Method for producing cathode active material having olivine structure

Abstract

A method for producing a cathode active material includes providing a first mixture containing a mixed metal composition and phosphoric acid or a mixed metal composition and water. The mixed metal composition includes nickel, cobalt, manganese, or a combination thereof. A salt of iron, manganese, cobalt, or a combination thereof is added to adjust the stoichiometry of the mixed metal composition. The stoichiometrically adjusted mixed metal composition in water is contacted with a phosphorus-containing compound. The stoichiometrically adjusted mixed metal phosphate is further contacted with a lithium-containing compound to obtain a cathode active material having at least one phase with an olivine structure.

Description

[Background technology]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 63 / 399,879, filed in the U.S. Patent and Trademark Office on August 22, 2022, and claims all benefit 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, improved methods for recovering and recycling used batteries remain needed. It would be particularly advantageous to provide a method for preparing cathode active materials with specific structures for new batteries from other than virgin 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 an acidic solution comprising phosphoric acid to form a first solution, the mixed metal composition comprising nickel, cobalt, manganese, 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 Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof; adding a salt of iron, manganese, cobalt, or a combination thereof to the first solution to obtain a second solution; and combining the second solution with an alkaline lithium-containing solution to form a cathode active material, wherein the cathode active material comprises at least one phase having an olivine structure.

[0004] In one embodiment, a method of making a cathode active material includes contacting a mixed metal composition with an acidic solution comprising phosphoric acid 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 Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof; adding a salt of iron, manganese, or a combination thereof to the first solution to obtain a second solution; and combining the second solution with an alkaline lithium-containing solution to form a cathode active material, wherein the cathode active material comprises at least one phase having an olivine 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 mixture, the mixed metal composition comprising nickel, cobalt, manganese, 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 Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof; adding a salt of iron, manganese, or a combination thereof to the first mixture to obtain a second mixture; combining the second mixture with a phosphate-containing compound to obtain a third mixture; combining the third mixture with a lithium-containing compound and a carbon-containing compound to obtain a cathode active material precursor; and heat-treating the cathode active material precursor under conditions effective to obtain a cathode active material, wherein the cathode active material comprises at least one phase having an olivine structure.

[0006] In one aspect, a method of manufacturing a cathode active material includes contacting a mixed metal composition with water to form a first mixture, the mixed metal composition including manganese and a compound including Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof in an amount greater than 0 and up to 2 weight percent based on the total weight of the mixed metal composition; adding a salt of iron, manganese, or a combination thereof to the first mixture to obtain a second mixture; combining the second mixture with a phosphorus-containing compound to obtain a third mixture; combining the third mixture with a lithium-containing compound and a carbon-containing compound to obtain a cathode active material precursor; and heat-treating the cathode active material precursor under conditions effective to obtain a cathode active material, wherein the cathode active material includes at least one phase having an olivine structure.

[0007] In one aspect, the cathode active material is Li 1-x M y Fe 1-y has the formula PO4 and includes a first phase having an olivine structure; and a second phase, wherein M is Ni, Co, Mn, or a combination thereof; 0 < x ≦ 0.5; 0 < y ≦ 1; 0.95 < (M + Fe):P < 1.1; 1.0 < Li:(M + Fe) < 1.05; 0.95 < Li:P < 1.05; and the second phase is derived from recycled feedstock.

[0008] In one aspect, the cathode active material has the formula Li 1-x M y Fe 1-y and includes a first phase having an olivine structure, wherein M is Ni, Co, Mn, or a combination thereof; 0 < x ≦ 0.5; 0 < y ≦ 1; 0.95 < (M + Fe):P < 1.1; 1.0 < Li:(M + Fe) < 1.05; 0.95 < Li:P < 1.05; and wherein the first phase further includes Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof.

[0009] The features described above and other features are illustrated by the following detailed description. DETAILED DESCRIPTION OF THE INVENTION

[0010] Detailed Description 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 an olivine 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.

[0011] 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 acetate, a mixed metal hydroxide, or a combination thereof. In a particular aspect, the mixed metal composition comprises a mixed metal sulfate.

[0012] In one embodiment, the mixed metal composition includes nickel, cobalt, manganese, or a combination thereof. For example, the mixed metal composition may preferably include nickel, cobalt, and manganese. In one embodiment, the mixed metal composition may include manganese. The mixed metal composition may further include greater than 0 to 2 weight percent of a compound including 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 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 5 to 750 ppm, or 5 to 1000 ppm, or 25 to 1000 ppm, or 25 to 750 ppm, or 50 to 750 ppm, or 100 to 750 ppm of a compound including 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 one or more of 0.5 to 1.5 weight percent Co, 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. In one embodiment, the mixed metal composition may include lithium. When 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.

[0013] In one embodiment, the mixed metal composition includes nickel, cobalt, and manganese (e.g., where nickel, cobalt, and manganese are present as major components in the mixed metal composition). For example, the nickel, cobalt, 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, the nickel, cobalt, 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 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 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 5 to 750 ppm, or 5 to 1000 ppm, or 25 to 1000 ppm, or 25 to 750 ppm, or 50 to 750 ppm, or 100 to 750 ppm of a compound including 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 can include 0.5 to 1.5 weight percent Co, 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. In one embodiment, the mixed metal composition can include lithium.When 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 manganese (e.g., where manganese is present as a major component in the mixed metal composition). For example, 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, 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 comprising 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 0.1 weight percent, or greater than 0 to 0.01 weight percent (100 ppm) of a compound including 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 5 to 750 ppm, or 5 to 1000 ppm, or 25 to 1000 ppm, or 25 to 750 ppm, or 50 to 750 ppm, or 100 to 750 ppm of a compound including 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, or 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 may include nickel and greater than 0 to 2 weight percent Co, Al, Cu, Fe, Mg, F, Si, or a combination thereof, based on the total weight of the mixed metal composition. In one embodiment, the mixed metal composition may include nickel and manganese and greater than 0 to 2 weight percent Co, Al, Cu, Fe, Mg, F, Si, or a combination thereof, based on the total weight of the mixed metal composition. In one embodiment, the mixed metal composition may include manganese and greater than 0 to 2 weight percent Co, Al, Cu, Fe, Mg, F, Si, or a combination thereof, based on the total weight of the mixed metal composition.

[0016] The mixed metal composition can be obtained, for example, from spent lithium-ion batteries, lithium-ion battery manufacturing waste, etc., or a combination thereof. For example, the mixed metal composition can be obtained from recycled feedstock, preferably post-industrial recycled feedstock, post-customer recycled feedstock, or a combination thereof. In one embodiment, the Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof, of compounds containing Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof, originates from recycled feedstock, such as spent batteries or battery manufacturing waste. Spent lithium-ion batteries (or any previous 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). 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 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 them with a solvent suitable for dissolving the electrode particles or by dissolving the binder 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 subjected 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 to a temperature of, for example, less than 20°C, or 10-18°C, or 15°C, to crystallize the mixed metal composition.

[0017] 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 10% or less, e.g., 1-10%, or 5-10%, based on the total weight of the mixed metal composition product.

[0018] The mixed metal composition may be soluble in an aqueous solution having a pH of 5 or less, such as greater than 0 to 5 or less, or 1 to 5, or 2 to 5, or 3 to 5, or 1 to 4, or 1 to 3, or 2 to 3.

[0019] In one embodiment, the mixed metal composition may be contacted with an acidic solution to form a first solution. The acidic solution includes phosphoric acid. In one embodiment, the acidic solution may include phosphoric acid and one or more of oxalic acid, acetic acid, and nitric acid. The first solution may have a pH of 5 or less, e.g., greater than 0 to 5 or less, or 1 to 5, or 2 to 5, or 3 to 5, or 1 to 4, or 1 to 3, or 2 to 3.

[0020] The method further includes adding a salt of nickel, iron, manganese, cobalt, or a combination thereof to the first solution to obtain a second solution. In one embodiment, the salt can be a virgin material (i.e., a material that has not been recovered or recycled from used lithium-ion batteries or previously used). In one embodiment, the salt of iron, manganese, cobalt, or a combination thereof is a sulfate or hydroxide thereof (e.g., iron sulfate, manganese sulfate, cobalt sulfate, iron hydroxide, manganese hydroxide, cobalt hydroxide, or a combination thereof). In one embodiment, the salt includes FeSO4, MnSO4, CoSO4, or a combination thereof. The use of hydrates of FeSO4, MnSO4, and CoSO4 is also mentioned.

[0021] The salts can be added in amounts effective to achieve the desired stoichiometric ratio of nickel, cobalt, manganese, and iron. For example, salts of nickel, iron, manganese, cobalt, or combinations thereof can be added to the first solution in amounts effective to provide a molar ratio of Ni:Co:Mn:Fe of greater than 0 to 0.5: greater than 0 to 0.5: greater than 0 to 1: greater than 0 to 1, preferably 0.05:0.05:0.4:0.5.

[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, based on the total weight of the second solution.

[0023] The second solution can have a pH that is the same as or different from the pH of the first solution. In one embodiment, the pH of the second solution can be less than 7, or less than 6.5, such as greater than 0 to less than 7, or from 1 to less than 7, or from 1 to less than 6.5, or from 1 to 6, or from 2 to 6, or from 2 to 5. As noted above, salts are added to achieve the desired stoichiometry of nickel, cobalt, manganese, iron, 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 comprise 0.0001 to 2 weight percent of Al, Cu, Fe, Mg, Na, Ca, Zn, F, Li, or a combination thereof, based on the total weight of the stoichiometrically adjusted mixed metal composition, or 0.0001 to 2 weight percent of Al, Cu, Fe, Mg, Na, Ca, Zn, F, Li, or a combination 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., Al, Cu, Fe, Mg, Na, Ca, Zn, F, Li, or a combination thereof) are not 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 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 an alkaline lithium-containing solution to form a cathode active material. The alkaline lithium-containing solution can include, for example, lithium hydroxide, lithium carbonate, lithium bicarbonate, or a combination thereof. In one embodiment, the alkaline lithium-containing solution can include lithium hydroxide. The alkaline lithium-containing solution can be combined with the second solution in an amount such that the resulting solution has a pH greater than 7, preferably between 7 and 10, or between 7 and 9, or between 7 and 8.

[0026] The second solution can be combined with an alkaline lithium-containing solution to provide the cathode active material as a precipitate. Combining the alkaline lithium-containing solution with the second solution can optionally involve stirring, for example, at a speed of 500-1500 RPM and a temperature of 25-90°C.

[0027] The method can further include isolating the precipitated cathode active material. Isolation can be performed using a suitable liquid-solid separation technique, such as filtration, centrifugation, 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).

[0028] In one embodiment, the isolated cathode active material can be further combined with a conductive carbon material. For example, the cathode active material can optionally be combined with conductive carbon black. In one embodiment, the carbon black is 100 μm or more. 2 / g and an oil adsorption number (OAN) of greater than 100 milliliters per 100 grams. An example of a commercially available carbon black suitable for use in the present disclosure is LITX-HP available from Cabot Corporation.

[0029] Alternatively, in one embodiment, the mixed metal composition may be contacted with water to form a first mixture. The first mixture may be in the form of a slurry. In one embodiment, the first mixture may have a solids content of 10 weight percent or greater. The mixed metal composition may be as described above. For example, in one embodiment, the mixed metal composition may include nickel, cobalt, manganese, 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 including Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof. In one embodiment, the mixed metal composition may include manganese and greater than 0 to 2 weight percent, based on the total weight of the mixed metal composition, of a compound including Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof.

[0030] The method further includes adding a salt of iron, manganese, or a combination thereof to the first mixture to obtain a second mixture. In one embodiment, the salt can be virgin material (i.e., material that has not been recovered or recycled from used lithium-ion batteries or other used materials). In one embodiment, the salt of iron, manganese, or a combination thereof is a sulfate or hydroxide thereof (e.g., iron sulfate, manganese sulfate, iron hydroxide, manganese hydroxide, or a combination thereof). In one embodiment, the salt includes FeSO4, MnSO4, or a combination thereof. The use of hydrates of FeSO4 and MnSO4 is also mentioned.

[0031] The salts may be added in amounts effective to achieve the desired stoichiometric ratio of nickel, manganese, and iron.

[0032] The mixed metal composition of the first mixture (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 mixture. 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, based on the total weight of the second mixture.

[0033] In addition to the stoichiometrically adjusted mixed metal composition, the second mixture may further include 0.0001 to 2 weight percent of Al, Cu, Fe, Mg, Na, Ca, Zn, F, Li, or a combination thereof, based on the total weight of the stoichiometrically adjusted mixed metal composition, or 0.0001 to 2 weight percent of Al, Cu, Fe, Mg, Na, Ca, Zn, F, Li, or a combination 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., Al, Cu, Fe, Mg, Na, Ca, Zn, F, Li, or a combination thereof) are not removed and therefore remain present in the second mixture. In one embodiment, these components are not added to either the first or second mixture. Rather, in one embodiment, these components 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.

[0034] The method further comprises combining the second mixture with a phosphoric acid-containing compound to provide a third mixture. The phosphoric acid-containing compound can comprise a phosphate, such as phosphoric acid, dibasic phosphoric acid, monobasic phosphoric acid, or a combination thereof. In one embodiment, the phosphoric acid-containing compound comprises phosphoric acid.

[0035] In addition to the stoichiometrically adjusted mixed metal composition and the phosphate-containing compound, the third mixture may further include 0.0001 to 2 weight percent of Al, Cu, Fe, Mg, Na, Ca, Zn, F, Li, or a combination thereof, based on the total weight of the stoichiometrically adjusted mixed metal composition, or 0.0001 to 2 weight percent of Al, Cu, Fe, Mg, Na, Ca, Zn, F, Li, or a combination 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., Al, Cu, Fe, Mg, Na, Ca, Zn, F, Li, or a combination thereof) are not removed and therefore remain present in the third mixture. In one embodiment, these components are not added to any of the first, second, or third mixtures. Rather, in one embodiment, these components 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.

[0036] The method further includes combining the third mixture with a lithium-containing compound and a carbon-containing compound to provide a cathode active material precursor, and heat-treating the cathode active material precursor under conditions effective to provide a cathode active material including at least one phase having an olivine structure. Exemplary lithium compounds can include lithium hydroxide, lithium carbonate, lithium oxide, lithium oxalate, or combinations thereof. In one embodiment, the lithium compound can include lithium hydroxide.

[0037] The carbon-containing compound can be a conductive carbon compound, such as carbon black. In one embodiment, the carbon black is 2It may have a BET surface area of less than / g and an oil absorption number (OAN) of more than 100 milliliters per 100 grams. An example of a commercially available carbon black suitable for use in the present disclosure is LITX-HP available from Cabot Corporation. In one aspect, the carbon-containing compound may include carbohydrates such as glucose, sucrose, etc., or a combination thereof. The carbon-containing compound is preferably conductive or can be made conductive after heat treatment.

[0038] The heat treatment of the mixture may include firing at a temperature of 550 to 950 °C for 4 to 48 hours in the presence of an inert atmosphere (e.g., nitrogen, argon).

[0039] In one aspect, the method may further include reducing the particle size of the third mixture before the heat treatment. The reduction of the particle size may be achieved using any known mechanical grinding method such as wet grinding. The slurry may be wet ground to provide a final D50 particle size of, for example, 100 to 500 nanometers.

[0040] Thus, the cathode active material may include a metal containing Li, Fe, and Ni, Co, Mn, or a combination thereof. The total amount of Li, Ni, Co, Mn, and Fe can be present in a Li:(Ni, Co, Mn, and Fe) ratio of 1:1 to 1.05:1. The cathode active material may include phosphorus in a (Ni, Co, Mn, and Fe):phosphorus ratio of 0.95:1 to 1.1:1. Lithium and phosphorus can be present in a Li:P ratio of 0.95 to 1.05.

[0041] For example, the cathode active material is of the formula Li 1-x M y Fe 1-y It may contain a compound of PO4, where M is Ni, Co, Mn, or a combination thereof, 0 < x ≤ 0.​​​1-y The compound of PO4 has an olivine structure. The olivine structure can be confirmed, for example, using X-ray diffraction (XRD).

[0042] The cathode active material produced by the method disclosed herein contains at least one phase having an olivine structure. As understood by those skilled in solid state science, the "olivine structure" as used herein means that the compound has the same structure as olivine, i.e., MgFeSiO4. The olivine structure can refer to a phase having an orthorhombic crystal structure and a space group of Pbnm. The olivine structure of the cathode active material can be characterized, for example, using X-ray diffraction (XRD).

[0043] The cathode active material produced by the method of this specification represents another aspect of this disclosure.

[0044] For example, in one aspect, the cathode active material is Li 1-x M y Fe 1-y has the formula of PO4, has a first phase with an olivine structure, and may include a second phase, where M is Ni, Co, Mn, or a combination thereof; 0 < x ≦ 0.5; 0 < y ≦ 1; 0.95 < (M + Fe):P < 1.1; 1.0 < Li:(M + Fe) < 1.05; 0.95 < Li:P < 1.05; and the second phase is derived from the recycled feedstock. For example, the second phase may include a compound containing one or more of Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, or Li, or a combination thereof. In one aspect, the second phase derived from the 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 aspect, Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, or Li, or a combination thereof may be derived from the recycled feedstock.

[0045] In one aspect, the cathode active material is Li 1-x M y Fe 1-yIt may include a first phase having the formula of PO4 and an olivine structure, where M is Ni, Co, Mn, or a combination thereof; 0 < x ≤ 0.5; 0 < y ≤ 1; 0.95 < (M + Fe):P < 1.1; 1.0 < Li:(M + Fe) < 1.05; 0.95 < Li:P < 1.05; where the first phase further includes Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof.

[0046] In one aspect, the cathode active material can be used in combination with an unused cathode active material (i.e., one not manufactured using recycled feedstock). For example, the cathode active material is Li 1-x M y Fe 1-y It may include a first cathode active material including a first phase having the formula of PO4 and an olivine structure; and a second phase derived from recycled feedstock; and a second cathode active material including a cathode active material derived from unused feedstock. In one aspect, the cathode active material may include a first cathode active material including a first phase and further including Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof; and a second cathode active material including a cathode active material derived from unused feedstock. The cathode active material of the present disclosure and the unused cathode active material can be combined at 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.

[0047] The cathode active materials disclosed herein may exhibit one or more advantageous properties. For example, the cathode active materials may have a discharge capacity of greater than 100 mAh / g (e.g., 150 mAh / g) at a C / 20 discharge rate in a half cell over 100 cycles at 20°C when used with a lithium anode and an electrolyte comprising 1 M LiPF6 in a 1:1 volume ratio of ethylene carbonate:dimethyl carbonate. In one embodiment, the cathode active material may have a discharge capacity of 120 mAh / g at a 5C rate or 100 mAh / g at a 10C rate over 100 cycles. The C rate represents the current that discharges the cell in 1 hour, and therefore 10C represents the current that discharges the cell in 6 minutes.

[0048] The cathode active materials described herein can be particularly useful in battery cathodes. Accordingly, 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 produced using recycled feedstock).

[0049] The present disclosure is further illustrated by the following non-limiting examples. [Example]

[0050] Comparative Example 1 Commercial battery-grade metal sulfates (NiSO4, CoSO4, MnSO4, FeSO4) are dissolved in 0.5 molar (M) phosphoric acid (H3PO4) with a stoichiometric ratio of Ni:Co:Mn:Fe of 0.1:0.1:0.3:0.5 and a total:phosphorus ratio of (Ni + Co + Mn + Fe) of 1:1. Lithium hydroxide solution is added dropwise over 30 minutes, maintaining the solution temperature at 100°C or the boiling point of the solution. The lithium:phosphorus ratio is 3:1. The solid precipitate is separated from the solution and dried under nitrogen. X-ray diffraction (XRD) analysis indicates that an olivine crystal structure is obtained.

[0051] Example 1 Mixed metal sulfates produced from recycled streams are dissolved in phosphoric acid. Battery-grade metal sulfates are added to adjust the stoichiometry of Ni:Co:Mn:Fe to 0.1:0.1:0.4:0.5. The total (Ni + Co + Mn + Fe) to phosphorus ratio is 1:1. Lithium hydroxide solution is added dropwise over 30 minutes, maintaining the solution temperature at 100°C or the boiling point of the solution. The lithium to phosphorus ratio is 3:1. The solid precipitate is separated from the solution and dried under nitrogen. X-ray diffraction (XRD) analysis indicates that an olivine crystal structure is obtained.

[0052] Example 2 The materials prepared in Comparative Example 1 and Example 1 are mixed with conductive carbon black (e.g., LITX-HP available from Cabot Corporation) in a 95:5 weight ratio using a ball mill to obtain a carbon-modified cathode active material.

[0053] Comparative Example 2 Commercial battery-grade Ni(OH)2, Co(OH)2, MnCO3, and FeCO4 are added to water at 10 wt% solids in a 0.05:0.05:0.4:0.5 Ni:Co:Mn:Fe stoichiometry. Phosphoric acid is added to the slurry. The total (Ni + Co + Mn + Fe):phosphorus ratio is 1:1. Lithium hydroxide solution is added dropwise over 30 minutes in an amount to give a 1:1 Li:P ratio. Glucose (2.5 wt. percent) and sucrose (2.5 wt. percent) are added to the slurry and mixed for an additional 30 minutes. The resulting slurry is milled to obtain a final D50 particle size of less than 150 nanometers.

[0054] Example 3 Olivine-type cathode active material is produced using mixed metal hydroxide (Ni, Co, Mn hydroxide) produced from a recycled stream as the raw material. The mixed metal hydroxide composition is stoichiometrically adjusted using MnCO3 and FeCO4 to give a Ni:Co:Mn:Fe ratio of 0.05:0.05:0.4:0.5, and the slurry is adjusted with water to a 10% solids loading. Phosphoric acid is added to the slurry. The total metal (Ni + Co + Mn + Fe):phosphorus ratio is 1:1. Lithium hydroxide solution is added dropwise over 30 minutes in an amount to give a Li:P ratio of 1:1. Glucose (2.5 weight percent) and sucrose (2.5 weight percent) are added to the slurry and mixed for an additional 30 minutes. The resulting slurry is milled to obtain a final D50 particle size of less than 150 nanometers.

[0055] Example 4 The milled slurries of Comparative Example 2 and Example 3 are further dried using conventional drying methods, including pan drying, spray drying, etc. The dried solids are then heat-treated at 650°C under nitrogen to obtain the desired cathode active material. X-ray diffraction (XRD) analysis indicates that an olivine crystal structure is obtained.

[0056] The present disclosure further includes the following aspects.

[0057] Embodiment 1: A method of making a cathode active material, the method comprising: contacting a mixed metal composition with an acidic solution comprising phosphoric acid to form a first solution, the mixed metal composition comprising nickel, cobalt, manganese, 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 Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof; adding a salt of iron, manganese, cobalt, or a combination thereof to the first solution to obtain a second solution; and combining the second solution with an alkaline lithium-containing solution to form a cathode active material, wherein the cathode active material comprises at least one phase having an olivine structure.

[0058] Embodiment 2: A method of making a cathode active material, the method comprising: contacting a mixed metal composition with an acidic solution comprising phosphoric acid 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 Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof; adding a salt of iron, manganese, or a combination thereof to the first solution to obtain a second solution; and combining the second solution with an alkaline lithium-containing solution to form a cathode active material; wherein the cathode active material comprises at least one phase having an olivine structure.

[0059] Embodiment 3: The method of embodiment 1 or 2, further comprising combining the cathode active material with a conductive carbon, preferably conductive carbon black.

[0060] Embodiment 4: The method of any of embodiments 1 or 2-3, wherein the mixed metal composition is obtained by a process comprising contacting electrode particles comprising nickel, cobalt, manganese, or combinations thereof; and greater than 0 to 2 weight percent, based on the total weight of the mixed metal composition, of a compound comprising Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or combinations thereof, 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.

[0061] Embodiment 5: The method of any of Embodiments 2-3, wherein the mixed metal composition is obtained by a process comprising: contacting electrode particles comprising manganese and greater than 0 to 2 weight percent, based on the total weight of the mixed metal composition, of a compound comprising Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof, 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.

[0062] Embodiment 6: The method of any one of embodiments 1-5, wherein the mixed metal composition is soluble in an aqueous solution having a pH of 5 or less.

[0063] Embodiment 7: The method of any of embodiments 1-6, wherein the mixed metal composition comprises a mixed metal sulfate, a mixed metal nitrate, a mixed metal acetate, a mixed metal hydroxide, or a combination thereof.

[0064] Embodiment 8: The method of any one of embodiments 1-7, wherein the mixed metal composition comprises a mixed metal sulfate.

[0065] Embodiment 9: The method of any one of embodiments 1 to 8, wherein the acidic solution comprises phosphoric acid and one or more of oxalic acid, acetic acid, or nitric acid.

[0066] Embodiment 10: The method of any one of embodiments 1-9, 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.

[0067] Embodiment 11: The method of any of embodiments 1-10, 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.

[0068] Embodiment 12: The method of any of embodiments 1-11, 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, or 5 to 100 ppm F, each based on the total weight of the mixed metal composition.

[0069] Embodiment 13: The method of any of embodiments 1-12, wherein the first solution has a pH of less than 5.

[0070] Embodiment 14: The method of any one of embodiments 1-13, wherein the salt of iron, manganese, cobalt, or a combination thereof is a sulfate or hydroxide thereof.

[0071] Embodiment 15: The embodiment of any one of embodiments 1-14, wherein a salt of iron, manganese, cobalt, or a combination thereof is added to the first solution in an amount effective to provide a molar ratio of Ni:Co:Mn:Fe of greater than 0 to 0.5: greater than 0 to 0.5: greater than 0 to 1: greater than 0 to 1, preferably 0.05:0.05:0.4:0.5.

[0072] Embodiment 16: Any of embodiments 1-15, wherein the second solution comprises 0.0001 to 2 weight percent Al, Cu, Fe, Mg, Na, Ca, Zn, F, Li, or a combination thereof, based on the total weight of the solution.

[0073] Embodiment 17: Any of embodiments 1-21, wherein the alkaline lithium-containing solution comprises lithium hydroxide, lithium carbonate, lithium bicarbonate, or a combination thereof, preferably lithium hydroxide.

[0074] Embodiment 18: The method of embodiment 17, wherein the alkaline lithium-containing solution is combined with the second solution in an amount effective to provide a pH of greater than 7, preferably between 7 and 10, or between 7 and 9, or between 7 and 8.

[0075] Embodiment 19: The embodiment of any of embodiments 1-18, further comprising isolating the cathode active material.

[0076] Embodiment 20: A method for producing a cathode active material, the method comprising: contacting a mixed metal composition with water to form a first mixture, the mixed metal composition comprising nickel, cobalt, manganese, 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 Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof; adding a salt of iron, manganese, or a combination thereof to the first mixture to obtain a second mixture; combining the second mixture with a phosphate-containing compound to obtain a third mixture; combining the third mixture with a lithium-containing compound and a carbon-containing compound to obtain a cathode active material precursor; and heat-treating the cathode active material precursor under conditions effective to obtain a cathode active material, wherein the cathode active material comprises at least one phase having an olivine structure.

[0077] Embodiment 21: A method of producing a cathode active material, the method comprising: contacting a mixed metal composition with water to form a first mixture, 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 Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof; adding a salt of iron, manganese, or a combination thereof to the first mixture to obtain a second mixture; combining the second mixture with a phosphate-containing compound to obtain a third mixture; combining the third mixture with a lithium-containing compound and a carbon-containing compound to obtain a cathode active material precursor; and heat-treating the cathode active material precursor under conditions effective to obtain a cathode active material, wherein the cathode active material comprises at least one phase having an olivine structure.

[0078] Embodiment 22 The method of embodiment 20 or 21, wherein the phosphate-containing compound comprises a phosphate comprising phosphoric acid, dibasic phosphate, monobasic phosphate, or a combination thereof, preferably a phosphate comprising phosphoric acid.

[0079] Aspect 23: An aspect which is Aspects 20 to 22, wherein the first mixture is a slurry having a solids content of 10 weight percent or more based on the total weight of the slurry.

[0080] Aspect 24: A cathode active material produced by the method according to any one of Aspects 1 to 23.

[0081] Aspect 25: A cathode active material comprising a first phase having the formula Li 1-x M y Fe 1-y PO4 and having an olivine structure; and a second phase, wherein M is Ni, Co, Mn, or a combination thereof; 0 < x ≦ 0.5; 0 < y ≦ 1; 0.95 < (M + Fe):P < 1.1; 1.0 < Li:(M + Fe) < 1.05; 0.95 < Li:P < 1.05; and the second phase is derived from a recycled feedstock.

[0082] Aspect 26: The cathode active material according to Aspect 25, wherein the second phase contains one or more of Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, or Li.

[0083] Aspect 27: The cathode active material according to any one of Aspects 25 to 26, wherein the second phase derived from the recycled feedstock is present in an amount of 1 to 99 weight percent based on the total weight of the cathode active material.

[0084] Aspect 28: A cathode active material comprising a first phase having the formula Li 1-x M y Fe 1-y PO4 and having an olivine structure, wherein M is Ni, Co, Mn, or a combination thereof; 0 < x ≦ 0.5; 0 < y ≦ 1; 0.95 < (M + Fe):P < 1.1; 1.0 < Li:(M + Fe) < 1.05; 0.95 < Li:P < 1.05; and the first phase further contains Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof.

[0085] Embodiment 29: The cathode active material of embodiment 28, wherein Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof is derived from recycled feedstock.

[0086] Embodiment 30: The cathode active material of embodiment 25, comprising: a first cathode active material comprising a first phase; and a second phase derived from recycled feedstock; and a second cathode active material comprising a cathode active material derived from virgin feedstock.

[0087] Embodiment 31: The cathode active material of embodiment 28, comprising: a first cathode active material comprising a first phase, the first cathode active material further comprising Al, 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 virgin feedstock.

[0088] Embodiment 32: The cathode active material of embodiment 30 or 31, wherein the first cathode active material and the second cathode active material are combined in a weight ratio of 1:99 to 99:1.

[0089] The compositions and methods may alternatively comprise, consist of, or consist essentially of any suitable material, step, or ingredient 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.

[0090] 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 order, quantity, or importance; rather, they are used to distinguish one element from another. The terms "a," "an," and "the" do not denote limitations of quantity and are to be interpreted as covering 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 listed elements and is open, allowing for the presence of one or more similar elements not specified. Furthermore, it should be understood that the described elements can be combined in any suitable manner in the various embodiments.

[0091] 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.

[0092] 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.

[0093] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill 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 explicitly defined herein.

[0094] U.S. Provisional Patent Application No. 63 / 399,879, filed August 22, 2022, is incorporated herein by reference in its entirety for all purposes.

[0095] While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents may occur to 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 an acidic solution comprising phosphoric acid to form a first solution, the mixed metal composition comprising: nickel, cobalt, manganese, or combinations thereof; and a compound comprising greater than 0 to 2 weight percent Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof, based on the total weight of the mixed metal composition; Including, adding a salt of iron, manganese, cobalt, or a combination thereof to said first solution to obtain a second solution; combining the second solution with an alkaline lithium-containing solution to form a cathode active material; wherein the cathode active material comprises at least one phase having an olivine structure.

2. 1. A method of making a cathode active material, the method comprising: contacting a mixed metal composition with an acidic solution comprising phosphoric acid 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 Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof; Including, adding a salt of iron, manganese, or a combination thereof to said first solution to obtain a second solution; combining the second solution with an alkaline lithium-containing solution to form a cathode active material; wherein the cathode active material comprises at least one phase having an olivine structure.

3. The method of claim 1 further comprising combining the cathode active material with conductive carbon, preferably conductive carbon black.

4. The mixed metal composition may be: nickel, cobalt, manganese, or combinations thereof; and greater than 0 to 2 weight percent, based on the total weight of the mixed metal composition, of a compound comprising Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof; Electrode particles comprising contacting with a leach solution, preferably containing sulfuric acid; precipitating a mixed metal composition from the leachate; and Isolating the mixed metal composition from the leachate The method of claim 1, obtained by a method comprising:

5. The mixed metal composition may be: manganese, and greater than 0 to 2 weight percent, based on the total weight of the mixed metal composition, of a compound comprising Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof; Electrode particles comprising contacting with a leach solution, preferably containing sulfuric acid; precipitating a mixed metal composition from the leachate; and Isolating the mixed metal composition from the leachate 3. The method of claim 2, obtained by a method comprising:

6. 10. The method of claim 1, wherein the mixed metal composition is soluble in an aqueous solution having a pH of 5 or less.

7. The method of claim 1 , wherein the mixed metal composition comprises a mixed metal sulfate, a mixed metal nitrate, a mixed metal acetate, a mixed metal hydroxide, or a combination thereof.

8. The method of claim 1 , wherein the mixed metal composition comprises a mixed metal sulfate.

9. The method of claim 1 , wherein the acidic solution comprises phosphoric acid and one or more of oxalic acid, acetic acid, or nitric acid.

10. The method of claim 1, 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.

11. 10. The method of claim 1, wherein the mixed metal composition is obtained from recycled feedstock, preferably from post-industrial recycled feedstock, post-consumer recycled feedstock, or a combination thereof.

12. 10. The method of claim 1, 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, or 5 to 100 ppm F, each based on the total weight of the mixed metal composition.

13. The method of claim 1 , wherein the first solution has a pH of less than 5.

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

15. 10. The method of claim 1, wherein a salt of iron, manganese, cobalt, or a combination thereof is added to the first solution in an amount effective to provide a molar ratio of Ni:Co:Mn:Fe of greater than 0 to 0.5: greater than 0 to 0.5: greater than 0 to 1: greater than 0 to 1, preferably 0.05:0.05:0.4:0.

5.

16. 10. The method of claim 1, wherein the second solution comprises 0.0001 to 2 weight percent of Al, Cu, Fe, Mg, Na, Ca, Zn, F, Li, or a combination thereof, based on the total weight of the solution.

17. 10. The method of claim 1, wherein the alkaline lithium-containing solution comprises lithium hydroxide, lithium carbonate, lithium bicarbonate, or a combination thereof, preferably lithium hydroxide.

18. 18. The method of claim 17, wherein the alkaline lithium-containing solution is combined with the second solution in an amount effective to provide a pH greater than 7, preferably between 7 and 10, or between 7 and 9, or between 7 and 8.

19. The method of claim 1 further comprising isolating the cathode active material.

20. 1. A method of making a cathode active material, the method comprising: contacting a mixed metal composition with water to form a first mixture, the mixed metal composition comprising: nickel, cobalt, manganese, or combinations thereof; and greater than 0 to 2 weight percent, based on the total weight of the mixed metal composition, of a compound comprising Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof; adding a salt of iron, manganese, or a combination thereof to said first mixture to obtain a second mixture; combining the second mixture with a phosphoric acid-containing compound to obtain a third mixture; combining the third mixture with a lithium-containing compound and a carbon-containing compound to obtain a cathode active material precursor; and heat treating the cathode active material precursor under conditions effective to obtain a cathode active material. wherein the cathode active material comprises at least one phase having an olivine structure.

21. 1. A method of making a cathode active material, the method comprising: contacting a mixed metal composition with water to form a first mixture, 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 Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof; adding a salt of iron, manganese, or a combination thereof to said first mixture to obtain a second mixture; combining the second mixture with a phosphoric acid-containing compound to obtain a third mixture; combining the third mixture with a lithium-containing compound and a carbon-containing compound to obtain a cathode active material precursor; and heat treating the cathode active material precursor under conditions effective to obtain a cathode active material. wherein the cathode active material comprises at least one phase having an olivine structure.

22. 21. The method of claim 20, wherein the phosphate-containing compound comprises a phosphate comprising phosphoric acid, dibasic phosphoric acid, monobasic phosphoric acid, or a combination thereof, preferably phosphoric acid.

23. 21. The method of claim 20, wherein the first mixture is a slurry having a solids content of 10 weight percent or greater, based on the total weight of the slurry.

24. A cathode active material produced by the method of claim 1.

25. Li １－ｘ M ｙ Fe １－ｙ P.O. ４ a first phase having an olivine structure and having the formula Second phase:

1. A cathode active material comprising: where: M is Ni, Co, Mn, or a combination thereof; 0<x≦0.5; 0<y≦1; 0.95<(M+Fe): P<1.1; 1.0<Li:(M+Fe)<1.05; 0.95<Li:P<1.05; The second phase is derived from recycled feedstock, the cathode active material.

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

27. 26. The cathode active material of claim 25, wherein the second phase derived from recycled feedstock is present in an amount of 1 to 99 weight percent, based on the total weight of the cathode active material.

28. Li １－ｘ M ｙ Fe １－ｙ P.O. ４ 1. A cathode active material comprising a first phase having an olivine structure, having a formula of M is Ni, Co, Mn, or a combination thereof; 0<x≦0.5; 0<y≦1; 0.95<(M+Fe):P<1.1; 1.0<Li:(M+Fe)<1.05; 0.95<Li:P<1.05; wherein the first phase further comprises Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or a combination thereof.

29. 30. The cathode active material of claim 28, wherein the Al, Cu, Fe, Mg, Na, Ca, Zn, F, Si, Li, or combinations thereof are derived from recycled feedstocks.

30. a first cathode active material comprising a first phase; and a second phase derived from recycled feedstock; and a second cathode active material comprising a cathode active material derived from virgin feedstock; 26. The cathode active material of claim 25, comprising:

31. a first cathode active material comprising a first phase and further comprising Al, 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 virgin feedstock; 30. The cathode active material of claim 28 comprising:

32. 31. The cathode active material of claim 30, 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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