Carbonylation of lithium ion battery materials

Abstract

This invention relates to the recovery of nickel and cobalt from lithium ion battery materials comprising nickel, cobalt, and manganese, such as cathode active materials (CAM) and / or black mass (BM) derived from battery materials.

Description

[0001] BASF SE B25.185P-WO

[0002] 67056 Ludwigshafen am Rhein 09.12.2025 / lg / np / jl

[0003] Carbonylation of lithium ion battery materials

[0004] Field of the invention

[0005] This invention relates to the recovery of nickel and cobalt from lithium ion battery materials comprising nickel, cobalt, and manganese, such as cathode active materials (CAM) and / or black mass (BM) derived from battery materials.

[0006] Background

[0007] Lithium ion battery materials contain valuable metals such as lithium, aluminum, copper, nickel, cobalt, and / or manganese that can be recovered and recycled to conserve natural resources. Processes for recycling lithium ion battery materials generally comprise mechanical comminution of lithium ion batteries, lithium ion battery waste, lithium ion battery production scrap, lithium ion cell production scrap, or lithium ion cathode active material to obtain black mass, a particulate material comprising the active components of the battery electrodes such as graphite and cathode active material, which may also include impurities from the casing, electrode foils, cables, separator, and electrolyte. The black mass then is further processed to recover the valuable metals, for instance, by hydrometallurgical treatment.

[0008] US 2023 / 155202 A1 discloses a process for the recovery of transition metals from battery materials comprising (0.1 ) providing a battery material which comprises oxidic nickel and / or cobalt compounds, (1.1 ) heating the battery material above 350° C. to yield a reduced material which contains nickel and / or cobalt in elemental form, (2.1 ) carbonylating the reduced material with carbon monoxide optionally in the presence of a reactive gas to yield a solid carbonylation residue and a volatile carbonyl which comprises nickel and / or cobalt carbonyl containing compounds, and (3.1 ) separating the volatile carbonyl from the solid carbonylation residue by evaporation. US 2024 / 055681 A1 discloses a process for recovering materials from an energy storage device electrode, comprising reducing an electrode active material mixture to form a reduced mixture, wherein the electrode active material mixture comprises a nickel oxide, a cobalt oxide, and a lithium material selected from the group consisting of a lithium salt, a lithium oxide and combinations thereof; performing a first carbonylation and a subsequent first decomposition on the reduced mixture to isolate a nickel product comprising nickel metal form a first carbonylated material; and performing a second decomposition on the first carbonylated material to isolate a cobalt product comprising cobalt metal form a residue material.

[0009] US 2024 / 344175 A1 discloses a process for a process for recovering one or more metals from black mass. The process includes separating lithium from the black mass such that a lithium-depleted black mass is obtained, and converting at least a portion of the lithium-depleted black mass, via a reactive process, to at least a non-lithium elemental metal. For instance, the lithium-depleted black mass is contacted with gaseous carbon monoxide to produce a metal carbonyl material-comprising material, e.g., a material comprising nickel carbonyl and cobalt carbonyl.

[0010] US 2021 / 269894 A1 provides a method for recovering nickel and cobalt, the method comprising a first step of heat-treating lithium nickel cobalt aluminum oxide to produce a mixture; a second step of water-washing the mixture produced in the first step to obtain a residue; and a third step of heat-treating the residue obtained in the second step. The heat-treatment of the residue includes primary and secondary heat-treatments performed respectively in first and second reactors connected to each other via a guide line. The primary heat treatment includes heat-treating the residue at 50°C to 200°C in the first reactor having a reducing atmosphere containing carbon dioxide, carbon monoxide and a mixture thereof, to produce a cobalt metal powder and a nickel-containing gas from the residue. The nickel-containing gas produced in the primary heat treatment is transferred from the first reactor to the second reactor via the guide line maintained at a temperature of 70°C to 90°C. In the secondary heat treatment, a heat treatment is performed in the second reactor having an atmosphere of the nickel-containing gas transferred from the first reactor at 150°C to 350°C to produce nickel.

[0011] It is an object of the present disclosure to provide an improved recycling process for lithium ion battery materials comprising nickel, cobalt, and manganese, such as cathode active materials (CAM) and / or black mass (BM) derived from lithium ion battery materials.

[0012] Summary of the invention

[0013] The present disclosure provides a process for the recovery of nickel and cobalt from lithium ion battery materials comprising nickel, cobalt, and manganese, such as cathode active materials (CAM) and / or black mass (BM) derived from battery materials.

[0014] CAM and / or BM first are subjected to a reductive heat treatment under H2 to reduce Ni2+and Co2+present in the CAM and / or BM to Ni and Co, respectively. The reduced CAM and / or BM then is washed with water to remove lithium salts. Sulfur is added to the reduced and Li-depleted CAM and / or BM, and the mixture is reacted with carbon monoxide, or a mixture of carbon monoxide and nitrogen monoxide. Nickel tetracarbonyl and dicobalt octacarbonyl or nitrosyl cobalt tricarbonyl nitrosyl are produced, as well as a residue depleted of nickel and cobalt.

[0015] Detailed description

[0016] The present disclosure provides a process for the recovery of nickel and cobalt from lithium ion battery materials comprising nickel, cobalt, and manganese, such as cathode active materials (CAM) and / or black mass (BM), comprising the steps of a) reducing the CAM and / or BM with hydrogen to obtain reduced CAM and / or BM, b) washing the reduced CAM and / or BM with water to remove water-soluble lithium salts and obtain reduced and lithium-depleted CAM and / or BM, c) adding sulfur to the reduced and lithium-depleted CAM and / or BM, and d) reacting the mixture of reduced and lithium-depleted CAM and / or BM and sulfur with carbon monoxide to obtain nickel tetracarbonyl, dicobalt octacarbonyl, and a residue depleted of nickel and cobalt; or reacting the mixture of reduced and lithium-depleted CAM and / or BM and sulfur with a mixture of carbon monoxide and nitrogen monoxide to obtain nickel tetracarbonyl, cobalt tricarbonyl nitrosyl, and a residue depleted of nickel and cobalt.

[0017] In the present disclosure, the term “black mass” (BM) refers to materials derived from, for example, a lithium ion battery, lithium ion battery waste, lithium ion battery production scrap, lithium ion cell production scrap, lithium ion cathode active material, and / or combinations thereof by mechanical processes such as mechanical comminution. For example, black mass may be derived from battery scrap by mechanically treating the battery scrap to obtain the active components of the electrodes such as graphite and cathode active material and may include impurities from the casing, electrode foils, cables, separator, and electrolyte. In some examples, the battery scrap may be subjected to a heat treatment to pyrolyze organic (e.g., electrolyte) and polymeric (e.g., separator and binder) materials. Such a heat treatment may be performed before or after mechanical comminution of the battery material.

[0018] Lithium ion batteries can comprise a variety of different cathode materials, for instance, lithium cobalt oxide (LiCoCh), lithium manganese oxide (LiMn2O4 spinel, or Li2MnO3-based lithium-rich layered materials, LMR-NMC), lithium nickel manganese cobalt oxide (LiNiMnCoCh or NMC) and lithium nickel cobalt aluminum oxides (LiNixCoyAIzCh with x + y + z = 1 or NCA).

[0019] Lithium ion batteries may be disassembled, after discharging and optionally drying them, punched, milled, for example in a hammer mill, and / or shredded, for example in an industrial shredder. From this kind of mechanical processing the active material of the battery electrodes may be obtained. A light fraction such as housing parts made from organic plastics and aluminum foil or copper foil may be removed, for example, in a forced stream of gas, air separation or classification.

[0020] Battery scraps may stem from, e.g., used batteries or from production waste such as off-spec material. In some embodiments a battery material is obtained from mechanically treated battery scraps, for example from battery scraps treated in a hammer mill or in an industrial shredder. Such material may have an average particle diameter (D50) ranging from 1 pm to 1 cm, such as from 1 pm to 500 pm, for example, from 3 to 250 pm.

[0021] Larger parts of the battery scrap like the housings, the wiring and the electrode carrier films may be separated mechanically such that the corresponding materials may be excluded from the battery material that is employed in the process.

[0022] Mechanically treated battery scrap may be subjected to a solvent treatment to dissolve and separate polymeric binders used to bind the transition metal oxides to current collector films, or, e.g., to bind graphite to current collector films. Suitable solvents are N-methylpyrrolidone, N,N-dimethyl-formamide, N,N- dimethylacetamide, N-ethylpyrrolidone, and dimethylsulfoxide, in pure form, as mixtures of at least two of the foregoing, or as a mixture with 1 % to 99 % by weight of water.

[0023] Mechanically treated battery scrap may be subjected to a heat treatment in a wide range of temperatures under different atmospheres. The temperature range is usually in the range of 100°C to 900°C. Lower temperatures below 300°C may serve to evaporate residual solvents from the battery electrolyte, at higher temperatures the binder polymers may decompose while at temperatures above 400°C the composition of the inorganic materials may change as some transition metal oxides may become reduced either by the carbon contained in the scrap material or by introducing reductive gases. In some embodiments, a reduction of lithium metal oxides may be avoided by keeping the temperature below 400°C and / or by removing carbonaceous materials before the heat treatment.

[0024] In some embodiments, the battery material comprises at least one chosen from lithiated nickel cobalt manganese oxide, lithiated nickel cobalt aluminum oxide, lithium ion battery scrap, black mass derived from a lithium ion battery, and combinations there.

[0025] In some embodiments, the battery material comprises lithiated nickel cobalt manganese oxide of formula Lii+x(NiaCobMncM1d)i-xO2, wherein M1 is chosen from Mg, Ca, Ba, Al, Ti, Zr, Zn, Mo, V and Fe, zero < x < 0.2, 0.1 < a < 0.95, zero < b < 0.9 (such as 0.05 < b < 0.5), zero < c < 0.6, zero < d < 0.1 , and a + b + c + d = 1 . Exemplary lithiated nickel cobalt manganese oxides include Li(i+x)[Nio.33Coo.33Mno.33](i-x)02, Li(i+X)[Nio.5Coo.2Mno.3](i-x)02, Li(i+X)[Nio.6Coo.2Mno.2](i-x)02, Li(i+X)[Nio.7Coo.2Mno.3](i-x)02, Li(i+x)[Nio.8Coo.iMno.i](i-x)02 each with x as defined above, and Li[Nio.85COo.13Alo.02]02.

[0026] In some embodiments, the battery material comprises lithiated nickel-cobalt aluminum oxides of formula Li[NihCo lj]O2+r, wherein h ranges from 0.8 to 0.9, i ranges from 0.1 to 0.3, j ranges from 0.01 to 0.10, and r ranges from zero to 0.4.

[0027] In some embodiments, the battery material comprises nickel, cobalt, manganese, copper, aluminum, iron, phosphorus, or combinations thereof.

[0028] In some embodiments, the battery material comprises LixMO2 wherein x is an integer greater than or equal to one, and M is chosen from metals, transition metals, rare earth metals, and combinations thereof.

[0029] In the present disclosure, the term "cathode active material" (CAM) means a material being present in a cathode of a lithium ion battery as the active component. The CAM may either be an off-spec material from CAM production, a material retrieved from an off-spec cathode, or a CAM material retrieved from a lithium ion battery. The CAM is either a layered oxide (such as lithium cobalt oxide) or a spinel (such as lithium manganese oxide). Examples of cathode active materials include lithium cobalt oxide (LiCoCh), lithium manganese oxide (LiM^CU), and lithium nickel manganese cobalt oxide (LiNiMnCoCh or NMC).

[0030] In some embodiments, the cathode active material comprises one or more chosen from lithiated nickel cobalt manganese oxide and lithiated nickel cobalt aluminum oxide. In some embodiments, the cathode active material comprises lithiated nickel cobalt manganese oxide of formula Lii+x(NiaCobMncM1 d)i-xO2, wherein M1 is chosen from Mg, Ca, Ba, Al, Ti, Zr, Zn, Mo, V and Fe, zero < x < 0.2, 0.1 < a < 0.95, zero < b < 0.9 (such as 0.05 < b < 0.5), zero < c < 0.6, zero < d < 0.1 , and a + b + c + d = 1. Exemplary lithiated nickel cobalt manganese oxides include Li(i+x)[Nio.33Coo.33Mno.33](i-x)02, Li(i+x)[Nio.5Coo.2Mno.3](i-x)02, Li(i+X)[Nio.6Coo.2Mno.2](i-x)02, Li(i+X)[Nio.7Coo.2Mno.3](i-x)02, Li(i+x)[Nio.8Coo.iMno.i](i-x)02 each with x as defined above, and Li[Nio.85COo.13Alo.02]02.

[0031] In some embodiments, the cathode active material comprises lithiated nickelcobalt aluminum oxides of formula Li[NihCo lj]O2+r, wherein h ranges from 0.8 to 0.9, i ranges from 0.1 to 0.3, j ranges from 0.01 to 0.10, and r ranges from zero to 0.4.

[0032] In some embodiments, the cathode active material comprises lithiated manganese oxides of formula Li(i+x)Mn2-x-y-zMyMzO4, wherein x ranges from zero to 0.2; y+z ranges from zero to 0.1 ; and M’ is chosen from Al, Mg, Fe, Ti, V, Zr and Zn.

[0033] In some embodiments, the cathode active material comprises a compound of formula xLi(i+i / 3)M(2 / 3)O2 * yLiMCh * zLiM’Ch, wherein M comprises at least one metal of Mn, Ni, Co of oxidation state +4 , M’ is at least one transition metal, and 0 < x < 1 , 0 < y < 1 , 0 < z < 1 and x + y + z = 1 . The process of the present disclosure comprises the steps of a) reducing the CAM and / or BM with hydrogen to obtain reduced CAM and / or BM, b) washing the reduced CAM and / or BM with water to remove water-soluble lithium salts and obtain reduced and lithium-depleted CAM and / or BM, c) adding sulfur to the reduced and lithium-depleted CAM and / or BM, and d) reacting the mixture of reduced and lithium-depleted CAM and / or BM and sulfur with carbon monoxide to obtain nickel tetracarbonyl, dicobalt octacarbonyl, and a residue depleted of nickel and cobalt; or reacting the mixture of reduced and lithium-depleted CAM and / or BM and sulfur with a mixture of carbon monoxide and nitrogen monoxide to obtain nickel tetracarbonyl, cobalt tricarbonyl nitrosyl, and a residue depleted of nickel and cobalt.

[0034] In step a), CAM and / or BM is subjected to a reductive heat treatment under H2 to reduce Ni2+and Co2+to Ni and Co, respectively. A temperature is chosen which is sufficient for the quantitative reduction of Ni and Co. In some embodiments of the process, a temperature in the range of from 350°C to 500°C is chosen, e.g., 450°C. In some embodiments of the process, reaction time is in the range of from 0.5 hours to 2 hours, e.g., 1 hour. In some embodiments of the process, hydrogen flow rate is in the range of from 10 to 50 Nl / hr, e.g., 20 Nl / hr.

[0035] In step b), the reduced CAM and / or BM is washed with water to remove water- soluble lithium salts and obtain reduced and lithium-depleted CAM and / or BM. In some embodiments of the process, mass ratio of water to reduced CAM and / or BM is in the range of from 1 :2 to 2:1. In some embodiments of the process, washing is performed by dispersing reduced CAM and / or BM in water using a stirrer or mixer, and subsequently recovering the reduced and lithium- depleted CAM and / or BM by filtration. In some embodiments of the process, washing is repeated several times. The reduced and lithium-depleted CAM and / or BM is dried before performing the next process step c).

[0036] In step c), sulfur is added to the reduced and lithium-depleted CAM and / or BM.

[0037] In some embodiments of the process, sulfur is added in an amount of from 0.1 wt% to 5.0 wt%, for instance, from 0.5 wt% to 3.0 wt%, e.g., from 0.75 wt% to 1 .5 wt%, relative to the total weight of the reduced and lithium-depleted CAM and / or BM. In some embodiments of the process, the reduced and lithium- depleted CAM and / or BM and sulfur are thoroughly mixed to obtain a uniform mixture.

[0038] In step d), the mixture of reduced and lithium-depleted CAM and / or BM and sulfur is reacted with carbon monoxide to obtain nickel tetracarbonyl, dicobalt octacarbonyl, and a residue depleted of nickel and cobalt, or reacted with a mixture of carbon monoxide and nitrogen monoxide to obtain nickel tetracarbonyl, cobalt tricarbonyl nitrosyl, and a residue depleted of nickel and cobalt.

[0039] To recover nickel and cobalt from the mixture, pressures in the range of from 10 bar to 200 bar, e.g., from 20 bar to 120 bar, for instance, from 30 bar to 80 bar, may be used. At low pressures, formation of nickel tetracarbonyl and dicobalt octacarbonyl or cobalt tricarbonyl nitrosyl proceeds slower.

[0040] Temperatures in the range of from 20°C to 250°C, e.g., from 60°C to 200°C, or from 120°C to 160°C may be used in the process of the present disclosure. It has been found that the formation of nickel tetracarbonyl and dicobalt octacarbonyl or cobalt tricarbonyl nitrosyl proceeds very slowly at temperatures below 80°C, so that it is preferred to use higher temperatures.

[0041] In some embodiments, the reaction time is in the range of from 1 hour to 120 hours, e.g., from 8 hours to 48 hours, for instance, from 20 hours to 40 hours.

[0042] In some embodiments of the process, the mixture of reduced and lithium- depleted CAM and / or BM and sulfur is reacted with carbon monoxide to recover nickel and cobalt in the form of a carbonyl complex, i.e., nickel tetracarbonyl and dicobalt octacarbonyl. In some embodiments of the process, a mixture of carbon monoxide and nitrogen monoxide is used to recover nickel and cobalt in the form of nickel tetracarbonyl and cobalt tricarbonyl nitrosyl. The mixture of carbon monoxide and nitrogen monoxide comprises from 97.5 to 99.9 vol% carbon monoxide and from 0.1 to 2.5 vol% nitrogen monoxide. In some embodiments of the process, the mixture of carbon monoxide and nitrogen monoxide comprises from 98 to 99.98 vol% carbon monoxide and from 0.2 to 2.0 vol% nitrogen monoxide. In some embodiments of the process, the mixture of carbon monoxide and nitrogen monoxide comprises from 98.5 to 99.7 vol% carbon monoxide and from 0.3 to 1 .5 vol% nitrogen monoxide.

[0043] In a particular embodiment of the process, the mixture of reduced and lithium- depleted CAM and / or BM and sulfur is reacted with a gas mixture containing 99.5 vol% carbon monoxide and 0.5 vol% nitrogen monoxide at a pressure of 30 bar to 120 bar and at a temperature of 120°C to 160°C, for a time period of 20 hrs to 44 hrs.

[0044] The nickel tetracarbonyl and cobalt tricarbonyl nitrosyl formed are swept from the reactor by the gas flow and can be recovered from the gas stream, e.g., by condensation.

[0045] According to literature, the production of Co2(CO)s requires gas pressures of about 300 bar. We have found that significant cobalt carbonylation rates can be achieved under much milder conditions when a mixture of reduced and lithium- depleted CAM and / or BM and sulfur is used as starting material and NO is added to produce Co(CO)3NO. The process of the present disclosure allows for recovering both nickel and cobalt from CAM and / or BM comprising nickel, cobalt, and manganese.

[0046] Examples

[0047] The carbonylation experiments were carried out in an autoclave. 7 g of the solid feedstock were filled into two small containers (3.5 g each) consisting of sintered steel with 60 pm pore size, which were mounted to the lid of the autoclave. The set-up allowed for the following parameter ranges: T = room temperature - 200 °C, p = 1 - 200 bar, and a flow rate between 5 and 20 NL / h. Duration of carbonylation was varied between 8 hours and 72 hours. In a typical experiment, the gas streams would be pre-heated before entering the autoclave via an inlet and leaving it via an outlet.

[0048] Feedstock

[0049] Experiments were conducted with CAM and / or BM that had been subjected to a reductive heat treatment under H2 at a temperature of 450°C for 1 hour to reduce Ni2+and Co2+to Ni and Co, respectively, and subsequently had been washed with water to remove water-soluble lithium salts. The composition of the feedstock is shown in Table 1 .

[0050] Sample Preparation

[0051] The feedstock was first dried at T = 105 °C and p = 5 mbar for 2 h and then comminuted by grinding with mortar and pestle.

[0052] Yield Determination

[0053] The carbonylation yields of the respective metals of interest (Ni / Co) were calculated based on the amount of metal removed from the starting material during the experiment. To this end, ICP measurements were performed on the remnant solid.

[0054] Table 1 Feedstock composition and phases identified by XRD.

[0055] In the experiments, the fundamental reaction parameters (temperature, pressure, and time) were varied to investigate their influence on the yield of Ni(CO)4 and Co2(CO)s or Co(CO)3NO, respectively. The results are shown in Table 2. All experiments were carried out at a flow rate of 5 NL / h.

[0056] Table 2 Reaction parameters and yields of carbonylation experiments

[0057] * Comparative example

Claims

BASF SE B25.185P-WO67056 Ludwigshafen am Rhein 09.12.2025 / lg / np / jlClaims1. A process for the recovery of nickel and cobalt from cathode active materials (CAM) and / or black mass (BM) derived from lithium ion battery materials comprising nickel, cobalt, and manganese, comprising the steps of a) reductive heat treatment of the CAM and / or BM with hydrogen to obtain reduced CAM and / or BM, b) washing the reduced CAM and / or BM with water to remove water- soluble lithium salts and obtain reduced and lithium-depleted CAM and / or BM, c) adding sulfur to the reduced and lithium-depleted CAM and / or BM, and d) reacting the mixture of reduced and lithium-depleted CAM and / or BM and sulfur with carbon monoxide to obtain nickel tetracarbonyl, dicobalt octacarbonyl, and a residue depleted of nickel and cobalt; or reacting the mixture of reduced and lithium-depleted CAM and / or BM and sulfur with a mixture of carbon monoxide and nitrogen monoxide to obtain nickel tetracarbonyl, cobalt tricarbonyl nitrosyl, and a residue depleted of nickel and cobalt.

2. The process of claim 1 , wherein in step a) CAM and / or BM is subjected to a reductive heat treatment under H2 at a temperature in the range of from 350°C to 500°C for a reaction time in the range of from 0.5 hours to 2 hours to reduce Ni2+and Co2+present in the CAM and / or BM to Ni° and3. The process of claim 1 or 2, wherein in step b) the mass ratio of water to reduced CAM and / or BM is in the range of from 1 :2 to 2: 1 .

4. The process of any one of claims 1 to 3, wherein in step c), sulfur is added to the reduced and lithium-depleted CAM and / or BM in an amount of from 0.1 wt% to 5.0 wt%, relative to the total weight of the reduced and lithium- depleted CAM and / or BM.

5. The process of any one of claims 1 to 4, wherein in step d), the mixture of reduced and lithium-depleted CAM and / or BM and sulfur is reacted with carbon monoxide to obtain nickel tetracarbonyl, dicobalt octacarbonyl, and a residue depleted of nickel and cobalt.

6. The process of any one of claims 1 to 4, wherein in step d), the mixture of reduced and lithium-depleted CAM and / or BM and sulfur is reacted with a mixture of carbon monoxide and nitrogen monoxide to obtain nickel tetracarbonyl, cobalt tricarbonyl nitrosyl, and a residue depleted of nickel and cobalt.

7. The process of any one of claims 1 to 6, wherein gas pressure in step d) is in the range of from 10 bar to 200 bar.

8. The process of any one of claims 1 to 7, wherein the reaction temperature in step d) is in the range of from 20°C to 250°C.

9. The process of claim 6, wherein in step d) the mixture of reduced and lithium-depleted CAM and / or BM and sulfur is reacted with a mixture of carbon monoxide and nitrogen monoxide at pressures of from 30 bar to 80 bar.

10. The process of claim 9, wherein in step d) the mixture of reduced and lithium-depleted CAM and / or BM and sulfur is reacted with a mixture of carbon monoxide and nitrogen monoxide at temperatures in the range of from 120°C to 160°C.11 . The process of any one of claims 1 to 10, wherein in step d) the mixture of reduced and lithium-depleted CAM and / or BM and sulfur is reacted with carbon monoxide or a mixture of carbon monoxide and nitrogen monoxide for a time interval in the range of from 1 hour to 120 hours.

12. The process of any one of claims 6 to 11 , wherein in step d) the gas mixture contains from 97.5 vol% to 99.9 vol% carbon monoxide and from 0.1 vol% to 2.5 vol% nitrogen monoxide.

13. The process of claim 12, wherein in step d) the mixture of reduced and lithium-depleted CAM and / or BM and sulfur is reacted with the gas mixture at a total pressure in the range of from 30 bar to 80 bar, and at a temperature in the range of from 120°C to 160°C.

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