Method for regenerating Li and Ni from solution

Abstract

Disclosed herein are methods for recycling elements such as lithium and / or nickel from solutions, for example, recovering reusable lithium and nickel from waste streams produced by the delithiation of lithium nickel oxide materials.

Description

Technical Field

[0001] This application claims the benefit of priority of U.S. Provisional Application No. 63 / 119,790, filed on December 1, 2020, the entire content of which is incorporated herein by reference.

[0002] Disclosed herein are methods for recycling elements, such as lithium and / or nickel, from a solution, for example, methods for recovering reusable lithium and nickel from waste streams generated by the delithiation of lithium nickel oxide materials.

Background Art

[0003] The increased dependence on lithium-ion batteries in a wide range of technical fields has heightened the need for cost-effective and time-efficient methods for extracting valuable elements such as nickel and lithium from waste streams generated during battery production and recycling. In the delithiation process, a large amount of waste that usually has to be processed is generated, increasing the cleaning time and processing cost. Furthermore, recycling processes that use oxidizing agents may not provide effective separation of the extracted components, making it impossible to perform the individual recovery of the desired materials. Such defects reduce the amount of material that can be recovered and increase both the amount of waste generated and the cost associated with the extraction of contaminants from aqueous waste streams.

[0004] Furthermore, multistage co-extraction for simultaneously recovering multiple materials such as both nickel and lithium has been reported. These methods can extract individual materials, but require a total of six steps with four co-extraction stages to produce the individually extracted materials. Thus, these co-extraction methods are expensive and time-consuming as each step is performed individually and different solvents are required for each step.

Summary of the Invention

Problems to be Solved by the Invention

[0005] Therefore, in this field, there is a need for extraction methods that improve efficiency and yield, for example, for extracting lithium and / or nickel from battery manufacturing or recycling waste streams. [Means for solving the problem]

[0006] Delithiation processes are typically carried out by reacting lithiated metal oxide materials with an acid to elute lithium. Delithiation processes are well known in the art and include, for example, the process described in U.S. Patent No. 8,298,706, which involves subjecting LiNiMOz materials to aqueous oxidizing mineral acids such as sulfuric acid, nitric acid, hydrochloric acid, perchloric acid, or oleum (i.e., fuming sulfuric acid). In the alternative process developed by the inventors, delithiation performance can be improved by using hypochlorite in combination with mineral acids. The addition of hypochlorite, however, presents specific challenges with respect to the recovery of lithium, sodium, metals, or other materials from waste disposal or waste streams. Therefore, a novel method for recycling elements such as lithium and / or nickel from waste streams generated by delithiation treatment, including hypochlorite and mineral acids, may be useful for improving overall production performance while reducing costs.

[0007] Disclosed herein is a method for isolating lithium and / or nickel, the method being: (A) Delithiation of lithium nickel oxide (LNO) material in the presence of mineral acid and hypochlorite to produce delithiated nickel oxide (DLNO) material and waste stream, wherein the waste stream contains chloride ions, lithium ions and nickel ions; and (B1) Precipitate Ni(OH)2 from waste stream to produce a lithium-rich solution. Includes.

[0008] In some embodiments, the waste stream contains Li at a concentration in the range of about 0.5 g / L to about 250 g / L, such as about 20 g / L to about 150 g / L. In some embodiments, the amount of lithium present in the waste stream is about 1 g / L to about 200 g / L, about 15 g / L to about 175 g / L, about 20 g / L to about 150 g / L, about 25 g / L to about 125 g / L, about 30 g / L to about 100 g / L, about 40 g / L to about 75 g / L, or about 50 g / L to about 60 g / L. In some embodiments, the waste stream contains Li at a concentration in the range of about 0.5 g / L to about 88 g / L, such as about 20 g / L to about 80 g / L, about 20 g / L to about 60 g / L. In some embodiments, the amount of lithium present in the waste stream is about 1 g / L to about 88 g / L, about 20 g / L to about 60 g / L.

[0009] In some embodiments, the amount of nickel present in the waste stream is in the range of about 0.5 g / L to about 400 g / L, such as about 20 g / L to about 200 g / L. In some aspects, the amount of nickel present in the waste stream is about 1.0 g / L to about 300 g / L, about 15 g / L to about 250 g / L, about 20 g / L to about 200 g / L, about 25 g / L to about 150 g / L, about 30 g / L to about 100 g / L, about 40 g / L to about 75 g / L, or about 50 g / L to about 60 g / L.

[0010] In some embodiments, the lithium-rich solution has Ni at 1000 ppm (parts per million) or less 2+ (e.g., Ni at 500 ppm or less 2+ 、Ni at 100 ppm or less 2+ 、Ni at 10 ppm or less 2+ 、Ni at 9 ppm or less 2+ 、Ni at 8 ppm or less 2+ 、Ni at 7 ppm or less 2+ 、Ni at 6 ppm or less 2+ ,Ni at 5 ppm or less 2+ ,Ni at 4 ppm or less 2+ ,Ni at 3 ppm or less 2+ ,Ni at 2 ppm or less 2+ ,or Ni at 1 ppm or less 2+It contains nickel at a concentration of ).

[0011] In some embodiments, the lithium-rich solution contains less than 10% by mass of the amount of Ni present in the waste stream (e.g., less than 1%, less than 0.1%, less than 0.01%, less than 0.001%, or less than 0.0001%).

[0012] In some embodiments, the hypochlorite is selected from calcium hypochlorite, lithium hypochlorite, and sodium hypochlorite.

[0013] In some embodiments, the method further comprises treating the waste stream by solvent extraction in the presence of introduced LiOH, introduced NaOH, or a combination thereof. In some embodiments, the hypochlorite is a calcium hypochlorite salt, and the method further comprises treating the waste stream by solvent extraction in the presence of introduced LiOH, introduced NaOH, or a combination thereof.

[0014] In some embodiments, the method is: (C) Concentrating a lithium-rich solution to produce a concentrated lithium-rich solution. It also includes.

[0015] In some embodiments, the lithium-rich solution or concentrated lithium-rich solution contains one or more polyvalent ions (e.g., aluminum, silicon, magnesium, calcium, cobalt, manganese, etc.).

[0016] In some embodiments, the method is: (D1) Lithium-rich solution or concentrated lithium-rich solution is subjected to ion exchange. + To remove at least some of the other polyvalent ions and generate a LiCl stream, It also includes.

[0017] In some embodiments, the hypochlorite is selected from calcium hypochlorite and sodium hypochlorite; step (D1) is: A lithium-rich solution or concentrated lithium-rich solution is subjected to solvent extraction in the presence of added HCl to remove at least some polyvalent ions and produce a LiCl stream; Separating Na from the LiCl stream using solvent extraction to produce a NaCl stream; The optional enrichment of the LiCl stream; It also includes.

[0018] In some embodiments, the method further includes subjecting at least a portion of the NaCl stream to electrolysis to produce NaOH, H2 gas, and Cl2 gas.

[0019] In some embodiments, the method further includes heating at least a portion of H2 gas in an HCl burner to produce HCl. In some embodiments, at least a portion of the produced HCl is recycled as process input.

[0020] In some embodiments, the method further includes reacting at least a portion of Cl2 gas with Ca(OH)2, NaOH, or LiOH to produce calcium hypochlorite, sodium hypochlorite, or lithium hypochlorite. In some embodiments, at least a portion of the produced calcium hypochlorite or sodium hypochlorite is recycled as process input.

[0021] In some embodiments, the hypochlorite is lithium hypochlorite salt; and the method is: (D2) Converting a lithium-rich solution or concentrated lithium-rich solution into a Li2CO3 stream. It also includes.

[0022] In some embodiments, step (D2) includes treating a lithium-rich solution or concentrated lithium-rich solution with a reagent to produce a Li2CO3 stream. In some embodiments, the reagent is soda ash.

[0023] In some embodiments, the method is: (E) Isolating LiOH from the LiCl stream or Li2CO3 stream. It also includes.

[0024] In some embodiments, the isolated LiOH is in liquid form, crystalline form, or both. In some embodiments, at least a portion of the isolated LiOH is in liquid form. In some embodiments, at least a portion of the isolated LiOH is recycled as process input.

[0025] In some embodiments, the method further includes reacting at least a portion of the isolated LiOH with Cl2 gas to produce lithium hypochlorite. In some embodiments, at least a portion of the produced lithium hypochlorite is recycled as process input.

[0026] In some embodiments, the method further includes crystallizing LiOH monohydrate from at least a portion of isolated LiOH.

[0027] In some embodiments, step (E) is: (F) The LiCl stream is subjected to electrolysis to produce LiOH liquid, H2 gas, and Cl2 gas. (G) Precipitating LiOH monohydrate from LiOH liquid, It also includes.

[0028] In some embodiments, the method further includes heating at least a portion of H2 gas in an HCl burner in the presence of at least a portion of Cl2 gas to produce HCl. In some embodiments, at least a portion of the produced HCl is recycled as process feed.

[0029] In some embodiments, the method further includes reacting at least a portion of Cl2 gas with Ca(OH)2 to produce calcium hypochlorite. In some embodiments, at least a portion of the produced calcium hypochlorite is recycled as process input.

[0030] In some embodiments, the method further includes reacting at least a portion of liquid LiOH with at least a portion of Cl2 gas to produce lithium hypochlorite. In some embodiments, at least a portion of the produced lithium hypochlorite is recycled as process input.

[0031] In some embodiments, the method further includes reacting at least a portion of the NaOH produced by electrolysis with at least a portion of Cl2 gas to produce sodium hypochlorite. In some embodiments, at least a portion of the produced sodium hypochlorite is recycled as process input.

[0032] In some embodiments, step (E) is: The process involves separating Li from Na in a LiCl stream to produce NaCl using solvent extraction in the presence of introduced NaOH; Optionally, the LiCl stream may be enriched to produce a concentrated LiCl stream; The process involves subjecting a LiCl stream or concentrated LiCl stream to electrolysis to convert LiCl into LiOH liquid, H2 gas, and Cl2 gas; Includes.

[0033] In some embodiments, the method further includes precipitating LiOH monohydrate from a LiOH liquid.

[0034] In some embodiments, the method further includes heating at least a portion of H2 gas in an HCl burner in the presence of at least a portion of Cl2 gas to produce HCl. In some embodiments, at least a portion of the produced HCl is recycled as process feed.

[0035] In some embodiments, the method further reacts at least a portion of the Cl2 gas with Ca(OH)2 to produce calcium hypochlorite. In some embodiments, at least a portion of the produced calcium hypochlorite is recycled as process input.

[0036] In some embodiments, the method further includes subjecting at least a portion of the generated NaCl to electrolysis to produce NaOH. In some embodiments, at least a portion of the generated NaOH is recycled as process input.

[0037] In some embodiments, step (E): The process involves treating a Li2CO3 stream with calcium hydroxide to produce LiOH. Includes.

[0038] In some embodiments, the method is continuous. In some embodiments, process inputs are generated during the operation of the process and recycled within the process.

[0039] In some embodiments, the mineral acid is selected from sulfuric acid, nitric acid, hydrochloric acid, perchloric acid, and oleum. In some embodiments, the mineral acid is HCl.

[0040] In some embodiments, the waste stream has a pH of 2 to 6.

[0041] In some embodiments, the LNO material is selected from the LiNixMyOz material, where: M is selected from metals; x is selected from a number between 0 and 1.999; y is selected from a number between 0 and 1.999; and z is selected from the numbers 1 through 4.

[0042] In some embodiments, M is selected from transition metals, post-transition metals, and combinations thereof. In some embodiments, M is selected from Ni, Co, Mn, Ti, Zr, Nb, Hf, V, Cr, Sn, Cu, Mo, W, Fe, Si, B, and any combination of the above. In some embodiments, M is present in atomic percentages from 0% to 99.9% (e.g., 0% to 70%, 0% to 30%, 0% to 20%, 0% to 10%, less than 0% to 10%).

[0043] In some embodiments, the LNO material is selected from LiNiMOz materials. In some embodiments, M is selected from transition metals, post-transition metals, and combinations thereof. In some embodiments, M is selected from Ni, Co, Mn, Ti, Zr, Nb, Hf, V, Cr, Sn, Cu, Mo, W, Fe, Si, B, and any combination thereof. In some embodiments, M is present in atomic percentages from 0% to 99.9% (e.g., 0% to 70%, 0% to 30%, 0% to 20%, 0% to 10%, less than 0% to 10%).

[0044] In some embodiments, the LiNiMOz material is selected from LiNiCoAlOz and LiNiCoAlM'Oz materials, where M' is selected from metals. In some embodiments, M' is selected from transition metals, post-transition metals, and combinations thereof. In some embodiments, M' is Mg.

[0045] In some embodiments, the method further includes forming an LNO material using Ni(OH)2 produced by the method, LiOH monohydrate produced by the method, or both.

[0046] Also disclosed herein are methods for isolating lithium and / or nickel, the methods being: (A) Delithiation of lithium nickel oxide (LNO) material in the presence of mineral acid and calcium hypochlorite salt to produce delithiated nickel oxide (DLNO) material and waste stream, wherein the waste stream contains chloride ions, lithium ions and nickel ions; (B) Precipitating Ni(OH)2 from the waste stream to produce a concentrated lithium-rich solution; (C) To produce a concentrated lithium-rich solution by arbitrarily concentrating a lithium-rich solution; (D) Li is subjected to ion exchange of a lithium-rich solution or a concentrated lithium-rich solution. + To remove at least some of the other polyvalent ions and generate a LiCl stream; (E) Electrolyzing a LiCl stream to produce LiOH liquid, H2 gas, and Cl2 gas; (F) Precipitating LiOH monohydrate from LiOH liquid; (G)i) reacting at least a portion of liquid LiOH and / or (ii) redissolved LiOH monohydrate with at least a portion of Cl2 gas to produce lithium hypochlorite; (H) Producing HCl by heating at least a portion of H2 gas in an HCl burner in the presence of at least a portion of Cl2 gas; Includes.

[0047] Alternatively, the methods disclosed herein may be modified to obtain purified wastewater. [Brief explanation of the drawing]

[0048] [Figure 1]Figure 1A shows a method for producing LiNiMOz material and recycling one or more elements from the product. Figure 1B shows a method for separating Ni(OH)2, HCl, hypochlorite, LiOH, and water from a waste stream. [Figure 2] Figure 2 shows a method for processing the waste stream generated from the use of Ca(ClO)2 in the delithiation reaction. [Figure 3] Figure 3 shows a method for treating the waste stream generated from the use of calcium hypochlorite salts in the delithiation reaction. [Figure 4] Figure 4 shows a method for treating the waste stream generated from the use of lithium hypochlorite salts in the delithiation reaction. [Figure 5] Figure 5 shows an alternative method for processing the waste stream generated from the use of lithium hypochlorite in the delithiation reaction. [Figure 6] Figure 6 shows a method for treating the waste stream generated from the use of sodium hypochlorite salts in the delithiation reaction. [Modes for carrying out the invention]

[0049] Non-exclusive exemplary embodiments

[0050] Some embodiments of this disclosure, though not limited to them, include:

[0051] 1. A method for producing LiOH monohydrate and Ni(OH)2 from a waste stream, the method being: (A') A step of delithiating LiNiMOz in the presence of HCl and hypochlorite to produce delithiated LiNiMOz and a waste stream (mother liquor), wherein the waste stream contains chloride ions and Ni in amounts of lithium and nickel. 2+ / Li + Steps including the solution of; (B') In the presence of added LiOH, added NaOH, or a combination thereof, solvent exchange and / or precipitation occurs, Ni 2+ / Li + A step of processing a solution to produce a lithium-rich solution containing Ni(OH)2 and optionally one or more polyvalent ions, wherein the Ni(OH)2 is optionally used to produce the LiNiMOz; (C') The step of optionally concentrating a lithium-rich solution to produce a concentrated lithium-rich solution; (D') Li is subjected to ion exchange of a lithium-rich solution or a concentrated lithium-rich solution. + The steps include removing other polyvalent ions to generate a LiCl stream, or converting the lithium-rich solution into a Li2CO3 stream; (E') A step of subjecting the LiCl stream or the Li2CO3 stream from step (D') to isolation of LiOH, wherein the LiOH is liquid, crystalline or both; A method that includes this.

[0052] 2. Step (E') is: (F') A step of subjecting the LiCl stream to electrolysis to produce LiOH liquid, H2 gas, and Cl2 gas, wherein optionally at least a portion of the LiOH liquid is reused as LiOH introduced in step (B'); (G') A step of precipitating LiOH monohydrate from the LiOH liquid, wherein the LiOH monohydrate may optionally be used for the production of LiNiMOz; The method according to Embodiment 1, including the method described above.

[0053] 3. The method according to Embodiment 2, wherein the H2 gas is heated in an HCl burner to produce HCl, and optionally the HCl is used in step (A').

[0054] 4. The method according to Embodiment 2 or 3, wherein the Cl2 gas is reacted with Ca(OH)2 and sodium hypochlorite to produce calcium hypochlorite, and optionally, at least a portion of the calcium hypochlorite is used in step (A').

[0055] 5. Step (E') is: In the presence of introduced NaOH, solvent exchange is used to separate Li from Na in the LiCl stream to produce NaCl; Optionally, the LiCl stream may be concentrated; The LiCl stream is subjected to electrolysis to convert LiCl into LiOH liquid, H2 gas, and Cl2 gas, wherein optionally, at least a portion of the LiOH liquid is reused as the LiOH introduced in step (B'); The method according to Embodiment 1, including the method described above.

[0056] 6. The method according to Embodiment 5, further comprising precipitating LiOH monohydrate from the LiOH liquid, wherein the LiOH monohydrate can optionally be used to produce LiNiMOz.

[0057] 7. The method according to Embodiment 5, wherein the H2 gas is optionally heated together with the Cl2 gas in an HCl burner to produce HCl, and the HCl is optionally used in step (A') or step (D').

[0058] 8. The method according to Embodiment 5 or 6, wherein the Cl2 gas is reacted with Ca(OH)2 and sodium hypochlorite to produce calcium hypochlorite, and optionally, at least a portion of the calcium hypochlorite is used in step (A').

[0059] 9. The method according to Embodiment 5, wherein NaCl is subjected to electrolysis to produce NaOH, and optionally, the NaOH is used as the NaOH to be added.

[0060] 10. Step (D') is: The process involves treating a lithium-rich solution or a concentrated lithium-rich solution with soda ash or other reactants to produce the Li2CO3 stream. The method according to Embodiment 1, further comprising:

[0061] 11. The method according to Embodiment 10, further comprising treating the Li2CO3 stream with calcium carbonate to produce LiOH.

[0062] 12. Optionally, the LiOH may be subjected to solvent exchange to remove polyvalent ions; Optionally, transfer at least a portion of the LiOH to step (B'); The process involves reacting at least a portion of the LiOH with Cl2 gas to produce lithium hypochlorite, wherein optionally, at least a portion of the lithium hypochlorite is used in step (A'); Optionally, LiOH monohydrate may be crystallized from the LiOH, and optionally, the LiOH monohydrate may be used to produce the LiNiMOz; The method according to embodiment 10 or 11, further comprising:

[0063] 13. Step (E') is: The LiCl stream is subjected to electrolysis to produce LiOH liquid, H2 gas, and Cl2 gas, wherein optionally, at least a portion of the LiOH liquid is reused as the LiOH introduced in step (B'); The process involves precipitating LiOH monohydrate from the LiOH liquid, wherein the LiOH monohydrate may optionally be used to produce LiNiMOz; The method according to Embodiment 1, further comprising:

[0064] 14. Reacting at least a portion of the LiOH liquid with the Cl2 gas and sodium hypochlorite to produce lithium hypochlorite, wherein optionally, at least a portion of the lithium hypochlorite is used as the hypochlorite in step (A'). The method according to Embodiment 13, further comprising:

[0065] 15. The method according to Embodiment 13 or 14, wherein the H2 gas is optionally subjected to an HCl burner in the presence of the Cl2 gas to produce HCl, and the HCl is optionally used in step (D').

[0066] 16. Step (D') is: A lithium-rich solution or concentrated lithium-rich solution is subjected to solvent exchange in the presence of added HCl to remove polyvalent ions and produce the LiCl stream, wherein the method involves separating Na from the LiCl stream using solvent exchange to produce the NaCl stream; Optionally, the LiCl stream may be concentrated; The method according to Embodiment 1, including the method described above.

[0067] 17. The method according to Embodiment 16, wherein step (E') is to subject the LiCl stream to electrolysis to convert LiCl to LiOH liquid, wherein optionally at least a portion of the LiOH liquid is reused as LiOH to be introduced in step (B').

[0068] 18. The method according to Embodiment 16, wherein the NaCl stream is subjected to electrolysis to produce NaOH, H2 gas, and Cl2 gas, and optionally at least a portion of the NaOH is used in step (B').

[0069] 19. The method according to any one of Embodiments 16, 17, or 18, wherein the H2 gas is heated in an HCl burner to produce HCl, and optionally the HCl is used in step (A'), (D'), or both.

[0070] 20. The method according to Embodiment 18 or 19, wherein the Cl2 gas is reacted with Ca(OH)2 or NaOH (optionally the NaOH in Embodiment 18) to produce calcium hypochlorite or sodium hypochlorite, and optionally at least a portion of the sodium hypochlorite or calcium hypochlorite is used in step (A') as the hypochlorite added.

[0071] 21. The method according to any one of Embodiments 1 to 20, wherein the method is continuous.

[0072] 22. The method according to any one of Embodiments 1 to 21, wherein at least a portion of the hypochlorite (optionally liquid or solid) in step (A') is produced by the method described above.

[0073] 23. The method according to any one of Embodiments 1 to 22, wherein HCl in step (A') is the product of the method.

[0074] 24. The method according to any one of Embodiments 1 to 23, wherein the LiOH introduced is a product produced by the method described above.

[0075] 23. The method according to any one of Embodiments 1 to 24, wherein M in LiNiMOz exists as an atomic percentage of 0 to 99.9, optionally 0 to 70, optionally 0 to 30, optionally 0 to 20, optionally 0 to 10, or optionally 0 to less than 10.

[0076] 24. The method according to Embodiment 23, wherein M is selected from the group consisting of Ni, Co, Mn, Ti, Zr, Nb, Hf, V, Cr, Sn, Cu, Mo, W, Fe, Si, B, other transition metals or post-transition metals, or any combination thereof.

[0077] 25. The method according to Embodiment 24, wherein M is Mn, Mg, Al, Co, and / or most other transition metals or post-transition metals.

[0078] 26. The method according to Embodiment 25, wherein LiNiMOz is LiNiCoAlOz, LiNiCoAlM'Oz, and M' is optionally a transition metal, post-transition metal, Mg, or the like.

[0079] 27. The method according to any one of embodiments 1 to 26, wherein the pH of the waste stream is 2 to 6.

[0080] 28. The method according to any one of Embodiments 1 to 27, wherein the LiNiMOz is formed using Ni(OH)2 produced by the method, LiOH monohydrate produced by the method, or a combination thereof.

[0081] Provided here is a method for obtaining reusable materials that can function as precursors for the production of battery electrode active materials. The production of battery materials, particularly those required for use in the cathodes of lithium-ion batteries, requires the synthesis and subsequent lithiation of precursor metal hydroxide materials. Lithitation of these materials forms crystalline electrochemically active materials with lithium positions in their crystal structure during firing, thereby enabling more robust cycles when the material is used in a battery. For charging, particularly for primary lithium-ion batteries, the cathode material needs to be delithiated. Delithiation prepares the electrochemically active material for the absorption of lithium into its crystal structure during discharge.

[0082] The methods disclosed herein enable the recycling of robust waste streams to produce materials such as Ni(OH)2 and LiOH monohydrate, which can be replenished and returned for reactions for the production of LiNiMOz materials and further recycling reactions. Thus, in some embodiments, the methods disclosed herein are sequential, meaning that at least one product of the method is fed back to an earlier stage of the recycling process or to an upstream reaction for the production or processing of LiNiMOz materials.

[0083] Lithium nickel oxide materials (referred to herein as "LNO" without being limited to a specific chemical formula) are typically produced by co-precipitating hydroxide reaction products, such as nickel hydroxide alone or with other metal hydroxides. These resulting materials are then combined with lithium hydroxide in a calcination step to form lithium nickel oxide. The LNO is then delithiated with an acid, such as a mineral acid, such as HCl, and a hypochlorite (e.g., calcium hypochlorite, sodium hypochlorite, lithium hypochlorite, or a combination thereof) to produce delithiated nickel oxide (DLNO), which can be used as a cathode active material in electrochemical batteries or for other applications. The DLNO is separated from the mother liquor (ML) in a solid-liquid separation step (SLS). As a result of the delithiation reaction, the mother liquor may contain some or all of Ni, Ca, Na, Li, and K in the form of chlorides, hypochlorites, or other chloride species. Depending on the method used, different mother liquor treatments may be employed to recover Ni(OH)2 and LiOH monohydrate for subsequent use in the further production of LNO material.

[0084] The methods described herein can utilize waste streams generated from LNO material.

[0085] In some embodiments, the LNO material is selected from the LiNixMyOz material, where, Each of x and y is independently selected from a number between 0 and 1.999, or any value or range between them; and z is selected from numbers between 1 and 4, or any value or range between any approximately 2 and any approximately 4.

[0086] In some embodiments, z is approximately 2, and each of x and y is selected from a number between 0 and 0.999. In some embodiments, z is approximately 4, and each of x and y is selected from a number between 1 and 1.999, and M is one element or combination of elements (e.g., 2, 3, 4, 5, or more elements). Exemplarily, M in the LNO materials described herein may be a metal, e.g., Mn, Mg, Al, Co, and / or most other transition metals or post-transition metals, or combinations thereof. For example, the transition metal may be any transition metal suitable for use in an electrochemical cell. Exemplary examples of transition metals include, but are not limited to, Ni, Co, Mn, Ti, Zr, Nb, Hf, V, Cr, Sn, Cu, Mo, W, Fe, Si, B, or other transition metals. Exemplary examples of LNO materials include, but are not limited to, LiNiCoMnM'Oz, LiNiCoMgM'Oz, LiNiCoAlOz, or LiNiCoAlM'Oz, where M' is optionally a transition metal, post-transition metal, Mg, or others, and may not be present in some embodiments.

[0087] Lithium compounds and nickel compounds can be used to produce electrochemically active compounds, such as LNO materials. Optionally, the lithium compound may be lithium hydroxide, lithium oxide, lithium carbonate, lithium nitrate, lithium sulfate, lithium acetate, lithium peroxide, lithium bicarbonate, or lithium halides, or any combination thereof.

[0088] The method for recovering the material from the mother liquor may vary depending on the identity of the hypochlorite and the recycled product to be isolated. “Hypochlorite,” as used herein, includes calcium, lithium, or sodium hypochlorite, or any combination thereof. Generally, waste material is provided as a source of Li and Ni for extraction or isolation by the methods provided herein. The term “waste” as used herein refers to Ni at concentrations suitable for extraction. 2+ and Li +It is defined as a liquid or solid composition containing either or both of the following. “Waste” does not have to be a composition that is a spent product of another preceding process, but may be a product of an upstream process, such as the leaching of Ni or Li from a prior treatment step of the desired LNO material. Optionally, as used herein, “Waste” is a waste stream from continuous or discontinuous leaching of Ni and Li generated during, for example, the delithiation of LNO with a mineral acid (optionally used for cathode formation in a primary or secondary electrochemical cell).

[0089] As used herein, "ppm" or "parts per million" refers to milligrams per liter (mg / L).

[0090] As used herein, “battery grade” refers to a purity of at least 95% (for example, at least 99%).

[0091] LiNiMOz materials can be delithiated in such a manner that they yield a chloride matrix having Li and Ni that can be used for subsequent isolation according to the methods described herein. Optionally, delithiation is carried out by methods substantially recognized in the art, exemplified by the method described in U.S. Patent No. 8,298,706, for example, by subjecting the LiNiMOz material to an aqueous hydrochloric acid or perchloric acid solution at a desired delithiation temperature. The acidic solution may have a concentration of 1 mol / liter or more (e.g., 3 mol / liter or more, 6 mol / liter or more, 8 mol / liter or more, or 10 mol / liter or more) and / or 12 mol / liter or less (e.g., 10 mol / liter or less, 8 mol / liter or less, 6 mol / liter or less, or 3 mol / liter or less). Optionally, the concentration of the acidic solution may be between 0.1 mol / liter and 10 mol / liter (e.g., between 1 mol / liter and 10 mol / liter, or between 4 mol / liter and 8 mol / liter, etc.). Optionally, the delithiation temperature is between 0°C and 5°C, but in some embodiments, the delithiation temperature is 10°C or higher, optionally 60°C or higher. The resulting slurry is mixed at the delithiation temperature for about 0.5 to 40 hours, and the solids are left as a re-slurry or allowed to settle, after which the solid delithiation material is optionally isolated and washed for use in cathode formation. The supernatant removed from washing is used in further embodiments of the method provided herein for waste liquid Ni 2+ / Li + It can be used as a solution.

[0092] The waste stream (mother liquor) from the delithiation process is Ni as specified herein. 2+ / Li + It is sometimes called a solution and in some embodiments it may contain Li at concentrations ranging from about 0.5 g / L to about 250 g / L, for example, about 20 g / L to about 150 g / L. In some embodiments it contains Ni 2+ / Li +The amount of lithium present in the solution is approximately 1 g / L to 200 g / L, 15 g / L to 175 g / L, 20 g / L to 150 g / L, 25 g / L to 125 g / L, 30 g / L to 100 g / L, 40 g / L to 75 g / L, or 50 g / L to 60 g / L.

[0093] In some embodiments, 2+ / Li + The amount of nickel present in the solution can range from approximately 0.5 g / L to approximately 400 g / L, and arbitrarily from approximately 20 g / L to approximately 200 g / L. In some embodiments, Ni 2+ / Li + The amount of nickel present in the solution is approximately 1.0 g / L to 300 g / L, 15 g / L to 250 g / L, 20 g / L to 200 g / L, 25 g / L to 150 g / L, 30 g / L to 100 g / L, 40 g / L to 75 g / L, or 50 g / L to 60 g / L.

[0094] Ni 2+ / Li + Figure 1B shows a general procedure for processing a solution to produce Ni(OH)2 and LiOH monohydrate. 2+ / Li +The waste stream in solution form is subjected to solvent extraction and / or precipitation reactions to precipitate Ni(OH)2 and / or remove polyvalent ions or other impurities that may affect subsequent processing steps. The precipitated Ni(OH)2 can be used as a precursor material for the production of further LNO materials. A lithium-rich solution, possibly containing lithium in the form of lithium chloride, is also produced. The LiCl stream can be subjected to further purification steps to produce and separate LiOH(liquid) and regenerate HCl and hypochlorite, which can optionally be reused itself for the production of further DLNO materials. LiOH(liquid) can optionally be used itself for subsequent Ni precipitation reactions in the recycling process itself. Optionally, at least a portion of the LiOH(liquid) can then be crystallized to form a LiOH monohydrate material, which can optionally be used itself for the production of LNO materials. Overall, the processing produces Ni(OH)2 and LiOH monohydrate, which can be reused for the production of LNO materials. In some embodiments, the method also produces HCl and / or hypochlorite, which can be used in delithiation reactions, such as the delithiation of LNO material. In some embodiments, the method provided herein is continuous and is performed in conjunction with a DLNO production process to not only continuously produce subsequent DLNO material but can also support the recycling of Ni and Li in the waste stream from the delithiation process during the production of DLNO material.

[0095] Some embodiments of this disclosure provide a process for generating recycled material from a waste stream, where the recycled material may comprise at least LiOH monohydrate and Ni(OH)2. In some embodiments, a method for processing a waste stream generated from the use of Ca(ClO)2 in a delithiation reaction is shown in Figure 2. Briefly, nickel and calcium are removed by precipitation and / or solvent extraction. For solvent extraction (SX) of Ca, HCl produced in a later step after electrolysis can be used to remove calcium. For precipitation of Ni, LiOH can be used to provide a sufficient base to cause precipitation, and in some embodiments, all or part of the LiOH is generated in the recycling process.

[0096] Exemplary, Ni precipitation can be carried out as described in U.S. Patent Application Publication 2021 / 0130927A1. In some embodiments, Ni(OH)2 can be added to the calcination step. The stream is optionally concentrated using evaporation or other techniques to reduce the fluid load in downstream processes and to reduce the size of the apparatus. Polyvalent impurities are then removed using ion exchange (IX) in a process that can at least partially utilize the HCl later produced in the same process. Alternatively, polyvalent impurities are removed using ion exchange (IX) before the stream is optionally concentrated using evaporation (i.e., in some embodiments, the ion exchange step is performed before the concentration step). Optionally, the concentration step is omitted. The resulting LiCl stream is then electrolyzed to convert LiCl to LiOH. Some of the LiOH can be recycled back to the Ni precipitation step as added LiOH. Battery-grade LiOH monohydrate crystals are produced from LiOH in the crystallization step and, in some embodiments, can be recycled back to the calcination step in the production of LNO material.

[0097] As shown in Figure 2, the LiCl electrolysis step produces H2 and Cl2. At least a portion of the H2 and / or at least a portion of the Cl2 from the electrolysis step can optionally be used to produce HCl, which can be used in a delithiation reaction to produce DLNO. In some embodiments, another portion or the remainder of the Cl2 gas can be reacted with fresh Ca(OH)2 to produce Ca(ClO)2. The HCl and Ca(ClO)2 can be recycled back into the delithiation and / or solvent extraction (SX) or ion exchange (IX) steps. Furthermore, Ca(ClO)2 can be reused in the delithiation reaction.

[0098] In some embodiments, methods that may be used after delithiation with calcium hypochlorite are shown in Figure 3. Briefly, nickel and calcium can be removed by precipitation or solvent extraction. Optionally, Ca is removed by reaction with soda ash, producing a calcium carbonate residue and a lithium-rich solution. Ni(OH)2 can be recycled back to the calcination step during the production of the LNO material. The lithium-rich solution is optionally concentrated using evaporation or other techniques to reduce the fluid load in downstream processes and reduce the size of the equipment. Polyvalent ion impurities are then removed using ion exchange (IX). Alternatively, polyvalent ion impurities are removed using ion exchange (IX) before optionally concentrating the lithium-rich solution. In the next step, Li is separated from Na using solvent extraction (SX) (e.g., the solvent extraction process described in U.S. Patent Application Publication No. 2021 / 0130927A1). The recovered LiCl stream is optionally further concentrated and then electrolyzed to convert LiCl to LiOH. Some of the LiOH can be recycled back to the Ni precipitation step. Battery-grade LiOH monohydrate crystals are produced in the crystallization step and can be recycled back to the calcination step. In some embodiments, electrolysis can be used to convert NaCl, which is produced when separating Li from Na, into NaOH, which can be used in the Li / Na separation step. H2 and Cl2 produced from each electrolysis step may be used to produce HCl. NaOH and HCl can be recycled back to the Li solvent extraction, ion exchange, and delithiation steps.

[0099] In some embodiments, the waste stream can be generated by the delithiation of LNO with lithium hypochlorite salt. 2+ / Li +The solution processing may be carried out as shown in Figure 4, for example. Briefly, nickel is removed by precipitation (e.g., precipitation with added LiOH) or solvent extraction. Ni(OH)2 can be recycled back for the production of LNO material. The lithium-rich stream is concentrated using evaporation or other techniques to reduce the fluid load in downstream processes and reduce the size of the equipment. Technical grade lithium carbonate (Li2CO3 stream) is produced by reaction with soda ash and then converted to LiOH using Ca(OH)2. Additional polyvalent impurities are then removed using ion exchange. In the next step, some of the LiOH can be recycled back to the Ni precipitation step. Another portion of the LiOH can be reacted with Cl2 gas to produce LiClO and recycled back to the delithiation reaction. Battery grade LiOH crystals are produced from LiOH in the crystallization step and recycled back to the calcination step.

[0100] In other embodiments, when lithium hypochlorite is used in the delithiation reaction, the waste stream can be recycled, as illustrated in Figure 5. This method is similar in some aspects to the methods shown in Figures 2 and 3 and includes the generation of LiCl vapor and subsequent lithium electrolysis. Briefly, Ni is removed by precipitation (optionally using LiOH added) or solvent extraction (optionally as described in U.S. Patent Application Publication 2021 / 0130927A1). Ni(OH)2 can be recycled back into the subsequent generation of LNO material. The lithium-rich solution is then concentrated using evaporation or other techniques to reduce the fluid load in downstream processes and reduce the size of the equipment. Additional polyvalent impurities can be removed using ion exchange to generate LiCl vapor. Alternatively, additional polyvalent impurities may be removed using ion exchange before the concentration of the lithium-rich solution. The LiCl vapor can then be converted to LiOH using electrolysis. Some of the LiOH can be recycled back into the Ni precipitation step as added LiOH. Battery-grade LiOH crystals may be produced from a portion of LiOH in a crystallization step and can be recycled back for the subsequent production of LNO material. In some embodiments, H2 and Cl2 produced from the electrolysis step may be used to produce LiClO and HCl, which can be recycled back for delithiation and ion exchange steps, respectively.

[0101] In some embodiments, the delithiation reaction is carried out using a sodium hypochlorite salt. In some embodiments, recycling of the waste stream generated in this delithiation can be performed as shown in Figure 6. Briefly, nickel is removed by precipitation or solvent extraction (optionally as described in U.S. Patent Application Publication 2021 / 0130927A1). Ni(OH)2 can be recycled back into the production of LNO material. The resulting lithium-rich solution is then concentrated using evaporation or other techniques to reduce the fluid load in downstream processes and reduce the size of the equipment. Subsequently, ion exchange is used to remove any remaining polyvalent impurities and produce a LiCl stream. Alternatively, ion exchange can be used to remove polyvalent impurities before concentrating the lithium-rich solution. In the next step, Li is separated from Na using solvent extraction (optionally as described in U.S. Patent Application Publication 2021 / 0130927A1). The recovered LiCl stream is optionally further concentrated. The resulting LiCl stream is optionally subjected to lithium solvent extraction to separate NaCl, and then electrolyzed to convert LiCl to LiOH. A portion of the LiOH can be recycled back to the Ni precipitation step as input LiOH. Battery-grade LiOH monohydrate crystals are produced in the crystallization step and can then be recycled back to the calcination step in the production of LNO material. Alternatively, as shown in Figure 6, electrolysis can be used on the NaCl stream produced from the Na / Li separation step to produce NaOH. A portion of the NaOH or LiOH can be recycled back to precipitate Ni. The H2 and Cl2 produced from each electrolysis may be used to produce HCl and NaClO, which can be recycled back to the IX step and the delithiation step, respectively.

[0102] Table 1 shows exemplary non-limiting processes for producing LiOH monohydrate and Ni(OH)2 from the waste stream described herein.

[0103] [Table 1]

[0104] In some embodiments, 2+ / Li + Extracting Ni from a solution can optionally be done by direct precipitation of Ni, for example, by using LiOH added to produce Ni(OH)2. Exemplarily, the LiOH added is Ni 2+ / Li + Provide sufficient base so that the pH of the solution is adjusted to approximately 8 to approximately 12.5, or optionally to approximately 10 to approximately 12.5. As illustrated in Figure 6, it is understood that the LiOH added may be substituted with other base materials such as NaOH. The LiOH or NaOH added is Ni in the chamber. 2+ / Li + By bringing the material into contact with a solution and holding it for a desired time and at a desired temperature, optionally between -5°C and 120°C, the formation of Ni(OH)2 can be enabled.

[0105] Nickel precipitation can be carried out in a circuit comprising a set of reaction vessels, a thickener, and a filter. The overflow of the thickener is sent to calcium removal, and the underflow is sent to a solid-liquid separation device (e.g., a filter press). The filter cake product, mainly containing nickel hydroxide, is considered reusable for subsequent LNO material production or other applications.

[0106] The resulting precipitated Ni product can then be filtered and washed to form the final Ni(OH)2 material, which can be directly used for the subsequent production of LNO material, and optionally, for the production of lithium cathode electrochemically active material.

[0107] Ni isolation is performed by arbitrarily selecting Ni below 1000 ppm (parts per million). 2+ (For example, Ni below 500 ppm) 2+ Ni below 100 ppm 2+ Ni below 10 ppm 2+ Ni below 9 ppm 2+Ni below 8 ppm 2+ Ni below 7 ppm 2+ Ni below 6 ppm 2+ Ni less than 5 ppm 2+ Ni below 4 ppm 2+ Ni less than 3 ppm 2+ Ni less than 2 ppm 2+ , or Ni less than 1 ppm 2+ This yields a lithium-rich solution containing Ni at a concentration of ).

[0108] Lithium-rich solutions optionally contain Ni 2+ / Li + The solution contains less than 10 mass percent of Ni. In some embodiments, the lithium-rich solution contains Ni 2+ / Li + The amount of Ni in the solution is less than 1 percent, for example, Ni 2+ / Li + The amount of Ni in the solution is less than 0.1 percent, less than 0.01 percent, less than 0.001 percent, or less than 0.0001 percent, etc.

[0109] As shown in Figure 2, when calcium hypochlorite is used as the delithiation solution in the delithiation reaction, a calcium removal step can be added. In Figure 2, such a step is shown as CaSX (i.e., calcium solvent extraction). 2+ / Li + Ca in solution 2+ For example, formula (C8H 17 Extraction may be carried out using an organic extractant such as di-(2-ethylhexyl)phosphate (D2EPHA) having O)2PO2H. In some embodiments, the organic extractant may contain up to 30% v / v D2EPHA. In some embodiments, extraction may be carried out at a pH of about 3. Ca 2+ NaOH may be added to maintain the pH after extraction. 2+The loaded extract containing the compound can be exfoliated with HCl to produce Ca(Cl)2 at an acidic pH (e.g., pH 1-2) and a concentration of about 3-6 mol / L. The resulting lithium-rich solution can then be used for subsequent processing.

[0110] As shown in Figure 3, when calcium hypochlorite is used in the delithiation reaction, calcium becomes Ni 2+ / Li + The solution can be optionally precipitated in a series of stirred tanks. The calcium concentration in the solution can be optionally reduced to a maximum of 100 mg / L by adding soda ash (Na2CO3) as a 25% w / w solution, forming calcium carbonate. The discharged slurry is filtered, and the filter cake, mainly consisting of calcium carbonate, is discarded or used in other processes. The resulting lithium-rich solution is used for subsequent processing.

[0111] Lithium hypochlorite can be used in several embodiments as a hypochlorite for delithiation reactions. In some embodiments, such as the embodiment shown in Figure 4, a lithium-rich solution is subjected to the conversion of lithium to lithium carbonate. Briefly, the lithium-rich solution is heated to 90-95°C, and Li2CO3 precipitates from the purified mother liquor stream by the addition of soda ash, producing a Li2CO3 slurry. This discharged slurry is filtered and the Li2CO3 solid is washed to produce an intermediate technical grade Li2CO3 product. The vapor of the intermediate Li2CO3 product is sent to the lithium conversion, as shown in Figure 4. The poor liquid containing sodium and potassium impurities can be sent to a wastewater treatment facility.

[0112] The lithium conversion shown in Figure 4 can be carried out by supplying lithium carbonate to a series of stirred reactors. Slaked lime slurry is added and reacted with the lithium carbonate feedstock to produce a LiOH solution and an insoluble calcium carbonate precipitate. To achieve the target outlet concentration of 2% by mass LiOH, process condensates can be added to the reactor. The resulting slurry can be fed to a bank of filter presses (operating in parallel and configured in a duty / standby arrangement) to remove residual solids from the LiOH solution. The solid cake (70% by mass solids), mainly calcium carbonate and a small amount of residual unreacted lithium carbonate, may be disposed of.

[0113] Furthermore, as shown in Figures 2 to 6, the methods disclosed herein may include an ion exchange step for removing polyvalent ions. In some embodiments, an ion exchange medium having a high affinity for trivalent and divalent metal ions is loaded, washed with process condensate, and then eluted with a dilute hydrochloric acid solution. The purified raffinate (LiCl solution) containing less than 1 ppm of trivalent and divalent metal ions is supplied to the next unit operation of each process. A weakly acidic microporous cation exchange resin (e.g., having iminodiacetic acid or aminophosphone functional groups) can be used. A commercially available cation exchange resin is, but is not limited to, Lanxess TP-207.

[0114] As shown in Figures 3 and 6, in some embodiments, the method may include lithium solvent extraction for separating sodium from a lithium-rich solution. In some embodiments, lithium is selectively extracted into an organic solution using a lithium solvent extraction process, leaving impurities such as sodium and potassium in the raffinate. A portion of the raffinate solution, which is mostly sodium chloride and some potassium chloride, may be bled to prevent potassium accumulation, as shown in Figure 6. In some embodiments, sodium hydroxide, produced by NaCl electrolysis, is added as a pH adjuster. The lithium-supported organic material is then scrubbed using a weakly acidic solution to remove entrained and co-extracted impurities. After scrubbing, lithium is removed from the organic phase using hydrochloric acid (HCl) to produce a lithium chloride solution. Residual organic material is removed from the strip solution and raffinate solution using a multimedia filter. The LiCl stream may be fed to LiCl electrolysis. The raffinate solution, which mainly contains sodium chloride and potassium chloride, is sent to NaCl electrolysis to produce NaOH, H2, and Cl2 gas, and can be used downstream itself.

[0115] As shown in Figures 2, 3, 5, and 6, in some embodiments, the stream can be subjected to lithium electrolysis. The LiCl stream from the previous step is supplied to LiCl electrolysis in a bipolar cell divided into two compartments. When current is applied, chlorine gas is produced at the anode and hydrogen at the cathode. The hydrogen and chlorine gases can be sent to a hydrochloric acid burner and converted to hydrochloric acid. When current is passed through the electrolysis cell, metal ions present in the lithium chloride brine pass through a membrane to maintain charge balance and produce lithium hydroxide on the cathode side. Water is added as a dilution source for the cathode compartment. The lithium hydroxide-rich solution can then be reused or sent to the crystallization of LiOH·H2O. Periodic purging may be required during anolite discharge to avoid the accumulation of impurities. The single-cell voltage is up to approximately 5V, and the operating amperage is up to approximately 2-4kA / m 2 That is the case.

[0116] As shown in Figures 3 and 6, in some embodiments, the NaCl removed from the LiCl stream is subjected to NaCl electrolysis to produce NaOH, H2, and Cl2, all of which can be reused at other points in the process. In the NaCl electrolysis circuit, saturated saline solution is supplied to the membrane electrolysis, where an electric current is supplied to cause an electrochemical reaction, producing chlorine gas in the anode compartment and hydrogen gas, sodium hydroxide, and potassium hydroxide in the cathode compartment. The semipermeable membrane between the anode and cathode contains sodium ions (Na + ) selectively allows water molecules to pass through, and chloride ions (Cl - ) and hydroxyl ion (OH - This prevents the permeation of ) into the solution. Some of the generated sodium hydroxide is used as a pH adjuster for lithium SX (Figures 3 and 6). The remainder is considered a marketable by-product.

[0117] As shown in Figure 6, in some embodiments, a commercially available sodium chloride salt is added to the NaCl electrolysis feedstock to produce a saturated NaCl solution before NaCl electrolysis. Some of the sodium hydroxide and potassium hydroxide produced by NaCl electrolysis can be used as pH adjusters in the nickel precipitation and lithium solvent extraction steps. The remainder, along with some of the chlorine gas produced, can be sent to bleach to produce sodium hypochlorite (NaClO), which can be used in the delithiation reaction.

[0118] The purified lithium hydroxide is fed into a crude lithium hydroxide crystallizer, where lithium hydroxide monohydrate solid is crystallized from solution as crude lithium hydroxide in an evaporator. The discharge from the crude lithium hydroxide crystallizer may be a slurry stream containing lithium hydroxide monohydrate solid in a saturated lithium hydroxide solution. The lithium hydroxide slurry from the crystallizer can be dehydrated using a centrifuge.

[0119] As shown in Figures 4 and 5, in some embodiments, a portion of the LiOH may be sent to a bleaching area to produce LiClO, which can be used in the delithiation reaction. The dissolved lithium hydroxide is recrystallized as pure lithium hydroxide monohydrate in a separate crystallizer. The slurry of pure lithium hydroxide may be dehydrated using a centrifuge and sent to a LiOH·H2O dryer to remove excess water and produce a pure lithium hydroxide monohydrate product.

[0120] In some embodiments, a purified lithium hydroxide or sodium hydroxide solution or dissolved Ca(OH)2 (Figure 2) can be reacted with chlorine gas in a conversion module to produce a solution containing approximately equivalent moles of chloride and hypochlorous acid (ClO). This solution may be used to regenerate hypochlorite for any recycling or delithiation process as provided herein. In some embodiments, the reaction is exothermic, and a heat exchanger may be used to control the temperature of the hypochlorite solution. The concentration of the hypochlorite solution is determined by the concentration of the Li, Na, or Ca hydroxide solution. The hypochlorite-generating solution can be recycled upstream and used as an oxidizing agent in a delithiation process.

[0121] In some embodiments, HCl can be produced by burning together the chlorine and hydrogen gases generated by NaCl electrolysis and / or LiCl electrolysis. The high-temperature hydrogen chloride is cooled and absorbed into water in an isothermal gravity film absorber to form hydrochloric acid (33% by mass). In some embodiments, a portion of the HCl may be recycled for use as a stripping solution for Ca or Li solvent extraction and as an eluent for ion exchange steps, while the remainder can be returned and recycled for use in delithiation reactions.

[0122] Figures 2, 3, 5, and 6 illustrate a lithium chloride electrolysis step used in several embodiments of this disclosure. From a chemical standpoint, lithium chloride electrolysis is similar to sodium chloride or potassium chloride electrolysis. Implementations differ because lithium ions in the cell may behave more like protons than like other alkali metal ions, affecting membrane selection and requiring different internal cell hydraulics to achieve good performance. The alkali metal (i.e., lithium) passes through a cation exchange membrane to maintain charge balance and produce lithium hydroxide on the canode side. Sodium and potassium present in the feedstock pass through the ion exchange membrane together with the lithium. The cation exchange membrane has slight selectivity, but this slight selectivity is not sufficient for meaningful lithium / sodium separation. As a result, sodium and potassium will be present in the catholite product in similar ratios to the feedstock. LiCl brine can be supplied to the anode chamber of the cell. At the anode, chlorine is produced by the following reaction: Cl - → 1 / 2Cl2+e - (1)

[0123] The current is mainly Li + Transported by ions, Li + The ions pass through a cation exchange membrane that separates the anolite chamber and the catholite chamber. At the cathode, hydrogen ions and hydroxide ions are generated by the following reaction: H2O+e - → 1 / 2H2 + OH - (2)

[0124] LiOH is produced in the electrolysis chamber. The electrolysis products include LiOH, Cl2 gas, and H2 gas. HCl is produced in a separate HCl synthesis unit by burning H2 and Cl2. The overall chemical reactions in the two compartments of the cell are as follows: LiCl+H2O→1 / 2H2+1 / 2Cl2+LiOH (3)

[0125] The reversible voltage is approximately 2 to 5V (for example, approximately 2 to 3.5V), depending on the pH of the compartment.

[0126] After precipitation, the resulting LiOH monohydrate product can be filtered, washed, and / or used directly for subsequent LNO material production, such as for the production of lithium cathode electrochemically active materials. [Examples]

[0127] The following embodiments are illustrative and not intended to limit the scope of the disclosure in any way.

[0128] Example: Preparation of a delithiation mother liquor using lithium hypochlorite. 344 kg of water and 54 kg of lithium nickel oxide substantially free of other compounds were packed into an overhead stirring vessel to fluidize the solid material. 54 kg of concentrated hydrochloric acid and 228 kg of 12.3% by mass lithium hypochlorite solution were then packed into the vessel to induce oxidative delithiation of the lithium nickel oxide. After all reactants were packed into the vessel, the vessel was operated at 50°C for 3 hours. After chemical treatment, the solid was separated from the liquid using a filter press. The remaining solution was used as the delithiated mother liquor for further treatment.

[0129] Example: Precipitation of calcium and nickel from synthesis raw material solution using a 1:10% w / w LiOH aqueous solution.

[0130] The synthesized feed solution is a mixture of large amounts of chloride salts, mimicking the solution produced by delithiating LNO using calcium hypochlorite (see Solution A in Table 2).

[0131] A 4L glass leaching vessel equipped with a mixer, pH electrode / meter, and heating mantle was assembled. The target amount of feed solution was added to the reactor and heated to the target temperature of 50°C. A 10% LiOH aqueous solution was added to the target pH of 10 (87 kg / m³ in the feed solution). 3 The solution was slowly added to the reactor until the target pH (±0.1) was reached. The target pH was maintained for 60 minutes. 80 mL of slurry was removed from the reactor, its mass was measured, and it was filtered. The mass, specific gravity (SG), pH, and oxidation-reduction potential (ORP) of the filtrate were measured. One drop of concentrated HCl was added to the sample, aliquots were separated for analysis (Solution B, see Table 2), and the solids were returned to the reactor. Next, the target amount of 25% Na2CO3 solution (5.9 kg / m³ in the feed solution) was added to the reactor. 3 ) was added. The contents of the reactor were mixed for approximately 60 minutes. The mass of the final pulp was measured, and the contents of the reactor were filtered. The mass, SG, pH, and ORP of the filtrate were measured, and one drop of concentrated HCl was added to separate aliquots for analysis (Solution C, Table 2). The solids were then washed with deionized (DI) water (2 × 500 mL displacement), and the dried samples were analyzed (Final Residue, Table 2).

[0132] [Table 2]

[0133] Example 2: Precipitation of calcium and nickel from synthesis raw material solution using 25% w / w NaOH aqueous solution

[0134] The synthesized feed solution is a mixture of large amounts of chloride salts, mimicking the solution (Solution A, Table 3) produced by delithiating LNO using calcium hypochlorite.

[0135] A 4L glass leaching vessel equipped with a mixer, pH electrode / meter, and heating mantle was assembled. After measuring the mass and density, the target amount of feed solution was added to the reactor. The reactor was heated to the target temperature of 50°C. A 25% NaOH aqueous solution was slowly added to the reactor until the target pH of 11 (94.6 kg / m³ in the feed solution) was reached. The target pH (±0.1) was maintained for 60 minutes. 80 mL of slurry was taken from the reactor, its mass was measured, and it was filtered (see Solution B, Table 3 for analysis). Next, the target amount of 30% Na₂CO₃ solution (3.9 kg / m³ in the feed solution) was added to the reactor. The contents of the reactor were mixed for approximately 60 minutes. The mass of the final pulp was measured, and the contents of the reactor were filtered (see Solution C, Table 3 for analysis). The solids were then washed with deionized (DI) water (2 × 500 mL displacement), and the dried samples were analyzed (final residue, Table 3).

[0136] [Table 3]

[0137] Example 3: Precipitation of calcium and nickel from synthesis feed solution using 10% w / w LiOH solution The synthesized feed solution is a mixture of large amounts of chloride salts, mimicking the solution (Solution A in Table 4) produced by delithiating LNO using calcium hypochlorite.

[0138] A 4L glass leaching vessel equipped with a mixer, pH electrode / meter, and heating mantle was assembled. The density and mass of the feed solution were measured. The target amount of feed solution was added to the reactor and heated to the target temperature of 50°C. A 10% LiOH aqueous solution was added to the target pH of 10 (1.5 kg / m³ in the feed solution or brine). 3The slurry was slowly added to the reactor until the target pH (±0.1) was reached. The target pH was maintained for 60 minutes. 80 mL of slurry was removed from the reactor, its mass was measured, and it was filtered. The mass, specific gravity (SG), pH, and oxidation-reduction potential (ORP) of the filtrate were measured. One drop of concentrated HCl was added to the sample, an aliquot was separated for analysis, and the solid was returned to the reactor. The contents of the reactor were mixed for approximately 60 minutes. The mass of the final pulp was measured, and the contents of the reactor were filtered. The mass, SG, pH, and ORP of the filtrate were measured, one drop of concentrated HCl was added, and an aliquot was separated for analysis (Solution B, Table 4). The solid was then washed with deionized (DI) water (2 × 500 mL displacement), and the dried sample was analyzed (final residue, Table 4).

[0139] [Table 4]

[0140] Example: Loading and performance of an ion exchange (IX) column

[0141] 1 L of 50 g / L NaOH was prepared using concentrated (50% w / w) NaOH. 100 mL of resin was washed four times with DI water at 2 BV (bed volume) to remove decomposition products. 100 mL of the washed resin was measured and transferred to an appropriately sized column (e.g., a 500 mL column). The NaOH solution was injected into the resin-containing column at 5 BV / h (= 1250 mL / h or ~20 mL / min) for 1 hour using an upflow method. The packed resin was transferred to a Buchner filter and washed four times with deionized water. 5 mL of the packed resin was collected and dried at 100°C to a constant mass.

[0142] For Ni precipitation, two precipitation tanks were used in series, and a third tank was used as a feed tank for filtration. A 10% LiOH solution was used for precipitation, and the delithiated mother liquor solution was supplied at a rate of 200 mL / min. In one example, LiOH was added to the first and second tanks at a flow rate of 0.5 g / min in a ratio of 50% / 50% by mass. Two ion exchange columns were used in series, with the second column functioning as abrasive in case of breakthrough.

[0143] [Table 5]

[0144] Various modifications of this disclosure, in addition to those shown and described herein, will be obvious to those skilled in the art in which this disclosure relates. Such modifications are also intended to be included within the scope of this disclosure.

[0145] Unless otherwise specified, it will be understood by those skilled in the art that all reagents are available from sources known in the art.

[0146] This description of a particular aspect is essentially illustrative and not intended to limit the scope of the Disclosure or its application or use, and they may be modified. Materials and methods are described in relation to the non-limiting definitions and terms contained herein. These definitions and terms are not designed to function as limitations on the scope or practice of the Disclosure and are presented for illustrative and explanatory purposes only. Methods or compositions are described as a sequence of individual steps or using specific materials, but a person skilled in the art will understand that steps or materials may be interchangeable, so that the description of the Disclosure may include steps arranged in multiple parts or in many ways, as is easily understood by a person skilled in the art.

[0147] Terms such as “first,” “second,” and “third” may be used in this specification to describe various elements, components, regions, layers, and / or sections, but it will be understood that these elements, components, regions, layers, and / or sections should not be limited by the use of these terms. These terms are used solely to distinguish one element, component, region, layer, or section from another element, component, region, layer, or section. Accordingly, the first “element,” “component,” “region,” “layer,” or “section” described below may be referred to as the second (or other) element, component, region, layer, or section without departing from the teachings of this specification.

[0148] The terms used herein are intended solely to describe and not to limit certain aspects of the disclosure. Where used herein, the singular forms “a,” “an,” and “the” are intended to include the plural forms, which include “at least one” or “one or more,” unless the content expressly indicates otherwise. Furthermore, where used herein, “or” means “and / or.” Where used herein, the term “and / or” includes any and all combinations of one or more of the enumerated items relating to the disclosure. Where used herein, the terms “comprise” and / or “comprises” and / or “comprising,” or “includes” and / or “including” identify the presence of the described features, regions, integers, steps, operations, elements, and / or components, but do not exclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and / or groups thereof. The term “or combination thereof” means a combination that includes at least one of the aforementioned elements.

[0149] Unless otherwise defined, all terms used herein (including technical and scientific terms) have the same meaning as those generally understood by an ordinary person skilled in the art to which this disclosure pertains. Terms as defined in commonly used dictionaries should be interpreted as having the meaning consistent with their meaning in the context of the relevant technology and this disclosure, and it will be further understood that they should not be interpreted in an idealized or overly formal sense unless expressly defined herein.

[0150] In some embodiments, the terms “about” or “approximately” mean within one, two, three, or four standard deviations of a value. In some embodiments, the terms “about” or “approximately” mean within 30%, 25%, 20%, 15%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, or 0.05% of a given value or range.

[0151] The patents, publications, and applications referenced herein represent the level of skill of those skilled in the art in which this disclosure relates. These patents, publications, and applications are incorporated herein by reference in such a way that each individual patent, publication, or application is incorporated herein by reference specifically and individually.

[0152] The above description illustrates specific aspects of this disclosure, but is not intended to limit its implementation.

Claims

1. A method for separating lithium and nickel, the method being: (A) A step of delithiating a lithium nickel oxide (LNO) material in the presence of a mineral acid and a hypochlorite to produce a delithiated nickel oxide (DLNO) material and a waste stream, wherein the waste stream comprises chloride ions, lithium ions and nickel ions; (B1) Ni(OH) from the waste stream ２ The steps include: precipitating to produce a lithium-rich solution, the lithium-rich solution containing one or more polyvalent ions; (D1) The lithium-rich solution or concentrated lithium-rich solution is subjected to ion exchange to remove polyvalent ions other than Li+ and generate a LiCl stream. A method comprising the step of (E) isolating LiOH from a LiCl stream.

2. The method according to claim 1, wherein the hypochlorite is selected from calcium hypochlorite, lithium hypochlorite, and sodium hypochlorite.

3. The method according to claim 1, further comprising treating the waste stream by solvent extraction in the presence of introduced LiOH, introduced NaOH, or a combination thereof.

4. The method according to claim 3, wherein the hypochlorite is calcium hypochlorite.

5. (A) The step of delithiating a lithium nickel oxide (LNO) material in the presence of HCl as the mineral acid; (B2) The step of treating the waste stream by solvent extraction in the presence of introduced LiOH, introduced NaOH, or a combination thereof to produce a lithium-rich solution; The method according to claim 1, including the method described in claim 1.

6. (C) A step of concentrating the lithium-rich solution to produce the concentrated lithium-rich solution, The method according to any one of claims 1 to 5, further comprising:

7. The hypochlorite salt is selected from calcium hypochlorite and sodium hypochlorite; step (D1) is: The lithium-rich solution or the concentrated lithium-rich solution is subjected to solvent extraction in the presence of added HCl to remove polyvalent ions and generate the LiCl stream. The process involves separating Na from the LiCl stream using solvent extraction to produce an NaCl stream, The LiCl stream may be enriched as needed, The method according to claim 1, further comprising:

8. At least a portion of the NaCl stream is subjected to electrolysis to produce NaOH, H ２ gas, and Cl ２ The method according to claim 7, further comprising generating a gas.

9. The aforementioned H ２ The method according to claim 8, further comprising heating at least a portion of the gas with an HCl burner to produce HCl.

10. The aforementioned Cl ２ At least a portion of the gas is Ca(OH) ２ The method according to claim 8, further comprising reacting with NaOH to produce calcium hypochlorite or sodium hypochlorite.

11. The aforementioned hypochlorite is lithium hypochlorite salt; the method is, (D2) The lithium-rich solution or the concentrated lithium-rich solution, Li ２ CO ３ Steps to convert to a stream, The method according to any one of claims 1 to 5, further comprising:

12. Step (D2) is: Treating the lithium-rich solution or the concentrated lithium-rich solution with soda ash to produce a Li ２ CO ３ stream; The method according to claim 11, including the method described in claim 11.

13. The method according to claim 1, wherein the isolated LiOH is in liquid form, crystalline form, or both.

14. The method according to claim 1, wherein at least a portion of the isolated LiOH is in liquid form.

15. At least a portion of the isolated LiOH is converted to Cl ２ The method according to claim 1, further comprising reacting with a gas to produce lithium hypochlorite.

16. The method according to claim 1, further comprising crystallizing a LiOH monohydrate from at least a portion of the isolated LiOH.

17. Step (E) is: (F) LiCl stream is subjected to electrolysis to produce LiOH liquid, H ２ gas, and Cl ２ Steps to generate gas; (G) The step of precipitating LiOH monohydrate from the LiOH liquid; The method according to claim 1, including the method described in claim 1.

18. The aforementioned Cl ２ In the presence of at least a portion of the gas, the H ２ The method according to claim 17, further comprising heating at least a portion of the gas with an HCl burner to produce HCl.

19. The aforementioned Cl ２ At least a portion of the gas is Ca(OH) ２ The method according to claim 17, further comprising reacting with to produce calcium hypochlorite.

20. At least a portion of the LiOH liquid is the Cl ２ The method according to claim 17, further comprising reacting with at least a portion of the gas to produce lithium hypochlorite.

21. Step (E) is: Separating Li from Na in the LiCl stream to produce NaCl by using solvent extraction in the presence of introduced NaOH; Optionally, the LiCl stream may be concentrated to generate a concentrated LiCl stream; The LiCl stream or the concentrated LiCl stream is subjected to electrolysis to produce LiCl as LiOH liquid and H ２ gas, and Cl ２ Converting to gas; The method according to claim 1, including the method described in claim 1.

22. The method according to claim 21, further comprising precipitating LiOH monohydrate from the LiOH liquid.

23. The aforementioned H ２ At least a portion of the gas, the Cl ２ The method according to claim 21, further comprising generating HCl by heating with an HCl burner in the presence of at least a portion of the gas.

24. The aforementioned Cl ２ At least a portion of the gas is Ca(OH) ２ The method according to claim 21, further comprising reacting with to produce calcium hypochlorite.

25. The method according to claim 21, further comprising subjecting at least a portion of the generated NaCl to electrolysis to produce NaOH.

26. Step (E) is: The Li ２ CO ３ The stream was treated with calcium hydroxide to produce LiOH and CaCO2. ３ To generate, The method according to claim 1, including the method described in claim 1.

27. At least a portion of the LiOH obtained in step (E) is subjected to ion exchange; The ion-exchanged LiOH is crystallized to obtain battery-grade lithium hydroxide monohydrate; The method according to claim 26, further comprising:

28. The LiOH obtained in step (E) is subjected to ion exchange; At least a portion of the ion-exchanged LiOH is converted to Cl ２ The process involves reacting it with gas to produce lithium hypochlorite, The method according to claim 26, further comprising:

29. The method according to claim 1, wherein the mineral acid is HCl.

30. The waste stream having a pH of 2 to 6, according to any one of claims 1 to 29.

31. The LNO material is selected from the LiNixMyOz material, where: M is selected from metals; x is selected from a number between 0 and 1.999; y is selected from numbers between 0 and 1.999; and The method according to any one of claims 1 to 30, wherein z is selected from the numbers 1 to 4.

32. The method according to claim 31, wherein M is selected from transition metals, post-transition metals, and combinations thereof.

33. The method according to claim 31, wherein M is selected from Ni, Co, Mn, Ti, Zr, Nb, Hf, V, Cr, Sn, Cu, Mo, W, Fe, Si, B, and any combination thereof.

34. The method according to any one of claims 31 to 33, wherein the LNO material is selected from LiNiMOz materials.

35. The method according to claim 34, wherein the LiNiMoz material is selected from LiNiCoAlOz and LiNiCoAlM'Oz material, where M' is selected from metals.

36. Ni(OH) produced by the above method ２ The method according to any one of claims 1 to 35, further comprising forming an LNO material using LiOH monohydrate or both produced by the method described above.

37. (A) A step of delithiating a lithium nickel oxide (LNO) material in the presence of a mineral acid and a calcium hypochlorite salt to produce a delithiated nickel oxide (DLNO) material and a waste stream, wherein the waste stream comprises chloride ions, lithium ions and nickel ions; (B) Ni(OH) from the waste stream ２ The steps include: precipitating to produce a lithium-rich solution; (C) The step of optionally concentrating the lithium-rich solution to produce a concentrated lithium-rich solution; (D) The lithium-rich solution or the concentrated lithium-rich solution is subjected to ion exchange to obtain Li ＋ The steps include removing other polyvalent ions and generating a LiCl stream; (E) The LiCl stream is subjected to electrolysis to produce LiOH liquid and H ２ gas, and Cl ２ Steps to generate gas; (F) The step of precipitating LiOH monohydrate from the LiOH liquid; (G) (i) at least a portion of the LiOH liquid and / or (ii) the redissolved LiOH monohydrate, the Cl ２ The steps include: generating lithium hypochlorite by reacting it with at least a portion of the gas; (H) The above H ２ At least a portion of the gas, the Cl ２ The steps include: generating HCl by heating with an HCl burner in the presence of at least a portion of the gas; The method according to claim 1, including the method described in claim 1.

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