Method for producing cathode active material having spinel structure

Abstract

A method of making a cathode active material comprising contacting a mixed metal composition with water to form a first solution, the mixed metal composition comprising nickel, manganese, or nickel and manganese. A salt of nickel, manganese, or a combination thereof is added to the first solution to obtain a second solution, which can be further combined with a co-solvent to obtain a third solution. The third solution can be further combined with a basic solution to obtain a precipitate, and the precipitate can be combined with a lithium compound to obtain a cathode active material having at least one phase having a spinel structure.

Description

[Background technology]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 63 / 338,485, filed in the U.S. Patent and Trademark Office on May 5, 2022, and claims all benefits arising therefrom under 35 U.S.C. § 119, the contents of which are incorporated herein by reference in their entirety.

[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 a method for preparing cathode active materials with specific structures for new batteries, other than from new raw materials. Summary of the Invention

[0003] In one embodiment, a method of making a cathode active material includes contacting a mixed metal composition with water to form a first solution, the mixed metal composition comprising nickel and greater than 0 to 2 weight percent of a compound comprising Co, Mn, Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof, based on the total weight of the mixed metal composition; adding a salt of nickel, manganese, or a combination thereof to the first solution to obtain a second solution; adding a co-solvent to the second solution to obtain a third solution; combining the third 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 under conditions effective to provide a cathode active material, wherein the cathode active material comprises at least one phase having a spinel structure.

[0004] In one embodiment, a method of making a cathode active material includes contacting a mixed metal composition with water to form a first solution, the mixed metal composition comprising nickel and manganese, and greater than 0 to 2 weight percent, based on the total weight of the mixed metal composition, of a compound comprising Co, Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof; adding a salt of nickel, manganese, or a combination thereof to the first solution to obtain a second solution; adding a co-solvent to the second solution to obtain a third solution; combining the third 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 under conditions effective to provide a cathode active material, wherein the cathode active material comprises at least one phase having a spinel structure.

[0005] In one embodiment, a method of making a cathode active material includes contacting a mixed metal composition with water to form a first solution, the mixed metal composition comprising manganese and greater than 0 to 2 weight percent, based on the total weight of the mixed metal composition, of a compound comprising Co, Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof; adding a salt of nickel, manganese, or a combination thereof to the first solution to obtain a second solution; adding a co-solvent to the second solution to obtain a third solution; combining the third 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 under conditions effective to provide a cathode active material, wherein the cathode active material comprises at least one phase having a spinel structure.

[0006] In one embodiment, the cathode active material is Li 1+x M 2+y O 4-z A zand a second phase, wherein M is Ni and Mn; A is an oxygen vacancy, F, Cl, or a combination thereof; 0≦x≦0.2; 0≦y≦0.1; 0≦z≦0.1; and the second phase is derived from recycled feedstock.

[0007] In one embodiment, the cathode active material is Li 1+x M 2+y O 4-z A z and a first phase having a spinel structure, where M is Ni, and Mn, A is an oxygen vacancy, F, Cl, or a combination thereof, and 0≦x≦0.2, 0≦y≦0.1, 0≦z≦0.1, and where the first phase further comprises Co, Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof.

[0008] The above-noted and other features are illustrated by the following figures and detailed description.

[0009] The following figures represent exemplary embodiments. [Brief description of the drawings]

[0010] [Figure 1] FIG. 1 shows a flow chart of an exemplary method according to the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The present inventors have discovered methods for remanufacturing batteries and battery materials, particularly cathode active materials, and precursors thereof, where the cathode active material has at least one phase having a spinel structure. Cathode active materials produced according to the methods described herein are expected to exhibit comparable or improved battery performance despite using a high percentage of raw materials derived from spent batteries or battery manufacturing scrap.

[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] In one embodiment, the mixed metal composition includes nickel. Nickel may be present in the mixed metal composition in an amount of at least 5 weight percent, or at least 10 weight percent, or at least 15 weight percent, or at least 18 weight percent, based on the total weight of the mixed metal composition. In one embodiment, nickel may be present in the mixed metal composition in an amount of 5 to 98 weight percent, or 5 to 85 weight percent, or 5 to 75 weight percent, or 5 to 50 weight percent, or 15 to 25 weight percent, based on the total weight of the mixed metal composition. The mixed metal composition may further include greater than 0 to 2 weight percent of a compound including Co, Mn, Al, 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 Co, Mn, Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof, based on the total weight of the mixed metal composition. In one embodiment, the mixed metal composition may include greater than 0 to 1000 ppm, or greater than 0 to 750 ppm, or between 5 and 750 ppm, or between 5 and 1000 ppm, or between 25 and 1000 ppm, or between 25 and 750 ppm, or between 50 and 750 ppm, or between 100 and 750 ppm of a compound including Co, Mn, Al, 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 0.5 to 1.5 weight percent Co, 50 to 300 ppm Cu, 50 to 200 ppm Al, 5 to 100 ppm Fe, and 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. If present, lithium may preferably be present in the mixed metal composition in an amount of 100 to 1000 ppm, based on the total weight of the mixed metal composition.

[0014] In one embodiment, the mixed metal composition includes nickel and manganese (e.g., where nickel and manganese are present as major components of the mixed metal composition). For example, nickel and manganese may be present in the mixed metal composition in an amount of at least 5 weight percent, or at least 10 weight percent, or at least 15 weight percent, or at least 18 weight percent, based on the total weight of the mixed metal composition. In one embodiment, nickel and manganese may be present in the mixed metal composition in an amount of 5 to 98 weight percent, or 5 to 85 weight percent, or 5 to 75 weight percent, or 5 to 50 weight percent, or 15 to 25 weight percent, based on the total weight of the mixed metal composition. The mixed metal composition may further include greater than 0 to 2 weight percent of a compound including Co, Al, 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 Co, Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof, based on the total weight of the mixed metal composition. In one embodiment, the mixed metal composition may include greater than 0 to 1000 ppm, or greater than 0 to 750 ppm, or between 5 and 750 ppm, or between 5 and 1000 ppm, or between 25 and 1000 ppm, or between 25 and 750 ppm, or between 50 and 750 ppm, or between 100 and 750 ppm of a compound including Co, Al, 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 0.5 to 1.5 weight percent Co, 50 to 300 ppm Cu, 50 to 200 ppm Al, 5 to 100 ppm Fe, and 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. If present, lithium may preferably be present in the mixed metal composition in an amount of 100 to 1000 ppm, based on the total weight of the mixed metal composition.

[0015] In one embodiment, the mixed metal composition includes manganese. The manganese may be present in the mixed metal composition in an amount of at least 5 weight percent, or at least 10 weight percent, or at least 15 weight percent, or at least 18 weight percent, based on the total weight of the mixed metal composition. In one embodiment, the manganese may be present in the mixed metal composition in an amount of 5 to 98 weight percent, or 5 to 85 weight percent, or 5 to 75 weight percent, or 5 to 50 weight percent, or 15 to 25 weight percent, based on the total weight of the mixed metal composition. The mixed metal composition may further include greater than 0 to 2 weight percent of a compound including Co, Al, 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 Co, Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof, based on the total weight of the mixed metal composition. In one embodiment, the mixed metal composition may include greater than 0 to 1000 ppm, or greater than 0 to 750 ppm, or between 5 and 750 ppm, or between 5 and 1000 ppm, or between 25 and 1000 ppm, or between 25 and 750 ppm, or between 50 and 750 ppm, or between 100 and 750 ppm of a compound including Co, Al, 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 0.5 to 1.5 weight percent Co, 50 to 300 ppm Cu, 50 to 200 ppm Al, 5 to 100 ppm Fe, and 5 to 100 ppm F, each based on the total weight of the mixed metal composition. In one embodiment, the mixed metal composition may further include lithium. In one embodiment, lithium may be preferably present in the mixed metal composition in an amount of 100 to 1000 ppm, based on the total weight of the mixed metal composition.

[0016] In one embodiment, the mixed metal composition may include nickel and from greater than 0 to 2 weight percent Co, Al, Cu, Fe, Mg, F, Si, or combinations thereof, based on the total weight of the mixed metal composition. In one embodiment, the mixed metal composition may include nickel and manganese and from greater than 0 to 2 weight percent Co, Al, Cu, Fe, Mg, F, Si, or combinations thereof, based on the total weight of the mixed metal composition. In one embodiment, the mixed metal composition may include manganese and from greater than 0 to 2 weight percent Co, Al, Cu, Fe, Mg, F, Si, or combinations thereof, based on the total weight of the mixed metal composition.

[0017] The mixed metal composition can be obtained, for example, from used lithium ion batteries, lithium ion battery manufacturing waste, etc., or combinations thereof. For example, 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 compounds containing Co, Mn, Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or combinations thereof originate from recycled feedstocks, such as used batteries or battery manufacturing waste. Used 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 solid battery components (e.g., case, electrodes, tabs, headers, fuses, etc.) from volatile components (e.g., electrolyte solvent). Electrolyte salts (e.g., LiPF 6) can be removed by immersion in a suitable solvent (e.g., propylene carbonate) and the remaining undissolved materials (e.g., electrode material, current collector) can be isolated, for example, by filtration. The electrode particles can be separated from the residual current collector material, for example, by contacting the electrode particles with a suitable solvent to dissolve them or by dissolving the binders to release them, 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., 2-5 molar (M) sulfuric acid), 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 between 10 and 18° C., or 15° C., to crystallize the mixed metal composition.

[0018] The precipitated or recrystallized mixed metal composition can be isolated using any suitable solid-liquid separation technique, such as, for example, filtration, centrifugation, or a combination thereof. In one embodiment, the mixed metal composition can be dehydrated to a moisture content of 10% or less, e.g., 1-10%, or 5-10%, based on the total weight of the mixed metal composition product.

[0019] The mixed metal composition may be contacted with water to form a first solution. The first solution has a pH effective to dissolve the mixed metal composition, which may be selected by one of ordinary skill in the art without undue experimentation. In one embodiment, the first solution may 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 may be preferred to ensure dissolution of the mixed metal hydroxide.

[0020] The method further includes adding a salt of nickel, manganese, or a combination thereof to the first solution to obtain a second solution. In one embodiment, the salt may be a virgin material (i.e., a material that has not been recovered or recycled from used lithium ion batteries or has not been previously used). In one embodiment, the salt of nickel, manganese, or a combination thereof is a sulfate or hydroxide thereof (e.g., nickel sulfate, manganese sulfate, nickel hydroxide, manganese hydroxide, or a combination thereof). In one embodiment, the salt is NiSO 4 and MnSO 4 Including NiSO 4 and MnSO 4 The use of hydrates of the formula (I) is also mentioned.

[0021] The salts may be added in amounts effective to achieve the desired stoichiometric ratio of nickel and manganese. For example, a salt of nickel, manganese, or a combination thereof may be added to the first solution in an amount effective to provide a molar ratio of Ni:Mn of greater than 0 to 0.5:0 to 2, for example, 0.5:1.5.

[0022] 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 an amount appropriate to provide 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.

[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, manganese, or a combination 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 comprise 0.0001-2 weight percent of Co, Mn, Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or combinations thereof, based on the total weight of the stoichiometrically adjusted mixed metal composition, or 0.0001-2 weight percent of Co, Al, 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 additional components of the mixed metal composition (e.g., Co, Mn, Al, 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 in one embodiment, these components are not added to either the first or second solution. Rather, in one embodiment, these components originate from the mixed metal feedstock used in the methods of the present disclosure, for example from recycled batteries or battery scrap, and are present at the start of the method.

[0025] The method further includes adding a co-solvent to the second solution to obtain a third solution. The co-solvent is miscible with water and does not cause precipitation of the mixed metal composition. Examples of co-solvents include, for example, C 1-8 Alcohol, C. 1-8 Alkylenediol, C 1-8 In one embodiment, the co-solvent may include ethanol, isopropanol, ethylene glycol, diethylene glycol, or a combination thereof.

[0026] The co-solvent can be added to the second solution such that the third solution contains the co-solvent in an amount of 1 to 50 weight percent, preferably 5 to 15 weight percent, based on the total weight of the third solution.

[0027] The third solution may have the same or different pH as the first solution. In one embodiment, the pH of the third solution may be less than 7, or less than 6.5. Mention is made of the use of a third solution having a pH of 4 to 6.5, or 4.5 to 6.

[0028] In addition to the stoichiometrically adjusted mixed metal composition, water, and co-solvent, the third solution may further comprise 0.0001-2 weight percent of Co, Mn, Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof, based on the total weight of the stoichiometrically adjusted mixed metal composition, or 0.0001-2 weight percent of Co, Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination 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., Co, Mn, Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof) have not been removed and therefore remain present in the third solution. It should be noted that these components are not added to any of the first, second, or third solutions. Rather, they originate from the mixed metal feedstock used in the process of the present disclosure, for example from recycled batteries or battery scrap, and are present at the start of the process.

[0029] The method further comprises combining the third solution with a basic solution to form a precipitate. In one embodiment, the basic solution can be added to the third solution. In one embodiment, the third solution is preferably added to the basic solution to form a precipitate.

[0030] 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, an alkali metal carbonate, an alkali metal bicarbonate, or a combination thereof. The combination of the basic solution with the third solution may be performed, for example, at a temperature of 25-90° C. and with stirring at a speed of 500-1500 RPM.

[0031] In one embodiment, the basic solution may include an alkali metal carbonate, an alkali metal bicarbonate, or a combination thereof. In one embodiment, when used in combination, the alkali metal carbonate and alkali metal bicarbonate may be present in a molar ratio of 1.04:1 to 1:1.04, preferably 1.01:1 to 1:1.01. In certain embodiments, the molar ratio of alkali metal carbonate:alkali metal bicarbonate may be 1:1. When the basic solution includes an alkali metal carbonate, an alkali metal bicarbonate, or a combination thereof, the basic solution may be combined with the third solution in an amount effective to provide a pH greater than 7, preferably 7 to 10, or 7 to 9, or 7 to 8.

[0032] In one embodiment, the basic solution can include an alkali metal hydroxide and optionally ammonia. In one embodiment, the basic solution can include an alkali metal hydroxide and ammonia, and the molar ratio of alkali metal hydroxide:ammonia can be, for example, 2:1 to 1:2, 3:2 to 2:3, 1.04:1 to 1:1.04, and preferably 1.01:1 to 1:1.01. In certain embodiments, the molar ratio of alkali metal hydroxide:ammonia can be 1:1. When the basic solution includes an alkali metal hydroxide and ammonia, the basic solution can be combined with the third solution in an amount effective to provide a pH of 10 or greater, preferably 10-13, and more preferably 11-12. In one embodiment, particularly when the basic solution includes an alkali metal hydroxide and optionally ammonia, no precipitation occurs or is separated from the third solution at a pH of less than 10.

[0033] Combining the basic solution with the third solution can co-precipitate a purified mixed metal composition having a desired ratio, for example, of Ni and Mn, referred to herein for brevity as the "precipitate." For example, the precipitate can be Ni(OH) 2 and Mn(OH) 2 In one embodiment, the precipitate may comprise NiCO, preferably in a molar ratio of >0 to 0.5: >0 to 2, preferably 0.5:1.5. 3 and MnCO 3 in a molar ratio of preferably greater than 0 to 0.5: greater than 0 to 2, preferably 0.5:1.5. The precipitate may further contain 5 to 100 ppm Li, for example 10 to 25 ppm Li, based on the total weight of the precipitate.

[0034] Optionally, a chelating agent can be added to the third solution. If a chelating agent is added, it can be added to the third 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 third solution.

[0035] The method can further include isolating the precipitate. Isolation can be achieved using any suitable liquid-solid separation technique, including, for example, filtration, centrifugation, or the like, or a combination thereof. The precipitate can be washed (e.g., with deionized water, distilled water, or a combination thereof) and dried (e.g., at a temperature of 80-100° C., e.g., 85-95° C., under nitrogen).

[0036] The method further includes adding a lithium compound to the precipitate to form a lithiated precursor mixture (also referred to herein for brevity as a "mixture"), and heat treating the precursor mixture under conditions effective to provide a cathode active material comprising at least one phase having a spinel structure. 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.

[0037] The mixture heat treatment can include calcining in the presence of air at a temperature of 550-950° C. for 4-48 hours. In one embodiment, the mixture heat treatment can include calcining in the presence of air at a first temperature of 800-1000° C. for a first period of time, followed by calcining at a second temperature of 600-800° C. for a second period of time.

[0038] Thus, the cathode active material can include Li and metals including Ni and Mn. The Li and metals (i.e., Ni and Mn) can be present in a Li:metal ratio of 1:1.67 to 1:2.1, preferably 1:2. For example, the cathode active material can be a compound represented by the formula: Li 1+x M 2+y O 4-z A z where M is Ni and Mn, A is an oxygen vacancy, F, Cl or a combination thereof, and 0≦x≦0.2, 0≦y≦0.1, and 0≦z≦0.1, and where the compound according to the formula: Li 1+x M 2+y O 4-z A z The compound has a spinel structure. In one embodiment, the resulting cathode active material is 1+x Ni 0.5 Mn 1.5 O 4 [wherein 0≦x≦0.2], preferably LiNi 0.5 Mn 1.5 O 4Other cathode active materials may be obtained by the methods described herein using alternative battery chemistries, alternative composition stoichiometries, or both.

[0039] The cathode active materials prepared by the methods described herein contain at least one phase having a spinel structure. As used herein, "spinel structure," as understood by those skilled in the art of solid state science, refers to a compound that is isostructural to spinel, i.e., MgAl 2 O 4 The spinel structure is the same as that of MO. 6 Cubic crystal structures containing octahedra (where M is Ni and Mn) and Fd-3m or P4 3 The spinel structure of the cathode active material can be characterized using, for example, X-ray diffraction (XRD).

[0040] Cathode active materials prepared by the methods described herein represent another aspect of the present disclosure.

[0041] In one embodiment, the cathode active material is Li 1+x M 2+y O 4-z A z and a second phase, wherein M is Ni and Mn; A is oxygen vacancy, F, Cl, or a combination thereof; 0≦x≦0.2; 0≦y≦0.1; 0≦z≦0.1; and the second phase is derived from a recycled feedstock. For example, the second phase can include a compound including one or more of Co, Al, 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 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. In one embodiment, Co, Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof can be derived from a recycled feedstock.

[0042] In one aspect, the cathode active material can include a first phase having a spinel structure of the formula: Li 1+x M 2+y O 4-z A z where M is Ni and Mn; A is an oxygen vacancy, F, Cl, or a combination thereof; 0 ≦ x ≦ 0.2; 0 ≦ y ≦ 0.1; 0 ≦ z ≦ 0.1; and where the first phase further includes Co, Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof.

[0043] The cathode active material can optionally further include a layered phase. The layered phase is a compound having a layered structure, for example, an isostructural LiCoO 2 compound. For example, the layered phase can include a layered Li u MO 2 phase, where 0 < u < 1.5, and where M is Ni, Co, Mn, Al, or a combination thereof. In one aspect, the layered phase includes layered LiNi x Co y Mn 1-x-y O 2 where 0 ≦ x ≦ 1, 0 ≦ y ≦ 1, and x + y = 1. The layered phase can be derived from recycled feedstock or can be virgin layered phase (i.e., not prepared using recycled feedstock). In one aspect, the layered phase is derived from recycled feedstock. The layered phase can include one or more of: Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof. In one aspect, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof can be derived from recycled feedstock.

[0044] When present, the first phase and the layered phase may be present in the cathode active material in a weight ratio of from 1:99 to 99:1, or from 10:90 to 90:10, or from 20:80 to 80:20, or from 30:70 to 70:30, or from 40:60 to 60:40, or from 45:55 to 55:45.

[0045] In one embodiment, the cathode active material can be used in combination with a virgin cathode active material (i.e., not prepared using recycled feedstock). For example, the cathode active material can be a cationically unsaturated ... 1+x M 2+y O 4-z A z and a second phase derived from a recycled feedstock; and a second cathode active material comprising a cathode active material derived from a virgin feedstock. In one embodiment, the cathode active material may comprise a first cathode active material comprising a first phase and further comprising Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof; and a second cathode active material comprising a cathode active material derived from a virgin feedstock. 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.

[0046] The cathode active materials disclosed herein can exhibit one or more advantageous properties. For example, the cathode active materials can be used in combination with a lithium anode and 1M LiPF 6in 1:1 ethylene carbonate:dimethyl carbonate by volume at 20° C. for 100 cycles in a half cell at a discharge rate of C / 20. In one embodiment, the cathode active material can have a discharge capacity of 110 mAh / g at a rate of 5C or 90 mAh / g at a rate of 10C for 100 cycles. The C rate represents the current that discharges the cell in 1 hour, and thus 10C represents the current that discharges the cell in 6 minutes.

[0047] The cathode active materials described herein can be particularly useful in battery cathodes. Thus, a battery cathode can include a cathode active material produced by the methods described herein, optionally in combination with virgin cathode active material (i.e., not prepared using recycled feedstocks).

[0048] The present disclosure is further illustrated by the following non-limiting examples. EXAMPLES

[0049] Comparative Example 1 Metal sulfate (MSO) salts with a concentration of 2 moles / liter (M) and a stoichiometric ratio of Ni:Mn of 1:3 were used. 4 ) An aqueous solution is prepared using battery grade starting materials. Ethanol is added to the metal sulfate solution at a concentration of 10 weight percent based on the total weight of the solution.

[0050] NH as precipitant 4 HCO 3 or (NH 4 ) 2 CO 3 A 3-liter (L) continuous stirred tank reactor (CSTR) was charged with 0.15 M NH 4 HCO 3 or (NH 4 ) 2 CO 3 solution, followed by metal sulfate solution (MSO4 ) is co-added to form a precipitate. The precipitate slurry is stirred at a temperature of 25 to 80 °C for 3 to 24 hours.

[0051] The precipitate is filtered and washed with water. To ensure the removal of sulfate ions or metal impurity ions remaining on the surface of the precipitate, the conductivity of the filtrate is monitored until it is well below 400 μS / cm. Next, the filtered wet cake is dried at 90 °C under N 2 flow to obtain the precursor cathode active material (pCAM).

[0052] The cathode active material (CAM) is produced from the pCAM of Comparative Example 1 by mixing the pulverized pCAM with a lithium source (e.g., LiOH, Li 2 CO 3 , Li 2 C 2 O 4 ) at a molar ratio of Li:M of 0.5 < Li:M < 0.6. The mixture is calcined in air at a temperature of 850 °C for 24 hours, and then calcined at 600 °C for 10 hours. After cooling, the CAM is pulverized and sieved using a 350-mesh sieve. Analysis using ICP-OES shows that Ni:Mn is 1:3. Analysis using X-ray diffraction (XRD) shows that a spinel crystal structure is obtained.

[0053] Example 1 A metal sulfate (MSO 4 ) aqueous solution having a stoichiometric ratio of Ni:Mn of 1:3 and a concentration of 2 mol / liter (M) is prepared using 30 wt% recycled mixed metal sulfate and 70 wt% battery-grade starting materials (i.e., NiSO 4 and MnSO 4 ). The recycled mixed metal sulfate (MMS) contains 20 wt% Ni and 0.86 wt% Co along with trace impurities (Al, Cu, etc.). Ethanol is added to the metal sulfate solution at a concentration of 10 weight percent based on the total weight of the solution.

[0054] As a precipitating agent, NH 4 HCO3 or (NH 4 )CO 3 is used. A 3-liter (L) continuous stirred tank reactor (CSTR) is charged with a 0.15 molar (M) solution of NH 4 HCO 3 or (NH 4 )CO 3 , followed by co-addition of a metal sulfate solution (MSO 4 ) to form a precipitate. The precipitate slurry is stirred at a temperature of 25 to 80 °C for 3 to 24 hours.

[0055] The precipitate is filtered and washed with water. The conductivity of the filtrate is monitored to ensure that sulfate ions or metal impurity ions remaining on the precipitate surface are removed until it is well below 400 μS / cm. Next, the filtered wet cake is dried under a stream of N 2 at 90 °C to obtain a precursor cathode active material (pCAM).

[0056] The cathode active material (CAM) is produced from the pCAM of Example 1 by mixing the ground pCAM with a lithium source (e.g., LiOH, Li 2 CO 3 , Li 2 C 2 O 4 ) at a Li:M molar ratio of 0.5 < Li:M < 0.6. The mixture is calcined in air at a temperature of 850 °C for 24 hours, followed by calcination at 600 °C for 10 hours. After cooling, the CAM is ground and sieved using a 350-mesh sieve. Analysis using ICP-OES shows that Ni:Mn is 1:3. Analysis using X-ray diffraction (XRD) shows that a spinel crystal structure is obtained.

[0057] Example 2 A cathode active material is prepared using the same materials and procedures as in Example 1, except that diethylene glycol is used as a co-solvent instead of ethanol during precipitation.

[0058] The present disclosure further includes the following aspects.

[0059] Aspect 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 and greater than 0 to 2 weight percent, based on a total weight of the mixed metal composition, of a compound comprising Co, Mn, Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof; adding a salt of nickel, manganese, or a combination thereof to the first solution to obtain a second solution; adding a co-solvent to the second solution to obtain a third solution; combining the third 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 under conditions effective to provide a cathode active material, wherein the cathode active material comprises at least one phase having a spinel structure.

[0060] Embodiment 2: 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 and manganese, and greater than 0 to 2 weight percent of a compound comprising Co, Al, 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, manganese, or a combination thereof to the first solution to obtain a second solution; adding a co-solvent to the second solution to obtain a third solution; combining the third 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 under conditions effective to provide a cathode active material, wherein the cathode active material comprises at least one phase having a spinel structure.

[0061] Embodiment 3: 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 manganese and greater than 0 to 2 weight percent, based on a total weight of the mixed metal composition, of a compound comprising Co, Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof; adding a salt of nickel, manganese, or a combination thereof to the first solution to obtain a second solution; adding a co-solvent to the second solution to obtain a third solution; combining the third 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 under conditions effective to provide a cathode active material, wherein the cathode active material comprises at least one phase having a spinel structure.

[0062] Aspect 4: The method of any one of aspects 1 to 3, wherein the co-solvent is C 1-8 Alcohol, C. 1-8 Alkylenediol, C 1-8 Preferably, the co-solvent comprises ethanol, isopropanol, ethylene glycol, diethylene glycol, or a combination thereof.

[0063] Embodiment 5: The method of any of embodiments 1-4, wherein the co-solvent is present in the third solution in an amount from 1 to 50 weight percent, preferably from 5 to 15 weight percent, based on the total weight of the third solution.

[0064] Embodiment 6: The method of any of embodiments 1 or 4-5, wherein the mixed metal composition is obtained by a process comprising: contacting electrode particles comprising nickel and greater than 0 to 2 weight percent of a compound comprising Co, Mn, Al, Cu, Fe, Mg, Na, Ca, Zn, F, 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.

[0065] Embodiment 7: The method of any of embodiments 2 or 4-5, wherein the mixed metal composition is obtained by a process comprising: contacting electrode particles comprising nickel and manganese, and greater than 0 to 2 weight percent of a compound comprising Co, Al, Cu, Fe, Mg, Na, Ca, Zn, F, 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.

[0066] Embodiment 8: The method of any of embodiments 3-5, wherein the mixed metal composition is obtained by a process comprising: contacting electrode particles comprising manganese and greater than 0 to 2 weight percent of a compound comprising Co, Al, Cu, Fe, Mg, Na, Ca, Zn, F, Li, or a combination thereof, based on the 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.

[0067] Embodiment 9: The method of any of embodiments 1-8, 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.

[0068] Embodiment 10: The method of any one of embodiments 1-9, wherein the mixed metal composition comprises a mixed metal sulfate.

[0069] Embodiment 11: The method of any of embodiments 1-10, wherein the mixed metal composition further comprises lithium, preferably in an amount between 100 and 1000 ppm based on the total weight of the mixed metal composition.

[0070] Example 12: The method of any of Examples 1-11, 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.

[0071] Example 13: The method of any of Examples 1-12, wherein the mixed metal composition comprises 0.5 to 1.5 weight percent Co, 50 to 300 ppm Cu, 50 to 200 ppm Al, 5 to 100 ppm Fe, and 5 to 100 ppm F, each based on a total weight of the mixed metal composition.

[0072] Embodiment 14: The method according to any of embodiments 1-13, wherein the first solution has a pH of less than 7, or less than 6.5.

[0073] Embodiment 15: The method of any one of embodiments 1-14, wherein the salt of nickel, manganese, or a combination thereof is a sulfate or hydroxide thereof.

[0074] Embodiment 16: The method of any of embodiments 1-15, comprising adding a salt of nickel or manganese to the first solution in an amount effective to provide a molar ratio of Ni:Mn of greater than 0 to 0.5:greater than 0 to 2, preferably 0.5:1.5.

[0075] Aspect 17. The method of aspect 16, wherein the salt is NiSO 4 and MnSO 4 A method comprising:

[0076] Embodiment 18: The method according to any of embodiments 1-17, wherein the second solution has a pH of less than 7, or less than 6.5.

[0077] Embodiment 19: The method of any of embodiments 1 or 4-18, wherein the second solution contains 0.0001 to 2 weight percent Co, Mn, Al, Cu, Fe, Mg, Na, Ca, Zn, F, Li, or a combination thereof, based on the total weight of the solution.

[0078] Embodiment 20: The method of any of embodiments 2 or 4-18, wherein the second solution contains 0.0001 to 2 weight percent Co, Al, Cu, Fe, Mg, Na, Ca, Zn, F, Li, or a combination thereof, based on a total weight of the solution.

[0079] Embodiment 21: The method of any of embodiments 3-18, wherein the second solution contains 0.0001 to 2 weight percent Co, Al, Cu, Fe, Mg, Na, Ca, Zn, F, Li, or a combination thereof, based on the total weight of the solution.

[0080] Embodiment 22 The method of any of embodiments 1-21, wherein the basic solution comprises a base comprising an alkali metal hydroxide, ammonia, an alkali metal carbonate, an alkali metal bicarbonate, or a combination thereof.

[0081] Embodiment 23 The method of embodiment 22, wherein the basic solution comprises a base comprising an alkali metal carbonate, an alkali metal bicarbonate, or a combination thereof, wherein preferably, the alkali metal carbonate and alkali metal bicarbonate 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.

[0082] Embodiment 24: The method according to embodiment 23, wherein the basic solution is combined with the third solution in an amount effective to give a pH greater than 7, preferably between 7 and 10, or between 7 and 9, or between 7 and 8.

[0083] Embodiment 25 The method of embodiment 22, wherein the basic solution comprises an alkali metal hydroxide, preferably sodium hydroxide, and ammonia, more preferably 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.

[0084] Embodiment 26 The method according to embodiment 25, wherein the basic solution is combined with the third solution in an amount effective to provide a pH of 10 or greater, preferably 10-13, more preferably 11-12.

[0085] Embodiment 27: The method of any of embodiments 1 to 26, further comprising adding a chelating agent to the third solution, preferably wherein the chelating agent is present in the third solution in an amount of 0.1 to 10 M.

[0086] Embodiment 28 The method according to embodiment 23 or 24, wherein the precipitate is NiCO 3 and M. n CO 3 in a molar ratio of preferably >0-0.5:>0-2, preferably 0.5:1.5.

[0087] Example 29: The method of example 25 or 26, wherein the precipitate is Ni(OH). 2 and Mn(OH) 2 in a molar ratio of preferably >0-0.5:>0-2, preferably 0.5:1.5.

[0088] Embodiment 30 The method according to any of embodiments 1 to 29, wherein the precipitate comprises from 5 to 100 ppm Li, preferably from 10 to 25 ppm Li, based on the total weight of the precipitate.

[0089] Example 31: The method according to any of Examples 1-30, wherein the lithium compound comprises lithium hydroxide, lithium carbonate, lithium oxide, lithium oxalate, or a combination thereof.

[0090] Embodiment 32 The method of any of embodiments 1-31, wherein the cathode active material includes Li in a Li:metal ratio from 1:1.9 to 1:2.1, or from 1:2 to 1:2.1.

[0091] Embodiment 33: The method of any of embodiments 1-32, wherein the heat treatment comprises calcining in the presence of air at a temperature of 550-950° C. for 4-48 hours.

[0092] Embodiment 34: The method of any of embodiments 1-33, wherein the heat treatment comprises calcining in the presence of air at a first temperature of 800-1000° C. for a first period of time, followed by calcination at a second temperature of 600° C. to less than 800° C. for a second period of time.

[0093] Embodiment 35: The method according to any of embodiments 1 to 34, further comprising stirring the third solution at a temperature of 25 to 90° C. and at a speed of 500 to 1500 RPM.

[0094] Embodiment 36: The method according to any one of embodiments 1 to 35, further comprising isolating the precipitate.

[0095] Example 37: A cathode active material produced by the method of any of Examples 1-36.

[0096] Aspect 38: Li 1+x M 2+y O 4-z A z and a second phase; wherein M is Ni and Mn; A is an oxygen vacancy, F, Cl, or a combination thereof; 0≦x≦0.2; 0≦y≦0.1; 0≦z≦0.1; and the second phase is derived from a recycled feedstock.

[0097] Example 39: The cathode active material of example 38, wherein the second phase comprises one or more of Co, Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, or Li.

[0098] Embodiment 40: The cathode active material of embodiment 38 or 39, wherein the second phase is derived from recycled feedstock and is present in an amount from 1 to 99 weight percent, based on the total weight of the cathode active material.

[0099] Aspect 41: A cathode active material comprising: Li 1+x M 2+y O 4-z A z having the formula and having a first phase with a spinel structure, where M is Ni and Mn, and A is an oxygen vacancy, F, Cl, or a combination thereof, 0 ≦ x ≦ 0.2, 0 ≦ y ≦ 0.1, 0 ≦ z ≦ 0.1, and where the first phase further comprises Co, Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof, the cathode active material.

[0100] Aspect 42: The cathode active material of Aspect 41, wherein Co, Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof is derived from recycled feedstock, the cathode active material.

[0101] Aspect 43: The cathode active material according to any one of Aspects 38 to 42, wherein the first phase comprises LiNi 0.5 Mn 1.5 O 4 the cathode active material.

[0102] Aspect 44: The cathode active material according to any one of Aspects 38 to 43, preferably further comprising a layered phase having a structure isomorphic to LiCoO 2 the cathode active material.

[0103] Aspect 45: The cathode active material of Aspect 44, wherein the layered phase comprises a layered phase having the formula Li u MO 2 where 0 < u < 1.5 and M is Ni, Co, Mn, Al, or a combination thereof, the cathode active material.

[0104] Aspect 46: The cathode active material of Aspect 44 or 45, wherein the layered phase comprises layered LiNi x Co y Mn 1-x-y O 2 where 0 ≦ x ≦ 1, 0 ≦ y ≦ 1, and x + y = 1, the cathode active material.

[0105] Example 47: The cathode active material of any of Examples 44-46, wherein the layered phase is derived from recycled feedstock.

[0106] Example 48: The cathode active material of example 47, wherein the layered phase comprises one or more of Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof.

[0107] Example 49: The cathode active material of example 47 or 48, wherein the layered phase further comprises Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof.

[0108] Embodiment 50: The cathode active material of embodiment 49, wherein the Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or combinations thereof are derived from recycled feedstocks.

[0109] Embodiment 51: The cathode active material of any of embodiments 44-50, wherein the first phase and the layered phase are present 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.

[0110] Example 52: The cathode active material of example 38, comprising: a first cathode active material comprising a first phase; a second phase derived from a recycled feedstock; and a second cathode active material comprising a cathode active material derived from a virgin feedstock.

[0111] Example 53: The cathode active material of example 41, comprising: a first cathode active material comprising a first phase, further comprising Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof; and a second cathode active material comprising a cathode active material derived from a virgin feedstock.

[0112] Example 54: The cathode active material of example 52 or 53, wherein the first cathode active material and the second cathode active material are combined in a weight ratio of 1:99 to 99:1.

[0113] 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.

[0114] 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.

[0115] 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.

[0116] 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.

[0117] 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.

[0118] U.S. Provisional Patent Application No. 63 / 338,485, filed May 5, 2022, is hereby incorporated by reference in its entirety for all purposes.

[0119] 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 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, and A compound comprising greater than 0 to 2 weight percent Co, Mn, Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof, based on the total weight of the mixed metal composition. Contains; adding a salt of nickel, manganese, or a combination thereof to said first solution to obtain a second solution; adding a co-solvent to said second solution to obtain a third solution; combining said third solution with a basic solution to form a precipitate; adding a lithium compound to the precipitate to form a mixture; and heat treating said mixture under conditions effective to provide a cathode active material. Including, wherein the cathode active material comprises at least one phase having a spinel structure.

2. 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 and manganese, and Greater than 0 to 2 weight percent of a compound containing Co, Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof, based on the total weight of the mixed metal composition. Contains; adding a salt of nickel, manganese, or a combination thereof to said first solution to obtain a second solution; adding a co-solvent to said second solution to obtain a third solution; combining said third 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 under conditions effective to provide a cathode active material; Including, wherein the cathode active material comprises at least one phase having a spinel structure.

3. 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: Manganese, and Greater than 0 to 2 weight percent of a compound containing Co, Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof, based on the total weight of the mixed metal composition. Contains; adding a salt of nickel, manganese, or a combination thereof to said first solution to obtain a second solution; adding a co-solvent to said second solution to obtain a third solution; combining said third solution with a basic solution to form a precipitate; adding a lithium compound to the precipitate to form a mixture; and heat treating said mixture under conditions effective to provide a cathode active material. Including, wherein the cathode active material comprises at least one phase having a spinel structure.

4. The co-solvent is C １－８ Alcohol, C １－８ Alkylenediol, C １－８ alkylene triols, or combinations thereof; 10. The method of claim 1, wherein optionally the co-solvent is present in the third solution in an amount of 1 to 50 weight percent based on the total weight of the third solution.

5. The mixed metal composition may include the following: Nickel, and A compound containing greater than 0 to 2 weight percent Co, Mn, Al, Cu, Fe, Mg, Na, Ca, Zn, F, Li, or a combination thereof, based on the total weight of the mixed metal composition. 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 process comprising:

6. The mixed metal composition may include the following: Nickel and manganese, and A compound comprising greater than 0 to 2 weight percent Co, Al, Cu, Fe, Mg, Na, Ca, Zn, F, Li, or a combination thereof, based on the total weight of the mixed metal composition. 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 according to claim 2, obtained by a process comprising:

7. The mixed metal composition may include the following: Manganese, and A compound containing greater than 0 to 2 weight percent Co, Al, Cu, Fe, Mg, Na, Ca, Zn, F, Li, or a combination thereof, based on the total weight of the mixed metal composition. 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 according to claim 3, obtained by a process comprising:

8. 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.

9. The method of claim 1 , wherein the mixed metal composition further comprises lithium.

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

11. 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.

12. 2. The method of claim 1, wherein the salt of nickel, manganese, or a combination thereof is a sulfate or hydroxide thereof.

13. 2. The method of claim 1 comprising adding a nickel or manganese salt to the first solution in an amount effective to provide a molar ratio of Ni:Mn of greater than 0-0.5:greater than 0-2.

14. 10. The method of claim 1, wherein the basic solution is combined with the third solution in an amount effective to provide a pH of greater than 7.

15. 10. The method of claim 1, wherein the basic solution is combined with the third solution in an amount effective to provide a pH of 10 or greater.

16. The precipitate is NiCO ３ and M. ｎ CO ３ The method of claim 1 , comprising:

17. The precipitate is Ni(OH). ２ and Mn(OH) ２ The method of claim 1 , comprising:

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

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

20. The method of claim 1 , wherein the cathode active material comprises Li in a Li:metal ratio of 1:1.9 to 1:2.

1.

21. A cathode active material produced by the method of any one of claims 1 to 20.

22. Li １＋ｘ M ２＋ｙ O ４－ｚ A ｚ and a first phase having a spinel structure; and Second phase:

1. A cathode active material comprising: M is Ni and Mn; A is an oxygen vacancy, F, Cl, or a combination thereof; 0≦x≦0.2; 0≦y≦0.1; 0≦z≦0.1 and the second phase is derived from recycled feedstock.

23. 23. The cathode active material of claim 22, wherein the second phase comprises one or more of Co, Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, or Li.

24. Li １＋ｘ M ２＋ｙ O ４－ｚ A ｚ a first phase having a formula of 1. A cathode active material comprising: M is Ni and Mn; A is an oxygen vacancy, F, Cl, or a combination thereof; 0≦x≦0.2, 0≦y≦0.1, 0≦z≦0.1, 13. The cathode active material of claim 12, wherein the first phase further comprises Co, Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof.

25. 25. The cathode active material of claim 24, wherein the Co, Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or combinations thereof are derived from recycled feedstocks.

26. The cathode active material of any of claims 22 through 25, further comprising a layered phase.

27. The layered phase is Li ｕ M.O. ２ 27. The cathode active material of claim 26, comprising a layered phase having a formula: where 0<u<1.5 and M is Ni, Co, Mn, Al, or a combination thereof.

28. The layered phase is layered LiNi ｘ Co ｙ Mn １－ｘ－ｙ O ２ 27. The cathode active material of claim 26, comprising:

29. 27. The cathode active material of claim 26, wherein the layered phase is derived from recycled feedstock.

30. 30. The cathode active material of claim 29, wherein the layered phase comprises one or more of Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or combinations thereof.

31. 30. The cathode active material of claim 29, wherein the layered phase further comprises Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or combinations thereof.

32. 32. The cathode active material of claim 31 , wherein the Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or combinations thereof are derived from recycled feedstocks.

33. a first cathode active material comprising a first phase and a second phase derived from a recycled feedstock; and A second cathode active material comprising a cathode active material derived from a virgin feedstock.

23. The cathode active material of claim 22 comprising:

34. a first cathode active material comprising a first phase and further comprising Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof; and A second cathode active material comprising a cathode active material derived from a virgin feedstock.

25. The cathode active material of claim 24 comprising:

35. 35. The cathode active material of claim 33 or 34, wherein the first cathode active material and the second cathode active material are combined in a weight ratio of 1:99 to 99:1.

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