Method for purifying a leaf solution

Abstract

The present invention relates to a method for purifying a leach solution of a material comprising one or more metals in a zero oxidation state and one or more selected from the group consisting of metal oxides, metal hydroxides, metal carbonates and combinations thereof wherein the method comprises providing a leach mixture, after stirring the leach mixture for a first period of time during a total period of time, the leach mixture is treated with activated carbon, after which stirring continues for a second period of time during the total period of time to obtain an activated carbon enriched leach mixture, and subjecting the activated carbon enriched leach mixture to a separation process to obtain a residue and a purified leach solution in the form of an aqueous solution comprising metal ions as a supernatant.

Description

Technical Field

[0001] The present disclosure relates to methods for purifying leaching solutions of materials such as, for example, battery materials, methods for separating various metals and metal compounds from materials such as, for example, battery materials, and methods for recycling lithium-ion battery materials. Background Art

[0002] High-purity lithium is a valuable resource. Many sources of lithium, 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 the recycling of lithium-ion batteries. Lithium-ion battery materials are complex mixtures of various elements and compounds, and it may be desirable to remove various non-lithium impurities. Such impurities may exist in various oxidation states, which may affect, for example, the efficiency of a leaching process. For example, in some leaching processes, high oxidation state metals may be leached more or less efficiently 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.

[0003] Therefore, there is a need for leaching methods that can efficiently and effectively leach complex mixtures of various elements and compounds, such as mixed metals coexisting in multiple 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 for removing valuable metals, such as nickel and cobalt, from materials with high recovery and high purity.

[0004] WO 2021 / 174348 A1 discloses a method for processing ferrous material from a lithium iron phosphate battery, the method comprising a) receiving a ferrous material feed; b) acid leaching the ferrous material at a pH of less than 4 to produce a pregnant leach solution (PLS), the pregnant leach solution comprising at least 80% of lithium from the ferrous material feed and at least a portion of iron and phosphorus from the ferrous material feed; providing a first intermediate solution after completing step b); and separating at least 90% of the iron and phosphorus from the first intermediate solution to provide an output solution.

[0005] However, in some leaching processes, undesirable emulsification may occur, which may affect the efficiency of, for example, a separation process subsequent to the corresponding leaching process. Therefore, there is a need for methods for at least partially removing undesirable emulsifiers and / or dispersants from the corresponding leaching solution of the material, thereby making the corresponding subsequent separation process still more efficient and effective. Summary of the Invention

[0006] Disclosed herein are methods for providing a purified leach solution of a material comprising one or more metals in a zero oxidation state and one or more selected from the group consisting of metal oxides, metal hydroxides, metal carbonates, and combinations thereof. Each such method comprises contacting the material with an acidic aqueous solution having a pH of less than 6 and comprising one or more acids selected from, for example, HCl, H2SO4, CH3SO3H, HNO3 at a temperature in the range of 20°C to 110°C for a total time period in the range of 20 minutes to 10 hours, thereby forming a leach mixture of the material during the contacting, and after stirring the leach mixture for a first time period during the total time period, treating the leach mixture with activated carbon, and thereafter continuing stirring for a second time period during the total time period to obtain an activated carbon-rich leach mixture, and subjecting the activated carbon-rich leach mixture to a separation process (e.g., such as filtration) to obtain a separation residue (e.g., such as a dry filter cake) and a purified leach solution in the form of an aqueous solution comprising metal ions as a supernatant (e.g., such as a filtrate).

[0007] Also disclosed are methods comprising leaching the material by processing the material as previously described 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 comprising mechanically pulverizing at least one 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 to obtain a black substance, and leaching the black substance by processing the black substance as previously described. DETAILED DESCRIPTION

[0008] Disclosed herein are methods for providing a purified leach solution of a material comprising one or more metals in a zero oxidation state and one or more selected from the group consisting of metal carbonates, metal oxides, metal hydroxides, and combinations thereof. Each such method comprises contacting the material with an acidic aqueous solution having a pH of less than 6 and comprising one or more acids selected from, for example, HCl, H2SO4, CH3SO3H, HNO3 at a temperature in the range of 20°C to 110°C for a total time period in the range of 20 minutes to 10 hours, thereby forming a leach mixture of the material during the contacting, and after stirring the leach mixture for a first time period during the total time period, treating the leach mixture with activated carbon, and thereafter continuing stirring for a second time period during the total time period to obtain an activated carbon-rich leach mixture, and subjecting the activated carbon-rich leach mixture to a separation process (e.g., such as filtration) to obtain a separation residue (e.g., such as a dry filter cake) and a purified leach solution in the form of an aqueous solution comprising metal ions as a supernatant (e.g., such as a filtrate).

[0009] In some embodiments, the acidic aqueous solution comprises at least one acid selected from HCl, H2SO4, CH3SO3H, HNO3, and combinations thereof. In some embodiments, the acidic aqueous solution further comprises one or more selected from O2, N2O, and combinations thereof.

[0010] In some embodiments, the acidic aqueous solution comprises H2SO4. In some embodiments, the acidic aqueous solution comprises H2SO4 and O2. In some embodiments, the acidic aqueous solution comprises O2 and the O2 is provided in the form of air. In some embodiments, the acidic aqueous solution comprises sulfur dioxide, SO2. In some embodiments, the acidic aqueous solution comprises less than or equal to 3% by volume of sulfur dioxide. In some embodiments, the acidic aqueous solution comprises air having less than or equal to 3% by volume of sulfur dioxide.

[0011] In some embodiments, contacting the material with an acidic aqueous solution having a pH less than 6 results in the formation of hydrogen gas, and the oxidant selected from O2 (eg, air), N2O, and combinations thereof is added after the formation of the hydrogen gas.

[0012] In some embodiments, one or more of the metal oxides or metal hydroxides selected from nickel, cobalt, or manganese contains these metals in the +2 oxidation state in an amount ranging from 5 wt % to 10 wt %, from 10 wt % to 20 wt %, or from 20 wt % to 50 wt % relative to the total weight of the one or more of the metal oxides or metal hydroxides selected from nickel, cobalt, or manganese.

[0013] The expressions “% by weight” and “wt.-%” and “weight percent” and “weight ratio” are used synonymously herein.

[0014] In some embodiments, the acidic aqueous solution has an acid concentration ranging from 18 mol / L to 0.0001 mol / L.

[0015] In some embodiments, contacting the material with the acidic aqueous solution at a temperature in the range of 20°C to 110°C for a total time period in the range of 20 minutes to 10 hours comprises:

[0016] The material was suspended in deionized water to obtain an intermediate suspension,

[0017] The intermediate suspension is subsequently treated, for example dropwise, with an amount of one or more acids selected from, for example, HCl, H2SO4, CH3SO3H, HNO3 and combinations thereof, to obtain a reaction mixture as a leaching mixture.

[0018] In some embodiments, contacting the material with the acidic aqueous solution at a temperature in the range of 20°C to 110°C for a total time period in the range of 20 minutes to 10 hours further comprises

[0019] The reaction mixture is stirred first under an inert gas and then under aerobic conditions, and

[0020] One or more oxidizing agents selected from the group consisting of O2, N2O, and combinations thereof are added to the reaction mixture to obtain a leaching mixture.

[0021] In some embodiments, contacting the material with the acidic aqueous solution at a temperature in the range of 20°C to 110°C for a total time period in the range of 20 minutes to 10 hours further comprises

[0022] The reaction mixture is stirred first under an inert gas and then under aerobic conditions, and

[0023] One or more reducing agents and / or bases are added to obtain a leach mixture.

[0024] In some embodiments, contacting the material with the acidic aqueous solution at a temperature in the range of 20°C to 110°C for a total time period in the range of 20 minutes to 10 hours further comprises

[0025] The reaction mixture is stirred first under an inert gas and then under aerobic conditions, and

[0026] adding one or more oxidizing agents to the reaction mixture, and

[0027] One or more reducing agents and / or bases are added to obtain a leach mixture.

[0028] In some embodiments, the activated carbon is selected from activated carbon powder and granular activated carbon (eg, with 12x40 mesh). In principle, any form / structure of activated carbon can be used as long as it can operate well in the corresponding method.

[0029] The amount of activated carbon used to treat the material is selected to be in the range of 0.1 weight percent to 10 weight percent, in some embodiments, the amount of activated carbon used to treat the material is selected to be in the range of 0.5 weight percent to 5 weight percent, and in some embodiments, the amount of activated carbon used to treat the material is selected to be in the range of 1 weight percent to 2.5 weight percent, where each weight percent is based on the total weight of the material used.

[0030] In some embodiments, when the experimental conditions are otherwise identical and the same results are achieved (i.e., a purified leach solution), the amount of activated carbon used to treat the material is related to the second time period by a monotonically decreasing function, i.e., the smaller the amount of activated carbon selected (within the range of 0.1 weight percent to 10 weight percent as previously mentioned), the longer the second time period to be selected. As used herein, a purified leach solution is a leach solution that is substantially free of emulsifiers and / or dispersants, as indicated, for example, by a time to phase separation of less than 2 minutes after addition of the organic solvent and shaking of the resulting two-phase system.

[0031] The second time period to be selected ranges from 20 minutes to 6 hours. The first and second time periods add up to the total time period. In some embodiments, the first time period is 0 seconds, i.e., the leach mixture is treated with activated carbon without prior stirring. In some embodiments, the activated carbon is added to the acidic aqueous solution simultaneously with the material. In some embodiments, the activated carbon is added to the acidic aqueous solution after the material. In this case, the second time period may be equivalent to the total time period.

[0032] In some embodiments, the separation method can be achieved by filtration to obtain a filter cake and a filtrate as a supernatant; by sedimentation to obtain a precipitate and a supernatant; or by centrifugation to obtain a precipitate and a supernatant.

[0033] In some embodiments, the material is a battery material, which is a lithium-ion battery material comprising 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, and / or wherein the battery material comprises one or more selected from the group consisting of nickel, cobalt, manganese, and combinations thereof.

[0034] In some embodiments, the one or more metals in the zero oxidation state are selected from lithium, nickel, cobalt, copper, aluminum, iron, manganese, rare earth metals, and combinations thereof. In some embodiments, the metal carbonate is selected from lithium carbonate. 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. In some embodiments, the metal hydroxide is selected from lithium hydroxide, nickel hydroxide, cobalt hydroxide, copper hydroxide, aluminum hydroxide, iron hydroxide, manganese hydroxide, alkaline earth metal hydroxide, rare earth hydroxide, and combinations thereof.

[0035] In some embodiments, the material is selected as a battery material comprising:

[0036] 0.1 to 10 weight percent of lithium,

[0037] 0 to 60 weight percent of nickel,

[0038] 0 to 20 weight percent of cobalt,

[0039] 0 to 20 weight percent of copper,

[0040] 0 to 20 weight percent of aluminum,

[0041] 0 to 20 weight percent of iron, and

[0042] 0 to 20 weight percent manganese;

[0043] Each weight percentage is based on the total weight of the battery materials.

[0044] In some embodiments, the disclosed methods include subjecting at least one material to a heat treatment step. In some embodiments, the material (such as, for example, a battery material or a precursor thereof) is pyrolyzed prior to contacting the material with the acidic aqueous solution.

[0045] In some embodiments, the acidic aqueous solution comprises O2, the O2 is provided in the form of air, and the air is bubbled through the acidic aqueous solution.

[0046] Also disclosed are methods comprising processing a material according to the previously described embodiments of the inventive method 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.

[0047] In some embodiments, separating the metal ions comprises one or more of solid / liquid separation, extraction, precipitation, crystallization, and combinations thereof.

[0048] Further disclosed is a method comprising:

[0049] Mechanically pulverizing at least one material, such as a 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, to obtain a black mass, and

[0050] The black mass was subjected to a method according to the previously described embodiment of the method of the invention.

[0051] definition:

[0052] As used herein, unless otherwise indicated, "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. Thus, the terms "a" (or "an"), "one or more," and "at least one" are used interchangeably herein.

[0053] As used herein, the term "material" refers to an element, component, and / or substance that constitutes or can be made into something.

[0054] As used herein, an "acidic aqueous solution" is an aqueous solution capable of oxidizing a metal in its zero oxidation state having a pH of less than 7. For example, some acidic aqueous solutions can oxidize some metals in their zero oxidation state but not others.

[0055] As used herein, an "oxidant" is a compound that is capable of oxidizing a metal in oxidation state zero. For example, some oxidants are capable of oxidizing some metals in oxidation state zero but not others.

[0056] 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.

[0057] As used herein, a "leaching mixture" is the reaction mixture formed during the contacting step.

[0058] 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.

[0059] As used herein, 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.

[0060] As used herein, the term "sparging" refers to the dispersion of a gas through a liquid.

[0061] 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.

[0062] Material:

[0063] 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.

[0064] In some embodiments, the material comprises one or more selected from lithium, nickel, cobalt, manganese, and combinations thereof.

[0065] In some embodiments, the one or more metals in the zero oxidation state are selected from lithium, nickel, cobalt, copper, aluminum, iron, manganese, rare earth metals, and combinations thereof.

[0066] In some embodiments, the metal carbonate is selected from lithium carbonate.

[0067] 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.

[0068] In some embodiments, the metal hydroxide is selected from lithium hydroxide, nickel hydroxide, cobalt hydroxide, copper hydroxide, aluminum hydroxide, iron hydroxide, manganese hydroxide, alkaline earth metal hydroxides, rare earth hydroxides, and combinations thereof.

[0069] 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 percentage is based on the total weight of the material.

[0070] In some embodiments, the material or its precursor is pyrolyzed prior to processing by embodiments of the present methods. In some embodiments, the pyrolysis is performed under an inert atmosphere, an oxidizing atmosphere, a reducing atmosphere, or a combination thereof.

[0071] In some embodiments, the material has a weight ratio of lithium to the combined weight of nickel, cobalt, manganese, copper, aluminum, iron, and phosphorus ranging from 0.01 to 10, 0.01 to 5, 0.01 to 2, or 0.01 to 1.

[0072] In some embodiments, the material is a lithium-ion battery material comprising 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.

[0073] "Black matter" refers to materials containing lithium that are obtained 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, by mechanical methods such as mechanical comminution. 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, separators, and electrolytes. In some instances, the battery waste can be subjected to a heat treatment to pyrolyze organic (e.g., electrolyte) and polymer (e.g., separators and binders) materials. This heat treatment can be performed before or after the mechanical comminution of the battery material. In some embodiments, the black matter is subjected to a heat treatment.

[0074] Lithium-ion batteries can be disassembled, punched, ground (e.g., in a hammer mill, rotor mill), and / or shredded (e.g., in an industrial shredder). This mechanical processing can yield the active materials for the battery electrodes. Lightweight fractions (e.g., housing parts made of organic plastics and aluminum or copper foil) can be removed, for example, by forced airflow, air separation, or classification or screening.

[0075] Battery waste can be derived from, for example, spent batteries or production waste such as off-spec materials. In some embodiments, the material is obtained from mechanically processed battery waste, such as battery waste processed in a hammer mill, rotor mill, or industrial shredder. Such material can have an average particle size (D) ranging from 1 μm to 1 cm, such as 1 μm to 500 μm, and further such as 3 μm to 250 μm. 50 ).

[0076] Larger parts of the battery waste, like housings, wiring and electrode carrier films, can be mechanically separated so that the corresponding materials can be excluded from the battery material used in the process.

[0077] The mechanically treated battery waste can be subjected to a solvent treatment to dissolve and separate the polymer binder used to bond the transition metal oxide to the current collector film, or, for example, to bond graphite to the current collector film. Suitable solvents are N-methylpyrrolidone, N,N-dimethylformamide, 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.

[0078] In some embodiments, the mechanically processed battery waste can be subjected to thermal treatment under different atmospheres and over a wide range of temperatures.

[0079] In some embodiments, the heat treatment is carried out at a temperature in the range of 350°C to 900°C. In some embodiments, the heat treatment is carried out at a temperature in the range of 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 from the pyrolyzed organic (polymer) component under the heat treatment conditions. In some embodiments, the reducing agent is formed by adding a reducing gas such as H2 and / or CO.

[0080] 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.

[0081] In some embodiments, the material comprises a material having the formula Li x A 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.

[0082] In some embodiments, the material comprises nickel, cobalt, manganese, copper, aluminum, iron, phosphorus, or combinations thereof.

[0083] 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.

[0084] 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.

[0085] Leaching solution:

[0086] A method for purifying a leaching solution of a material comprises contacting the material comprising one or more metals in a zero oxidation state and one or more selected from metal oxides, metal hydroxides, and combinations thereof with an acidic aqueous solution having a pH of less than 6. During the contacting, a leaching mixture of the material is formed.

[0087] The acidic aqueous solution comprises one or more acids selected from HCl, H2SO4, CH3SO3H, HNO3, and combinations thereof. In some embodiments, the acidic aqueous solution comprises at least one selected from H2SO4, O2, N2O, and combinations thereof. In some embodiments, the acidic aqueous solution comprises H2SO4. The acidic aqueous solution further comprises one or more selected from O2, N2O, and combinations thereof. In some embodiments, the acidic aqueous solution comprises an acid that is also an oxidizing agent, such as, for example, H2SO4. In some embodiments, the 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 acidic aqueous solution comprises an acid and an oxidizing agent. In some embodiments, the acidic aqueous solution comprises an acid that is also an oxidizing agent and further comprises an oxidizing agent that is not an acid.

[0088] In some embodiments, the leach mixture is treated by reducing one or more selected from metal oxides, metal hydroxides, and combinations thereof with a reducing agent. In some embodiments, the reducing agent is one or more selected from SO2, metabisulfites, bisulfites, thiosulfates, dithionites, H2O2, H2, and combinations thereof.

[0089] In some embodiments, the black material is slurried in water at a weight percentage of the black material ranging from 5% to 30% based on the total weight of the slurry. In some embodiments, the slurried black material 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 material by adding an acid. In some embodiments, the weight ratio of H2SO4 to the black material in the acidic aqueous solution ranges from 1:1 to 2:1. In some embodiments, H2SO4 is added during the contacting step to adjust the pH.

[0090] 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.

[0091] Contacting the material with the acidic aqueous solution is performed at a temperature ranging from 20° C. to 110° C. In some embodiments, contacting the material with the acidic aqueous solution is performed for a duration ranging from 20 minutes to 10 hours.

[0092] In some embodiments, the acidic aqueous solution comprises air. In some embodiments, the air comprises less than or equal to 3% by volume of sulfur dioxide. In some embodiments, contacting the material with the acidic aqueous solution having a pH less than 6 comprises bubbling air through the acidic aqueous solution. In some embodiments, the air is bubbled through the acidic aqueous solution at a rate of up to 20% solution volume per minute. In some embodiments, the air is bubbled through the acidic aqueous solution at a rate ranging from 0.1% to 20% solution volume per minute. The rate refers to the volume of O2bubbled through the acidic aqueous solution per minute, i.e., it is equal to about 21% of the volume of air bubbled through the solution.

[0093] In some embodiments, the acidic aqueous solution has a pH ranging from -1.0 to 3.

[0094] In some embodiments, contacting the material with the acidic aqueous solution having a pH less than 6 comprises first contacting the material with an acid, and subsequently adding an oxidizing agent selected from the group consisting of O2, N2O, and combinations thereof. In some embodiments, contacting the material with the acidic aqueous solution having a pH less than 6 comprises first contacting the material with an acid, resulting in the formation of hydrogen gas, and after the formation of hydrogen gas (i.e., after the formation of hydrogen gas has subsided), adding an oxidizing agent selected from the group consisting of O2, N2O, and combinations thereof. In some embodiments, contacting the material with the 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 after the formation of hydrogen gas (i.e., after the formation of hydrogen gas has subsided), adding an oxidizing agent selected from the group consisting of O2, N2O, and combinations thereof. In some embodiments, contacting the material with the 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% by volume, e.g., less than 1% by volume, e.g., less than 0.1% by volume, adding an oxidizing agent selected from the group consisting of O2, N2O, and combinations thereof.

[0095] In some embodiments, excess oxidizing gas O2(as in air) and / or N2O is recycled from the exhaust gas back into the leaching reactor.

[0096] In some embodiments, the optional reducing agent comprises SO2and the SO2is bubbled through the solution at a rate of up to 20% solution volume per minute. In some embodiments, the SO2is bubbled through the solution at a rate ranging from 0.1% to 20% solution volume per minute. In some embodiments, the SO2is bubbled through the solution for 1 hour to 3 hours.

[0097] In some embodiments, the optional reducing step is performed at ambient temperature.

[0098] In some embodiments, the method is performed batch-wise.

[0099] In some embodiments, contacting the material with the acidic aqueous solution is performed at ambient pressure. In some embodiments, contacting the material with the acidic aqueous solution is performed at elevated pressure.

[0100] In some embodiments, the contacting step is continued at a temperature in the range of 20°C to 110°C for a total time period in the range of 20 minutes to 10 hours. The second time period within the total time period is in the range of 20 minutes to 6 hours. In some embodiments, the second time period within the total time period is in the range of 1 hour to 5 hours. In some embodiments, the second time period within the total time period is in the range of 2 hours to 4 hours. The second time period is highly correlated with the amount of activated carbon used to treat the material. The amount of activated carbon is selected to be in the range of 0.1 weight percent to 10 weight percent, in some embodiments, the amount of activated carbon used to treat the material is selected to be in the range of 0.5 weight percent to 5 weight percent, and in some embodiments, the amount of activated carbon used to treat the material is selected to be in the range of 1 weight percent to 2.5 weight percent, where each weight percent is based on the total weight of the material, and the carbon used to treat the material is related to the second time of treatment with the activated carbon.

[0101] In some embodiments, the amount of the active section follows a monotonically decreasing function, i.e., the smaller the amount of activated carbon selected within the amount range described above, the longer the second time period selected in order to obtain a purified leach solution in the form of an aqueous solution comprising metal ions after the separation step.

[0102] An advantage of the purification method presented herein is that the emulsifiers and / or dispersing agents present in the provided leach mixture are at least partially adsorbed by the added activated carbon and these emulsifiers and / or dispersing agents can be extracted or separated, for example filtered out from the leach mixture together with the activated carbon in a separation step, thereby leaving a purified leach solution. The purified leach solution can be subjected to additional specific separation steps in order to isolate the specific metal ions of interest.

[0103] Such emulsifiers and / or dispersants present in the leaching mixture may be from the group consisting of Si, C, O, nanoparticles with a particle size < 500 nm, gel-like SiOx networks, polysiloxanes and derivatives, organic residues from previous pyrolysis of organic binders, and combinations thereof. In some cases, Si-containing surfactants are produced when the corresponding binder was not sufficiently pyrolyzed during a previous heat treatment of the material (such as, for example, the black mass).

[0104] Nanoparticles with a particle size of <500 nm can be, for example, SiO2, Cu, or intact CAM (cathode active material). Organic binders typically used in batteries include PVDF (polyvinylidene fluoride), SBR (styrene-butadiene), and any combination thereof. The gel-like SiOx network, polysiloxane, and organic residues themselves act as emulsifiers or dispersants, keeping the particles suspended / dispersed.

[0105] In some embodiments, the method comprises purifying a leachate solution of a material as 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, 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 (e.g., any water). In some embodiments, 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 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 combined 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 combined 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 combined 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, the 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.

[0107] In some embodiments, a substantially pure metal ion solution is a solution comprising a metal ion, a counterion, and a solvent; wherein the total weight of the metal ion and the counterion 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 a metal ion, a counterion, and a solvent; wherein the total weight of the metal ion and the counterion 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 a metal ion, a counterion, and a solvent; wherein the total weight of the metal ion and the counterion 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 a metal ion, a counterion, and a solvent; wherein the total weight of the metal ion and the counterion 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 a metal ion, a counterion, and a solvent; wherein the total weight of the metal ion and the counterion 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, counterions, and a solvent; wherein the combined weight of the metal ions and counterions is at least 99% by weight of the solution excluding the weight of the solvent.

[0108] 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.

[0109] 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.

[0110] Oxidants:

[0111] In some embodiments, the 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.

[0112] In some embodiments, the 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 acidic aqueous solution comprises an acid that is an oxidizing agent and an oxidizing agent that is not an acid. In some embodiments, the acidic aqueous solution comprises an acid that is not an oxidizing agent and an oxidizing agent that is an acid. In some embodiments, the acidic aqueous solution comprises an acid that is an oxidizing agent and an oxidizing agent that is an acid. In some embodiments, the 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.

[0113] Examples

[0114] The following examples are intended to be illustrative and are not meant to limit the scope of the present disclosure in any way.

[0115] abbreviation

[0116] %percentage

[0117] wt.-% weight percentage

[0118] ppm parts per million

[0119] Lithium

[0120] Nickel

[0121] Cobalt

[0122] Mn

[0123] Cu

[0124] Al

[0125] Fe

[0126] Phosphorus

[0127] F Fluorine

[0128] Calcium

[0129] C carbon

[0130] Si

[0131] Titanium

[0132] Potassium K

[0133] Mg

[0134] Na sodium

[0135] Zn

[0136] Black matter

[0137] For the examples provided below, the black material was obtained by mechanically crushing lithium-ion batteries and subsequently separating the black material as a fine powder from the other components of the lithium-ion batteries. The black material was obtained by a process involving the pyrolysis of battery waste. This material may contain small amounts of sulfur. The metals analyzed exist as oxidized compounds (such as MnO, CoO, NiO), as salts (such as LiF, LiO, LiOH, LiAlO2, Li2CO3), and / or as zero-oxidation state metals (such as nickel, cobalt, and copper). The carbon is elemental carbon, primarily in the form of graphite with some soot or coke.

[0138] The following table provides the corresponding composition of the black substance used in the following examples.

[0139] Table 1: Composition of the black substance used in examples 1, 2, 3, 4, 7 and 8, wherein in the table only elements contained with an amount equal to or greater than 0.01 wt.-% are listed. Each weight percentage (wt.-%) is relative to the total weight of the black substance used.

[0140]

[0141] Table 2: Composition of the black substance used in example 5, wherein in the table only elements contained with an amount greater than 0.01 wt.-% are listed. Each weight percentage (wt.-%) is relative to the total weight of the black substance used.

[0142]

[0143] Table 3: Composition of the black substance used in example 6, wherein in the table only elements contained with an amount greater than 0.01 wt.-% are listed. Each weight percentage (wt.-%) is relative to the total weight of the black substance used.

[0144]

[0145] Example 1

[0146] leaching

[0147] In this example, 50 g of a heat treated black substance obtained from battery scrap processing were suspended in deionized water to obtain an intermediate suspension and then heated to 95 °C. The intermediate suspension was then treated dropwise with an amount of H2SO4 until a pH was reached sufficient to leach valuable metals. The reaction mixture was stirred first under inert and then under aerobic conditions for a total time period of 5.5 h. In addition, an oxidizing agent was added to the reaction mixture during the leaching under aerobic conditions. The resulting leach mixture was stirred. After a first time period of 5 h of stirring, the leach mixture was treated with 2.5 g of analytical grade activated carbon powder, after which the heating was stopped and it was stirred for a second time period of 30 min. An activated carbon enriched leach mixture was obtained. The activated carbon enriched leach mixture was allowed to cool to 60 °C and then filtered off through a filter chute. In this way, a purified leach solution as filtrate and a dry filter cake can be obtained.

[0148] phase separation

[0149] After allowing the filtrate to sit overnight, 10 mL of kerosene was placed in the reaction vessel, which was then treated with 20 mL of the filtrate. The resulting two-phase system was shaken vigorously for 1 minute, after which the phases separated within 60 seconds. This same procedure was repeated 5 days later, after which the phases again separated within 60 seconds.

[0150] The time until phase separation occurs is hereinafter referred to as waiting time.

[0151] Example 2 (comparison)

[0152] leaching

[0153] In this example, 50 g of heat-treated black material obtained from battery waste processing was suspended in deionized water to obtain an intermediate suspension, which was then heated to 95°C. The intermediate suspension was then treated dropwise with a certain amount of H2SO4 until a pH sufficient to leach the valuable metals was reached. The reaction mixture was stirred first under inert conditions and then under aerobic conditions for a total period of 6 hours. Additionally, an oxidizing agent was added to the reaction mixture during the aerobic leaching. The suspension was cooled to 60°C and then filtered through a filter chute. In this way, a filtrate and a dry filter cake were obtained. The total organic carbon (TOC) content was determined to be 0.017% by weight, where each weight percentage is based on the total weight of the filtrate.

[0154] phase separation

[0155] After allowing the filtrate to stand overnight, 10 mL of kerosene was placed in the reaction vessel, which was then treated with 20 mL of the filtrate. The resulting two-phase system was shaken vigorously for 1 min. No phase separation occurred.

[0156] Example 3

[0157] leaching

[0158] In this example, 50 g of heat-treated black material obtained from battery waste processing was suspended in deionized water to obtain an intermediate suspension, which was then heated to 95°C. The intermediate suspension was then treated dropwise with a certain amount of H2SO4 until a pH sufficient to leach valuable metals was reached. The reaction mixture was stirred first under inert conditions and then under aerobic conditions for a total period of 5 hours. Additionally, an oxidizing agent was added to the reaction mixture during the aerobic leaching process. The resulting leach mixture was stirred. After a first stirring period of 2 hours, the leach mixture was treated with 0.1 g of 12x20 mesh granular activated carbon, followed by a second stirring period of 3 hours. This yielded an activated carbon-rich leach mixture. The activated carbon-rich leach mixture was cooled to 60°C and then filtered through a filter chute. This yielded a filtrate and a dry filter cake. The total organic carbon (TOC) content was determined to be 0.013 wt%, where each weight percentage is based on the total weight of the filtrate.

[0159] phase separation

[0160] After allowing the filtrate to stand overnight, 10 mL of kerosene was placed in the reaction vessel, which was then treated with 20 mL of the filtrate. The resulting two-phase system was shaken vigorously for 1 min, after which almost complete phase separation occurred after 90 s.

[0161] Example 4

[0162] leaching

[0163] In this example, 75 g of heat-treated black material obtained from battery waste processing was suspended in deionized water to obtain an intermediate suspension, which was then heated to 95°C. The intermediate suspension was then treated dropwise with a certain amount of H2SO4 until a pH sufficient to leach valuable metals was reached. The reaction mixture was stirred first under inert conditions and then under aerobic conditions for a total period of 6 hours. Additionally, an oxidizing agent was added to the reaction mixture during the aerobic leaching process. The resulting leach mixture was stirred. After a first stirring period of 3 hours, the leach mixture was treated with 0.38 g of 12x40 mesh granular activated carbon to obtain an activated carbon-rich leach mixture, after which stirring was continued for a second period of 3 hours. The leach mixture was cooled to 60°C and then filtered through a filter chute. In this manner, a filtrate and a dry filter cake were obtained. The total organic carbon (TOC) content was determined to be 0.015 wt%, where each weight percentage is based on the total weight of the filtrate.

[0164] phase separation

[0165] After allowing the filtrate to stand overnight, 10 mL of kerosene was placed in the reaction vessel, which was then treated with 20 mL of the filtrate. The resulting two-phase system was vigorously shaken for 1 min. The resulting two-phase system was vigorously shaken for 1 min, and almost complete phase separation occurred within 90 s.

[0166] Example 5

[0167] leaching

[0168] In this example, 75 g of black material obtained from battery waste processing was suspended in deionized water to obtain an intermediate suspension, which was then heated to 95°C. The intermediate suspension was then treated dropwise with a certain amount of H2SO4 until a pH sufficient to leach valuable metals was reached. The reaction mixture was stirred first under inert conditions and then under aerobic conditions for a total period of 5 hours. Additionally, an oxidizing agent was added to the reaction mixture during the aerobic leaching process. The resulting leach mixture was stirred. After a first stirring period of 2 hours, the leach mixture was treated with 0.75 g of 12x40 mesh granular activated carbon to obtain an activated carbon-rich leach mixture, after which stirring was continued for a second period of 3 hours. The leach mixture was cooled to 60°C and then filtered through a filter chute. In this manner, a filtrate and a dry filter cake were obtained. The total organic carbon (TOC) content was determined to be 0.0036 wt%, where each weight percentage is based on the total weight of the filtrate.

[0169] phase separation

[0170] After allowing the filtrate to stand overnight, 10 mL of kerosene was placed in the reaction vessel, which was then treated with 20 mL of the filtrate. The resulting two-phase system was vigorously shaken for 1 min. The resulting two-phase system was vigorously shaken for 1 min, after which phase separation occurred within 90 s.

[0171] Example 6

[0172] leaching

[0173] In this example, 75 g of black material obtained from battery waste processing was suspended in deionized water to obtain an intermediate suspension, which was then heated to 95°C. The intermediate suspension was then treated dropwise with a certain amount of H2SO4 until a pH sufficient to leach valuable metals was reached. The reaction mixture was stirred first under inert conditions and then under aerobic conditions for a total period of 6 hours. Additionally, an oxidizing agent was added to the reaction mixture during the aerobic leaching process. The resulting leach mixture was stirred. After a first stirring period of 2 hours, the reaction mixture was treated with 0.75 g of 12x40 mesh granular activated carbon to obtain an activated carbon-rich leach mixture, after which stirring was continued for a second period of 4 hours. The activated carbon-rich leach mixture was cooled to 60°C and then filtered through a filter chute. In this manner, a filtrate and a dry filter cake were obtained. The total organic carbon (TOC) content was determined to be 0.028 wt%, where each weight percentage is based on the total weight of the filtrate.

[0174] phase separation

[0175] After allowing the filtrate to stand overnight, 10 mL of kerosene was placed in the reaction vessel, which was then treated with 20 mL of the filtrate. The resulting two-phase system was shaken vigorously for 1 min, after which the phases separated within 60 s.

[0176] Example 7

[0177] leaching

[0178] 50 g of heat-treated black material obtained from battery waste processing was suspended in deionized water to obtain an intermediate suspension, which was then heated to 95°C. The intermediate suspension was then treated dropwise with a certain amount of H2SO4 until a pH sufficient to leach the valuable metals was reached. The reaction mixture was stirred first under inert conditions and then under aerobic conditions for a total period of 6 hours and 30 minutes. Additionally, an oxidizing agent was added to the reaction mixture during the aerobic leaching period. The resulting leach mixture was stirred. After a first stirring period of 6 hours, the leach mixture was treated with 0.5 g of 12x40 mesh granular activated carbon to obtain an activated carbon-rich leach mixture, after which stirring was continued for a second period of 30 minutes. The activated carbon-rich leach mixture was cooled to 60°C and then filtered through a filter chute. In this way, a filtrate and a dry filter cake were obtained.

[0179] phase separation

[0180] After allowing the filtrate to stand overnight, 10 mL of kerosene was placed in the reaction vessel, which was then treated with 20 mL of the filtrate. The resulting two-phase system was shaken vigorously for 1 min, after which no phase separation was observed.

[0181] Example 8

[0182] leaching

[0183] 50 g of heat-treated black material obtained from battery waste processing was suspended in deionized water to obtain an intermediate suspension, which was then heated to 95°C. The intermediate suspension was then treated dropwise with a certain amount of H2SO4 until a pH sufficient to leach the valuable metals was reached. The reaction mixture was stirred first under inert conditions and then under aerobic conditions for a total period of 5 hours and 30 minutes. Additionally, an oxidizing agent was added to the reaction mixture during the aerobic leaching period. The resulting leach mixture was stirred. After a first stirring period of 5 hours, the leach mixture was treated with 2.5 g of 12x40 mesh granular activated carbon to obtain an activated carbon-rich leach mixture, after which stirring was continued for a second period of 30 minutes. The activated carbon-rich leach mixture was cooled to 60°C and then filtered through a filter chute. In this way, a filtrate and a dry filter cake were obtained.

[0184] phase separation

[0185] After allowing the filtrate to stand overnight, 10 mL of kerosene was placed in the reaction vessel, which was then treated with 20 mL of the filtrate. The resulting two-phase system was shaken vigorously for 1 min, after which the phases separated within 2 min.

[0186] Comparing Examples 1, 4, 5, 6 and 8 with Example 2, it is appreciated that treating the leach mixture with activated carbon can result in enhanced leaching performance, such as, for example, improved phase separation associated with better separation of metal ions.

[0187] Comparing Examples 4, 5, and 6 with Example 2, it is recognized that better phase separation can be achieved in Examples 4, 5, and 6 compared to Example 2, and thus the TOC content is not necessarily reduced by the addition of activated carbon. In the method according to the present invention, when activated carbon is added, the TOC content is not substantially reduced or remains substantially unchanged.

[0188] Comparing Example 4 with Example 8, it is recognized that when treating a leach mixture with activated carbon, the amount of activated carbon used is related to the second period of time for stirring after adding the activated carbon. The higher the amount of activated carbon, the shorter the second period of time must be in order to achieve phase separation, i.e., to achieve complete phase separation and / or to achieve phase separation within a tolerable waiting time. For example, the tolerable waiting time until phase separation occurs can be set to 2 minutes. Examples 4 and 8 show that such a tolerable waiting time can be maintained when using 0.5% by weight of activated carbon and a second period of 3 hours, and when using 5% by weight of activated carbon and a second period of 0.5 hours (each weight percentage (wt%) is based on the total weight of the material treated with the activated carbon).

[0189] Comparing Example 5 and Example 6, it is recognized that for the same amount of activated carbon above the minimum amount, if a longer second time period is selected, the waiting time can be reduced. Although the waiting time is 90 seconds in Example 5, where the amount of activated carbon is 1 wt % and the second time period is 3 hours, the waiting time is only 60 seconds in Example 6, where the amount of activated carbon is the same but the second time period is 4 hours.

[0190] Comparing Example 5 with Example 6, it is apparent that, when the same amount of activated carbon is used, phase separation is achieved more rapidly when the second period of time for stirring after the addition of the activated carbon is longer. It should be noted that the specific composition of the black substance (material) has been shown to have no effect on the observed dependence of the second period of time on the waiting time, at least on the observed trend dependence.

[0191] Comparing Examples 3, 4, and 5, it is recognized that when treating a leachate mixture with activated carbon, in order to obtain satisfactory phase separation within a given permissible waiting time, the amount of activated carbon used must be greater than or equal to a minimum amount. If the permissible waiting time is, for example, 2 minutes (as selected in Examples 3, 4, and 5 of the present invention), the minimum amount of activated carbon must be within the range of 0.5% by weight, each weight percentage (wt%) being based on the total weight of the material treated with the activated carbon.

[0192] Comparing Example 1 with Example 8, it is recognized that when treating the leach mixture with activated carbon, at least similar results are achieved with activated carbon powder and granular activated carbon.

[0193] Comparing Example 7 with Example 8, it is again recognized that when treating the leach mixture with activated carbon, a minimum amount of activated carbon must be used for a given second period of time for stirring after adding the activated carbon.

Claims

1. A method for providing a purified leach solution of a material comprising one or more metals in a zero oxidation state and one or more selected from metal oxides, metal hydroxides, metal carbonates, and combinations thereof, wherein the method comprises: contacting the material with an acidic aqueous solution having a pH of less than 6 and comprising one or more acids at a temperature in the range of 20°C to 110°C for a total period of time in the range of 20 minutes to 10 hours, thereby forming a leach mixture during the contacting, treating the leach mixture with activated carbon after stirring the leach mixture for a first period of time during the total period of time, and thereafter continuing the stirring for a second period of time during the total period of time to obtain a leach mixture enriched in activated carbon, The activated carbon-rich leachate mixture is subjected to a separation process to obtain a residue and a purified leachate solution as a supernatant in the form of an aqueous solution comprising metal ions.

2. The method according to claim 1, wherein Contacting the material with the acidic aqueous solution at a temperature in the range of 20°C to 110°C for a total time period in the range of 20 minutes to 10 hours comprises: The material was suspended in deionized water to obtain an intermediate suspension, The intermediate suspension is then treated with an amount of one or more of these acids to obtain a reaction mixture.

3. The method according to claim 2, further comprising: The reaction mixture is stirred first under an inert gas and then under aerobic conditions, and One or more oxidizing agents and / or One or more reducing agents are added to the reaction mixture.

4. The method according to any one of claims 1 to 3, wherein The separation method for obtaining the residue and the purified leachate solution as a supernatant in the form of an aqueous solution containing metal ions is selected from one or more of filtration, sedimentation, centrifugation and a combination thereof.

5. A method according to any one of the preceding claims, wherein The activated carbon is selected from activated carbon powder and granular activated carbon.

6. The method according to claim 5, wherein: The amount of activated carbon used to treat the leach mixture is selected to be in an amount ranging from 0.1 weight percent to 10 weight percent, wherein each weight percent is based on the total weight of the material.

7. The method according to claim 6, wherein: The amount of the activated carbon used to treat the leach mixture is related to the second time period by a monotonically decreasing function within the amount range.

8. A method according to any one of the preceding claims, wherein The second time period ranges from 20 minutes to 6 hours, and the first time period and the second time period are summed up to form the total time period.

9. A method according to any one of the preceding claims, wherein The material is a lithium-ion battery material comprising one or more selected from a black substance, a cathode active material, a cathode, a cathode active material precursor, and combinations thereof, and / or wherein the material comprises one or more selected from lithium, nickel, cobalt, manganese, and combinations thereof.

10. A method according to any one of the preceding claims, wherein The one or more metals in zero oxidation state are selected from lithium, nickel, cobalt, copper, aluminum, iron, manganese, rare earth metals and combinations thereof, and / or wherein the metal carbonates are selected from lithium carbonates, and / or wherein the metal oxides are selected from nickel oxides, cobalt oxides, copper oxides, aluminum oxides, iron oxides, manganese oxides, rare earth oxides and combinations thereof, and / or wherein the metal hydroxides are selected from nickel hydroxide, cobalt hydroxide, copper hydroxide, aluminum hydroxide, iron hydroxide, manganese hydroxide, lithium hydroxide, rare earth hydroxide, alkaline earth metal hydroxide and combinations thereof.

11. A method according to any one of the preceding claims, wherein The emulsifier and / or dispersing agent present in the formed leach mixture is at least partially adsorbed by the added activated carbon and separated from the leach mixture together with the activated carbon during the separation process, leaving the purified leach solution.

12. The method according to claim 11, wherein The emulsifiers and / or dispersing agents present in the leaching mixture are from the group consisting of Si, C, O, nanoparticles with a particle size < 500 nm, gel-like SiOx networks, polysiloxanes and derivatives, organic residues from previous pyrolysis of organic binders and combinations thereof.

13. A method comprising: Processing a battery material according to any one of claims 1 to 12 to obtain an aqueous solution containing 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.

14. The method according to claim 13, wherein Separating the metal ions includes one or more of solid / liquid separation, extraction, precipitation, crystallization, and combinations thereof.

15. A method comprising: mechanically pulverizing 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 to obtain a black substance as a material, and The black substance is subjected to a method according to any one of claims 1 to 12, the method optionally further comprising subjecting the black substance to a heat treatment step before subjecting the black substance to the method according to any one of claims 1 to 12.

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