connected to form a cyclic ring; and wherein 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 to C5 alkyl groups. In some embodiments, R1 and R2 are the same and are selected from C1 to C5 alkyl groups. In some embodiments, R1 and R2 together represent a cyclic alkyl ring; wherein R1 and R2 contain 2 to 5 ring carbon atoms.

[0044] As used herein, "alkyl" or "alkyl group" includes straight chain, branched chain and cyclic hydrocarbons.

[0045] As used herein, the term "lithium ion battery electrolyte solvent" refers to a composition obtained from a lithium ion battery, wherein the composition comprises one or more alkyl carbonates.

[0046] As used herein, the term "cathode active material" refers to a material that is capable of storing and releasing electrical charge in the form of lithium ions.

[0047] As used herein, the term "ore" refers to a naturally occurring solid material from which metals and concentrates derived therefrom may be extracted, for example, by flotation.

[0048] Disclosed herein is a method for extracting one or more metals from a material, wherein the method comprises: contacting the material with an acidic aqueous solution having a pH of 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 substantially pure metal ion solution and / or at least one substantially pure solid metal ion salt. Further disclosed is a method for recycling at least one battery material selected from lithium ion batteries, lithium ion battery waste, lithium ion battery production waste, lithium ion battery cell production waste, lithium ion cathode active materials, and combinations thereof.

[0049] Material:

[0050] The present disclosure provides methods for extracting one or more metals from a material, and the material comprises one or more metal oxides. In some embodiments, the metal oxide comprises a metal in a high-valent oxidation stage that cannot be completely leached by acid leaching alone without an electron transfer agent, resulting in a lower-valent metal species. An example is manganese (IV) oxide, which is poorly soluble in sulfuric acid, but dissolves to manganese (II) sulfate in the presence of an electron transfer agent or a reducing agent like hydrogen peroxide and sulfur dioxide.

[0051] In some embodiments, the material comprises a p Mq M’ r O s cathode active material; 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 ranges from 1 to 1.4; q ranges from 0.6 to 2; r ranges from 0 to 1; and s ranges from 2 to 4.

[0052] In some embodiments, the material comprises a cathode active material having the formula Li (1+x) (Ni a Co b Mn c M’ d ) (1-x) O2, 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 a + b + c + d = 1.

[0053] In some embodiments, the material comprises a cathode active material having the formula Li[Ni h Co i Al j O 2+r , wherein: 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.

[0054] In some embodiments, the material comprises a cathode active material having the formula Li (1+x) Mn 2-x-z M’ z O4, wherein: 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.

[0055] In some embodiments, the material comprises a cathode active material having the formula xLi( 1+1 / 3) M (2 / 3) O2·yLiMO2·zLiM’O2, wherein M’ comprises at least one metal in an oxidation state of +4. In some embodiments, the material comprises a cathode active material having the formula xLi (1+1 / 3) M (2 / 3) O2·yLiMO2·zLiM’O2, wherein M comprises at least one of Mn, Ni, Co in an oxidation state of +4, M’ is at least one transition metal, and 0 < x < 1, 0 < y < 1, 0 < z < 1 and x + y + z = 1.

[0056] In some embodiments, the material comprises at least one lithium ion battery material selected from the group consisting of lithium ion batteries, lithium ion battery waste, lithium ion battery production waste, black matter, lithium ion battery cell production waste, lithium ion cathode active materials, and combinations thereof.

[0057] In some embodiments, the material comprises: 0.1 weight percent to 10 weight percent lithium, 0 weight percent to 60 weight percent nickel, 0 weight percent to 20 weight percent cobalt, 0 weight percent to 20 weight percent copper, 0 weight percent to 20 weight percent aluminum, 0 weight percent to 20 weight percent iron, and 0 weight percent to 20 weight percent manganese; wherein each weight percent is based on the total weight of the material and the sum of nickel, cobalt, and manganese is greater than zero weight percent.

[0058] In some embodiments, 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.

[0059] In some embodiments, the material is a lithium ion battery material including one or more selected from the group consisting of a black substance, a cathode active material, a cathode, a cathode active material precursor, and combinations thereof.

[0060] In some embodiments, the material comprises one or more selected from nickel, cobalt, manganese, and combinations thereof.

[0061] 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.

[0062] In some embodiments, the metal oxide is selected from nickel oxide, cobalt oxide, copper oxide, aluminum oxide, iron oxide, manganese oxide, rare earth oxide, and combinations thereof.

[0063] 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.

[0064] In some embodiments, the material includes: 0.1 weight percent to 10 weight percent lithium, 0 weight percent to 60 weight percent nickel, 0 weight percent to 20 weight percent cobalt, 0 weight percent to 20 weight percent copper, 0 weight percent to 20 weight percent aluminum, 0 weight percent to 20 weight percent iron, and 0 weight percent to 20 weight percent manganese; wherein each weight percent is based on the total weight of the material.

[0065] In some embodiments, the material or its precursor is pyrolyzed prior to leaching. In some embodiments, the pyrolysis is performed under an inert atmosphere, an oxidizing atmosphere, a reducing atmosphere, or a combination thereof.

[0066] In some embodiments, the material is a lithium ion battery material including one or more selected from the group consisting of a black substance, a cathode active material, a cathode, a cathode active material precursor, and combinations thereof.

[0067] "Black matter" refers to a material containing lithium, which is obtained by mechanical methods such as mechanical pulverization from, for example, lithium-ion batteries, lithium-ion battery waste, lithium-ion battery production waste, lithium-ion battery cell production waste, lithium-ion cathode active materials, and / or combinations thereof. For example, black matter can be obtained from battery waste by mechanically treating the battery waste to obtain active components of electrodes such as graphite and cathode active materials, and may contain impurities from casings, electrode foils, cables, diaphragms, and electrolytes. In some instances, the battery waste can be subjected to heat treatment to pyrolyze organic (e.g., electrolytes) and polymer (e.g., diaphragms and adhesives) materials. Such heat treatment can be performed before or after the mechanical pulverization of the battery material. In some embodiments, the black matter is subjected to heat treatment.

[0068] Lithium-ion batteries can be disassembled, punched, ground (e.g. in a hammer mill, rotary mill), and / or, for example, shredded (in an industrial shredder). The active materials of the battery electrodes can be obtained by such mechanical processing. Light fractions (e.g. housing parts made of organic plastics and aluminum or copper foil) can be removed, for example, by forced air flow, air separation or classification or screening.

[0069] Battery waste can be derived from, for example, waste batteries or production waste such as rejected materials. In some embodiments, the material is obtained from mechanically processed battery waste, such as battery waste processed in a hammer mill, rotary mill, or industrial shredder. Such material can have an average particle size (D50) ranging from 1 μm to 1 cm, such as 1 μm to 500 μm, and further such as 3 μm to 250 μm.

[0070] Larger parts of the battery waste, like housings, wiring and electrode carrier films, can be separated mechanically, so that the corresponding materials can be excluded from the battery material used in the method.

[0071] The mechanically treated battery waste can be subjected to a solvent treatment in order to dissolve and separate the polymer binder used to bind the transition metal oxide to the current collector film, or, for example, to bind graphite to the current collector film. Suitable solvents are N-methylpyrrolidone, N,N-dimethyl-formamide, N,N-dimethylacetamide, N-ethylpyrrolidone and dimethyl sulfoxide, 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.

[0072] In some embodiments, the mechanically treated battery waste can be subjected to heat treatment in different atmospheres over a wide temperature range. In some embodiments, the temperature range is 100°C to 900°C. In some embodiments, lower temperatures below 300°C can be used to evaporate residual solvents in the battery electrolyte, at higher temperatures, the binder polymer may decompose, and at temperatures above 400°C, the composition of the inorganic material may change because some transition metal oxides may be reduced by carbon contained in the waste or by the introduction of reducing gases. In some embodiments, reduction of lithium metal oxides can be avoided by maintaining the temperature below 400°C and / or by removing carbonaceous materials prior to heat treatment.

[0073] 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, oxidizing or reducing atmosphere. In some embodiments, the heat treatment is carried out under an inert or reducing atmosphere. In some embodiments, the reducing agent is formed by pyrolyzed organic (polymer) components under heat treatment conditions. In some embodiments, a reducing gas such as H2 and / or CO is added.

[0074] In some embodiments, the material includes at least one selected from the group consisting of lithiated nickel cobalt manganese oxide, lithiated nickel cobalt aluminum oxide, lithium metal phosphate, lithium ion battery waste, black matter, and combinations thereof.

[0075] In some embodiments, the material includes a material having the formula Li x The lithium metal phosphate of MPO4, wherein x is an integer greater than or equal to 1, and M is selected from the group consisting of metals, transition metals, rare earth metals, and combinations thereof.

[0076] In some embodiments, the material includes a material having the formula Li 1+x (Ni a Co b Mn c M1 d ) 1-xLithiated nickel cobalt manganese oxides of O2, where 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 (such as 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 (1-x) O2, Li (1+x) [Ni 0.8 Co 0.1 Mn 0.1 (1-x) O2 (each having x defined as above), and Li[Ni 0.85 Co 0.13 Al 0.02 O2.

[0077] In some embodiments, the material comprises a lithiated nickel cobalt aluminum oxide having 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.

[0078] In some embodiments, the material contains nickel, cobalt, manganese, copper, aluminum, iron, phosphorus, or a combination thereof.

[0079] ​​​​​In some embodiments, the material has a weight ratio of lithium to the total weight of nickel, cobalt, manganese, copper, aluminum, iron, and phosphorus in a range of 0.01 to 10. In some embodiments, the material has a weight ratio of lithium to the total weight of nickel, cobalt, manganese, copper, aluminum, iron, and phosphorus in a range of 0.01 to 5. In some embodiments, the material has a weight ratio of lithium to the total weight of nickel, cobalt, manganese, copper, aluminum, iron, and phosphorus in a range of 0.01 to 2. In some embodiments, the material has a weight ratio of lithium to the total weight of nickel, cobalt, manganese, copper, aluminum, iron, and phosphorus in a range of 0.01 to 1.

[0080] In some embodiments, the material includes Li x MO2, wherein x is an integer greater than or equal to 1, and M is selected from the group consisting of metals, transition metals, rare earth metals, and combinations thereof.

[0081] In some embodiments, a method for recycling lithium-ion battery materials comprises mechanically pulverizing at least one selected from lithium-ion batteries, lithium-ion battery waste, lithium-ion battery production waste, lithium-ion battery cell production waste, lithium-ion cathode active materials, and combinations thereof to obtain a black substance.

[0082] 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 wt % to 10 wt % of the material has a standard electrode potential in the range of +0.1 V to +0.8 V and 0.1 wt % to 60 wt % of the material has a standard electrode potential in the range of -1.7 V to -0.01 V, based on the total weight of the material.

[0083] 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. Some exemplary standard electrode potentials of 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) = -0.44 V), and Ni / Ni 2+ (E(0) = -0.23 V).

[0084] In some embodiments, one or more selected from metal oxides, metal hydroxides, and combinations thereof each have a standard electrode potential ranging from +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 ranging from 0.15 V to 1.83 V. Some exemplary metal ions, such as metal ions that may be produced by dissolution of an oxide or hydroxide, and standard electrode potentials of metal oxides and / or metal hydroxides include: 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).

[0085] In some embodiments, the material is an ore. In some embodiments, the material is an ore comprising at least 0.1 wt % manganese based on the total weight of the material. In some embodiments, the material is an ore comprising at least 1 wt % manganese based on the total weight of the material. In some embodiments, the material is an ore comprising at least 10 wt % manganese based on the total weight of the material.

[0086] In some embodiments, the material is an ore comprising 0.1 wt % to 65 wt % manganese, based on the total weight of the material. In some embodiments, the material is an ore comprising 0.1 wt % to 50 wt % manganese, based on the total weight of the material. In some embodiments, the material is an ore comprising 0.1 wt % to 25 wt % manganese, based on the total weight of the material. In some embodiments, the material is an ore comprising 0.1 wt % to 10 wt % manganese, based on the total weight of the material. In some embodiments, the material is an ore comprising 1 wt % to 65 wt % manganese, based on the total weight of the material. In some embodiments, the material is an ore comprising 10 wt % to 65 wt % manganese, based on the total weight of the material. In some embodiments, the material is an ore comprising 25 wt % to 65 wt % manganese, based on the total weight of the material. In some embodiments, the material is an ore comprising 50 wt % to 65 wt % manganese, based on the total weight of the material.

[0087] In some embodiments, the material comprises MnO 2. In some embodiments, the material comprises pyrolusite.

[0088] In some embodiments, the material is derived from manganese ore extraction.

[0089] Alkyl carbonate:

[0090] The present disclosure includes the step of reducing one or more metal oxides selected from nickel oxide, cobalt oxide, and manganese oxide from a material with an alkyl carbonate.

[0091] In some embodiments, the alkyl carbonate is a cyclic alkyl carbonate.

[0092] In some embodiments, the cyclic alkyl carbonate is selected from ethylene carbonate, propylene carbonate, and butylene carbonate.

[0093] In some embodiments, the alkyl carbonate is selected from diethyl carbonate, dimethyl carbonate, dipropyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, and fluoroalkyl carbonate.

[0094] In some embodiments, the alkyl carbonate comprises lithium ion battery electrolyte condensate.

[0095] This can be obtained, for example, from the crushed cell material by a drying procedure at a temperature in the range of 25° C. to 300° C. at an absolute pressure in the range of 1013 mbar and 0.1 mbar. In some embodiments, the electrolyte condensate is obtained by washing the crushed 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 are methanol, ethanol, propanol, isopropanol, methyl formate, methyl acetate, alkyl carbonates such as dimethyl carbonate, 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 directly added to the leaching reactor as a reducing agent.

[0096] 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.

[0097] In some embodiments, the material is a cathode active material, the alkyl carbonate is dipropyl carbonate, and a mass ratio of the material to the alkyl carbonate ranges from 1:3 to 1:0.2.

[0098] In some embodiments, the material is a cathode active material, the alkyl carbonate is dimethyl carbonate, and the mass ratio of the material to the alkyl carbonate ranges from 1:2 to 1:0.1.

[0099] In some embodiments, the material is a cathode active material, the alkyl carbonate is a mixed ethyl carbonate / methyl carbonate, and the mass ratio of the material to the alkyl carbonate ranges from 1:2 to 1:0.1.

[0100] In some embodiments, the material is a 1% to 20% Mn ore, the alkyl carbonate is ethylene carbonate, and the molar ratio of manganese to alkyl carbonate within the material ranges from 1:2 to 10:1.

[0101] method:

[0102] The present disclosure provides methods for extracting one or more metals from a material, wherein the methods comprise contacting the material with an acidic aqueous solution having a pH of 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.

[0103] In some embodiments, the acidic aqueous solution has an acid concentration in the range of 18mol / L to 0.0001mol / L. In some embodiments, the acidic aqueous solution has an acid concentration in the range of 18mol / L to 0.001mol / L. In some embodiments, the acidic aqueous solution has an acid concentration in the range of 18mol / L to 0.01mol / L. In some embodiments, the acidic aqueous solution has an acid concentration in the range of 18mol / L to 0.1mol / L. In some embodiments, the acidic aqueous solution has an acid concentration in the range of 18mol / L to 1mol / L. In some embodiments, the acidic aqueous solution has an acid concentration in the range of 18mol / L to 10mol / L. In some embodiments, the acidic aqueous solution has an acid concentration in the range of 17mol / L to 1mol / L. In some embodiments, the acidic aqueous solution has an acid concentration in the range of 16mol / L to 1mol / L.

[0104] In some embodiments, the acidic aqueous solution comprises H2SO4.

[0105] In some embodiments, the method comprises: extracting one or more metals from a material according to the methods disclosed herein to obtain an aqueous solution comprising metal ions, and separating the metal ions to obtain at least one substantially pure metal ion solution and / or at least one substantially pure solid metal ion salt.

[0106] In some embodiments, the material or its precursor is pyrolyzed prior to leaching.

[0107] Some embodiments are methods for recycling at least one battery material selected from lithium-ion batteries, lithium-ion battery waste, lithium-ion battery production waste, lithium-ion battery cell production waste, lithium-ion cathode active materials, and combinations thereof, wherein the method comprises: optionally, heat treating the at least one battery material at a temperature ranging from 350°C to 900°C, mechanically crushing the at least one battery material to obtain a black material, optionally, sorting the black material to obtain a fine fraction and a coarse fraction, and subjecting the black material, 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.

[0108] In some embodiments is a method for leaching a material comprising one or more metals in a zero oxidation state and one or more selected from metal oxides, metal hydroxides, and combinations thereof, wherein the method comprises contacting the material with an oxidizing acidic aqueous solution having a pH of less than 6, and subsequently reducing the one or more selected from the metal oxides, metal hydroxides, and combinations thereof with an alkyl carbonate.

[0109] In some embodiments, the leaching method comprises contacting the material with an oxidizing acidic aqueous solution having a pH of less than 6, and subsequently reducing one or more selected from metal oxides, metal hydroxides, and combinations thereof with a reducing agent. In some embodiments, 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.

[0110] 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 oxidant, such as, for example, H2SO4. In some embodiments, the oxidizing acidic aqueous solution comprises an oxidant 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 oxidant. In some embodiments, the oxidizing acidic aqueous solution comprises an acid that is also an oxidant and further comprises an oxidant that is not an acid. In some embodiments, the oxidant 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 oxides),

[0111] In some embodiments, the oxidizing acidic aqueous solution comprises H2SO4 and O2. In some embodiments, the oxidizing acidic aqueous solution comprises O2 and O2 is provided in the form of air.

[0112] In some embodiments, additional metal oxide and / or metal hydroxide is added after the contacting step and before the reducing step.

[0113] In some embodiments, in addition to the alkyl carbonate, the reducing agent further comprises one or more selected from SO2, pyrosulfite, bisulfite, thiosulfate, dithionite, H2O2, H2, and combinations thereof.

[0114] In some embodiments, the black matter is slurried in water at a weight percentage of the black matter ranging from 5% to 30% based on the total weight of the slurry. In some embodiments, the slurried black matter is contacted with an oxidizing acidic aqueous solution having a pH of less than 6. In some embodiments, the oxidizing acidic aqueous solution having a pH of less than 6 is formed from the slurried black matter by adding an acid and / or an oxidizing agent. In some embodiments, the weight ratio of H2SO4 to the black matter in the oxidizing acidic aqueous solution is 1:1 to 2:1. In some embodiments, H2SO4 is added during the contacting step to adjust the pH.

[0115] In some embodiments, the black material is provided as a slurry. In some embodiments, the black material is provided as a slurry in water. In some embodiments, the black material is provided as a slurry in an aqueous side stream from a subsequent processing step, such as, for example, a wash liquid from a filter. In some embodiments, the black material 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, for example, a wash 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 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, for example, a wash liquid from a filter. In some embodiments, the mixed hydroxide precipitate is provided as a solid.

[0116] In some embodiments, contacting the material with the oxidizing acidic aqueous solution is performed at a temperature ranging from 50° C. to 110° C. In some embodiments, contacting the material with the oxidizing acidic aqueous solution is performed for a duration ranging from 2 hours to 4 hours. In some embodiments, contacting the material with the oxidizing acidic aqueous solution is performed at a first temperature and the reducing step is performed at a second temperature, and the second temperature ranges from 70% to 20% of the first temperature.

[0117] In some embodiments, the oxidizing acidic aqueous solution comprises air. In some embodiments, the air comprises less than or equal to 3% by volume sulfur dioxide. In some embodiments, contacting the material with the oxidizing acidic aqueous solution having a pH less than 6 comprises bubbling air through the oxidizing acidic aqueous solution. In some embodiments, air is bubbled through the oxidizing acidic aqueous solution at a rate of up to 20% solution volume per minute.

[0118] In some embodiments, the oxidizing acidic aqueous solution has a pH in the range of -1.0 to 3.

[0119] In some embodiments, contacting the 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 oxidant selected from O2, N2O, and combinations. In some embodiments, contacting the material with an oxidizing acidic aqueous solution having a pH of less than 6 comprises first contacting the material with an acid, thereby forming hydrogen gas, and after the hydrogen gas is formed, adding an oxidant selected from O2, N2O, a metal oxide with an oxidation state greater than or equal to +3, a nickel manganese cobalt oxide, a cathode active material, and combinations. In some embodiments, contacting the material with an oxidizing acidic aqueous solution having a pH of less than 6 comprises first contacting the material with an acid, thereby forming hydrogen gas, monitoring the formation of hydrogen gas by gas chromatography and / or a hydrogen sensor, and after the hydrogen gas is formed, adding an oxidant selected from O2, N2O, and combinations. 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, resulting in 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 vol%, e.g., less than 1 vol%, e.g., less than 0.1 vol%, adding an oxidant selected from O2, N2O, and combinations.

[0120] 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.

[0121] In some embodiments, excess oxidizing gas O2 (such as in air) and / or N2O is recycled from the exhaust gas back to the leaching reactor.

[0122] In some embodiments, in addition to alkyl carbonate, the reducing agent further comprises SO2, and SO2 is purged through the solution at a rate of up to 20% solution volume / minute for 1 to 3 hours. In some embodiments, in addition to alkyl carbonate, the reducing agent further comprises SO2, and SO2 is provided as a mixture with O2 or air containing 10% or more SO2. In some embodiments, in addition to alkyl carbonate, the reducing agent further comprises SO2, and SO2 is not provided as a mixture with O2 or air. In some embodiments, in addition to alkyl carbonate, the reducing agent further comprises SO2, and SO2 is provided as a pure gas with a purity of at least 90%, for example 99%, or as a mixture with an inert gas, such as nitrogen and / or argon.

[0123] In some embodiments, the reducing step is performed at ambient temperature.

[0124] In some embodiments, after the contacting step, the method further comprises adding a base. In some embodiments, the base is selected from CaO, a hydroxide salt, a carbonate, and a combination 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 a combination thereof.

[0125] In some embodiments, the method is performed batchwise.

[0126] In some embodiments, the method is performed continuously in at least two reaction vessels. In some embodiments, the method is performed continuously in, for example, three, four, five, six, seven or more reaction vessels. In some embodiments, the black substance is added to the first reaction vessel, the oxidant is added to the second and / or third reaction vessel, the cathode active material and / or the mixed hydroxide precipitate is added to the fourth reaction vessel, and the reductant is added to the fourth, fifth and / or sixth reaction vessel.

[0127] In some embodiments, excess sulfur dioxide is recycled from the exhaust gas back to the reactor.

[0128] In some embodiments, a reflux condenser is fitted to at least one reaction vessel.

[0129] In some embodiments, contacting the material with the oxidizing acidic aqueous solution is performed at ambient pressure. In some embodiments, contacting the material with the oxidizing acidic aqueous solution is performed at elevated pressure.

[0130] In some embodiments, the contacting step is for a duration ranging from 10 minutes to 10 hours at a temperature ranging from 20°C to 100°C. In some embodiments, the contacting step is for a duration ranging from 3 hours to 5 hours at 100°C. In some embodiments, the contacting step is for a duration ranging from 3 hours to 5 hours at 60°C. In some embodiments, the contacting step is for a duration ranging from 3 hours to 5 hours at 25°C.

[0131] In some embodiments, the reducing step is continued for a duration ranging from 10 minutes to 10 hours at a temperature ranging from 20°C to 100°C. In some embodiments, the reducing step is continued for a duration ranging from 3 hours to 5 hours at 100°C. In some embodiments, the reducing step is continued for a duration ranging from 3 hours to 5 hours at 60°C. In some embodiments, the reducing step is continued for a duration ranging from 3 hours to 5 hours at 25°C.

[0132] In some embodiments, methods disclosed herein include leaching a material to obtain an aqueous solution comprising metal ions, and separating the metal ions to obtain at least one substantially pure metal ion solution and / or at least one substantially pure solid metal ion salt.

[0133] In some embodiments, a substantially pure solid metal ion salt is a solid comprising a metal ion and a counterion; wherein the total weight of the metal ion and the counterion is at least 50% by weight of the solid excluding the weight of the solvent, such as all water. In some embodiments, a substantially pure solid metal ion salt is a solid comprising a metal ion and a counterion; wherein the total weight of the metal ion and the counterion is at least 70% by weight of the solid excluding the weight of the solvent. In some embodiments, a substantially pure solid metal ion salt is a solid comprising a metal ion and a counterion; wherein the total weight of the metal ion and the counterion is at least 80% by weight of the solid excluding the weight of the solvent. In some embodiments, a substantially pure solid metal ion salt is a solid comprising a metal ion and a counterion; wherein the total weight of the metal ion and the counterion is at least 90% by weight of the solid excluding the weight of the solvent. In some embodiments, a substantially pure solid metal ion salt is a solid comprising a metal ion and a counterion; wherein the total weight of the metal ion and the counterion is at least 95% by weight of the solid excluding the weight of the solvent. In some embodiments, a substantially pure solid metal ion salt is a solid comprising a metal ion and a counterion; wherein the total weight of the metal ion and the counterion is at least 99% by weight of the solid excluding the weight of the solvent.

[0134] In some embodiments, a substantially pure metal ion solution is a solution comprising metal ions, counterions, and a solvent; wherein the total weight of the metal ions and counterions is at least 50% by weight of the solution excluding the weight of the solvent. In some embodiments, a substantially pure metal ion solution is a solution comprising metal ions, counterions, and a solvent; wherein the total weight of the metal ions and counterions is at least 70% by weight of the solution excluding the weight of the solvent. In some embodiments, a substantially pure metal ion solution is a solution comprising metal ions, counterions, and a solvent; wherein the total weight of the metal ions and counterions is at least 80% by weight of the solution excluding the weight of the solvent. In some embodiments, a substantially pure metal ion solution is a solution comprising metal ions, counterions, and a solvent; wherein the total weight of the metal ions and counterions is at least 90% by weight of the solution excluding the weight of the solvent. In some embodiments, a substantially pure metal ion solution is a solution comprising metal ions, counterions, and a solvent; wherein the total weight of the metal ions and counterions is at least 95% by weight of the solution excluding the weight of the solvent. In some embodiments, a substantially pure metal ion solution is a solution comprising metal ions, counter ions, solvent; wherein the total weight of the metal ions and counter ions is at least 99% by weight of the solution excluding the weight of the solvent.

[0135] In some embodiments, separating the metal ions to obtain at least one substantially pure metal ion solution and / or at least one substantially pure solid metal ion salt comprises one or more of solid / liquid separation, extraction, precipitation, crystallization, and combinations thereof.

[0136] In some embodiments, the method may be performed partially or entirely as a continuous method controlled by sensors and actuators as part of a computer-based process control system.

[0137] Oxidants:

[0138] In some embodiments, the oxidizing acidic aqueous solution comprises an oxidant. In some embodiments, the oxidant is an acid, such as, for example, H2SO4, HNO3, and combinations thereof. In some embodiments, the oxidant is not an acid, such as, for example, O2, N2O, and combinations thereof.

[0139] In some embodiments, metal oxides having an oxidation state greater than or equal to +3 are used as oxidants.

[0140] 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.

[0141] In some embodiments, the oxidant has a standard electrode potential in the range of +0.1 V to +1.5 V. In some embodiments, the oxidant has a standard electrode potential in the range of +0.4 V to +1.3 V. In some embodiments, the oxidant has a standard electrode potential in the range of +1 V to +1.5 V.

[0142] reducing agent:

[0143] In some embodiments, the reducing agent is an alkyl carbonate.

[0144] Without wishing to be bound by theory, it is believed that the alkyl carbonate can reduce the metal oxide by the following reaction:

[0145] In some embodiments, the reducing agent further comprises one or more selected from SO2, pyrosulfite, bisulfite, dithionite, thiosulfate, H2O2, H2, and combinations thereof.

[0146] Hydrogen peroxide can act as a reducing agent or an oxidizing agent, depending on the reaction partners. Possible oxidation and reduction reactions are: and In some embodiments, the standard electrode potential of the reaction partners affects which reaction occurs. For example, under certain conditions, permanganate (MnO4 - ) is reduced by hydrogen peroxide, while Fe 2+ In some embodiments, more acidic conditions favor oxidation reactions because H + to form water, and less acidic conditions favor the reduction reaction because H + In some embodiments, depending on the metal(s) M and the conditions used, the following reactions may or may not occur: and

[0147] Exemplary Batch Method:

[0148] Figure 1 An exemplary batch method (100) consistent with some embodiments of the present disclosure is depicted. In some embodiments, a material (102), such as a black material comprising nickel, cobalt, and manganese materials, is acid leached (101) in a continuously stirred reaction vessel comprising an acidic aqueous solution having a pH less than 1. In some embodiments, hydrogen gas is evolved. In some embodiments, an oxidant such as O2 and / or N2O is added (103). In some embodiments, the pH is adjusted to a pH in the range of 1 to 2 with, for example, 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 obtained liquid phase (106) and solid phase (105) are separated by solid / liquid separation, such as filtration, centrifugation, and / or sedimentation.

[0149] Exemplary Continuous Process:

[0150] Figure 2An exemplary continuous method (200) consistent with some embodiments of the present disclosure is depicted. In some embodiments, a material (202), such as a black material comprising nickel, cobalt, and manganese materials, is acid leached in a continuously stirred reaction vessel (201) comprising an acidic aqueous solution having a pH less than 1. In some embodiments, the acid leaching is further performed in one or more additional continuously stirred reaction vessels (203). In some embodiments, an oxidant, such as O2 and / or N2O, is added (205) to the continuously stirred reaction vessel (204). In some embodiments, the acid leaching in the presence of the added oxidant is further performed 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 to 2 with, for example, a cathode active material and / or a mixed hydroxide precipitate, and a reducing agent, such as an alkyl carbonate, is introduced (208) into the continuously stirred reaction vessel (207). In some embodiments, the leaching in the presence of the added reducing agent is further performed in one or more additional continuously stirred reaction vessels (209). In some embodiments, the obtained liquid phase (211) and solid phase (210) are separated by solid / liquid separation such as filtration, centrifugation and / or sedimentation.

[0151] If one, more than one, or all of the group members are present in, used in, or otherwise relevant to a given product or method, a claim or description including "or" or "and / or" between at least one member of the group is considered satisfied unless otherwise stated or otherwise obvious from the context. The present disclosure includes embodiments in which exactly one member of the group is present in, used in, or otherwise relevant to a given product or method. The present disclosure includes embodiments in which more than one or all of the group members are present in, used in, or otherwise relevant to a given product or method.

[0152] In addition, the present disclosure encompasses all variants, combinations and arrangements in which at least one limitation, element, clause and illustrative term from at least one listed claim is introduced into another claim. For example, any claim subordinate to another claim may be modified to include at least one limitation seen in any other claim subordinate to the same basic claim. In the case where the element is presented in a list (such as in the form of a Markush group), each subgroup of the element is also disclosed, and any element may be removed from the group. It should be understood that, generally, in the case where the disclosure or the aspect of the disclosure is referred to as comprising specific elements and / or features, the embodiment of the disclosure or the aspect of the disclosure is composed of or substantially composed of such elements and / or features. For the purpose of brevity, these embodiments are not specifically stated in words herein. In the case of giving a range, endpoints are included. In addition, unless otherwise specified or otherwise clearly understood from the context and those of ordinary skill in the art, the value represented as a range in the different embodiments of the present disclosure may adopt any specific value or subrange within the described range, unless the context clearly indicates otherwise.

[0153] Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments disclosed herein. Such equivalents are intended to be encompassed by the following claims.

[0154] Examples

[0155] The following examples are intended to be illustrative and are not meant to limit the scope of the present disclosure in any way.

[0156] abbreviation

[0157] % Percent

[0158] K2CO3 Potassium carbonate

[0159] Na2CO3 Sodium carbonate

[0160] Na2B4O7 Sodium Tetraborate

[0161] PA level professional analysis level

[0162] nd Undetermined

[0163] wt% weight percentage

[0164] NaOH Sodium hydroxide

[0165] Lithium

[0166] Nickel

[0167] Co Cobalt

[0168] Mn Manganese

[0169] Cu Copper

[0170] Al Aluminum

[0171] Fe Iron

[0172] Phosphorus

[0173] F Fluorine

[0174] Ca Calcium

[0175] Exemplary Elemental Analysis

[0176] Elemental analysis of the solid samples was performed by digestion in nitric acid and hydrochloric acid (feed sample and Examples 1 and 2) or by K2CO3-Na2CO3 / Na2B4O7 melt digestion and dissolution of the molten residue in hydrochloric acid (Examples 3 and 4).

[0177] The metals in the obtained sample solutions were determined by optical emission spectroscopy using inductively coupled plasma (ICP-OES).

[0178] Some element concentrations were also measured by X-ray fluorescence using an Epsilon 4DY-6024 from Malvern Panalytical that had been calibrated with data from ICP-OES measurements.

[0179] For sample preparation for the determination of total fluorine content (solid samples), elemental analysis of fluorine and fluoride was performed according to DIN EN 14582:2016-12; detection method was measurement with an ion-selective electrode. DIN 38405-D4-2:1985-07 (water samples; digestion of inorganic solids, followed by acid-loaded distillation and determination of fluoride using an ion-selective electrode).

[0180] The total carbon of the gas obtained after combustion of the sample was determined by gas chromatography with a thermal conductivity detector.

[0181] Sulfur is determined by catalytic combustion of the sample in an inert gas / oxygen atmosphere, where it is converted into a mixture of SO2 and SO3. The SO3 formed is subsequently reduced to SO2 using copper particles. After drying and separation of the combustion gases, the sulfur is detected via thermal conductivity or IR spectroscopy and quantified as SO2.

[0182] Condensate from electrolyte solvent

[0183] The condensate of the electrolyte solvent used in Example 4 was obtained by drying shredded 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 combined with mass spectrometry.

[0184] Cathode active material

[0185] The cathode active material (CAM) used in Examples 1 and 2 is a material known as HED TM NCM's commercially available CAM from BASF Corp. has a composition of 49.8 wt% Ni, 5.9 wt% Co, 2.6 wt% Mn, and 7.3 wt% Li.

[0186] Example 1

[0187] In this example, the cathode active material was leached and no alkyl carbonate was used.

[0188] Under stirring, 25.06g NCM111 material is suspended in 145.5g deionized water. In this suspension, 60g sulfuric acid (96wt.%) is slowly added during 70min under stirring. It is observed that the temperature rises from room temperature to 50°C. Subsequently, the reaction mixture is heated to 80°C. The mixture is kept at this temperature for 30min and then further heated to 100°C. The mixture is kept at 100°C for another 80min. Afterwards, the mixture is cooled to room temperature and the remaining residue is filtered. The residue is dried to obtain 14.75g dry solid residue. The solid residue is analyzed by ICP-OES and the results are provided in Table 1.

[0189] Example 2

[0190] In this example, the cathode active material is leached and an alkyl carbonate is used.

[0191] Example 2 was carried out according to the procedure described in Example 1, except that 7.5 g of diethyl carbonate was added during a 30 min period at 80° C., and the resulting mixture was maintained at 100° C. for 60 min. Example 2 yielded 10.64 g of a dry solid residue. The solid residue was analyzed by ICP-OES and the results are provided in Table 1.

[0192] Example 3

[0193] In this example, the cathode active material is leached and an alkyl carbonate is used.

[0194] Example 3 was carried out according to the procedure described in Example 1, except that 6.6 g of ethylene carbonate was added in melt form at 80° C. over a period of 30 min, and the resulting mixture was kept at 100° C. for 60 min. At the end of the procedure, no solid residue was present. The solid residue was analyzed by ICP-OES and the results are provided in Table 1.

[0195] Example 4

[0196] In this example, the cathode active material is leached and a condensate of an electrolyte solvent comprising an alkyl carbonate is used.

[0197] Example 4 was carried out according to the procedure described in Example 1, except that 7.3 g of condensate of the electrolyte solvent was added during a 30 min period at 80° C., and the resulting mixture was maintained at 92° C. for 60 min. Example 4 yielded 4.51 g of a dry solid residue. The solid residue was analyzed by ICP-OES and the results are provided in Table 1.

[0198] Table 1:

[0199]

[0200] Comparing Example 1 with Examples 2 to 4, it was observed that the addition of one or more alkyl carbonates increased the leaching efficiency. Without wishing to be bound by theory, it is believed that the alkyl carbonate acts as a reducing agent to increase the leaching efficiency.

Claims

1. A method for extracting one or more metals from a material, wherein the method comprises: contacting the material with an acidic aqueous solution having a pH of less than 7 at a temperature in the range of 20°C to 100°C for a duration in the range of 10 minutes to 10 hours, and One or more metal oxides selected from nickel oxide, cobalt oxide and manganese oxide are reduced from the material with an alkyl carbonate at a temperature in the range of 20°C to 100°C for a duration in the range of 10 minutes to 10 hours.

2. The method according to claim 1, wherein: The alkyl carbonate is a cyclic alkyl carbonate.

3. The method according to claim 2, wherein: The cyclic alkyl carbonate is selected from ethylene carbonate, propylene carbonate and butylene carbonate.

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

5. The method according to claim 1, wherein: The alkyl carbonate comprises a lithium ion battery electrolyte solvent.

6. The method according to any one of claims 1 to 5, wherein: The molar ratio of the one or more metal oxides selected from nickel oxide, cobalt oxide and manganese oxide to the alkyl carbonate in the material ranges from 1:2 to 10:

1.

7. The method according to any one of claims 1 to 6, wherein: The material comprises a material having the formula Li p M q M' r O s A cathode active material; 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 ranges from 1 to 1.4; q ranges from 0.6 to 2; r ranges from 0 to 1; and s ranges from 2 to 4.

8. The method according to any one of claims 1 to 7, wherein: The material comprises a material having the formula Li (1+x) (Ni a Co b Mn c M ’ d ) (1-x) Cathode active material for O2, wherein: M ’ 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.

9. The method according to any one of claims 1 to 8, wherein: The material comprises a material having the formula Li[Ni h Co i Al j ]O 2+r A cathode active material, wherein: 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 The range of r is 0 to 0.

4.

10. The method according to any one of claims 1 to 9, wherein: The material comprises a material having the formula Li (1+x) Mn 2-x-z M ’ z O4 cathode active material, wherein: x ranges from 0 to 0.2; z ranges from 0 to 0.1; and M ’ Selected from Al, Mg, Ni, Co, Fe, Ti, V, Zr and Zn.

11. The method according to any one of claims 1 to 10, wherein: The material comprises a material having the formula xLi (1+1 / 3) M (2 / 3) O2·yLiMO2·zLiM'O2 cathode active material, where M ’ Contains at least one metal in oxidation state +4.

12. The method according to claim 11, wherein: The material comprises a cathode active material having the formula xLi (1+1 / 3) M (2 / 3) O2·yLiMO2·zLiM’O2, wherein M comprises at least one metal among Mn, Ni, Co in an oxidation state of +4, M’ is at least one transition metal, and 0 < x < 1, 0 < y < 1, 0 < z < 1 and x + y + z = 1.

13. The method according to any one of claims 1 to 12, wherein: The material comprises at least one lithium ion battery material selected from the group consisting of lithium ion batteries, lithium ion battery waste, lithium ion battery production waste, black matter, lithium ion battery cell production waste, lithium ion cathode active material, and combinations thereof.

14. The method according to any one of claims 1 to 13, wherein: This material contains: 0.1 to 10 weight percent of lithium, 0 to 60 weight percent of nickel, 0 to 20 weight percent of cobalt, 0 to 20 weight percent of copper, 0 to 20 weight percent of aluminum, 0 to 20 weight percent of iron, and 0 to 20 weight percent manganese; Wherein each weight percent is based on the total weight of the material and the sum of nickel, cobalt and manganese is greater than zero weight percent.

15. The method according to any one of claims 1 to 14, wherein: The acidic aqueous solution has an acid concentration ranging from 18 mol / L to 0.0001 mol / L.

16. The method according to any one of claims 1 to 15, wherein: The acidic aqueous solution contains H2SO4.

17. The method according to any one of claims 1 to 16, wherein: The acidic aqueous solution has a pH ranging from -1.0 to 3.

18. A method comprising: extracting one or more metals from the material according to any one of claims 1 to 17 to obtain an aqueous solution comprising metal ions, and The metal ions are separated to obtain at least one substantially pure metal ion solution and / or at least one substantially pure solid metal ion salt.

19. A method for recycling at least one battery material selected from the group consisting of lithium ion batteries, lithium ion battery waste, lithium ion battery production waste, lithium ion battery cell production waste, lithium ion cathode active materials, and combinations thereof, wherein the method comprises: Optionally, heat treating the at least one battery material at a temperature ranging from 350° C. to 900° C., mechanically pulverizing 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 The black mass, optionally the fine fraction, the coarse fraction, or the fine fraction and the coarse fraction is subjected to a method according to any one of claims 1 to 18.

20. The method according to claim 1, wherein: 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 wherein the method comprises: contacting the material with an oxidizing acidic aqueous solution having a pH of less than 6 at a temperature in the range of 20°C to 100°C for a duration in the range of 10 minutes to 10 hours, and Subsequently, one or more selected from metal oxides, metal hydroxides, and combinations thereof present in the material is reduced with an alkyl carbonate at a temperature ranging from 20° C. to 100° C. for a duration ranging from 10 minutes to 10 hours.

21. The method according to claim 20, wherein: The oxidizing acidic aqueous solution has a pH ranging from -1.0 to 3.

22. The method according to any one of claims 1 to 4, 20 and 21, wherein: The material is an ore comprising from 0.1 wt % manganese to 65 wt % manganese based on the total weight of the material.

23. The method according to claim 22, wherein: The material contains pyrolusite.

24. The method according to any one of claims 1-4, 20 and 21, wherein: The material comes from manganese ore extraction.

25. The method according to any one of claims 22 to 24, wherein: The material contains MnO2.

26. The method of claim 20, wherein: The oxidizing acidic aqueous solution comprises at least one selected from H2SO4, O2, N2O, and combinations thereof.

27. The method according to claim 20, wherein: The oxidizing acidic aqueous solution contains H2SO4.

28. The method of claim 20, wherein: The oxidizing acidic aqueous solution comprises at least one acid selected from HCl, H2SO4, CH3SO3H, HNO3, and combinations thereof.

29. The method according to any one of claims 1 to 19, wherein: The reducing step further comprises contacting the material with one or more selected from SO2, pyrosulfite, bisulfite, thiosulfate, H2O2, H2, and combinations thereof.

30. The method according to any one of claims 1 to 19, wherein: Prior to contacting the material with the acidic aqueous solution, the material or a precursor thereof is pyrolyzed.

31. The method of claim 20, wherein: The oxidizing acidic aqueous solution contains H2SO4 and O2.

32. The method of claim 20, wherein: The oxidizing acidic aqueous solution contains O2 and the O2 is provided in the form of air.

33. The method of any one of claims 1 to 19, further comprising adding additional metal oxide and / or metal hydroxide after the contacting step and before the reducing step.

34. The method of claim 20, wherein: Contacting the material with an oxidizing acidic aqueous solution having a pH of less than 6 includes contacting the material with the acidic aqueous solution, thereby forming hydrogen gas, and after the hydrogen gas is formed, adding an oxidant selected from O2, N2O, and combinations thereof.

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

36. The method of claim 20, wherein: The subsequent reducing step begins at least 1 minute after the start of the contacting step, at least 10 minutes after the start of the contacting step, at least 30 minutes after the start of the contacting step, at least 1 hour after the start of the contacting step.

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

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