Active material particles, processes thereof, and apparatuses useful in the manufacture thereof

Abstract

Active materials (e.g., alkali-metal metal phosphate (e.g., lithium iron phosphate), alkali-metal metal oxide and / or alkali-metal metal cyanide materials), preparation processes, and apparatuses useful in the manufacture thereof are described. Well-ordered active material particles (e.g., lithium iron phosphate particles) prepared by the processes and manufacturing apparatuses disclosed herein are also described.

Description

TSLA.786WO PATENT ACTIVE MATERIAL PARTICLES, PROCESSES THEREOF, AND APPARATUSES USEFUL IN THE MANUFACTURE THEREOF INCORPORATION BY REFERENCE TO ANY PRIORITY APPLICATIONS

[0001] Any and all applications for which a foreign or domestic priority claim is identified, for example, in the Application Data Sheet or Request as filed with the present application are hereby incorporated by reference under 37 CFR 1.57, and Rules 4.18 and 20.6, such as U.S. Provisional Application No.63 / 513,316, filed July 12, 2023, and which is hereby incorporated by reference in its entirety and for all purposes. BACKGROUND Field

[0002] The present disclosure relates generally to energy storage devices, and specifically to processes for preparing cathode active material and systems for forming the same. Description of the Related Art

[0003] Energy storage devices, such as lithium-ion batteries or sodium ion batteries, are desirable for their optimized cost, safety, lifespan, and moderate energy density. Current methods of cathode manufacturing require a large number of steps and expensive apparatuses. For example, some conventional cathode material manufacturing processes (e.g., in the manufacture of lithium iron phosphate active materials) require furnaces that can calcinate or calcine fine particles. Thus, new methods that reduce or eliminate processing steps in the manufacturing of battery raw materials may aid to decrease the end-use cost of batteries. SUMMARY

[0004] For purposes of summarizing the disclosure and the advantages achieved over the prior art, certain objects and advantages of the disclosure are described herein. Not all such objects or advantages may be achieved in any particular embodiment. Thus, for example, those skilled in the art will recognize that the invention may be embodied or carried out in a manner that achieves or optimizes one advantage or group of advantages as taughtherein without necessarily achieving other objects or advantages as may be taught or suggested herein.

[0005] All of these embodiments are intended to be within the scope of the invention herein disclosed. These and other embodiments will become readily apparent to those skilled in the art from the following detailed description of the preferred embodiments having reference to the attached figures, the invention not being limited to any particular preferred embodiment(s) disclosed.

[0006] In aspects, a process of preparing lithium iron phosphate is described. The process comprises: combining an iron-based material, a lithium source and a carbon source to form a first mixture; forming a plurality of initial particles in a chamber from the first mixture; recirculating the plurality of initial particles into the chamber concurrently during the forming of the plurality of initial particles to form a plurality of subsequent particles; calcinating the plurality of subsequent particles to form a plurality of calcinated particles comprising lithium iron phosphate.

[0007] In some embodiments, the first mixture further comprises a phosphorus source. In some embodiments, the phosphorus source is selected from the group consisting of H3PO4, H3PO3, P2O5, monoammonium phosphate, diammonium phosphate, urea phosphate, ammonium iron phosphates, lithium iron phosphate, LiPO3, Li3PO3, Li3PO4, LiH2PO4, Li2HPO4, LiH2PO3, Li2HPO3, and combinations thereof. In some embodiments, the iron-based material is selected from the group consisting of an iron oxide, an anhydrous iron phosphate, an iron phosphate hydrate, an iron metal, and combinations thereof. In some embodiments, the iron-based material is selected from the group consisting of FeOOH, FeO, FePO4, Fe2O3, Fe3O4, and combinations thereof. In some embodiments, the iron-based material comprises a phosphorus source. In certain embodiments, a molar ratio of iron and phosphate in the iron- based material is about 1:1.5 to 1.5:1.

[0008] In some embodiments, the lithium source is selected from the group consisting of LiOH, Li2CO3, LiPO3, Li3PO3, Li3PO4, LiH2PO4, Li2HPO4, LiH2PO3, Li2HPO3, lithium iron oxides, lithium iron phosphate, and combinations thereof. In some embodiments, the carbon source is selected from the group consisting of a sugar, a natural polymer, a synthetic polymer, a carbonaceous material, and combinations thereof. In certain embodiments, the carbon source is selected from the group consisting of a monosaccharide, adisaccharide, an oligosaccharide, a starch, a gum, polyvinyl alcohol (PVA), polyethylene glycol (PEG), a sugar alcohol, pitch, coke, asphaltite, uintahite, asphaltum, gilsonite, sweeteners, mannitol, erythritol, polyethylene-polypropylene-oxide block copolymers, detergents, fatty acids, fatty acid esters, modified starches, modified celluloses, carboxy methyl cellulose, graphite, activated carbon, urea, polyvinylpyrrolidone (PVP), styrene-butadiene rubber (SBR), polyvinylidene fluoride (PVDF), and combinations thereof. In some embodiments, the carbon source comprises less than 2 wt.% ash. In some embodiments, wherein the first mixture further comprises a functional additive.

[0009] In some embodiments, the initial particles have a D50particle size GLVWULEXWLRQ^UDQJH^IURP^DERXW^^^^^^P^WR^DERXW^^^^^P^ In some embodiments, the subsequent particles have a D50 SDUWLFOH^VL]H^GLVWULEXWLRQ^UDQJH^IURP^DERXW^^^^P^WR^DERXW^^^^^^^^P^ In some embodiments, the first mixture further comprises a liquid. In some embodiments, the liquid comprises water. In some embodiments, the first mixture is substantially free of a liquid.

[0010] In another aspect, a lithium iron phosphate material is described. The lithium iron phosphate material comprises lithium iron phosphate particles with a D50size GLVWULEXWLRQ^ UDQJH^ IURP^ DERXW^ ^^^^ ^P^ WR^ DERXW^ ^^^^^^ ^P^ In some embodiments, the percentage of iron in the lithium channels (FeLi%) of the lithium iron phosphate particles is less than 2%.

[0011] In another aspect, a system for forming a lithium iron phosphate material is described. The system for forming a lithium iron phosphate material comprises: a chamber; a granulating apparatus comprising a granulator in fluid communication with the chamber, an apparatus volume comprising an outlet and an inlet, and a recirculation path in fluid communication with the outlet and the inlet; and a furnace in fluid communication with the outlet, wherein the furnace is configured to contain particles with a D50particle size distribution of at least about 5 ^m.

[0012] In some embodiments, the granulator comprises a spray dry granulator. In some embodiments, the furnace comprises a rotary kiln, a rotary furnace, a roller hearth kiln, a roller hearth furnace, a batch furnace, a batch drum furnace, or a crucible pusher kiln.

[0013] In another aspect, a process of preparing an active material is disclosed. In some embodiments, the process comprises: combining an alkali metal source and a second metal source to form a first mixture; forming a plurality of initial particles from the first mixturein a chamber; recirculating at least some of the plurality of initial particles to the chamber concurrently during the forming of the plurality of initial particles to form a plurality of subsequent particles; and calcinating the plurality of subsequent particles to form a plurality of calcinated particles comprising active material.

[0014] In some embodiments, the combining the alkali metal source and the second metal source comprises milling. In some embodiments, the recirculating at least some of the plurality of initial particles comprises combining the recirculated initial particles with additional first mixture. In some embodiments, the alkali metal source comprises a lithium source or a sodium source. In some embodiments, the second metal source comprises Fe, Mn, Mg, Al, Ca, Ti, Co, Ni, Cr, V, or combinations thereof. In some embodiments, the active material comprises alkali-metal metal phosphate, alkali-metal metal oxide, alkali-metal metal cyanide, and combinations thereof.

[0015] In some embodiments, the active material comprises lithium iron phosphate (LFP), lithium nickel manganese cobalt oxide (NMC), lithium nickel manganese oxide (LNMO), lithium nickel cobalt aluminum oxide (NCA), lithium manganese oxide (LMO), lithium cobalt oxide (LCO), a lithium titanate, a lithium nickel cobalt aluminum oxide (NCA), sodium cobalt oxide, sodium iron hexacyanoferrate, sodium manganese oxide, sodium iron phosphate, sodium vanadium phosphate, sodium transition metal oxides, sodium nickel manganese oxide, or combinations thereof.

[0016] In some embodiments, the alkali metal source comprises a lithium source and wherein the lithium source is selected from the group consisting of LiOH, LiOHyH2O, Li2CO3, LiPO3, Li3PO3, Li3PO4, LiH2PO4, Li2HPO4, LiH2PO3, Li2HPO3, lithium iron oxides, lithium iron phosphate, and combinations thereof. In some embodiments, the alkali metal source comprises a sodium source and wherein the sodium source is selected from the group consisting of NaOH, Na2CO3, NaCl, NaHC濢3, NaNO3, Na2SO4, NaPO3, Na3PO4, NaH2PO4, Na2HPO4, sodium poly- and meta- phosphates, and hydrates forms thereof, and combinations thereof. In some embodiments, the second metal source comprises a nickel-based material. In some embodiments, the nickel-based material comprises metallic nickel, nickel oxide, nickel hydroxide, nickel carbonate, or combination thereof. In some embodiments, the second metal source comprises a manganese-based material. In some embodiments, the manganese-based material is selected from the group consisting of metallic manganese, manganese oxide,manganese hydroxide, manganese carbonate, and combination thereof. In some embodiments, the second metal source comprises a cobalt-based material. In some embodiments, the cobalt- based material is selected from the group consisting of metallic cobalt, cobalt oxide, cobalt hydroxide, cobalt carbonate, and combination thereof. In some embodiments, the second metal source comprises a precursor cathode active material (pCAM). In some embodiments, the second metal source comprises hydroxide pCAM, oxide pCAM, or a combination thereof. In some embodiments, the second metal source comprises nickel cobalt manganese hydroxide (hydroxide pCAM NMC), nickel cobalt manganese hydroxide (oxide pCAM NMC), or a combination thereof.

[0017] In some embodiments, the initial particles have a D50 particle size GLVWULEXWLRQ^ UDQJH^ IURP^ DERXW^ ^^^^ ^P^ WR^ DERXW^ ^^^ ^P^ In some embodiments, the initial particles have a D10 particle size distribution range from about 0.0^^^P^WR^DERXW^5 ^P. In some embodiments, the initial particles have a D90 particle size distribution range from about 0.5 ^P^ to about 50 ^P. In some embodiments, the subsequent particles have a D50particle size GLVWULEXWLRQ^UDQJH^IURP^DERXW^^^^P^WR^DERXW^5^^^^^^P^ In some embodiments, the subsequent particles have a D50particle size distribution range from about 100 ^P^WR^DERXW^5^^^^^^P^ In some embodiments, the subsequent particles have a D10particle size distribution range from about 10 ^P^WR^DERXW^1^^^^^^P^ In some embodiments, the subsequent particles have a D90 particle size distribution range from about 200 ^P^WR^DERXW^5 cm.

[0018] In some embodiments, the combining the alkali metal source and the second metal source comprises combining with a liquid and wherein the first mixture is a slurry. In some embodiments, the forming the plurality of initial particles comprises spray drying the first mixture.

[0019] In some embodiments, the first mixture is substantially free of a liquid. In some embodiments, the forming the plurality of initial particles comprises mechanical granulation. In some embodiments, mechanical granulation comprises milling, sieving, mixing, blending, compacting, or combinations thereof. In some embodiments, the forming the plurality of initial particles comprises compacting the first mixture by a roller compactor.

[0020] In some embodiments, the percentage of the second metal in alkali metal position in the active material is less than about 2%. In some embodiments, the first mixture further comprises a carbon source. In some embodiments, the carbon source is selected fromthe group consisting of a sugar, a natural polymer, a synthetic polymer, a carbonaceous material, and combinations thereof. In some embodiments, the carbon source is selected from the group consisting of a monosaccharide, a disaccharide, an oligosaccharide, a starch, a gum, polyvinyl alcohol (PVA), polyethylene glycol (PEG), a sugar alcohol, pitch, coke, asphaltite, uintahite, asphaltum, gilsonite, sweeteners, mannitol, erythritol, polyethylene-polypropylene- oxide block copolymers, detergents, fatty acids, fatty acid esters, modified starches, modified celluloses, carboxy methyl cellulose, graphite, activated carbon, urea, polyvinylpyrrolidone (PVP), styrene-butadiene rubber (SBR), polyvinylidene fluoride (PVDF), and combinations thereof. In some embodiments, the carbon source comprises less than 2 wt.% ash. In some embodiments, the first mixture further comprises a functional additive.

[0021] In some embodiments, the active material comprises lithium iron phosphate. In some embodiments, the first mixture further comprises a phosphorus source. In some embodiments, the phosphorus source is selected from the group consisting of H3PO4, H3PO3, P2O5, monoammonium phosphate, diammonium phosphate, urea phosphate, ammonium iron phosphates, lithium iron phosphate, LiPO3, Li3PO4, LiH2PO4, Li2HPO4, LiH2PO3, Li2HPO3, and combinations thereof. In some embodiments, the second metal source is an iron-based material and wherein the iron-based material is selected from the group consisting of an iron oxide, an anhydrous iron phosphate, an iron phosphate hydrate, an iron metal, and combinations thereof. In some embodiments, the iron-based material is selected from the group consisting of FeOOH, FeO, FePO4, Fe2O3, Fe3O4, Fe, Fe3P, Fe2P, metallic iron, and combinations thereof. In some embodiments, the iron-based material comprises a phosphorus source. In some embodiments, a molar ratio of iron and phosphate in the iron- based material is in a range of about 1:1.5 to 1.5:1.

[0022] In another aspect, a system for forming a lithium iron phosphate material is disclosed. The system comprises a housing defining a chamber; a granulating apparatus comprising a granulator in fluid communication with the chamber, the granulating apparatus defining a volume comprising an outlet and an inlet, and a recirculation path in fluid communication with the outlet and the inlet; and a furnace in fluid communication with the outlet, wherein the furnace is configured to contain particles with a D50 particle size GLVWULEXWLRQ^RI^DW^OHDVW^DERXW^^^^P^

[0023] In some embodiments, the granulator comprises a spray dry granulator, a roller compactor, or a combination thereof. In some embodiments, the granulating apparatus further comprises a particle size classification device in fluid communication with the furnace. In some embodiments, the furnace is a continuous particle conveying furnace. In some embodiments, the furnace comprises a furnace chamber configured to be in direct contact with at least some of the particles. In some embodiments, the direct contact between the furnace chamber and the particles provides heat conduction from the furnace chamber to the particles in addition to heat radiation. In some embodiments, the furnace is a non-crucible furnace. In some embodiments, the furnace comprises a rotary kiln, a rotary furnace, a roller hearth kiln, a roller hearth furnace, a batch furnace, a batch drum furnace, or a crucible pusher kiln. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] FIG.1 is a flowchart of a process for preparing an active material, according to some embodiments.

[0025] FIG. 2 is a flowchart of a wet process for preparing an active material, according to some embodiments.

[0026] FIG. 3 is a flowchart of a dry process for preparing an active material, according to some embodiments.

[0027] FIG. 4 is a flowchart of a process for preparing lithium iron phosphate, according to some embodiments.

[0028] FIG.5 is a flowchart of a wet process for preparing lithium iron phosphate, according to some embodiments.

[0029] FIG.6 is a flowchart of a dry process for preparing lithium iron phosphate, according to some embodiments.

[0030] FIG. 7A is a flow diagram of a spray drying process for preparing lithium iron phosphate, according to some embodiments.

[0031] FIG. 7B is a flow diagram of a dry process for preparing lithium iron phosphate, according to some embodiments.

[0032] FIG. 8 is a schematic diagram of a system for forming an active material via a wet process, according to some embodiments.

[0033] FIG. 9 is a schematic diagram of a system for forming an active material via a dry process, according to some embodiments.

[0034] FIG. 10 is a schematic diagram of a system for forming an active material via a dry process, according to some embodiments.

[0035] FIG. 11 is a schematic diagram of the stages and related temperatures of a quasi-continuous process for forming an active material, according to some embodiments.

[0036] FIG. 12A is an image of lithium iron phosphate precursor initial particles, according to some embodiments.

[0037] FIG. 12B is an image of lithium iron phosphate precursor subsequent particles, according to some embodiment.

[0038] FIG. 12C is an image of lithium iron phosphate precursor subsequent particles, according to some embodiment.

[0039] FIG.13 is a scanning electron microscope (SEM) image of the lithium iron phosphate material prepared by spray granulation, according to some embodiments.

[0040] FIG. 14 provides an XRD pattern of lithium iron phosphate material prepared by spray granulation, according to some embodiments.

[0041] FIG.15 is a line graph of the electrochemical performance of a cathode foil including lithium iron phosphate material prepared by spray granulation, according to some embodiments.

[0042] FIG. 16 is a dot graph of the percentage of iron in the lithium channels (FeLi%) of various lithium iron phosphate particles, according to some embodiments.

[0043] FIG.17A provides an XRD pattern of lithium iron phosphate with relatively high order prepared by a process according to some embodiments.

[0044] FIG.17B provides an XRD pattern of lithium iron phosphate with relatively high order prepared by a process according to some embodiments.

[0045] FIG. 18A provides an XRD pattern of lithium iron phosphate powder with relatively low order.

[0046] FIG. 18B provides an XRD pattern of lithium iron phosphate powder with relatively low order.

[0047] FIG. 19A provides an XRD pattern of lithium iron phosphate material prepared by a dry process, before calcination, compared to an iron(III) oxide hydroxide standard.

[0048] FIG. 19B provides an XRD pattern of lithium iron phosphate material prepared by a dry process, after calcination, compared to a lithium iron phosphate standard.

[0049] FIG. 20A provides an XRD pattern of lithium iron phosphate material prepared by a dry process, before calcination, compared to a magnetite raw material standard.

[0050] FIG. 20B provides an XRD pattern of lithium iron phosphate material prepared by a dry process, after calcination, compared to a lithium iron phosphate standard.

[0051] FIG. 21 is an SEM image of the lithium iron phosphate material prepared by a spray drying process, according to some embodiments.

[0052] FIG. 22 provides an XRD pattern of lithium iron phosphate material prepared by a spray drying process, according to some embodiments.

[0053] FIG. 23 is an image of the lithium iron phosphate material prepared by a spray drying process.

[0054] FIG. 24 provides an XRD pattern of lithium iron phosphate material prepared by a spray drying process.

[0055] FIG.25 is a line graph of the electrochemical performance of a cathode foil including lithium iron phosphate material prepared by a spray drying process.

[0056] FIG. 26 provides an XRD pattern of lithium iron phosphate material prepared by a spray drying process.

[0057] FIG. 27A and 27B are images of spray dried lithium iron phosphate precursor initial particles formed with lactose before calcination, according to some embodiments.

[0058] FIGS. 27C and 27D are the images of spray dried lithium iron phosphate material formed with mannitol before calcination, according to some embodiments.

[0059] FIG.28A is a particle size distribution plot of the slurry before wet milling respectively, according to some embodiments.

[0060] FIG. 28B is a particle size distribution plot of the slurry after wet milling respectively, according to some embodiments.

[0061] FIG. 28C is a particle size distribution plot of the slurry after wet milling according to some embodiments.

[0062] FIG. 28D is an XRD pattern of the spry dried lithium iron phosphate precursor particles according to some embodiments.

[0063] FIG. 28E is an image of the spry dried lithium iron phosphate precursor particles according to some embodiments.

[0064] FIG. 29A is an SEM image of an electrode film prepared with 93.8wt.% spray dried lithium iron phosphate powder according to some embodiments.

[0065] FIG. 29B is an SEM image of an electrode film prepared with 93.8wt.% spray dried lithium iron phosphate powder according to some embodiments.

[0066] FIG. 29C is an SEM image of an electrode film prepared with 93.8wt.% commercial lithium iron phosphate powder according to some embodiments.

[0067] FIG.30 is a line graph of the electrochemical testing results of the electrodes prepared with spray dried and commercial lithium iron phosphate powders according to some embodiments.

[0068] FIGS. 31A-31F are SEM images of the spray dried lithium iron phosphate granules with 1.5wt.% Carboxymethyl Cellulose (CMC) binder before calcination according to some embodiments.

[0069] FIGS.31G-31K are SEM images of the spray dried lithium iron phosphate granules with 15 wt.% mannitol binder before calcination according to some embodiments.

[0070] FIGS. 32A-32F are SEM images of the spray dried lithium manganese oxide granules with 1.6 wt.% Carboxymethyl Cellulose (CMC) binder after calcination according to some embodiments.

[0071] FIGS. 32G-32H are SEM images of the spray dried lithium manganese oxide granules with 15 wt.% mannitol binder after calcination according to some embodiments.

[0072] FIGS. 32J-32K are the SEM images of the spray dried lithium manganese oxide granules with 15 wt.% mannitol binder after calcination according to some embodiments.

[0073] FIG. 33 is an XRD pattern of the lithium manganese oxide material with different amount of binder after calcination according to some embodiments.

[0074] FIG. 34A is a line graph of specific capacity vs cycle for a half cell with a cathode comprising the commercial lithium manganese oxide material (baseline), spray dried lithium manganese oxide granules with 15wt.% mannitol binder, and spray dried lithium manganese oxide granules with 1.6 wt.% CMC binder, according to some embodiments.

[0075] FIG.34B is a line graph of normalized capacity vs cycle for a half cell with a cathode comprising the commercial lithium manganese oxide material (baseline), spray dried lithium manganese oxide granules with 15wt.% mannitol binder, and spray dried lithium manganese oxide granules with 1.6 wt.% CMC binder, according to some embodiments.

[0076] FIG. 35A is an image of the granules formed by roller compactor before calcination according to some embodiments.

[0077] FIG. 35B is an image of the granules formed by roller compactor after calcination according to some embodiments.

[0078] FIG.36A is an SEM image of a mixture jet milled after 1 hour according to some embodiments.

[0079] FIG. 36B is an SEM image of a mixture jet milled after 5 hours according to some embodiments.

[0080] FIG.36C is an SEM image of a mixture jet milled after 10 hours according to some embodiments.

[0081] FIG.37A is a line graph of the first cycle irreversible capacity of a half coin cell with the calcinated granules formed from a roller compactor as the cathode active material according to some embodiments.

[0082] FIG. 37B is a line graph of the percentage of nickel in the lithium layer (NiLi%) of lithium nickel manganese cobalt oxide (NMC) formed from roller compactor, according to some embodiments.

[0083] FIG. 38A is an XRD pattern of the jet milled powder mixture after 1 hour according to some embodiments.

[0084] FIG.38B is an XRD pattern of the jet milled powder mixture after 10 hours according to some embodiments.

[0085] FIG.39 is a line graph of the cycle performance of half coin cells using the calcinated lithium nickel manganese cobalt oxide (NMC) granules as the cathode active material according to some embodiments.

[0086] FIGS.40A and 40B are images of the large lithium nickel manganese cobalt oxide (NMC) granules prepared by a roller compactor before calcination according to some embodiments.

[0087] FIGS.40C and 40D are images of the large lithium nickel manganese cobalt oxide (NMC) granules prepared by a roller compactor after calcination according to some embodiments. DETAILED DESCRIPTION

[0088] The present disclosure may be understood by reference to the following detailed description. It is noted that, for purposes of illustrative clarity, certain elements in various drawings may not be drawn to scale, may be represented schematically or conceptually, or otherwise may not correspond exactly to certain physical configurations of embodiments.

[0089] Provided herein are various embodiments of active materials for an energy storage device, and the active material precursors, preparation processes, and apparatuses useful in the manufacture thereof. In some embodiments, the active materials comprise an alkali metal element. In some embodiments, the alkali metal element of the active material is selected from Li, Na, K, Rb, Cs, and combinations thereof. In some embodiments, the alkali metal element of the active material is Li, Na, or combinations thereof. In some embodiments, the active materials comprise a second metal element. In some embodiments, the second metal element of the active materials is selected from Fe, Mn, Mg, Al, Ca, Ti, Co, Ni, Cr, V, and combinations thereof.

[0090] Some embodiments of the present disclosure relate to a process for preparing an active material. In some embodiments, the process for preparing the active material comprises preparing a plurality of initial particles of the active material precursor, recirculating at least some of the initial particles to form larger subsequent particles of the active material precursor. Due to the larger sizes of the subsequent particles and / or lack of fine particles, the subsequent particles may be calcinated using high throughput furnaces and / or furnaces that are not able to process fine particles. Advantageously, the disclosed processes may have a high material efficiency, lower calcination time and help reduce or eliminate corrosion.

[0091] In some embodiment, the subsequent particles of the active material precursor comprise homogeneous distribution of the active material precursor and have well- ordered particle structures. In some embodiments, the subsequent particles of the active material precursor are calcinated to form the particles of the active material. In some embodiments, the process is a wet process where a solvent is involved in at least one step of the process. In some embodiments, the process is a dry process where no or substantially no solvent is used in the process. Active Material

[0092] In some embodiments, active materials for an energy storage device are disclosed herein. In some embodiments, the active materials comprise an alkali metal element. In some embodiments, the alkali metal element of the active material is selected from Li, Na, K, Rb, Cs, and combinations thereof. In some embodiments, the alkali metal element of the active material is Li, Na, or combinations thereof. In some embodiments, the alkali metal element is selected based on the type of the energy storage device that is manufactured. In some embodiments, the alkali metal element comprises lithium for a lithium-ion energy storage device. In some embodiments, the alkali metal element comprises sodium for a sodium-ion energy storage device. In some embodiments, the active materials further comprise a second metal element. In some embodiments, the second metal element of the active materials is selected from Fe, Mn, Mg, Al, Ca, Ti, Co, Ni, Cr, V, and combinations thereof. In some embodiments, the active material is substantially free of carbon.

[0093] In some embodiments, the active materials comprise alkali-metal metal phosphate, alkali-metal metal oxide and / or alkali-metal metal cyanide (e.g., lithium iron phosphate, sodium iron phosphate, lithium iron oxide, sodium iron oxide, lithium iron cyanide, sodium iron cyanide, sodium transition metal oxides) materials. In some embodiments, the alkali-metal metal phosphate, alkali-metal metal oxide and / or alkali-metal metal cyanide is selected from lithium iron phosphate (LFP) (e.g., LiFePO4), lithium nickel manganese cobalt oxide (NMC) (e.g., LiNixMnyCozO2, where x, y and z are above zero and x + y + z = 1), lithium nickel manganese oxide (LNMO), lithium nickel cobalt aluminum oxide (NCA) (e.g., LiNixCoyAlzO2, where x, y, and z are above zero and x + y澾瀍 = 1), lithium manganese oxide (LMO) (e.g., LiMn2O4), lithium cobalt oxide (LCO) (e.g., LiCoO2), a lithium titanate (LTO),sodium cobalt oxide (eg., Nax&R2^ where x is above zero), sodium iron hexacyanoferrate (e.g., 1Dೋ)H>)H^&1^^@, where x is above zero), sodium manganese oxide (e.g., Nax0Q2^ where x is above zero), sodium iron phosphate (e.g., 1D)H32^^, sodium vanadium phosphate (Nax9232^ where x is above zero), sodium transition metal oxides (e.g., Nax02^, where x is above zero), sodium nickel manganese oxide (e.g., NaNixMny2^, where x and y are above zero and x + y = 1), and combinations thereof. In some embodiments, the molar ratio of the alkali metal element to the total amount of the other metals in the active materials is, is about, is at least, is at least about, is at most, is at most about, 1.01, 1.02, 1.03, 1.04, 1.05, 1.06, 1.07, 1.08, 1.09, 1.1, 1.15, or any ranges of values therebetween.

[0094] In some embodiments, the active material comprises active material particles having a D50 particle size of, of about, of at least, or of at least about, 1 μm, 5 μm, 10 μm, 20 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, 125 μm, 150 μm, 175 μm, 200 μm, 225 μm, 250 μm, 275 μm, 300 μm, 325 μm, 350 μm, 375 μm, 400 μm, 425 μm, 450 μm, 475 μm, 500 μm, 525 μm, 550 μm, 575 μm, 600 μm, 625 μm, 650 μm, 675 μm, 700 μm, 725 μm, 750 μm, 775 μm, 800 μm, 825 μm, 850 μm, 875 μm, 900 μm, 925 μm, 950 μm, 975 μm, 1000 μm, 1025 μm, 1050 μm, 1075 μm, 1100 μm, 1125 μm, 1150 μm, 1175 μm, 1200 μm or 1225 μm, 2000 μm, 5000 μm, 1 cm, 2 cm, 3 cm, 4 cm, 5 cm, or 10 cm, or any range of values therebetween. For example, in some embodiments, the D50 particle size distribution of the subsequent particles is or is about in any one of the following ranges: 30 μm – 10 cm, 100 μm – 1 cm, 500 μm – 1 cm, 800 μm – 1 cm, 1000 μm – 1 cm, 100 μm – 0.5 cm, or 500 μm – 0.5 cm.

[0095] In some embodiments, the active material comprises active material particles having a D90particle size of, of about, of at least, or of at least about, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 825 μm, 850 μm, 875 μm, 900 μm, 925 μm, 950 μm, 975 μm, 1000 μm, 11200 μm or 1225 μm, 2000 μm, 5000 μm, 1 cm, 5 cm, 10 cm, or 15 cm, or any range of values therebetween.

[0096] In some embodiments, the active material comprises active material particles having a D10 particle size of, of about, of at least, or of at least about, 5 μm, 10 μm, 15 μm, 20 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 825 μm, 850 μm, 875μm, 900 μm, 925 μm, 950 μm, 975 μm, 1000 μm, 11200 μm or 1225 μm, 2000 μm, 5000 μm, 1 cm, 5 cm, or any range of values therebetween.

[0097] The D50 particle size represents the median of particle size distributions, at which 50% of the sample’s volume has a smaller particle size, i.e., the D50 particle size splits the distribution with half above and half below this particle size. The D90 particle size represents that 90% of the sample’s volume has a smaller particle size than the D90particle size. The D10particle size represents that 10% of the sample’s volume has a smaller particle size than the D10particle size.

[0098] In some embodiments, the active material particles have well-ordered particle structures. In some embodiments, the active material particles have homogenous or substantially homogenous distribution of the active material throughout the particles. In some embodiments, the percentage of the second metal element within the alkali metal element is uniform or substantially uniform throughout the particle. In some embodiments, the percentage of second metal in the alkali metal position (e.g., layer, channel) (MA%, where M represents the second metal element and A represents alkali metal element) is, is about, is at most, or is at most about, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.5%, 4%, 4.5%, 5%, or any range of values therebetween. For example, in some embodiments, the percentage of second metal in the alkali metal position (MA%) is or is about any one of the following ranges: 0.1% - 5%, 0.4% - 2%, 0.8% - 1.6%, 0.8% - 1.2%, or 0.6% - 0.9%. In some embodiments, the alkali metal position is the alkali metal layer, the alkali metal channel, or other alkali metal position. In some embodiments, the well-ordered structures may improve process yields and efficiencies, as well as material performance.

[0099] For example, when the active material is lithium iron phosphate, the percentage of iron in the lithium channels (FeLi%) is uniform or substantially uniform throughout the particle. In some embodiments, the lithium iron phosphate particles comprise lithium iron phosphate with well-ordered structures, represented by the percentage of iron in the lithium channels (FeLi%). In some embodiments, the percentage of iron in the lithium channels (FeLi%) is, is about, is at most, or is at most about, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%,2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9% or 3%, or any range of values therebetween. For example, in some embodiments, the percentage of iron in the lithium channels (FeLi%) is or is about any one of the following ranges: 0.1% - 3%, 0.4% - 2%, 0.8% - 1.6%, 0.8% - 1.2%, or 0.6% - 0.9%. In some embodiments, the percentage of the iron in the lithium channels (FeLi%) is calculated based on the molar ratio. Electrode film

[0100] In some embodiments, an electrode film may comprise at least one active material, a binder, and optionally a conductive additive. In some embodiments, the active materials disclosed herein may be used in an electrode film. In some embodiments, the electrode film can include an active material of, of about, of at least, of at least about, of at most, of at most about, 80 wt.%, 85 wt.% 90 wt.%, 91 wt.%, 92 wt.%, 93 wt.%, 94 wt.%, 95 wt.%, 96 wt.%, 97 wt.%, 98 wt.%, 99 wt.%, or any ranges therebetween, of the electrode film.

[0101] In some embodiments, the electrode film comprises a cathode film or an anode film. In some embodiments, the electrode film is an anode electrode film. In some embodiments, the anode electrode film comprises an anode active material. In some embodiments, the anode active material may comprise synthetic graphite, natural graphite, hard carbon, soft carbon, graphene, mesoporous carbon, silicon, silicon oxides, silicon carbide, graphite and silicon comprising composites, tin, tin oxides, germanium, lithium titanate, lithium metal, lithium metal alloys, mixtures, or composites of the aforementioned materials.

[0102] In some embodiments, the electrode film is a cathode electrode film. In some embodiments, the cathode electrode film comprises a cathode active material. In some embodiments, the cathode active material may include, for example, a metal oxide, metal sulfide, metal phosphate, or metal cyanide. In some embodiments, the cathode active materials comprise alkali-metal metal phosphate, alkali-metal metal oxide and / or alkali-metal metal cyanide materials.

[0103] In some embodiments, the cathode active material comprises a lithium metal oxide, lithium metal phosphate, lithium metal cyanide. In some embodiments, the lithium metal oxide can be, for example, a lithium nickel manganese cobalt oxide (NMC), a lithium manganese oxide (LMO), a lithium iron phosphate (LFP), a lithium cobalt oxide (LCO), a lithium titanate (LTO), and / or a lithium nickel cobalt aluminum oxide (NCA). Insome embodiments, cathode active materials can comprise, for example, a layered transition metal oxide (such as LiCoO2 (LCO), Li(NiMnCo)O2 (NMC) and / or LiNi0.8Co0.15Al0.05O2 (NCA)), a spinel manganese oxide (such as LiMn2O4 (LMO) and / or LiMn1.5Ni0.5O4 (LMNO)), an olivine (such as LiFePO4), chalcogenides (LiTiS2), tavorite (LiFeSO4F), silicon, silicon oxide (SiOx), aluminum, tin, tin oxide (SnOx), manganese oxide (MnOx), molybdenum oxide (MoO2), molybdenum disulfide (MoS2), nickel oxide (NiOx), or copper oxide (CuOx). The cathode active material can comprise sulfur or a material including sulfur, such as lithium sulfide (Li2S), or other sulfur-based materials, or a mixture thereof. In some embodiments, the cathode film comprises a sulfur or a material including sulfur active material at a concentration of at least 50 wt%. In some embodiments, the cathode film comprising a sulfur or a material including sulfur active material has an areal capacity of at least 10 mAh / cm2. In some embodiments, the cathode film comprising a sulfur or a material including sulfur active material has an electrode film density of 1 g / cm3. In some embodiments, the cathode film comprising a sulfur or a material including sulfur active material further comprises a binder.

[0104] In some embodiments, the cathode active material comprises sodium metal phosphate, sodium metal oxide and / or sodium metal cyanide. In some embodiments, the cathode active material comprises sodium cobalt oxide (eg.g., Nax&R2^^, sodium iron hexacyanoferrate (e.g., 1Dೋ)H>)H^&1^^@^, sodium manganese oxide (e.g., Nax0Q2^), sodium iron phosphate (e.g., 1D)H32^^, sodium vanadium phosphate (Nax9232^), sodium transition metal o[LGHV^^1D[02^^, sodium nickel manganese o[LGH^^1D1L^^^0Q^^^2^^, and combinations thereof. In some embodiments, the cathode active material comprises at least one active material formed with the methods or process disclosed herein.

[0105] In some embodiments, the conductive additive may comprise a conductive carbon additive, such as carbon black and / or carbon nanotube. In some embodiments, the electrode film comprises the conductive additive of, of about, of at least, of at least about, of at most, of at most about, 6 wt.%, 5 wt.% 4.5 wt.%, 4wt.%, 3.5 wt.%, 3 wt.%, 2.5 wt.%, 2 wt.%, 1.5 wt.%, 1 wt.%, 0.5 wt.%, or any ranges therebetween, of the electrode film. In some embodiments, the electrode film may not include a conductive additive.

[0106] In some embodiments, the electrode film comprises a binder of, of about, of at least, of at least about, of at most, of at most about, 20 wt.%, 15 wt.% 10 wt.%, 9 wt.%, 8 wt.%, 7 wt.%, 6 wt.%, 5 wt.%, 4 wt.%, 3 wt.%, 2 wt.%, 1.5 wt.%, or any ranges therebetween,of the electrode film. In some embodiments, the binder comprises a polymeric binder material. The binder can include polytetrafluoroethylene (PTFE), a polyolefin, polyalkylenes, polyethers, styrene-butadiene, co-polymers of polysiloxanes, a polysiloxane, branched polyethers, polyvinylethers, co-polymers thereof, and / or admixtures thereof. The binder can include a cellulose, for example, carboxymethylcellulose (CMC). In some embodiments, the polyolefin can include polyethylene (PE), polypropylene (PP), polyvinylidene fluoride (PVDF), co-polymers thereof, and / or mixtures thereof. For example, the binder can include polyvinylene chloride, poly(phenylene oxide) (PPO), polyethylene-block-poly(ethylene glycol), poly(ethylene oxide) (PEO), poly(phenylene oxide) (PPO), polyethylene-block- poly(ethylene glycol), polydimethylsiloxane (PDMS), polydimethylsiloxane- coalkylmethylsiloxane, co-polymers thereof, and / or admixtures thereof. In some embodiments, the binder may be a thermoplastic. In some embodiments, the binder comprises a fibrillizable polymer. In certain embodiments, the binder comprises, consists essentially, or consists of PTFE. In some embodiments, the electrode film comprises, comprises at least, comprises at most 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 binders.

[0107] In some embodiments, the electrode film may provide a high electrode material loading, or a high active material loading (which may be expressed as mass of active material per unit area of electrode film or current collector) of, of about, of at least, of at least about, 10 mg / cm2, 12 mg / cm2, 13 mg / cm2, 14 mg / cm2, 15 mg / cm2, 16 mg / cm2, 17 mg / cm2, 18 mg / cm2, 19 mg / cm2, 20 mg / cm2, 21 mg / cm2, 22 mg / cm2, 23 mg / cm2, 24 mg / cm2, 25 mg / cm2, 26 mg / cm2, 27 mg / cm2, 28 mg / cm2, 29 mg / cm2, 30 mg / cm2, 40 mg / cm2, 50 mg / cm2, 60 mg / cm2, 70 mg / cm2, 80 mg / cm2, 90 mg / cm2or 100 mg / cm2, or any range of values therebetween.

[0108] In some embodiments, the electrode film may provide areal capacity (which may be expressed as capacity per unit area of electrode film or current collector) of, of about, at least, or at least about 1.5 mAh / cm2, 2 mAh / cm2, 3 mAh / cm2, 3.5 mAh / cm2, 3.8 mAh / cm2, 4 mAh / cm2, 4.3 mAh / cm2, 4.5 mAh / cm2, 4.8 mAh / cm2, 5 mAh / cm2, 5.5 mAh / cm2, 6 mAh / cm2, 6.5 mAh / cm2, 6.6 mAh / cm2, 7 mAh / cm2, 7.5 mAh / cm2, 8 mAh / cm2or 10 mAh / cm2, 10 mAh / cm2, 20 mAh / cm2, 30 mAh / cm2, 40 mAh / cm2, 50 mAh / cm2, or any range of values therebetween. In some embodiments, the areal capacity is charging capacity. In further embodiments, the areal capacity is discharging capacity.

[0109] In some embodiments, the electrode film may provide a specific capacity (which may be expressed as capacity per mass of active material) of about 150 mAh / g, about 160 mAh / g, about 170 mAh / g, about 175 mAh / g, about 176 mAh / g, about 177 mAh / g, about 179 mAh / g, about 180 mAh / g, about 185 mAh / g, about 190 mAh / g, about 196 mAh / g, about 200 mAh / g, about 250 mAh / g, about 300 mAh / g, about 350 mAh / g, about 354 mAh / g or about 400 mAh / g, or any range of values therebetween. In some embodiments, the specific capacity is charging capacity. In further embodiments, the specific capacity is discharging capacity. In some embodiments, the electrode may be an anode and / or a cathode. In some embodiment, the specific capacity may be a first charge and / or discharge capacity. In further embodiments, the specific capacity may be a charge and / or discharge capacity measured after the first charge and / or discharge.

[0110] In some embodiments, the electrode film may provide a coulombic efficiency, for example, a 1stcycle coulombic efficiency (which may be expressed as a percent of the discharge capacity divided by the charge capacity) of about, or at least about, 85%, 86%, 87%, about 88%, about 89%, about 90%, about 91%, about 92%, about 93%, about 94% or about 95%, or any range of values therebetween, for example such as 90.1%, 90.5% and 91.9%, or any range of values therebetween.

[0111] In some embodiments, the electrode film may provide a discharge capacity retention percentage (which may be expressed by the discharge capacity at a given rate divided by the initial discharge capacity measured at C / 10) of about or at least about 10%, about or at least about 20%, about or at least about 30%, about or at least about 40%, about or at least about 50%, about or at least about 60%, about or at least about 70%, about or at least about 80%, about or at least about 90%, about or at least about 98%, about or at least about 99%, about or at least about 99.9% or about or at least about 100%, or any range of values therebetween. In some embodiments, the discharge rate to calculate capacity retention during charge-discharge cycling is or is at least C / 10, C / 5, C / 3, C / 2, 1C, 1.5C or 2C, or any value therebetween. Energy Storage Device

[0112] In some embodiments, the energy storage devices include for example, capacitors, batteries, capacitor-battery hybrids and / or fuel cells. Energy storage devices of thepresent disclosure include the electrolyte discussed herein, a cathode, an anode, a separator and a housing, wherein the electrolyte, cathode and anode are disposed within the housing. In some embodiments, an energy storage device as provided herein is a lithium-ion battery or sodium-ion battery. Each of the cathode and anode include an electrode film and a current collector that form the electrode. The electrode films generally comprise one or more active materials, for example, anode active materials or cathode active materials as provided herein. Preparation Process for Active Materials

[0113] Processes for preparing an active material for an energy storage device are disclosed. The process may include combining the ingredients to form a first mixture; forming a plurality of initial particles of active material precursor; recirculating at least some the initial particles; and combining additional first mixture with the recirculated initial particles to form a plurality of subsequent particles. The plurality of subsequent particles may be calcined to form a plurality of calcinated particles comprising an active material. In some embodiments, calcination may be carried out in a furnace that is not configured to accommodate fine particle sizes (e.g., initial particles). In some embodiments, the process is a wet process where a solvent is involved in at least one step of the process, such as in the step of forming the first mixture. In some embodiments, the process is a dry process where no or substantially no solvent is used in the step of forming the first mixture.

[0114] In some embodiments, the active material precursor comprises an alkali- metal metal phosphate precursor, alkali-metal metal oxide precursor, alkali-metal metal cyanide precursor, or combinations thereof. In some embodiments, the initial particles comprising an alkali-metal metal phosphate precursor, alkali-metal metal oxide precursor, and / or alkali-metal metal cyanide precursor may be recirculated to form larger subsequent particles comprising alkali-metal metal phosphate precursor, alkali-metal metal oxide precursor and / or alkali-metal metal cyanide precursor. In some embodiments, the subsequent particles may be calcinated to form alkali-metal metal phosphate particles, alkali-metal metal cyanide particles and / or alkali-metal metal oxide particles.

[0115] FIG. 1 schematically illustrates a process 100 for preparing an active material according to some embodiments. As illustrated in FIG. 1, the process 100 comprises forming a first mixture by combining the ingredients 102. In some embodiments, combiningthe ingredient comprises mixing the ingredients. In some embodiments, the ingredients comprise an alkali metal source and a second metal source. In some embodiments, the ingredients comprise an optional carbon source. In some embodiments, the ingredients are milled before being combined. In some embodiments, combining the ingredient comprises milling the ingredients. In some embodiments, milling the ingredient comprises jet milling. In some embodiments, the process 100 further comprises a step 104 of forming a plurality of particles of active material precursor from the first mixture. In some embodiments, the process 100 comprises a step 106 of separating the particles. In some embodiments, separating the particles comprises separating the separating subsequent particles from the initial particles. In some embodiments, the subsequent particles are particles having a particle size above a threshold or with a certain range. In some embodiments, separating the particles comprises classifying the particles, such as by sieving the particles with a sieve having a threshold mesh size. In some embodiments, the process 100 comprises collecting the subsequent particles comprising active material precursor 108. In some embodiments, the process 100 comprises recirculate the initial particles 112. In some embodiments, the initial particles are recirculated to step 102 to be mixed with additional first mixture. In some embodiments, milling is performed before the initial particles comprising the active material precursor are recirculated to step 102. In some embodiments, the recirculated particles are milled together with additional first mixture. With continued reference to FIG. 1, the process 100 may further comprise calcinating the collected subsequent particles comprising the active material precursor to form a plurality of calcinated particles comprising the active material 110. In some embodiments, calcinating the collected subsequent particles comprises calcinating with a crucible. In some embodiments, calcinating is interchangeable with calcining in this disclosure. In some embodiments, the process 100 is a dry process where a liquid is not involved in the step 104. In some embodiments, the process 100 is a wet process that involves a liquid in step 104.

[0116] In some embodiments, the process for preparing an active material includes a wet process. For example, FIG. 2 is a flowchart of wet process 200 for preparing an active material, according to some embodiments. The wet process 200 includes forming a first mixture comprising an alkali metal source, a second metal source, a liquid and an optional carbon source 202. In some embodiments, the liquid comprises water. In some embodiments,the first mixture is a slurry. In some embodiments, forming a first mixture comprises wet milling the first mixture. In some embodiments, the alkali metal source and the second metal source are milled before forming the first mixture. In some embodiments, the wet process 200 comprises forming a plurality of particles of active material precursor 204 from the first mixture. In some embodiments, forming a plurality of particles comprises spray drying the first mixture. In some embodiments, the wet process 200 comprises a step 206 of separating the particles. In some embodiments, separating the particles comprises separating the separating subsequent particles from the initial particles. In some embodiments, the subsequent particles are particles having a particle size above a threshold or with a certain range. In some embodiments, separating the particles comprises classifying the particles, such as by sieving the particles with a threshold mesh size. In some embodiments, the wet process 200 comprises collecting the subsequent particles comprising active material precursor 208. In some embodiments, the wet process 200 comprises recirculate the initial particles 212. In some embodiments, the initial particles are recirculated to step 202 to be mixed with additional first mixture. In some embodiments, milling is performed before the particles comprising the active material precursor are recirculated to step 202. In some embodiments, the recirculated particles are milled together with additional first mixture. In some embodiments, milling is performed before the particles comprising the active material precursor are recirculated to step 202. In some embodiments, the recirculated particles are milled together with additional first mixture. The collected subsequent particles comprising the active material precursor are calcinated to form a plurality of calcinated particles comprising active material 210.

[0117] In some embodiments, the process for preparing an active material includes a dry process. For example, FIG. 3 is a flowchart of dry process 300 for preparing an active material according to some embodiments. The dry process 300 includes forming a first mixture comprising an alkali metal source, a second metal source and optionally a carbon additive. In some embodiments, the first mixture is a dry first mixture that is absent or substantially absent any solvent. In some embodiments, dry process 300 comprises forming a plurality of particles of active material precursor 304. In some embodiments, forming a plurality of particles comprises mechanical granulation. In some embodiments, forming a plurality of particles comprises compacting the first mixture. In some embodiments, the dry process 300 comprises a step 306 of separating the particles. In some embodiments, separating the particles comprisesseparating the separating subsequent particles from the initial particles. In some embodiments, the subsequent particles are particles having a particle size above a threshold or with a certain range. In some embodiments, separating the particles comprises classifying the particles, such as by sieving the particles with a threshold mesh size. In some embodiments, the dry process 300 comprises collecting the subsequent particles comprising active material precursor 308. In some embodiments, the dry process 300 comprises recirculate the initial particles 312. In some embodiments, the initial particles are recirculated to step 302 to be mixed with additional first mixture. In some embodiments, milling is performed before the particles comprising the active material precursor are recirculated to step 302. In some embodiments, the recirculated particles are milled together with additional first mixture. In some embodiments, milling is performed before the particles comprising the active material precursor are recirculated to step 302. In some embodiments, the recirculated particles are milled together with additional first mixture. The plurality of collected subsequent particles are calcinated to form a plurality of calcinated particles comprising the active material 312.

[0118] In some embodiments, the alkali metal source comprises a lithium source, a sodium source, or a combination thereof. In some embodiments, the lithium source is selected from the group consisting of LiOH, LiOHyH2O, Li2CO3, LiPO3, Li3PO3, Li3PO4, LiH2PO4, Li2HPO4, LiH2PO3, Li2HPO3, lithium iron oxides, lithium iron phosphate, and hydrates forms thereof, and combinations thereof. In some embodiments, the sodium source is selected from the group consisting of NaOH, Na2CO3, NaCl, NaHC濢3, NaNO3, Na2SO4, NaPO3, Na3PO4, NaH2PO4, Na2HPO4, sodium poly- and meta- phosphates, and hydrates forms thereof, and combinations thereof.

[0119] In some embodiments, the second metal element of the active materials is selected from Fe, Mn, Mg, Al, Ca, Ti, Co, Ni, Cr, V, and combinations thereof. In some embodiments, the second metal source comprises metal, oxide, hydroxide or any forms of the second metal. In some embodiments, the second metal source comprises an iron-based material, a nickel-based material, a manganese-based material, a cobalt-based material, an aluminum-based material or combinations thereof. In some embodiments, the iron-based material is selected from the group consisting of an iron oxide, an anhydrous iron phosphate, an iron phosphate hydrate, an iron metal, and combinations thereof. In some embodiments, the iron-based material is selected from the group consisting of FeOOH, FeO, FePO4, Fe2O3,Fe3O4, Fe4(P2O7)3, FeCO3, Fe2(CO3)3, Fe3P, Fe2P, siderite, FeC2O4, Fe3(PO4)2, Fe2O7P2, FeSO4, FeF2, FeF3, Fe(C5H7O2)3, FeBr3, FeCl3, iron(III)-chloridoxide, FeO(OH), FeI3, Fe(NO3)3, Fe3(PO4)2, Fe2(SO4)3, FeSCN2+, ferrous gluconate, ferrous lactate, Fe2N, Fe3N4, Fe4N, Fe7N3, Fe16N2, Fe(CO)5, FeH3O3P, iron tartrate, ammonium iron phosphate, lithium iron phosphate, iron pyrophosphate, iron containing alloys, iron containing scrap metal, iron metal, iron metal alloy, cast iron, and hydrates forms thereof, and combinations thereof. In some embodiments, a nickel-based material comprises metallic nickel, nickel oxide, nickel hydroxide, nickel carbonate, and combination thereof. In some embodiments, a manganese- based material is selected from the group consisting of metallic manganese, manganese oxide, manganese hydroxide, manganese carbonate, and combination thereof. In some embodiments, a cobalt-based material is selected from the group consisting of metallic cobalt, cobalt oxide, cobalt hydroxide, cobalt carbonate, and combination thereof. In some embodiments, the second metal source comprises a precursor absent the alkali metal in the intended active material. In some embodiments, the second metal source comprises precursor cathode active material (pCAM). In some embodiments, the second metal source comprises hydroxide pCAM, oxide pCAM, or a combination thereof. In some embodiments, the second metal source comprises nickel cobalt manganese hydroxide (hydroxide pCAM NMC), nickel cobalt manganese hydroxide (oxide pCAM NMC), or a combination thereof.

[0120] In some embodiments, the molar ratio of the alkali metal source and the second metal source in the first mixture is based on the active material to be formed. In some embodiments, the molar ratio of the second metal to the alkali metal source in the first mixture is, is about, is at least, or is at least about, 2:1, 1.9:1, 1.8:1, 1.7:1, 1.6:1, 1.5:1, 1.4:1, 1.3:1, 1.2:1, 1.1:1, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9 or 1:2, or any range of values therebetween.

[0121] In some embodiments, the first mixture comprises a carbon source. In some embodiments, the carbon source is selected from the group consisting of a sugar, a natural polymer, a synthetic polymer, a carbonaceous material, and combinations thereof. In some embodiments, the carbon source is selected from the group consisting of a monosaccharide, a disaccharide, an oligosaccharide, a starch, a gum, polyvinyl alcohol (PVA), polyethylene glycol (PEG), a sugar alcohol, pitch, coke, asphaltite, uintahite, asphaltum, gilsonite, sweeteners, mannitol, erythritol, polyethylene-polypropylene-oxide block copolymers,detergents, fatty acids, fatty acid esters, modified starches, modified celluloses, carboxy methyl cellulose, graphite, activated carbon, urea, polyvinylpyrrolidone (PVP), styrene-butadiene rubber (SBR), polyvinylidene fluoride (PVDF), and combinations thereof. In some embodiments, the carbon source comprises a detergent. In some embodiments, the surface of the carbon source is modified with a functional group. In some embodiments, the carbon source functions as a binder. In some embodiments, the carbon source is added in the first mixture when the intended active material comprises phosphorus. In some embodiments, the first mixture does not comprise a carbon source when the intended active material does not comprise phosphorus. In some embodiments, the amount of ash in the carbon source is, is about, is at most, or is at most about, 0.1 wt. %, 0.2 wt. %, 0.3 wt. %, 0.4 wt. %, 0.5 wt. %, 0.6 wt. %, 0.7 wt. %, 0.8 wt. %, 0.9 wt. %, 1 wt. %, 1.1 wt. %, 1.2 wt. %, 1.3 wt. %, 1.4 wt. %, 1.5 wt. %, 1.6 wt. %, 1.7 wt. %, 1.8 wt. %, 1.9 wt. %, 2 wt. %, 2.1 wt. %, 2.2 wt. %, 2.3 wt. %, 2.4 wt. %, 2.5 wt. %, 2.6 wt. %, 2.7 wt. %, 2.8 wt. %, 2.9 wt. % or 3 wt. %, or any range of values therebetween. In some embodiments, the carbon source comprises a detergent with less than 1 wt.% ash. In some embodiments, the detergent comprises a non-ionic surfactant.

[0122] In some embodiments, the first mixture comprises a liquid. In some embodiments, the liquid comprises water. In some embodiments, the first mixture is free of, or is substantially free of, a liquid and / or water. In some embodiments, water (e.g., steam) formed from the reaction on ingredients of the first mixture is extracted from the reaction chamber. In some embodiments, the first mixture contains no detectable processing solvents, processing solvent residues, or processing solvent impurities. Processing solvents or traditional solvents include organic solvents and water. In some embodiments, the first mixture may be solvent-free. In some embodiments, the lithium iron phosphate material may be solvent-free. In some embodiments, the first mixture further comprises a functional additive. In some embodiments, the functional additive is selected from the group consisting of dispersants, anti-foaming additives, colorants, sweeteners, dopants, coating additives, metal oxides, boric acid, borates, graphite, and combinations thereof.

[0123] In some embodiments, the ingredients, such as the alkali metal source and / or the second metal source, are primary particles before being combined to form the first mixture. In some embodiments, the ingredients are milled before being combined to form the first mixture. In some embodiments, the first mixture is milled before forming the initialparticles. In some embodiments, the ingredients have a D50particle size of, of about, of at most, or of at most about, 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1 μm, 1.1 μm, 1.2 μm, 1.3 μm, 1.4 μm, 1.5 μm, 1.6 μm, 1.7 μm, 1.8 μm, 1.9 μm, 2 μm, 2.1 μm, 2.2 μm, 2.3 μm, 2.4 μm, 2.5 μm, 2.6 μm, 2.7 μm, 2.8 μm, 2.9 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, 125 μm, or 150 μm, or any range of values therebetween.

[0124] In some embodiments, the initial particles of the active material precursor have a D50 particle size distribution range of, of about, of at most, or of at most about, 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1 μm, 1.1 μm, 1.2 μm, 1.3 μm, 1.4 μm, 1.5 μm, 1.6 μm, 1.7 μm, 1.8 μm, 1.9 μm, 2 μm, 2.1 μm, 2.2 μm, 2.3 μm, 2.4 μm, 2.5 μm, 2.6 μm, 2.7 μm, 2.8 μm, 2.9 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, 125 μm, or 150 μm, or any range of values therebetween. For example, in some embodiments, the D50particle size distribution of the precursor particles is or is about in any one of the following ranges: 0.1 μm – 10 μm, 1 μm – 10 μm, 0.1 μm – 3 μm, 3 μm – 5 μm, 6 μm – 10 μm, or 0.1 μm – 5 μm. In some embodiments, the initial particles are defined as the particles formed directly from the first mixture before any particles of the active material precursor are recirculated.

[0125] In some embodiments, the initial particles of the active material precursor have a D10particle size distribution range of, of about, of at most, or of at most about, 0.01 μm, 0.02 μm, 0.05 μm, 0.1 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1 μm, 1.1 μm, 1.2 μm, 1.3 μm, 1.4 μm, 1.5 μm, 1.6 μm, 1.7 μm, 1.8 μm, 1.9 μm, 2 μm, 2.1 μm, 2.2 μm, 2.3 μm, 2.4 μm, 2.5 μm, 2.6 μm, 2.7 μm, 2.8 μm, 2.9 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, or any range of values therebetween.

[0126] In some embodiments, the initial particles of the active material precursor have a D90 particle size distribution range of, of about, of at most, or of at most about, 0.5 μm , 1 μm, 1.1 μm, 1.2 μm, 1.3 μm, 1.4 μm, 1.5 μm, 1.6 μm, 1.7 μm, 1.8 μm, 1.9 μm, 2 μm, 2.1 μm, 2.2 μm, 2.3 μm, 2.4 μm, 2.5 μm, 2.6 μm, 2.7 μm, 2.8 μm, 2.9 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, 200 μm, 500 μm, 1000 μm, or any range of values therebetween.

[0127] In some embodiments, all or substantially all the subsequent particles produced in the processes disclosed herein have a particle size at least, at least about, 20 μm, 50 μm, 100 μm, or any ranges therebetween. In some embodiments, the process disclosed herein is a dust free process where no or substantially no subsequent particles having a particle size less than, less than about 20 μm, 50 μm, or 100 μm, are produced.

[0128] In some embodiments, the collected subsequent particles comprises a D50particle size of, of about, of at least, or of at least about, 5 μm, 10 μm, 15 μm, 20 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 825 μm, 850 μm, 875 μm, 900 μm, 925 μm, 950 μm, 975 μm, 1000 μm, 11200 μm or 1225 μm, 2000 μm, 5000 μm, 1 cm, 5 cm, or any range of values therebetween.

[0129] In some embodiments, the collected subsequent particles comprise a D90 particle size of, of about, of at least, or of at least about, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 825 μm, 850 μm, 875 μm, 900 μm, 925 μm, 950 μm, 975 μm, 1000 μm, 11200 μm or 1225 μm, 2000 μm, 5000 μm, 1 cm, 5 cm, 10 cm, or 15 cm, or any range of values therebetween.

[0130] In some embodiments, the collected subsequent particles have a D10 particle size of, of about, of at least, or of at least about, 1 μm, 5 μm, 10 μm, 15 μm, 20 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 825 μm, 850 μm, 875 μm, 900 μm, 925 μm, 950 μm, 975 μm, 1000 μm, 11200 μm or 1225 μm, 2000 μm, 5000 μm, 1 cm, or any range of values therebetween.

[0131] In some embodiments, the subsequent particles are collected if they cannot pass a sieve having a mesh size of, of about, of at least, or of at least about, 20 μm, 50 μm 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 400 μm, 500 μm, 600 μm, 900 μm, 1000 μm, 2000 μm, 5000 μm, 1 cm, 2 cm, 3 cm, 4 cm, 5 cm, or 10 cm, or any range of values therebetween.

[0132] In some embodiments, the percentage of the initial particles formed directly from the first mixture being collected is, is about, is at least, is at least about, at most, at most about, 10%, 20% 30% 40%, 50%, 60%, or any ranges therebetween, of the weight of the first mixture. In some embodiments, the percentage of the formed subsequent particles being collected after one recirculation is, is about, is at least, is at least about, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99%, or any ranges therebetween, of the weight of all the first mixture.

[0133] In some embodiments, some, none or all of the initial particles may be recirculated to form subsequent particles at any given time during the process. In some embodiments, initial particles are recirculated to form subsequent particles at a recirculation rate of, of about, of at most, or of at most about, 0%, 0.5%, 1%, 2%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100%, or any range of values therebetween (e.g., 1-50%, 5-45%, 10-25%, 30-60%, 40-55%).

[0134] In some embodiments, the collected and / or subsequent particles are calcinated. In some embodiments, calcination is performed at an oxidizing gas (e.g., air, oxygen, oxygen-containing gas, oxygen enriched air) concentration of, of about, of at most, or of at most about, 0.05 vol.%, 0.1 vol.%, 0.2 vol.%, 0.3 vol.%, 0.4 vol.%, 0.5 vol.%, 0.6 vol.%, 0.7 vol.%, 0.8 vol.%, 0.9 vol.% or 1 vol.%, or any range of values therebetween. In some embodiments, calcination is performed under an inert atmosphere. In some embodiments, calcination is performed under nitrogen. In some embodiments, calcination is performed under argon. In some embodiments, calcination is performed in the presence of a reducing gas selected from the group consisting of hydrogen methane, natural gas, propane, butane, carbon monoxide, and combinations thereof. In some embodiments, the concentration of the reducing gas is, is about, is at most, or is at most about, 0.5 vol.%, 1 vol.%, 1.5 vol.%, 2 vol.%, 2.5 vol.%, 3 vol.%, 3.5 vol.%, 4 vol.%, 4.5 vol.%, 5 vol.%, 5.5 vol.%, 6 vol.%, 6.5 vol.%, 7 vol.%, 7.5 vol.%, 8 vol.%, 8.5 vol.%, 9 vol.%, 9.5 vol.% or 10 vol.%, or any range of values therebetween. In some embodiments, calcination is performed under air, oxygen, oxygen enriched air, and / or ozone. In some embodiments, calcination is performed under a mixtureof gasses. In some embodiments, for example, calcination is performed under a mixture of an inert gas a reducing gas. In some embodiments, the calcination is performed in a furnace such as a rotary furnace. In some embodiments, the duration of the calcination is, is about, is at least, is at least about, is at most, is at most about, 10 min, 30 min, 40 min, 50 min, 60 min, 1.1 h, 1.2 h, 1.5 h, 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, 5 h, 5.5 h, 6 h, 7 h, 8 h, 9 h, 10 h, or any range of values therebetween. In some embodiments, the duration of the calcination is, is about, is at least, is at least about, is at most, is at most about, 100oC, 200oC, 300oC, 400oC, 500oC, 600oC, 700oC, 800oC, 900oC, 1000oC, 1200oC, 1500oC, 2000oC, or any range of values therebetween.

[0135] The processes for forming an active material disclosed herein are versatile and can be used for various active materials. Advantageously, in some embodiments, the disclosed process shortens the calcination times, improves the yields, improves the batch-to- batch consistency, simplifies the calcination steps and milling steps. In some embodiments, the particles formed during the processes may have a particle size larger than 100 microns, such that the process is dust free (i.e., no particles having a particle size less than 20 microns, 50 microns, or 100 microns are formed). Advantageously, a dust free process may help make the production environment safer, heathier for the workers, improve the product quality and lower the production cost. Lithium Iron Phosphate Preparation Process

[0136] The process of the present disclosure may include combining an iron-based material, a carbon source, and a lithium source to form a first mixture; the first mixture is mixed to form a plurality of initial particles; and combining the first mixture together with the plurality of initial particles to form a plurality of subsequent particles. The plurality of subsequent particles may be calcinated to form a plurality of calcinated particles comprising lithium iron phosphate. In some embodiments, calcination may be carried out in a furnace that is not configured to accommodate fine particle sizes (e.g., initial particles). For example, FIG. 4 is a flowchart of process 400 for preparing lithium iron phosphate, according to one embodiment. The process 400 includes forming a first mixture comprising an iron-based material, a lithium source, and a carbon source 402. The first mixture is mixed to form a plurality of initial particles 404. In step 406, the plurality of initial particles are recirculatedand combined with an additional amount of the first mixture from step 402. In step 408, a plurality of subsequent particles are formed. The plurality of subsequent particles are calcinated to form a plurality of calcinated particles comprising lithium iron phosphate 410. In some embodiments, lithium iron phosphate 410 comprises a carbon coating.

[0137] In some embodiments, the process for preparing lithium iron phosphate includes a wet process. For example, FIG. 5 is a flowchart of wet process 500 for preparing lithium iron phosphate, according to one embodiment. The wet process 500 includes forming a first mixture comprising an iron-based material, a lithium source, a carbon source, and a liquid 502. The first mixture is dried 504, to form a plurality of initial particles 506. The plurality of initial particles are recirculated and combined with an additional amount of the first mixture from step 502, and dried together with the plurality of initial particles 508 to form a plurality of subsequent particles 510. The plurality of subsequent particles are calcinated to form a plurality of calcinated particles comprising lithium iron phosphate 512.

[0138] In some embodiments, the process for preparing lithium iron phosphate includes a dry process. For example, FIG. 6 is a flowchart of dry process 600 for preparing lithium iron phosphate, according to one embodiment. The dry process 600 includes forming a first mixture comprising an iron-based material, a lithium source, and a carbon source 602. the dry process further comprises forming a plurality of initial particles 604. In some embodiments, forming the plurality of initial particles comprises mechanical granulation. In step 606, the plurality of initial particles are recirculated and combined with an additional amount of the first mixture from the step 602. The dry process 600 further comprises forming a plurality of subsequent particles 608. In some embodiments, forming the plurality of subsequent particles comprises mechanical granulation. The plurality of subsequent particles are calcinated to form a plurality of calcinated particles comprising lithium iron phosphate 610.

[0139] The iron-based material comprises iron. In some embodiments, the iron- based material is selected from the group consisting of an iron oxide, an anhydrous iron phosphate, an iron phosphate hydrate, an iron metal, and combinations thereof. In some embodiments, the iron-based material is selected from the group consisting of FeOOH, FeO, FePO4, Fe2O3, Fe3O4, Fe4(P2O7)3, FeCO3, Fe2(CO3)3, Fe, Fe3P, Fe2P, siderite, FeC2O4, Fe3(PO4)2, Fe2O7P2, FeSO4, FeF2, FeF3, Fe(C5H7O2)3, FeBr3, FeCl3, iron(III)-chloridoxide, FeI3, Fe(NO3)3, Fe3(PO4)2, Fe2(SO4)3, FeSCN2+, ferrous gluconate, ferrous lactate, Fe2N,Fe3N4, Fe4N, Fe7N3, Fe16N2, Fe(CO)5, FeH3O3P, iron tartrate, ammonium iron phosphate, , , iron containing alloys, iron containing scrap metal, iron powder, , cast iron, and hydrates forms thereof, and combinations thereof. In some embodiments, the lithium source is selected from the group consisting of LiOH, LiOHyH2O, Li2CO3, LiPO3, Li3PO3, Li3PO4, LiH2PO4, Li2HPO4, LiH2PO3, Li2HPO3, lithium iron oxides, lithium iron phosphate, and hydrates forms thereof, and combinations thereof.

[0140] In certain embodiments, the first mixture comprises a phosphorus source. In some embodiments, the iron-based material comprises the phosphorus source. In some embodiments, the phosphorus source is different than the iron-based material. In some embodiments, the phosphorus source is selected from the group consisting of H3PO4, H3PO3, P2O5, monoammonium phosphate, diammonium phosphate, urea phosphate, ammonium iron phosphates, lithium iron phosphate, LiPO3, Li3PO3, Li3PO4, LiH2PO4, Li2HPO4, LiH2PO3, Li2HPO3, and combinations thereof. In some embodiments, the molar ratio of the iron to phosphate in the first mixture is, is about, is at least, or is at least about, 2:1, 1.9:1, 1.8:1, 1.7:1, 1.6:1, 1.5:1, 1.4:1, 1.3:1, 1.2:1, 1.1:1, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9 or 1:2, or any range of values therebetween. For example, in some embodiments, the molar ratio of the iron-based material to phosphoric acid is or is about in any one of the following ranges: 1.4:1 to 1:1.3, 1.5:1 to 1:1.3, 1.1:1 to 1:1.1, 1:1.5 to 1.5:1, 1:1.5 to 1.2:1, 1:1 to 1.2:1, 1:1.2 to 1.1:1, or 1.2:1 to 1:2. System for Forming Active Materials

[0141] Some embodiments of the present disclosure relate to a system for forming an active material, such as a lithium iron phosphate material. In some embodiments, a system for forming an active material comprises a chamber and a furnace. In some embodiments, an alkali metal source, a second metal source, and a carbon source are combined in the chamber to form a first mixture, and the first mixture is mixed in the chamber to form a plurality of precursor particles. In some embodiments, the first mixture is combined together with the plurality of precursor particles to form a plurality of subsequent particles. In some embodiments, the plurality of subsequent particles are calcinated in the furnace to form a plurality of calcinated particles comprising lithium iron phosphate.

[0142] In some embodiments, a system for forming an active material comprises a chamber, a spray drier, and a furnace. For example, FIG. 7A is a flow diagram of a spray drying process for preparing an active material, such as a lithium iron phosphate. As illustrated in FIG. 7A, in some embodiments, an iron-based material, a lithium source, a phosphorus source, a carbon source, and water are combined and stirred in a first reactor. Other formulation may be used for different active material. As illustrated in FIG. 7A, the resulting mixture is passed through a spray drier, forming a plurality of initial particles. The plurality of initial particles are recirculated and mixed in a second reactor, forming a plurality of subsequent particles. In some embodiments, passing the resulting mixture through a spay drier forms subsequent particles. The plurality of subsequent particles are dried in a furnace, forming a plurality of calcinated particles comprising lithium iron phosphate.

[0143] In some embodiments, a system for forming an active material is a dry process system. For example, FIG. 7B is a flow diagram of a dry process for preparing the active material, such as a lithium iron phosphate. As illustrated in FIG. 7B, in some embodiments, an iron-based material, a lithium source, a phosphorus source, and a carbon source are combined and mixed in a reactor, forming a first mixture. Other formulation of ingredients may be used for forming other active materials. In some embodiments, as illustrated in FIG. 7B, the iron-based material, the lithium source, the phosphorus source, and the carbon source of the first mixture are reacted to form a plurality of initial particles. In some embodiments, the plurality of initial particles are recirculated and reacted with an additional amount of the iron-based material, the lithium source, a phosphorus source, and the carbon source of the first mixture to form a plurality of subsequent particles. The plurality of subsequent particles are passed through a furnace, forming a plurality of calcinated particles comprising lithium iron phosphate.

[0144] In some embodiments, a system for forming an active material comprises a chamber, a granulating apparatus, a recirculation path, and a furnace. In some embodiments, the chamber comprises a fluidized bed. In some embodiments, the fluidized bed is configured to suspend active material precursor particles within a fluidizing medium, through an upward flow or recirculation of the fluidizing medium. In some embodiments, the fluidizing medium may be a gas, such as air or nitrogen, or a liquid, such as water or a solvent.

[0145] In some embodiments, the granulating apparatus comprises a granulator in fluid communication with the chamber, an apparatus volume comprising an outlet and an inlet, and a recirculation path in fluid communication with the outlet and the inlet. In some embodiments, the granulator comprises a spray dry granulator, a compactor, or a combination thereof. In some embodiments, the compactor comprises a roller compactor. In some embodiments, the furnace is in fluid communication with the outlet. In some embodiments, the furnace is configured to contain particles with a D50particle size distribution of, of about, of at least, or of at least about, 1 μm, ^^^P^^^^^P^^5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, 125 μm, 150 μm, 175 μm, 200 μm, 225 μm, 250 μm, 275 μm, 300 μm, 325 μm, 350 μm, 375 μm, 400 μm, 425 μm, 450 μm, 475 μm, 500 μm, 525 μm, 550 μm, 575 μm, 600 μm, 625 μm, 650 μm, 675 μm, 700 μm, 725 μm, 750 μm, 775 μm, 800 μm, 825 μm, 850 μm, 875 μm, 900 μm, 925 μm, 950 μm, 975 μm, 1000 μm, 1025 μm, 1050 μm, 1075 μm, 1100 μm, 1125 μm, 1150 μm, 1175 μm, 1200 μm or 1225 μm, 1 cm, 5 cm, 10 cm, or any range of values therebetween. In some embodiments, the furnace is configured to contain particles with a D90particle size of, of about, of at least, or of at least about, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 825 μm, 850 μm, 875 μm, 900 μm, 925 μm, 950 μm, 975 μm, 1000 μm, 11200 μm or 1225 μm, 2000 μm, 5000 μm, 1 cm, 5 cm, 10 cm, or 15 cm, or any range of values therebetween. In some embodiments, the furnace is configured to contain particles with a D10particle size of, of about, of at least, or of at least about, 5 μm, 10 μm, 15 μm, 20 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 825 μm, 850 μm, 875 μm, 900 μm, 925 μm, 950 μm, 975 μm, 1000 μm, 11200 μm or 1225 μm, 2000 μm, 5000 μm, 1 cm, 5 cm, or any range of values therebetween.

[0146] In some embodiments, the system further comprises a deagglomeration mill. In certain embodiments, deagglomeration mill is selected from the group consisting of a jet mill, a crusher, a roller mill, an impact classifier mill, a spiral jet mill, and a ball mill. In some embodiments, the system further comprises a recirculation mill. In certain embodiments, recirculation mill comprises a pin mill or a roller mill. In some embodiments, the systemcomprises at least one of a mechanical post granulator, a high intensity mixer, a blender, a cyclone recirculation apparatus, a mill recirculator, and a classifier recirculator. In some embodiments, the mechanical granulator comprises a compactor.

[0147] In some embodiments, the system further comprises a particle size classification device. In certain embodiments, the particle size classification device comprises a classifier, an air classifier, a classifier cascade, a sieve, a cyclone, a centrifuge, a filter, or a combination thereof. In some embodiments, the sieve is selected from the group consisting of a rotary sieve, a drum sieve, a jet sieve, a vibratory sieve, or tapping sieve. In some embodiments, the particle size classification device is configured to classify or separate relatively larger particles (e.g., subsequent particles) having a D50 particle size distribution range of, of about, of at most, of at most about, of at least, or of at least about, 1 μm^^^^^P^^^^ ^P^^5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, 125 μm, 150 μm, 175 μm, 200 μm, 225 μm, 250 μm, 275 μm, 300 μm, 325 μm, 350 μm, 375 μm, 400 μm, 425 μm, 450 μm, 475 μm, 500 μm, 525 μm, 550 μm, 575 μm, 600 μm, 625 μm, 650 μm, 675 μm, 700 μm, 725 μm, 750 μm, 775 μm, 800 μm, 825 μm, 850 μm, 875 μm, 900 μm, 925 μm, 950 μm, 975 μm, 1000 μm, 1025 μm, 1050 μm, 1075 μm, 1100 μm, 1125 μm, 1150 μm, 1175 μm, 1200 μm, 1225 μm, 1250 μm, 1275 μm, 1300 μm, 1325 μm, 1350 μm, 1375 μm, 1400 μm, 1425 μm, 1450 μm, 1475 μm, 1500 μm, 1525 μm, 1550 μm, 1575 μm, 1600 μm, 1625 μm, 1650 μm, 1675 μm, 1700 μm, 1725 μm, 1750 μm, 1775 μm, 1800 μm, 1825 μm, 1850 μm, 1875 μm, 1900 μm, 1925 μm, 1950 μm, 1975 μm, 2000 μm, 2025 μm, 2050 μm, 2075 μm, 2100 μm, 2125 μm, 2150 μm, 2175 μm, 2200 μm, 2225 μm, 2250 μm, 2275 μm, 2300 μm, 2325 μm or 2350 μm, 5000 μm, 1 cm, 5 cm, 10 cm, or any range of values therebetween. In some embodiments, the particle size classification device is configured to classify or separate relatively larger particles (e.g., subsequent particles) having a D90 particle size of, of about, of at least, or of at least about, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 825 μm, 850 μm, 875 μm, 900 μm, 925 μm, 950 μm, 975 μm, 1000 μm, 11200 μm or 1225 μm, 2000 μm, 5000 μm, 1 cm, 5 cm, 10 cm, or 15 cm, or any range of values therebetween. In some embodiments, the particle size classification device isconfigured to classify or separate relatively larger particles (e.g., subsequent particles) having a D10 particle size of, of about, of at least, or of at least about, 5 μm, 10 μm, 15 μm, 20 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 825 μm, 850 μm, 875 μm, 900 μm, 925 μm, 950 μm, 975 μm, 1000 μm, 11200 μm or 1225 μm, 2000 μm, 5000 μm, 1 cm, 5 cm, or any range of values therebetween. In some embodiments, the particle size classification device is configured to classify or separate relatively smaller particles (e.g., initial particles) having a D50particle size distribution range of, of about, of at most, of at most about, of at least, or of at least about, 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1 μm, 1.1 μm, 1.2 μm, 1.3 μm, 1.4 μm, 1.5 μm, 1.6 μm, 1.7 μm, 1.8 μm, 1.9 μm, 2 μm, 2.1 μm, 2.2 μm, 2.3 μm, 2.4 μm, 2.5 μm, 2.6 μm, 2.7 μm, 2.8 μm, 2.9 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, 105 μm, 110 μm, 115 μm, 120 μm, 125 μm, 130 μm, 135 μm, 140 μm, 145 μm, 150 μm, 155 μm, 160 μm, 165 μm, 170 μm or 175 μm, or any range of values therebetween.

[0148] In some embodiments, the sieve comprises an upper deck sieve and a lower deck sieve. In some embodiments, the particles of the active material precursor is collected between the upper deck sieve and the lower deck sieve. In some embodiments, a cyclone can be used as a particle size classification device. In further embodiments, a cyclone can be used to recirculate materials and / or particles within the chamber. For example, in some embodiments, the cyclone is configured to classify and remove active material precursor subsequent particles from the granulating apparatus. In other embodiments, the cyclone is configured to combine the active material precursor initial particles from the granulating apparatus. In some embodiments, the base of the granulator can be rectangular. In some embodiments, the base of the granulator can be round. In some embodiments, the granulator comprises a filter and / or a cyclone. In some embodiments, for example, a filter can be used to recirculate active material precursor initial particles inside the granulator.

[0149] By way of example, FIG. 8 is a schematic of a system 800 for forming an active material. System 800 includes reactor chamber 801, feed tank 802, granulating apparatus 803, rotary furnace 809, and deagglomeration mill 810. Reactor chamber 801 is influid communication with feed tank 802, and feed tank 802 is in fluid communication with granulating apparatus 803. Granulating apparatus 803 comprises granulator 804, inlet 805, outlet 806, classifying chamber 807, and recirculation mill 808. Feed tank 802 is in fluid communication with inlet 805. In some embodiments, recirculation mill 808 is in fluid communication with inlet 805. In other embodiments, recirculation mill 808 is in fluid communication with granulator 804. In certain embodiments, outlet 806 is in fluid communication with rotary furnace 809. In some embodiments, rotary furnace 809 is in fluid communication with deagglomeration mill 810.

[0150] FIG. 9 presents another example of a system 900 for forming an active material. System 900 includes a mixer 906, granulating apparatus 920, a rotary furnace 919, and deagglomeration mill 918. The feed tanks 901, 902, 903 are in fluid communication with the mixer 906, and the mixer 906 is in fluid communication with granulating apparatus 920. Granulating apparatus 920 comprises a blender 908, granulator 910, and a classifying chamber 922. The ingredients are fed into the mixer 906 from the feeding tanks 901-904 to form a first mixture. The mixer is in fluid communication with the first inlet 925 of the blender 908 and the output 927 of the blender is in communication with the granulator 910. Thus, the first mixture is supplied into the blender 908 and then supplied to the granulator 910 after being blended. In some embodiments, the blender comprises a waring blender and the ingredients may be blended under high shear. The granulator is in fluid communication with the classifying chamber 922 and the classifying chamber is in fluid communication with the second inlet 925 of the blender. In some embodiments, the particles or granules formed in the granulator and classified as not meeting a threshold in the classifying chamber are supplied back into the blender through the second inlet 925. The particles recirculated back to the blender 925 are milled and mixed with additional first mixture. The classifying chamber is also in fluid communication with the rotary furnace and the particles or granules within the desired size range may be supplied to the rotary furnace to be calcinated. In some embodiments, the calcination is with oxygen supplied from oxygen tank 912. In certain embodiments, the rotary furnace 919 is in fluid communication with deagglomeration mill 918. In some embodiments, the calcinated particles may be washed, coated, and / or dried in the chamber 916.

[0151] In some embodiments, the granulator comprises a roller compactor. In some embodiments, a roller compactor may comprise a pair of rollers and a feeding tank. In some embodiments, the ingredients, such as powders, are feed through the feed tank to the rollers. In some embodiments, the two rollers compress the powders to form a dense sheet, ribbons, and / or briquette. The roller compactor may further comprise a size reduction component configured to break down the compacted material into granules of the desired size using milling, grinding equipment, or other methods. In some embodiments, large sized fragments, such as millimeter ranged or centimeter ranged fragments, are produced. In some embodiments, the roller compactor is configured to produce granules having a D50 size of, of about, of at least, of at least about, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 350 μm, 400 μm, 450 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, 1000 μm, 1100 μm, 1200 μm, 1300 μm, 1400 μm, 1500 μm, 1600 μm, 1700 μm, 1800 μm, 1900 μm, 2000 μm, 3000 μm, 5000 μm, 1 cm, 5 cm, 10 cm, or any range of values therebetween. Various designs may be possible for a roller compactor. In some embodiments, the roller compactors can be used herein.

[0152] In some embodiments, the furnace is a continuous furnace configured to continuously convey particles, powders and / or granules. In some embodiments, the furnace does not require or include a crucible. In some embodiments, the furnace comprises or is a non-crucible furnace. In some embodiments, the furnace comprises a furnace chamber. In some embodiments, the furnace chamber is configured to hold the particles. In some embodiments, furnace chamber is connected to a heating source. In some embodiments, the furnace chamber comprises a furnace chamber wall that may be in direct contact with the particles to be heated. In some embodiments, the furnace chamber is configured to heat the particles by conductive heating and / or radiative heating. As such, in some embodiments, such the furnace is configured to contain particles with a particle size distributions (e,g,, D50, D10, D90) or minimum particle sizes as discussed herein. In some embodiments, the furnace comprises a rotary furnace, a roller hearth kiln, a roller hearth furnace, a rotary kiln, a batch furnace, a batch drum furnace, or a crucible pusher kiln. In some embodiments, the furnace can be heated to a temperature of, of about, of at least, or of at least about, 500 °C, 525 °C, 550 °C, 575 °C, 600 °C, 625 °C, 650 °C, 675 °C, 680 °C, 700 °C, 725 °C, 750 °C, 775 °C, 800 °C, 825 °C, 850 °C, 875 °C, 900 °C, 925 °C, 950 °C, 975 °C, 1000 °C, 1025 °C, 1050 °C, 1075°C, 1100 °C, 1125 °C, 1150 °C, 1175 °C, 1200 °C or 1225 °C, or any range of values therebetween. For example, in some embodiments, the furnace can be heated to a temperature of or of about in any one of the following ranges: 500 °C – 1,100 °C, 680 °C – 850 °C, or 700 °C – 800 °C. In some embodiments, the furnace is not required to be able to calcinate or calcine fine particles (e.g., having a D50 particle size less than 20 microns, 50 microns, or 100 microns), which is less efficient than a furnace that cannot accommodate fine particles. In some embodiments, the furnace capable of calcinating the fine particles is more complex than a furnace that is not capable of calcinating the fine particles. In some embodiments, the furnace capable of calcinating the fine particles requires a container or a crucible (e.g., ceramic or metal crucibles) to hold the fine particles to avoid dust or contamination. As there is a container or crucible to hold the particles, the heating may be through irradiative heating alone, which is less efficient relative to other furnaces (e.g., non-crucible furnaces). In some embodiments, a system for forming an active material comprises a continuous process. In some embodiments, the system of a continuous process comprises a chamber, a milling classifier, a recirculation path, and a furnace. For example, FIG.10 is a schematic of a continuous process system 1000 for forming an active material. Continuous process system 1000 includes feed tanks 1001, 1002, and 1003, for storing the ingredients such as an alkali metal source, a second metal source, and a carbon source respectively, a granulating apparatus 1005 comprising a granulator 1004, a recirculation path, a classifier and a mill, a rotary furnace 1006, and a deagglomeration mill 1007.

[0153] In some embodiments, a system for forming an active material comprises a quasi-continuous process. FIG. 11 is a diagram of the stages and related temperatures of a quasi-continuous process for forming an active material, such as a lithium iron phosphate material. For example, at Stage (I) a chamber is prefilled at a temperature of about 240 °C. At Stage (II), a reaction mixture is added to the chamber and the reaction mixture temperature is reduced to about 180 °C. At Stage (III), additional reactants are added to the reaction mixture, and the reaction mixture is increased to about 240 °C. In some embodiments, the additional reactants are added via a sprayer at Stage (III). At Stage (IV), the temperature of the reaction mixture is maintained, and steam is purged out of the system, and the process is repeated. Table 1 summarizes the sequence of a quasi-continuous process for forming a lithium iron phosphate material, according to one embodiment.Table 1 Round Stage (I) Stage (II) Stage (III) Stage (IV) Combining reaction mixture Addition of a comprising iron-bas Maintain 1 Prefill ed phosphorus source, material, a lithium source, such as H temperature and 3PO4, via and a carbon source spray addition purge steam DiscAddition of a phosphorus Addition of a Maintain 2hargeto 50%source, an iron-based lithium sour temperature and material, and a carbon source ce purge steam Addition of a phosphorus Addition of a source, an iron-based solvent, such a Maintain 3Discharges to 50%material, a lithium source, water, via spray temperature and and a carbon source addition purge steam Addition of a phosphorus Addi Maintain 4Dischargesource, an i tion of a to 50%ron-based temperature and material, and a carbon source lithium source purge steam EXAMPLES

[0154] Example embodiments of the present disclosure, including processes, materials and / or resultant products, are described in the following examples. Example 1 – Lithium Iron Phosphate Material Preparation by Spray Granulation

[0155] A slurry comprising 68 kg lactose, 264 kg phosphoric acid, 205 kg iron oxide, 350 kg iron phosphate, 197 kg lithium hydroxide, and 1,140 kg deionized water was prepared in a stirred tank reactor. The slurry comprised of particles with a D50 particle size distribution range of 1 ^P - 4 ^P. The slurry was milled via jet milling to obtain a median particle size of 0.5 ^P or smaller. The milled slurry was calcined under nitrogen atmosphere and heated to about 750 °C for about one hour, and then cooled to room temperature.

[0156] FIG. 12A is an image of lithium iron phosphate precursor initial particles. FIG. 12B is an image of lithium iron phosphate precursor subsequent particles. FIG. 12C is an image of lithium iron phosphate precursor subsequent particles.

[0157] FIG. 13 is an image of the graph of the lithium iron phosphate material prepared by spray granulation. FIG. 14 provides the XRD pattern of lithium iron phosphate material prepared. The resulting lithium iron phosphate material kept the particle size andshowed the XRD pattern of phase pure LFP. Analysis of the XRD pattern of FIG. 14 shows the respective Li / Fe / P ratio and a carbon level of 3%. Example 2 – Cathode Foil Preparation and Electrochemistry

[0158] Cathode foils comprising the lithium iron phosphate material prepared by the process described in Example 1 were prepared. The resulting particle comprised bimodal particles, which provided a high-density electrode. Respective cathode foils were produced with a 90 / 5 / 5 mixture and yielded electrodes with a density of 2.4 g / cc. The electrodes that were tested in coin cells and provided a capacity of 158 mAh / g. FIG. 15 provides the electrochemical performance of the cathode foil comprising the lithium iron phosphate material prepared by the process described to Example 1. Example 3 – Percentage of Iron in the Lithium Channels of Lithium Iron Phosphate Material

[0159] Six samples of lithium iron phosphate material were prepared utilizing the process and systems disclosed herein were prepared (Samples 1-6), and seven comparative samples of lithium iron phosphate were prepared utilizing known processes and systems were prepared (Samples 7-13). The percentage of iron in the lithium channels (FeLi%) of the lithium iron phosphate of each sample prepared was determined and summarized in FIG.16. FIG.16 is a graph of the percentage of iron in the lithium channels (FeLi%) of Samples 1-14. As demonstrated by FIG.16, the percentage of iron in the lithium channels (FeLi%) of the lithium iron phosphate material prepared by the process described herein, such as Samples 1-6, was less than that of the percentage of iron in the lithium channels (FeLi%) of commercially available lithium iron phosphate, 2%. Example 4 – XRD Analysis of Lithium Iron Phosphate Material

[0160] The X-ray diffraction (XRD) spectra of the lithium iron phosphate composition prepared in Example 1 was collected and compared to commercially available lithium iron phosphate. For example, FIGS. 17A and 17B provide XRD patterns of lithium iron phosphate material prepared by the process described to Example 1. The percentage of iron in the lithium channels (FeLi%) of the lithium iron phosphate material of FIG.17A is about 0.817%, while the percentage of iron in the lithium channels (FeLi%) of the lithium ironphosphate material of FIG. 17B is about 0.923%. provides an XRD pattern of lithium iron phosphate with relatively high order prepared by a process according to some embodiments. In comparison, FIGS. 18A and 18B provide XRD patterns of commercially available lithium iron phosphate. The percentage of iron in the lithium channels (FeLi%) of the commercially available lithium iron phosphate tested in FIG. 18A is about 1.584%, while the percentage of iron in the lithium channels (FeLi%) of the commercially available lithium iron phosphate tested in FIG. 17B is about 1.584%.

[0161] Accordingly, lithium iron phosphate material prepared by the process described herein resulted in relatively higher order of iron in the lithium channels compared to commercially available lithium iron phosphate. Example 5 – XRD Analysis of Lithium Iron Phosphate Material Prepared by a Dry Process, compared to Iron(III) Oxide Hydroxide and an LFP Standard

[0162] A mixture comprising P2O5, FeOOH, lithium hydroxide, lactose, and starch was prepared by a dry process. Before calcination, the X-ray diffraction (XRD) spectra of the lithium iron phosphate material was collected and compared to an iron(III) oxide hydroxide standard. FIG. 19A provides the XRD pattern of lithium iron phosphate material before calcination, compared to FeOOH, which was used as the iron-based material in the reaction mixture. FIG. 19B provides the XRD pattern of the lithium iron phosphate material, after calcination at 735 °C for five hours, compared to a lithium iron phosphate standard. Example 6 – XRD Analysis of Lithium Iron Phosphate Material Prepared by a Dry Process, compared to Magnetite and an LFP Standard

[0163] A mixture comprising P2O5, Fe3O4, lithium hydroxide, lactose, and starch was prepared by a dry process. Before calcination, the X-ray diffraction (XRD) spectra of the lithium iron phosphate material was collected and compared to a magnetite standard. FIG. 20A provides the XRD pattern of lithium iron phosphate material before calcination. FIG.20B provides the XRD pattern of the lithium iron phosphate material, after calcination at 735 °C for five hours, compared to a lithium iron phosphate standard.Example 7 –Lithium Iron Phosphate Material Prepared by Spray Granulation

[0164] A mixture comprising FePO4, FeOOH, lithium hydroxide, H3PO4, lactose, and starch was prepared by spray granulation. FIG. 21 is an image of the lithium iron phosphate material prepared by spray granulation. FIG. 22 provides the XRD pattern of lithium iron phosphate material prepared. Example 8 – Lithium Iron Phosphate Material Preparation by a Spray Dryer

[0165] A slurry comprising 0.74 kg lactose, 2.05 kg phosphoric acid (85%), 3.2 kg FeOOH, 1.52 kg LiOH·H2O (57%), 2.08 kg monoammonium phosphate (MAP) (99%), and 15 kg deionized water was prepared in a stirred tank reactor. The slurry was dispersed with a recirculation disperser (IKA) for about one hour to obtain a stable dispersion. The dispersion was spray dried with a two fluid nozzle (3.5 bar air pressure) in a spray drier with outlet temperature of 120 °C and drying gas inlet temperature of 250-300 °C. The resulting powder had a D50particle size distribution of about 6.8 ^P, with a residual moisture of 1-4%.

[0166] The powder was heated to about 750 °C with a heating ramp of 5 °C / min and a dwell time of 60 minutes at max temperature under nitrogen. The calcination was performed in a batch furnace with a crucible under nitrogen atmosphere, in a continuous roller hearth furnace. The calcinated lithium iron phosphate material had a D50 particle size distribution range of 6.7 ^P, and a residual moisture of less than 1,000 ppm. The carbon level of the lithium iron phosphate material was 1.3%, with a BET of 14 m2 / g. FIG.23 is an image of the graph of the lithium iron phosphate material prepared by a spray drying process, and FIG.24 provides the XRD pattern of the prepared lithium iron phosphate material. Example 9 – Cathode Foil Preparation and Electrochemistry

[0167] Cathode foils comprising the lithium iron phosphate material prepared by the process described in Example 8 were prepared. Respective cathode foils were produced with a 90 / 5 / 5 mixture and yielded electrodes with a density of 2.4 g / cc. The electrodes that were tested in coin cells and provided a capacity of 154-155 mAh / g. FIG. 25 provides the electrochemical performance of the cathode foil comprising the lithium iron phosphate material prepared by the process described in Example 8. Compared to the granular material higher processing losses are observed by diffuses losses and handling.Example 10 –Lithium Iron Phosphate Material Prepared by a Wet Milling and Spray Dryer

[0168] A slurry comprising 12.9 kg FePO4, 2.9 kg Li2CO3, 1.7 kg lactose, and 20 kg deionized water was prepared in a stirred tank reactor. The obtained dispersion was spray dried, and a total of 2,440 g of lithium iron phosphate powder was collected. The powder was heated to about 750 °C with a heating ramp of 5 °C / min and a dwell time of 60 minutes at max temperature under nitrogen. The calcination was performed in a batch furnace with a crucible under nitrogen atmosphere, in a continuous roller hearth furnace. The resulting powder had a residual moisture of less than 1,000 ppm and a BET of 17 m2 / g. FIG. 26 provides the XRD pattern of lithium iron phosphate material prepared.

[0169] In addition, cathode foils comprising the lithium iron phosphate material prepared by the process described in Example 9 were prepared. The electrochemical performance tests yielded a product with 153 mAh / g at C / 10 discharge capacity. Example 11 –Lithium Iron Phosphate Material Prepared by Wet Milling and Spray Dryer

[0170] A slurry comprising 11.5 kg LiOH·H2O, 12 kg FeOOH, 20.4 kg FePO4, 15.5 kg H3PO4, 5 kg lactose, and 70 kg deionized water was prepared in a stirred tank reactor. Similarly, another slurry comprising 11.5 kg LiOH·H2O, 12 kg FeOOH, 20.4 kg FePO4, 15.5 kg H3PO4, 5 kg mannitol, and 70 kg deionized water was prepared in a stirred tank reactor. The slurry comprises about 45% of solid content and has a low viscosity. The slurry was wet milled to have a D50 particle size of about 0.5 micron to about 0.8 micron. The obtained dispersion was spray dried at an inlet temperature of about 200oC and a bed temperature of about 95oC. The collected particles were calcinated similar to Example 8.

[0171] FIGS. 27A and 27B are the images of the lithium iron phosphate material formed with lactose before calcination. FIGS.27C and 27D are the images of the lithium iron phosphate material formed with mannitol before calcination. Example 12 –Lithium Iron Phosphate (LFP) Material Prepared by a Spray Dryer

[0172] A suspension comprising 843 kg LiOH, 885 kg FeOOH, 1500 kg FePO4, 1133 kg H3PO4, 367 kg mannitol, and 3350 kg deionized water was prepared in a stirred tank reactor. The suspension comprises about 50wt.% solid content. The suspension was beadmilled to reduce the particle size in two milling passes with 1.2 - 1.4 mm zirconia beads at 75% filling degree. In the first pass, the rotational speed was at 10 m / s at feed rate of 1400 l / h. In the second pass, the rotational speed was at 12 m / s at feed rate of 700 l / h. Table 2 summarizes the particle size before and after jet milling. The suspension was dried in a spray granulation process performed in a fluidized bed. The suspension was sprayed into the process chamber via two fluid nozzle at a nozzle air pressure of 2.6 bar with a spray rate up to 1.5 l / min to a 2300 m3 / h hot air stream at temperature of 153°C. The product temperature was at 86°C. The outlet temperature was at 82°C. The bulk density of the granules was at 630 g / l. The moisture content was at 0.99 wt.%. After spray dry, the granules comprising the lithium iron phosphate (LFP) precursor were formed. Table 2 summaries the particle size of the spray dried granules.

[0173] The granules were calcined for 1 h at 740°C or 780°C in nitrogen atmosphere. The granules were fed to the 1.5° inclined rotary kiln at 50 kg / h. The granules calcinated at 740°C were jet milled at a nozzle air pressure of 3 bar, a classifier speed of 3800 rpm and a throughput of 380 kg / h. The granules calcinated at 780°C were jet milled at a nozzle air pressure of 3 bar, a classifier speed of 4600 rpm and a throughput of 311 kg / h. After calcination, the granules comprising the lithium iron phosphate (LFP) were formed. Table 2 summarizes the particle size characterization of the particles at different stages. Table 2 Spray Calcinated Calcinated Collected Collected Before After Material Dried Granules Granules Powders Powders Jet Jet Characterization Granules at 740°C at 780°C (calcinated (Calcinated Milling Milling at 740°C) at 780°C) 0.16 90 μm 52.8 μm 59.1 μm 0.69 μm 0.89 μm D10 0.57 μm μm 1.18 205 μm 95.2 μm 99.3 μm 2.71 μm 3.03 μm, D50 5.32 μm μm 19.76 3.64 433 μm 181.4 μm 190.8 μm 10.6 μm 7.68 μm D90 μm μm 25.2 / / / / / D99 / μmCarbon level / / / 1.27 wt.% 1.16 wt.% / / Surface area / / 12 m2 22 / g 11.3 m / g / / 18 m / g (BET SSA) 0.75 / / / / / Tap density / g / cm3 / 2.3 / / / / / Pellet density g / cm3

[0174] FIGS.28A and 28B are the particle size distribution plot of the slurry before and after wet milling respectively. As illustrated in FIGS. 28A and 28B, the particle size distribution becomes narrower and the particles sizes are reduced. FIG. 28C illustrates the particle size distribution plot of the slurry after wet milling with mean value, D50, D10, D90 and other parameters. FIG. 28D is an XRD pattern of the spry dried LFP material. FIG. 28E is an image of the LFP granules formed from spray drying. Example 13 –Lithium Iron Phosphate (LFP) Material Prepared by a Spray Dryer

[0175] A suspension comprising 858 kg LiOH, 3000 kg FePO4, 370 kg mannitol, and 3000 kg deionized water was prepared in a stirred tank reactor. The suspension comprises about 56.4 wt.% solid content. The suspension was bead milled to reduce the particle size in two milling passes with 0.6-0.8 mm zirconia beads at 85% filling degree. In the first pass, the rotational speed was at 10 m / s at feed rate of 1000 l / h. In the second pass, the rotational speed was at 12 m / s at feed rate of 1400 l / h. After bead milling, the D50 and D90 particle size of the particles in the suspension were 1.39 μm and 3.15 μm respectively. The suspension was diluted with 300 kg of deionized water to a solid content of 52 wt.% and then dried in a spray granulation process performed in a fluidized bed. The suspension was sprayed into the process chamber via two fluid nozzle at a nozzle air pressure of 2.6 bar with a spray rate up to 1 l / min to a 3000 m3 / h hot air stream at temperature of 117°C. The moisture content was at 1.4 wt.%. The D10, D50 and D90 of the spray dried granules were 116 μm, 174 μm and 256 μm. The bulk density of the granules was at 847 g / l. After spray dry, the granules comprising the lithium iron phosphate (LFP) precursor were formed.

[0176] The granules were calcined for 1 h at 740°C, 760°C, or 780°C in nitrogen atmosphere. The granules were fed to the 1.5° inclined rotary kiln at 40 kg / h at 1.3 rpm. The calcinated granules were jet milled at a nozzle air pressure of 3 bar, a classifier speed of 3000- 5000 rpm and a throughput of 300-400 kg / h. Table 3 summarizes the particle size characterization of the particles at different stages. Table 3 Spray Calcinated Calcinated Calcinated Milled Milled Milled Dried Granules Granules at Granules Collected Collected Collected Material Granules at 740°C 760°C at 780°C Powders Powders Powders Characterization (calcinated (calcinated (Calcinated at 740°C) at 760°C) at 780°C) D10 116 μm, 84.9 μm 99.6 μm, 111.7 μm 0.45 μm, 0.53 μm 0.55 μm D50 174 μm 125.9 μm 150.8 μm 167.5 μm 1.49 μm 1.41 μm 1.49 μm D90 256 μm 186.6 μm 219.9 μm 236.5 μm, 3.33 μm 3.20 μm 3.34 μm Carbon level / 1.77 wt.% 1.8 wt.% 1.79 wt.% / / Surface area / 14.8 m2 / g 15 m2 / g 14.4m2 / g / / (BET SSA) Example 14 – Cathode Foil Preparation

[0177] Cathode foils comprising the LFP active material in Example 12 and commercial LFP material were prepared. The electrode film comprises 93.8 wt% or 96.8 wt% active material.

[0178] FIG. 29A is an SEM image of an electrode film prepared with 93.8wt.% spray dried LFP powder (not wet milled). FIG. 29B is an SEM image of an electrode film prepared with 93.8wt.% spray dried LFP powder (wet milled). FIG. 29C is an SEM image of an electrode film prepared with 93.8wt.% commercial LFP powder.

[0179] FIG. 30 are the electrochemical testing results of the electrodes prepared with spray dried LFP powders (wet-milled and not wet-milled) and commercial LFP. As illustrated in FIG. 30, the spray dried LFP material has similar specific capacity as the commercially available LFP material.Example 15 – Study of Binder Amount

[0180] Lithium iron phosphate with different additives were formed with the methods similar to Example 12. FIGS. 31A-31F are the SEM images of the spray dried LFP granules with 1.6 wt.% Carboxymethyl Cellulose (CMC) binder. FIGS.31G-31K are the SEM images of the spray dried LFP granules with 15 wt.% mannitol binder.

[0181] FIGS. 32A-32F are the SEM images of the spray dried lithium manganese oxide (LMO) granules with 1.6 wt.% Carboxymethyl Cellulose (CMC) binder after calcination. FIGS. 32G-32K are the SEM images of the spray dried LMO granules with 15 wt.% mannitol binder after calcination. The SEM images show that binders cover the surface of the granules, such that there would be no dust escaped from the apparatus during manufacturing.

[0182] FIG.33 are the XRD pattern of the LMO material with different amount of binder. As illustrated in FIG. 33, the calcinated particles with different amount of binders match the XRD pattern of LMO.

[0183] FIGS.34A and 34B are the plots of specific capacity or normalized capacity vs cycle respectively for the commercial LMO material (baseline), spray dried LMO granules with 15wt.% mannitol binder and spray dried LMO granules with 1.6 wt.% CMC binder. As illustrated in FIGS.34A and 34B, the spray dried LMO granules with 15wt.% mannitol binder is more stable comparing to the spray dried LMO granules with 1.6% CMC binder. Example 16 –Lithium Manganese Oxide (LMO) Material Prepared by a Spray Dryer

[0184] A suspension comprising 1234 g Li2CO3, 4800 g Mn3O4, 30.17g CMC, and 7000 g deionized water was prepared in a stirred tank reactor. The suspension comprises about 42 wt.% solid content. The suspension was bead milled to reduce the particle size in one milling pass with 0.6-0.8 mm zirconia beads at 85% filling degree. The rotational speed was at 10 m / s at feed rate of 170 g / min. After bead milling, the D50 and D90 particle size of the particles in the suspension were 1.6 μm and 7.4 μm respectively. The suspension was diluted with deionized water to a solid content of 34 wt.% and then dried in a spray granulation process performed in a fluidized bed. The suspension was sprayed into the process chamber via two fluid nozzle at a nozzle air pressure of 2.6 bar with a spray rate up to 50 g / min to a 75 m3 / h hotair stream at temperature of 100°C. The product temperature was at 87°C. The D50 and D90 of the spray dried granules are 127 μm and 216 μm respectively. The bulk density of the granules was at 951 g / l. The moisture content was at 0.6 wt.%. After spray dry, the granules comprising the lithium manganese oxide (LMO) precursor were formed. Example 17 –Lithium Manganese Oxide (LMO) Material Prepared by a Spray Dryer

[0185] A suspension comprising 1234 g Li2CO3, 4800 g Mn3O4, 905.1g mannitol, and 7000 g deionized water was prepared in a stirred tank reactor. The suspension comprises about 47.1 wt.% solid content. The suspension was bead milled to reduce the particle size in one milling pass with 0.6-0.8 mm zirconia beads at 85% filling degree. The rotational speed was at 10 m / s at feed rate of 85 g / min. After bead milling, the D50 and D90 particle size of the particles in the suspension were 5.6 μm and 8.35 μm respectively. The suspension was diluted with deionized water to a solid content of 38 wt.% and then dried in a spray granulation process performed in a fluidized bed. The suspension was sprayed into the process chamber via two fluid nozzle at a nozzle air pressure of 2.6 bar with a spray rate up to 45 g / min to a 90 m3 / h hot air stream at temperature of 75°C. The product temperature was at 87°C. The D50 and D90 of the spray dried granules are 181 μm and 319 μm respectively. The moisture content was at 0.84 wt.%. After spray dry, the granules comprising the lithium manganese oxide (LMO) precursor were formed. Example 18 – Lithium Iron Manganese Oxide Prepared by a Dryer

[0186] 1360 g of LiOH was dispersed in 7000 g water and neutralized by slowly adding 2650 g of H3PO4solution with 85% concentration by weight. 600 g of mannitol and 1500 g of iron phosphate and 2000 g of manganese oxide were added subsequently. The formed suspension has 45.3 wt.% of solids. The suspension was bead milled to reduce the particle size in a milling pass with 0.6-0.8 mm zirconia beads at 85% filling degree. The rotational speed was at 10 m / s at feed rate of 85 g / min. After bead milling, the D50 and D90 particle size of the particles in the suspension were 0.44 μm and 0.77 μm respectively. The suspension was diluted to a solid content of 43 wt.% and then dried in a spray granulation process performed in a fluidized bed. The suspension was sprayed into the process chamber via two fluid nozzle at a nozzle air pressure of 2.6 bar with a spray rate up to50 g / min to a 96 m3 / h hot air stream at temperature of 88.3°C. The moisture content was at 6.57 wt.%. The D50 and D90 of the spray dried granules were 159 μm and 349 μm. The bulk density of the granules was at 595 g / l. After spray dry, the granules comprising the lithium iron manganese oxide precursor were formed. Example 19 – Ni-containing Cathode Active Material Prepared by a Roller Compactor

[0187] LiOH·H2O and precursor cathode active material (pCAM) Ni83 (Ni0.8Mn0.08Co0.12O) with a Li / Me (Me represents all the metals in the pCAM) molar ratio of about 1:1.02. Other lithium sources and second metal sources were mixed with or without a carbon source as summarized in Table 3 with a Li / Me (Me represents all the metals in the second metal source) molar ratio of about 1:1.02. The powder mixture was jet milled for 1 hours, 5 hours or 10 hours. The jet milled mixture was then fed to the roller compactor. More than 80 wt.% of the granules produced after one recirculation of the initial granules have a D50 particle size more than the desired size. The collected granules were calcinated in a rotary furnace as similar in Example 8 for 1 hour, 5 hours, or 10 hours. FIG.35A is an image of the formed granules having a size larger than the sieve size. FIG.35B is an image of the calcinated granules. Table 4 Sample No. Li source Second Metal Source Carbon Source 9 LiOH·H2O Hydroxide pCAM NCM 811 N / A (Ni0.8Mn0.1Co0.1(OH)2) 10 LiOH·H2O Oxide pCAM NCM 811 N / A (Ni0.8Mn0.1Co0.1O) 11 LiOH·H2O Ni-Hydroxide (Ni(OH)x), Cobalt oxide N / A hydroxide (CoOOH), Mn-oxide (MnxOy) 12 LiOH·H2O Ni metal, Cobalt oxide hydroxide N / A (CoOOH), Mn-Oxide (MnxOy)13 LiOH·H2O Ni Oxide (NixOy), Cobalt oxide N / A (CoxOy), Mn oxide (MnxOy) in a ratio to form NMC 811, Ni83, Ni91, etc. 14 LiOH·H2O Hydroxide pCAM NCM 811 Graphite (Ni0.8Mn0.1Co0.1(OH)2) 15 LiOH·H2O Oxide pCAM NCM 811 Graphite (Ni0.8Mn0.1Co0.1O) 16 LiOH·H2O Ni-Hydroxide (Ni(OH)x), Cobalt oxide Graphite hydroxide (CoOOH), Mn-oxide (MnxOy) 17 LiOH·H2O Ni metal, Cobal oxide hydroxide Graphite (CoOOH), Mn-Oxide (MnxOy) 18 LiOH·H2O Ni Oxide (NixOy), Cobalt oxide Graphite (CoxOy), Mn oxide (MnxOy) in a ratio to form NMC 811, Ni83, Ni91, etc. 19 LiOH·H2O FePO4 Sugar 20 Li2CO3 FeOOH, FePO4, NH4H2PO4 Sugar

[0188] FIGS.36A, 36B and 36C are the SEM images of the mixture jet milled after 1hour, 5 hours, and 10 hours respectively. FIG. 37A is a plot of the first cycle irreversible capacity of a half coin cell with the calcinated granules formed herein as the cathode active material. as illustrated in FIG. 37A, the granules formed with longer calcination time shows larger irreversible capacity. FIG.37B is a plot of the Li / Ni cation mixing in the granules with different calcination time. As illustrated in FIG.37B, with longer calcination time, the Li and Ni cations are mixed better. FIG.38A and FIG. 38B are the XRD pattern of the jet milled powder mixture after 1 hour and 10 hours respectively. As illustrated in FIGS. 38A and 38B, the powder mixture with 1 and 10 hour jet milling has a percentage of the Ni in the Li layer (NiLi%) of 1.795% and 2.815% respectively, which shows that longer jet milling produces better cation mixing. FIG. 39 is a plot of the cycle performance of half coin cells using the calcinated granules as the cathode active material. As illustrated in FIG.39, the half coin cells have initial specific capacity of about 220 mAh / g.

[0189] FIGS. 40A and 40B are images of the large granules prepared by a roller compactor. FIGS. 40C and 40D are granules after calcination.

[0190] While certain embodiments of the inventions have been described, these embodiments have been presented by way of example only, and are not intended to limit the scope of the disclosure. Indeed, the novel methods and systems described herein may be embodied in a variety of other forms. Furthermore, various omissions, substitutions and changes in the systems and methods described herein may be made without departing from the spirit of the disclosure. The accompanying claims and their equivalents are intended to cover such forms or modifications as would fall within the scope and spirit of the disclosure. Accordingly, the scope of the present inventions is defined only by reference to the appended claims.

[0191] Features, materials, characteristics, or groups described in conjunction with a particular aspect, embodiment, or example are to be understood to be applicable to any other aspect, embodiment or example described in this section or elsewhere in this specification unless incompatible therewith. All of the features disclosed in this specification (including any accompanying claims, abstract and drawings), and / or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations where at least some of such features and / or steps are mutually exclusive. The protection is not restricted to the details of any foregoing embodiments. The protection extends to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any novel one, or any novel combination, of the steps of any method or process so disclosed.

[0192] Furthermore, certain features that are described in this disclosure in the context of separate implementations can also be implemented in combination in a single implementation. Conversely, various features that are described in the context of a single implementation can also be implemented in multiple implementations separately or in any suitable subcombination. Moreover, although features may be described above as acting in certain combinations, one or more features from a claimed combination can, in some cases, be excised from the combination, and the combination may be claimed as a subcombination or variation of a subcombination.

[0193] Moreover, while operations may be depicted in the drawings or described in the specification in a particular order, such operations need not be performed in the particular order shown or in sequential order, or that all operations be performed, to achieve desirable results. Other operations that are not depicted or described can be incorporated in the example methods and processes. For example, one or more additional operations can be performed before, after, simultaneously, or between any of the described operations. Further, the operations may be rearranged or reordered in other implementations. Those skilled in the art will appreciate that in some embodiments, the actual steps taken in the processes illustrated and / or disclosed may differ from those shown in the figures. Depending on the embodiment, certain of the steps described above may be removed, others may be added. Furthermore, the features and attributes of the specific embodiments disclosed above may be combined in different ways to form additional embodiments, all of which fall within the scope of the present disclosure. Also, the separation of various system components in the implementations described above should not be understood as requiring such separation in all implementations, and it should be understood that the described components and systems can generally be integrated together in a single product or packaged into multiple products. For example, any of the components for an energy storage system described herein can be provided separately, or integrated together (e.g., packaged together, or attached together) to form an energy storage system.

[0194] For purposes of this disclosure, certain aspects, advantages, and novel features are described herein. Not necessarily all such advantages may be achieved in accordance with any particular embodiment. Thus, for example, those skilled in the art will recognize that the disclosure may be embodied or carried out in a manner that achieves one advantage or a group of advantages as taught herein without necessarily achieving other advantages as may be taught or suggested herein.

[0195] For purpose of this disclosure, in some embodiments, primary particles may be smallest distinct entities from which larger structures, clusters, or aggregates are formed. Conditional language, such as “can,” “could,” “might,” or “may,” unless specifically stated otherwise, or otherwise understood within the context as used, is generally intended to convey that certain embodiments include, while other embodiments do not include, certain features, elements, and / or steps. Thus, such conditional language is not generally intended to imply thatfeatures, elements, and / or steps are in any way required for one or more embodiments or that one or more embodiments necessarily include logic for deciding, with or without user input or prompting, whether these features, elements, and / or steps are included or are to be performed in any particular embodiment.

[0196] Conjunctive language such as the phrase “at least one of X, Y, and Z,” unless specifically stated otherwise, is otherwise understood with the context as used in general to convey that an item, term, etc. may be either X, Y, or Z. Thus, such conjunctive language is not generally intended to imply that certain embodiments require the presence of at least one of X, at least one of Y, and at least one of Z.

[0197] Language of degree used herein, such as the terms “approximately,” “about,” “generally,” and “substantially” as used herein represent a value, amount, or characteristic close to the stated value, amount, or characteristic that still performs a desired function or achieves a desired result. For example, the terms “approximately”, “about”, “generally,” and “substantially” may refer to an amount that is within less than 10% of, within less than 5% of, within less than 1% of, within less than 0.1% of, and within less than 0.01% of the stated amount, depending on the desired function or desired result.

[0198] The scope of the present disclosure is not intended to be limited by the specific disclosures of preferred embodiments in this section or elsewhere in this specification, and may be defined by claims as presented in this section or elsewhere in this specification or as presented in the future. The language of the claims is to be interpreted broadly based on the language employed in the claims and not limited to the examples described in the present specification or during the prosecution of the application, which examples are to be construed as non-exclusive.

Claims

WHAT IS CLAIMED IS:

1. A process of preparing an active material, comprising: combining an alkali metal source and a second metal source to form a first mixture; forming a plurality of initial particles from the first mixture in a chamber; recirculating at least some of the plurality of initial particles to the chamber concurrently during the forming of the plurality of initial particles to form a plurality of subsequent particles; calcinating the plurality of subsequent particles to form a plurality of calcinated particles comprising active material.

2. The process of Claim 1, wherein the combining the alkali metal source and the second metal source comprises milling.

3. The process of Claim 1 or 2, wherein the recirculating at least some of the plurality of initial particles comprises combining the recirculated initial particles with additional first mixture.

4. The process of any one of Claims 1-3, wherein the alkali metal source comprises a lithium source or a sodium source.

5. The process of any one of Claims 1-4, wherein the second metal source comprises Fe, Mn, Mg, Al, Ca, Ti, Co, Ni, Cr, V, or combinations thereof.

6. The process of any one of Claims 1-5, wherein the active material comprises alkali-metal metal phosphate, alkali-metal metal oxide, alkali-metal metal cyanide, or combinations thereof.

7. The process of any one of Claims 1-6, wherein the active material comprises lithium iron phosphate (LFP), lithium nickel manganese cobalt oxide (NMC), lithium nickel manganese oxide (LNMO), lithium nickel cobalt aluminum oxide (NCA), lithium manganese oxide (LMO), lithium cobalt oxide (LCO), a lithium titanate, a lithium nickel cobalt aluminum oxide (NCA), sodium cobalt oxide, sodium iron hexacyanoferrate, sodium manganese oxide, sodium iron phosphate, sodium vanadium phosphate, sodium transition metal oxides, sodium nickel manganese oxide, and combinations thereof.

8. The process of any one of Claims 1-7, wherein the alkali metal source comprises a lithium source and wherein the lithium source is selected from the group consistingof LiOH, LiOHyH2O, Li2CO3, LiPO3, Li3PO3, Li3PO4, LiH2PO4, Li2HPO4, LiH2PO3, Li2HPO3, lithium iron oxides, lithium iron phosphate, and combinations thereof.

9. The process of any one of Claims 1-8, wherein the alkali metal source comprises a sodium source and wherein the sodium source is selected from the group consisting of NaOH, Na2CO3, NaCl, NaHC濢3, NaNO3, Na2SO4, NaPO3, Na3PO4, NaH2PO4, Na2HPO4, sodium poly- and meta- phosphates, and hydrates forms thereof, and combinations thereof.

10. The process of any one of Claims 1-9, wherein the second metal source comprises a nickel-based material.

11. The process of Claim 10, wherein the nickel-based material comprises metallic nickel, nickel oxide, nickel hydroxide, nickel carbonate, and combination thereof.

12. The process of any one of Claims 1-11, wherein the second metal source comprises a manganese-based material.

13. The process of Claim 12, wherein the manganese-based material is selected from the group consisting of metallic manganese, manganese oxide, manganese hydroxide, manganese carbonate, and combination thereof.

14. The process of any one of Claims 1-13, wherein the second metal source comprises a cobalt-based material.

15. The process of Claim 14, wherein the cobalt-based material is selected from the group consisting of metallic cobalt, cobalt oxide, cobalt hydroxide, cobalt carbonate, and combination thereof.

16. The process of any one of Claims 1-15, wherein the second metal source comprises a precursor cathode active material (pCAM).

17. The process of Claim 16, wherein the second metal source comprises hydroxide pCAM, oxide pCAM, or a combination thereof.

18. The process of Claim 16 or 17, wherein the second metal source comprises nickel cobalt manganese hydroxide (hydroxide pCAM NMC), nickel cobalt manganese hydroxide (oxide pCAM NMC), or a combination thereof.

19. The process of any one of Claims 1-18, wherein the initial particles have a D50 SDUWLFOH^VL]H^GLVWULEXWLRQ^UDQJH^IURP^DERXW^^^^^^P^WR^DERXW^^^^^P^20. The process of any one of Claims 1-19, wherein the initial particles have a D10particle size distribution range from about 0.0^^^P^WR^DERXW^5 ^P^ 21. The process of any one of Claims 1-20, wherein the initial particles have a D90 particle size distribution range from about 0.5 ^P^WR^DERXW^50 ^P^ 22. The process of any one of Claims 1-21, wherein the subsequent particles have a D50SDUWLFOH^VL]H^GLVWULEXWLRQ^UDQJH^IURP^DERXW^^^^P^WR^DERXW^5^^^^^^P^ 23. The process of Claim 22, wherein the subsequent particles have a D50particle size distribution range from about 100 ^P^WR^DERXW^5^^^^^^P^ 24. The process of any one of Claims 1-23, wherein the subsequent particles have a D10 particle size distribution range from about 10 ^P^WR^DERXW^1^^^^^^P^ 25. The process of any one of Claims 1-24, wherein the subsequent particles have a D90 particle size distribution range from about 200 ^P^WR^DERXW^5 cm.

26. The process of any one of Claims 1-25, wherein the combining the alkali metal source and the second metal source comprises combining with a liquid and wherein the first mixture is a slurry.

27. The process of Claim 26, wherein the forming the plurality of initial particles comprises spray drying the first mixture.

28. The process of any one of Claims 1-27, wherein the first mixture is substantially free of a liquid.

29. The process of Claim 28, wherein the forming the plurality of initial particles comprises mechanical granulation.

30. The process of Claim 29, wherein mechanical granulation comprises milling, sieving, mixing, blending, compacting, or combinations thereof.

31. The process of any one of Claims 28-30, wherein the forming the plurality of initial particles comprises compacting the first mixture by a roller compactor.

32. The process of any one of Claims 1-31, wherein a percentage of the second metal in alkali metal position in the active material is less than about 2%.

33. The process of any one of Claims 1-32, wherein the first mixture further comprises a carbon source.

34. The process of Claim 33, wherein the carbon source is selected from the group consisting of a sugar, a natural polymer, a synthetic polymer, a carbonaceous material, and combinations thereof.

35. The process of Claim 33 or 34, wherein the carbon source is selected from the group consisting of a monosaccharide, a disaccharide, an oligosaccharide, a starch, a gum, polyvinyl alcohol (PVA), polyethylene glycol (PEG), a sugar alcohol, pitch, coke, asphaltite, uintahite, asphaltum, gilsonite, sweeteners, mannitol, erythritol, polyethylene-polypropylene- oxide block copolymers, detergents, fatty acids, fatty acid esters, modified starches, modified celluloses, carboxy methyl cellulose, graphite, activated carbon, urea, polyvinylpyrrolidone (PVP), styrene-butadiene rubber (SBR), polyvinylidene fluoride (PVDF), and combinations thereof.

36. The process of any one of Claims 33-35, wherein the carbon source comprises less than 2 wt.% ash.

37. The process of any one of Claims 1-36, wherein the first mixture further comprises a functional additive.

38. The process of any one of Claims 1-37, wherein the active material comprises lithium iron phosphate.

39. The process of Claim 38, wherein the first mixture further comprises a phosphorus source.

40. The process of Claim 39, wherein the phosphorus source is selected from the group consisting of H3PO4, H3PO3, P2O5, monoammonium phosphate, diammonium phosphate, urea phosphate, ammonium iron phosphates, lithium iron phosphate, LiPO3, Li3PO4, LiH2PO4, Li2HPO4, LiH2PO3, Li2HPO3, and combinations thereof.

41. The process of any one of Claims 38-40, wherein the second metal source is an iron-based material and wherein the iron-based material is selected from the group consisting of an iron oxide, an anhydrous iron phosphate, an iron phosphate hydrate, an iron metal, and combinations thereof.

42. The process of Claim 41, wherein the iron-based material is selected from the group consisting of FeOOH, FeO, FePO4, Fe2O3, Fe3O4, Fe, Fe3P, Fe2P, metallic iron, and combinations thereof.

43. The process of Claim 42, wherein the iron-based material comprises a phosphorus source.

44. The process of Claim 43, wherein a molar ratio of iron and phosphate in the iron-based material is in a range of about 1:1.5 to 1.5:

1.

45. A system for forming a lithium iron phosphate material, comprising: a housing defining a chamber; a granulating apparatus comprising a granulator in fluid communication with the chamber, the granulating apparatus defining a volume comprising an outlet and an inlet, and a recirculation path in fluid communication with the outlet and the inlet; and a furnace in fluid communication with the outlet, wherein the furnace is configured to contain particles with a D50 particle size distribution of at least about 5 ^m.

46. The system of Claim 45, wherein the granulator comprises a spray dry granulator, a roller compactor, or a combination thereof.

47. The system of Claim 45 or 46, wherein the granulating apparatus further comprises a particle size classification device in fluid communication with the furnace.

48. The system of any one of Claims 45-47, wherein the furnace is a continuous particle conveying furnace.

49. The system of any one of Claims 45-48, wherein the furnace comprises a furnace chamber configured to be in direct contact with at least some of the particles.

50. The system of any one of Claims 45-49, wherein the direct contact between the furnace chamber and the particles provides heat conduction from the furnace chamber to the particles in addition to heat radiation.

51. The system of any one of Claims 45-50, wherein the furnace is a non-crucible furnace.

52. The system of any one of Claims 45-51, wherein the furnace comprises a rotary kiln, a rotary furnace, a roller hearth kiln, a roller hearth furnace, a batch furnace, a batch drum furnace, or a crucible pusher kiln.

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