Electrolysis of Li2SO4 in the low pH range

Abstract

Disclosed herein is a method comprising electrolyzing an aqueous solution comprising lithium, wherein the aqueous solution has a pH of less than 0.5. Also disclosed is a method comprising electrolyzing a first aqueous solution comprising lithium to obtain a second aqueous solution comprising lithium and an acidic aqueous solution having a pH of less than 0.5, adjusting the pH of the second aqueous solution with an acidic aqueous solution to obtain a third aqueous solution comprising lithium having a pH of less than 0.5, and electrolyzing the third aqueous solution comprising lithium. Further disclosed is a method comprising stripping a liquid medium comprising lithium with an acidic aqueous solution to obtain an aqueous solution comprising lithium, and electrolyzing the aqueous solution comprising lithium. Further disclosed is a method for preparing a liquid medium comprising lithium.

Description

[Technical field]

[0001] Disclosed herein is a method comprising electrolyzing an aqueous solution comprising lithium, wherein the aqueous solution has a pH of less than 0.5. Also disclosed is a method comprising electrolyzing a first aqueous solution comprising lithium to obtain a second aqueous solution comprising lithium and an acidic aqueous solution having a pH of less than 0.5, adjusting the pH of the second aqueous solution with an acidic aqueous solution to obtain a third aqueous solution comprising lithium having a pH of less than 0.5, and electrolyzing the third aqueous solution comprising lithium. Further disclosed is a method comprising stripping a liquid medium comprising lithium with an acidic aqueous solution to obtain an aqueous solution comprising lithium, and electrolyzing the aqueous solution comprising lithium. Further disclosed is a method for preparing a liquid medium comprising lithium. [Background technology]

[0002] High-purity lithium is a valuable resource. Many lithium sources, such as lithium-ion batteries, lithium-ion battery waste, lithium-containing water (e.g., groundwater), and lithium-containing ores, are complex mixtures of various elements and compounds. To obtain high-purity lithium, it may be desirable to remove various non-lithium impurities. Electrolysis of aqueous solutions containing lithium provides an exemplary means to obtain high-purity lithium. In some electrolysis processes, the current density is limited by the pH of the aqueous solution. In some electrolysis processes, the pH can be adjusted, for example, by adding a base to the aqueous solution containing lithium. However, adding a base can form undesirable salts and produce undesirable solid particles. Such particles can be difficult to remove and make the purification process expensive. Additionally, some lithium purification processes use a stripping step prior to electrolysis to transfer the lithium from the liquid medium to an aqueous solution. In some such processes, fresh acid, such as H2SO4, is added as a stripping agent. Summary of the Invention [Problem to be solved by the invention]

[0003] Thus, there is a need for an economical process with high lithium recovery and high lithium purity. There is a need for improved electrolysis performance. There is also a need for economical production and use of stripping agents such as H2SO4. In some embodiments, it is desirable to perform the electrolysis at different pH levels. In some embodiments, it is desirable not to adjust the pH level prior to performing the electrolysis. In some embodiments, it is desirable to produce lithium from a solution that already has a low pH level. [Means for solving the problem]

[0004] Disclosed herein is a process comprising electrolyzing an aqueous solution comprising lithium, wherein the aqueous solution has a pH less than 0.5. In some embodiments, the aqueous solution comprises sulfate. In some embodiments, the pH of the aqueous solution is adjusted along a gradient ranging from -1 to 0.5. In some embodiments, the pH of the aqueous solution is adjusted upwards along a gradient ranging from -1 to 0.5. In some embodiments, the pH of the aqueous solution is adjusted downwards along a gradient ranging from -1 to 0.5. In some embodiments, the method comprises electrolyzing a first aqueous solution comprising lithium to obtain a second aqueous solution comprising lithium and an acidic aqueous solution having a pH less than 0.5, adjusting the pH of the second aqueous solution with an acidic aqueous solution to obtain a third aqueous solution comprising lithium having a pH less than 0.5, and electrolyzing the third aqueous solution. In some embodiments, the first aqueous solution has a pH greater than 0.5. In some embodiments, the electrolysis of the first aqueous solution is performed in a different electrolysis cell than the electrolysis of the third aqueous solution. In some embodiments, the method includes stripping the lithium-containing liquid medium with an acidic aqueous solution to obtain an aqueous solution containing lithium, and electrolyzing the lithium-containing aqueous solution to obtain an aqueous solution deficient in lithium; wherein the lithium-deficient aqueous solution is fed upstream of the method as an acidic aqueous solution, the liquid medium comprises less than 50% by weight water based on the total weight of the liquid medium, and the lithium-deficient aqueous solution has a lower lithium concentration than the aqueous solution containing lithium. In some embodiments, the lithium-deficient aqueous solution has a lithium concentration greater than zero. In some embodiments, the liquid medium comprises less than 5% by weight water based on the total weight of the liquid medium. In some embodiments, the lithium-deficient aqueous solution has a lithium concentration in the range of about 20 g / L to about 100 g / L. In some embodiments, the aqueous solution containing lithium has a lithium concentration in the range of about 20 g / L to about 100 g / L.In some embodiments, a method of preparing a lithium-containing liquid medium comprises electrolyzing an aqueous solution containing lithium at a pH of less than 0.5 to obtain a lithium-deficient aqueous solution, and extracting the lithium-deficient aqueous solution with a liquid medium; wherein the liquid medium comprises less than 50% water by weight based on the total weight of the liquid medium, and the lithium-deficient aqueous solution has a lower lithium concentration than the lithium-containing aqueous solution. [Brief description of the drawings]

[0005] [Figure 1] FIG. 1 illustrates an exemplary electrolysis cell. [Diagram 2] FIG. 2 illustrates an exemplary method consistent with certain embodiments of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0006] 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.

[0007] The term "material" as used herein refers to elements, components, and / or substances that make up or can make something.

[0008] The term "about" as used herein refers to ±5% of the stated numerical value. Unless otherwise specified, all numerical values ​​are intended to be modified by the term "approximately."

[0009] As used herein, the term "electrolysis" refers to chemical decomposition caused by passing an electric current through a liquid or solution containing ions.

[0010] Detailed Description of the Drawings FIG. 1 illustrates an exemplary electrolysis cell (100). The electrolysis cell (100) is supplied with an aqueous solution containing lithium (101). In some embodiments, the aqueous solution containing lithium is obtained by a method including 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, and leaching the black mass to obtain an aqueous solution containing lithium. In some embodiments, the aqueous solution containing lithium is obtained by leaching a lithium-containing ore. In some embodiments, the aqueous solution containing lithium is lithium-containing groundwater. In some embodiments, the aqueous solution containing lithium is obtained by leaching a battery material. In some electrolysis cells, such as the exemplary cell illustrated in FIG. 1, one or more membranes may be present. Two such membranes are illustrated in FIG. 1 as vertical dashed lines. Li + Positive ions such as SO4 tend to migrate toward the negatively charged electrode. 2- Negative ions such as , tend to migrate towards the positively charged electrode. During electrolysis, basic hydroxide ions may form near the negative electrode, increasing the local pH. During electrolysis, acidic protons may form near the positive electrode, decreasing the local pH. Near the negative electrode (102), a lithium-rich and / or more basic aqueous solution is obtained. Near the positive electrode (104), a lithium-deficient and / or acidic aqueous solution is obtained. Also, a lithium-deficient and / or more acidic aqueous solution, a lithium-rich and / or more basic aqueous solution, or an aqueous solution having substantially the same lithium concentration and / or pH may be obtained (103). Here, enriched, depleted, more basic, and more acidic refer to the properties of the aqueous solution relative to the aqueous solution containing the supplied lithium (101), respectively.

[0011] FIG. 2 illustrates an exemplary method consistent with some embodiments of the present disclosure. A liquid medium containing lithium is stripped with an acidic aqueous solution to obtain an aqueous solution containing lithium (201). The aqueous solution containing lithium may be a first aqueous solution containing lithium, which may be electrolyzed to obtain a second aqueous solution containing lithium and an acidic aqueous solution having a pH of less than 0.5 (202); the pH of the second aqueous solution may be adjusted with the acidic aqueous solution to obtain a third aqueous solution containing lithium having a pH of less than 0.5 (206); the third aqueous solution containing lithium may be electrolyzed (202). The electrolysis step or steps (202) may be performed in one or more electrolysis cells and may be performed one or more times. The aqueous solution containing lithium is electrolyzed (202) to obtain an aqueous solution deficient in lithium, which may be provided upstream in the process as an acidic aqueous solution in the stripping step (201) (204). The aqueous solution deficient in lithium is extracted with a liquid medium to obtain a liquid medium containing lithium (203). The lithium-containing liquid medium may be provided (205) to a stripping step (201) upstream in the process. Each of the stripping step (201), electrolysis step (202), and extraction step (203), with or without each or any of the steps shown in the figure, may be performed independently, may be performed in any order, may be performed one or more times, and may be performed with or without providing each or any of the various liquids resulting from each of the stripping step (201), electrolysis step (202), and extraction step (203), upstream (204), (205), and (206).

[0012] Detailed Description of the Invention For example, disclosed herein are methods that include electrolyzing an aqueous solution comprising lithium, where the aqueous solution has a pH of less than 0.5. In some embodiments, the methods include electrolyzing an aqueous solution comprising lithium, where the aqueous solution has a pH of less than 0.4. In some embodiments, the methods include electrolyzing an aqueous solution comprising lithium, where the aqueous solution has a pH of less than 0.3. In some embodiments, the methods include electrolyzing an aqueous solution comprising lithium, where the aqueous solution has a pH of less than 0.2. In some embodiments, the methods include electrolyzing an aqueous solution comprising lithium, where the aqueous solution has a pH of less than 0.1. In some embodiments, the methods include electrolyzing an aqueous solution comprising lithium, where the aqueous solution has a pH of less than 0. In some embodiments, the methods include electrolyzing an aqueous solution comprising lithium, where the aqueous solution has a pH in the range of -1 to 0.5. In some embodiments, the methods include electrolyzing an aqueous solution comprising lithium, where the aqueous solution has a pH in the range of 0 to 0.5. In some embodiments, the method includes electrolyzing an aqueous solution containing lithium, wherein the aqueous solution has a pH in the range of 0 to 0.4. In some embodiments, the method includes electrolyzing an aqueous solution containing lithium, wherein the aqueous solution has a pH in the range of 0 to 0.3. In some embodiments, the method includes electrolyzing an aqueous solution containing lithium, wherein the aqueous solution has a pH in the range of 0 to 0.2. In some embodiments, the method includes electrolyzing an aqueous solution containing lithium, wherein the aqueous solution has a pH in the range of 0 to 0.1.

[0013] In some embodiments, the aqueous solution comprises a sulfate salt.

[0014] In some embodiments, the pH of the aqueous solution is adjusted along a gradient ranging from -1 to 0.5. In some embodiments, the pH of the aqueous solution is adjusted upward and / or downward along a gradient ranging from -1 to 0.5. In some embodiments, the pH of the aqueous solution is adjusted along a gradient ranging from 0 to 0.5.

[0015] In some embodiments, the pH of the aqueous solution is adjusted upward along a gradient ranging from -1 to 0.5. In some embodiments, the pH of the aqueous solution is adjusted upward along a gradient ranging from 0 to 0.5. In some embodiments, the pH of the aqueous solution is adjusted upward along a gradient ranging from 0 to 0.5 by adding a base.

[0016] In some embodiments, the pH of the aqueous solution is adjusted downward along a gradient ranging from -1 to 0.5. In some embodiments, the pH of the aqueous solution is adjusted downward along a gradient ranging from 0 to 0.5. In some embodiments, the pH of the aqueous solution is adjusted downward along a gradient ranging from 0 to 0.5 by adding an acid.

[0017] In some embodiments, the method includes electrolyzing a first aqueous solution comprising lithium to obtain a second aqueous solution comprising lithium and an acidic aqueous solution having a pH less than 0.5, adjusting the pH of the second aqueous solution with the acidic aqueous solution to obtain a second aqueous solution comprising lithium having a pH less than 0.5, and electrolyzing the third aqueous solution.

[0018] In some embodiments, the first aqueous solution has a pH greater than 0.5.

[0019] In some embodiments, the electrolysis of the first aqueous solution is carried out in a different electrolysis cell than the electrolysis of the third aqueous solution.

[0020] In some embodiments, the method comprises the steps of stripping a lithium-containing liquid medium with an acidic aqueous solution to obtain an aqueous solution comprising lithium, and electrolyzing the lithium-containing aqueous solution to obtain a lithium-deficient aqueous solution; where the lithium-deficient aqueous solution is provided upstream of the method as an acidic aqueous solution, the liquid medium comprises less than 50% water by weight relative to the total weight of the liquid medium, and the lithium-deficient aqueous solution has a lower lithium concentration than the lithium-containing aqueous solution.

[0021] In some embodiments, the lithium deficient aqueous solution has a lithium concentration greater than zero.

[0022] In some embodiments, the liquid medium comprises less than 5% water by weight, based on the total weight of the liquid medium. In some embodiments, the liquid medium comprises less than 10% water by weight, based on the total weight of the liquid medium. In some embodiments, the liquid medium comprises less than 20% water by weight, based on the total weight of the liquid medium. In some embodiments, the liquid medium comprises less than 1% water by weight, based on the total weight of the liquid medium. In some embodiments, the liquid medium comprises less than 0.1% water by weight, based on the total weight of the liquid medium. In some embodiments, the liquid medium is immiscible with water. In some embodiments, the liquid medium is an organic solvent. In some embodiments, the liquid medium comprises at least one chelating agent for lithium.

[0023] In some embodiments, the lithium deficient aqueous solution has a lithium concentration in the range of about 20 g / L to about 100 g / L. In some embodiments, the lithium deficient aqueous solution has a lithium concentration in the range of about 30 g / L to about 100 g / L. In some embodiments, the lithium deficient aqueous solution has a lithium concentration in the range of about 40 g / L to about 100 g / L. In some embodiments, the lithium deficient aqueous solution has a lithium concentration in the range of about 50 g / L to about 100 g / L. In some embodiments, the lithium deficient aqueous solution has a lithium concentration in the range of about 60 g / L to about 100 g / L. In some embodiments, the lithium deficient aqueous solution has a lithium concentration in the range of about 70 g / L to about 100 g / L. In some embodiments, the lithium deficient aqueous solution has a lithium concentration in the range of about 80 g / L to about 100 g / L. In some embodiments, the lithium deficient aqueous solution has a lithium concentration in the range of about 90 g / L to about 100 g / L. In some embodiments, the lithium deficient aqueous solution has a lithium concentration in the range of about 20 g / L to about 90 g / L. In some embodiments, the lithium deficient aqueous solution has a lithium concentration in the range of about 20 g / L to about 80 g / L. In some embodiments, the lithium deficient aqueous solution has a lithium concentration in the range of about 20 g / L to about 70 g / L. In some embodiments, the lithium deficient aqueous solution has a lithium concentration in the range of about 20 g / L to about 60 g / L. In some embodiments, the lithium deficient aqueous solution has a lithium concentration in the range of about 20 g / L to about 50 g / L. In some embodiments, the lithium deficient aqueous solution has a lithium concentration in the range of about 20 g / L to about 40 g / L. In some embodiments, the lithium deficient aqueous solution has a lithium concentration in the range of about 20 g / L to about 30 g / L. In some embodiments, the lithium deficient aqueous solution has a lithium concentration in the range of about 30 g / L to about 90 g / L. In some embodiments, the lithium deficient aqueous solution has a lithium concentration ranging from about 40 g / L to about 80 g / L, in some embodiments, the lithium deficient aqueous solution has a lithium concentration ranging from about 50 g / L to about 70 g / L.

[0024] In some embodiments, the aqueous solution containing lithium has a lithium concentration in the range of about 20 g / L to about 100 g / L. In some embodiments, the aqueous solution containing lithium has a lithium concentration in the range of about 30 g / L to about 100 g / L. In some embodiments, the aqueous solution containing lithium has a lithium concentration in the range of about 40 g / L to about 100 g / L. In some embodiments, the aqueous solution containing lithium has a lithium concentration in the range of about 50 g / L to about 100 g / L. In some embodiments, the aqueous solution containing lithium has a lithium concentration in the range of about 60 g / L to about 100 g / L. In some embodiments, the aqueous solution containing lithium has a lithium concentration in the range of about 70 g / L to about 100 g / L. In some embodiments, the aqueous solution containing lithium has a lithium concentration in the range of about 80 g / L to about 100 g / L. In some embodiments, the aqueous solution containing lithium has a lithium concentration in the range of about 90 g / L to about 100 g / L. In some embodiments, the aqueous solution containing lithium has a lithium concentration in the range of about 20 g / L to about 90 g / L. In some embodiments, the aqueous solution containing lithium has a lithium concentration in the range of about 20 g / L to about 80 g / L. In some embodiments, the aqueous solution containing lithium has a lithium concentration in the range of about 20 g / L to about 70 g / L. In some embodiments, the aqueous solution containing lithium has a lithium concentration in the range of about 20 g / L to about 60 g / L. In some embodiments, the aqueous solution containing lithium has a lithium concentration in the range of about 20 g / L to about 50 g / L. In some embodiments, the aqueous solution containing lithium has a lithium concentration in the range of about 20 g / L to about 40 g / L. In some embodiments, the aqueous solution containing lithium has a lithium concentration in the range of about 20 g / L to about 30 g / L. In some embodiments, the aqueous solution containing lithium has a lithium concentration in the range of about 30 g / L to about 90 g / L. In some embodiments, the aqueous solution containing lithium has a lithium concentration in the range of about 40 g / L to about 80 g / L. In some embodiments, the aqueous solution containing lithium has a lithium concentration in the range of about 50 g / L to about 70 g / L.

[0025] In some embodiments, a method of preparing a lithium-containing liquid medium comprises electrolyzing an aqueous solution containing lithium at a pH of less than 0.5 to obtain a lithium-deficient aqueous solution, and extracting the lithium-deficient aqueous solution with a liquid medium; wherein the liquid medium comprises less than 50% water by weight based on the total weight of the liquid medium, and the lithium-deficient aqueous solution has a lower lithium concentration than the lithium-containing aqueous solution.

[0026] In some embodiments, the electrolysis cell includes at least one membrane. In some embodiments, the electrolysis cell includes at least two membranes. In some embodiments, the electrolysis cell includes two membranes. The membrane may be any known lithium ion conductive membrane for use in the electrolysis of aqueous solutions containing lithium. In some embodiments, the at least one membrane is selected from ceramic membranes, polymeric membranes, and combinations thereof. In some embodiments, the polymeric membrane is a sulfonated membrane. In some embodiments, the sulfonated membrane has a hydrocarbon backbone or a PTFE backbone. In some embodiments, the sulfonated membrane is a sulfonated polyarylene ether or polyphenylsulfone, such as polyarylene ether Ultrason® or polyphenylsulfone Ultrason®. In some embodiments, the polymeric membrane is at least one selected from perfluorinated membranes, cation exchange membranes, PEEK-reinforced membranes, styrene / divinylbenzene membranes, and combinations thereof. In some embodiments, the membrane is a fluorinated copolymer having sulfonic acid groups. In some embodiments, the membrane is a perfluorosulfonate polymer membrane. In some embodiments, the perfluorosulfonate polymer membrane is NAFION from EI du Pont de Nemours.

[0027] The electrochemical cell includes a cathode and an anode. An exemplary electrochemical cell is an ICI FM01. In some embodiments, the cell is configured in a unipolar or bipolar configuration. The cathode may be any cathode known for the electrolysis of aqueous solutions containing lithium. The anode may be any anode known for the electrolysis of aqueous solutions containing lithium. In some embodiments, the anode is at least one selected from a metal electrode, a metal oxide electrode, an electrode coated with a platinum group metal, and an electrode coated with a platinum group metal oxide. In some embodiments, the thickness of the coating on the anode ranges from 1 micron to 100 microns. In some embodiments, the anode is titanium. In some embodiments, the anode has a shape selected from a mesh, a plate, a wire, a foam, and a felt. In some embodiments, the anode is a sheet, a rod, a flat, a corrugated, a rectangular, an asymmetric, or a combination thereof. In some embodiments, the anode has iridium oxide coated on a titanium substrate. In some embodiments, the anode includes a conductive substrate having a surface coating of a metal oxide doped with at least one noble metal. In some embodiments, the metal oxide is selected from titanium, tantalum, niobium, zirconium, and combinations thereof. In some embodiments, the precious metal is selected from platinum, ruthenium, palladium, iridium, rhodium, osmium, and combinations thereof. In some embodiments, the cathode is at least one selected from a metal electrode, a metal oxide electrode, an electrode having a platinum group metal, and an electrode coated with a platinum group metal oxide. In some embodiments, the thickness of the coating on the cathode ranges from 1 micron to 100 microns. In some embodiments, the cathode is at least one selected from a nickel electrode and a stainless steel electrode. In some embodiments, the cathode has a shape selected from a mesh, a plate, a wire, a foam, and a felt. In some embodiments, the cathode is a sheet, a rod, a flat, a corrugated, a rectangular, an asymmetric, or a combination thereof.In some embodiments, the cathode is a stainless steel electrode. In some embodiments, the cathode is selected from porous metals. In some embodiments, the cathode includes stainless steel, nickel, cobalt, titanium, steel, lead, platinum, and combinations thereof.

[0028] In some embodiments, at least 1, at least 2, at least 10, at least 100, at least 500 electrolytic cells are stacked one after the other in fluid communication. The stack of electrolytic cells has an inlet and an outlet. In some embodiments, the method includes electrolyzing an aqueous solution containing lithium in a stack of electrolytic cells having a pH gradient from the inlet to the outlet. In some embodiments, the method includes electrolyzing an aqueous solution containing lithium in a stack of electrolytic cells having a pH gradient that decreases from the inlet to the outlet. In some embodiments, the method includes electrolyzing an aqueous solution containing lithium in a stack of electrolytic cells having a pH gradient that decreases from the inlet to the outlet, where the inlet has a pH greater than 0.5 and the outlet has a pH less than 0.5. In some embodiments, the method includes electrolyzing an aqueous solution containing lithium in a stack of electrolytic cells having a pH gradient that decreases from the inlet to the outlet, where the inlet has a pH greater than 0.5 and the outlet has a pH less than 0.5, and the stack includes at least 100 electrolytic cells connected in series in fluid communication.

[0029] 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.

[0030] 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.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] 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.

[0035] 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.

[0036] In some embodiments, the battery material has the formula Li x The lithium metal phosphate includes a lithium metal phosphate of MPO4, where x is an integer equal to or greater than 1, and M is selected from metals, transition metals, rare earth metals, and combinations thereof.

[0037] In some embodiments, the battery material has the formula Li 1+x (Ni a Co b Mnc M 1 d ) 1-x containing lithium nickel cobalt manganese oxide of O2, 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. Exemplary lithium nickel cobalt manganese oxides include Li (1+x) [Ni 0.33 Co 0.33 Mn 0.33 (1-x) O2, Li (1+x) [Ni 0.5 Co 0.2 Mn 0.3 (1-x) O2, Li (1+x) [Ni 0.6 Co 0.2 Mn 0.2 (1-x) O2, Li (1+x) [Ni 0.7 Co 0.2 Mn 0.3 (1-x) O2 (wherein x is as defined above), and Li[Ni (1+x) [Ni 0.8 Co 0.1 Mn 0.1 (1-x) O2 (each x is as defined above), and Li[Ni 0.85 Co 0.13 Al 0.02 O2 is included.

[0038] In some embodiments, the battery material comprises 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.

[0039] ​​​​​In some embodiments, the battery material includes nickel, cobalt, manganese, copper, aluminum, iron, phosphorous, or combinations thereof.

[0040] 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 100. 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.

[0041] In some embodiments, the battery material is Li x The compound includes MO2, where x is an integer equal to or greater than 1, and M is selected from metals, transition metals, rare earth metals, and combinations thereof.

[0042] 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.

[0043] Additional Embodiments Some embodiments of the present disclosure include, but are not limited to, the following.

[0044] 1. A method comprising the step of electrolyzing an aqueous solution containing lithium, said aqueous solution having a pH of less than 0.5.

[0045] 2. The method of embodiment 1, wherein the aqueous solution comprises a sulfate salt.

[0046] 3. The method according to any one of the preceding claims, wherein the pH of the aqueous solution is adjusted along a gradient ranging from -1 to 0.5.

[0047] 4. The method according to embodiment 3, wherein the pH of the aqueous solution is adjusted upward along a gradient ranging from -1 to 0.5.

[0048] 5. The method of embodiment 3, wherein the pH of the aqueous solution is adjusted downward along a gradient ranging from -1 to 0.5.

[0049] 6. A method comprising the steps of electrolyzing a first aqueous solution containing lithium to obtain a second aqueous solution containing lithium and an acidic aqueous solution having a pH less than 0.5, adjusting the pH of the second aqueous solution with the acidic aqueous solution to obtain a third aqueous solution containing lithium having a pH less than 0.5, and electrolyzing the third aqueous solution containing lithium by the method according to any one of embodiments 1 to 5.

[0050] 7. The method of embodiment 6, wherein the first aqueous solution has a pH greater than 0.5.

[0051] 8. The method of any one of claims 6 to 7, wherein the electrolysis of the first aqueous solution is carried out in a different electrolysis cell than the electrolysis of the third aqueous solution.

[0052] 9. A process comprising the steps of stripping a liquid medium comprising lithium with an aqueous acidic solution to obtain an aqueous solution comprising lithium, and electrolyzing the aqueous solution comprising lithium by the process according to any one of the preceding embodiments to obtain an aqueous solution deficient in lithium, wherein the aqueous solution deficient in lithium is fed upstream of the process as an aqueous acidic solution, the liquid medium comprising less than 50% by weight of water relative to the total weight of the liquid medium, and the aqueous solution deficient in lithium has a lower lithium concentration than the aqueous solution comprising lithium.

[0053] 10. The method of embodiment 9, wherein the lithium-deficient aqueous solution has a lithium concentration greater than zero.

[0054] 11. The method of any one of claims 9 to 10, wherein the liquid medium comprises less than 5% by weight of water based on the total weight of the liquid medium.

[0055] 12. The method of embodiment 9, wherein the lithium-deficient aqueous solution has a lithium concentration in the range of about 20 g / L to about 100 g / L.

[0056] 13. The method of embodiment 9, wherein the aqueous solution containing lithium has a lithium concentration in the range of about 20 g / L to about 100 g / L.

[0057] 14. A method for preparing a liquid medium containing lithium, comprising the steps of electrolyzing an aqueous solution containing lithium by the method according to any one of embodiments 1 to 8 to obtain a lithium-deficient aqueous solution, and extracting the lithium-deficient aqueous solution with a liquid medium, wherein the liquid medium comprises less than 50% by weight of water relative to the total weight of the liquid medium, and the lithium-deficient aqueous solution has a lower lithium concentration than the aqueous solution containing lithium.

[0058] 15. The method according to any one of embodiments 9 to 13, wherein the lithium-containing liquid medium is prepared according to the method according to claim 14.

[0059] 16. An aqueous solution containing lithium is electrolyzed, and the aqueous solution has a pH of less than 0.5 and a current of 0.1 A / cm 2 ~1.5A / cm 2 16. The method of any one of the preceding claims, having a current density in the range of

[0060] 17. An aqueous solution containing lithium is electrolyzed, and the aqueous solution has a pH of less than 0.5 and a current of 0.1 A / cm 2 ~1A / cm 2 17. The method of any one of the preceding claims, having a current density in the range of

[0061] 18. An aqueous solution containing lithium is electrolyzed, and the aqueous solution has a pH of less than 0.5 and a current of 0.3 A / cm 2 ~1A / cm 2 18. The method of any one of the preceding claims, having a current density in the range of

[0062] 19. An aqueous solution containing lithium is electrolyzed, and the aqueous solution has a pH of less than 0.5 and a current of 0.4 A / cm 2 ~0.9A / cm 2 19. The method of any one of the preceding claims, having a current density in the range of

[0063] 20. The method according to any one of the preceding claims, wherein an aqueous solution containing lithium is electrolyzed, the aqueous solution having a pH of less than 0.5 and a voltage in the range of 0V to 5V.

[0064] 21. The method according to any one of the preceding claims, wherein an aqueous solution containing lithium is electrolyzed, the aqueous solution having a pH of less than 0.5 and a voltage in the range of 0V to 3.5V.

[0065] 22. The method according to any one of the preceding claims, wherein an aqueous solution containing lithium is electrolyzed, the aqueous solution having a pH of less than 0.5 and a temperature in the range of 20°C to 95°C.

[0066] 23. The method according to any one of the preceding claims, wherein an aqueous solution containing lithium is electrolyzed, the aqueous solution having a pH of less than 0.5 and a temperature in the range of 30°C to 90°C.

[0067] 24. The method according to any one of the preceding claims, wherein an aqueous solution containing lithium is electrolyzed, the aqueous solution having a pH of less than 0.5 and a temperature in the range of 40°C to 85°C.

[0068] 25. The method according to any one of the preceding claims, wherein an aqueous solution containing lithium is electrolyzed, the aqueous solution having a pH of less than 0.5 and a temperature in the range of 50°C to 85°C.

[0069] 26. The method of any one of the preceding embodiments, wherein no base is added to the aqueous solution containing lithium.

[0070] 27. The method of any one of the preceding embodiments, wherein the pH of the aqueous solution containing lithium is not adjusted upward.

[0071] 28. 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 black mass; leaching the black mass to obtain an aqueous solution comprising lithium; and treating the aqueous solution according to the method of any one of embodiments 1 to 27.

[0072] 29. The method of any one of embodiments 6 to 8, wherein the first aqueous solution containing lithium is obtained by a method 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; and leaching the black mass to obtain an aqueous solution containing lithium.

[0073] 30. The method of any one of the preceding claims, wherein the aqueous solution containing lithium is obtained by leaching a lithium-containing ore.

[0074] 31. The method of any one of the preceding claims, wherein the aqueous solution containing lithium is lithium-containing groundwater.

[0075] 32. The method of any one of embodiments 6 to 8, wherein the first aqueous solution containing lithium is obtained by leaching a lithium-containing ore.

[0076] 33. The method of any one of embodiments 6 to 8, wherein the first aqueous solution containing lithium is lithium-containing groundwater.

[0077] 34. The method of any one of the preceding embodiments, wherein the aqueous solution containing lithium is obtained by leaching a battery material.

[0078] 35. The method of any one of embodiments 6 to 8, wherein the first aqueous solution containing lithium is obtained by leaching a battery material.

[0079] A claim or description including "or" or "and / or" between at least one member of a group is deemed to be satisfied when 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 indicated to the contrary or clear from the context. The present disclosure includes embodiments in which exactly one member of the group is present in, employed in, or otherwise relevant to a given product or method. The present 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.

[0080] 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.

[0081] 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.

Claims

1. A method comprising the step of electrolyzing an aqueous solution containing lithium, wherein the aqueous solution has a pH of less than 0.

5.

2. The method according to claim 1, wherein the aqueous solution contains a sulfate.

3. The method according to claim 1 or 2, wherein the pH of the aqueous solution is adjusted along a gradient in the range of -1 to 0.

5.

4. The method according to claim 3, wherein the pH of the aqueous solution is adjusted to increase along a gradient in the range of -1 to 0.

5.

5. The method according to claim 3, wherein the pH of the aqueous solution is adjusted to decrease along a gradient in the range of -1 to 0.

5.

6. A method comprising the step of electrolyzing a first aqueous solution containing lithium to obtain a second aqueous solution containing lithium and an acidic aqueous solution having a pH of less than 0.5, adjusting the pH of the second aqueous solution with the acidic aqueous solution to obtain a third aqueous solution containing lithium having a pH of less than 0.5, and electrolyzing the third aqueous solution containing lithium by the method according to claim 1.

7. The method according to claim 6, wherein the first aqueous solution has a pH greater than 0.

5.

8. The method according to claim 6, wherein the electrolysis of the first aqueous solution is performed in an electrolysis cell different from that of the third aqueous solution.

9. A method comprising the step of stripping a liquid medium containing lithium with an acidic aqueous solution to obtain an aqueous solution containing lithium, and electrolyzing the aqueous solution containing lithium by the method according to claim 1 to obtain a lithium-deficient aqueous solution, wherein the lithium-deficient aqueous solution is supplied upstream of the method as an acidic aqueous solution, the liquid medium contains less than 50% by mass of water with respect to the total mass of the liquid medium, and the lithium-deficient aqueous solution has a lower lithium concentration than the aqueous solution containing lithium.

10. The method according to claim 9, wherein the lithium-deficient aqueous solution has a lithium concentration greater than zero.

11. The method according to claim 9 or 10, wherein the liquid medium contains less than 5% by mass of water with respect to the total mass of the liquid medium.

12. The method according to claim 9, wherein the lithium-deficient aqueous solution has a lithium concentration in the range of about 20 g / L to about 100 g / L.

13. The method according to claim 9, wherein the aqueous solution containing lithium has a lithium concentration in the range of about 20 g / L to about 100 g / L.

14. A method for preparing a liquid medium containing lithium, comprising the steps of electrolyzing an aqueous solution containing lithium by the method according to claim 1 or 2 to obtain a lithium-deficient aqueous solution, and extracting the lithium-deficient aqueous solution with a liquid medium, wherein the liquid medium contains less than 50% by mass of water based on the total mass of the liquid medium, and the lithium-deficient aqueous solution has a lower lithium concentration than the aqueous solution containing lithium.

15. The method according to claim 9, wherein the liquid medium containing lithium is prepared according to the method according to claim 14.

16. The aqueous solution containing lithium has a pH of less than 0.5 and is electrolyzed at a current density in the range of 0.1 A / cm ２ to 1.5 A / cm ２ The method according to claim 1 or 2, wherein the electrolysis is carried out at a current density in the range of 0.1 A / cm

17. The aqueous solution containing lithium has a pH of less than 0.5 and is electrolyzed at a current density in the range of 0.1 A / cm ２ to 1 A / cm ２ The method according to claim 1 or 2

18. The aqueous solution containing lithium has a pH of less than 0.5 and is electrolyzed at a current density in the range of 0.3 A / cm ２ to 1 A / cm ２ The method according to claim 1 or 2, wherein the electrolysis is carried out at a current density in the range of 0.3 A / cm to 1 A / cm.

19. The aqueous solution containing lithium has a pH of less than 0.5 and is electrolyzed at a current density in the range of 0.4 A / cm ２ to 0.9 A / cm ２ The method according to claim 1 or 2, wherein the electrolysis is carried out at a current density in the range of 0.4 A / cm

20. The method according to claim 1 or 2, wherein the aqueous solution containing lithium has a pH of less than 0.5 and is electrolyzed at a voltage in the range of 0 V to 5 V.

21. The method according to claim 1 or 2, wherein the aqueous solution containing lithium has a pH of less than 0.5 and is electrolyzed at a voltage in the range of 0 V to 3.5 V.

22. The method according to claim 1 or 2, wherein the aqueous solution containing lithium has a pH of less than 0.5 and a temperature in the range of 20 °C to 95 °C.

23. The method according to claim 1 or 2, wherein the aqueous solution containing lithium has a pH of less than 0.5 and a temperature in the range of 30 °C to 90 °C.

24. The method according to claim 1 or 2, wherein the aqueous solution containing lithium has a pH of less than 0.5 and a temperature in the range of 40 °C to 85 °C.

25. The method according to claim 1 or 2, wherein the aqueous solution containing lithium has a pH of less than 0.5 and a temperature in the range of 50 °C to 85 °C.

26. The method according to claim 1 or 2, wherein no base is added to the aqueous solution containing lithium.

27. The method according to claim 1 or 2, wherein the pH of the aqueous solution containing lithium is not adjusted by rising.

28. A method for recycling lithium-ion battery materials, comprising the steps of mechanically grinding at least one selected from lithium-ion batteries, lithium-ion battery wastes, lithium-ion battery manufacturing scraps, lithium-ion cell manufacturing scraps, lithium-ion cathode active materials, and combinations thereof to obtain a black mass, leaching the black mass to obtain an aqueous solution containing lithium, and treating the aqueous solution according to the method according to claim 1 or 2.

29. The method according to any one of claims 6 to 8, obtained by a method comprising a step of mechanically pulverizing at least one selected from a first aqueous solution containing lithium, a lithium-ion battery, lithium-ion battery waste, lithium-ion battery manufacturing scrap, lithium-ion cell manufacturing scrap, a lithium-ion cathode active material, and combinations thereof to obtain a black mass, and a step of leaching the black mass to obtain an aqueous solution containing lithium.

30. The method according to claim 1 or 2, wherein the aqueous solution containing lithium is obtained by leaching a lithium-containing ore.

31. The method according to claim 1 or 2, wherein the aqueous solution containing lithium is lithium-containing groundwater.

32. The method according to any one of claims 6 to 8, wherein the first aqueous solution containing lithium is obtained by leaching a lithium-containing ore.

33. The method according to any one of claims 6 to 8, wherein the first aqueous solution containing lithium is lithium-containing groundwater.

34. The method according to claim 1 or 2, wherein the aqueous solution containing lithium is obtained by leaching battery materials.

35. The method according to any one of claims 6 to 8, wherein the first aqueous solution containing lithium is obtained by leaching battery materials.

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