How to recycle lithium-ion battery materials

Abstract

Disclosed herein is a method for removing lithium from a battery material, comprising contacting the battery material with an aqueous medium comprising a salt of calcium hypochlorite to form a mixture, and separating solids from liquids in the mixture to obtain an aqueous solution comprising lithium ions. Also disclosed is a method for recycling lithium ion battery material.

Description

[Technical field]

[0001] The project leading to this application has been funded by the European Union's Horizon 2020 research and innovation programme under specific grant agreement No EIT / RAW MATERIALS / SGA2020 / 1, project agreement no. 19211.

[0002] Disclosed herein is a method for removing lithium from a battery material, comprising contacting the battery material with an aqueous medium comprising at least one salt selected from calcium hypochlorite, lithium hypochlorite, and combinations thereof to form a mixture, and separating solids from liquids in the mixture to obtain an aqueous solution comprising lithium ions. Also disclosed is a method for recycling lithium ion battery material. [Background technology]

[0003] Lithium-ion battery materials are a valuable source of lithium. Removal of lithium from the battery materials is an important step for recycling the lithium-ion battery materials. Lithium-ion battery materials are complex mixtures of various elements and compounds, and it may be desirable to separate various non-lithium impurities. Removal of lithium from the battery materials using, for example, sodium hypochlorite increases the pH due to self-deactivation, resulting in unsatisfactory lithium recovery rates and / or unsatisfactory lithium purity. Summary of the Invention [Problem to be solved by the invention]

[0004] Therefore, there is a need for methods of removing lithium from battery materials and recycling lithium-ion battery materials, including economical methods with high lithium recovery and high lithium purity. [Means for solving the problem]

[0005] Disclosed herein is a method for removing lithium from a battery material, comprising contacting the battery material with an aqueous medium comprising at least one salt selected from calcium hypochlorite, lithium hypochlorite, and combinations thereof to form a mixture, and separating solids from liquids in the mixture to obtain an aqueous solution comprising lithium ions.

[0006] In some embodiments, the battery material comprises at least one selected from lithiated nickel cobalt manganese oxide, lithiated nickel cobalt aluminum oxide, lithium metal phosphate, lithium ion battery scrap, and black chunks from lithium ion batteries.

[0007] In some embodiments, the battery material has the formula Li x MPO 4 wherein x is an integer equal to or greater than 1 and M is selected from metals, transition metals, rare earth metals, and combinations thereof.

[0008] In some embodiments, the battery material has the formula Li 1+x (Ni a Co b Mn c M 1 d ) 1-x O 2 Lithium nickel cobalt manganese oxide of the formula: 1 is selected from Mg, Ca, Ba, Al, Ti, Zr, Zn, Mo, V and Fe, 0≦x≦0.2, 0.1≦a≦0.95, and 0≦b≦0.9 (e.g., 0.05 <b≦0.5)であり、0≦c≦0.6であり、0≦d≦0.1であり、a+b+c+d=1である。

[0009] In some embodiments, the battery material has the formula Li[Ni h Co i Al j ]O 2+rwherein h is in the range of 0.8 to 0.90, i is in the range of 0.1 to 0.3, j is in the range of 0.01 to 0.10, and r is in the range of 0 to 0.4.

[0010] In some embodiments, the battery material includes nickel, cobalt, manganese, copper, aluminum, iron, phosphorous, or combinations thereof.

[0011] In some embodiments, the battery material has a mass ratio of lithium to the total mass of nickel, cobalt, manganese, copper, aluminum, iron, and phosphorus in the range of 0.01 to 10. In some embodiments, the battery material has a mass ratio of lithium to the total mass of nickel, cobalt, manganese, copper, aluminum, iron, and phosphorus in the range of 0.01 to 5. In some embodiments, the battery material has a mass ratio of lithium to the total mass of nickel, cobalt, manganese, copper, aluminum, iron, and phosphorus in the range of 0.01 to 2. In some embodiments, the battery material has a mass ratio of lithium to the total mass of nickel, cobalt, manganese, copper, aluminum, iron, and phosphorus in the range of 0.01 to 1.

[0012] In some embodiments, the mass ratio of the at least one salt selected from calcium hypochlorite, lithium hypochlorite, and combinations thereof to the total mass of the battery materials in the contacting step is in the range of 0.1-100.

[0013] In some embodiments, the contacting step is carried out at a temperature ranging from 20° C. to 100° C. and has a duration ranging from 10 minutes to 10 hours.

[0014] In some embodiments, the separating step comprises at least one process selected from filtration, decantation, centrifugation, sedimentation, and combinations thereof to separate solids from liquids.

[0015] In some embodiments, the method further comprises purifying the aqueous solution comprising lithium ions by at least one process selected from adsorption, ion exchange, precipitation, crystallization, nanofiltration, concentration by water removal, drowning-out crystallization, redissolving the lithium salt in an organic solvent, and combinations thereof.

[0016] In some embodiments, the method further comprises subjecting the aqueous solution containing lithium ions to a chlor-alkali-electrolysis process to obtain lithium hydroxide and chlorine gas.

[0017] In some embodiments, chlorine gas is used to produce chlorinated lime and / or lithium hypochlorite.

[0018] In some embodiments, chlorinated lime and / or lithium hypochlorite produced from chlorine gas obtained from chlor-alkali electrolysis is used to remove lithium from the battery materials.

[0019] In some embodiments, the calcium hydroxide is recovered from the solids.

[0020] In some embodiments, calcium hydroxide is used to make chlorinated lime.

[0021] Also disclosed herein is a method of recycling lithium ion battery materials, comprising the steps of mechanically pulverizing at least one selected from lithium ion batteries, lithium ion battery waste, lithium ion battery manufacturing scrap, lithium ion cell manufacturing scrap, lithium ion cathode active material, and combinations thereof to obtain a black mass, contacting the black mass with an aqueous medium comprising at least one salt selected from calcium hypochlorite, lithium hypochlorite, and combinations thereof, and separating the solids from the liquid to obtain an aqueous solution comprising lithium ions. [Brief description of the drawings]

[0022] [Figure 1] FIG. 1 shows an exemplary method for removing lithium from battery materials and / or recycling lithium-ion battery materials. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0023] definition As used herein, "a" or "an" entity refers to one or more of that entity; for example, "a" "compound" refers to one or more compounds or at least one compound, unless otherwise specified. Thus, the terms "a" (or "an"), "one or more," and "at least one" are used interchangeably herein.

[0024] The term "material" as used herein refers to elements, components, and / or substances that make up or can make something.

[0025] As used herein, the term "about" refers to ±5% of the numerical value stated. Unless otherwise specified, all numerical values ​​are intended to be modified by the term "approximately."

[0026] As used herein, the term "electrolysis" refers to chemical decomposition caused by passing an electric current through a liquid or solution containing ions.

[0027] As used herein, the term "chlor-alkali-electrolysis" refers to the process of producing chlorine gas by electrolysis from a liquid or solution containing chloride ions.

[0028] As used herein, the term "electrolysis" refers to chemical decomposition caused by passing an electric current through a liquid or solution containing ions.

[0029] As used herein, the term "chlorinated lime" refers to a mixture of calcium chloride, calcium hydroxide, and calcium hypochlorite.

[0030] Black lump "Black mass" refers to lithium-containing material obtained by mechanical processing, such as mechanical grinding, from, for example, lithium ion batteries, lithium ion battery waste, lithium ion battery manufacturing scrap, lithium ion cell manufacturing scrap, lithium ion cathode active material, and / or combinations thereof. For example, black mass is obtained from battery scrap by mechanically processing the battery scrap to obtain active components of the electrodes, such as graphite and cathode active material, and may include impurities from the casing, electrode foil, cable, separator, and electrolyte. In some examples, the battery scrap may be subjected to a heat treatment to pyrolyze organic (e.g., electrolyte) and polymeric materials (e.g., separator and binder). Such heat treatment may be performed before or after mechanical grinding of the battery materials.

[0031] Lithium-ion batteries may be disassembled, punched, crushed, for example in a hammer mill, and / or shredded, for example in an industrial shredder. Such mechanical treatments provide the active material of the battery electrodes. Light fractions such as organic plastics and housing parts made of aluminum or copper foil can be removed, for example, by forced gas flow, air separation, or classification.

[0032] Battery scrap can come from, for example, used batteries, or manufacturing waste, such as off-spec materials. In some embodiments, the battery material is obtained from mechanically processed battery scrap, such as battery scrap processed in a hammer mill or industrial shredder. Such material can have an average particle size (D50) ranging from 1 μm to 1 cm, such as from 1 to 500 μm, and further such as from 3 to 250 μm.

[0033] Large portions of the battery scrap, such as housings, wiring, and electrode carrier films, can be mechanically separated such that the corresponding materials are excluded from the battery materials employed in the process.

[0034] The mechanically treated battery scrap may be subjected to a solvent treatment to dissolve and separate the polymer binders used to bind the transition metal oxides to the current collector film or, for example, to bind graphite to the current collector film. Suitable solvents include N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N-ethylpyrrolidone, and dimethylsulfoxide, either 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.

[0035] The mechanically treated battery scrap can be subjected to heat treatment in different atmospheres and at a wide range of temperatures. The temperature range is usually in the range of 100°C to 900°C. Lower temperatures below 300°C help to evaporate residual solvent from the battery electrolyte, higher temperatures may decompose the binder polymer, and temperatures above 400°C may change the composition of the inorganic materials since some transition metal oxides are reduced by carbon contained in the scrap material or by the introduction of reducing gas. In some embodiments, reduction of lithium metal oxides can be avoided by keeping the temperature below 400°C and / or removing the carbonaceous material before heat treatment.

[0036] In some embodiments, the battery material comprises at least one selected from lithiated nickel cobalt manganese oxide, lithiated nickel cobalt aluminum oxide, lithium metal phosphate, lithium ion battery scrap, black chunks from lithium ion batteries, and combinations thereof.

[0037] In some embodiments, the battery material has the formula Li x MPO 4 wherein x is an integer equal to or greater than 1 and M is selected from metals, transition metals, rare earth metals, and combinations thereof.

[0038] In some embodiments, the battery material has the formula Li 1+x (Ni a Cob Mn c M 1 d ) 1-x O 2 comprising lithium nickel cobalt manganese oxide, wherein M 1 is selected from Mg, Ca, Ba, Al, Ti, Zr, Zn, Mo, V, and Fe, 0 ≦ x ≦ 0.2, 0.1 ≦ a ≦ 0.95, 0 ≦ b ≦ 0.9 (e.g., 0.05 < b ≦ 0.5), 0 ≦ c ≦ 0.6, 0 ≦ d ≦ 0.1, and a + b + c + d = 1. Exemplary lithium nickel cobalt manganese oxides include Li (1+x) [Ni 0.33 Co 0.33 Mn 0.33 (1-x) O 2 Li (1+x) [Ni 0.5 Co 0.2 Mn 0.3 (1-x) O 2 Li (1+x) [Ni 0.6 Co 0.2 Mn 0.2 (1-x) O 2 Li (1+x) [Ni 0.7 Co 0.2 Mn 0.3 (1-x) O 2 Li (1+x) [Ni 0.8 Co 0.1 Mn 0.1 (1-x) O 2 (each x being as defined above), and Li[Ni 0.85 Co 0.13 Al 0.02 O 2 is included.

[0039] In some embodiments, the battery material has the formula Li[Ni h Co i Al j O 2+r ​​​​​wherein h is in the range of 0.8 to 0.90, i is in the range of 0.1 to 0.3, j is in the range of 0.01 to 0.10, and r is in the range of 0 to 0.4.

[0040] In some embodiments, the battery material includes nickel, cobalt, manganese, copper, aluminum, iron, phosphorous, or combinations thereof.

[0041] In some embodiments, the battery material has a mass ratio of lithium to the total mass of nickel, cobalt, manganese, copper, aluminum, iron, and phosphorus in the range of 0.01 to 10. In some embodiments, the battery material has a mass ratio of lithium to the total mass of nickel, cobalt, manganese, copper, aluminum, iron, and phosphorus in the range of 0.01 to 5. In some embodiments, the battery material has a mass ratio of lithium to the total mass of nickel, cobalt, manganese, copper, aluminum, iron, and phosphorus in the range of 0.01 to 2. In some embodiments, the battery material has a mass ratio of lithium to the total mass of nickel, cobalt, manganese, copper, aluminum, iron, and phosphorus in the range of 0.01 to 1.

[0042] In some embodiments, the battery material is Li x MO 2 wherein x is an integer equal to or greater than 1 and M is selected from metals, transition metals, rare earth metals, and combinations thereof.

[0043] In some embodiments, a method of recycling lithium ion battery materials includes mechanically crushing at least one selected from lithium ion batteries, lithium ion battery waste, lithium ion battery manufacturing scrap, lithium ion cell manufacturing scrap, lithium ion cathode active material, and combinations thereof to obtain black agglomerates.

[0044] Leaching: In some embodiments, a method for removing lithium from a battery material includes contacting the battery material with an aqueous medium comprising at least one salt selected from calcium hypochlorite, lithium hypochlorite, and combinations thereof to form a mixture. In some embodiments, a method for recycling lithium ion battery material includes mechanically grinding at least one selected from lithium ion batteries, lithium ion battery waste, lithium ion battery manufacturing scrap, lithium ion cell manufacturing scrap, lithium ion cathode active material, and combinations thereof to obtain a black mass, and contacting the black mass with an aqueous medium comprising at least one salt selected from calcium hypochlorite, lithium hypochlorite, and combinations thereof.

[0045] Without wishing to be bound by theory, calcium hypochlorite is 2 An exemplary lithium metal oxide such as: 4LiMO can be oxidized to release lithium as lithium chloride. 2 +Ca(ClO) 2 +H 2 O → 2LiCl + 4MO 2 +Ca(OH) 2 +2LiOH. Formula 3CaCl(OCl)·Ca(OH) 2 5H 2 Using chlorinated lime of O, 2LiOH+CaCl 2 Considering the possibility of the equilibrium ⇔2LiCl + Ca(OH), the reaction of chlorinated lime with lithium metal oxide is expressed as follows: 6LiMO 2 +[3CaCl(OCl)·Ca(OH) 2 5H 2 O]→6LiCl+6MO 2 +4Ca(OH) 2 +2H 2 O.

[0046] Alternatively, the use of sodium hypochlorite can proceed according to the following formula: 2LiMO 2 +NaClO+H 2 O → LiCl + LiOH + MO 2+NaOH. Sodium hydroxide will eventually raise the pH so much that the oxidation potential of hypochlorite may drop too low for the reaction to continue, so an acid may be needed to lower the pH.

[0047] The use of lithium hypochlorite can proceed according to the following formula: 2LiMO 2 +LiClO+H 2 O → LiCl + 2LiOH + MO 2 Lithium hydroxide will eventually raise the pH so much that the oxidation potential of hypochlorite may drop too low for the reaction to continue, so acid may be added to lower the pH.

[0048] In contrast, when calcium hypochlorite is used, the pH value may be semi-buffered due to the low solubility of calcium hydroxide. Thus, when reacting lithium-containing materials with chlorinated lime, the lithium is recovered as lithium chloride, but a significant amount of calcium may be present as less soluble calcium hydroxide.

[0049] In some embodiments, the contacting step is performed at a temperature ranging from 20° C. to 100° C. for a duration ranging from 10 minutes to 10 hours. In some embodiments, the contacting step is performed at 100° C. for a duration ranging from 3 hours to 5 hours. In some embodiments, the contacting step is performed at 60° C. for a duration ranging from 3 hours to 5 hours. In some embodiments, the contacting step is performed at 25° C. for a duration ranging from 3 hours to 5 hours.

[0050] Solid-liquid separation: In some embodiments, a method for removing lithium from a battery material includes contacting the battery material with an aqueous medium comprising at least one salt selected from calcium hypochlorite, lithium hypochlorite, and combinations thereof to form a mixture, and separating the solids from the liquid in the mixture to obtain an aqueous solution comprising lithium ions. In some embodiments, a method for recycling lithium ion battery material includes mechanically pulverizing at least one selected from lithium ion batteries, lithium ion battery waste, lithium ion battery manufacturing scrap, lithium ion cell manufacturing scrap, and lithium ion cathode active material to obtain a black mass, contacting the black mass with an aqueous medium comprising at least one salt selected from calcium hypochlorite, lithium hypochlorite, and combinations thereof, and separating the solids from the liquid to obtain an aqueous solution comprising lithium ions.

[0051] The reaction slurry containing insoluble residues from the black mass, e.g., carbon such as graphite, and solid calcium hydroxide obtained from the leaching process may be separated into a liquid solution and a solid residue by solid-liquid separation. In some embodiments, the lithium-depleted solid residue may be recovered. In some embodiments, calcium hydroxide is used to produce chlorinated lime.

[0052] In some embodiments, the separating step comprises at least one process selected from filtration, decantation, centrifugation, flocculation, sedimentation, and combinations thereof to separate solids from liquids.

[0053] Li / Ca separation: In some embodiments, the method of removing lithium from the battery material further comprises purifying the aqueous solution containing lithium ions by at least one process selected from adsorption, ion exchange, precipitation, crystallization, nanofiltration, concentration by water removal, drowning crystallization, redissolving the lithium salt in an organic solvent, and combinations thereof. In some embodiments, the method of recycling lithium ion battery material further comprises purifying the aqueous solution containing lithium ions by at least one process selected from adsorption, ion exchange, precipitation, crystallization, nanofiltration, concentration by water removal, drowning crystallization, redissolving the lithium salt in an organic solvent, and combinations thereof.

[0054] The filtrate, which contains lithium chloride, dissolved calcium hydroxide, and some impurities such as aluminates, phosphates, fluorides, silicates, etc., may be concentrated by evaporation of the water, which can precipitate less soluble calcium salts such as calcium aluminate, calcium fluoride, and calcium silicate.

[0055] The lithium chloride solution can be further purified, for example, by precipitation, ion exchange, adsorption reaction, nanofiltration, purification by crystallization of lithium chloride, and / or solvent exchange with one or more solvents selective for dissolving lithium chloride. Such solvents are alcohols, such as methanol and ethanol. The lithium chloride aqueous solution may be purified by drowning-out crystallization by adding a less polar solvent, such as ethanol, propanol, and / or isopropanol, to the aqueous solution. The drowning-out crystallization process is described, for example, in Taboada, Mariea Elisa et al., "Process design for drowning-out crystallization of lithium hydroxide monohydrate." Chemical engineering research and design 85.9(2007):1325-1330.

[0056] Lithium / calcium separation may include nanofiltration, calcium precipitation as oxalate, fluoride, phosphate, carbonate and / or hydroxide, crystallization in water and / or methanol, solvent exchange, and / or ion exchange.

[0057] In some embodiments, calcium hydroxide is used to make chlorinated lime.

[0058] Li / Na separation: In some embodiments, the method of removing lithium from the battery material further comprises separating the lithium ions from the sodium ions. In some embodiments, the method of recycling lithium ion battery material further comprises separating the lithium ions from the sodium ions.

[0059] The process for separating lithium ions from calcium ions can also function as a process for separating lithium ions from sodium ions, and similarly, the process for separating lithium ions from sodium ions can also function as a process for separating lithium ions from calcium ions.

[0060] In some embodiments, the process for separating lithium ions from sodium ions is at least one selected from lithium precipitation, for example as a carbonate salt, lithium solvent extraction, lithium adsorption, lithium ion exchange, and combinations thereof.

[0061] Conversion of Li salts to LiOH: In some embodiments, the lithium salt may be converted to the hydroxide form (LiOH). For example, Li 2 CO 3 is Ca(OH) 2 It can be converted to LiOH by reaction with

[0062] In some embodiments, the method of removing lithium from the battery material further comprises subjecting the aqueous solution containing lithium ions to at least one selected from reaction with a hydroxide, LiCl electrolysis, electrodialysis, and combinations thereof. In some embodiments, the method of recycling lithium ion battery material further comprises subjecting the aqueous solution containing lithium ions to at least one selected from treatment with a hydroxide, LiCl electrolysis, electrodialysis, and combinations thereof.

[0063] In some embodiments, the method of removing lithium from the battery material further comprises subjecting the aqueous solution containing lithium ions to a chlor-alkali-electrolysis process to obtain lithium hydroxide and chlorine gas. In some embodiments, the method of recycling lithium ion battery material further comprises subjecting the aqueous solution containing lithium ions to a chlor-alkali-electrolysis process to obtain lithium hydroxide and chlorine gas.

[0064] The lithium chloride solution can be subjected to chlor-alkali-electrolysis to obtain lithium hydroxide and chlorine gas. Several electrolysis processes are described, for example, in RU2713360 and EP3589762. The obtained lithium hydroxide can be recovered and further purified if necessary. The chlorine gas can be recovered and in a preferred embodiment, the chlorine gas is used to produce chlorinated lime. In another preferred embodiment, the recovered calcium hydroxide is used to produce chlorinated lime. The calcium hydroxide can be separated from the solid residue by techniques such as graphite flotation, carrier flotation, and / or carrier magnetic separation.

[0065] LiOH H 2 O crystallization: In some embodiments, the lithium hydroxide can be further purified by crystallization.

[0066] Exemplary methods: FIG. 1 shows an exemplary method for removing lithium from battery materials and / or recycling lithium-ion battery materials (100). The material can be treated in an aqueous medium with calcium hypochlorite (101). A solid-liquid separation, such as filtration, decantation, centrifugation, and / or settling flocculation, can follow (102). A lithium-depleted solid residue can be recovered (108) and can include calcium salts, such as calcium hydroxide. The lithium-containing liquid portion can be subjected to Li / Ca separation (103) and calcium salts can be recovered (109). For example, nanofiltration, calcium precipitation, crystallization in water and / or methanol, solvent exchange, and / or ion exchange can be used to separate the lithium and calcium species. Calcium species can be precipitated as oxalates, fluorides, phosphates, carbonates, and / or hydroxides. Calcium species can be precipitated as hydroxides, for example, by treatment with LiOH, NaOH, and / or KOH. The lithium salt solution may be further subjected to Li / Na separation (104), such as, for example, lithium precipitation as carbonate, solvent extraction, lithium absorption, lithium ion exchange, etc. The lithium salt may be, for example, Ca(OH) 2 LiOH (105) may be converted to LiOH (106) by reaction with LiCl, LiCl electrolysis, and / or electrodialysis. Optionally, Cl from LiCl electrolysis may be converted to LiOH (107). 2 can be recycled to produce calcium hypochlorite. Lithium hydroxide can then be crystallized (106) to produce LiOH H 2 Lithium salts such as 1,2-dihydropyridine and 1,2-dihydropyridine can be obtained (107).

[0067] Embodiment Some embodiments of the present disclosure include, but are not limited to, the following.

[0068] 1. A method for removing lithium from a battery material, comprising the steps of contacting the battery material with an aqueous medium containing at least one salt selected from calcium hypochlorite, lithium hypochlorite, and combinations thereof to form a mixture, and separating solids from liquids in the mixture to obtain an aqueous solution containing lithium ions.

[0069] 2. The method according to Embodiment 1, wherein the battery material includes at least one selected from lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, lithium metal phosphate, lithium ion battery scrap, and black mass derived from lithium ion batteries.

[0070] 3. The method according to Embodiment 1 or 2, wherein the battery material includes a lithium metal phosphate of the formula Li x MPO 4 wherein x is an integer of 1 or more, and M is selected from metals, transition metals, rare earth metals, and combinations thereof.

[0071] 4. The method according to any one of Embodiments 1 to 3, wherein the battery material includes a lithium nickel cobalt manganese oxide of the formula Li 1+x (Ni a Co b Mn c M 1 d ) 1-x O 2 wherein M 1 is selected from Mg, Ca, Ba, Al, Ti, Zr, Zn, Mo, V, and Fe, 0 ≦ x ≦ 0.2, 0.1 ≦ a ≦ 0.95, 0 ≦ b ≦ 0.9 (for example, 0.05 < b ≦ 0.5), 0 ≦ c ≦ 0.6, 0 ≦ d ≦ 0.1, and a + b + c + d = 1.

[0072] 5. The method according to any one of Embodiments 1 to 4, wherein the battery material includes a lithium nickel cobalt aluminum oxide of the formula Li[Ni h Co i Al j O 2+r wherein h ranges from 0.8 to 0.90, i ranges from 0.1 to 0.3, j ranges from 0.01 to 0.10, and r ranges from 0 to 0.4.

[0073] 6. The method of any one of the preceding claims, wherein the battery material comprises nickel, cobalt, manganese, copper, aluminum, iron, phosphorus, or a combination thereof.

[0074] 7. The method of any one of the preceding claims, wherein the battery material has a mass ratio of lithium to the total mass of nickel, cobalt, manganese, copper, aluminum, iron, and phosphorus in the range of 0.01-10, 0.01-5, 0.01-2, or 0.01-1.

[0075] 8. The method according to any one of embodiments 1 to 7, wherein in the contacting step, a mass ratio of at least one salt selected from calcium hypochlorite, lithium hypochlorite, and combinations thereof to a total mass of the battery material is in the range of 0.1 to 100, 0.1 to 70, 0.1 to 50, 0.1 to 30, 1 to 100, 10 to 100, 30 to 100, or 50 to 100.

[0076] 9. The method according to any one of the preceding embodiments, wherein the contacting step is carried out at a temperature ranging from 20° C. to 100° C. and has a duration ranging from 10 minutes to 10 hours.

[0077] 10. The method according to any one of the preceding claims, wherein the separating step comprises at least one process selected from filtration, decantation, centrifugation, sedimentation and combinations thereof to separate solids from liquids.

[0078] 11. The method of any one of the preceding claims, further comprising purifying the aqueous solution containing lithium ions by at least one process selected from adsorption, ion exchange, precipitation, crystallization, nanofiltration, concentration by water removal, drowning crystallization, redissolving the lithium salt in an organic solvent, and combinations thereof.

[0079] 12. The method of any one of the preceding claims, further comprising subjecting the aqueous solution containing lithium ions to a chlor-alkali-electrolysis process to obtain lithium hydroxide and chlorine gas.

[0080] 13. The method of embodiment 12, wherein the chlorine gas is used to produce chlorinated lime and / or lithium hypochlorite.

[0081] 14. The method of any one of the preceding embodiments, wherein calcium hydroxide is recovered from the solids.

[0082] 15. The method of embodiment 14, wherein the calcium hydroxide is used to produce chlorinated lime.

[0083] 16. A method for recycling lithium ion battery materials, comprising: mechanically crushing at least one selected from lithium ion batteries, lithium ion battery waste, lithium ion battery manufacturing scrap, lithium ion cell manufacturing scrap, lithium ion cathode active material, and combinations thereof to obtain a black mass; contacting the black mass with an aqueous medium comprising at least one salt selected from calcium hypochlorite, lithium hypochlorite, and combinations thereof; and separating the solids from the liquid to obtain an aqueous solution comprising lithium ions.

[0084] 17. The method of any one of the preceding embodiments, wherein the at least one salt is calcium hypochlorite.

[0085] 18. The method according to embodiment 13, wherein chlorinated lime and / or lithium hypochlorite produced from chlorine gas obtained from chlor-alkali-electrolysis is used to remove lithium from the battery material according to any one of the methods according to embodiments 1 to 17.

[0086] 19. The method of any one of the preceding embodiments, wherein the initial pH of the mixture in the contacting step is less than 11, less than 10.9, less than 10.8, less than 10.7, or less than 10.6.

[0087] 20. The method of any one of the preceding embodiments, wherein the final pH of the mixture in the contacting step is less than 10, less than 9, or less than 8.

[0088] 21. The method of any one of the preceding embodiments, wherein the pH of the mixture during the contacting step ranges from 5 to less than 11, less than 10.9, less than 10.8, less than 10.7, or less than 10.6.

[0089] 22. The battery material and / or black mass contains less than 5% by mass, less than 1% by mass, or less than 0.1% by mass of lithium carbonate Li based on the total mass of the battery material and / or black mass. 2 CO 3 22. The method of any one of the preceding claims, comprising:

[0090] 23. The method of any one of the preceding claims, wherein the battery material and / or black mass comprises less than 5% by weight, less than 1% by weight, or less than 0.1% by weight of lithium iron phosphate and iron phosphate, based on the total weight of the battery material and / or black mass.

[0091] A claim or description including "or" or "and / or" between at least one member of a group means that one, more than one, or all of the members of the group are present in, employed in, or otherwise relevant to a given product or method, unless stated to the contrary or clear from the context. The disclosure includes embodiments in which exactly one member of the group is present in, employed in, or otherwise relevant to a given product or method. The disclosure includes embodiments in which more than one, or all group members are present in, employed in, or otherwise relevant to a given product or method.

[0092] Furthermore, the disclosure encompasses all variations, combinations, and modifications in which at least one limitation, element, clause, and descriptive term from at least one of the claims described is introduced into another claim. For example, a claim that is dependent on another claim can be amended to include at least one limitation found in the other claim that is dependent on the same underlying claim. When elements are present as a list, such as in a Markouche group format, each subgroup of elements is also disclosed, and any element(s) can be removed from the group. In general, when the disclosure or aspects of the disclosure are referred to as including certain elements and / or features, it is to be understood that an embodiment of the disclosure or aspects of the disclosure consists of or consists essentially of such elements and / or features. For brevity, those embodiments are not specifically described herein. When ranges are given, the endpoints are included. Furthermore, unless otherwise indicated or clear from the context and understanding of one of ordinary skill in the art, values ​​expressed as ranges can assume any particular value or subrange within the stated range in different embodiments of the disclosure, unless the context clearly dictates otherwise.

[0093] Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the disclosure described herein which equivalents are intended to be encompassed by the following claims. EXAMPLES

[0094] The following examples are intended to be illustrative and are not intended to limit the scope of the disclosure in any way.

[0095] Abbreviation % Percent K 2 CO 3 Potassium carbonate Na 2 CO 3 Sodium carbonate Na 2 B4 O 7 Sodium Tetraborate PA Grade Professional Analysis Grade nd undecided Na 2 S 2 O 8 Sodium persulfate Mass % Mass Percent (NH 4 ) 2 S 4 O 8 Ammonium persulfate Ca(ClO) 2 Calcium hypochlorite NaClO Sodium hypochlorite NaOH Sodium hydroxide Li Lithium Ni Nickel Co Cobalt Mn Manganese Cu Copper Al Aluminum Fe Iron P. Lin F Fluorine Ca Calcium.

[0096] elemental analysis Elemental analysis of lithium, calcium, and manganese was carried out according to the following process.

[0097] The reagents used were deionized water, hydrochloric acid (36%), K 2 CO 3 -Na 2 CO 3 Mixture (dry), Na 2 B 4 O 7 (dry), and 50% by volume hydrochloric acid (1:1 mixture of deionized water and hydrochloric acid (36%)). All reagents were PA grade.

[0098] Weigh out 0.2 to 0.25 g of black lump into a Pt crucible and add K 2 CO 3 -Na 2 CO 3 / Na2 B 4 O 7 The samples were prepared by adding the fusion product. The samples were burned in an unshielded flame and then incinerated in a muffle furnace at 600 °C. The remaining ash was 2 CO 3 -Na 2 CO 3 / Na 2 B 4 O 7 (0.8g / 0.2g) and melted until a clear melt was obtained. The cooled molten cake was dissolved in 30mL of water and 12mL of 50% by volume hydrochloric acid was added. The solution was filled up to the specified volume of 100mL. Samples were prepared in triplicate and a blank sample was prepared for reference.

[0099] Li, Ca, and Mn in the obtained sample solutions were determined by optical emission spectroscopy using inductively coupled plasma (ICP-OES). An ICP-OES Agilent 5100 SVDV was used with the following characteristics: wavelengths: Li 670.783 nm; Ca 396.847 nm; Mn 257.610 nm; internal standard: Sc 361.383 nm; dilution factors: Li 100, Ca 10, Mn 100; calibration: external.

[0100] Elemental analysis of fluorine and fluoride was carried out according to DIN EN 14582:2016-12 for sample preparation for overall fluorine content determination (waste samples); detection method was ion-selective electrode measurement; DIN 38405-D4-2:1985-07 (water samples; decomposition of inorganic solids followed by acid-supported distillation and determination of fluoride with an ion-selective electrode).

[0101] Other metal impurities and phosphorus were similarly determined by elemental analysis using ICP-OES (Inductively Coupled Plasma-Optical Emission Spectroscopy) or ICP-MS (Inductively Coupled Plasma-Mass Spectroscopy). Total carbon was determined after combustion with a thermal conductivity detector.

[0102] Black lump The black mass was obtained by mechanically crushing the lithium ion batteries and then separating the black mass as a fine powder from the other components of the lithium ion batteries. The black mass had an elemental composition according to Table 1, as determined by elemental analysis.

[0103] [Table 1]

[0104] Example 1 The black mass (30 g) was suspended in deionized water (200 g) to which calcium hypochlorite (Merck 211389) (30 g) containing 65% active chlorine was added in portions under stirring. After addition, the reactor contents were heated to the desired temperature. After the reaction time, the reactor contents were cooled to room temperature and filtered. The filtrate residue was washed with deionized water to obtain a combined filtrate and filtrate residue, followed by vacuum drying at 70° C. overnight. Both the filtrate and filtrate residue were analyzed by elemental analysis. The elemental recoveries were calculated from the analytical data. The results are summarized in Table 2.

[0105] [Table 2]

[0106] The molar ratio of Li to Cl used was 0.1-0.4. No base metal ions were detected in the obtained filtrate. During experiment 2c, the pH value was monitored. After the addition of calcium hypochlorite, the pH immediately increased to 6-10.5. A few minutes after the addition of hypochlorite, the pH value was 7 and further decreased during the reaction to a final value of 6.3. These changes in the pH value indicate a more complicated reaction scheme than the equation given in the discussion above.

[0107] Example 2 100 g of black mass 3 was added to 1066 g of 15% by mass NaClO aqueous solution (molar ratio Li / Cl 0.4-2.1). The mixture was heated to 50°C under stirring and 83 g of 6M hydrochloric acid was added. The pH value dropped from 9 to 5, and the pH value of the solution remained at 5 thereafter. The experiment was stopped 5 hours after the addition of hydrochloric acid. The suspension was filtered and the solid residue was washed with deionized water and dried. Elemental analysis of the filtrate and solid residue showed a lithium recovery of 71%. Traces of Ni, Co, Cu and Fe were detected in the filtrate.

[0108] Example 3 Using the reagents and reaction conditions shown in Table 3, the procedure was the same as in Example 2, except that sodium persulfate was used instead of sodium hypochlorite. The molar ratio of Li to persulfate was 0.1 to 0.07. Even in the filtrate from the experiment in which sodium hydroxide was not used, 0.36% Ni and 0.03% Co were detected. In the experiment in which sodium hydroxide was added, no base metal ions were detected.

[0109] [Table 3]

[0110] Example 4 The same procedure as in Example 2 was carried out using the reagents and reaction conditions shown in Table 4, except that ammonium persulfate was used instead of sodium hypochlorite. The molar ratio of Li to persulfate was 0.1 to 0.07. 0.36% Ni and 0.03% Co were detected in the filtrate.

[0111] [Table 4]

[0112] It was observed that calcium hypochlorite gave higher lithium recovery than sodium hypochlorite or ammonium persulfate. Furthermore, the calcium hydroxide formed maintained the pH value of the reaction solution at a level high enough to avoid dissolution of the base metals, yet low enough to allow the reaction to continue.

Claims

1. contacting the battery materials with an aqueous medium comprising at least one salt selected from calcium hypochlorite, lithium hypochlorite, and combinations thereof to form a mixture; and separating the solid from the liquid in the mixture to obtain an aqueous solution containing lithium ions. A method for extracting lithium from a battery material, comprising:

2. 10. The method of claim 1, wherein the battery material comprises at least one selected from lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, lithium metal phosphate, lithium ion battery scrap, and black chunks from lithium ion batteries.

3. wherein the battery material is of the formula Li ｘ MPO ４ where x is an integer of 1 or more, and M is selected from metals, transition metals, rare earth metals, and combinations thereof), the method according to claim 1 or 2.

4. wherein the battery material is of the formula Li １＋ｘ (Ni ａ Co ｂ Mn ｃ M １ ｄ ) １－ｘ O ２ (wherein, M １ is selected from Mg, Ca, Ba, Al, Ti, Zr, Zn, Mo, V, and Fe, 0≦x≦0.2, 0.1≦a≦0.95, 0≦b≦0.9, or 0.05<b≦0.5; 0≦c≦0.6, 0≦d≦0.1, a + b + c + d = 1) 3. The method of claim 1 or 2, comprising the lithium nickel cobalt manganese oxide of

5. The battery material is of the formula Li[Ni ｈ Co ｉ Al ｊ O ２＋ｒ (wherein h is in the range of 0.8 to 0.90; i is in the range of 0.1 to 0.3, j is in the range of 0.01 to 0.10, r is in the range of 0 to 0.4) 3. The method of claim 1 or 2, comprising lithiated nickel cobalt aluminum oxide of

6. 3. The method of claim 1 or 2, wherein the battery material comprises nickel, cobalt, manganese, copper, aluminum, iron, phosphorus, or a combination thereof.

7. 3. The method of claim 1 or 2, wherein the battery material has a mass ratio of lithium to the total mass 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.

8. 3. The method according to claim 1, wherein in the contacting step, a mass ratio of calcium hypochlorite to the total mass of the battery materials is in the range of 0.1 to 100.

9. 3. The process of claim 1 or 2, wherein the contacting step is carried out at a temperature ranging from 20°C to 100°C and for a duration ranging from 10 minutes to 10 hours.

10. 3. The method of claim 1 or 2, wherein the separating step comprises at least one process selected from filtration, decantation, centrifugation, sedimentation, flocculation, and combinations thereof to separate solids from liquids.

11. The method according to claim 1 or 2, further comprising purifying an aqueous solution containing lithium ions by at least one process selected from adsorption, ion exchange, precipitation, crystallization, nanofiltration, concentration by water removal, leaching crystallization, redissolution of lithium salts in organic solvents, and combinations thereof.

12. The method according to claim 1 or 2, further comprising subjecting an aqueous solution containing lithium ions to a chlorine-alkali electrolysis process to obtain lithium hydroxide and chlorine gas.

13. The method according to claim 12, wherein the chlorine gas is used to produce calcium hypochlorite and / or lithium hypochlorite.

14. The method according to claim 1 or 2, wherein calcium hydroxide is recovered from a solid.

15. The method according to claim 14, wherein the calcium hydroxide is used to produce calcium hypochlorite.

16. A step of mechanically grinding at least one selected from a lithium-ion battery, a lithium-ion battery waste, a lithium-ion battery manufacturing scrap, a lithium-ion cell manufacturing scrap, a lithium-ion cathode active material, and combinations thereof to obtain a black mass, a step of contacting the black mass with an aqueous medium containing at least one salt selected from calcium hypochlorite, lithium hypochlorite, and combinations thereof, and a step of separating solids from a liquid to obtain an aqueous solution containing lithium ions A method for recycling lithium-ion battery materials.

17. The method according to claim 1 or 2, wherein at least one salt is calcium hypochlorite.

18. The method according to claim 13, wherein calcium hypochlorite and / or lithium hypochlorite produced from chlorine gas obtained from chlorine-alkali electrolysis is used to extract lithium from battery materials according to the method according to claim 1 or 2.

19. The method according to claim 1 or 2, wherein the initial pH in the contacting step of the mixture is less than 11.

20. The method according to claim 1 or 2, wherein the final pH in the contacting step of the mixture is less than 10.

21. The method according to claim 1 or 2, wherein the pH during the contacting step of the mixture ranges from 5 to less than 11.

22. The battery material and / or the black mass contains less than 5% by mass of lithium carbonate Li ２ CO ３ based on the total mass of the battery material and / or the black mass, according to the method of claim 1 or 2.

23. The method according to claim 1 or 2, wherein the battery material and / or the black mass contains less than 5% by mass of lithium iron phosphate and iron phosphate with respect to the total mass of the battery material and / or the black mass.

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