Active material particles, method therefor, and device useful for the

Abstract

Active materials (e.g., alkali metal phosphates (e.g., lithium iron phosphate), alkali metal oxides, and / or alkali metal cyanide materials), methods of making, and devices useful for their manufacture are described herein. Also described are active material particles (e.g., lithium iron phosphate particles) having a good degree of order prepared by the methods and manufacturing apparatuses disclosed herein.

Description

[0001] INCORPORATION BY REFERENCE OF ANY PRIORITY APPLICATION Any and all applications identified in the Application Data Sheet or the Request filed with the present application as having a foreign or domestic priority claim are incorporated by reference under 37 CFR 1.57 and 4.18 and 20.6, as of the date of filing of the present application, July 12, 2023, and are hereby incorporated by reference in their entirety as if fully set forth below and for all purposes. TECHNICAL FIELD

[0002] The present disclosure relates generally to energy storage devices, and in particular to a method for preparing a cathode active material and a system for forming the same. BACKGROUND

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

[0004] For purposes of summarizing the disclosure and the accomplished advantages, certain objects and advantages of the present disclosure are described herein. Not all of such objects or advantages can be achieved in any particular embodiment. Thus, for example, those skilled in the art will recognize that the application can be practiced with one or more advantages as taught herein without necessarily achieving other objects or advantages as can be taught or suggested by certain described embodiments.

[0005] All of these embodiments are intended to be within the scope of the inventions disclosed herein. These and other embodiments will become apparent to those skilled in the art upon consideration of the detailed description with reference to the accompanying drawings. The application is not limited to any particular preferred embodiment, described herein, with reference to the following detailed description.

[0006] In some aspects, a method of preparing lithium iron phosphate is described. The method includes: combining an iron-based material, a lithium source, and a carbon source to form a first mixture; forming a plurality of initial particles from the first mixture in a chamber; concurrently recycling the plurality of initial particles into the chamber to form a plurality of subsequent particles during the forming of the plurality of initial particles; and calcining the plurality of subsequent particles to form a plurality of calcined 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 H3PO4, H3PO3, P2O5, monoammonium phosphate, diammonium phosphate, urea phosphate, ferric ammonium phosphate, lithium iron phosphate, LiPO3, Li3PO3, Li3PO4, LiH2PO4, Li2HPO4, LiH2PO3, Li2HPO3, and combinations thereof. In some embodiments, the iron-based material is selected from iron oxide, anhydrous iron phosphate, iron phosphate hydrate, iron metal, and combinations thereof. In some embodiments, the iron-based material is selected from FeOOH, FeO, FePO4, Fe2O3, Fe3O4, and combinations thereof. In some embodiments, the iron-based material comprises a phosphorus source. In some embodiments, the molar ratio of iron to 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 LiOH, Li2CO3, LiPO3, Li3PO3, Li3PO4, LiH2PO4, Li2HPO4, LiH2PO3, Li2HPO3, lithium iron oxide, lithium iron phosphate, and combinations thereof. In some embodiments, the carbon source is selected from sugars, natural polymers, synthetic polymers, carbonaceous materials, and combinations thereof. In some embodiments, the carbon source is selected from monosaccharides, disaccharides, oligosaccharides, starch, gums, polyvinyl alcohol (PVA), polyethylene glycol (PEG), sugar alcohols, bitumen, coke, bitumen rock, hard asphalt, tar, natural hard asphalt, sweeteners, mannitol, erythritol, polyoxyethylene-polyoxypropylene block copolymers, detergents, fatty acids, fatty acid esters, modified starch, modified cellulose, carboxymethyl cellulose, graphite, activated carbon, urea, polyvinylpyrrolidone (PVP), styrene-butadiene rubber (SBR), polyvinylidene fluoride (PVDF), and combinations thereof. In some embodiments, the carbon source contains less than 2% by weight of ash. In some embodiments, the first mixture further comprises functional additives.

[0009] In some embodiments, the initial particles have a density of about 0.1 μm to about 10 μm. 50 Particle size distribution range. In some embodiments, the subsequent particles have a Dsize of approximately 5 μm to approximately 1,000 μm. 50 Particle size distribution range. 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 liquid.

[0010] In another aspect, a lithium iron phosphate material is described. The lithium iron phosphate material comprises Di having a diameter of about 100 μm to about 1,000 μm. 50 Lithium iron phosphate particles with varying particle size distributions. In some embodiments, the percentage of iron (Fe) in the lithium channels of the lithium iron phosphate particles. Li(%) less than 2%.

[0011] In another aspect, a system for forming lithium iron phosphate material is described. The system for forming lithium iron phosphate material includes: a chamber; a granulation apparatus including a granulator in fluid communication with the chamber, a device volume comprising an outlet and an inlet, and a recirculation path in fluid communication with the outlet and inlet; and a furnace in fluid communication with the outlet, wherein the furnace is configured to accommodate D 50 Particles with a size distribution of at least about 5 μm.

[0012] In some embodiments, the granulator includes a spray-drying granulator. In some embodiments, the furnace includes 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 method for preparing an active material is disclosed. In some embodiments, the method includes: 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; simultaneously recycling at least some of the plurality of initial particles back to the chamber to form a plurality of subsequent particles during the formation of the plurality of initial particles; and calcining the plurality of subsequent particles to form a plurality of calcined particles containing the active material.

[0014] In some embodiments, combining the alkali metal source and the second metal source includes grinding. In some embodiments, recycling at least some of the initial particles includes combining the recycled initial particles with a further 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 phosphates, alkali metal oxides, alkali metal cyanides, or 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), lithium titanate, lithium nickel cobalt aluminum oxide (NCA), sodium cobalt oxide, sodium iron hexacyanoferrate, sodium manganese oxide, sodium iron phosphate, sodium vanadium phosphate, sodium transition metal oxide, 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 LiOH, LiOH·H2O, Li2CO3, LiPO3, Li3PO3, Li3PO4, LiH2PO4, Li2HPO4, LiH2PO3, Li2HPO3, lithium iron oxide, 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 NaOH, Na2CO3, NaCl, NaHCO3, NaNO3, Na2SO4, NaPO3, Na3PO4, NaH2PO4, Na2HPO4, sodium polyphosphate, and sodium metaphosphate, their hydrated forms, 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 combinations thereof. In some embodiments, the second metal source comprises a manganese-based material. In some embodiments, the manganese-based material is selected from metallic manganese, manganese oxide, manganese hydroxide, manganese carbonate, and combinations thereof. In some embodiments, the second metal source comprises a cobalt-based material. In some embodiments, the cobalt-based material is selected from metallic cobalt, cobalt oxide, cobalt hydroxide, cobalt carbonate, and combinations 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 density of about 0.1 μm to about 10 μm. 50 Particle size distribution range. In some embodiments, the initial particles have a density of approximately 0.01 μm to approximately 5 μm. 10 Particle size distribution range. In some embodiments, the initial particles have a density of approximately 0.5 μm to approximately 50 μm. 90 Particle size distribution range. In some embodiments, the subsequent particles have a Dsize of approximately 5 μm to approximately 5,000 μm. 50 Particle size distribution range. In some embodiments, the subsequent particles have a Dsize of approximately 100 μm to approximately 5,000 μm. 50 Particle size distribution range. In some embodiments, the subsequent particles have a Dsize of approximately 10 μm to approximately 1,000 μm. 10 Particle size distribution range. In some embodiments, the subsequent particles have a density of approximately 200 μm to approximately 5 cm. 90 Particle size distribution range.

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

[0019] In some embodiments, the first mixture is substantially free of liquid. In some embodiments, forming multiple initial particles includes mechanical granulation. In some embodiments, mechanical granulation includes grinding, sieving, mixing, blending, compacting, or a combination thereof. In some embodiments, forming multiple initial particles includes compacting the first mixture using a roller compactor.

[0020] In some embodiments, the percentage of the second metal at the alkali metal site 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 from sugars, natural polymers, synthetic polymers, carbonaceous materials, and combinations thereof. In some embodiments, the carbon source is selected from monosaccharides, disaccharides, oligosaccharides, starch, gums, polyvinyl alcohol (PVA), polyethylene glycol (PEG), sugar alcohols, bitumen, coke, bitumen rock, hard asphalt, tar, natural hard asphalt, sweeteners, mannitol, erythritol, polyoxyethylene-polyoxypropylene block copolymers, detergents, fatty acids, fatty acid esters, modified starch, modified cellulose, carboxymethyl cellulose, graphite, activated carbon, urea, polyvinylpyrrolidone (PVP), styrene-butadiene rubber (SBR), polyvinylidene fluoride (PVDF), and combinations thereof. In some embodiments, the carbon source contains less than 2% by weight of ash. In some embodiments, the first mixture further comprises functional additives.

[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 H3PO4, H3PO3, P2O5, monoammonium phosphate, diammonium phosphate, urea phosphate, ferric ammonium phosphate, 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 said iron-based material is selected from iron oxide, anhydrous iron phosphate, iron phosphate hydrate, iron metal, and combinations thereof. In some embodiments, the iron-based material is selected from 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, the molar ratio of iron to phosphate in the iron-based material is in the range of about 1:1.5 to 1.5:1.

[0022] In another aspect, a system for forming lithium iron phosphate material is disclosed. The system includes: a housing defining a chamber; a granulation apparatus including a granulator in fluid communication with the chamber, the granulation apparatus defining a volume comprising an outlet and an inlet, and a recirculation path in fluid communication with the outlet and inlet; and a furnace in fluid communication with the outlet, wherein the furnace is configured to accommodate D 50 Particles with a size distribution of at least about 5 μm.

[0023] In some embodiments, the granulator includes a spray-dried granulator, a roller compactor, or a combination thereof. In some embodiments, the granulation apparatus further includes a particle size classifier in fluid communication with the furnace. In some embodiments, the furnace is a furnace for continuously conveying particles. In some embodiments, the furnace includes 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 both thermal radiation and thermal conduction from the furnace chamber to the particles. In some embodiments, the furnace is a non-crucible furnace. In some embodiments, the furnace includes a rotary kiln, a rotary furnace, a roller hearth kiln, a batch furnace, a batch drum furnace, or a crucible pusher kiln. Attached Figure Description

[0024] FIG. 1 This is a flowchart of a method for preparing active materials according to some implementation schemes.

[0025] FIG. 2 This is a flowchart of a wet process for preparing active materials according to some implementation schemes.

[0026] FIG. 3 This is a flowchart of a dry method for preparing active materials according to some implementation schemes.

[0027] FIG. 4 This is a flowchart of a method for preparing lithium iron phosphate according to some implementation schemes.

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

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

[0030] FIG. 7A This is a flowchart of a spray drying method for preparing lithium iron phosphate according to some implementation schemes.

[0031] FIG. 7B This is a flowchart of a dry process for preparing lithium iron phosphate according to some implementation schemes.

[0032] FIG. 8This is a schematic diagram of a system for forming active materials via a wet process, according to some implementation schemes.

[0033] FIG. 9 This is a schematic diagram of a system for forming active materials via a dry method, according to some implementation schemes.

[0034] FIG. 10 This is a schematic diagram of a system for forming active materials via a dry method, according to some implementation schemes.

[0035] FIG. 11 This is a schematic diagram of the stages and associated temperatures of a quasi-continuous process for forming active materials according to some implementation schemes.

[0036] FIG. 12A Images of initial particles of lithium iron phosphate precursor according to some implementation schemes.

[0037] FIG. 12B Images of subsequent particles of lithium iron phosphate precursor according to some implementation schemes.

[0038] FIG. 12C Images of subsequent particles of lithium iron phosphate precursor according to some implementation schemes.

[0039] FIG. 13 The images are scanning electron microscope (SEM) images of lithium iron phosphate materials prepared by spray granulation according to some implementation schemes.

[0040] FIG. 14 The image shows the XRD pattern of lithium iron phosphate material obtained by spray granulation according to some implementation schemes.

[0041] FIG. 15 Line graphs showing the electrochemical performance of cathode foils of lithium iron phosphate materials prepared by spray granulation according to some implementation schemes.

[0042] FIG. 16 To determine the percentage of iron (Fe) in the lithium channels of various lithium iron phosphate particles according to some implementation schemes. Li A dot plot of %.

[0043] FIG. 17A XRD patterns of lithium iron phosphate with high order, obtained by methods according to some implementation schemes, are presented.

[0044] FIG. 17B XRD patterns of lithium iron phosphate with high degree of order, obtained by methods according to some implementation schemes, are presented.

[0045] FIG. 18A The XRD pattern of lithium iron phosphate powder with low order is shown.

[0046] FIG. 18B The XRD pattern of lithium iron phosphate powder with low order is shown.

[0047] FIG. 19A The XRD pattern of lithium iron phosphate material prepared by dry method before calcination is presented and compared with the iron(III) hydroxide standard.

[0048] FIG. 19B The XRD pattern of lithium iron phosphate material prepared by dry method after calcination is presented and compared with lithium iron phosphate standard.

[0049] FIG. 20A The XRD pattern of lithium iron phosphate material prepared by dry method before calcination is presented and compared with the standard magnetite raw material.

[0050] FIG. 20B The XRD pattern of lithium iron phosphate material prepared by dry method after calcination is presented and compared with lithium iron phosphate standard.

[0051] FIG. 21 SEM images of lithium iron phosphate materials prepared by spray drying according to some implementation schemes.

[0052] FIG. 22 The image shows the XRD pattern of lithium iron phosphate material prepared by spray drying according to some implementation schemes.

[0053] FIG. 23 Image of lithium iron phosphate material prepared by spray drying.

[0054] FIG. 24 The image shows the XRD pattern of lithium iron phosphate material prepared by spray drying.

[0055] FIG. 25 Line graph showing the electrochemical performance of a cathode foil containing lithium iron phosphate material prepared by spray drying.

[0056] FIG. 26 The image shows the XRD pattern of lithium iron phosphate material prepared by spray drying.

[0057] FIG. 27A and 27B Images of initial particles of spray-dried lithium iron phosphate precursor formed with lactose according to some implementation schemes before calcination.

[0058] FIG. 27C and 27D Images of spray-dried lithium iron phosphate material formed with mannitol according to some implementation schemes before calcination.

[0059] FIG. 28AThe particle size distribution curves of the slurry before wet grinding are shown according to some implementation schemes.

[0060] FIG. 28B The particle size distribution curves of the slurry after wet grinding are shown according to some implementation schemes.

[0061] FIG. 28C This is a particle size distribution curve of the slurry after wet grinding, based on some implementation schemes.

[0062] FIG. 28D XRD patterns of spray-dried lithium iron phosphate precursor particles according to some implementation schemes.

[0063] FIG. 28E Images of spray-dried lithium iron phosphate precursor particles according to some implementation schemes.

[0064] FIG. 29A SEM images of electrode films prepared from 93.8% by weight of spray-dried lithium iron phosphate powder according to some implementation schemes.

[0065] FIG. 29B SEM images of electrode films prepared from 93.8% by weight of spray-dried lithium iron phosphate powder according to some implementation schemes.

[0066] FIG. 29C SEM images of electrode films prepared using 93.8% by weight of commercially available lithium iron phosphate powder according to some implementation schemes.

[0067] FIG. 30 Line graphs showing the electrochemical test results of electrodes prepared using spray-dried and commercially available lithium iron phosphate powder according to some implementation schemes.

[0068] FIG. 31A-31F SEM images of spray-dried lithium iron phosphate particles with 1.5% by weight carboxymethyl cellulose (CMC) binder before calcination, according to some embodiments.

[0069] FIG. 31G-31K SEM images of spray-dried lithium iron phosphate particles with 15% mannitol binder according to some embodiments before calcination.

[0070] FIG. 32A-32F SEM images of spray-dried lithium manganese oxide particles with 1.6% by weight carboxymethyl cellulose (CMC) binder after calcination, according to some embodiments.

[0071] FIG. 32G-32H SEM images of spray-dried lithium manganese oxide particles with 15% mannitol binder according to some embodiments after calcination.

[0072] FIG. 32J-32KSEM images of spray-dried lithium manganese oxide particles with 15% mannitol binder according to some embodiments after calcination.

[0073] FIG. 33 XRD patterns of lithium manganese oxide materials with different amounts of binder after calcination, according to some implementation schemes.

[0074] FIG. 34A Linear graphs of the specific capacity versus cycling of a half-cell having a cathode comprising commercially available lithium manganese oxide material (baseline), spray-dried lithium manganese oxide particles with 15 wt% mannitol binder, and spray-dried lithium manganese oxide particles with 1.6 wt% CMC binder, according to some embodiments.

[0075] FIG. 34B Normalized capacity versus cycling curves for a half-cell having a cathode comprising commercially available lithium manganese oxide material (baseline), spray-dried lithium manganese oxide particles with 15 wt% mannitol binder, and spray-dried lithium manganese oxide particles with 1.6 wt% CMC binder, according to some embodiments.

[0076] FIG. 35A Images of particles formed by a roller compactor according to some implementation schemes before calcination.

[0077] FIG. 35B Images of particles formed by a roller compactor according to some implementation schemes after calcination.

[0078] FIG. 36A SEM images of the mixture after 1 hour of jet milling according to some implementation schemes.

[0079] FIG. 36B SEM images of the mixture after 5 hours of jet milling according to some implementation schemes.

[0080] FIG. 36C SEM images of the mixture after 10 hours of jet milling according to some implementation schemes.

[0081] FIG. 37A Line graph of the first-cycle irreversible capacity of a half-button cell using calcined particles formed from a roller compactor as the cathode active material, according to some implementation schemes.

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

[0083] FIG. 38A XRD pattern of a jet-milled powder mixture after 1 hour, according to some implementation schemes.

[0084] FIG. 38B XRD pattern of a powder mixture after 10 hours of jet milling, according to some implementation schemes.

[0085] FIG. 39 Line graphs showing the cycle performance of half-button batteries using calcined lithium nickel manganese cobalt oxide (NMC) particles as the cathode active material according to some implementation schemes.

[0086] FIG. 40A and 40B Images of large lithium nickel manganese cobalt oxide (NMC) particles obtained by roller compaction according to some implementation schemes before calcination.

[0087] FIG. 40C and 40D Images of large lithium nickel manganese cobalt oxide (NMC) particles obtained by roller compaction according to some implementation schemes after calcination. Detailed Implementation

[0088] This disclosure can be understood by referring to the following detailed description. It should be noted that, for clarity, some elements in the various figures may not be drawn to scale, may be represented in an illustrative or conceptual manner, or may not precisely correspond to certain physical configurations of the embodiments.

[0089] This document provides active materials and precursors for energy storage devices, preparation methods, and various embodiments of devices that can be used in their manufacture. In some embodiments, the active material comprises 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 a combination thereof. In some embodiments, the active material comprises a second metal element. In some embodiments, the second metal element of the active material is selected from Fe, Mn, Mg, Al, Ca, Ti, Co, Ni, Cr, V, and combinations thereof.

[0090] Some embodiments of this disclosure relate to a method for preparing an active material. In some embodiments, the method for preparing an active material includes: preparing a plurality of initial particles of an active material precursor; and recycling at least some of the initial particles to form larger subsequent particles of the active material precursor. Due to the larger size of the subsequent particles and / or the lack of fine particles, high-yield furnaces and / or furnaces incapable of handling fine particles can be used to calcine the subsequent particles. Advantageously, the disclosed method can have high material efficiency, shorter calcination time, and helps to reduce or eliminate corrosion.

[0091] In some embodiments, the subsequent particles of the active material precursor comprise a uniform distribution of the active material precursor and have a well-ordered particle structure. In some embodiments, the subsequent particles of the active material precursor are calcined to form particles of the active material. In some embodiments, the method is a wet method, wherein a solvent is involved in at least one step of the method. In some embodiments, the method is a dry method, wherein no solvent is used or substantially no solvent is used in the method.

[0092] Active material In some embodiments, this document discloses active materials for energy storage devices. In some embodiments, the active material comprises 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 a combination thereof. In some embodiments, the alkali metal element is selected based on the type of energy storage device being manufactured. In some embodiments, for lithium-ion energy storage devices, the alkali metal element comprises lithium. In some embodiments, for sodium-ion energy storage devices, the alkali metal element comprises sodium. In some embodiments, the active material also comprises a second metal element. In some embodiments, the second metal element of the active material is selected from Fe, Mn, Mg, Al, Ca, Ti, Co, Ni, Cr, V, and combinations thereof. In some embodiments, the active material is substantially carbon-free.

[0093] In some embodiments, the active material comprises alkali metal phosphates, alkali metal oxides, and / or alkali metal cyanides (e.g., lithium iron phosphate, sodium iron phosphate, lithium iron oxide, sodium iron oxide, lithium iron cyanide, sodium iron cyanide, sodium transition metal oxide). In some embodiments, the alkali metal phosphate, alkali metal oxide, and / or alkali metal cyanide are selected from lithium iron phosphate (LFP) (e.g., LiFePO4) and lithium nickel manganese cobalt oxide (NMC) (e.g., LiNi). x Mn y Co z O2, where x, y, and z are greater than zero and x + y + z = 1), lithium nickel manganese oxide (LNMO), lithium nickel cobalt aluminum oxide (NCA) (e.g., LiNi x Co y Al z O2, where x, y, and z are greater than zero and x + y + z = 1), lithium manganese oxide (LMO) (e.g., LiMn2O4), lithium cobalt oxide (LCO) (e.g., LiCoO2), lithium titanate (LTO), sodium cobalt oxide (e.g., Na) xCoO2, where x is greater than zero), sodium ferric hexacyanoferrate (e.g., Na) x Fe[Fe(CN)6], where x is greater than zero), sodium manganese oxides (e.g., Na) x MnO2, where x is greater than zero), sodium iron phosphate (e.g., NaFePO4), sodium vanadium phosphate (Na x VOPO4, where x is greater than zero), sodium transition metal oxides (e.g., Na) x MO2, where x is greater than zero), sodium nickel manganese oxides (e.g., NaNi x MnyO2, where x and y are greater than zero and x + y = 1) and combinations thereof. In some embodiments, the molar ratio of the total amount of alkali metal elements to other metals in the active material is, about, at least, at least about, at most, or 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 range thereof.

[0094] In some embodiments, the active material comprises having a diameter of, or is about, or is at least or is 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, etc. 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 D at 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 value range in between 50 Active material particles of varying sizes. For example, in some embodiments, the D of subsequent particles... 50The particle size distribution is in or approximately in any 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 a Dm having a value of at least, about, or 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 value range thereof. 90 Active material particles of varying sizes.

[0096] In some embodiments, the active material comprises a Dm having a value of at least or 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 value range thereof. 10 Active material particles of varying sizes.

[0097] D 50 Particle size represents the median of the particle size distribution; 50% of the sample volume has a smaller particle size than this, i.e., D. 50 The particle size divides the distribution into two halves, one half larger than the given particle size and the other half smaller. D 90 Particle size represents 90% of the sample volume having a particle size smaller than D. 90 Granularity. D 10 Particle size represents 10% of the sample volume with particles smaller than D. 10 Granularity of particle size.

[0098] In some embodiments, the active material particles have a well-ordered particle structure. In some embodiments, the active material particles have a uniform or substantially uniform distribution of active material throughout the particle. 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 (M...) of the second metal in the alkali metal site (e.g., layer, channel)... A The percentage of the second metal in the alkali metal position (M represents the second metal element, and A represents the 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 value range between these values. For example, in some embodiments, the percentage of the second metal in the alkali metal position (M) is... A The percentage is or is 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 site is an alkali metal layer, an alkali metal channel, or other alkali metal site. In some embodiments, a well-ordered structure can improve method yield and efficiency, as well as material properties.

[0099] For example, when the active material is lithium iron phosphate, the percentage of iron (Fe) in the lithium channel... Li The percentage of iron (Fe) is uniform or substantially uniform throughout the particle. In some embodiments, the lithium iron phosphate particles contain lithium iron phosphate with a well-ordered structure, determined by the percentage of iron (Fe) in the lithium channels. Li The percentage (%) indicates the amount of iron in the lithium channel. In some implementations, this percentage is used to represent the percentage of iron (Fe) in the lithium channel. Li The percentage 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 value range between these values. For example, in some embodiments, the percentage of iron (Fe) in the lithium channel... LiThe percentage (%) is or is 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 iron (Fe) in the lithium channel is... Li %) is calculated based on molar ratio.

[0100] Electrode film In some embodiments, the electrode membrane 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 the electrode membrane. In some embodiments, the electrode membrane may comprise active material in any range of 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 between.

[0101] In some embodiments, the electrode membrane comprises a cathode membrane or an anode membrane. In some embodiments, the electrode membrane is an anode electrode membrane. In some embodiments, the anode electrode membrane 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 oxide, silicon carbide, a composite comprising graphite and silicon, tin, tin oxide, germanium, lithium titanate, lithium metal, lithium metal alloys, mixtures, or composites of the foregoing.

[0102] In some embodiments, the electrode membrane is a cathode electrode membrane. In some embodiments, the cathode electrode membrane comprises a cathode active material. In some embodiments, the cathode active material may include, for example, metal oxides, metal sulfides, metal phosphates, or metal cyanides. In some embodiments, the cathode active material comprises alkali metal phosphates, alkali metal oxides, and / or alkali metal cyanide materials.

[0103] In some embodiments, the cathode active material comprises lithium metal oxide, lithium metal phosphate, or lithium metal cyanide. In some embodiments, the lithium metal oxide may be, for example, lithium nickel manganese cobalt oxide (NMC), lithium manganese oxide (LMO), lithium iron phosphate (LFP), lithium cobalt oxide (LCO), lithium titanate (LTO), and / or lithium nickel cobalt aluminum oxide (NCA). In some embodiments, the cathode active material may comprise, for example, layered transition metal oxides (such as LiCoO2 (LCO), Li(NiMnCo)O2 (NMC), and / or LiNi... 0.8 Co 0.15 Al 0.05O2 (NCA)), spinel manganese oxides (such as LiMn2O4 (LMO) and / or LiMn 1.5 Ni 0.5 O4 (LMNO)), olivine (such as LiFePO4), chalcogenides (LiTiS2), tavorite (LiFeSO4F), silicon, silicon oxides (SiO2) x ), aluminum, tin, tin oxide (SnOx), manganese oxide (MnO) x ), molybdenum oxide (MoO2), molybdenum disulfide (MoS2), nickel oxide (NiO x ) or copper oxide (CuO) x The cathode active material may contain sulfur or include sulfur-based materials, such as lithium sulfide (Li₂S), or other sulfur-based materials, or mixtures thereof. In some embodiments, the cathode membrane contains sulfur or includes sulfur-based active materials at a concentration of at least 50% by weight. In some embodiments, the cathode membrane containing sulfur or including sulfur-based active materials has a concentration of at least 10 mAh / cm². 2 The areal capacity. In some embodiments, the cathode membrane containing sulfur or comprising sulfur-active materials has a capacity of 1 g / cm³. 3 The electrode film density. In some embodiments, the cathode film containing sulfur or a material comprising sulfur-active materials also includes 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 (e.g., Na...). x CoO2), sodium ferric hexacyanoferrate (e.g., Na) x Fe[Fe(CN)6]), sodium manganese oxides (e.g., Na) x MnO2), sodium iron phosphate (e.g., NaFePO4), sodium vanadium phosphate (Na x The cathode active material comprises at least one active material formed using the methods or processes disclosed herein, including sodium VOPO4, sodium transition metal oxide (NaxMO2), sodium nickel manganese oxide (NaNi0.5Mn0.5O2), and combinations thereof. In some embodiments, the cathode active material comprises at least one active material formed using the methods or processes disclosed herein.

[0105] In some embodiments, the conductive additive may comprise conductive carbon additives, such as carbon black and / or carbon nanotubes. In some embodiments, the electrode film comprises conductive additives in any range from 6% to about, at least, at least about, at most, or at most about about about 6% by weight, 5% by weight, 4.5% by weight, 4% by weight, 3.5% by weight, 3% by weight, 2.5% by weight, 2% by weight, 1.5% by weight, 1% by weight, or 0.5% by weight. In some embodiments, the electrode film may not contain conductive additives.

[0106] In some embodiments, the electrode membrane comprises a binder in any range of 20% by weight, 15% by weight, 10% by weight, 9% by weight, 8% by weight, 7% by weight, 6% by weight, 5% by weight, 4% by weight, 3% by weight, 2% by weight, 1.5% by weight, or between these percentages. In some embodiments, the binder comprises a polymeric binder material. The binder may include polytetrafluoroethylene (PTFE), polyolefins, polyalkylene compounds, polyethers, styrene-butadiene, polysiloxane copolymers, polysiloxanes, branched polyethers, polyethylene ethers, copolymers thereof, and / or mixtures thereof. The binder may include cellulose, such as carboxymethyl cellulose (CMC). In some embodiments, the polyolefin may include polyethylene (PE), polypropylene (PP), polyvinylidene fluoride (PVDF), copolymers thereof, and / or mixtures thereof. For example, the binder may include polyvinyl chloride, polyphenylene oxide (PPO), polyethylene-polyethylene glycol block copolymer, polyethylene oxide (PEO), polyphenylene oxide (PPO), polyethylene-polyethylene glycol block copolymer, polydimethylsiloxane (PDMS), polydimethylsiloxane-alkylmethylsiloxane copolymer, copolymers thereof, and / or mixtures thereof. In some embodiments, the binder may be a thermoplastic material. In some embodiments, the binder comprises a fibrillable polymer. In some embodiments, the binder comprises PTFE, is substantially composed of PTFE, or is composed of PTFE. In some embodiments, the electrode membrane 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 membrane may be provided with a concentration of approximately 10 mg / cm³. 2 12 mg / cm 2 13 mg / cm 2 14 mg / cm 2 15 mg / cm 2 16 mg / cm 2 17 mg / cm 2 18 mg / cm 2 19 mg / cm 2 20 mg / cm 2 21 mg / cm 2 22 mg / cm 2 23 mg / cm 2 24 mg / cm 2 25 mg / cm 2 26 mg / cm 2 27 mg / cm 228 mg / cm 2 29 mg / cm 2 30 mg / cm 2 40 mg / cm 2 50 mg / cm 2 60 mg / cm 2 70 mg / cm 2 80 mg / cm 2 90 mg / cm 2 Or 100 mg / cm 2 High electrode material loading or high active material loading (which can be expressed as the mass of active material per unit area of ​​electrode film or current collector) or any value range thereof.

[0108] In some embodiments, the electrode film may be provided with a value of approximately 1.5 mAh / cm³. 2 2mAh / cm 2 3 mAh / cm 2 3.5 mAh / cm 2 3.8 mAh / cm 2 4 mAh / cm 2 4.3 mAh / cm 2 4.5 mAh / cm 2 4.8mAh / cm 2 5 mAh / cm 2 5.5 mAh / cm 2 6 mAh / cm 2 6.5 mAh / cm 2 6.6 mAh / cm 2 7 mAh / cm 2 7.5mAh / cm 2 8 mAh / cm 2 or 10 mAh / cm 2 10 mAh / cm 2 20 mAh / cm 2 30 mAh / cm 2 40 mAh / cm 2 50mAh / cm 2 The areal capacity (which can be expressed as the capacity per unit area of ​​electrode film or current collector) or any value range thereof. In some embodiments, the areal capacity is the charging capacity. In other embodiments, the areal capacity is the 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 value between these ranges. In some embodiments, the specific capacity is the charge capacity. In other embodiments, the specific capacity is the discharge capacity. In some embodiments, the electrode may be an anode and / or a cathode. In some embodiments, the specific capacity may be a first charge and / or discharge capacity. In other embodiments, the specific capacity may be the 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 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 thereof, such as 90.1%, 90.5% and 91.9% or any range thereof, for example, the first-cycle coulombic efficiency (which may be expressed as a percentage of discharge capacity divided by charge capacity).

[0111] In some embodiments, the electrode film may provide a discharge capacity retention percentage (which may be expressed by dividing the discharge capacity at a given rate by the initial discharge capacity measured at C / 10) within a range 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 value between these ranges. In some embodiments, the discharge rate used to calculate the capacity retention rate during charge-discharge cycles is at least C / 10, C / 5, C / 3, C / 2, 1C, 1.5C, or 2C, or any value between these ranges.

[0112] Energy storage device In some embodiments, the energy storage device includes, for example, a capacitor, a battery, a capacitor-battery hybrid device, and / or a fuel cell. The energy storage device disclosed herein includes an electrolyte, cathode, anode, separator, and housing discussed herein, wherein the electrolyte, cathode, and anode are disposed within the housing. In some embodiments, the energy storage device provided herein is a lithium-ion battery or a sodium-ion battery. Each of the cathode and anode includes an electrode film forming an electrode and a current collector. The electrode film typically contains one or more active materials, such as the anode active material or cathode active material provided herein.

[0113] Method of making active material A method for preparing active materials for energy storage devices is disclosed. The method may include: combining components to form a first mixture; forming a plurality of initial particles of an active material precursor; recycling at least some of the initial particles; and combining a further portion of the first mixture with the recycled initial particles to form a plurality of subsequent particles. The plurality of subsequent particles may be calcined to form a plurality of calcined particles containing the active material. In some embodiments, calcination may be performed in a furnace not configured to accommodate fine particle sizes (e.g., the initial particles). In some embodiments, the method is a wet method, wherein a solvent is involved in at least one step of the method, such as in the step of forming the first mixture. In some embodiments, the method is a dry method, wherein no solvent is used 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 phosphate precursor, an alkali metal oxide precursor, an alkali metal cyanide precursor, or a combination thereof. In some embodiments, initial particles comprising an alkali metal phosphate precursor, an alkali metal oxide precursor, and / or an alkali metal cyanide precursor may be recycled to form larger subsequent particles comprising the same precursor. In some embodiments, the subsequent particles may be calcined to form alkali metal phosphate particles, alkali metal cyanide particles, and / or alkali metal oxide particles.

[0115] FIG. 1 The diagram schematically illustrates a method 100 for preparing an active material according to some embodiments. For example... FIG. 1As illustrated, method 100 includes forming a first mixture 102 by combining components. In some embodiments, the combined components include a blending component. In some embodiments, the components include an alkali metal source and a second metal source. In some embodiments, the components include an optional carbon source. In some embodiments, the components are ground before combination. In some embodiments, the combined components include a grinding component. In some embodiments, the grinding component includes jet milling. In some embodiments, method 100 further includes a step 104 of forming a plurality of active material precursor particles from the first mixture. In some embodiments, method 100 includes a step 106 of separating particles. In some embodiments, separating particles includes separating subsequent particles from initial particles. In some embodiments, the subsequent particles are particles with a particle size greater than a threshold or within a certain range. In some embodiments, separating particles includes classifying the particles, such as by sieving the particles with a sieve having a threshold sieve aperture size. In some embodiments, method 100 includes collecting subsequent particles 108 containing active material precursors. In some embodiments, method 100 includes recycling initial particles 112. In some embodiments, the initial particles are recycled to step 102 to be mixed with another first mixture. In some embodiments, the initial particles containing the active material precursor are milled before being recycled to step 102. In some embodiments, the recycled particles are milled together with a separate first mixture. (Continue to reference) FIG. 1 Method 100 may further include calcining the collected subsequent particles containing the active material precursor to form a plurality of calcined particles 110 containing the active material. In some embodiments, calcining the collected subsequent particles includes calcination in a crucible. In some embodiments, calcination in this disclosure may be interchanged with roasting. In some embodiments, method 100 is a dry method, wherein no liquid is involved in step 104. In some embodiments, method 100 is a wet method, wherein a liquid is involved in step 104.

[0116] In some embodiments, the methods for preparing the active material include wet processes. For example, FIG. 2This is a flowchart of a wet process 200 for preparing active materials according to some embodiments. The wet process 200 includes forming a first mixture 202 comprising an alkali metal source, a second metal source, a liquid, and optionally a carbon source. In some embodiments, the liquid comprises water. In some embodiments, the first mixture is a slurry. In some embodiments, forming the first mixture includes wet milling the first mixture. In some embodiments, the alkali metal source and the second metal source are milled prior to forming the first mixture. In some embodiments, the wet process 200 includes forming a plurality of active material precursor particles 204 from the first mixture. In some embodiments, forming the plurality of particles includes spray drying the first mixture. In some embodiments, the wet process 200 includes a particle separation step 206. In some embodiments, particle separation includes separating subsequent particles from the initial particles. In some embodiments, the subsequent particles are particles with a particle size greater than a threshold or within a certain range. In some embodiments, particle separation includes particle classification, such as by sieving particles having a threshold sieve aperture size. In some embodiments, the wet process 200 includes collecting subsequent particles 208 containing active material precursors. In some embodiments, the wet process 200 includes recycling initial particles 212. In some embodiments, the initial particles are recycled to step 202 to be mixed with a further first mixture. In some embodiments, the particles containing the active material precursor are milled before being recycled to step 202. In some embodiments, the recycled particles are milled together with a further first mixture. In some embodiments, the particles containing the active material precursor are milled before being recycled to step 202. In some embodiments, the recycled particles are milled together with a further first mixture. The collected subsequent particles containing the active material precursor are calcined to form a plurality of calcined particles 210 containing the active material.

[0117] In some embodiments, the methods for preparing the active materials include dry methods. For example, FIG. 3This is a flowchart of a 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 free of or substantially free of any solvent. In some embodiments, the dry process 300 includes forming a plurality of active material precursor particles 304. In some embodiments, forming the plurality of particles includes mechanical granulation. In some embodiments, forming the plurality of particles includes compacting the first mixture. In some embodiments, the dry process 300 includes a particle separation step 306. In some embodiments, particle separation includes separating subsequent particles from the initial particles. In some embodiments, the subsequent particles are particles with a particle size greater than a threshold or within a certain range. In some embodiments, particle separation includes particle classification, such as by sieving particles having a threshold sieve aperture size. In some embodiments, the dry process 300 includes collecting subsequent particles 308 containing the active material precursor. In some embodiments, the dry process 300 includes recycling the initial particles 312. In some embodiments, the initial particles are recycled to step 302 to be mixed with another first mixture. In some embodiments, the particles containing the active material precursor are milled before being recycled to step 302. In some embodiments, the recycled particles are milled together with a further first mixture. In some embodiments, the particles containing the active material precursor are milled before being recycled to step 302. In some embodiments, the recycled particles are milled together with a further first mixture. The plurality of collected subsequent particles are calcined to form a plurality of calcined particles 312 containing the active material.

[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 LiOH, LiOH·H₂O, Li₂CO₃, LiPO₃, Li₃PO₃, Li₃PO₄, LiH₂PO₄, Li₂HPO₄, LiH₂PO₃, Li₂HPO₃, lithium iron oxide, lithium iron phosphate, their hydrated forms, and combinations thereof. In some embodiments, the sodium source is selected from NaOH, Na₂CO₃, NaCl, NaHCO₃, NaNO₃, Na₂SO₄, NaPO₃, Na₃PO₄, NaH₂PO₄, Na₂HPO₄, sodium polyphosphate, and sodium metaphosphate, their hydrated forms, and combinations thereof.

[0119] In some embodiments, the second metal element of the active material is selected from Fe, Mn, Mg, Al, Ca, Ti, Co, Ni, Cr, V, and combinations thereof. In some embodiments, the second metal source comprises any form of metal, oxide, hydroxide, or second metal. In some embodiments, the second metal source comprises iron-based materials, nickel-based materials, manganese-based materials, cobalt-based materials, aluminum-based materials, or combinations thereof. In some embodiments, the iron-based material is selected from iron oxide, anhydrous iron phosphate, iron phosphate hydrate, iron metal, and combinations thereof. In some embodiments, the iron-based material is selected from FeOOH, FeO, FePO4, Fe2O3, Fe3O4, Fe4(P2O7)3, FeCO3, etc. 3、 Fe2(CO3)3, Fe3P, Fe2P, siderite, FeC2O4, Fe3(PO4)2, Fe2O7P2, FeSO4, FeF2, FeF 3、 Fe(C5H7O2)3, FeBr 3、 FeCl3, ferric chloride oxychloride (III), FeO(OH), FeI3, Fe(NO3)3, Fe3(PO4)2, Fe2(SO4)3, FeSCN 2+ Ferrous gluconate, ferrous lactate, Fe2N, Fe3N4, Fe4N, Fe7N3, Fe 16 N2, Fe(CO)5, FeH3O3P, ferric tartrate, ammonium iron phosphate, lithium iron phosphate, iron pyrophosphate, iron-containing alloys, iron-containing scrap metal, ferrous metals, ferrous metal alloys, cast iron, and their hydrated forms and combinations thereof. In some embodiments, the nickel-based material comprises metallic nickel, nickel oxide, nickel hydroxide, nickel carbonate, and combinations thereof. In some embodiments, the manganese-based material is selected from metallic manganese, manganese oxide, manganese hydroxide, manganese carbonate, and combinations thereof. In some embodiments, the cobalt-based material is selected from metallic cobalt, cobalt oxide, cobalt hydroxide, cobalt carbonate, and combinations thereof. In some embodiments, the second metal source comprises a precursor that is free of alkali metals in the intended active material. 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 combinations thereof. In some embodiments, the second metal source comprises nickel cobalt manganese hydroxide (hydroxide pCAM NMC), nickel cobalt manganese hydroxide (oxide pCAM NMC), or combinations thereof.

[0120] In some embodiments, the molar ratio of the alkali metal source to 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 thereof.

[0121] In some embodiments, the first mixture contains a carbon source. In some embodiments, the carbon source is selected from sugars, natural polymers, synthetic polymers, carbonaceous materials, and combinations thereof. In some embodiments, the carbon source is selected from monosaccharides, disaccharides, oligosaccharides, starch, gums, polyvinyl alcohol (PVA), polyethylene glycol (PEG), sugar alcohols, bitumen, coke, bitumen rock, hard asphalt, tar, natural hard asphalt, sweeteners, mannitol, erythritol, polyoxyethylene-polyoxypropylene block copolymers, detergents, fatty acids, fatty acid esters, modified starch, modified cellulose, carboxymethyl cellulose, graphite, activated carbon, urea, polyvinylpyrrolidone (PVP), styrene-butadiene rubber (SBR), polyvinylidene fluoride (PVDF), and combinations thereof. In some embodiments, the carbon source contains a detergent. In some embodiments, the surface of the carbon source is modified with functional groups. In some embodiments, the carbon source acts as a binder. In some embodiments, the carbon source is added to the first mixture when the expected active material contains phosphorus. In some embodiments, when the expected active material does not contain phosphorus, the first mixture does not contain a carbon source. In some embodiments, the amount of ash in the carbon source is, about, at most, or 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 value between these ranges. In some embodiments, the carbon source contains a detergent with less than 1 wt% ash. In some embodiments, the detergent contains a nonionic surfactant.

[0122] In some embodiments, the first mixture comprises a liquid. In some embodiments, the liquid comprises water. In some embodiments, the first mixture contains no or substantially no liquid and / or water. In some embodiments, water (e.g., vapor) formed by the reaction of the components of the first mixture is extracted from the reaction chamber. In some embodiments, the first mixture is free of detectable processing solvents, processing solvent residues, or processing solvent impurities. Processing solvents or conventional 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 also comprises functional additives. In some embodiments, the functional additives are selected from dispersants, defoamers, colorants, sweeteners, dopants, coating additives, metal oxides, boric acid, borates, graphite, and combinations thereof.

[0123] In some embodiments, the components, such as an alkali metal source and / or a second metal source, are primary particles before being combined to form the first mixture. In some embodiments, the components are ground before being combined to form the first mixture. In some embodiments, the first mixture is ground before forming the initial particles. In some embodiments, the component has a thickness of, about, up to, or up to 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 D at µm, 75 µm, 80 µm, 85 µm, 90 µm, 95 µm, 100 µm, 125 µm or 150 µm or any value range therebetween 50 granularity.

[0124] In some embodiments, the initial particles of the active material precursor have a particle size of 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, or more than 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, 1.0 ... 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 D at µm, 70 µm, 75µm, 80 µm, 85 µm, 90 µm, 95 µm, 100 µm, 125 µm or 150 µm or any value range therebetween 50 Particle size distribution range. For example, in some embodiments, the D of the precursor particles... 50 The particle size distribution is in or about any 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 particles formed directly from the first mixture prior to recycling any active substance precursor particles.

[0125] In some embodiments, the initial particles of the active material precursor have a particle size of 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, or more than 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, 1.0 µm, or more than about 0.1 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, 1.0 µm, 0.02 µm, 0.05 µm, 0.05 µm, 0.05 µm, 0.05 µm, 0.05 µm, 0 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 D at µm, 55 µm, 60 µm, 65 µm, 70 µm, 75 µm, 80 µm, 85 µm, 90 µm, 95 µm, 100 µm or any value range in between 10 Particle size distribution range.

[0126] In some embodiments, the initial particles of the active material precursor have a particle size of 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, or more than 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, 2.0 ... 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 D at µm, 1000 µm or any value range in between 90 Particle size distribution range.

[0127] In some embodiments, all or substantially all of the subsequent particles generated in the methods disclosed herein have a particle size of at least, at least about 20 µm, 50 µm, 100 µm, or any range thereof. In some embodiments, the methods disclosed herein are a dust-free method in which no or substantially no subsequent particles with a particle size smaller than, less than about 20 µm, 50 µm, or 100 µm are generated.

[0128] In some implementations, the collected subsequent particles comprise D values ​​of at least or 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 thereof. 50 granularity.

[0129] In some implementations, the collected subsequent particles comprise D values ​​of at least or 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 thereof. 90 granularity.

[0130] In some implementations, the collected subsequent particles have a Dm of at least or 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 value range thereof. 10 granularity.

[0131] In some implementations, if subsequent particles cannot pass through a sieve having an aperture size of at least 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 value between thereof, they are collected.

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

[0133] In some embodiments, at any given time during the process, some initial particles, none of the initial particles, or all of the initial particles may be recycled to form subsequent particles. In some embodiments, the initial particles are recycled at a recycling rate of 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 ​​between these values ​​(e.g., 1-50%, 5-45%, 10-25%, 30-60%, 40-55%) to form subsequent particles.

[0134] In some embodiments, the collected and / or subsequent particles are calcined. In some embodiments, calcination is carried out at an oxidizing gas concentration (e.g., air, oxygen, oxygen-containing gas, oxygen-enriched air) of 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 value between these ranges. In some embodiments, calcination is carried out under an inert atmosphere. In some embodiments, calcination is carried out under nitrogen. In some embodiments, calcination is carried out under argon. In some embodiments, calcination is carried out in the presence of a reducing gas selected from hydrogen, methane, natural gas, propane, butane, carbon monoxide, and combinations thereof. In some embodiments, the concentration of the reducing gas is approximately, at most, or 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 value between these ranges. In some embodiments, calcination is carried out in air, oxygen, oxygen-enriched air, and / or ozone. In some embodiments, calcination is carried out in a gas mixture. In some embodiments, for example, calcination is carried out in a mixture of inert and reducing gases. In some embodiments, calcination is carried out in a furnace such as a rotary kiln. In some embodiments, the duration of calcination is, about, at least, at least about, at most, 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 value range between these. In some embodiments, the duration of calcination is, about, at least, at least about, at most, at most about 100°C, 200°C, 300°C, 400°C, 500°C, 600°C, 700°C, 800°C, 900°C, 1000°C, 1200°C, 1500°C, 2000°C, or any value range between these.

[0135] The methods disclosed herein for forming active materials are general and applicable to a wide variety of active materials. Advantageously, in some embodiments, the disclosed methods shorten calcination time, improve yield, improve batch-to-batch consistency, and simplify calcination and grinding steps. In some embodiments, the particles formed during the process can have a particle size greater than 100 micrometers, making the method dust-free (i.e., not forming particles smaller than 20, 50, or 100 micrometers). Advantageously, dust-free methods can help make the production environment safer, healthier for workers, improve product quality, and reduce production costs.

[0136] Method of making lithium iron phosphate The method disclosed herein may include: combining an iron-based material, a carbon source, and a lithium source to form a first mixture; mixing the first mixture to form a plurality of initial particles; and combining the first mixture with the plurality of initial particles to form a plurality of subsequent particles. The plurality of subsequent particles may be calcined to form a plurality of calcined particles containing lithium iron phosphate. In some embodiments, calcination may be performed in a furnace not configured to accommodate fine particle sizes (e.g., initial particles). For example, FIG. 4 This is a flowchart of a method 400 for preparing lithium iron phosphate according to one embodiment. Method 400 includes forming a first mixture 402 comprising an iron-based material, a lithium source, and a carbon source. The first mixture is mixed to form a plurality of initial particles 404. In step 406, the plurality of initial particles are recycled and 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 calcined to form a plurality of calcined particles 410 comprising lithium iron phosphate. In some embodiments, the lithium iron phosphate 410 comprises a carbon coating.

[0137] In some embodiments, the method for preparing lithium iron phosphate includes a wet process. For example, FIG. 5 This is a flowchart of a wet process 500 for preparing lithium iron phosphate according to one embodiment. The wet process 500 includes forming a first mixture 502 comprising an iron-based material, a lithium source, a carbon source, and a liquid. The first mixture 504 is dried to form a plurality of initial particles 506. The plurality of initial particles are recycled 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 calcined to form a plurality of calcined particles 512 containing lithium iron phosphate.

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

[0139] Iron-based materials contain iron. In some embodiments, the iron-based material is selected from iron oxide, anhydrous iron phosphate, iron phosphate hydrate, iron metals, and combinations thereof. In some embodiments, the iron-based material is selected from FeOOH, FeO, FePO4, Fe2O3, Fe3O4, Fe4(P2O7)3, FeCO3, etc. 3、 Fe2(CO3)3, Fe, Fe3P, Fe2P, siderite, FeC2O4, Fe3(PO4)2, Fe2O7P2, FeSO4, FeF2, FeF 3、 Fe(C5H7O2)3, FeBr 3、 FeCl3, ferric chloride (III), FeI3, Fe(NO3)3, Fe3(PO4)2, Fe2(SO4)3, FeSCN 2 + Ferrous gluconate, ferrous lactate, Fe2N, Fe3N4, Fe4N, Fe7N3, Fe 16 N2, Fe(CO)5, FeH3O3P, ferric tartrate, ammonium iron phosphate, iron-containing alloys, iron-containing scrap metal, iron powder, cast iron, and their hydrated forms, as well as combinations thereof. In some embodiments, the lithium source is selected from LiOH, LiOH·H2O, Li2CO3, LiPO3, Li3PO3, Li3PO4, LiH2PO4, Li2HPO4, LiH2PO3, Li2HPO3, lithium iron oxide, lithium iron phosphate, and their hydrated forms, as well as combinations thereof.

[0140] In some embodiments, the first mixture contains a phosphorus source. In some embodiments, the iron-based material contains a phosphorus source. In some embodiments, the phosphorus source is different from the iron-based material. In some embodiments, the phosphorus source is selected from H3PO4, H3PO3, P2O5, monoammonium phosphate, diammonium phosphate, urea phosphate, iron ammonium phosphate, lithium iron phosphate, LiPO3, Li3PO3, Li3PO4, LiH2PO4, Li2HPO4, LiH2PO3, Li2HPO3, and combinations thereof. In some embodiments, the molar ratio of iron to phosphate in the first mixture is, about, at least or 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 thereof. For example, in some embodiments, the molar ratio of the iron-based material to phosphoric acid is in or about any 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.

[0141] System for forming active material Some embodiments of this disclosure relate to a system for forming an active material such as lithium iron phosphate. In some embodiments, the system for forming the active material includes 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 with the plurality of precursor particles to form a plurality of subsequent particles. In some embodiments, the plurality of subsequent particles are calcined in a furnace to form a plurality of calcined particles containing lithium iron phosphate.

[0142] In some implementations, the system for forming the active material includes a chamber, a spray dryer, and a furnace. For example, FIG. 7A This is a flowchart of a spray drying method for preparing active materials such as lithium iron phosphate. FIG. 7A As illustrated, in some embodiments, iron-based materials, lithium sources, phosphorus sources, carbon sources, and water are combined and stirred in a first reactor. Other formulations may be used for different active materials. FIG. 7AAs illustrated, the resulting mixture is passed through a spray dryer to form multiple initial particles. These initial particles are then recycled and mixed in a second reactor to form multiple subsequent particles. In some embodiments, the resulting mixture is passed through a spray dryer to form subsequent particles. These subsequent particles are then dried in a furnace to form multiple calcined particles containing lithium iron phosphate.

[0143] In some implementations, the system used to form the active material is a dry process system. For example, FIG. 7B This is a flowchart of a dry process for preparing active materials such as lithium iron phosphate. FIG. 7B As illustrated, in some embodiments, iron-based materials, lithium sources, phosphorus sources, and carbon sources are combined and mixed in a reactor to form a first mixture. Other formulations can be used to form other active materials. In some embodiments, such as... FIG. 7B As shown, the lithium, phosphorus, and carbon sources of the first mixture are reacted to form a plurality of initial particles. In some embodiments, the plurality of initial particles are recycled and reacted with an additional amount of the iron-based material, lithium, phosphorus, and carbon sources of the first mixture to form a plurality of subsequent particles. The plurality of subsequent particles are passed through a furnace to form a plurality of calcined particles containing lithium iron phosphate.

[0144] In some embodiments, the system for forming the active material includes a chamber, a granulation device, a recirculation path, and a furnace. In some embodiments, the chamber contains a fluidized bed. In some embodiments, the fluidized bed is configured to suspend the active material precursor particles within the fluidized medium by upward flow or recirculation of the fluidizing medium. In some embodiments, the fluidizing medium can be a gas such as air or nitrogen, or a liquid such as water or a solvent.

[0145] In some embodiments, the granulation apparatus includes a granulator in fluid communication with a chamber, a device volume including an outlet and an inlet, and a recirculation path in fluid communication with said outlet and inlet. In some embodiments, the granulator includes a spray-dried granulator, a compactor, or a combination thereof. In some embodiments, the compactor includes a roller compactor. In some embodiments, the furnace is in fluid communication with an outlet. In some embodiments, the furnace is configured to contain materials having a diameter of at least 1 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, 150 µm, 175 µm, 200 µm, 225 µm, or 250 µm. 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 D in the range of µm, 1 cm, 5 cm, 10 cm or any value in between 50Particles with a particle size distribution. In some embodiments, the furnace is configured to contain particles having a D-size distribution of at least or 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 value between thereof. 90 Particles of a particle size. In some embodiments, the furnace is configured to contain particles having a D-value of at least or 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 value between thereof. 10 Particle size.

[0146] In some embodiments, the system further includes a deagglomerating mill. In some embodiments, the deagglomerating mill is selected from jet mills, crushers, roller mills, impact classifiers, spiral jet mills, and ball mills. In some embodiments, the system further includes a recirculating mill. In some embodiments, the recirculating mill includes a pin-disc mill or a roller mill. In some embodiments, the system includes at least one of a mechanical post-granulator, a high-intensity mixer, a blender, a cyclone recirculation unit, a mill recirculator, and a classifier recirculator. In some embodiments, the mechanical granulator includes a compactor.

[0147] In some embodiments, the system further includes a particle size classification device. In some embodiments, the particle size classification device includes a classifier, an air classifier, a cascade classifier, a sieve, a cyclone separator, a centrifuge, a filter, or a combination thereof. In some embodiments, the screen is a rotating screen, a drum screen, a jet screen, a vibrating screen, or a percussion screen.In some embodiments, the particle size classification device is configured to have a D of, of about, at most, at most about, at least, or at least about 1 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, 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 value range therebetween. [[ID=~1]] 50Relatively large particles (e.g., subsequent particles) within a particle size distribution range are graded or separated. In some embodiments, the particle size classification device is configured to pair particles having a value of D of at least or 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 thereof. 90 Relatively large particles (e.g., subsequent particles) are graded or separated. In some embodiments, the particle size classification device is configured to pair particles having a value of D0 of at least or 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 thereof. 10Relatively large particles (e.g., subsequent particles) are graded or separated. In some embodiments, the particle size classification device is configured in pairs to have a particle size of at least or 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, etc. 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, 75µm, 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 D at µm, 150 µm, 155 µm, 160 µm, 165 µm, 170 µm or 175 µm or any value range therebetween 50 Relatively small particles (e.g., initial particles) within a particle size distribution range are classified or separated.

[0148] In some embodiments, the sieve comprises an upper sieve and a lower sieve. In some embodiments, active material precursor particles are collected between the upper and lower sieves. In some embodiments, a cyclone separator can be used as a particle size classification device. In other embodiments, a cyclone separator can be used to recirculate the material and / or particles within the chamber. For example, in some embodiments, the cyclone separator is configured to classify and remove subsequent particles of the active material precursor from the granulation unit. In other embodiments, the cyclone separator is configured to combine the initial particles of the active material precursor from the granulation unit. In some embodiments, the base of the granulator can be rectangular. In some embodiments, the base of the granulator can be circular. In some embodiments, the granulator includes a filter and / or a cyclone separator. In some embodiments, for example, a filter can be used to recirculate the initial particles of the active material precursor within the granulator.

[0149] For example, FIG. 8 This is a schematic diagram of a system 800 for forming active materials. System 800 includes a reactor chamber 801, a feed tank 802, a granulation device 803, a rotary kiln 809, and a deagglomeration mill 810. The reactor chamber 801 is in fluid communication with the feed tank 802, and the feed tank 802 is in fluid communication with the granulation device 803. The granulation device 803 includes a granulator 804, an inlet 805, an outlet 806, a classification chamber 807, and a recirculating mill 808. The feed tank 802 is in fluid communication with the inlet 805. In some embodiments, the recirculating mill 808 is in fluid communication with the inlet 805. In other embodiments, the recirculating mill 808 is in fluid communication with the granulator 804. In some embodiments, the outlet 806 is in fluid communication with the rotary kiln 809. In some embodiments, the rotary kiln 809 is in fluid communication with the deagglomeration mill 810.

[0150] FIG. 9 Another example of a system 900 for forming an active material is presented. System 900 includes a mixer 906, a granulation unit 920, a rotary kiln 919, and a deagglomeration mill 918. Feed tanks 901, 902, and 903 are in fluid communication with mixer 906, and mixer 906 is in fluid communication with granulation unit 920. Granulation unit 920 includes a blender 908, a granulator 910, and a classification chamber 922. Components are fed from feed tanks 901-904 into mixer 906 to form a first mixture. The mixer is in fluid communication with a first inlet 925 of blender 908, and the outlet 927 of blender 927 is in fluid communication with granulator 910. Thus, the first mixture is fed into blender 908 and then, after blending, into granulator 910. In some embodiments, the blender includes a Waring blender, and the components can be blended under high shear. The granulator is in fluid communication with the classification chamber 922, which is in fluid communication with the second inlet 925 of the mixer. In some embodiments, particles or particles formed in the granulator and classified as not meeting the threshold in the classification chamber are fed back to the mixer through the second inlet 925. The particles recycled back to the mixer 925 are ground and mixed with another first mixture. The classification chamber is also in fluid communication with a rotary kiln, and particles or particles within the desired size range can be fed to the rotary kiln for calcination. In some embodiments, calcination uses oxygen supplied from an oxygen tank 912. In some embodiments, the rotary kiln 919 is in fluid communication with a deagglomeration mill 918. In some embodiments, the calcined particles can be washed, coated, and / or dried in chamber 916.

[0151] In some embodiments, the pellet mill includes a roller compactor. In some embodiments, the roller compactor may include a pair of rollers and a feed hopper. In some embodiments, an ingredient, such as powder, is fed to the rollers through the feed hopper. In some embodiments, the two rollers compress the powder into dense sheets, strips, and / or briquettes. The roller compactor may also include a size-reducing component configured to break the compacted material into particles of the desired size using grinding, abrasive equipment, or other methods. In some embodiments, large-size fragments, such as millimeter- or centimeter-sized fragments, are produced. In some embodiments, the roller compactor is configured to produce a diameter of at least 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 Particles with a D50 size of cm, 10 cm, or any value in between. Roller compactors can have various designs. In some embodiments, a roller compactor may 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 does not include a crucible. In some embodiments, the furnace includes or is a crucible-free furnace. In some embodiments, the furnace includes a furnace chamber. In some embodiments, the furnace chamber is configured to hold particles. In some embodiments, the furnace chamber is connected to a heating source. In some embodiments, the furnace chamber includes a chamber wall that can directly contact the particles to be heated. In some embodiments, the furnace chamber is configured to heat the particles by conductive heating and / or radiant heating. Therefore, in some embodiments, such a furnace is configured to accommodate particles having a particle size distribution as discussed herein (e.g., D...). 50 D 10 D 90The furnace may contain particles of the smallest possible size or the smallest particle size. In some embodiments, the furnace includes a rotary kiln, 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 may be heated to a temperature of 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 value between these values. For example, in some embodiments, the furnace can be heated to temperatures in or about any of the following ranges: 500°C – 1,100°C, 680°C – 850°C, or 700°C – 800°C. In some embodiments, the furnace does not need to be capable of calcining or roasting fine particles (e.g., having a D50 particle size of less than 20 micrometers, 50 micrometers, or 100 micrometers), which is less efficient than furnaces that cannot accommodate fine particles. In some embodiments, furnaces capable of calcining fine particles are more complex than those that cannot. In some embodiments, furnaces capable of calcining fine particles require containers or crucibles (e.g., ceramic or metal crucibles) to hold the fine particles to avoid dust or contamination. Due to the presence of containers or crucibles for holding the particles, heating can only be achieved through radiation, which is less efficient compared to other furnaces (e.g., non-crucible furnaces). In some embodiments, the system for forming the active material includes a continuous process. In some embodiments, the continuous process system includes a chamber, a grinding classifier, a recycling path, and a furnace. For example, FIG. 10 This is a schematic diagram of a continuous process system 1000 for forming active materials. The continuous process system 1000 includes feed tanks 1001, 1002, and 1003, which are used to store components such as an alkali metal source, a second metal source, and a carbon source, respectively; a granulation device 1005, which includes a granulator 1004, a recycling path, a classifier, and a mill; a rotary kiln 1006; and a deagglomeration mill 1007.

[0153] In some implementations, the system used to form the active material includes a quasi-continuous method. FIG. 11This diagram illustrates the stages and associated temperatures of a quasi-continuous process for forming active materials, such as lithium iron phosphate materials. For example, in stage (I), the chamber is pre-filled at a temperature of approximately 240°C. In stage (II), the reaction mixture is added to the chamber and the temperature of the reaction mixture is lowered to approximately 180°C. In stage (III), additional reactants are added to the reaction mixture, and the temperature of the reaction mixture is raised to approximately 240°C. In some embodiments, the additional reactants are added via a sprayer in stage (III). In stage (IV), the temperature of the reaction mixture is maintained, and vapors are purged from the system, and the process is then repeated. Table 1 summarizes the quasi-continuous process flow for forming lithium iron phosphate materials according to one embodiment.

[0154] Table 1

[0155] Example Example implementations of this disclosure include methods, materials, and / or resulting products, as described in the following examples.

[0156] Example 1 - Preparation of lithium iron phosphate material by spray granulation A slurry containing 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 contained D... 50 The particle size distribution ranges from 1 μm to 4 μm. The slurry is ground by jet milling to obtain a median particle size of 0.5 μm or smaller. The ground slurry is calcined under a nitrogen atmosphere and heated to approximately 750°C and held for about one hour, then cooled to room temperature.

[0157] FIG. 12A Image of initial particles of lithium iron phosphate precursor. FIG. 12B Images of particles following the lithium iron phosphate precursor. FIG. 12C Images of particles following the lithium iron phosphate precursor.

[0158] FIG. 13 Image of lithium iron phosphate material produced by spray granulation. FIG. 14 The XRD pattern of the prepared lithium iron phosphate material is shown. The obtained lithium iron phosphate material maintains the particle size and shows an XRD pattern of pure LFP phase. FIG. 14 Analysis of the XRD pattern revealed the corresponding Li / Fe / P ratio and a carbon content of 3%.

[0159] Example 2 - Cathode foil preparation and electrochemistry Cathode foils comprising lithium iron phosphate material prepared by the method described in Example 1 were prepared. The resulting particles comprised bimodal particles, providing a high-density electrode. The corresponding cathode foils were prepared using a 90 / 5 / 5 mixture, and the resulting electrode had a density of 2.4 g / cc. These electrodes were tested in a coin cell and provided a capacity of 158 mAh / g. FIG. 15 Electrochemical properties of a cathode foil comprising a lithium iron phosphate material prepared by the method described in Example 1 are provided.

[0160] Example 3 - Percent iron in lithium channel for lithium iron phosphate material Six lithium iron phosphate material samples (samples 1-6) were prepared using the methods and systems disclosed herein, and seven comparative lithium iron phosphate samples (samples 7-13) were prepared using known methods and systems. The percentage of iron (Fe) in the lithium channels of lithium iron phosphate in each prepared sample was determined. Li %) and summarized in FIG. 16 middle. FIG. 16 The percentage of iron (Fe) in the lithium channels of samples 1-14 Li A graph with %). For example... FIG. 16 As shown, the percentage of iron (Fe) in the lithium channels of lithium iron phosphate materials (such as samples 1-6) prepared by the method described in this paper is... Li The percentage of iron (Fe) in the lithium channel of commercially available lithium iron phosphate is lower than that in other lithium iron phosphate products. Li %) - 2%.

[0161] Example 4 - XRD analysis of lithium iron phosphate material X-ray diffraction (XRD) spectra of the lithium iron phosphate composition prepared in Example 1 were collected and compared with commercially available lithium iron phosphate. For example, FIG. 17A and 17B The XRD pattern of the lithium iron phosphate material prepared by the method described in Example 1 is shown. FIG. 17A The percentage of iron (Fe) in the lithium channels of lithium iron phosphate materials Li The percentage was approximately 0.817%, while FIG. 17B The percentage of iron (Fe) in the lithium channels of lithium iron phosphate materials Li The percentage is approximately 0.923%. XRD patterns of lithium iron phosphate with relatively high order, prepared according to methods according to some embodiments, are provided. In contrast, FIG. 18A and 18B XRD patterns of commercially available lithium iron phosphate are provided. FIG. 18A The percentage of iron (Fe) in the lithium channel of commercially available lithium iron phosphate tested in China. Li The percentage was approximately 1.584%, while... FIG. 17B The percentage of iron (Fe) in the lithium channel of commercially available lithium iron phosphate tested in China. Li The percentage is approximately 1.584%.

[0162] Therefore, compared with commercially available lithium iron phosphate, the lithium iron phosphate material prepared by the method described in this paper exhibits a relatively high degree of iron ordering in the lithium channels.

[0163] Example 5 - XRD analysis of lithium iron phosphate material made by dry method compared to iron (III) hydroxide oxide and LFP standard FIG. 19A A mixture comprising P2O5, FeOOH, lithium hydroxide, lactose, and starch was prepared by a dry process. X-ray diffraction (XRD) spectra of the lithium iron phosphate material were collected prior to calcination and compared with iron(III) hydroxide standards. FIG. 19B XRD patterns of lithium iron phosphate materials before calcination are provided and compared with FeOOH, an iron-based material used in the reaction mixture. Example 6 - XRD analysis of lithium iron phosphate material made by dry method compared to magnetite and LFP standard XRD patterns of lithium iron phosphate materials calcined at 735°C for five hours are provided and compared with lithium iron phosphate standards.

[0164] FIG. 20A FIG. 20B A mixture comprising P2O5, Fe3O4, lithium hydroxide, lactose, and starch was prepared by a dry process. X-ray diffraction (XRD) spectra of the lithium iron phosphate material were collected prior to calcination and compared with magnetite standards. Example 7 - Lithium iron phosphate material made by spray granulation XRD patterns of lithium iron phosphate materials before calcination are provided. FIG. 21 XRD patterns of lithium iron phosphate materials calcined at 735°C for five hours are provided and compared with lithium iron phosphate standards.

[0165] FIG. 22 A mixture containing FePO4, FeOOH, lithium hydroxide, H3PO4, lactose and starch was prepared by spray granulation. Example 8 - Preparation of lithium iron phosphate material by spray dryer Image of lithium iron phosphate material produced by spray granulation. FIG. 23 The XRD pattern of the prepared lithium iron phosphate material is provided.

[0166] FIG. 24 A slurry containing 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 in an in-circulation disperser (IKA) for approximately one hour to obtain a stable dispersion. The dispersion was then spray-dried in a spray dryer using a two-fluid nozzle (3.5 bar) at an outlet temperature of 120 °C and an inlet temperature of 250–300 °C for the drying gas. The resulting powder had a density of approximately 6.8 μm. 50 Particle size distribution, residual moisture content is 1-4%.

[0167] The powder was heated to approximately 750°C under nitrogen atmosphere using a heating ramp at a rate of 5°C / min, with a residence time at the highest temperature of 60 minutes. Calcination was performed in a continuous roller hearth furnace with a crucible under a nitrogen atmosphere. The calcined lithium iron phosphate material had a density of 6.7 μm. 50 The particle size distribution is wide and the residual moisture content is less than 1,000 ppm. This lithium iron phosphate material has a carbon content of 1.3% and a BET of 14 m. 2 / g. Example 9 - Cathode foil preparation and electrochemistry Image of lithium iron phosphate material prepared by spray drying. FIG. 25 The XRD pattern of the prepared lithium iron phosphate material is provided.

[0168] Example 10 - Lithium iron phosphate material made by wet milling and spray dryer Cathode foils comprising lithium iron phosphate material prepared by the method described in Example 8 were prepared. The corresponding cathode foils were prepared using a 90 / 5 / 5 mixture, and the resulting electrodes had a density of 2.4 g / cc. These electrodes were tested in coin cells and provided capacities of 154-155 mAh / g. FIG. 26 Electrochemical performance of a cathode foil comprising lithium iron phosphate material prepared by the method described in Example 8 is provided. Higher processing losses were observed compared to granular materials due to diffusion and operational losses.

[0169] Example 11 - Lithium iron phosphate material made by wet milling and spray dryer A slurry containing 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 resulting dispersion was spray-dried, and a total of 2,440 g of lithium iron phosphate powder was collected. The powder was heated to approximately 750 °C under nitrogen atmosphere with a heating ramp of 5 °C / min, and the residence time at the maximum temperature was 60 min. Calcination was carried out in a continuous roller hearth furnace with a crucible under a nitrogen atmosphere. The resulting powder had a residual moisture content of less than 1,000 ppm and a pH of 17 m... 2 / g of BET. FIG. 27A The XRD pattern of the prepared lithium iron phosphate material is provided.

[0170] In addition, a cathode foil comprising the lithium iron phosphate material prepared by the method described in Example 9 was prepared. Electrochemical performance testing showed that the product had a discharge capacity of 153 mAh / g at C / 10.

[0171] FIG. 27C 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 slurries contained approximately 45% solids and had low viscosity. The slurries were wet-milled to a D50 particle size of approximately 0.5 μm to approximately 0.8 μm. The resulting dispersion was spray-dried at an inlet temperature of approximately 200 °C and a bed temperature of approximately 95 °C. The collected particles were calcined, similar to that in Example 8.

[0172] Example 12 - Lithium iron phosphate (LFP) material made by spray dryer and 27B Image of lithium iron phosphate material formed from lactose before calcination. Table 2 and 27D Image of lithium iron phosphate material formed with mannitol before calcination.

[0173] FIG. 28A A suspension containing 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 contained approximately 50% by weight of solids. The suspension was bead-milled in two passes using 1.2–1.4 mm zirconia beads with a 75% filling ratio to reduce particle size. In the first pass, the rotational speed was 10 m / s and the feed rate was 1400 l / h. In the second pass, the rotational speed was 12 m / s and the feed rate was 700 l / h. Table 2 summarizes the particle size before and after spray milling. The suspension was dried in a fluidized bed by spray granulation. The suspension was sprayed into a process chamber at a temperature of 153°C and a nozzle pressure of 2.6 bar at a spray rate of up to 1.5 l / min via a two-fluid nozzle at a temperature of 2300 m³ / min. 3 The product was spray-dried in a hot air stream at a rate of 86°C. The outlet temperature was 82°C. The particle bulk density was 630 g / L. The moisture content was 0.99% by weight. After spray drying, particles containing lithium iron phosphate (LFP) precursors were formed. Table 2 summarizes the particle size of the spray-dried particles.

[0174] The particles were calcined at 740°C or 780°C for 1 hour in a nitrogen atmosphere. The particles were then fed into a 1.5° inclined rotary kiln at a rate of 50 kg / h. Particles calcined at 740°C were jet-milled at a nozzle pressure of 3 bar, a classifier speed of 3800 rpm, and a flux of 380 kg / h. Particles calcined at 780°C were jet-milled at a nozzle pressure of 3 bar, a classifier speed of 4600 rpm, and a flux of 311 kg / h. After calcination, particles containing lithium iron phosphate (LFP) were formed. Table 2 summarizes the particle size characterization of the particles at different stages.

[0175] FIG. 28A

[0176] FIG. 28C and 28B These are particle size distribution diagrams of the slurry before and after wet grinding. FIG. 28D and 28B As shown, the particle size distribution becomes narrower and the particle size decreases. FIG. 28E The particle size distribution of the slurry after wet grinding is shown, including the average value, D50, D10, D90 and other parameters. Example 13 - Lithium iron phosphate (LFP) material made by spray dryer XRD pattern of spray-dried LFP material. Table 3 Image of LFP particles formed from spray drying.

[0177] Example 14 - Cathode foil preparation 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 contained approximately 56.4 wt% solids. The suspension was bead-milled in two passes using 0.6–0.8 mm zirconia beads at 85% packing to reduce particle size. In the first pass, the rotational speed was 10 m / s and the feed rate was 1000 l / h. In the second pass, the rotational speed was 12 m / s and the feed rate was 1400 l / h. After bead milling, the D50 and D90 particle sizes in the suspension were 1.39 µm and 3.15 µm, respectively. The suspension was diluted with 300 kg of deionized water to a solids content of 52 wt% and then dried in a fluidized bed by spray granulation. The suspension was injected into a 3000 m³ process chamber at a temperature of 117°C via a dual-fluid nozzle at a nozzle pressure of 2.6 bar and a spray rate of up to 1 l / min. 3 Spray-dried particles are placed in a hot air stream at a density of 1.4% by weight. The D10, D50, and D90 of the spray-dried particles are 116 µm, 174 µm, and 256 µm, respectively. The particle bulk density is 847 g / L. After spray drying, particles containing lithium iron phosphate (LFP) precursors are formed.

[0178] The particles were calcined in a nitrogen atmosphere at 740°C, 760°C, or 780°C for 1 hour. The particles were then fed into a 1.5° inclined rotary kiln at 1.3 rpm at a rate of 40 kg / h. The calcined particles were then jet-milled at a nozzle pressure of 3 bar, a classifier speed of 3000–5000 rpm, and a flux of 300–400 kg / h. Table 3 summarizes the particle size characterization at different stages.

[0179] FIG. 29A

[0180] FIG. 29B A cathode foil comprising the LFP active material from Example 12 and a commercially available LFP material was prepared. The electrode film contained 93.8% by weight or 96.8% by weight of the active material.

[0181] FIG. 29C SEM image of an electrode film prepared using 93.8% by weight of spray-dried LFP powder (without wet milling). FIG. 30 SEM image of an electrode film prepared using 93.8% by weight of spray-dried LFP powder (wet-milled). FIG. 30 SEM image of an electrode film prepared using 93.8% by weight of commercially available LFP powder.

[0182] Example 15 - Binder amount study Electrochemical test results are presented for electrodes made using spray-dried LFP powder (both wet-milled and non-wet-milled) and commercially available LFP. FIG. 31A-31F As shown, spray-dried LFP materials have a specific capacity similar to commercially available LFP materials.

[0183] FIG. 31G-31K Lithium iron phosphate with different additives was formed using a method similar to that of Example 12. FIG. 32A-32F SEM image of spray-dried LFP particles with 1.6% by weight of carboxymethyl cellulose (CMC) binder. FIG. 32G-32K SEM image of spray-dried LFP particles with 15% mannitol binder.

[0184] FIG. 33 SEM image of spray-dried lithium manganese oxide (LMO) particles with 1.6 wt% carboxymethyl cellulose (CMC) binder after calcination. FIG. 33 SEM images of spray-dried LMO particles with 15% mannitol binder after calcination. These SEM images show that the binder covers the particle surface, preventing dust from escaping from the device during manufacturing.

[0185] FIG. 34A XRD patterns of LMO materials with different amounts of binder. For example... FIG. 34A As shown, calcined particles with different amounts of binder are matched with the XRD pattern of LMO.

[0186] Example 16 - Lithium manganese oxide (LMO) material made by spray dryer and 34B The graphs show the specific capacity or normalized capacity versus cycling for commercially available LMO material (baseline), spray-dried LMO particles with 15 wt% mannitol binder, and spray-dried LMO particles with 1.6 wt% CMC binder, respectively. Example 17 - Lithium manganese oxide (LMO) material made by spray dryer and 34B As shown, spray-dried LMO particles with 15% by weight mannitol binder are more stable than spray-dried LMO particles with 1.6% CMC binder.

[0187] Example 18 - Lithium iron manganese oxide made by spray dryer A suspension comprising 1234 g Li₂CO₃, 4800 g Mn₃O₄, 30.17 g CMC, and 7000 g deionized water was prepared in a stirred tank reactor. The suspension contained approximately 42 wt% solids. The suspension was bead-milled in a single grinding step using 0.6–0.8 mm zirconia beads at a filling density of 85% to reduce particle size. The rotational speed was 10 m / s, and the feed rate was 170 g / min. After bead milling, the D50 and D90 particle sizes in the suspension were 1.6 µm and 7.4 µm, respectively. The suspension was diluted with deionized water to a solids content of 34 wt% and then dried in a fluidized bed by spray granulation. The suspension was sprayed into a 75 m³ process chamber at 100 °C via a two-fluid nozzle at a nozzle pressure of 2.6 bar and a spray rate of up to 50 g / min. 3 The product was spray-dried in a hot air stream at a temperature of 87°C. The D50 and D90 of the spray-dried particles were 127 µm and 216 µm, respectively. The particle bulk density was 951 g / L. The moisture content was 0.6% by weight. After spray drying, particles containing lithium manganese oxide (LMO) precursors were formed.

[0188] ​ A suspension comprising 1234 g Li₂CO₃, 4800 g Mn₃O₄, 905.1 g mannitol, and 7000 g deionized water was prepared in a stirred tank reactor. The suspension contained approximately 47.1% by weight of solids. The suspension was bead-milled in a single grinding step using 0.6–0.8 mm zirconia beads at a filling density of 85% to reduce particle size. The rotational speed was 10 m / s, and the feed rate was 85 g / min. After bead milling, the D50 and D90 particle sizes in the suspension were 5.6 µm and 8.35 µm, respectively. The suspension was diluted with deionized water to a solids content of 38% by weight and then dried in a fluidized bed by spray granulation. The suspension was sprayed into a 90 m³ process chamber at 75 °C through a two-fluid nozzle at a nozzle pressure of 2.6 bar and a spray rate of up to 45 g / min. 3 The product was spray-dried in a hot air stream at a temperature of 87°C. The D50 and D90 of the spray-dried particles were 181 µm and 319 µm, respectively. The moisture content was 0.84% ​​by weight. After spray drying, particles containing lithium manganese oxide (LMO) precursors were formed.

[0189] ​ 1360 g of LiOH was dispersed in 7000 g of deionized water and neutralized by the slow addition of 2650 g of an 85 wt% H3PO4 solution. Subsequently, 600 g of mannitol, 1500 g of ferric phosphate, and 2000 g of manganese oxide were added. The resulting suspension had a solids content of 45.3 wt%. The suspension was bead-milled in a grinding process using 0.6–0.8 mm zirconia beads with a filling density of 85% to reduce particle size. The rotational speed was 10 m / s, and the feed rate was 85 g / min. After bead milling, the D50 and D90 particle sizes in the suspension were 0.44 µm and 0.77 µm, respectively. The suspension was diluted to a solids content of 43 wt% and then dried in a fluidized bed by spray granulation. The suspension was sprayed through a two-fluid nozzle at a nozzle pressure of 2.6 bar and a spray rate of up to 50 g / min into a 96 m³ process chamber at a temperature of 88.3 °C. 3 Spray-dried particles are placed in a hot air stream. The moisture content is 6.57% by weight. The D50 and D90 of the spray-dried particles are 159 µm and 349 µm, respectively. The particle bulk density is 595 g / L. After spray drying, particles containing lithium iron manganese oxide precursors are formed.

[0190] Example 19 - Ni-containing cathode active material produced by a roller compactor LiOH·H2O and precursor cathode active material (pCAM) Ni83 (Ni 0.8 Mn 0.08 Co 0.12 The Li / Me molar ratio (Me represents all metals in the pCAM) was approximately 1:1.02. Other lithium sources and a second metal source were mixed with or without a carbon source, as summarized in Table 3, where the Li / Me molar ratio (Me represents all metals in the second metal source) was approximately 1:1.02. This powder mixture was jet-milled for 1 hour, 5 hours, or 10 hours. The jet-milled mixture was then fed into a roller compactor. More than 80% by weight of the particles produced after one recycling of the initial particles had a D50 particle size greater than the desired size. The collected particles were calcined in a rotary kiln for 1 hour, 5 hours, or 10 hours, similar to Example 8. Figure 35A An image of particles that are larger than the sieve aperture size. Figure 35B Image of calcined particles.

[0191] Table 4

[0192] Figure 36A , 36BSEM images of the mixture after 1 hour, 5 hours, and 10 hours of jet milling, 36C and 36C are respectively. Figure 37A A graph showing the first-cycle irreversible capacity of a half-coin cell using the calcined particles formed in this paper as the cathode active material. (See figure.) Figure 37A As shown, particles formed with longer calcination times exhibit larger irreversible capacities. Figure 37B This is a diagram showing the mixing of Li / Ni cations in particles with different calcination times. (See diagram.) Figure 37B As shown, the Li and Ni cations mix better when the calcination time is longer. Figure 38A and Figure 38B The XRD patterns of the jet-milled powder mixture are shown after 1 hour and 10 hours, respectively. Figure 38A and 38B As shown, the powder mixtures obtained by jet milling at 1 hour and 10 hours have a Ni percentage of 1.795% and 2.815% in the Li layer, respectively (Ni Li The percentage indicates that longer jet milling produces better cationic mixing. Figure 39 The graph shows the cycle performance of a half-coin cell using calcined particles as the cathode active material. Figure 39 As shown, the half-button cell has an initial specific capacity of approximately 220 mAh / g.

[0193] Figure 40A and 40B Image of large particles prepared by a roller compactor. Figure 40C and 40D These are the particles after calcination.

[0194] While certain embodiments of the invention have been described, these embodiments are presented by way of example only and are not intended to limit the scope of this disclosure. In fact, the novel methods and systems described herein can be implemented in a variety of other forms. Furthermore, various omissions, substitutions, and changes can be made to the systems and methods described herein without departing from the spirit of this disclosure. The appended claims and their equivalents are intended to cover such forms or modifications that fall within the scope and spirit of this disclosure. Therefore, the scope of the invention is defined only by the appended claims.

[0195] Features, materials, characteristics, or groups described in connection with a particular aspect, embodiment, or example shall be construed as applicable to any other aspect, embodiment, or example described elsewhere in this section or specification, unless incompatible therewith. All features disclosed in this specification (including any appended claims, abstract, and drawings) and / or all steps of any method or process so disclosed may be combined in any combination, unless at least some such combinations of features and / or steps are mutually exclusive. Protection is not limited to the details of any of the foregoing embodiments. Protection extends to any novel one or any novel combination of features disclosed in this specification (including any appended claims, abstract, and drawings), or to any novel one or any novel combination of steps of any method or process so disclosed.

[0196] Furthermore, certain features described in the context of individual embodiments in this disclosure may also be implemented in combination in a single embodiment. Conversely, various features described in the context of a single embodiment may also be implemented individually in multiple embodiments or in any suitable sub-combination. Moreover, although features may be described above as functioning in certain combinations, in some cases, one or more features in a claimed combination may be removed from that combination, and that combination may be claimed as a sub-combination or a variation of a sub-combination.

[0197] Furthermore, while operations may be illustrated in the accompanying drawings or described in the specification in a specific order, such operations need not be performed in the specific order shown or sequentially, nor need all operations be performed to achieve the desired result. Other operations not illustrated or described may be incorporated into the example methods and processes. For example, one or more additional operations may be performed before, after, simultaneously with, or between any of the described operations. Furthermore, operations may be rearranged or reordered in other embodiments. Those skilled in the art will understand that in some embodiments, the actual steps taken in the illustrated and / or disclosed process may differ from those shown in the accompanying drawings. Depending on the embodiment, some steps in the above steps may be removed, and others may be added. Furthermore, features and attributes of the specific embodiments disclosed above may be combined in different ways to form other embodiments, all of which are within the scope of this disclosure. Moreover, the separation of various system components in the embodiments described above should not be construed as requiring such separation in all embodiments, and it should be understood that the described components and systems can generally be integrated together as a single product or packaged into multiple products. For example, any component of the energy storage system described herein may be provided separately or integrated together (e.g., packaged together or attached together) to form an energy storage system.

[0198] For the purposes of this disclosure, certain aspects, advantages, and novel features are described herein. Not all such advantages may be realized according to any particular embodiment. Thus, by way of example, those skilled in the art will recognize that this disclosure may be implemented or carried out in a manner that achieves one or a set of advantages as taught herein without necessarily achieving other advantages as may be taught or suggested herein.

[0199] For the purposes of this disclosure, in some embodiments, the primary particle may be the smallest independent entity from which it forms a larger structure, cluster, or aggregate. Conditional language, such as “may,” “possibly,” “perhaps,” or “may,” unless expressly stated otherwise or otherwise understood in the context as used, is generally intended to express that certain embodiments include certain features, elements, and / or steps, while other embodiments do not. Therefore, such conditional language is generally not intended to imply that a feature, element, and / or step is necessary in any way for one or more embodiments, or that one or more embodiments necessarily include logic for determining (whether or not there is user input or prompting) whether such features, elements, and / or steps will be included or performed in any particular embodiment.

[0200] Unless otherwise explicitly stated, connective language such as the phrase "at least one of X, Y, and Z" is understood in context as generally used to indicate that an item, term, etc., may be X, Y, or Z. Therefore, such connective 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.

[0201] The degree language used in this document, such as the terms “approximately,” “about,” “generally,” and “basically”, indicates a value, quantity, or characteristic that is close to the stated value, quantity, or characteristic and still performs the desired function or achieves the desired result. For example, the terms “approximately,” “about,” “usually,” and “basically” can refer to a quantity that is less than 10%, less than 5%, less than 1%, less than 0.1%, and less than 0.01% of the stated quantity, depending on the desired function or desired result.

[0202] The scope of this disclosure is not intended to be limited by the specific disclosure of preferred embodiments elsewhere in this section or specification, but may be defined by the claims as set forth in this section or specification or as to be proposed in the future. The language of the claims should be interpreted broadly based on the language used in the claims, and not limited to the examples described in this specification or during the examination of this application, which should be interpreted as non-exclusive.

Claims

1. A method of making an active material, the method 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 to form a plurality of subsequent particles concurrently with forming the plurality of initial particles; calcining the plurality of subsequent particles to form a plurality of calcined particles comprising an active material.

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

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

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

5. The method 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 method of any one of claims 1-5, wherein the active material comprises an alkali metal metal phosphate, an alkali metal metal oxide, an alkali metal metal cyanide, or combinations thereof.

7. The method 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), lithium titanate, lithium nickel cobalt aluminum oxide (NCA), sodium cobalt oxide, sodium iron hexacyanoferrate, sodium manganese oxide, sodium iron phosphate, sodium vanadium phosphate, sodium transition metal oxide, sodium nickel manganese oxide, and combinations thereof.

8. The method 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 consisting of LiOH, LiOH•H2O, Li2CO3, LiPO3, Li3PO3, Li3PO4, LiH2PO4, Li2HPO4, LiH2PO3, Li2HPO3, lithium iron oxide, lithium iron phosphate, and combinations thereof.

9. The method 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, NaHCO3, NaNO3, Na2SO4, NaPO3, Na3PO4, NaH2PO4, Na2HPO4, sodium polyphosphate, and sodium metaphosphate, and hydrated forms thereof, and combinations thereof.

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

11. The method of claim 10, wherein the nickel-based material comprises metallic nickel, nickel oxide, nickel hydroxide, nickel carbonate, and combinations thereof.

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

13. The method of claim 12, wherein the manganese-based material is selected from the group consisting of metallic manganese, manganese oxide, manganese hydroxide, manganese carbonate, and combinations thereof.

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

15. The method of claim 14, wherein the cobalt-based material is selected from the group consisting of metallic cobalt, cobalt oxide, cobalt hydroxide, cobalt carbonate, and combinations thereof.

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

17. The method of claim 16, wherein the second metal source comprises a hydroxide pCAM, an oxide pCAM, or a combination thereof.

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

19. The method of any one of claims 1-18, wherein the initial particles have a D 50 particle size distribution range of about 0.1 μm to about 10 μm.

20. The method of any one of claims 1-19, wherein the initial particles have a D50 of about 0.01 pm to about 5 pm. 10 particle size distribution range.

21. The method of any one of claims 1-20, wherein the initial particles have a D50 of about 0.5 μm to about 50 μm. 90 particle size distribution range.

22. The method of any one of claims 1-21, wherein the subsequent particles have a D50 of about 5 μm to about 5,000 μm. 50 particle size distribution range.

23. The method of claim 22, wherein the subsequent particles have a D50 of about 100 μm to about 5,000 μm. 50 Particle size distribution range.

24. The method of any one of claims 1-23, wherein the subsequent particles have a D50 of about 10 pm to about 1,000 pm. 10 particle size distribution range.

25. The method of any one of claims 1-24, wherein the subsequent particles have a D50 of about 200 μm to about 5 cm. 90 particle size distribution range.

26. The method of any one of claims 1-25, wherein 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 method of claim 26, wherein forming the plurality of initial particles comprises spray drying the first mixture.

28. The method of any one of claims 1-27, wherein the first mixture is substantially free of liquid.

29. The method of claim 28, wherein forming the plurality of initial particles comprises mechanical granulation.

30. The method of claim 29, wherein the mechanical granulation comprises milling, sieving, mixing, blending, compaction, or a combination thereof.

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

32. The method of any one of claims 1-31, wherein the percentage of second metal on alkali metal sites in the active material is less than about 2%.

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

34. The method 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 method 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, a polyvinyl alcohol (PVA), a polyethylene glycol (PEG), a sugar alcohol, bitumen, coke, asphaltite, gilsonite, asphalt, natural asphalt, a sweetener, mannitol, erythritol, a polyoxyethylene-polyoxypropylene block copolymer, a detergent, a fatty acid, a fatty acid ester, a modified starch, a modified cellulose, carboxymethyl cellulose, graphite, activated carbon, urea, polyvinylpyrrolidone (PVP), styrene-butadiene rubber (SBR), polyvinylidene fluoride (PVDF), and combinations thereof.

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

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

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

39. The method of claim 38, wherein the first mixture further comprises a phosphorus source.

40. The method 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 phosphate, lithium iron phosphate, LiPO3, Li3PO4, LiH2PO4, Li2HPO4, LiH2PO3, Li2HPO3, and combinations thereof.

41. The method 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 iron oxide, anhydrous iron phosphate, iron phosphate hydrate, iron metal, and combinations thereof.

42. The method 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 method of claim 42, wherein the iron-based material comprises a phosphorus source.

44. The method of claim 43, wherein the molar ratio of iron to phosphate in the iron-based material is in the range of about 1 : 1.5 to 1.5:

1.

45. A system for forming a lithium iron phosphate material, the system comprising: a housing defining a chamber; a granulation device comprising a granulator in fluid communication with the chamber, the granulator defining a volume comprising an outlet and an inlet, and a recirculation path in fluid communication with the outlet and the inlet; and 46. The system of claim 45, wherein the granulator comprises a spray-drying granulator, a roller compactor, or a combination thereof. a furnace in fluid communication with the outlet, wherein the furnace is configured to contain D 50 particles having a particle size distribution of at least about 5 μm.

47. The system of claim 45 or 46, wherein the granulation device 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 conveyor granule 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 granules.

50. The system of any one of claims 45-49, wherein the direct contact between the furnace chamber and the granules provides thermal conduction from the furnace chamber to the granules in addition to providing thermal 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 pusher kiln. ​

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