Method for producing cathode active material

Abstract

A method of making a cathode active material, the method comprising: contacting a mixed metal composition with water to form a first solution, the mixed metal composition comprising nickel, cobalt, manganese, aluminum, or a combination thereof, and greater than 0 to 2 weight percent, based on the total weight of the mixed metal composition, of a compound comprising Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof. Adding a salt of nickel, cobalt, manganese, aluminum, or a combination thereof to the first solution to obtain a second solution, which may be further combined with a basic solution to form a precipitate. The precipitate may be combined with a lithium compound and processed to provide the cathode active material.

Description

[Background technology]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 63 / 341,270, filed on May 12, 2022, and U.S. Provisional Patent Application No. 63 / 311,535, filed on February 18, 2022, in the U.S. Patent and Trademark Office, and claims all benefits arising therefrom under 35 U.S.C. § 119, the contents of which are incorporated herein by reference in their entireties. Summary of the Invention [Problem to be solved by the invention]

[0002] Lithium-ion batteries have become a popular power source for a variety of applications, such as consumer electronics and electric vehicles. Millions of cells have been produced. Nevertheless, there remains a need for improved methods for recovering and reusing used batteries. It would be particularly advantageous to provide an improved method for preparing cathode active materials for new batteries from other than virgin raw materials. [Means for solving the problem]

[0003] One aspect of the disclosure is a method of making a cathode active material, the method including: contacting a mixed metal composition with water to form a first solution, the mixed metal composition including nickel, cobalt, manganese, aluminum, or a combination thereof, and including greater than 0 to 2 weight percent of a compound including Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof, based on a total weight of the mixed metal composition; adding a salt of nickel, cobalt, manganese, aluminum, or a combination thereof to the first solution to obtain a second solution; combining the second solution with a basic solution to form a precipitate; adding a lithium compound to the precipitate to form a mixture; and heat treating the mixture to form a cathode active material.

[0004] Another aspect is a cathode active material comprising: a first layered Li x MO2 phase; and a second phase; where M is Ni, Co, Mn, Al, or a combination thereof, 0 < x < 1.4; and the second phase is derived from recycled feedstock.

[0005] Another aspect is a cathode active material comprising: a first phase; and a second phase; where the first phase comprises a first domain of formula Li2MnO3 and a second domain of formula LiMO2, where M is Ni, Co, Mn, Al, or a combination thereof, and the second phase is derived from recycled feedstock.

[0006] Another aspect is a method for producing a purified mixed metal composition, the method comprising: contacting a mixed metal composition comprising nickel, cobalt, manganese, aluminum, or a combination thereof, the mixed metal composition comprising greater than 0 to 2 weight percent of Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof based on the total weight of the mixed metal composition, with water to form a first solution; adding a salt of nickel, cobalt, manganese, aluminum, or a combination thereof to the first solution to obtain a second solution; combining the second solution and a basic solution to form a precipitate comprising a purified mixed metal composition.

[0007] Another aspect is a purified mixed metal composition comprising Ni(OH)2, Co(OH)2, and Mn(OH)2, preferably in a molar ratio of greater than 0 to greater than 0 to greater than 0, preferably 1:0.125:0.125, and at least one of Cu, Fe, Mg, Na, Ca, Zn, Al, F, Si, Li, or a combination thereof.

[0008] The features described above and other features are illustrated by the following drawings and detailed description.

[0009] The following figures represent exemplary embodiments.

Brief Description of the Drawings

[0010] [Figure 1A] 1A shows a scanning electron microscope (SEM) image of the precursor cathode active material prepared according to Comparative Example 1. The scale bar is 5 μm. [Figure 1B] FIG. 1B shows an SEM image of the cathode active material prepared according to Comparative Example 1 after calcination at 750° C. under oxygen. The scale bar is 5 μm. [Figure 2A] 2A shows an SEM image of the precursor cathode active material prepared according to Example 1. The scale bar is 5 μm. [Figure 2B] 2B shows an SEM image of the cathode active material prepared according to Example 1 after calcination in oxygen at 750° C. The scale bar is 5 μm. [Figure 3A] 3A shows an SEM image of the precursor cathode active material prepared according to Example 3. The scale bar is 5 μm. [Figure 3B] 3B shows an SEM image of the cathode active material prepared according to Example 3 after calcination in oxygen at 750° C. The scale bar is 5 μm. [Figure 4A] Figure 4A shows an SEM image of the precursor cathode active material prepared according to Example 4. The scale bar in Figure 4A is 5 μm. [Figure 4B] Figure 4B shows an SEM image of the precursor cathode active material prepared according to Example 4. The scale bar in Figure 4B is 20 μm. [Figure 4C] FIG 4C shows an SEM image of the cathode active material prepared according to Example 4 after calcination in oxygen at 750° C. The scale bar in FIG 4C is 5 μm. [Figure 4D] FIG 4D shows an SEM image of the cathode active material prepared according to Example 4 after calcination in oxygen at 750° C. The scale bar in FIG 4D is 20 μm. [Diagram 5] 5 is a graph of discharge capacity (mAh / g) versus cycle number for half-cells containing the cathode active materials of Comparative Examples 1 and 2, and Examples 1-4. The inset is a magnified view. [Figure 6A]FIG. 6A shows the C / 3 discharge capacity (mAh / g) of Comparative Examples 1 and 2 and Examples 1 to 4 after charging to 4.2 V. [Figure 6B] FIG. 6B shows the C / 3 discharge capacity (mAh / g) of Comparative Examples 1 and 2 and Examples 1 to 4 after charging to 4.5 V. [Figure 7] FIG. 7 is a graph of discharge capacity (mAh / g) versus cycle number for Comparative Examples 1 and 2, and Examples 1-4, when cycled at a C / 3 charge / discharge rate. [Figure 8] FIG. 8 is a graph of discharge capacity versus cycle number showing the full cell cycle life when charged and discharged at a C / 3 rate for Comparative Example 1 (circles), Example 1 (triangles), and Example 3 (inverted triangles). [Figure 9A-9F] 9A-9F are graphs of area specific impedance (ohm-cm2) versus voltage (V vs Li / Li+) showing the results of impedance analysis at cycles 7, 53, and 99 for Comparative Example 1 (circles), Example 1 (triangles), and Example 3 (inverted triangles), respectively. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The present inventors have discovered a method for remanufacturing batteries and battery materials, particularly cathode active materials, and precursors thereof. Cathode active materials produced according to the methods described herein advantageously exhibited comparable or improved battery performance, despite using a high percentage of raw materials derived from spent batteries or battery manufacturing scrap. Without wishing to be bound by theory, it is believed that the cathode active materials prepared according to the methods described contain phases derived from recycled feedstocks, resulting in the observed capacity enhancements.

[0012] Thus, one aspect of the present disclosure is a method of making a cathode active material from a mixed metal composition. In one aspect, the mixed metal composition comprises a mixed metal sulfate, a mixed metal nitrate, a mixed metal carbonate, a mixed metal halide, a mixed metal hydroxide, a mixed metal oxalate, or a combination thereof. In a particular aspect, the mixed metal composition comprises a mixed metal sulfate.

[0013] The mixed metal composition includes nickel, cobalt, manganese, aluminum, or combinations thereof. For example, the mixed metal composition may preferably include nickel and cobalt. The mixed metal composition may further include greater than 0 to 2 weight percent of a compound including Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof, based on the total weight of the mixed metal composition. For example, the mixed metal composition may include greater than 0 to 1.5 weight percent, or greater than 0.0001 to 1 weight percent, or greater than 0.001 to 0.5 weight percent, or greater than 0 to 0.1 weight percent, or greater than 0 to 0.01 weight percent (100 ppm) of a compound including Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof. In one embodiment, the mixed metal composition may include from 0 to 1000 ppm, or from 0 to 750 ppm, or from 5 to 750 ppm, or from 5 to 1000 ppm, or from 25 to 1000 ppm, or from 25 to 750 ppm, or from 50 to 750 ppm, or from 100 to 750 ppm of a compound including Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof. For example, the mixed metal composition may include from 50 to 300 ppm Cu, from 50 to 200 ppm Al, from 5 to 100 ppm Fe, and from 5 to 100 ppm F, each based on the total weight of the mixed metal composition. In one embodiment, the mixed metal composition may include lithium. When present, lithium may be preferably present in the mixed metal composition in an amount of from 100 to 1000 ppm based on the total weight of the mixed metal composition.

[0014] In one embodiment, the mixed metal composition may include nickel and cobalt and greater than 0 to 2 weight percent Cu, Fe, Mg, F, Si, or combinations thereof, based on the total weight of the mixed metal composition.

[0015] The mixed metal composition can be obtained, for example, from spent lithium ion batteries, lithium ion battery manufacturing waste, etc., or combinations thereof. For example, some or all of the mixed metal composition can be obtained from recycled feedstocks, preferably post-industrial recycled feedstocks, post-customer recycled feedstocks, or combinations thereof. In one embodiment, the Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or combinations thereof of the compounds containing Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or combinations thereof originates from recycled feedstocks, for example, spent batteries or battery manufacturing waste. Spent lithium ion batteries (or any prior lithium ion battery component source) can be crushed, granulated, shredded, etc., and subjected to a physical separation process to separate the solid battery components (e.g., case, electrodes, etc.) from the volatile components (e.g., electrolyte solvent). The electrolyte salt (e.g., LiPF6) can be removed by immersion in a suitable solvent (e.g., propylene carbonate), and the remaining undissolved materials (e.g., electrode materials, current collectors) can be isolated, for example, by filtration. The electrode particles can be separated from the residual current collector, for example, by contacting with a suitable solvent to dissolve the electrode particles, facilitating removal of the solid metal conductor components. The isolated electrode particles can be contacted with a leach solution to extract elements such as Ni, Co, Mn, Al, Li, and Fe. Exemplary leach solutions include, but are not limited to, sulfuric acid (e.g., 2-5M), optionally containing hydrogen peroxide. The resulting solution can be centrifuged or filtered to remove particles and exposed to conditions effective to cause crystallization or precipitation of the desired mixed metal composition. For example, the filtrate can be concentrated (e.g., in an evaporator) at 75-85°C, or 78-82°C, or 80°C. The concentrated solution can be cooled, for example, to a temperature below 20°C, or 10-18°C, or 15°C, to crystallize the mixed metal composition.

[0016] The precipitated or recrystallized mixed metal composition can be isolated, for example, using filtration, centrifugation, etc., or a combination thereof. In one embodiment, the mixed metal composition can be dehydrated to a moisture content of less than 10%, for example, 1-10%, or 5-10%.

[0017] The mixed metal composition is contacted with water to form a first solution. The first solution has a pH effective to dissolve the mixed metal composition, which can be selected by one of ordinary skill in the art without undue experimentation. In one embodiment, the first solution can have a pH of less than 7, such as less than 6.5. For example, if the mixed metal composition includes a mixed metal hydroxide, an acidic pH can be preferred to ensure dissolution of the mixed metal hydroxide.

[0018] The method further comprises adding a salt of nickel, cobalt, manganese, aluminum, or a combination thereof to the first solution to obtain a second solution. In one embodiment, the aforementioned salt may be a virgin material (i.e., a material that is not recovered or recycled from a used lithium-ion battery). In one embodiment, the salt of nickel, cobalt, manganese, aluminum, or a combination thereof is a sulfate or hydroxide thereof (e.g., nickel sulfate, cobalt sulfate, manganese sulfate, aluminum sulfate, nickel hydroxide, cobalt hydroxide, manganese hydroxide, aluminum hydroxide, or a combination thereof). In one embodiment, the salt comprises NiSO4, CoSO4, MnSO4, Al2(SO4)3, or a combination thereof.

[0019] The salts may be added in amounts effective to achieve the desired stoichiometric ratio of nickel, cobalt, manganese, aluminum, or combinations thereof. For example, nickel, cobalt, and manganese salts may be added to the first solution in amounts effective to provide a molar ratio of Ni:Co:Mn of greater than 0 to 1: greater than 0 to 1: greater than 0 to 1, e.g., 0.1 to 1:0.1 to 1:0.1 to 1, or 0.7 to 0.9:0.05 to 0.15:0.05 to 0.15. In one embodiment, such salts can be added to provide a molar ratio of Ni:Co:Mn of 6:2:2. In one embodiment, such salts can be added to provide a molar ratio of Ni:Co:Mn of 8:1:1 (e.g., 1:0.125:0.125).

[0020] The mixed metal composition of the first solution (e.g., recovered or recycled from spent lithium ion batteries or manufacturing scrap) can be contacted with virgin salt in any amount that provides a stoichiometrically adjusted mixed metal composition. In one embodiment, the mixed metal composition (i.e., of the first solution) can comprise 10 to 95 weight percent of the stoichiometrically adjusted mixed metal composition of the second solution. Within this range, the mixed metal composition can comprise 15 to 95 weight percent, or 20 to 95 weight percent, or 25 to 95 weight percent, or 30 to 90 weight percent of the stoichiometrically adjusted mixed metal composition.

[0021] In one embodiment, the salt comprises NiSO4, CoSO4, Al2(SO4)3, or a combination thereof. In one embodiment, nickel, cobalt, and aluminum salts can be added to the first solution in an amount effective to provide a molar ratio of Ni:Co:Al of greater than 0 to 1: greater than 0 to 1: greater than 0 to 1, such as 0.1 to 1:0.1 to 0.5:0.01 to 0.5, or 0.7 to 0.9:0.05 to 0.15:0.01 to 0.15. In one embodiment, the salt can be added to provide a molar ratio of Ni:Co:Al of 0.8:0.15:0.05. In certain embodiments, the first solution can include Ni and Co, and salts including NiSO4, CoSO4, or a combination thereof can be added to provide the desired Ni:Co ratio. Separately, a first solution including Al can be provided, and Al2(SO4)3 can be added. The first solution containing Ni and Co (after stoichiometric adjustment) can be subsequently combined with a solution containing Al (after addition of Al2(SO4)3) to provide a stoichiometrically adjusted mixed metal composition containing Ni, Co, and Al.

[0022] In one embodiment, the salts include NiSO4, MnSO4, CoSO4, Al2(SO4)3, or combinations thereof. In one embodiment, nickel, cobalt, aluminum, and manganese salts can be added to the first solution in an amount effective to provide a molar ratio of Ni:Mn:Co:Al of greater than 0-1: greater than 0-1: greater than 0-1: greater than 0-1, such as 0.1-1:0.1-0.5:0.1-0.5:0.01-0.5, or 0.7-0.9:0.05-0.15:0.05-0.15:0.01-0.15. In one embodiment, the salts can be added in an amount to provide a molar ratio of Ni:Mn:Co:Al of 0.8:0.05:0.05:0.1.

[0023] The second solution may have a pH that is the same or different than the pH of the first solution. In one embodiment, the pH of the second solution may be less than 7, or less than 6.5. As noted above, salts are added to achieve the desired stoichiometry of nickel, cobalt, manganese, aluminum, or combinations thereof, of the mixed metal composition of the second solution.

[0024] In addition to the stoichiometrically adjusted mixed metal composition, the second solution may further include 0.0001 to 2 weight percent of Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or combinations thereof, based on the total weight of the stoichiometrically adjusted mixed metal composition. In other words, the components of the mixed metal composition (e.g., Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or combinations thereof) have not been removed and therefore remain present in the second solution. Note that these components are not added to either the first or second solutions. Rather, they originate from the mixed metal feedstock used in the disclosed method, e.g., from recycled batteries or battery scrap, and are present at the start of the method.

[0025] The method further includes combining the second solution with a basic solution to form a precipitate. In one embodiment, the basic solution can be added to the second solution. In one embodiment, the second solution is preferably added to the basic solution to form a precipitate. The basic solution is mixed with the second solution in an amount effective to maintain or impart a pH of 10 or greater, preferably 10-13, more preferably 11-12. In one embodiment, at a pH of less than 10, no precipitate is formed or separated from the second solution. In one embodiment, the mixing of the basic solution with the second solution can be performed with stirring, for example, at a temperature of 25-90° C.

[0026] The basic solution is preferably an aqueous basic solution and thus may include a suitable base in water. The base may include, for example, an alkali metal hydroxide, ammonia, or a combination thereof. In one embodiment, the basic solution includes an alkali metal hydroxide (e.g., sodium hydroxide) and ammonia. When used in combination, the molar ratio of alkali metal hydroxide:ammonia may be, for example, 2:1 to 1:2, 3:2 to 2:3, 1.04:1 to 1:1.04, preferably 1.01:1 to 1:1.01. In a particular embodiment, the molar ratio of alkali metal hydroxide:ammonia may be 1:1.

[0027] Combining the basic solution with the second solution can, for example, co-precipitate a purified mixed metal composition having a desired ratio of Ni, Co, and Mn, referred to herein for brevity as the "precipitate." For example, the precipitate can include Ni(OH)2, CO(OH)2, and Mn(OH)2, preferably in a molar ratio of greater than 0 to greater than 1:0 to greater than 1:0 to greater than 1, preferably 6:2:2, 8:1:1 (1:0.125:0.125), or 9:0.5:0.5. The material precipitate can further include 5 to 100 ppm Li, for example 10 to 25 ppm Li, based on the total weight of the precipitate.

[0028] In one embodiment, the combination of the basic solution with the second solution can, for example, co-precipitate a precursor cathode active material having a desired ratio of Ni, Co, and Al. For example, the precipitate can include Ni(OH)2, Co(OH)2, and Al(OH)3, preferably in a molar ratio of greater than 0 to greater than 1:0 to greater than 1:0 to greater than 1, preferably 6:2:2, 8:1:1 (1:0.125:0.125), or 9:0.5:0.5. The precipitate can further include 5 to 100 ppm Li, for example 10 to 25 ppm Li, based on the total weight of the precipitate.

[0029] In one embodiment, combination of the basic solution with the second solution can co-precipitate a purified mixed metal composition having a desired proportion of, for example, Ni, Mn, Co, and Al. For example, the precipitate can include Ni(OH)2, Mn(OH)2, Co(OH)2, and Al(OH)3, preferably in a molar ratio of greater than 0 to 1:0 to 1:0 to 1:0 to 1. The precipitate can further include 5 to 100 ppm Li, for example, 10 to 25 ppm Li, based on the total weight of the precipitate.

[0030] Optionally, a chelating agent can be added to the second solution. If a chelating agent is added, it can be added to the second solution before, during, or after the addition of the basic solution. Exemplary chelating agents include, but are not limited to, 5-sulfosalicylic acid. If present, the chelating agent can be added in an amount sufficient to provide a concentration of 0.1-10M in the second solution.

[0031] In one embodiment, the method can further include isolating the precipitate. Isolation can be by any liquid-solid separation technique, including, for example, filtration, centrifugation, etc., or a combination thereof. The precipitate can be washed (e.g., with deionized water, distilled water, etc., or a combination thereof) and dried (e.g., at a temperature of 80-100° C., e.g., 85-95° C., under nitrogen).

[0032] The method further includes adding a lithium compound to the precipitate to form a lithiated precursor mixture (also referred to herein for brevity as "mixture"), and heat treating the precursor mixture under conditions effective to provide a cathode active material. Exemplary lithium compounds include lithium hydroxide, lithium carbonate, lithium oxide, lithium oxalate, or combinations thereof. In one embodiment, the lithium compound can include lithium hydroxide. Heat treating the mixture can include stirring at a temperature of 600-1000°C, 650-900°C, 700-800°C for 2-24 hours.

[0033] In one aspect, the cathode active material contains Ni, Co, Mn, Al, or a combination thereof in an amount corresponding to Formula 1: Li x MO2, where M is Ni, Co, Al, MnNi, Co, Al, or a combination thereof, and 0 ≦ x ≦ 1.4. In one aspect, 0 ≦ x ≦ 1.1.

[0034] In one aspect, the cathode active material contains Ni, Co, Mn, Al, or a combination thereof in an amount corresponding to Formula 2: Li x Ni y Co z Mn v O2, where 0 ≦ x ≦ 1.4 and 0 ≦ (y + z + v) ≦ 1.1. In one aspect, 0 ≦ x ≦ 1.1. In one aspect, the resulting cathode active material is Li x Ni 0.6 Co 0.2 Mn 0.2 , Li x Ni 0.8 Co 0.1 Mn 0.1、 or Li x Ni 0.9 Co 0.5 Mn 0.5 and may contain, where 0.9 < x < 1.1.

[0035] In one aspect, the cathode active material may contain Ni, Co, Mn, Al, or a combination thereof in an amount corresponding to Formula 3: mLi2MnO3·(1 - m)LiMO2, where M is Ni, Co, Mn, Al, or a combination thereof, and 0 < m < 1. For example, 0.2 ≦ m ≦ 0.5, or 0.33 < m < 0.5. In one aspect, M can be Ni, Co, and Mn. In one aspect, the ratio of Ni:Co:Mn is from greater than 0 to 1: greater than 0 to 1: greater than 0 to 1, preferably 1:0.33:0.33 (i.e., 6:2:2). In another aspect, M can be Ni, Co, and Al. In one aspect, M can be Ni, Co, and Al. In one aspect, the ratio of Ni:Co:Al is preferably greater than 0 to 1: greater than 0 to 1: greater than 0 to 1, preferably 1:0.056:0.056 (i.e., 90:5:5).

[0036] For example, in certain embodiments, the cathode active material is 0.33Li2MnO3·0.66LiNi 0.6 Co 0.2 Mn 0.2 O2 may be included.

[0037] Other cathode active materials can be obtained by the methods described herein using alternative battery chemistries, alternative compositional stoichiometries, or both.

[0038] The cathode active material prepared by the method described herein represents another aspect of the present disclosure.

[0039] For example, in one embodiment, the cathode active material may include a first layered Li x MO2 phase; and a second phase; where M is Ni, Co, Mn, Al, or a combination thereof, 0.9 < x < 1.4, and the second phase is derived from recycled materials. In one embodiment, 0.9 < x < 1.1. For example, the second phase can include a compound containing one or more of Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof. In one aspect, the second phase derived from recycled materials is one or more of Cu, Fe, Mg, Na, Ca, Zn, Al, F, Si, Li, or a combination thereof. In one aspect, the second phase obtained from recycled materials is present in an amount of 0.01 to 10 weight percent, 0.1 to 5 weight percent, or 0.2 to 2 weight percent based on the total weight of the cathode active material.

[0040] In one embodiment, the cathode active material can include a layered Li x MO2 phase, where M is Ni, Co, Mn, Al, or a combination thereof, 0.9 < x < 1.4, and further includes one or more of Cu, Fe, Mg, Na, Ca, Zn, F, Si, and Li, which can be derived from recycled materials. In one embodiment, 0.9 < x < 1.1.

[0041] In one embodiment, the cathode active material can include a first phase and a second phase. The first phase can include a first domain of formula Li2MnO3 and a second domain of formula LiMO2, where M is Ni, Co, Mn, Al, or a combination thereof. The second phase can be derived from a recycled feedstock. For example, the second phase can include a compound including one or more of Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof. In one embodiment, the second phase derived from a recycled feedstock is one or more of Cu, Fe, Mg, Na, Ca, Zn, Al, F, Si, Li, or a combination thereof. In one embodiment, the second phase derived from a recycled feedstock is present in an amount of 0.01 to 10 weight percent (wt%), 0.1 to 5 wt%, or 0.2 to 2 wt%, based on the total weight of the cathode active material.

[0042] The cathode active materials of the present disclosure can exhibit one or more advantageous properties. For example, the cathode active materials can have a discharge capacity of greater than 200 mAh / g at a discharge rate of C / 3 over 100 cycles in a half cell. In one embodiment, the cathode active materials can have a discharge capacity of greater than 180 mAh / g at a rate of C / 3 over 100 cycles in a full cell. These and other advantageous characteristics are further described in the examples below.

[0043] The cathode active material obtained by the methods described herein may be particularly useful in battery cathodes. Thus, a battery cathode may include a cathode active material produced by the methods described herein, optionally in combination with a virgin cathode active material (i.e., not produced using recycled feedstock). For example, the cathode active material of the present disclosure and the virgin cathode active material may be combined in a weight ratio of 1:99 to 99:1, or 10:90 to 90:10, or 20:80 to 80:20, or 30:70 to 70:30, or 40:60 to 60:40, or 45:55 to 55:45, or 50:50.

[0044] It may be further desirable to provide a purified mixed metal composition, e.g., a precursor cathode active material that has not yet been contacted with lithium to provide a final cathode active material. Thus, a method of making a purified mixed metal composition (i.e., a precursor cathode active material) represents another aspect of the present disclosure.

[0045] The method of producing a purified mixed metal composition includes contacting the mixed metal composition with water to form a first solution. The method further includes adding a salt of nickel, cobalt, manganese, aluminum, or a combination thereof to the first solution to provide a second solution, and combining the second solution with a basic solution to form a precipitate comprising the purified mixed metal composition. The mixed metal composition, first solution, second solution, basic solution, precipitate, and various conditions for the contacting, adding, and mixing steps can be as described above.

[0046] The precipitate comprising the purified mixed metal composition can be isolated, washed, and dried as already described in detail above. In one embodiment, the mixed metal composition can comprise Ni(OH)2, Co(OH)2, and Mn(OH)2, preferably in a molar ratio of greater than 0 to 1: greater than 0 to 1: greater than 0 to 1, preferably 6:2:2, 8:1:1 (1:0.125:0.125), or 9:0.5:0.5. In one embodiment, the mixed metal composition can comprise Ni(OH)2, CO(OH)2, and Al(OH)3. In one embodiment, the mixed metal composition can comprise Ni(OH)2, CO(OH)2, Mn(OH)2, and Al(OH)3. The precipitate can further comprise a compound comprising one or more of Cu, Fe, Mg, Na, Ca, Zn, Al, F, Si, Li, or a combination thereof. In one embodiment, the precipitate can further include one or more of Cu, Fe, Mg, Na, Ca, Zn, Al, F, Si, Li, or combinations thereof. For example, the precipitate can further include 5-100 ppm Li, such as 10-25 ppm Li, based on the total weight of the precipitated purified mixed metal composition. The precipitated purified mixed metal composition can optionally further include one or more of 50-300 ppm Cu, 50-200 ppm Al, 5-100 ppm Fe, and 5-100 ppm F, each based on the total weight of the mixed metal composition.

[0047] The present disclosure is further illustrated by the following non-limiting examples. EXAMPLES

[0048] Comparative Example 1 Battery grade starting materials were used to prepare a metal sulfate solution (MSO4) with a concentration of 2 moles / liter (M) and a stoichiometric ratio of Ni:Mn:Co of 8:1:1. The impurities of each starting material are shown in Table 1.

[0049] [Table 1]

[0050] NH3 solution (5M) and NaOH solution (2M) were fed separately and used as chelating and precipitating agents, respectively. A 3L continuous stir tank reactor (CSTR) was charged with 0.75M NH3 solution, followed by the addition of metal sulfate solution (MSO4), NH3, and NaOH. The flow rates of the MSO4 and NH3 feeds were maintained at 0.108L / h and 0.083L / h, respectively, and the NH3 / M ratio was kept constant at 1.92. The NaOH addition rate was also kept constant at 0.108L / h to promote continuous precipitation. The system reached a steady state after 48-50 hours, at which point all reagent concentrations were constant. The reaction temperature was maintained at 50°C and the stirring speed was 1085RPM. The pH of the solution was kept constant at 11.3 by adjusting the metal and NH3 / NaOH feeds. The solution was continuously purged with N2 as well as blanketed to prevent oxidation of the transition metals.

[0051] After the reaction reached a steady state, the precipitate was filtered and washed with water. The conductivity of the filtrate was monitored until it was well below 400 μS / cm to ensure the removal of any sulfate ions or metal impurity ions remaining on the surface of the precipitate. The filtered wet cake was then dried at 90° C. under N2 flow. The physical properties (tap density, particle size distribution, and surface morphology) of the precursor cathode active material (pCAM) are shown below.

[0052] Cathode active material (CAM) was prepared from the pCAM of Comparative Example 1 by mixing ground pCAM with lithium hydroxide monohydrate in a molar ratio of 1:1.05, followed by high temperature calcination under flowing oxygen. Mixing was performed using a LAB RAM sonic mixer with a furnace temperature ramp rate of 2°C / min until T1=750°C was reached. Residence time was 12 hours. After cooling, the CAM was ground and sieved using a 350 mesh sieve. The CAM prepared from the pCAM of Comparative Example 1 was analyzed using a scanning electron microscope (SEM), as shown in Figures 1A and 1B. Analysis by ICP-OES was consistent with Ni:Co:Mn being 8:1:1, as shown in Table 3.

[0053] Comparative Example 2 A cathode active material was prepared using the same materials and procedures as in Comparative Example 1, except that the temperature T1 during the CAM synthesis was 800°C.

[0054] Example 1 A metal sulfate solution (MSO4) was prepared using 30 wt% recycled mixed metal sulfate and 70 wt% battery grade starting materials (i.e., NiSO4, CoSO4, and MnSO4) with a concentration of 2M and a stoichiometric ratio of Ni:Mn:Co of 8:1:1. The recycled mixed metal sulfate (MMS) contains 20 wt% Ni and 0.86 wt% Co along with trace impurities (e.g., Al, Cu). The compositional components of the recycled mixed metal sulfate are shown in Table 2.

[0055] [Table 2]

[0056] A precursor cathode active material (pCAM) was prepared from the composition of Example 1 using the same process as described in Comparative Example 1, except that 30 wt% mixed metal sulfate (MMS) was used in the metal feed solution. A cathode active material (CAM) was prepared from the pCAM of Example 1 by mixing ground pCAM with lithium hydroxide monohydrate in a molar ratio of 1:1.05, followed by high temperature calcination under flowing oxygen. Mixing was performed using a LAB RAM sonic mixer, with a furnace temperature ramp rate of 2°C / min until 750°C was reached. The residence time at 750°C was 12 hours. After cooling, the CAM was ground and sieved using a 350 mesh sieve. The CAM prepared from the pCAM of Example 1 was analyzed using a scanning electron microscope (SEM), as shown in Figures 2A and 2B. Analysis by ICP-OES was consistent with Ni:Co:Mn being 8:1:1, as shown in Table 3.

[0057] Example 2 A cathode active material was prepared using the same materials and procedures as in Example 1, except that the temperature T1 during the CAM synthesis was 800°C.

[0058] Example 3 A metal sulfate solution (MSO4) was prepared using 60 wt% recycled mixed metal sulfate and 30 wt% battery grade raw materials (i.e., NiSO4, MnSO4, CoSO4) with a concentration of 2M and a stoichiometric ratio of Ni:Mn:Co of 8:1:1. The same process as in Example 1 was used to prepare pCAM and CAM, except that 60 wt% mixed metal sulfate (MMS) was used in the metal feed solution. The CAM prepared from the pCAM of Example 3 was analyzed using a scanning electron microscope (SEM), as shown in Figures 3A and 3B. Analysis by ICP-OES was consistent with Ni:Co:Mn being 8:1:1, as shown in Table 3.

[0059] Example 4 A metal sulfate solution (MSO4) was prepared with 90 wt% recycled mixed metal sulfate and 10 wt% battery grade starting materials at a concentration of 2M with a stoichiometric ratio of Ni:Mn:Co of 8:1:1. The same process as in Example 1 was used to prepare pCAM and CAM, except that 90 wt% mixed metal sulfate (MMS) was used in the metal feed solution. The CAM prepared from the pCAM of Example 4 was analyzed using scanning electron microscopy (SEM), as shown in Figures 4A-4D, which shows that the morphology and particle size distribution of pCAM and CAM are comparable compared to Comparative Example 1.

[0060] The physical properties of pCAM and CAM from Comparative Example 1 and Examples 1 and 3, as well as the results of ICP analysis, are summarized in Table 3. "CE" is used to indicate Comparative Example and "E" is used to indicate Example.

[0061] [Table 3]

[0062] Electrode preparation The CAM powder was mixed with conductive carbon black and polyvinylidene fluoride (PVDF) binder in a weight ratio of 84:8:8. The mixture was mixed using a THINKY mixer along with NMP to adjust the rheology of the slurry. The slurry was cast onto Al foil using a 254 micrometer (μm) doctor blade, followed by quick drying at 75°C to remove the NMP solvent. The cast film was then further dried at 100°C under vacuum to promote the curing of the PVDF and to completely remove the NMP. A coin-shaped half cell (CR2025) with a Li metal anode and a coin-shaped full cell with a graphite anode were assembled and tested using a MACCOR tester.

[0063] Rate Proficiency Test The half-cell was charged using a constant current / constant voltage (CC-CV) protocol with a C / 10 constant charge current of 4.2 V until it reached 4.2 V, and then constant voltage charging was performed until the charge current dropped to C / 20. The cells were discharged at different C-rates in cycles 1-15 with a discharge cutoff voltage of 2.5 V, as shown in Figure 5. The C-rate is defined using the discharge capacity at C / 10 rate. C-rate means the current at which the battery is discharged in 1 hour, for example, the C-rate of a battery with a discharge capacity of 1 ampere-hour would be 1 ampere.

[0064] A similar charging protocol was used for cycles 16-30, except that a charge cutoff voltage of 4.5 V was used. As shown in FIG. 5, the cathode active materials made from recycled feedstock (e.g., Example 4, which gave 215 mAh / g at C / 10 rate) provided higher capacity than materials made from battery-grade low-impurity materials (e.g., Comparative Example 1, which gave 200 mAh / g at C / 10 rate). The results shown in FIG. 5 suggest that cathode active materials made from recycled feedstock can provide comparable or improved discharge capacity compared to those made from battery-grade low-impurity feedstocks.

[0065] It was observed that the pCAM calcination temperature also affects the electrochemical performance. As shown in FIG. 5, the samples calcined at 800° C. (Comparative Example 2 and Example 2) show lower discharge capacity compared to the samples calcined at 750° C. (Comparative Example 1 and Example 1, respectively). Without being bound by theory, it is believed that excessive sintering of the primary particles and Li loss at high temperatures may contribute to the capacity loss observed when using higher calcination temperatures. Surface reconstruction of the CAM surface may also contribute to the capacity loss.

[0066] FIG. 6A shows a comparison of discharge capacity at C / 3 rate with a charge cutoff voltage of 4.2 V, and FIG. 6B shows a comparison of discharge capacity at C / 3 rate with a charge cutoff voltage of 4.5 V. For the cathode active material prepared from recycled MMS, a higher discharge capacity was observed at a cutoff voltage of 4.2 V. When a cutoff voltage of 4.5 V was used, a larger discharge capacity was observed with increasing amounts of recycled MMS. When a cutoff voltage of 4.5 V was used, a higher capacity was observed, and a statistically significant higher discharge capacity was observed when a high content (e.g., 90 wt%) of MMS was used in the production of pCAM and CAM materials. These results suggest that the use of recycled MMS in the metal feed solution for producing pCAM and CAM may be advantageous for electrochemical performance (e.g., rate capability and discharge capacity).

[0067] Half Cell Life The coin full cell cycle life performance was evaluated according to the test procedure described in J. Electrochem. Soc., 163 (2016) A2999, which is incorporated herein by reference in its entirety. To further differentiate the cycle life performance, a 3-hour constant voltage charge was added to each cycle to mimic accelerated aging. The half cells contain Li metal as the anode. Figure 7 shows that the capacity does not change significantly over 100 cycles at a C / 3 rate. This result suggests that the cathode material made from recycled MMS can perform comparable to that made from virgin battery grade material.

[0068] Full Cell Cycle Life and Hybrid Pulsed Power Characterization (HPPC) To better evaluate the performance of the cathode, full coin cells with graphite anodes were fabricated. Figure 8 shows the full cell cycle life of Comparative Example 1 (circles), Example 1 (triangles) and Example 3 (diamonds), showing no significant change in discharge capacity over 100 cycles when charged and discharged at C / 3 rate.

[0069] HPPC testing using both charge and discharge cycles was performed every 20 C / 3 cycles. Low cell impedance is preferred because an increase in impedance can negatively affect charge and discharge efficiency. Figure 9 shows that cells made with recycled MMS have low area specific impedance (ASI) during both charge and discharge cycles in HPPC testing. A lower ASI indicates better potential extended cycling performance.

[0070] The present disclosure further includes the following aspects.

[0071] Aspect 1: A method for making a cathode active material, the method comprising: contacting a mixed metal composition with water to form a first solution, the mixed metal composition comprising nickel, cobalt, manganese, aluminum, or a combination thereof; comprising greater than 0 to 2 weight percent, based on the total weight of the mixed metal composition, of a compound comprising Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof; adding a salt of nickel, cobalt, manganese, aluminum, or a combination thereof to the first solution to obtain a second solution; combining the second solution with a basic solution to form a precipitate; adding a lithium compound to the precipitate to form a mixture; and heat treating the mixture to form a cathode active material. The method includes:

[0072] Aspect 2: The method of aspect 1, wherein the mixed metal composition comprises nickel, cobalt, manganese, aluminum, or a combination thereof, and is obtained by a process comprising contacting electrode particles comprising compounds comprising greater than 0 to 2 weight percent of Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof, based on a total weight of the mixed metal composition, with a leach solution (preferably comprising sulfuric acid); precipitating the mixed metal composition from the leach solution; and isolating the mixed metal composition from the leach solution.

[0073]

[0023] Aspect 3: The method of aspect 1 or 2, wherein the mixed metal composition comprises a mixed metal sulfate, mixed metal nitrate, mixed metal carbonate, mixed metal halide, mixed metal hydroxide, mixed metal oxalate, or a combination thereof.

[0074]

[0023] Aspect 4: The method of any of Aspects 1-3, wherein the mixed metal composition comprises a mixed metal sulfate.

[0075] Embodiment 5: The method of any of embodiments 1-4, wherein the mixed metal composition comprises: nickel and cobalt, and greater than 0 to 2 weight percent Cu, Fe, Mg, F, or combinations thereof, based on a total weight of the mixed metal composition.

[0076] Aspect 6: The method of any of Aspects 1-5, wherein the mixed metal composition further comprises lithium, preferably in an amount of 100 to 1000 ppm based on the total weight of the mixed metal composition.

[0077]

[0023] Aspect 7. The method of any of Aspects 1-6, wherein the mixed metal composition is obtained from a recycled feedstock, preferably a post-industrial recycled feedstock, a post-customer recycled feedstock, or a combination thereof.

[0078] Embodiment 8: The method of any of embodiments 1-7, wherein the mixed metal composition comprises 50-300 ppm Cu, 50-200 ppm Al, 5-100 ppm Fe, and 5-100 ppm F, each based on a total weight of the mixed metal composition.

[0079] Aspect 9: The method of any of aspects 1 to 8, wherein the first solution has a pH of less than 7, or less than 6.5.

[0080] Aspect 10: The method of any one of aspects 1-9, wherein the salt of nickel, cobalt, manganese, aluminum, or a combination thereof is a sulfate or hydroxide thereof.

[0081] Embodiment 11: The method of any of embodiments 1-10, wherein the mixed metal composition comprises nickel, cobalt, and manganese, and the method comprises adding salts of nickel, cobalt, and manganese to the first solution in amounts effective to provide a molar ratio of Ni:Co:Mn of greater than 0 to 1:0 to 1:0 to 1, preferably 1:0.125:0.125.

[0082] Aspect 12: The method of aspect 11, wherein the salts include NiSO4, CoSO4, and MnSO4.

[0083] Aspect 13: The method of any of aspects 1 to 12, wherein the second solution has a pH of less than 7, or less than 6.5.

[0084] Embodiment 14: The method of any of embodiments 1 to 13, wherein the second solution contains 0.0001 to 2 weight percent of Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof, based on the weight of the solution.

[0085] Aspect 15: The method of any of aspects 1-14, wherein the basic solution comprises a base comprising an alkali metal hydroxide, ammonia, or a combination thereof, preferably sodium hydroxide and ammonia, wherein the sodium hydroxide and ammonia are present in a ratio of 1.04:1 to 1:1.04, preferably 1.01:1 to 1:1.01, more preferably 1:1.

[0086] Aspect 16: The method of any of aspects 1-15, wherein the basic solution is mixed with the second solution in an amount effective to provide a pH of 10 or greater, preferably 10-13, more preferably 11-12.

[0087] Aspect 17: The method of any one of aspects 1 to 16, wherein a precipitate is not separated from the second solution at a pH below 10.

[0088] Embodiment 18: The method of any of embodiments 1 to 17, further comprising adding a chelating agent to the second solution, wherein preferably the chelating agent is present in the second solution at a concentration of 0.1 to 10 M.

[0089] Aspect 19: The method of any of aspects 1 to 18, wherein the precipitate comprises Ni(OH)2, Co(OH)2, and Mn(OH)2 in a molar ratio of greater than 0 to 1: greater than 0 to 1: greater than 0 to 1, preferably 1:0.125:0.125.

[0090] Embodiment 20 The method of any one of embodiments 1 to 19, wherein the precipitate comprises 5 to 100 ppm Li, preferably 10 to 25 ppm Li, based on the total weight of the precipitate.

[0091] Example 21 The method of any one of Examples 1-20, wherein the lithium compound comprises lithium hydroxide, lithium carbonate, lithium oxide, lithium oxalate, or a combination thereof.

[0092] Aspect 22: The cathode active material comprises Ni, Co, Mn, Al, or a combination thereof, represented by the formula 1: Li x 22. The method of any of the preceding aspects, comprising comprising:

[0093] Embodiment 23: The method according to embodiment 22, wherein 0≦x≦1.1.

[0094] Aspect 24: The cathode active material comprises Ni, Co, Mn, Al, or a combination thereof, represented by the formula 2: Li x Niy Co z Mn v Containing in an amount corresponding to O2, where 0 ≦ x ≦ 1.4 and 0 ≦ (y + z + v) ≦ 1.1, the method according to any one of Aspects 1 to 23.

[0095] Aspect 25: The method according to Aspect 23, where 0 ≦ x ≦ 1.1.

[0096] Aspect 26: The cathode active material is LiNi 0.8 Co 0.1 Mn 0.1 Containing, the method according to any one of Aspects 1 to 25.

[0097] Aspect 27: The cathode active material contains Ni, Co, Mn, Al, or a combination thereof in an amount corresponding to Formula 3: mLi2MnO3·(1 - m)LiMO2, where M is Ni, Co, Mn, Al, or a combination thereof and 0 < m < 1, the method according to any one of Aspects 1 to 21.

[0098] Aspect 28: The method according to Aspect 27, where 0.2 < m < 0.5.

[0099] Aspect 29: The method according to either Aspect 27 or 28, where M is Ni, Co, and Mn.

[0100] Aspect 30: The method according to any one of Aspects 27 to 29, where the ratio of Ni:Co:Mn is greater than 0 to greater than 1:greater than 0 to greater than 1:greater than 0 to greater than 1, preferably 6:2:2.

[0101] Aspect 31: The method according to either Aspect 27 or 28, where M is Ni, Co, and Al.

[0102] Aspect 32: The method according to any one of Aspects 27, 28, and 31, where the ratio of Ni:Co:Al is greater than 0 to greater than 1:greater than 0 to greater than 1:greater than 0 to greater than 1, preferably 90:5:5.

[0103] Aspect 33: The cathode active material is 0.33Li2MnO3·0.66LiNi 0.6 Co0.2 Mn 0.2 The method according to embodiment 27, comprising MnO2.

[0104] Embodiment 34: The heat treatment includes stirring at a temperature of 600 to 1000 °C for 2 to 24 hours, and the method according to any one of embodiments 1 to 33.

[0105] Embodiment 35: The method according to any one of embodiments 1 to 34, further comprising stirring the second solution at a speed of 500 - 1500 RPM and a temperature of 25 to 90 °C.

[0106] Embodiment 36: The method according to any one of embodiments 1 to 35, further comprising isolating the precipitate.

[0107] Embodiment 37: The method according to any one of embodiments 1 to 36, further comprising combining the cathode active material with an unused cathode active material.

[0108] Embodiment 38: The method according to embodiment 37, wherein the cathode active material and the unused cathode active material are combined in a weight ratio of 1:99 to 99:1.

[0109] Embodiment 39: A cathode active material made by the method according to any one of embodiments 1 to 38.

[0110] Embodiment 40: A cathode active material comprising: a first layered LiMO2 phase; and a second phase; where M is Ni, Co, Mn, Al, or a combination thereof, 0 < x < 1.4, and the second phase is derived from a recycle feedstock. x MO2 phase; and a second phase; wherein M is Ni, Co, Mn, Al, or a combination thereof, 0 < x < 1.4, and the second phase is derived from a recycle feedstock.

[0111] Embodiment 41: The cathode active material according to embodiment 40, wherein 0 < x < 1.1.

[0112] Embodiment 42: The cathode active material according to embodiment 40 or 41, wherein the second phase comprises one or more of Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof.

[0113] Aspect 43: The cathode active material according to any one of Aspects 40 to 42, wherein the second phase is derived from a recycled feedstock and is present in an amount of 1 to 99 weight percent based on the total weight of the cathode active material.

[0114] Aspect 44: A cathode active material comprising a first layered phase containing Li x MO2, where M is Ni, Co, Mn, Al, or a combination thereof, 0 < x < 1.4, and wherein the first layered phase further contains Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof.

[0115] Aspect 45: The cathode active material according to Aspect 44, wherein 0 < x < 1.1.

[0116] Aspect 46: The cathode active material according to Aspect 44 or 45, wherein Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof is derived from a recycled feedstock.

[0117] Aspect 47: The cathode active material according to any one of Aspects 40 to 46, wherein the cathode active material has a discharge capacity higher than 200 mAh / g at a discharge rate of C / 3 over 100 cycles in a half cell.

[0118] Aspect 48: The cathode active material according to any one of Aspects 40 to 47, wherein the cathode active material has a discharge capacity greater than 180 mAh / g at a rate of C / 3 over 100 cycles in a full cell.

[0119] Aspect 49: A cathode active material comprising a first phase and a second phase, wherein the first phase comprises a first domain of formula Li2MnO3 and a second domain of formula LiMO2, where M is Ni, Co, Mn, Al, or a combination thereof, and the second phase is derived from a recycled feedstock.

[0120] Aspect 50: The cathode active material according to Aspect 49, wherein the second phase contains one or more of Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof.

[0121] Embodiment 51: The cathode active material of embodiment 49, wherein the first phase is derived from a recycled feedstock.

[0122] Embodiment 52: A method of producing a purified mixed metal composition, the method comprising: contacting a mixed metal composition comprising nickel, cobalt, manganese, aluminum, or a combination thereof, and greater than 0 to 2 weight percent Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof, based on a total weight of the mixed metal composition, with water to form a first solution; adding a salt of nickel, cobalt, manganese, aluminum, or a combination thereof to the first solution to provide a second solution; combining the second solution with a basic solution to form a precipitate comprising the purified mixed metal composition.

[0123] Embodiment 53: The method of embodiment 52, wherein the mixed metal composition is obtained by a process comprising contacting electrode particles comprising compounds comprising nickel, cobalt, manganese, aluminum, or a combination thereof, and greater than 0 to 2 weight percent of Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof, based on the total weight of the mixed metal composition, with a leachate preferably comprising sulfuric acid; precipitating the mixed metal composition from the leachate; and isolating the mixed metal composition from the leachate.

[0124]

[0046] Example 54. The method of example 52 or 53, wherein the purified mixed metal composition comprises 5 to 100 ppm Li, preferably 10 to 25 ppm Li, based on the total weight of the precipitate.

[0125] Embodiment 55: The method of any one of embodiments 52-54, wherein the mixed metal composition comprises a mixed metal sulfate, a mixed metal nitrate, a mixed metal carbonate, a mixed metal halide, a mixed metal hydroxide, a mixed metal oxalate, or a combination thereof, preferably a mixed metal sulfate.

[0126] Example 56: The method of any of Examples 52-55, wherein the mixed metal composition is obtained from a recycled feedstock, preferably a post-industrial recycled feedstock, a post-consumer recycled feedstock, or a combination thereof.

[0127] Embodiment 57: The method of any of embodiments 52-56, wherein the mixed metal composition comprises 50-300 ppm Cu, 50-200 ppm Al, 5-100 ppm Fe, and 5-100 ppm F, each based on the total weight of the mixed metal composition.

[0128] Embodiment 58: A method described in any of embodiments 52 to 57, wherein the first solution has a pH of less than 7, or less than 6.5.

[0129] Aspect 59: The method of any one of aspects 52 to 58, wherein the salt of nickel, cobalt, manganese, aluminum, or a combination thereof is a sulfate or hydroxide thereof.

[0130] Embodiment 60: The method of any of embodiments 52-59, wherein the mixed metal composition comprises nickel, cobalt, and manganese, and the method comprises adding salts of nickel, cobalt, and manganese to the first solution in amounts effective to provide a molar ratio of Ni:Co:Mn of greater than 0 to 1:0 to 1:0 to 1, preferably 1:0.125:0.125.

[0131] Embodiment 61: A method described in any of embodiments 52 to 60, wherein the second solution has a pH of less than 7, or less than 6.5.

[0132] Embodiment 62: The method of any of embodiments 52 to 61, wherein the basic solution comprises a base comprising an alkali metal hydroxide, ammonia, or a combination thereof, preferably sodium hydroxide and ammonia, more preferably the sodium hydroxide and ammonia are present in a ratio of 1.04:1 to 1:1.04, preferably 1.01:1 to 1:1.01, more preferably 1:1.

[0133] Embodiment 63: The method of any of embodiments 52-62, wherein the basic solution is mixed with the second solution in an amount effective to give a pH of 10 or greater, preferably 10-13, more preferably 11-12.

[0134] Embodiment 64: The method of any of embodiments 52 to 63, wherein no precipitate is separated from the second solution at a pH below 10.

[0135] Embodiment 65: The method of any of embodiments 52 to 64, further comprising adding a chelating agent to the second solution, wherein preferably the chelating agent is present in the second solution in an amount of 0.1 to 10 M.

[0136] Embodiment 66: The method of any of embodiments 52-65, wherein the purified mixed metal composition comprises Ni(OH)2, Co(OH)2, and Mn(OH)2, preferably in a molar ratio of greater than 0 to 1:greater than 0 to 1:greater than 0 to 1, preferably in a molar ratio of 1:0.125:0.125.

[0137] Example 67: A purified mixed metal composition produced by the method of any of Examples 52-66.

[0138] Embodiment 68: A purified mixed metal composition comprising Ni(OH), CO(OH), and Mn(OH); preferably in a molar ratio of greater than 0 to 1: greater than 0 to 1: greater than 0 to 1; and one or more of Cu, Fe, Mg, Na, Ca, Zn, Al, F, Si, Li, or combinations thereof.

[0139] Embodiment 69: The purified mixed metal composition of embodiment 68, comprising from 5 to 100 ppm Li, preferably from 10 to 25 ppm Li, based on the total weight of the precipitate.

[0140] The compositions and methods may alternatively comprise, consist of, or consist essentially of any suitable materials, steps, or ingredients disclosed herein. The compositions and methods may additionally, or alternatively, be formulated to be devoid of, or substantially free of, materials (or species), steps, or ingredients that are not necessary to achieve the function or purpose of the compositions, methods, and articles.

[0141] All ranges disclosed herein are inclusive of the endpoints, and the endpoints may be combined independently of one another. "Combinations" include blends, mixtures, alloys, reaction products, and the like. Terms such as "first," "second," and the like do not denote an order, quantity, or importance, but rather are used to distinguish one element from another. The terms "a" and "an" and "the" do not denote limitations of quantity, and are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. "Or" means "and / or" unless otherwise indicated. References throughout this specification to "embodiments" mean that the particular element described in connection with that embodiment is included in at least one embodiment described herein and may or may not be present in other embodiments. As used herein, the term "combinations thereof" includes one or more of the recited elements and is open, allowing for the presence of one or more similar elements not specified. Furthermore, it is to be understood that the recited elements may be combined in any suitable manner in the various embodiments.

[0142] Furthermore, it will be understood that the terms "comprises" and / or "comprising" or "includes" or "including" as used herein specify the presence of stated features, regions, integers, steps, operations, elements, or components, but do not exclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, or groups thereof.

[0143] Various embodiments are shown in the accompanying drawings. However, the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Like reference numerals refer to like elements throughout.

[0144] Unless otherwise defined, all terms used herein (including technical and scientific terms) have the same meaning as commonly understood by those skilled in the art to which this disclosure belongs. Furthermore, terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the relevant technology and this disclosure, and will not be interpreted in an idealized or overly formal sense unless expressly defined herein.

[0145] U.S. Provisional Patent Application No. 63 / 311,535, filed February 18, 2022, and U.S. Provisional Patent Application No. 63 / 341,270, filed May 12, 2022, are hereby incorporated by reference in their entireties for all purposes.

[0146] While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents may occur to the applicant or those skilled in the art that are not presently foreseen or may not be foreseen, and accordingly, the appended claims are intended to embrace all such alternatives, modifications, variations, improvements, and substantial equivalents as filed and as amended.

Claims

1. 1. A method of making a cathode active material, the method comprising: contacting a mixed metal composition with water to form a first solution, the mixed metal composition comprising: nickel, cobalt, manganese, aluminum, or combinations thereof; and greater than 0 to 2 weight percent of a compound containing Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof, based on the total weight of the mixed metal composition. Includes; adding a salt of nickel, cobalt, manganese, aluminum, or a combination thereof to the first solution to obtain a second solution; combining the second solution with a basic solution to form a precipitate; adding a lithium compound to the precipitate to form a mixture; and heat treating the mixture to form a cathode active material. A manufacturing method comprising:

2. The mixed metal composition comprises: nickel, cobalt, manganese, aluminum, or a combination thereof; and greater than 0 to 2 weight percent, based on the total weight of the mixed metal composition, of a compound comprising Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof. contacting electrode particles comprising the compound with a leaching solution; precipitating a mixed metal composition from the leach solution; and Isolating the mixed metal composition from the leach solution. The method of claim 1, obtained by a method comprising:

3. The method of claim 1 , wherein the mixed metal composition comprises a mixed metal sulfate, a mixed metal nitrate, a mixed metal carbonate, a mixed metal halide, a mixed metal hydroxide, a mixed metal oxalate, or a combination thereof.

4. The mixed metal composition may be: Nickel and cobalt, and greater than 0 to 2 weight percent Cu, Fe, Mg, F, or combinations thereof, based on the total weight of the mixed metal composition. The method of claim 1 , comprising:

5. 10. The method of claim 1, wherein the mixed metal composition further comprises 50 to 300 ppm Cu, 50 to 200 ppm Al, 5 to 100 ppm Fe, or 5 to 100 ppm F, each based on the total weight of the mixed metal composition.

6. 10. The method of claim 1, wherein at least a portion of the mixed metal composition is obtained from recycled feedstock.

7. 10. The method of claim 1, wherein the first solution has a pH of less than 7 or the second solution has a pH of less than 7.

8. 10. The method of claim 1, wherein the salt of nickel, cobalt, manganese, aluminum, or a combination thereof is a sulfate or hydroxide thereof.

9. 10. The method of claim 1, wherein the mixed metal composition comprises nickel, cobalt, and manganese, and the method comprises adding salts of nickel, cobalt, and manganese to the first solution in amounts effective to provide a molar ratio of Ni:Co:Mn of greater than 0 to 1: greater than 0 to 1: greater than 0 to 1, preferably 1:0.125:0.

125.

10. 10. The method of claim 1, wherein the basic solution is mixed with the second solution in an amount effective to provide a pH of 10 or greater, preferably 10-13, more preferably 11-12.

11. The precipitate is preferably prepared by mixing Ni(OH) in a molar ratio of >0-1: >0-1: >0-1, preferably 1:0.125:0.

125. ２ , Co(OH) ２ , and Mn(OH) ２ The method of claim 1 , comprising:

12. 2. The method of claim 1, wherein the precipitate contains 5 to 100 ppm Li, preferably 10 to 25 ppm Li, based on the total weight of the precipitate.

13. 10. The method of claim 1, wherein the lithium compound comprises lithium hydroxide, lithium carbonate, lithium oxide, lithium oxalate, or a combination thereof.

14. The cathode active material may comprise Ni, Co, Mn, Al, or a combination thereof, represented by Formula 1: Li ｘ MO ２ 2. The method of claim 1 , wherein M is Ni, Co, Mn, Al, or a combination thereof, and 0≦x≦1.

4.

15. The cathode active material may comprise Ni, Co, Mn, Al, or a combination thereof, represented by Formula 2: Li ｘ Ni ｙ Co ｚ Mn ｖ O ２ 2. The method of claim 1 , wherein 0≦x≦1.4 and 0≦(y+z+v)≦1.

1.

16. The cathode active material may comprise Ni, Co, Mn, Al, or a combination thereof, represented by Formula 3: mLi ２ MnO ３ ・(1-m)LiMO ２ in an amount corresponding to M is Ni, Co, Mn, Al, or a combination thereof; 0<m<1 The method of claim 1.

17. The cathode active material is 0.33Li ２ MnO ３ ・0.66LiNi ０．６ Co ０．２ Mn ０．２ O ２ The method of claim 1 , comprising:

18. The method of claim 1 further comprising combining the cathode active material with virgin cathode active material.

19. A cathode active material produced by the method of any one of claims 1 to 18.

20. First layered Li ｘ MO ２ phase; and Second Phase where: M is Ni, Co, Mn, Al, or a combination thereof, and 0<x<1.4; The second phase is derived from recycled feedstock. Cathode active material.

21. 21. The cathode active material of claim 20, wherein the second phase comprises one or more of Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or combinations thereof.

22. Li ｘ MO ２ 1. A cathode active material comprising a first layered phase comprising: M is Ni, Co, Mn, Al, or a combination thereof, and 0<x<1.4; the first layered phase further comprises Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof; Cathode active material.

23. 23. The cathode active material of claim 21 or 22, wherein the Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or combinations thereof are derived from recycled feedstocks.

24. A first phase, and Second Phase 1. A cathode active material comprising: The first phase has the formula Li ２ MnO ３ and a first domain of formula LiMO ２ wherein M is Ni, Co, Mn, Al, or a combination thereof; the second phase is derived from recycled feedstock; Cathode active material.

25. 25. The cathode active material of claim 24, wherein the second phase comprises one or more of Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or combinations thereof.

26. Preferably, Ni(OH) in a molar ratio of >0 to 1: >0 to 1: >0 to 1, preferably 1:0.125:0.125 ２ , CO(OH) ２ , and Mn(OH) ２ and Cu, Fe, Mg, Na, Ca, Zn, Al, F, Si, Li, or a combination thereof 1. A purified mixed metal composition comprising:

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