Method for Extracting Li and Ni from a Solution

Abstract

Nickel(II) / Lithium(I) (Ni 2+ / Li + A process is provided for extracting lithium and optionally nickel from a lithium-poor solution. The extraction is optionally carried out in a series of steps involving countercurrent flow of aqueous and organic streams, thereby producing a lithium-poor solution. The lithium-deficient solution can be treated so that the remaining Ni in the lithium-poor solution can be directly precipitated therefrom in the form of a Ni salt. Upon completion, the process provides recoverable nickel and / or lithium that can be recycled into batteries or sold for other uses.

Description

Technical Field

[0001] Cross - Reference to Related Applications This application claims priority to U.S. Provisional Application No. 62 / 930,186, filed on November 4, 2019, the entire content of which is incorporated herein by reference.

[0002] This disclosure relates to a method for recovering elements from a solution. More specifically, in some aspects, this disclosure relates to a method for recovering lithium and nickel, optionally produced from the waste stream after the delithiation of a lithium nickel oxide (e.g., LiNiO₂) material.

Background Art

[0003] Lithium - ion batteries are increasingly being used in important applications such as powering electric vehicles, mobile phones, and cameras. The increasing use of such batteries in a wide range of technical fields has led to a growing need to extract valuable elements such as nickel and lithium, either as waste streams from the manufacture of these materials or as waste streams from used lithium - ion batteries, in an efficient manner in terms of both cost and time. The materials extracted from these waste streams can be recycled back into the manufacturing process or sold and implemented in other related processes.

[0004] Unfortunately, current extraction or recycling methods often use various oxidizing agents that generate large amounts of waste that must be processed, thereby requiring clean - up time and cost. Further, these methods may not provide effective separation of the extracted components, thereby making it impossible to recover the individual materials. Such drawbacks reduce the amount of material that can be recovered and also increase both the amount of waste generated and the cost associated with the extraction of battery materials.

[0005] Multi-stage co-extraction has been attempted to simultaneously recover multiple materials such as both nickel and lithium. With these methods, materials can be produced that are extracted individually, but four co-extraction stages and a total of six steps are required to produce the individually extracted materials. Therefore, the current co-extraction process is very time-consuming because each step needs to be performed separately. Furthermore, the amount of solvent required during the co-extraction process is financially expensive because different solvents are required in each step.

[0006] Therefore, new methods are needed to improve the efficiency and output of extracting materials such as nickel and lithium from battery waste streams.

Summary of the Invention

[0007] The following summary is provided to facilitate some understanding of the innovative features unique to this disclosure and is not intended as a complete description. By taking the entire specification, claims, drawings, and abstract as a whole, various aspects of this disclosure can be fully understood.

[0008] A process for extracting lithium and nickel from a nickel(II) / lithium(I) (Ni 2+ / Li + ) solution optionally provided as a result of the delithiation of a material suitable for use in a lithium-ion battery is provided. In a particular loop process, it has been found that lithium and optionally nickel can be individually recovered substantially completely in a time-efficient and cost-effective manner. A process for extracting lithium and nickel from a Ni 2+ / Li + solution may optionally include providing a Ni 2+ / Li + solution containing an amount of lithium and an amount of nickel, and optionally treating the Ni 2+ / Li + solution with an acid or an alkaline agent (pH adjuster) to obtain a Ni 2+ / Li +Adjusting the pH of the solution to about 1.0 to about 10.0, optionally less than 7.0, and including Ni 2+ / Li + solution at that pH with a lithium selective extractant suitable for extracting lithium from the Ni 2+ / Li + solution, thereby further producing a Ni + solution (lithium-depleted solution) having less than 1000 parts per million of Li 2+ .

[0009] In some embodiments, the pH of the Ni 2+ / Li + solution after combination with the pH adjuster is less than 6.0. The pH adjuster is optionally selected from the group consisting of hydrochloric acid, sodium hydroxide, lithium hydroxide, potassium hydroxide, aqueous ammonia, and combinations of at least two of the foregoing. Optionally, the pH adjuster is not used in the system and the Ni 2+ / Li + solution is subjected to direct extraction.

[0010] In some embodiments, the lithium selective extractant is optionally an oxime, a trialkylphosphine oxide, an acid, or any combination thereof. Optionally, the lithium selective extractant is 2-hydroxy-5-nonylacetophenone oxime, LIX 54-100, LIX 55, CYANEX 936, and CYANEX 923, or any blend of two or more of these reagents.

[0011] In some embodiments, the pH of the Ni 2+ / Li + solution when treating the Ni 2+ / Li + solution with the lithium selective extractant is from 1.0 to 10.0. The step of treating the Ni 2+ / Li + solution with the nickel selective extractant is optionally performed at a pH less than 7.0, optionally resulting from a combination with a pH adjuster.

[0012] Optionally, the lithium selective extractant further comprises a hydrocarbon. The hydrocarbon is optionally selected from the group consisting of kerosene, paraffin, naphthene, and combinations of at least two of the foregoing. Optionally, the lithium selective extractant and the hydrocarbon are present in a volume percentage of 10:90 to 30:70.

[0013] The resulting lithium-depleted solution from lithium extraction is optionally less than 1000 parts per million of Li, optionally less than 100 parts per million of Li, optionally less than 10 parts per million of Li.

[0014] In some embodiments, the process further comprises treating the lithium-enriched solution obtained with a carbonating agent to produce a lithium salt. The carbonating agent is optionally selected from the group consisting of carbon dioxide (CO2), ammonium, sodium carbonate, ammonium carbonate, bicarbonate, and combinations of at least two of the foregoing. Optionally, lithium carbonate is filtered and washed and can be reused in subsequent processes.

[0015] The resulting lithium-depleted solution can be subjected to further isolation of Ni. Optionally, the lithium-depleted solution is treated with a carbonating agent or a pH adjuster to produce a precipitated nickel salt that can be collected. The carbonating agent is optionally selected from the group consisting of carbon dioxide (CO2), ammonium, sodium carbonate, ammonium carbonate, bicarbonate, and combinations of at least two of the foregoing. Optionally, nickel carbonate is filtered and washed.

Brief Description of the Drawings

[0016] The embodiments of the disclosure described in the drawings are illustrative and exemplary in nature and are not intended to limit the subject matter defined by the claims. The following detailed description of the illustrative embodiments of the disclosure can be understood when read in conjunction with the following drawings.

[0017]

Figure 1

Figure 2

Figure 3

[0018] A process is provided herein for separating lithium and optionally nickel from an input stream, which input stream is optionally the waste after delithiation of a LiNiO2 material. The process enables efficient and reliable recovery of lithium and optionally nickel from these streams, such that the resulting isolated nickel and lithium can be used for subsequent processes or for the formation of additional electrochemically active materials. The process provided herein according to some embodiments of the present disclosure utilizes one or more countercurrent organic and aqueous phase continuous loop systems to efficiently separate and extract nickel, lithium, or both from the input stream. A schematic diagram of the overall process according to some embodiments is shown in FIG. 1.

[0019] In some embodiments, the process uses successive and optionally multiple-step extraction, whereby each extraction need not be performed separately from other steps, providing a much more robust overall extraction process that, compared to conventional processes, optionally operates in a shorter time and produces less waste. Generally, the waste material is provided as a source of Li and optionally Ni for extraction or isolation by the processes provided herein. As used herein, the term "waste" refers to Ni 2+ and Li + in a liquid or solid composition containing both. The term "waste" need not be a spent product of another conventional process, but can be the result of an upstream process such as leaching of Ni or Li from a conventional processing step of the desired material. Optionally, the waste used herein is optionally a waste stream from the continuous or discontinuous leaching of Ni and Li produced during the delithiation of lithium nickel oxide, optionally using a mineral acid, which is optionally used for the formation of the cathode in a primary or secondary electrochemical cell.

[0020] Ni 2+ / Li + Waste materials in solution form can optionally include one or more extraction stages, one or more washing stages, and one or more stripping stages, and are subjected to a continuous multi-stage extraction process in which any or all of the foregoing are assembled in a continuous circuit. Optionally, the circuit design includes one or more washing stages. Optionally, the design includes two or more washing stages. The number of washing stages is at the discretion of the user and is not necessarily limited, but in some embodiments only a single washing stage is used.

[0021] The fluid circuit includes one or more extraction stages. The number of extraction stages is optionally from 1 to 10, or any value or range therebetween. Optionally, the number of extraction stages is from 2 to 10, from 2 to 8, from 2 to 6, from 3 to 10, from 3 to 8, from 3 to 6. Optionally, the number of extraction stages is 2, 3, 4, 5, 6, 7, or more than them. Optionally, the number of extraction stages is 6 or less, optionally 5 or less. The number of extraction stages in the circuit enables the efficient extraction of Li at each stage and the production of a single Li-enriched solution that is subjected to further processing to obtain isolated Li suitable for use in subsequent production processes. The resulting lithium-depleted solution (Ni 2+ solution) can also be subjected to subsequent Ni isolation.

[0022] Ni 2+ / Li +Regardless of whether lithium is separated from a solution or a lithium-poor solution, each extraction stage can be contained in a mixer-settler into which a pH adjuster, a Li-selective extractant, or both can optionally be introduced later. In an example where there are five extraction stages, the five mixer-settlers are fluidly connected such that the product from one extraction stage can be passed to a subsequent mixer-settler, and as the waste stream, the organic extraction solvent (containing one or more Li-selective extractants) that is passed in the opposite direction in series to promote the extraction of Li moves from one extraction stage to a subsequent extraction stage. An exemplary generalized process is illustrated in FIGS. 2A and 2B, with the difference that FIG. 2A illustrates the strip stages (S1 and S2) used in parallel and FIG. 2B illustrates the strip stages (S1 and S2) used in series. As illustrated in FIGS. 2A and 2B, it includes waste materials containing Ni and Li and used as a feed through the system (tank 1). The waste materials are fed from the extraction stage E1 in the first mixer-settler and combined with a lithium-selective extractant that moves in series in the opposite direction. Thus, the waste materials first contact the lithium-selective extractant at stage E1, move from E1 to E5, and the Li-selective extractant first enters the extraction stage at E5 and moves from E5 to E1. After the reaction at stage E1, the aqueous phase with Li removed moves to E2 and subsequently to E3, E4, and E5, such that Li is continuously removed and concentrated in the organic phase moving in the opposite direction. Next, the Li-enriched organic phase can optionally be scrubbed in a washing stage (W) and transferred directly to the strip stage(s).

[0023] The Li-enriched organic phase is optionally washed and then transferred, optionally in that order, to stripping steps S2 and S1 to strip Li from the Li-selective extractant solution (organic). For this purpose, each of the stripping steps is housed in a separate mixer-settler. Optionally, the number of stripping steps is one or more, and optionally two or more. The number of stripping steps is optionally four or less, optionally three or less, and optionally two or less. Similar to the extraction step described above, the stripping step includes a countercurrent of a stripping aqueous solution (e.g., an acid) to protonate the Li-selective extractant, strip Li from the Li-enriched organic phase, and form a Li salt.

[0024] Within each stripping step, the Li-enriched organic phase is exposed to a stripping solution containing an acid to exchange Li for hydrogen and pass the purified and concentrated lithium into a stripping aqueous phase for forming a Li salt. The Li salt can itself be used as an input material for subsequent manufacturing processes or the Li for subsequent use can be used for isolation of subsequent further elements (e.g., by an electrodeposition process or precipitation). The Li-depleted organic phase can then optionally be scrubbed in a washing step, returned to a storage tank, and / or transferred directly to a Li extraction step for subsequent extraction of Li from waste materials.

[0025] The lithium-depleted material (Ni 2+ solution) obtained as a result of the extraction step is transferred to a holding tank (tank 2) for subsequent Ni recovery or transferred directly to a Ni extraction process. Before being reintroduced into a subsequent Ni extraction process, the Ni 2+ solution can be subjected to ion exchange. The Ni extraction process is optionally a direct precipitation of Ni from the Ni 2+ solution (Figure 3). The result of the Ni 2+ extraction or precipitation is a Ni salt that can also serve as a recycled material for the production of additional materials or commodities.

[0026] More specifically, in some aspects of the present disclosure, nickel(II) / lithium(I) (Ni 2+ / Li+ ) A process for extracting lithium and optionally nickel from waste materials includes providing a Ni 2+ / Li + solution and optionally the waste materials. The lithium present in the Ni 2+ / Li + solution can be derived from any suitable lithium-containing and any suitable nickel-containing compounds. Exemplarily, the Ni 2+ / Li + solution is used in an electrochemical cell and can be a waste stream resulting from the delithiation of an electrochemically active material produced according to a delithiation method recognized in the art such as a LiNiO2 material, an NCM material, etc. Optionally, the Ni 2+ / Li + solution results from the delithiation of a LiNiO2 material or LiNiMO2, where M is any one of many metals such as Mn, Mg, Al, Co, and / or almost any other transition metal or post-transition metal. Other examples include LiNiCoAlO2, LiNiCoAlMO2, where M is optionally a transition metal, a post-transition metal, or Mg, etc. The transition metal can be any transition metal suitable for use in an electrochemical cell. 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.

[0027] The production of the electrochemically active material or other production of the Ni 2+ / Li + solution can be by a combination of a lithium compound and a nickel compound. Optionally, the lithium compound is lithium hydroxide, lithium oxide, lithium carbonate, lithium nitrate, lithium sulfate, lithium acetate, lithium peroxide, lithium bicarbonate, or lithium halide, or any combination thereof.

[0028] According to some embodiments, the Ni 2+ / Li +The amount of lithium present in the solution can range from about 5 g / L to about 250 g / L, optionally from about 20 g / L to about 150 g / L. In some embodiments, Ni 2+ / Li + The amount of lithium present in the solution is from about 10 g / L to about 200 g / L, from about 15 g / L to about 175 g / L, from about 20 g / L to about 150 g / L, from about 25 g / L to about 125 g / L, from about 30 g / L to about 100 g / L, from about 40 g / L to about 75 g / L, or from about 50 g / L to about 60 g / L.

[0029] In some embodiments of the present disclosure, Ni 2+ / Li + The nickel present in the solution can be derived from any suitable nickel-containing compound such as nickel hydroxide, oxide, oxyhydroxide, carbonate, or nitrate.

[0030] According to some embodiments, Ni 2+ / Li + The amount of nickel present in the solution can range from about 5 g / L to about 400 g / L, optionally from about 20 g / L to about 200 g / L. In some embodiments, Ni 2+ / Li + The amount of lithium present in the solution is from about 10 g / L to about 300 g / L, from about 15 g / L to about 250 g / L, from about 20 g / L to about 200 g / L, from about 25 g / L to about 150 g / L, from about 30 g / L to about 100 g / L, from about 40 g / L to about 75 g / L, or from about 50 g / L to about 60 g / L.

[0031] The LiNiO₂ material can be delithiated in a manner that produces a chloride matrix having Li and Ni, which can be used for subsequent isolation by the processes described herein. Optionally, the delithiation is substantially carried out by a process recognized in the art, illustratively by exposing the LiNiO₂ material to an aqueous solution of hydrochloric acid or perchloric acid at a desired delithiation temperature, such as by the process described in U.S. Patent No. 8,298,706. The aqueous acid solution can have a concentration of 1 mole / liter or more (e.g., 3 moles / liter or more, 6 moles / liter or more, 8 moles / liter or more, or 10 moles / liter or more) and / or 12 moles / liter or less (e.g., 10 moles / liter or less, 8 moles / liter or less, 6 moles / liter or less, or 3 moles / liter or less). Optionally, the concentration of the aqueous acid solution can be from 0.1 mole / liter to 10 moles / liter (e.g., from 1 mole / liter to 10 moles / liter, or from 4 moles / liter to 8 moles / liter). Optionally, the delithiation temperature is from 0°C to 5°C, although in some embodiments, the delithiation temperature is 10°C or more, optionally 60°C or more. The resulting slurry is mixed at the delithiation temperature for about 20 - 40 hours, the solid is allowed to settle, and subsequently, the solid delithiated material is optionally isolated and washed for use in cathode manufacture. The supernatant removed from the wash solution can be used as a waste stream Ni 2+ / Li + solution in further aspects of the processes provided herein.

[0032] In some embodiments of the present disclosure, a process for extracting nickel and / or lithium from a Ni 2+ / Li + solution involves, in one or more extraction stages, treating the Ni 2+ / Li + solution with a pH adjuster to adjust the Ni 2+ / Li +It includes adjusting the pH of the solution to about 1.0 to about 10.0. Suitable pH adjusters may include hydrochloric acid, calcium oxide, sodium hydroxide, potassium hydroxide, aqueous ammonia, or combinations thereof. Optionally, pH adjusters that introduce cations that interfere with the recovery of one or more metals from the desired solution into the system are excluded. Optionally, sodium salts are excluded from the pH adjuster. Optionally, potassium salts are excluded from the pH adjuster. Optionally, calcium salts are excluded from the pH adjuster.

[0033] Optionally, the pH adjuster is Li + in one or more extraction stages, Ni 2+ / Li + is provided in an amount and concentration to adjust the pH of the solution to about 1.0 to about 10.0. Optionally, the pH of the Ni 2+ / Li + solution after contact with the pH adjuster is about 1.0 to about 9.5, about 1.0 to about 9.0, about 1.0 to about 8.5, about 1.0 to about 8.0, about 1.0 to about 7.5, about 1.0 to about 7.0, about 1.0 to about 6.5, about 1.0 to about 6.0, or about 1.0 to about 5.5. Optionally, the pH adjuster is introduced in one or more extraction stages to adjust the pH of the solution to about 3.0 or higher, about 3.5, about 4.0, about 4.5, about 5.0, about 5.5, about 6.0, about 6.5, about 7.0, about 7.5, or about 8.0 or higher. Optionally, the pH is adjusted in one or more extraction stages by contact with the pH adjuster to make or maintain the pH of the extraction solution at about 1.0 to about 7.0.

[0034] In some aspects of the present disclosure, the process for extracting nickel and lithium from a Ni 2+ / Li + solution further includes treating the Ni 2+ / Li + solution with a lithium-selective extractant, and the lithium-selective extractant extracts lithium from the Ni 2+ / Li + solution at a desired pH, thereby 2+ / Li +It is suitable for generating a lithium solution having less Li than the solution.

[0035] Optionally, the lithium selective extractant is added up to 10% - 40% v / v, optionally 10% - 30% v / v, optionally 15% - 25% v / v. Optionally, the lithium selective extractant is added at a volume percentage of 10%, 15%, 20%, 25%, or 30%. The solution of the lithium selective extractant is optionally added to the aforementioned volume percentages from a substantially purified or saturated solution of the lithium selective extractant.

[0036] The lithium selective extractant is optionally an anion containing an extractant capable of extracting Li into the organic phase. Exemplary examples of such lithium selective extractants include, but are not limited to, phosphinic acid, phosphonic acid, phosphoric acid, carboxylic acid, hydroxamic acid, beta-diketone, trialkylphosphine oxide, or any combination thereof. More specific exemplary lithium selective extractants include 2-hydroxy-5-nonylacetophenone oxime (LIX 84-I), LIX 54-100, LIX 55 (BASF), CYANEX 936 (SOLVAY), and a mixture of four trialkylphosphine oxides R3P(O), R2R’P(O), RR’2(O), and R’3P(O) (wherein R is a linear C8-alkyl radical and R’ is a linear C6-alkyl radical) CYANEX 923 (SOLVAY), or any blend of two or more of these reagents. In some embodiments, the lithium selective extractant is an acid. Suitable acids can include 2-ethylhexylphosphonic acid, mono-2-ethylhexyl ester, neodecanoic acid, or combinations thereof.

[0037] The lithium selective extractant is Ni in one or more extraction stages 2+ / Li + Based on the total volume of the solution, at about 5 volume percent to about 50 volume percent, Ni 2+ / Li +can be added to the solution. Other suitable ranges of the lithium selective extractant include Ni 2+ / Li + Based on the total volume of the solution, it can be about 10 volume percent to about 45 volume percent, about 15 volume percent to about 40 volume percent, or about 20 volume percent to about 30 volume percent.

[0038] In a further aspect of the present disclosure, the lithium selective extractant further includes a hydrocarbon as a diluent. Suitable hydrocarbons can include kerosene, paraffin, naphthene, or combinations thereof. The lithium selective extractant and the hydrocarbon can be present together in various ratios. Optionally, the ratio of the nickel selective extractant to the hydrocarbon can be in the range of about 1:99 to about 99:1 based on volume. Optionally, the ratio of the lithium selective extractant to the hydrocarbon is about 50:50 to about 20:80 based on volume. Optionally, the ratio of the lithium selective extractant to the hydrocarbon is about 2:98 volume percent to about 45:55 by volume, about 3:97 by volume to about 40:60 by volume, about 5:95 by volume to about 40:60 by volume, about 7:93 by volume to about 35:65 by volume, or about 10:90 by volume to about 30:70 by volume, and each of the lithium selective extractant and the hydrocarbon is derived from a substantially isolated or saturated solution of each of the lithium selective extractant or the hydrocarbon.

[0039] The process provided herein optionally includes one or more extraction stages, in series or in parallel. Optionally, the lithium selective extractant, pH adjustment, or others are such that Ni 2+ / Li + The number of extraction stages in contact with the solution can be 1, 2, 3, 4, 5, 6, 7, or more than that number of stages. The multi-staging of the process provided herein provides rapid and robust extraction of lithium from the Ni 2+ / Li + solution. The result of one or more extraction stages is a lithium-enriched solution and a lithium-depleted solution that also contains Ni (e.g., Ni 2+ solution). The lithium-depleted solution (or the result of lithium extraction) optionally has Li of 1000 ppm or less.+ , Li of 500 ppm or less + , Li of 100 ppm or less + , Li of 10 ppm or less + , Li of 9 ppm or less + , Li of 8 ppm or less + , Li of 7 ppm or less + , Li of 6 ppm or less + , Li of 5 ppm or less + , Li of 4 ppm or less + , Li of 3 ppm or less + , Li of 2 ppm or less + , or Li of 1 ppm or less + It is. The lithium-poor solution is optionally processed sequentially to extract nickel from the lithium-poor solution.

[0040] In the lithium-poor solution, optionally, Ni 2+ / Li + The amount of Li in the solution is less than 10 percent by weight. Optionally, in the lithium-poor solution, optionally, Ni 2+ / Li + The amount of Li in the solution is less than 1 percent by weight, optionally less than 0.1 percent, optionally less than 0.01 percent, optionally less than 0.001 percent, optionally Ni 2+ / Li + The amount of Li in the solution is less than 0.0001 percent.

[0041] The lithium-enriched solution resulting from the extraction step is optionally subjected to one or more stripping steps to obtain an isolated Li product, optionally in the form of a Li salt. In one or more stripping steps, the pH of the lithium-enriched solution is decreased by an acid such as H2SO4 or a combination with other suitable acids. Acid is optionally added to decrease the pH from the pH of the extraction solution(s), optionally to about 3.0 or less, optionally 2.0 or less, thereby exchanging Li in the organic phase with hydrogen and thereby stripping Li from the Li-enriched solution and transferring it to the aqueous phase as a Li salt or for subsequent separation or use. The solution(s) obtained from one or more stripping stages are passed to a collection tank for direct use, washing, or scrubbing, or Li can be precipitated so that it can be collected and optionally used for one or more downstream processes or for the formation of other materials.

[0042] In some embodiments, Li is further precipitated from the resulting Li salt solution, optionally by contact with a carbonating agent, as the resulting carbonate or hydroxide. Examples of carbonating agents can include carbon dioxide and ammonia, carbon dioxide, sodium carbonate, ammonium carbonate, or combinations thereof. The carbonating agent is contacted with the Li solution in a chamber and incubated at a desired time and desired temperature, optionally between -5°C and 120°C, to allow for the formation of lithium carbonate salt. The lithium carbonate can be further washed or treated by other methods or can be used directly in the manufacture of a cathode electrochemically active material for use in primary or secondary batteries.

[0043] After precipitation, the resulting Li product can subsequently be filtered from the supernatant, washed, and can form lithium carbonate or lithium hydroxide that can be directly utilized, optionally for the manufacture of an electrochemically active material of a lithiated cathode, for the manufacture of subsequent materials.

[0044] The clarified aqueous solution is optionally subjected to nanofiltration or other processes to separate residual sulfates remaining from the preceding Li stripping stage, recover purified water, and this purified water can then be used for subsequent stripping in the Li isolation process.

[0045] The processes provided according to some aspects of the present disclosure may further include extracting Ni from a lithium-poor solution (Ni 2+ solution). The extraction of Ni is optionally performed by directly precipitating Ni using a carbonating agent or a pH adjuster, etc. to form a nickel salt. Examples of carbonating agents can include carbon dioxide and ammonia, carbon dioxide, sodium carbonate, ammonium carbonate, or combinations thereof. Exemplary pH adjusters are any agents capable of adjusting the pH of the solution to a pH of about 8 to about 12.5, optionally about 10 to about 12.5, and optionally sodium hydroxide, lithium hydroxide, potassium hydroxide, ammonium hydroxide, or combinations thereof. The carbonating agent or pH adjuster is contacted with the Ni 2+ solution in a chamber and incubated at a desired time and a desired temperature, optionally -5°C to 120°C, to enable the formation of nickel salt.

[0046] In a further aspect, prior to the isolation of lithium, nickel from the Ni 2+ / Li + solution can be isolated. Optionally, the Ni 2+ / Li + solution is treated with a carbonating agent or a pH adjuster to form a nickel salt. Examples of carbonating agents can include carbon dioxide and ammonia, carbon dioxide, sodium carbonate, ammonium carbonate, or combinations thereof. Exemplary pH adjusters are any agents capable of adjusting the pH of the solution to a pH of about 8 to about 12.5, optionally about 10 to about 12.5. The carbonating agent or pH adjuster is contacted with the Ni 2+ / Li + solution in a chamber and incubated at a desired time and a desired temperature, optionally -5°C to 120°C, to enable the formation of nickel salt.

[0047] The resulting precipitated Ni product is sequentially filtered from the supernatant and washed and can optionally be directly utilized for the production of subsequent materials or, optionally, for the production of the electrochemically active material of the lithiated cathode, a Ni material that can optionally form nickel carbonate.

[0048] The result of the isolation of Ni as carbonate or hydroxide is a supernatant containing Ni, optionally, Ni at 1000 ppm or less 2+ , 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+ The supernatant contains.

[0049] In the supernatant, optionally, the amount of Ni in the Ni 2+ solution or Ni 2+ / Li + solution is less than 10 percent by weight. Optionally, in the supernatant, optionally, the amount of Ni in the Ni 2+ solution or Ni 2+ / Li + solution is less than 1 percent by weight, optionally less than 0.1 percent by weight, optionally less than 0.01 percent by weight, optionally less than 0.001 percent by weight, optionally the amount of Ni in the Ni 2+ solution or Ni 2+ / Li + solution is less than 0.0001 percent by weight.

[0050] Next, the nickel-depleted solution obtained is optionally treated and optionally further isolated for the remaining lithium by adding a pH adjuster substantially as described above, producing a nickel-depleted solution having a pH of from about 1.0 to about 10.0. Optionally, the pH of the nickel-depleted solution after contact with the pH adjuster is from about 1.0 to about 9.5, from about 1.0 to about 9.0, from about 1.0 to about 8.5, from about 1.0 to about 8.0, from about 1.0 to about 7.5, from about 1.0 to about 7.0, from about 1.0 to about 6.5, from about 1.0 to about 6.0, or from about 1.0 to about 5.5. Optionally, the pH adjuster is introduced in one or more extraction stages to adjust the pH of the solution to about 3.0 or more, about 3.5, about 4.0, about 4.5, about 5.0, about 5.5, about 6.0, about 6.5, about 7.0, about 7.5, or about 8.0 or more. Optionally, the pH is adjusted in one or more extraction stages by contact with the pH adjuster to make or maintain the pH of the extraction solution from about 1.0 to about 7.0. The lithium selective extractant is added to the nickel-depleted solution at 10% to 40% v / v, optionally 10% to 30% v / v, optionally up to 15% to 25% v / v. Optionally, the lithium selective extractant is added at a volume percent of 10%, 15%, 20%, 25%, or 30%. Any lithium selective extractant provided herein in another manner can be used. The solution of the lithium selective extractant is optionally added from a substantially purified or saturated solution of the lithium selective extractant to the aforementioned volume percent.

[0051] The lithium selective extractant can be added to the nickel - poor solution at about 5 volume percent to about 50 volume percent, based on the total volume of the nickel - poor solution, in one or more extraction stages or simply in a lump. Other suitable ranges of the lithium selective extractant include about 10 volume percent to about 45 volume percent, about 15 volume percent to about 40 volume percent, or about 20 volume percent to about 30 volume percent, based on the total volume of the nickel - poor solution. The lithium selective extractant added to the nickel - poor solution may optionally further contain a hydrocarbon as a diluent. Suitable hydrocarbons can include kerosene, paraffin, naphthene, or combinations thereof. The lithium selective extractant and the hydrocarbon can be present together in various ratios. Optionally, the ratio of the lithium selective extractant to the hydrocarbon can be in the range of about 1:99 to about 99:1, based on volume. Optionally, the ratio of the lithium selective extractant to the hydrocarbon is about 50:50 to about 20:80, based on volume. Optionally, the ratio of the lithium selective extractant to the hydrocarbon is from about 2:98 volume percent to about 45:55 by volume, from about 3:97 by volume to about 40:60 by volume, from about 5:95 by volume to about 40:60 by volume, from about 7:93 by volume to about 35:65 by volume, or from about 10:90 by volume to about 30:70 by volume, and each of the lithium selective extractant and the hydrocarbon is derived from a substantially isolated or saturated solution of each of the lithium selective extractant or the hydrocarbon.

[0052] The result of lithium extraction from the nickel - poor solution is Li at 1000 ppm or less + , Li at 500 ppm or less + , Li at 100 ppm or less + , Li at 10 ppm or less + , Li at 9 ppm or less + , Li at 8 ppm or less + , Li at 7 ppm or less + , Li at 6 ppm or less + , Li at 5 ppm or less + , Li at 4 ppm or less + , Li at 3 ppm or less + , Li at 2 ppm or less +、 or Li at 1 ppm or less + and can be a lithium-poor solution.

[0053] The supernatant aqueous solution is optionally subjected to nanofiltration or other processes to recover purified water, and then the purified water can be used sequentially for subsequent stripping in the Li isolation process.

[0054] The extracted nickel, lithium, or both are optionally washed, the liquid material is filtered, and the product is suitable for use in one or more downstream processes.

[0055] The process, and the lithium and / or nickel produced thereby, achieve an extraction method that produces excellent recovery yields and results in materials that can be recycled or sold for use in lithium-ion batteries.

[0056] In addition to what is shown and described herein, various modifications of the present disclosure will be apparent to those of ordinary skill in the art above. Such modifications are also intended to be within the scope of the appended claims.

[0057] It is understood that all reagents are available from sources known in the art unless otherwise specified.

[0058] The description of specific embodiments is, in essence, merely exemplary and is never intended to limit the scope of the present disclosure, its application, or its use, and can of course vary. The materials and processes are described in relation to the non-limiting definitions and technical terms included herein. These definitions and technical terms are not designed to function as limitations on the scope or implementation of the present disclosure but are presented only for purposes of illustration and explanation. A process or composition is described as a sequence of individual steps or using specific materials, but the steps or materials can be interchangeable so that the description of the present disclosure can include multiple parts or steps arranged in many ways that are readily understood by those of ordinary skill in the art.

[0059] The terms "first", "second", "third", etc. can be used herein to describe various elements, components, regions, layers, and / or sections, but it should be understood that these elements, components, regions, layers, and / or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer, or section from another element, component, region, layer, or section. Thus, the "first element", "component", "region", "layer", or "section" discussed below could be referred to as a second (or other) element, component, region, layer, or section without departing from the teachings herein.

[0060] The terminology used herein is for the purpose of describing particular aspects of the disclosure only and is not intended to be limiting. As used herein, the singular forms "a", "an", and "the" are intended to include the plural forms including "at least one" unless the context clearly dictates otherwise. "Or" means "and / or". As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items. As used herein, the terms "comprises" and / or "comprising", or "includes" and / or "including" specify the presence of the stated feature, region, integer, step, operation, element, and / or component, but do not preclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and / or groups thereof. The term "or combinations thereof" means a combination including at least one of the foregoing elements.

[0061] Unless otherwise defined, all terms (including technical and scientific terms) used herein shall have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. Terms defined in commonly used dictionaries shall be interpreted to have a meaning consistent with the meaning in the context of the relevant art and this disclosure, and shall not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

[0062] The patents, publications, and applications referred to herein are indicative of the level of skill of those of ordinary skill in the art to which this disclosure pertains. These patents, publications, and applications are hereby incorporated by reference herein to the same extent as if each individual patent, publication, or application was specifically and individually incorporated by reference herein.

[0063] The foregoing description is illustrative of particular embodiments of the disclosure and is not meant to be limiting of their practice.

Claims

1. Nickel(II) / Lithium(I) (Ni ２＋ / Li ＋ ) A process for extracting nickel, lithium, or both from a solution, (A) Providing a Ni ２＋ / Li ＋ solution containing chloride ions and certain amounts of lithium and nickel; ２＋ / Li ＋ and (B) The Ni ２＋ / Li ＋ solution is treated with a pH adjuster to adjust the pH of the Ni ２＋ / Li ＋ solution to 1.0 to 6.0, and (C) the Ni ２＋ / Li ＋ solution is treated with a lithium selective extractant suitable for extracting lithium from the Ni ２＋ / Li ＋ solution, thereby producing a lithium-lean solution having less Li ２＋ / Li ＋ than the Ni ＋ solution; (D)treating the lithium-depleted solution with a carbonate to precipitate Ni from the lithium-depleted solution; A process comprising:

2. The process according to claim 1, further comprising filtering and washing the nickel precipitated from the lithium-depleted solution.

3. The lithium-poor solution contains less than 1000 parts per million of Li ＋ The process according to claim 1, comprising:

4. The process according to claim 1, wherein the pH adjuster is selected from the group consisting of hydrochloric acid, sodium hydroxide, potassium hydroxide, ammonium hydroxide, and combinations of at least two of the foregoing.

5. The process according to claim 1, wherein the lithium-selective extractant comprises phosphinic acid, phosphonic acid, phosphoric acid, carboxylic acid, hydroxamic acid, beta-diketone, trialkylphosphine oxide, or any combination thereof.

6. The process according to claim 5, wherein the lithium-selective extractant is a mixture of 1-phenyldecane-1,3-dione, four trialkylphosphine oxides R3P(O), R2R'P(O), RR'2(O) and R'3P(O) (wherein R represents a straight-chain C8 alkyl group and R' represents a straight-chain C6 alkyl group), and a tri-n-hexylphosphine oxide / tri-n-octylphosphine oxide compound having a CAS number 100786-00-3, or any blend of two or more of these reagents.

7. The process according to claim 1, wherein the lithium-selective extractant further comprises a hydrocarbon.

8. The process according to claim 7, wherein the hydrocarbon is selected from the group consisting of kerosene, paraffin, naphthene, and combinations of at least two of the foregoing.

9. The process according to claim 7, wherein the lithium-selective extractant and the hydrocarbon are present in a volume percentage of 10:90 to 50:

50.

10. The process according to claim 1, wherein step (C) is carried out at a pH of 1.0 to 6.

0.

11. The process according to claim 1, wherein steps (B) and (C) are repeated.

12. Before step (A), the process further comprises delithiation of the LiNiO ２ compound with hydrochloric acid or perchloric acid. The process according to claim 1.

13. Nickel(II) / Lithium(I) (Ni ２＋ / Li ＋ ) A process for extracting nickel, lithium, or both from a solution (A) Providing a Ni ２＋ / Li ＋ solution containing chloride ions and certain amounts of lithium and nickel, and ２＋ / Li ＋ ​ (B) said Ni ２＋ / Li ＋ treating the solution with a carbonating agent or a pH adjuster to precipitate a nickel salt, thereby producing a nickel-depleted solution; (C)treating the nickel-depleted solution with a pH adjuster to adjust the pH of the nickel-depleted solution to 1.0 to 6.0; (D) treating the nickel-lean solution with a lithium-selective extractant suitable for extracting lithium from the nickel-lean solution at the pH, at a pH of 1.0 to 6.0, whereby a lithium-lean solution having less Li than that contained in the nickel-lean solution is produced; ＋ comprising generating a lithium-lean solution having less Li than that contained in the nickel-lean solution; Here, the lithium selective extractant includes phosphinic acid, phosphonic acid, phosphoric acid, carboxylic acid, hydroxamic acid, beta-diketone, trialkylphosphine oxide, or a combination thereof, Process.

14. wherein the carbonating agent is selected from the group consisting of carbon dioxide (CO ２ ), sodium carbonate, ammonium carbonate, bicarbonate, and combinations of at least two of the foregoing, or The Ni ２＋ / Li ＋ The pH adjuster added to the solution is selected from the group consisting of sodium hydroxide, lithium hydroxide, potassium hydroxide, and ammonium hydroxide. The process according to claim 13.

15. The process according to claim 13, further comprising filtering and washing the nickel salt.

16. The process according to claim 13, wherein the nickel-depleted solution contains less than 1000 parts per million of Ni2+.

17. The process according to any one of claims 13 to 16, wherein the lithium-depleted solution contains less than 1000 parts per million of Li+.

18. The pH adjuster added to the nickel-depleted solution is selected from the group consisting of hydrochloric acid, lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide, and a combination of at least two of the foregoing, according to any one of claims 13 to 16. The process described.

19. The lithium selective extractant is a mixture of 1-phenyldecane-1,3-dione, four trialkylphosphine oxides R3P(O), R2R'P(O), RR'2(O) and R'3P(O) (wherein R represents a straight-chain C8 alkyl group and R' represents a straight-chain C6 alkyl group), and a tri-n-hexylphosphine oxide / tri-n-octylphosphine oxide compound having a CAS number of 100786-00-3, or any two or more of these reagents. The process according to claim 16, selected from the group consisting of any arbitrary blend.

20. The process according to any one of claims 13 to 16, wherein the lithium selective extractant further contains a hydrocarbon.

21. The process according to claim 20, wherein the hydrocarbon is selected from the group consisting of kerosene, paraffin, naphthene, and a combination of at least two of the foregoing.

22. The process according to claim 20, wherein the lithium selective extractant and the hydrocarbon are present in a volume percentage of 10:90 to 50:

50.

23. The process according to any one of claims 13 to 16, wherein step (D) is performed at a pH of 1.0 to 6.

0.

24. The process according to any one of claims 13 to 16, wherein steps (C) and (D) are repeated.

25. Before step (A), the process further comprises delithiating the LiNiO ２ compound with hydrochloric acid or perchloric acid. The process according to any one of claims 13 to 16.

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