Systems and methods for producing lithiated inorganic particles

Abstract

The present disclosure is directed to systems and methods of producing lithiated inorganic particles. The lithiated inorganic particles can be produced by mixing a lithium precursor, a liquid medium, a carbon precursor, and inorganic particles to form a precursor suspension. The precursor suspension can be spray dried to form precursor particles and then these precursor particles can be heated to form a lithiated inorganic powder that includes inorganic particles having a coating of carbon and lithium silicate.

Description

SYSTEMS AND METHODS FOR PRODUCING LITHIATED INORGANIC PARTICLES FIELD

[0001] This disclosure relates to systems and methods for producing lithiated inorganic particles. More specifically, this disclosure relates to systems and methods for producing inorganic particles with a coating of carbon and one or more lithium silicates. BACKGROUND

[0002] Silicon and silicon oxides are often used as anode active materials in lithium-ion batteries to improve the energy density of the batteries. However, in the first cycle of a lithium-ion battery, there can be irreversible loss of the active lithium from the cathode and / or electrolyte believed to be caused by the reaction of silicon or silicon oxide with lithium. Silicon oxide can be pre-doped with lithium to form lithium silicates that do not contribute to the charging / discharging and therefore improve the first cycle charge / discharge coulombic efficiency. SUMMARY

[0003] Described herein are systems and methods of producing lithiated inorganic particles. Specifically, these lithiated inorganic particles are created utilizing a spray drying process that can result in a narrow particle size distribution as well as low levels of impurities (e.g., iron) in the lithiated inorganic particles when compared to non-spray dry lithiation processes for inorganic particles.

[0004] In some embodiments, a method of producing a powder includes mixing a lithium precursor, a liquid medium, and inorganic particles to form a precursor suspension; spray drying the precursor suspension to form precursor particles; and heating the precursor particles to form a powder comprising inorganic particles having a coating comprising carbon and one or more lithium silicates. In some embodiments, the lithium precursor comprises inorganic lithium salts, organic lithium salts, lithium metals, lithium alloys, lithium oxides, or combinations thereof. In some embodiments, the precursor suspension comprises 0.05-10 wt.% lithium precursor. In some embodiments, the method includes mixing a carbon precursor in the precursor suspension, wherein the carbon precursor comprises pentane, hexane, 2-methylhexane, cyclopentane, cyclohexane, methylcyclohexane, heptane, 4-methylheptane, octane, cyclooctane, nonane, decane,Attorney Docket No.: L3-8120 WO benzene, toluene, xylene, ethylbenzene, amylbenzene, methylethylbenzene, diethylbenzene, mesitylene, 1,2,4-triethylbenzene, 1,3,5-triethylbenzene, amylbenzene, tetrahydronaphthalene, refinery heavy oil, pitch, polyethylene, polypropylene, polyacrylic acid, polymaleic acid, polyfumaric acid, polycrotonic acid, poly(pentenoic) acid, polymethacrylic acid, polydimethacrylic acid, poly(allyl alcohol), poly(n-propyl)acrylate, poly(hydroxymethyl)acrylate, poly(2-hydroxyethyl)acrylate, poly(2-carboxyethyl)acrylate, poly(3-ethoxy-3-oxopropyl)acrylate, poly(methylcarbamylethyl)acrylate, poly(2- hydroxyethyl)methacrylate, polyvinylpyrrolidone, polyacrylamide, polymethacrylamide, poly(N-isopropyl)acrylamide, polyvinylacetamide, polyvinyl alcohol, polyvinyl-N- methylacetamide, poly(N-hydroxymethyl)acrylamide, poly(N-hydroxyethyl)acrylamide, poly(N-methoxymethyl)acrylamide, poly(N-ethoxymethyl)acrylamide, polyacrylonitrile, sucrose, natural polymers such as cellulose and polysaccharides, or combinations thereof. In some embodiments, the precursor suspension comprises 0.25-15 wt.% carbon precursor. In some embodiments, the liquid medium comprises water, alcohols, esters, ketones, nitriles, halogenated hydrocarbons, or combinations thereof. In some embodiments, the inorganic particles comprise silicon oxide particles. In some embodiments, silicon oxide of the carbon coated silicon oxide particles has a formula of SiOx, where x is about 0.75-2. In some embodiments, the inorganic particles comprise carbon coated inorganic particles. In some embodiments, the precursor particle are heated to 700-1000oC. In some embodiments, the precursor particles are heated in an inert environment comprising an inert gas. In some embodiments, the lithium silicate comprises Li2SiO3, Li2Si2O5, Li4SiO4, Li8SiO6, Li6Si2O7, Li2Si3O7, or combinations thereof. In some embodiments, the inorganic particles having the coating comprising carbon and one or more lithium silicates has a Uniformity Factor of at least 1 calculated by the following formula: Uniformity Factor ൌ ெ^௫ ^^^^ ு^^^^௧^^ୌ^ , wherein the max peak height is a maximum height of a particle size distribution curve (measured by laser diffraction) of the inorganic particles having the coating comprising carbon and one or more lithium silicates and FWHM is a full width at half maximum height of the particle size distribution curve (measured by laser diffraction) of the inorganic particles having the coating comprising carbon and one or more lithium silicates.

[0005] In some embodiments, a powder includes inorganic particles having a coating comprising carbon and one or more lithium silicates, wherein the powder has a Uniformity Factor of at least 1 calculated by the following formula:Attorney Docket No.: L3-8120 WO Uniformity Factor ൌ ெ^௫ ^^^^ ு^^^^௧^^ୌ^ , wherein max peak height is a maximum height of a particle size distribution curve of the powder and FWHM is a full width at half maximum height of the particle size distribution curve of the powder. In some embodiments, the carbon content of the coated inorganic particles is 0.1-10 wt.%. In some embodiments, the lithium content of the coated inorganic particles is 0.1-5 wt.%. In some embodiments, the inorganic particles comprise silicon oxide particles. In some embodiments, silicon oxide of the silicon oxide particles has a formula of SiOx, where x is about 0.75-2. In some embodiments, the powder has an iron content that is within 5% of an iron content of the inorganic particles.

[0006] In some embodiments, an anode can include any of the powder disclosed above or herein. In some embodiments, a battery can include the anode. In some embodiments, the battery is a lithium-ion battery.

[0007] It will be appreciated that any of the variations, aspects, features and options described in view of the systems, methods, and / or powders apply equally to the systems, methods, powders, other devices / configurations, and vice versa. It will also be clear that any one or more of the above variations, aspects, features and options can be combined.

[0008] Additional advantages will be readily apparent to those skilled in the art from the following detailed description. The aspects and descriptions herein are to be regarded as illustrative in nature and not restrictive.

[0009] All publications, including patent documents, scientific articles and databases, referred to in this application are incorporated by reference in their entirety for all purposes to the same extent as if each individual publication were individually incorporated by reference. If a definition set forth herein is contrary to or otherwise inconsistent with a definition set forth in the patents, applications, published applications and other publications that are herein incorporated by reference, the definition set forth herein prevails over the definition that is incorporated herein by reference. BRIEF DESCRIPTION OF THE FIGURES

[0010] The disclosure will now be described, by way of example only, with reference to the accompanying drawings, in which:

[0011] FIG. 1 illustrates an example of a lithiated inorganic particle production process in accordance with some embodiments disclosed herein.Attorney Docket No.: L3-8120 WO

[0012] FIG. 2 illustrates an example of maximum peak height and full width at half maximum height (FWHM) for a particle size distribution curve (measured by laser diffraction) in accordance with some embodiments disclosed herein.

[0013] FIG.3 illustrates particle size distribution curves (measured by laser diffraction) of lithiated inorganic particles prepared from the spray drying process disclosed herein and lithiated inorganic particles from a paste process in accordance with some embodiments disclosed herein. DETAILED DESCRIPTION

[0014] Reference will now be made in detail to implementations and embodiments of various aspects and variations of devices, powders, systems, and methods described herein. Although several exemplary variations of the devices, powders, systems, and methods are described herein, other variations of the devices, powders, systems, and methods may include aspects of the devices, powders, systems, and methods described herein combined in any suitable manner having combinations of all or some of the aspects described.

[0015] Described herein are systems and methods of producing lithiated inorganic powder or particles. Lithium-ion batteries typically suffer from high first cycle active lithium losses resulting from reactions between lithium from the cathode and / or electrolyte and the anode material. This loss of lithium can permanently decrease the available energy by the consumption of lithium. It is common to compensate for this first cycle loss by pre-lithiating the electrode materials of a lithium-ion battery. Disclosed herein are systems and methods of creating pre-lithiated inorganic particles / powder that can be used as electrode (e.g., anode) materials in lithium-ion batteries.

[0016] FIG. 1 illustrates process 100 for forming lithiated inorganic particles 108 as disclosed herein. To form the lithiated inorganic particles, a precursor suspension 103 can be formed. In some embodiments, the precursor suspension 103 can be formed by mixing one or more lithium precursors 101a, one or more carbon precursors 101b, and / or one or more liquid mediums 101c with inorganic particles 104. In some embodiments, a precursor mixture 102 can be formed by mixing one or more lithium precursors 101a, one or more carbon precursors 101b, and / or one or more liquid mediums 101c. In some embodiments, the precursor mixture can be formed in a mixer. In some embodiments, the mixing can include a magnetic stirrer, an overhead stirrer, and / or a shaker, among others. In some embodiments, the one or more lithium precursors and / or the one or more carbon precursors can be dissolved, suspended, dispersed, slurried, and / or emulsified in the one or more liquidAttorney Docket No.: L3-8120 WO mediums to form the precursor mixture. In some embodiments, one or more carbon precursors may not be added to the precursor mixture or precursor suspension.

[0017] In some embodiments, the lithium precursor can be lithium metal-containing compounds such as inorganic lithium salts, organic lithium salts, non-salt lithium compounds that include lithium metals, lithium alloys, lithium oxides, lithium hydroxides, or combinations thereof. Mixtures of any two or more lithium compounds, or mixtures from different types of lithium precursors (e.g., a lithium alloy and an inorganic lithium salt) can be used as the lithium precursor. In some embodiments, the lithium metals and / or lithium alloys (e.g., with silicon, magnesium, and / or aluminum) can be the one or more lithium precursors, alone or in combinations with one or more organic and / or inorganic lithium salts. In some embodiments, the one or more lithium precursors can be in the form of a powder.

[0018] In some embodiments, the inorganic lithium salts can include lithium chloride, lithium bromide, lithium iodide, lithium chlorate, lithium carbonate, lithium bicarbonate, lithium nitrite, lithium nitrate, lithium sulfide, lithium sulfite, lithium sulfate, lithium phosphite, lithium phosphate, lithium hydroxide, or combinations thereof. In some embodiments, hydrated forms of these inorganic lithium salts (e.g., lithium hydroxide monohydrate) can also be used. In some embodiments, the organic lithium salts can include lithium acetate, lithium acetylacetate, lithium benzoate, lithium citrate, lithium formate, lithium oxalate, lithium salicylate, lithium tartrate, polymers comprising lithium, or combinations thereof. In some embodiments, when the lithium precursor includes an organic lithium salt and / or a polymer comprising lithium, some of the carbon in the lithium compounds may become part of the coating on the inorganic particles.

[0019] In some embodiments, the amount of lithium precursor in the precursor mixture can be an amount such that the lithium precursor(s) is slurried and / or dissolved in the liquid medium. In some embodiments, the amount of lithium precursor(s) in the precursor suspension can be about 0.01-15 wt.%, about 0.05-10 wt.%, about 0.1-5 wt.%, about 0.1- 4.5 wt.%. In some embodiments, the amount of lithium precursor(s) in the precursor suspension can be at least about 0.01 wt.%, at least about 0.05 wt.%, at least about 0.1 wt.%, at least about 0.5 wt.%, at least about 1 wt.%, at least about 2 wt.%, at least about 3 wt.%, or at least about 4 wt.%. In some embodiments, the amount of lithium precursor(s) in the precursor suspension can be at most about 15 wt.%, at most about 10 wt.%, at most about 8 wt.%, at most about 6 wt.%, at most about 5 wt.%., at most about 4.5 wt.%, at most about 4 wt.%, at most about 3 wt.%, at most about 2 wt.%, at most about 1 wt.%, or at most about 0.5 wt.%.Attorney Docket No.: L3-8120 WO

[0020] In some embodiments, the amount of lithium precursor(s) in the precursor suspension can an amount that the total weight percent of lithium in the precursor suspension can be about 0.001-5 wt.%, about 0.005-2 wt.%, about 0.01-1 wt.%, or about 0.01-0.75 wt.%. In some embodiments, the amount of lithium precursor(s) in the precursor suspension can an amount that the total weight percent of lithium in the precursor suspension is at least about 0.001 wt.%, at least about 0.005 wt.%, at least about 0.01 wt.%, at least about 0.02 wt.%, at least about 0.05 wt.%, at least about 0.1 wt.%, at least about 0.25 wt.%, at least about 0.5 wt.%, or at least about 0.7 wt.%. In some embodiments, the amount of lithium precursor(s) in the precursor suspension can an amount that the total weight percent of lithium in the precursor suspension is at most about 5 wt.%, at most about 2.5 wt.%, at most about 2 wt.%, at most about 1 wt.%, at most about 0.8 wt.%, at most about 0.75 wt.%, at most about 0.5 wt.%, at most about 0.25 wt.%, at most about 0.1 wt.%, or at most about 0.05 wt.%.

[0021] In some embodiments, the carbon precursors can be hydrocarbons (e.g., contain only carbon and hydrogen), organic compounds that contain one or more heteroatoms (e.g., oxygen and / or nitrogen), or combinations thereof. In some embodiments, the carbon precursors can have higher amounts of carbon relative to hydrogen (e.g., aromatic compounds). In some embodiments, the carbon precursors can be polymers, including polyolefins, heteroatom-containing polymers, or combinations thereof. In some embodiments, the carbon precursors can include pentane, hexane, 2-methylhexane, cyclopentane, cyclohexane, methylcyclohexane, heptane, 4-methylheptane, octane, cyclooctane, nonane, decane, benzene, toluene, xylene, ethylbenzene, amylbenzene, methylethylbenzene, diethylbenzene, mesitylene, 1,2,4-triethylbenzene, 1,3,5- triethylbenzene, amylbenzene, tetrahydronaphthalene, refinery heavy oil, pitch, polyethylene, polypropylene, polyacrylic acid, polymaleic acid, polyfumaric acid, polycrotonic acid, poly(pentenoic) acid, polymethacrylic acid, polydimethacrylic acid, poly(allyl alcohol), poly(n-propyl)acrylate, poly(hydroxymethyl)acrylate, poly(2- hydroxyethyl)acrylate, poly(2-carboxyethyl)acrylate, poly(3-ethoxy-3-oxopropyl)acrylate, poly(methylcarbamylethyl)acrylate, poly(2-hydroxyethyl)methacrylate, polyvinylpyrrolidone, polyacrylamide, polymethacrylamide, poly(N-isopropyl)acrylamide, polyvinylacetamide, polyvinyl alcohol, polyvinyl-N-methylacetamide, poly(N- hydroxymethyl)acrylamide, poly(N-hydroxyethyl)acrylamide, poly(N- methoxymethyl)acrylamide, poly(N-ethoxymethyl)acrylamide, polyacrylonitrile, sucrose, natural polymers such as cellulose and polysaccharides, or combinations thereof.Attorney Docket No.: L3-8120 WO

[0022] As stated above, the liquid medium can be a liquid such that the one or more lithium precursors and / or the one or more carbon precursors can be dissolved, suspended, dispersed, slurried, and / or emulsified in the liquid medium to form the precursor mixture. In some embodiments, the liquid medium can be a liquid such that the one or more lithium precursors, the one or more inorganic particles, and / or the one or more carbon precursors can be dissolved, suspended, dispersed, slurried, or emulsified in the liquid medium to form the precursor suspension. In some embodiments, the one or more lithium precursors and / or the one or more carbon precursors can be in different states in the liquid medium. For example, the lithium precursor may be dissolved in the liquid medium, whereas the carbon precursor can be suspended in the liquid medium.

[0023] In some embodiments, the amount of carbon precursor in the precursor mixture can be an amount such that the carbon precursor(s) is slurried or dissolved in the liquid medium. In some embodiments, the amount of carbon precursor(s) in the precursor suspension can be about 0.01-15 wt.%, about 0.1-5 wt.%, or about 0.5-2 wt.%. In some embodiments, the amount of carbon precursor(s) in the precursor suspension can be at least about 0.01 wt.%, at least about 0.25 wt.%, at least about 0.5 wt.%, at least about 0.6 wt.%, at least about 0.7 wt.%, at least about 0.75 wt.%, at least about 1 wt.%, at least about 5 wt.%, or at least about 10 wt.%. In some embodiments, the amount of carbon precursor(s) in the precursor suspension can be at most about 15 wt.%, at most about 10 wt.%, at most about 5 wt.%, at most about 2.5 wt.%, at most about 2 wt.%, at most about 1 wt.%, at most about 0.9 wt.%, at most about 0.85 wt.%, at most about 0.8 wt.%, or at most about 0.78 wt.%.

[0024] In some embodiments, the liquid medium can include one or more solvents. In some embodiments, the lithium precursor can be in one or more solvents, whether dissolved, suspended, dispersed, slurried, and / or emulsified, and the carbon precursor can separately be in one or more solvents, whether dissolved, suspended, dispersed, slurried, and / or emulsified, and the lithium precursor in its solvent(s) can be combined with the carbon precursor in its solvent(s) to form the precursor mixture. In some embodiments, the lithium precursor may have at least some ionic character and a polar solvent can be used as the one or more liquid mediums. In some embodiments, the carbon precursor may have limited solubility in a polar solvent, and can be dissolved in a nonpolar solvent to form a solution of the carbon precursor, which can then be combined with a solution of the lithium precursor to obtain the precursor mixture comprising the liquid mediums and the carbon precursor and the lithium precursor. In some embodiments, when the carbon precursor is dissolved in a nonpolar solvent, the nonpolar solvent can have some miscibility with the polar solvent inAttorney Docket No.: L3-8120 WO which the lithium precursor may be dissolved. In some embodiments, in a precursor mixture in which the lithium precursor and / or the carbon precursor are suspended, partially dissolved, slurried, emulsified, and / or dispersed, the coating formed from such precursor mixtures may be less uniform; however, such precursor mixtures may provide other advantages such as ease of transfer.

[0025] In some embodiments, the liquid medium can include a polar solvent, a nonpolar solvent, or a combination thereof. In some embodiments, the polar solvent(s) can be protic or aprotic. In some embodiments, the liquid medium can include mixtures of polar solvents including mixtures comprising an aprotic solvent and a protic solvent. In some embodiments, the polar solvent(s) can include water, alcohols, esters, ketones, nitriles, halogenated hydrocarbons, or combinations thereof. In some embodiments, the polar solvent(s) can include water, methanol, ethanol, n-propanol, 2-propanol, 1-butanol, 2- methyl-1-propanol, 1-methyl-1-propanol, cyclopropylmethanol, cyclobutanol, cyclopentanol, acetonitrile, propionitrile, hexanenitrile, benzonitrile, acetone, methyl ethyl ketone, pentanone, hexanone, heptanone, tetrahydrofuran, diethyl ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, butyl ethyl ether, cyclohexylmethyl ether, tetrahydrofuran, tetrahydropyran, 1,3-dioxane, 1,4-dioxane, 1,3-dioxolane, ethylene glycol, diethylene glycol, ethyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, hexyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, ethyl benzoate, dichloromethane, dibromomethane, dibromoethane, trichloromethane, tribromomethane, 1,2-dichloroethane, chlorobenzene, bromobenzene, dimethylformamide, dimethylsulfoxide, N-methyl pyrrolidinone, or combinations thereof. In some embodiments, nonpolar solvent(s) can include liquid aromatic hydrocarbons liquid aliphatic hydrocarbons, or combinations thereof. In some embodiments, liquid hydrocarbons can include pentane, hexane, 2-methylhexane, cyclopentane, cyclohexane, methylcyclohexane, heptane, 4-methylheptane, octane, cyclooctane, nonane, decane, benzene, toluene, xylene(s), ethylbenzene, mesitylene, methylethylbenzene, diethylbenzene, cumene, cymene, tetrahydronaphthalene, or combinations thereof. In some embodiments, if the liquid medium includes one or more carbon-containing components / solvents, some of the carbon from these components / solvents may become part of the coating on the inorganic particles.

[0026] In some embodiments, the amount of liquid medium in the precursor suspension can be about 10-95 wt.%, about 20-90 wt.%, about 30-90 wt.%, or about 40-85 wt.%. In some embodiments, the amount of liquid medium in the precursor suspension is at least about 10Attorney Docket No.: L3-8120 WO wt.%, at least about 20 wt.%, at least about 30 wt.%, at least about 40 wt.%, at least about 50 wt.%, at least about 60 wt.%, at least about 70 wt.%, at least about 75 wt.%, at least about 80 wt.%, or at least about 81 wt.%. In some embodiments, the amount of liquid medium in the precursor suspension is at most about 95 wt.%, at most about 90 wt.%, at most about 85 wt.%, or at most about 84 wt.%.

[0027] In some embodiments, the precursor mixture can be combined / mixed with inorganic particles 104 to form the precursor suspension 103. In some embodiments, the precursor suspensions can be formed in a mixer. In some embodiments, the precursor mixture can be added to the inorganic particles. In some embodiments, the inorganic particles can be added to the precursor mixture. In some embodiments, the inorganic particles and the precursor mixture can be added to a vessel (e.g., mixer) at the same time. In some embodiments, a precursor suspension can be formed by mixing the one or more lithium precursors, one or more carbon precursors, one or more liquid mediums, and / or the inorganic particles. In other words, a precursor mixture may not be first formed before mixing with the inorganic particles and the precursor suspension can be formed in a step of mixing all the various components.

[0028] In some embodiments, the inorganic particles can be inorganic oxide particles. In some embodiments, the inorganic particles include silicon, silicon oxides, or combinations thereof. In some embodiments, the inorganic particles are at least about 95 wt.%, at least about 98 wt.%, or at least about 99 wt.% silicon, neglecting impurities where impurities are elements other than silicon and oxygen. In some embodiments, the silicon oxides are of the formula SiOx where x is about 0.75-2, about 0.9-1.8, or about 0.9-1.5. In some embodiments, the inorganic particles include SiO, SiO2, or combinations thereof. In some embodiments, the inorganic particles include at least about 95 wt.%, at least about 98 wt.%, or at least about 99 wt.%, silicon oxides, neglecting impurities where impurities are elements other than silicon and oxygen. In some embodiments, the inorganic particles can include mixtures of different silicon oxides. In some embodiments, the mixtures of different silicon oxides can be in separate particles and / or particles in which different silicon oxides are present in the same particle.

[0029] In some embodiments, the inorganic particles can be coated inorganic particles. In some embodiments, the inorganic particles can have a carbon coating (e.g., the inorganic particles have been subjected to a carbonization surface treatment). For example, in some embodiments, the inorganic particles can be carbon coated silicon oxides. In some embodiments, having the inorganic particles already carbon coated can eliminate using aAttorney Docket No.: L3-8120 WO carbon precursor either in the precursor suspension and / or in the subsequent heating / reacting steps (e.g., hydrocarbon vapor) after spray drying as disclosed in more detail below. This elimination of hydrocarbon vapor in the heating step to form the lithium silicates can make the overall process more favorable for large scale continuous operation. In some embodiments, a specific surface area of the carbon coated silicon oxide inorganic particles can be about 0.1-10 m2 / g, about 0.5-5 m2 / g, or about 1-3 m2 / g. In some embodiments, the carbon content of the carbon coated silicon oxide particles is about 0.1- 15 wt.%, about 0.5-10 wt.%, or about 1-5 wt.%. In some embodiments, the carbon coated silicon oxide particles can have a silicon oxide core with a carbon coating shell around the core. In some embodiments, the carbon at least partially coats the silicon oxide particles.

[0030] In some embodiments, the precursor suspension includes inorganic particles in an amount of about 1-90 wt.%, about 5-80 wt.%, about 10-70 wt.%, or about 10-60 wt.%. In some embodiments, the precursor suspension includes inorganic particles in an amount of at least about 1 wt.%, at least about 5 wt.%, at least about 10 wt.%, at least 20 wt.%, at least 30 wt.%, at least 40 wt.%, or at least 50 wt.%. In some embodiments, the precursor suspension includes inorganic particles in an amount of at most about 90 wt.%, at most about 80 wt.%, at most about 70 wt.%, at most about 60 wt.%, at most about 50 wt.%, at most about 40 wt.%, at most about 30 wt.%, at most about 25 wt.%, at most about 20 wt.%, or at most about 15 wt.%.

[0031] In some embodiments, the inorganic particles have an average particle size of about 0.1-30 microns, about 0.5-20 microns, or about 0.5-10 microns. In some embodiments, the inorganic particles have an average particle size of at least about 0.1 microns, at least about 0.5 microns, at least about 1 micron, at least about 2.5 microns, at least about 5 microns, at least about 7.5 microns, at least about 10 microns, or at least about 20 microns. In some embodiments, the inorganic particles have an average particle size of at most about 30 microns, at most about 20 microns, at most about 15 microns, at most about 10 microns, at most about 7.5 microns, at most about 5 microns, at most about 2.5 microns, or at most about 1 micron.

[0032] In some embodiments, the amount of lithium precursor to inorganic particles in the precursor suspension is such that the Li:SiO molar ratio is about 0.001-1, about 0.005-0.5, or about 0.0095-0.342. In some embodiments, the amount of lithium precursor to inorganic particles in the precursor suspension is such that the Li:SiO molar ratio is at least about 0.001, at least about 0.005 at least about 0.0075, at least about 0.009, at least about 0.0095, at least about 0.01, at least about 0.1, at least about 0.2, or at least about 0.3. In someAttorney Docket No.: L3-8120 WO embodiments, the amount of lithium precursor to inorganic particles in the precursor suspension is such that the Li:SiO molar ratio is at most about 1, at most about 0.75, or at most about 0.5.

[0033] In some embodiments, the precursor mixture and the inorganic particles or the lithium precursor(s), carbon precursor(s), liquid medium(s), and / or the inorganic particles can be mixed together to form a suspension such that the lithium precursor(s), carbon precursor(s), and / or inorganic particles are dissolved, suspended, dispersed, slurried, and / or emulsified in the one or more liquid mediums to form the precursor suspension. In some embodiments, the inorganic particles can be suspended or dispersed in the precursor suspension (liquid medium of the precursor suspension) and the lithium precursor and / or carbon precursor can be slurried or dissolved in the precursor suspension (liquid medium of the precursor suspension).

[0034] In some embodiments, the amount of liquid medium in the precursor suspension (which can be formed from the precursor mixture and the inorganic particles) is enough such that it can be a pumpable fluid so that it can be spray dried. In some embodiments, the precursor suspension is not a paste or does not have a paste-like consistency. In some embodiments, the precursor suspension has a solids content of about 1-90 wt.%, about 5-80 wt.%, about 10-70 wt.%, or about 10-60 wt.%.

[0035] In some embodiments, the precursor mixture and / or the precursor suspensions can be formed in ambient air or in a controlled environment such as an inert environment. In some embodiments, the inert atmosphere can exclude water and / or oxygen. In some embodiments, the inert atmosphere can be an argon atmosphere. In some embodiments, the lithium precursor can be one that mildly reacts or is non-reactive to the one or more carbon precursors, one or more liquid mediums, and / or one or more inorganic particles.

[0036] In some embodiments, the precursor suspension can be spray dried 105 to form precursor particles that include lithium and the inorganic particles. In some embodiments, the spray drying includes setting up the parameters of the spray dryer (e.g., operational mode(s), inlet temperature, outlet temperature, feeding rate, gas flow, nozzle cleaner frequency, etc.). Unlike traditional processing, where the precursor suspension would have to be dried or the solvent would have to evaporated out of the precursor suspension in an oven (e.g., a vacuum oven) to form precursor particles, spray drying can allow for the precursor particles to be formed quickly and continuously without the need for an elongated evaporation step.Attorney Docket No.: L3-8120 WO

[0037] In some embodiments, the spray dryer can be operated such that the inlet has a temperature of about 180-450oC and / or the outlet has a temperature of about 80-250oC. In some embodiments, the heated drying medium for spray drying can be a gas. In some embodiments, the gas can be an inert gas. In some embodiments, the gas can be air or nitrogen. In some embodiments, the spray dryer can be warmed up until the inlet and outlet temperatures are stable. In some embodiments, the precursor suspension can be fed to the spray dryer to make the spray dried precursor particles.

[0038] In some embodiments, the spray dried precursor particles can include the inorganic particles, the lithium precursor(s), and / or the carbon precursor(s). In other words, the spray dried precursor particles can be made up of one or more of the inorganic particles, lithium precursor(s), and carbon precursor(s). In some embodiments, the spray dried precursor particles can include the inorganic particle with the lithium precursor(s) and / or carbon precursor(s) attached to the surface of the inorganic particles. In some embodiments, the spray dried precursor particles can be inorganic particles coated with the lithium precursor(s) and / or carbon precursor(s). In some embodiments, the spray drying can uniformly coat the inorganic particles with the lithium precursor(s) and / or carbon precursor(s). In some embodiments, no reaction besides drying can take place during the spray drying. In some embodiments, dehydration and / or decomposition of lithium hydroxide monohydride can happen during the spring drying.

[0039] In some embodiments, the Li:SiO molar ratio in the spray dried precursor particles is about 0.001-1, about 0.005-0.5, or about 0.0095-0.342. In some embodiments, the Li:SiO molar ratio in the spray dried precursor particles is at least about 0.001, at least about 0.005 at least about 0.0075, at least about 0.009, at least about 0.0095, at least about 0.01, at least about 0.1, at least about 0.2, or at least about 0.3. In some embodiments, the Li:SiO molar ratio in the spray dried precursor particles is at most about 1, at most about 0.75, at most about 0.5, at most about 0.4, at most about 0.35. In some embodiments, the amount of lithium in the spray dried precursor particles is about 0.05-10 wt.% or about 0.1-5 wt.%. In some embodiments, the amount of lithium in the spray dried precursor particles is at least about 0.01 wt.%, at least about 0.05 wt.%, at least about 0.1 wt.%, at least about 0.14 wt.%, or at least about 0.5 wt.%. In some embodiments, the amount of lithium in the spray dried precursor particles is at most about 10 wt.% or at most about 7 wt.%.

[0040] In some embodiments, the amount of lithium precursor(s) in the spray dried precursor particles can be about 0.1-35 wt.%, about 0.5-30 wt.%, or about 0.75-25 wt.%. In other words, the lithium precursor(s) can make up 0.1-35 wt.% of the spray dried precursorAttorney Docket No.: L3-8120 WO particles, for example. In some embodiments, the amount of lithium precursor(s) in the spray dried precursor particles can be at least about 0.1 wt.%, at least about 0.25 wt.%, at least about 0.5 wt.%, at least about 0.75 wt.%, at least about 0.8 wt.%, at least about 0.85 wt.%, at least about 1 wt.%, at least about 5 wt.%, at least about 10 wt.%, at least about 15 wt.%, or at least about 20 wt.%. In some embodiments, the amount of lithium precursor(s) in the spray dried precursor particles can be at most about 35 wt.%, at most about 30 wt.%, at most about 25 wt.%, at most about 24 wt.%, at most about 20 wt.%, at most about 10 wt.%, at most about 5 wt.%, at most about 2 wt.%, or at most about 1 wt.%.

[0041] In some embodiments, the amount of carbon precursor(s) in the spray dried precursor particles can be about 0.1-30 wt.%, about 1-15 wt.%, or about 3-10 wt.%. In other words, the carbon precursor(s) can make up 1-15 wt.% of the spray dried precursor particles, for example. In some embodiments, the amount of carbon precursor(s) in the spray dried precursor particles can be at least about 0.1 wt.%, at least about 1 wt.%, at least about 2 wt.%, at least about 3 wt.%, at least about 4 wt.%., or at least about 5 wt.%. In some embodiments, the amount of carbon precursor(s) in the spray dried precursor particles can be at most about 30 wt.%, at most about 15 wt.%, at most about 10 wt.%, at most about 8 wt.%, at most about 6 wt.%, at most about 5 wt.%, or at most about 4 wt.%.

[0042] In some embodiments, the amount of inorganic particles in the spray dried precursor particles can be about 50-95 wt.%, about 60-95 wt.%, or about 70-95 wt.%. In other words, the inorganic particles can make up 50-95 wt.% of the spray dried precursor particles, for example. In some embodiments, the amount of inorganic particles in the spray dried precursor particles can be at least about 50 wt.%, at least about 60 wt.%, at least about 65 wt.%, at least about 70 wt.%, at least about 72 wt.%, at least about 80 wt.%, at least about 85 wt.%, or at least about 90 wt.%. In some embodiments, the amount of inorganic particles in the spray dried precursor particles can be at most about 95 wt.%, at most about 94 wt.%, at most about 85 wt.%, at most about 80 wt.%., or at most about 75 wt.%.

[0043] In some embodiments, the uniformity (or narrowness) of the particle size distribution of the spray dried precursor particles can be measured by a Uniformity Factor calculated by the following formula: Uniformity Factor^^^^^^ ^^^^^^^^ ^^^^^^^^ℎ^^

[0044] Wherein Max Peak Heightof the particle size distribution curve of the spray dried precursor particles / powder and FWHM refers to theAttorney Docket No.: L3-8120 WO full width at half maximum height of the particle size distribution curve of the spray dried precursor particles / powder.

[0045] In some embodiments, the Uniformity Factor for the spray dried precursor particles disclosed herein can be at least about 0.85, at least about 0.9, at least about 0.95, at least about 1, or at least about 1.1. In some embodiments, the Uniformity Factor for the spray dried precursor particles disclosed herein can be at most about 10, at most about 7.5, at most about 5, at most about 2.5, or at most about 2. In contrast to the spray dried lithiated inorganic particles, non-spray dry lithiation processes for inorganic particles can have a Uniformity Factor that is less than 0.85, less than 0.9, less than 0.95, less than 1, or less than 1.1.

[0046] In some embodiments, the spray dried precursor particles can be heated in a reaction step (e.g., calcination) 106 such that lithium silicates and / or a carbon coating form. In some embodiments, the lithium can react with the inorganic particles to form lithium silicates. In some embodiments, heating the precursor particles can form a lithiated inorganic powder 108 that includes the inorganic particles that have a coating comprising carbon (e.g., pyrolysis result of carbon precursor(s)) and / or one or more lithium silicates. For example, in some embodiments, the lithiated inorganic powder can include the carbon coated silicon oxide particles that have one or more lithium silicates with one or more calcined carbons on the surface of the carbon coated silicon oxide particles. In addition, in some embodiments, there can be multiple coatings or multiple coating layers on the surface of the carbon coated silicon oxide particles.

[0047] In some embodiments, this heating / reaction step can take place in a reactor such as a stationary or rotary kiln.

[0048] In some embodiments, the spray dried precursor particles are heated to at least about 500oC, at least about 550oC, at least about 600oC, at least about 650oC, at least about 700oC, at least about 750oC, at least about 800oC, at least about 850oC, at least about 900oC, or at least about 950oC. In some embodiments, the spray dried precursor particles are heated to at most about 1200oC, at most about 1150oC, at most about 1100oC, at most about 1050oC, at most about 1000oC, at most about 950oC. In some embodiments, the spray dried precursor particles are heated to about 500-1200oC, about 600-1100oC, or about 700-1000oC. In some embodiments, the spray dried precursor particles are heated for about 0.1-10 hours, about 0.2-5 hours, 0.5-4 hours, or about 0.5-3 hours. In some embodiments, the spray dried precursor particles are heated for at most about 10 hours, or at most about 5 hours. InAttorney Docket No.: L3-8120 WO some embodiments, the spray dried precursor particles are heated for at least about 0.1 hours, or at least about 0.5 hours.

[0049] In some embodiments, the heating / reacting the spray dried precursor particles is performed in an inert environment to form the final lithiated inorganic powder. In some embodiments, the inert environment can be static or a flow of the inert gas or gases in the inert environment. In some embodiments, the inert environment can include argon, nitrogen, helium, or combinations thereof.

[0050] In a typical paste process to create lithiated silicon particles such as that described in PCT App. No. PCT / US2019 / 055980 (which is hereby incorporated by reference in its entirety), a precursor mixture is combined with inorganic particles to form a paste, the paste is then dried in an evaporator, the dried particles are then grinded to a powder, and then the particles are heated / reacted to form a lithium silicate and a carbon coating. In this typical paste process, a carbon precursor may be added as a gas (e.g., a hydrocarbon vapor) or liquid in the heating / reaction step. In some embodiments, because the inorganic particles in the processes disclosed herein can already have a carbon coating on them, the addition of this precursor carbon in the heating / reacting step can be eliminated. This can make the overall process more favorable to large scale continuous operation. In other embodiments, the heating / reaction steps disclosed herein can utilize a carbon precursor added as a gas (e.g., a hydrocarbon vapor) or liquid in the heating / reaction step. In such embodiments, the carbon precursor may not be included in the precursor mixture or an additional carbon precursor can be added in the heating / reaction step to become part of the carbon in the coating on the inorganic particles as described in PCT App. No. PCT / US2019 / 055980.

[0051] In addition, the typical paste process can include grinding the particles to a desired particle size distribution after the heating / reaction step. Grinding the particles can lead to an increase in impurities (e.g., iron) in the final particles especially if the grinding is conducted by ball milling (in an equipment with an iron containing surface that particles contact). In contrast, the processes disclosed herein utilize spray drying which can create a more uniform particle size distribution and can eliminate further grinding of particles, thereby decreasing the amount of impurities in the final lithiated inorganic powder. In some embodiments, the impurities are any element other than silicon, lithium, oxygen, and carbon in the powder. In some embodiments, the impurities are any metal other than silicon and lithium. In some embodiments, the amount of impurities (e.g., iron) in the lithiated inorganic particles is at most about 100 ppm, at most about 75 ppm, at most about 50 ppm, at most about 40 ppm, at most about 35 ppm, or at most about 30 ppm. In someAttorney Docket No.: L3-8120 WO embodiments, the lithiated inorganic particles have at least about 1 ppm, at least about 5 ppm, at least about 10 ppm, at least about 15 ppm, or at least about 20 ppm impurities (e.g., iron). In some embodiments, the amount of impurities can be measured using Inductively Coupled Plasma (ICP) Spectroscopy.

[0052] In some embodiments, the inorganic starting particles can include impurities. As such, in some embodiments, the lithiated inorganic particles / powder can have an amount of impurities less than or equal to 150%, less than or equal to 130%, less than or equal to 125%, less than or equal to 120%, less than or equal to 115%, less than or equal to 110%, less than or equal to 105%, less than or equal to 102.5%, less than or equal to 101%, less than or equal to 100.5%, less than or equal to 100.25%, or less than or equal to 100.1% of the impurities in the inorganic starting particles. For example, if the impurities in the inorganic starting particles were 30 ppm and the impurities in the lithiated inorganic particles / powder is 37 ppm, then the amount of impurities in the lithiated inorganic particles is 123.3% (37 / 30) of the impurities in the inorganic starting particles. In other words, the spray drying process may not or may minimally increase any impurities.

[0053] As stated above, the lithiated inorganic powder can include inorganic oxide particles that have a coating layer comprising carbon and lithium silicate. In some embodiments, the lithiated inorganic powder particles can have a core-shell structure, wherein the inorganic particles can form the core and the shell is a layer / coating that includes carbon (e.g,. carbon precursor) and / or lithium silicate(s) (as well as some unreacted lithium precursor(s) in some embodiments or a mixture of all of the above in some embodiments). In some embodiments, there may be multiple coatings on the inorganic particles. For example, the inorganic particles may have a carbon coating and / or a coating of lithium silicate, either on top of or under the carbon coating.

[0054] In some embodiments, the carbon content of the lithiated inorganic powder is about 0.1-20 wt.%, about 0.5-10 wt.%, or about 0.5-8 wt.%. In some embodiments, the carbon content of the lithiated inorganic powder is at least about 0.1 wt.% or at least about 0.5 wt.%. In some embodiments, the carbon content of the lithiated inorganic powder is at most about 20 wt.%, at most about 15 wt.%, at most about 10 wt.%, at most about 7.5 wt.%, at most about 5 wt.%, at most about 2.5 wt.%, or at most about 1 wt.%. In some embodiments, the carbon in the coating of the lithiated inorganic powder is non-crystalline.

[0055] In some embodiments, the lithium silicate(s) in the coating of the inorganic particles in the lithiated inorganic powder can be represented by the formula LiaSibOc, in which a is about 2 to about 8, b is about 1 to about 3, and c is about 3 to about 7. In some embodiments,Attorney Docket No.: L3-8120 WO the lithium silicates include Li2SiO3, Li2Si2O5, Li4SiO4, Li8SiO6, Li6Si2O7, Li2Si3O7, or combinations thereof. In some embodiments, the lithium silicates include Li2SiO3, Li2Si2O5, or combinations thereof. In some embodiments, the lithium silicates in the coating of the lithiated inorganic powder can have some crystallinity, which can allow particular lithium silicates to be probed by X-ray powder diffraction (XRD), and to be identified by their characteristic peaks for the (111) plane. For example, Li2SiO3is identified by a peak at 2θ=27° corresponding to the (111) plane of Li2SiO3. Li2Si2O5 is identified by a peak at 2θ=24.7° corresponding to the (111) plane of Li2Si2O5. Li4SiO4is identified by a peak at 2θ=28.3° corresponding to the (111) plane of Li4SiO4.

[0056] In some embodiments, the amount of lithium in the lithiated inorganic powder is about 0.01-15 wt.%, about 0.05-10 wt.%, or about 0.1-8 wt.%. In some embodiments, the amount of lithium in the lithiated inorganic powder is at least about 0.01 wt.%, at least about 0.05 wt.%, at least about 0.1 wt.%, at least about 0.15 wt.%, at least about 0.5 wt.%, at least about 1 wt.%, at least about 2.5 wt.%, at least about 3 wt.%, at least about 4 wt.%, or at least about 4.5 wt.%. In some embodiments, the amount of lithium in the lithiated inorganic powder is at most about 15 wt.%, at most about 10 wt.%, at most about 8 wt.%, at most about 6 wt.%, at most about 5 wt.%, at most about 4.5 wt.%, at most about 3 wt.%, at most about 2.5 wt.%, at most about 1 wt.%, or at most about 0.5 wt.%. In some embodiments, the lithium content can be measured using Inductively Coupled Plasma (ICP) Spectroscopy.

[0057] In some embodiments, the Li:SiO molar ratio in the lithiated inorganic powder is about 0.001-10, about 0.005-0.5, or about 0.0095-0.342. In some embodiments, the Li:SiO molar ratio in the lithiated inorganic powder is at least about 0.001, at least about 0.005 at least about 0.0075, at least about 0.009, at least about 0.0095, at least about 0.01, at least about 0.1, at least about 0.2, or at least about 0.3. In some embodiments, the Li:SiO molar ratio in the lithiated inorganic powder is at most about 10, at most about 1, at most about 0.75, at most about 0.5, at most about 0.4, at most about 0.35, at most about 0.1, at most about 0.05, or at most about 0.01.

[0058] As stated above, the lithiated inorganic particles created by the spray drying process described herein can result in a narrow or more uniform particle size distribution when compared to non-spray dry lithiation processes for inorganic particles. The uniformity (or narrowness) of the particle size distribution of the lithiated inorganic particles can be measured by a Uniformity Factor calculated by the following formula: ^^^^^^ ^^^^^^^^ ^^^^^^^^ℎ^^ UniformityAttorney Docket No.: L3-8120 WO

[0059] Wherein Max Peak Height refers to the maximum height of the particle size distribution curve of the lithiated inorganic particles / powder and FWHM refers to the full width at half maximum height of the particle size distribution curve of the lithiated inorganic particles / powder. For example, FIG.2 demonstrates the Max Peak Height and the FWHM for a particle size distribution curve.

[0060] In some embodiments, the particle size distribution instrument can be a Malvern mastersizer 300 (with small hydro module and a dispersant can be IPA). In some embodiments, the Max Peak Height and the FWHM can be obtained from standard particle size analysis software such as Excel or Origin.

[0061] In some embodiments, the Uniformity Factor for the lithiated inorganic particles disclosed herein can be at least about 0.85, at least about 0.9, at least about 0.95, at least about 1.0, or at least about 1.1. In some embodiments, the Uniformity Factor for the lithiated inorganic particles disclosed herein can be at most about 10, at most about 7.5, at most about 5, at most about 2.5, or at most about 2. In contrast to the spray dried lithiated inorganic particles, non-spray dry lithiation processes for inorganic particles can have a Uniformity Factor that is less than 0.85, less than 0.9, less than 0.95, less than 1, or less than 1.1.

[0062] In some embodiments, spray drying minimally changes the particle size distribution from the starting inorganic particles. In some embodiments, the lithiated inorganic powder has a particle size distribution with a D10 (i.e., size below which 10% of all particles are found) of about 0.1-10 microns, about 0.2-9 microns, about 1-7 microns, about 1-6 microns, or about 2-5 microns. In some embodiments, the lithiated inorganic powder has a particle size distribution with a D10 of greater than about 0.1, greater than about 0.5 microns, greater than about 1 micron, greater than about 2 microns, greater than about 3 microns, greater than about 4 microns, greater than about 5 microns, greater than about 6 microns, greater than about 7 microns, greater than about 8 microns, greater than about 9 microns, or greater than about 10 microns. In some embodiments, the lithiated inorganic powder has a particle size distribution with a D10 of less than about 10 microns, less than about 8 microns, less than about 7 microns, less than about 6 microns, less than about 5 microns, less than about 4 microns, less than about 3 microns, or less than about 2 microns.

[0063] In some embodiments, the lithiated inorganic powder has a particle size distribution with a D50 (i.e., size below which 50% of all particles are found) of about 1-30 microns, about 3-20 microns, about 4-15 microns, or about 6-12 microns. In some embodiments, the lithiated inorganic powder has a particle size distribution with a D50 of greater than about 1 micron, greater than about 2 microns, greater than about 3 microns, greater than about 4Attorney Docket No.: L3-8120 WO microns, greater than about 5 microns, greater than about 6 microns, greater than about 7 microns, greater than about 8 microns, greater than about 9 microns, greater than about 10 microns, greater than 12 microns, or greater than 15 microns. In some embodiments, the lithiated inorganic powder has a particle size distribution with a D50 of less than about 30 microns, less than about 25 microns, less than about 20 microns, less than about 15 microns, less than about 12 microns, less than about 10 microns, less than about 9 microns, less than about 8 microns, less than about 7 microns, less than about 6 microns, less than about 5 microns, or less than about 4 microns.

[0064] In some embodiments, the lithiated inorganic powder has a particle size distribution with a D90 (i.e., size below which 90% of all particles are found) of about 5-44 microns, about 5-30 microns, about 10-20 microns, or about 12-20 microns. In some embodiments, the lithiated inorganic powder has a particle size distribution with a D90 of greater than about 5 microns, greater than about 6 microns, greater than about 7 microns, greater than about 8 microns, greater than about 9 microns, greater than about 10 microns, greater than 12 microns, greater than 15 microns, greater than about 18 microns, or greater than about 20 microns. In some embodiments, the lithiated inorganic powder has a particle size distribution with a D90 of less than about 44 microns, less than about 35 microns, less than about 30 microns, less than about 25 microns, less than about 20 microns, less than about 19 microns, less than about 18 microns, less than about 17 microns, less than about 16 microns, less than about 15 microns, less than about 12 microns, or less than about 10 microns.

[0065] In some embodiments, the lithiated inorganic powder can have a Brunauer-Emmett- Teller (BET) specific surface area of about 0.1-20 m2 / g, about 0.5-10 m2 / g, about 1-8 m2 / g, or about 1-5 m2 / g. In some embodiments, the BET specific surface area can be greater than about 0.1 m2 / g, greater than about 0.5 m2 / g, greater than about 1 m2 / g, greater than about 1.5 m2 / g, greater than about 2 m2 / g, greater than about 2.25 m2 / g, greater than about 2.5 m2 / g, greater than about 2.75 m2 / g, greater than about 3 m2 / g, greater than about 3.5 m2 / g, greater than about 4 m2 / g, or greater than about 5 m2 / g. In some embodiments, the BET specific surface area can be less than about 20 m2 / g, less than about 10 m2 / g, less than about 8 m2 / g, less than about 5 m2 / g, less than about 4 m2 / g, less than about 3.5 m2 / g, less than about 3 m2 / g, less than about 2.75 m2 / g, less than about 2.5 m2 / g, less than about 2 m2 / g, less than about 1.5 m2 / g, or less than about 1 m2 / g.Attorney Docket No.: L3-8120 WO

[0066] In some embodiments, the Barrett-Joyner-Halenda (BJH) porosity or pore size distribution can be negligible. In some embodiments, the BET specific surface area and the BJH porosity or pore size distribution can be measured by a Micromeritics ASAP 2020 Plus.

[0067] In some embodiments, after the heating / reaction step, the lithiated inorganic powder can be cooled. In some embodiments, the lithiated inorganic powder can be washed (after cooling) with one or more liquid mediums (as described above) to remove any unreacted lithium precursors and / or carbon precursors and / or undesired by-products.

[0068] In some embodiments, after the heating / reaction step, the lithiated inorganic powder can be sieved 107. For example, the lithiated inorganic powder can be seived through a 325 mesh.

[0069] In some embodiments, the lithiated inorganic powder can be used as an electrode (e.g., anode) active material. In some embodiments, the lithiated inorganic powder can be coated onto a current collector (in the form of a slurry that includes the lithiated inorganic powder) (together with other anode additivies and / or other anode active material(s)). In some embodiments, at least a portion of this coated current collector can become at least part of an electrode (e.g., an anode). In some embodiments, an electrode (e.g., an anode) with the lithiated inorganic powder as the active material can be used in a battery (e.g., a lithium-ion battery). In some embodiments, the battery can include an anode, a cathode, a separator, and / or an electrolyte. In some embodiments, the battery can be a solid-state battery.

[0070] For the purpose of clarity and a concise description, features are described herein as part of the same or separate embodiments; however, it will be appreciated that the scope of the disclosure includes embodiments having combinations of all or some of the features described. EXAMPLES

[0071] The following examples are presented for purposes of illustration, and are not intended to impose limitations on the scope of this disclosure.

[0072] Examples 1-6 were made according to the following spray dry process as disclosed herein: 0.9-32.6g lithium hydroxide monohydrate and 5.5g polyvinylpyrrolidone were dissolved in 600g water to form a clear solution. Silicon monoxide (100g) was added to the clear solution and the solution was stirred to create a uniform suspension. The parameter of the spray dryer were then set up and the spray dyer was warmed up until the inlet (180 – 450 °C) and outlet (80 – 250 °C) temperatures were stable. Next, the suspension was fed toAttorney Docket No.: L3-8120 WO the spray dryer to make the spray dried precursor powder. The spray dried precursor powder was then loaded into a reactor with a temperature of 700-1000oC. After reacting, the reacted powder was collected and sieved (325 mesh) produce the lithiated inorganic powder.

[0073] Examples 8 and 8B were made according to the following paste process: A solution containing lithium hydroxide (10.1 wt%) and poly(acrylic acid) (7.9 wt%, PAA) was prepared by dissolving lithium hydroxide monohydrate (LiOH∙H2O) and PAA in water. Silicon monoxide (100.0 g, SiO), with an average particle size of 5 µm, was weighed into a beaker. The solution of LiOH and PAA was added to the SiO in the beaker dropwise with stirring until all SiO particles appeared wetted.71.2 g of the LiOH+PAA solution was used, corresponding to 7.2 g of LiOH and 5.6 g of PAA. The wet mixture was transferred into a drying oven, then heated to 90°C and held at 90°C for 12 hours. After the wet mixture was dried, the remaining material was ball milled to powder precursor and transferred into a reactor. The powder precursor was then heated to 950°C and held for 1.5 hours. After reacting, the reacted powder was collected and sieved (325 mesh) to produce the lithiated inorganic powder. Example 8C was similarly prepared except modified to get the given Li:Si molar ratio and Li wt.% as described in Table 1 below.

[0074] The lithium:silicon molar ratio and the lithium weight percentage of the lithiated inorganic particles of Examples 1-6 are shown in Table 1 below. As shown in Table 2, Example 7 was pristine silicon oxide (SiO) powder. TABLE 1 EXAMPLE Process Li:Si Molar Ratio Li wt.% 1 Spray Dry 0.0095 0.14 2 Spray Dry 0.019 0.28 3 Spray Dry 0.038 0.57 4 Spray Dry 0.076 1.13 5 Spray Dry 0.209 3.08 6 Spray Dry 0.342 5.04 7 Pristine SiO N / A N / A 8 Paste Process 0.076 1.13 8B Paste Process 0.076 1.13 8C Paste Process 0.019 0.28Attorney Docket No.: L3-8120 WO

[0075] FIG. 3 illustrates a particle size distribution comparing the spray dried lithiated inorganic powder of Examples 2 (P-2) and 4 (P-4) with the paste processed lithiated inorganic powder of Examples 8 (P-8) and 8C (P-8C). As shown in FIG. 3, the lithiated inorganic powder prepared through the spray drying process disclosed herein has a narrower and sharper particle size distribution pattern. This means that the lithiated inorganic powders disclosed herein have a more uniform particle size distribution. By comparing the spray dry process examples with the paste process examples that have the same Li:Si molar ratio and Li wt.% (e.g., comparing Example 2 with Example 8C and Example 4 with Example 8), the lithiated inorganic powder prepared through spray drying process has a narrower and sharper particle size distribution pattern, which means a more uniform particle size. Below is a Table 2 that includes the max peak heights, full width at half maximum, and Uniformity Factors for the various particle size distributions of the lithiated inorganic powder of Examples 2, 4, 8, and 8C. TABLE 2 EXAMPLE Process Li:Si Li wt.% Max FWHM Uniformity Molar Peak Factor Ratio Height 2 Spray Dry 0.019 0.28 12.63 10.13 1.25 8C Paste 10.19 12.63 0.81 0.019 0.28 Process 4 Spray Dry 0.076 1.13 13.25 11.10 1.19 8 Paste 9.99 13.59 0.74 0.076 1.13 Process

[0076] As shown in the Table above, the Uniformity Factor (ratio of maximum peak height over full width at half maximum) of the particle size distribution curves (shown in FIG.3) of the spray dried examples is greater (>=0.85) than the Uniformity Factors of the paste processed samples (N <0.85).

[0077] The lithiated inorganic powder of Examples 1-7 were also tested for their first discharge capacity, first charge capacity, and first cycle efficiency. These results are summarized in Table 3 below.

[0078] The electrode slurries included 92.5 wt% lithiated inorganic powder; 5.9 wt% carboxymethyl cellulose (CMC); 0.6 wt% styrene-butadiene rubber (SBR); 0.6 wt% carbonAttorney Docket No.: L3-8120 WO black; 0.4 wt% carbon nanotube; and water. The amount of water was such that the solid content was about 40 wt% of the slurry. The slurry was coated onto a copper foil current collector, and then the coating was dried and calendared to 30% porosity, forming an electrode containing coated particles comprising silicon. The loading of coated particles comprising silicon on the electrode was about 3 mg / cm2. Four coin cells were assembled from each calendared electrode, with lithium foil as the counter electrode and LiPF6 (1.2 M) in ethylene carbonate / ethyl methyl carbonate (30:70 wt / wt) as the electrolyte solution with 5% Fluoroethylene carbonate. The cells were cycled at C / 20 for 10 cycles. For comparison, pristine SiO without any treatment was also tested under the same conditions. TABLE 3 EXAMPLE 1stSTDEV 1stCharge STDEV 1stCycle STDEV Discharge (mAh / g) Capacity (mAh / g) Efficiency (%) Capacity (mAh / g) (%) (mAh / g) 1 2220 39 1909 38 86.0 0.1 2 2090 67 1790 58 85.6 0.2 3 1985 49 1709 38 86.1 0.2 4 1804 90 1563 79 86.7 0.2 5 1064 24 974 23 91.6 0.1 6 869 51 791 47 91.0 0.1 7 2498 39 1964 33 78.9 0.1

[0079] As shown in the above table, after lithiation, the lithiated inorganic powder with lithium content from 0.1-5 wt.% shows a higher 1stcycle efficiency than pristine SiO. This indicates the feasibility of doing pre-lithiation with the lithium content of at least 0.1 wt.% to improve at least first cycle efficiency.

[0080] Lastly, an ICP analysis was ran on Examples 3, 7, and 8. The results of the ICP analysis are shown in Table 4 below: TABLE 4 Element Example 7 Example 8 Example Example 3 Example 2 Amount Amount 8B Amount Amount Amount (ppm) (ppm) (ppm) (ppm) (ppm) Na <50 50 60 13 19Attorney Docket No.: L3-8120 WO Mg <10 11 11 3 4 Al <200 61 49 6 6 K <200 11 11 <10 <10 Ca <100 <10 <10 <10 <10 Mn 45 45 43 18 18 Fe 30 140 120 27 37 Co <3 N / A N / A <1 <1 Ni <5 N / A N / A 1 2

[0081] As shown in Table 3, a comparison of Example 7 (pristine SiO) to the spray dried lithiated inorganic powder of Example 3 indicates that lithiated inorganic powder prepared through spray drying has a similar iron content to that of pristine SiO, meaning no additional impurity was added. In contrast, the paste processed Examples 8 and 8B compared with spray dried lithiated inorganic powder of Examples 3 and 2 had a substantial increase in iron content when compared to both pristine SiO and the spray dried example. As such, spray drying can reduce impurities when compared to those made by the paste process. DEFINITIONS

[0082] Unless defined otherwise, all terms of art, notations and other technical and scientific terms or terminology used herein are intended to have the same meaning as is commonly understood by one of ordinary skill in the art to which the claimed subject matter pertains. In some cases, terms with commonly understood meanings are defined herein for clarity and / or for ready reference, and the inclusion of such definitions herein should not necessarily be construed to represent a substantial difference over what is generally understood in the art.

[0083] The terms “powders” and “particles” used herein are equivalent, except that a single powder refers to a plurality of particles. This disclosure can apply to a wide range of particles and powders.

[0084] As used herein, the word “layer(s)” and “coating(s)” are equivalent. Specifically, each term “layer(s)” or “coating(s)” as used in relation to a particle(s) indicates that at least a portion of the surface of such particle, substantially all, or all of the surface of such particle(s) is covered by or in contact with the “layer(s)” or “coating(s).” Similarly, the term “coated” in relation to a particle(s) indicates that at least a portion of the surface of theAttorney Docket No.: L3-8120 WO particle, substantially all, or all of the surface of the particle(s) is covered by or in contact with the substance(s) with which the particle(s) is said to be “coated.”

[0085] Reference to “about” a value or parameter herein includes (and describes) variations that are directed to that value or parameter per se. For example, description referring to “about X” includes description of “X”. In addition, reference to phrases “less than”, “greater than”, “at most”, “at least”, “less than or equal to”, “greater than or equal to”, or other similar phrases followed by a string of values or parameters is meant to apply the phrase to each value or parameter in the string of values or parameters.

[0086] As used herein, the singular forms “a,” “an,” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. It is also to be understood that the term “and / or” as used herein refers to and encompasses any and all possible combinations of one or more of the associated listed items. It is further to be understood that the terms “includes, “including,” “comprises,” and / or “comprising,” when used herein, specify the presence of stated features, integers, steps, operations, elements, components, and / or units but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, units, and / or groups thereof.

[0087] This application discloses several numerical ranges in the text and figures. The numerical ranges disclosed inherently support any range or value within the disclosed numerical ranges, including the endpoints, even though a precise range limitation is not stated verbatim in the specification because this disclosure can be practiced throughout the disclosed numerical ranges.

[0088] The above description is presented to enable a person skilled in the art to make and use the disclosure, and is provided in the context of a particular application and its requirements. Various modifications to the preferred embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments and applications without departing from the spirit and scope of the disclosure. Thus, this disclosure is not intended to be limited to the embodiments shown, but is to be accorded the widest scope consistent with the principles and features disclosed herein.

Claims

Attorney Docket No.: L3-8120 WO CLAIMS 1. A method of producing a powder comprising: mixing a lithium precursor, a liquid medium, and inorganic particles to form a precursor suspension; spray drying the precursor suspension to form precursor particles; and heating the precursor particles to form a powder comprising inorganic particles having a coating comprising carbon and one or more lithium silicates.

2. The method of claim 1, wherein the lithium precursor comprises inorganic lithium salts, organic lithium salts, lithium metals, lithium alloys, lithium oxides, lithium hydroxides, or combinations thereof.

3. The method of any one of claims 1-2, wherein the precursor suspension comprises 0.05-10 wt.% lithium precursor.

4. The method of any one of claims 1-3, further comprising mixing a carbon precursor in the precursor suspension, wherein the carbon precursor comprises pentane, hexane, 2-methylhexane, cyclopentane, cyclohexane, methylcyclohexane, heptane, 4-methylheptane, octane, cyclooctane, nonane, decane, benzene, toluene, xylene, ethylbenzene, amylbenzene, methylethylbenzene, diethylbenzene, mesitylene, 1,2,4-triethylbenzene, 1,3,5-triethylbenzene, amylbenzene, tetrahydronaphthalene, refinery heavy oil, pitch, polyethylene, polypropylene, polyacrylic acid, polymaleic acid, polyfumaric acid, polycrotonic acid, poly(pentenoic) acid, polymethacrylic acid, polydimethacrylic acid, poly(allyl alcohol), poly(n-propyl)acrylate, poly(hydroxymethyl)acrylate, poly(2- hydroxyethyl)acrylate, poly(2-carboxyethyl)acrylate, poly(3-ethoxy-3- oxopropyl)acrylate, poly(methylcarbamylethyl)acrylate, poly(2- hydroxyethyl)methacrylate, polyvinylpyrrolidone, polyacrylamide, polymethacrylamide, poly(N-isopropyl)acrylamide, polyvinylacetamide, polyvinyl alcohol, polyvinyl-N-methylacetamide, poly(N-hydroxymethyl)acrylamide, poly(N-hydroxyethyl)acrylamide, poly(N-methoxymethyl)acrylamide, poly(N- ethoxymethyl)acrylamide, polyacrylonitrile, sucrose, natural polymers such as cellulose and polysaccharides, or combinations thereof.Attorney Docket No.: L3-8120 WO 5. The method of claim 4, wherein the precursor suspension comprises 0.1-5 wt.% carbon precursor.

6. The method of any one of claims 1-5, wherein the liquid medium comprises water, alcohols, esters, ketones, nitriles, halogenated hydrocarbons, or combinations thereof.

7. The method of any one of claims 1-6, wherein the inorganic particles comprise silicon oxide particles.

8. The method of claim 7, wherein silicon oxide of the carbon coated silicon oxide particles has a formula of SiOx, where x is about 0.75-2.

9. The method of any one of claims 1-7, wherein the inorganic particles comprise carbon coated inorganic particles.

10. The method of any one of claims 1-9, wherein the precursor particles are heated to 700-1000oC.

11. The method of claim 10, wherein the precursor particles are heated in an inert gas.

12. The method of any one of claims 1-11, wherein the lithium silicate comprises Li2SiO3, Li2Si2O5, Li4SiO4, Li8SiO6, Li6Si2O7, Li2Si3O7, or combinations thereof.

13. The method of any one of claims 1-12, wherein the inorganic particles having the coating comprising carbon and one or more lithium silicates has a Uniformity Factor of at least 1 calculated by the following formula: Uniformity Factor ൌ ெ^௫ ^^^^ ு^^^^௧^^ୌ^ , wherein the max peak height is a maximum height of a particle size distribution curve of the inorganic particles having the coating comprising carbon and one or more lithium silicates and FWHM is a full width at half maximum height of the particle size distribution curve of the inorganic particles having the coating comprising carbon and one or more lithium silicates.

14. A powder comprising:Attorney Docket No.: L3-8120 WO inorganic particles having a coating comprising carbon and one or more lithium silicates, wherein the powder has a Uniformity Factor of at least 1 calculated by the following formula: Uniformity Factor ൌ ெ^௫ ^^^^ ு^^^^௧^^ୌ^ , wherein max peak height is a maximum height of a particle size distribution curve of the powder and FWHM is a full width at half maximum height of the particle size distribution curve of the powder.

15. The powder of claim 14, wherein the carbon content of the coated inorganic particles is 0.1-10 wt.%.

16. The powder of any one of claims 14-15, wherein the lithium content of the coated inorganic particles is 0.1-8 wt.%.

17. The powder of any one of claims 14-16, wherein the inorganic particles comprise silicon oxide particles.

18. The powder of any one of claims 14-17, wherein silicon oxide of the silicon oxide particles has a formula of SiOx,where x is about 0.75-2.

19. The powder of any one of claims 14-18, wherein the powder has an iron content that is less than or equal to 125% of an iron content of the inorganic particles.

20. An anode comprising the powder of any one of claims 14-19.

21. A battery comprising the anode of claim 20.

22. The battery of claim 21, wherein the battery is a lithium-ion battery.

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