WO2025072959A1

WO2025072959A1 - Graphitic-material-coated silicon particles, methods of making same, and uses thereof

Info

Publication number: WO2025072959A1
Application number: PCT/US2024/049312
Authority: WO
Inventors: Yong Lak Joo; Mohammad Abdul AZIZ; Yash JOSHI
Original assignee: Cornell University
Current assignee: Cornell University
Priority date: 2023-09-29
Filing date: 2024-09-30
Publication date: 2025-04-03
Anticipated expiration: 2026-03-29

Abstract

Graphitic-material-coated silicon particles and uses thereof and compositions thereof and methods of making graphitic-material-coated silicon particles. In various examples, a method of forming a plurality of graphitic-material-coated silicon particles comprises milling (e.g., air jet ball milling or the like) a mixture comprising one or more silicon particle(s), one or more graphitic material(s) (e.g., graphite, graphene, or the like, or any combination thereof), and one or more binder(s). In various examples, a graphitic-material-coated silicon particle comprises a silicon particle and one or more graphitic material(s), where the one or more graphitic material(s) is/are disposed on at least a portion, substantially all, or all of one or more surface(s) of the silicon particle. In various examples, an electrode or device (such as, for example, an electrochemical device or the like) comprises a plurality of graphitic-material-coated silicon particles.

Description

GRAPHITIC-MATERIAL-COATED SILICON PARTICLES, METHODS OF MAKING SAME, AND USES THEREOF

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application No. 63/586,841, filed September 29, 2023; the contents of the above-identified application are hereby fully incorporated herein by reference in their entirety.

BACKGROUND

[0002] Silicon has received tremendous attention as a lithium-ion battery (LIB) anode due to its high theoretical capacity (4200 mAh g-1, 10 times higher than that of graphite) and low working potential versus Li+/Li. However, the severe volume change (>300%) during the lithium insertion and extraction process generates strong mechanical stress which causes the pulverization of Si particles, continuous creation of solid-electrolyte interphase (SEI) layers and loss of electrical connection from current collector, leading to poor cyclic performance of the electrodes as well as low initial Coulombic efficiency. There are two typical strategies to overcome these shortcomings. One is to prepare submicron scale Si particles via milling process, and the other is to coat Si particle with carbon via coating process such as CVD (Chemical Vapor Deposition) which is costly and hard to scale-up.

SUMMARY OF THE DISCLOSURE

[0003] The present disclosure describes, inter alia, graphitic-material-coated silicon particles and compositions thereof and methods of making graphitic-material-coated silicon particles. In various examples, the present disclosure also provides electrodes and devices comprising graphitic-material-coated silicon particles.

[0004] In an aspect, the present disclosure provides graphitic-material-coated silicon particles. In various example, a graphitic-material-coated silicon particle comprises: a silicon particle, which may be an oxidized silicon particle (such as, for example, a partially oxidized silicon particle or completely oxidized silicon particle), comprising a size of about 10 nm (nm = nanometer(s)) to about 5 pm ((pm = micron(s)), including all 0.1 nm values and ranges therebetween (e.g., about 10 nm to 2 pm, about 100 nm to about 500 nm, or about 300 nm to about 700 nm, or about 300 nm to about 700 nm); and one or more graphitic material(s) comprising a size of about 2 nm (or a monolayer, bilayer, trilayer, or the like) to about 3 pm, including all 0.1 nm values and ranges therebetween (e.g., about 2 nm to about 50 nm, about 10 nm to about 100 nm, about 100 nm to about 3 pm), where the one or more graphitic material(s) is/are disposed on (such as, for example, coated on or the like) at least a portion, substantially all, or all of one or more surface(s) (e.g., exterior surface(s)) of the silicon particle. In various examples, the graphitic-material-coated silicon particle further comprises one or more binder(s).

[0005] In an aspect, the present disclosure provides compositions. In various examples, a composition comprises one or more graphitic-material-coated silicon particle(s) (such as, for example one or more graphitic-material-coated silicon particle(s) of the present disclosure and/or one or more graphitic-material-coated silicon particle(s) made by a method of the present disclosure). In various examples, the composition comprises at least two or more different (e.g., structurally different, compositionally different, or the like, or any combination thereof) graphitic-material-coated silicon particles. In various examples, the composition further comprises one or more active material(s) and/or one or more binder(s). In various examples, the composition is suitable (or configured) for use in a device (such as, for example, an electrochemical device or the like). In various examples, the composition is suitable (or configured) or use in an (or as an) electrode (such as, for example, an anode and/or a cathode of a device (such as, for example, an electrochemical device or the like)). [0006] In an aspect, the present disclosure provides methods of making one or more graphitic-material -coated silicon particle(s) (such as, for example one or more graphitic- material-coated silicon particle(s) of the present disclosure). In various examples, a method comprises in-situ graphitic material (e.g., graphene or the like) coating of silicon particles. In various examples, a method of making one or more graphitic-material-coated silicon particle(s) comprises one or more milling(s) and/or mixing(s). In various examples, the method comprises milling a mixture (e.g., a mixture comprising one or more silicon particle(s), one or more graphitic material(s), and optionally, one or more binder(s)). In various examples, the method further comprises forming the mixture prior to the milling. In various examples, a milling is ball milling (such as, for example, a planetary ball milling or the like) or the like and/or the milling device is a ball milling device (such as, for example, a planetary ball milling device or the like) or the like, the milling is jet milling (such as, for example, jet ball milling, air jet milling, air jet ball milling, or the like) or the like and/or the milling device is a jet milling device (such as, for example, a jet ball milling device, an air jet milling device, an air jet ball milling device, or the like) or the like, the milling is hammer milling or the like and/or the milling device is a hammer milling device or the like, the milling is pin milling or the like and/or the milling device is a pin milling device or the like, the milling is screen milling (such as, for example, conical screen milling or the like) or the like and/or the milling device is a screen milling device (such as, for example, conical screen milling device or the like) or the like.

[0007] In an aspect, the present disclosure provides electrodes. An electrode (such as, for example, an anode or a cathode) comprises one or more graphitic-material-coated silicon particle(s) of the present disclosure. In various examples, the electrode comprises at least two or more different (e.g., structurally different, compositionally different, or the like, or any combination thereof) graphitic-material-coated silicon particles. In various examples, the electrode further comprises one or more active material(s). In various examples, an active material is a conducing material. In various examples, the electrode further comprises one or more binder(s). In various examples, the electrode further comprises a current collector. In various examples, the electrode is suitable for (or configured for) use in a device (such as, for example, an electrochemical device or the like). In various examples, the electrode is suitable for (or configured for) use in a device (such as, for example, as an anode and/or a cathode of a device (such as, for example, an electrochemical device or the like)).

[0008] In an aspect, the present disclosure provides devices. A device comprises one or more electrode(s) of the present disclosure. In various examples, the device is an electrochemical device or the like (such as, for example, a battery, a supercapacitor, a fuel cell, an electrolyzer, an electrolytic cell, or the like).

[0009] In various examples, the present disclosure provides scalable fabrication of graphitic material (such as, for example, graphene or the like) coated silicon particles, which may be used for electrode materials, electrode additives, and the like. In various examples, use of an aqueous suspension of graphene in a milling process provides enhanced cell performance when combined with water-based slurry casting for electrode fabrication. In various examples, in situ milling of Si and coating of graphene (which may be formed from recycled streams (e.g., Si from solar cell waste or the like and/or exfoliated graphene from consumed lithium-ion batteries) is used to fabricate cost-effective high-capacity anode materials (which may be used in batteries, such as, for example, lithium-ion batteries).

BRIEF DESCRIPTION OF THE FIGURES

[0010] For a fuller understanding of the nature and objects of the disclosure, reference should be made to the following detailed description taken in conjunction with the accompanying figures.

[0011] FIG. 1 shows a schematic of in situ graphene coating on Si particles during jet milling. [0012] FIG. 2 shows average particle size (D50) (left) and DIO, D50, D90, and D99 of milled Si at particles at various milling times (right).

[0013] FIG. 3 shows SEM images of ball milled silicon (Si) particles, graphene only, and Si particles with graphene (Gr) for 1 hour, 2 hours, 3 hours, and 4 hours.

[0014] FIG. 4 shows energy-dispersive X-ray spectroscopy (EDX) mapping of A- carbon coated SiOx via CVD process and B- exfoliated graphene (exGr) coated silicon oxide particles (SiOx) during ball milling. Right to left - combined, silicon (Si) (in green) only and carbon (C) (in red) only.

[0015] FIG. 5 shows thermal gravimetric analysis (TGA) of mill coated SiOx and carbon coated SiOx via CVD.

[0016] FIG. 6 shows EDX mapping of A- exfoliated Gr coating process and B- CVD grown Gr coating. Right to left - combined, silicon (Si) (in green) only and carbon (C) (in red) only.

[0017] FIG. 7 shows TGA of chemical vapor deposition (CVD) grown graphene coated SiOx.

[0018] FIG. 8 shows first cycle discharge/charge profiles (top) and initial Coulombic efficiency (ICE) (bottom) of ex Gr coated SiOx. First cycle discharge/charge profiles carbon coated SiOx via CVD are also shown for comparison. The carbon content in both coated SiOx particles was kept the same at 2 wt.%.

[0019] FIG. 9 shows first cycle discharge/charge profiles (top) and initial Coulombic efficiency (ICE) (bottom) of CVD grown graphene coated SiOx anodes from two different slurry cast systems (water and N-methyl-2-pyrrolidone (NMP)).

[0020] FIG. 10 shows performance of Si/Gr anodes; A - first cycle discharge/charge profiles; B - initial Coulombic efficiency (ICE); C - rate capability; and D - 300 cycle performance at 0.3 C.

[0021] FIG. 11 shows a schematic of in situ Si milling, graphene exfoliation, and coating via air jet ball milling.

[0022] FIG. 12 shows Fourier-Transform Infrared (FT-IR) spectra of metallurgical silicon (MET SI or met Si) (before and after jet milling).

[0023] FIG. 13 shows Raman spectra of met Si (before and after jet milling).

[0024] FIG. 14 shows lithium-ion battery LIB (Si vs. Li) half-cell performance (formation): first cycle discharge/charge profiles (top) and initial Coulombic efficiency (ICE) (bottom). [0025] FIG. 15 shows plasma treatment temperature for metallurgical Si (MLSI), milled metallurgical Si (AMSI), solar Si (SSI), and milled solar Si (SMSI).

[0026] FIG. 16 shows lithium-ion battery (LIB) (Si vs. Li) half-cell performance (formation): first cycle discharge/charge profiles (top) and initial Coulombic efficiency (ICE) (bottom) for MLSI (plasma treated at 600 °C and 880 °C) and jet milled metallurgical Si (25 °C).

[0027] FIG. 17 shows lithium-ion battery (LIB) (Si vs. Li) half-cell performance (formation): first cycle discharge/charge profiles (top) and initial Coulombic efficiency (ICE) (bottom) for AMSI (plasma treated at 600 °C and 880 °C), SMSI (plasma treated at 600 °C and 880 °C), and jet milled metallurgical Si (25 °C).

[0028] FIG. 18 shows Raman spectroscopy characterization of microSi and jet milled microSi.

[0029] FIG. 19 shows a schematic representation of graphite/graphene coated silicon particles using LabRAM.

[0030] FIG. 20 shows SEM (A, B) and EDS mapping (C-E) of micro-Si (5-50 pm) with ACS graphene (1-2 pm) and PAA. Dry mixing at RAM (5 minutes) at 60 G.

[0031] FIG. 21 shows SEM images of Met Si (1-3 pm) + Carbon Super P (CSP)+ PAA, dry mixing at LabRAM for 5 minutes using vibration intensity of 60 G.

[0032] FIG. 22 shows SEM images of Met Si (1-3 pm) + Carbon Super P (CSP), dry mixing at LabRAM at (A, B) 5, (C, D)15, and (E, F) 30 minutes.

[0033] FIG. 23 shows lithium-ion battery (LIB) (Si vs. Li) performance of A- Met Si (1- 3 pm) + Carbon Super P (CSP)+ PAA with dry RAM operation at 5 min, 60 G, and B- Met Si (1-3 pm) + Carbon Super P (CSP) with dry LabRAM operation at 5 min, 60 G.

[0034] FIG. 24 shows A- an FTIR and B- Raman spectra of met Si, artificial graphite and PAA (before and after jet milling).

DETAILED DESCRIPTION OF THE DISCLOSURE

[0035] Although subject matter of the present disclosure is described in terms of certain embodiments and examples, other embodiments and examples, including embodiments and examples that do not provide all of the benefits and features set forth herein, are also within the scope of this disclosure. For example, various structural, logical, and process step changes may be made without departing from the scope of the disclosure.

[0036] As used herein, unless otherwise indicated, “about”, “substantially”, or “the like”, when used in connection with a measurable variable (such as, for example, a parameter, an amount, a temporal duration, or the like) or a list of alternatives, is meant to encompass variations of and from the specified value including, but not limited to, those within experimental error (which can be determined by, e.g., a given data set, an art accepted standard, etc. and/or with, e.g., a given confidence interval (e.g., 90%, 95%, or more confidence interval from the mean), such as, for example, variations of +/- 10% or less, +/-5% or less, +/-1% or less, and +/-0.1% or less of and from the specified value), insofar such variations in a variable and/or variations in the alternatives are appropriate to perform in the instant disclosure. As used herein, the term “about” may mean that the amount or value in question is the exact value or a value that provides equivalent results or effects as recited in the claims or taught herein. That is, it is understood that amounts, sizes, compositions, parameters, and other quantities and characteristics are not and need not be exact, but may be approximate and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error, or the like, or other factors known to those of skill in the art such that equivalent results or effects are obtained. In general, an amount, size, composition, parameter, or other quantity or characteristic, or alternative is “about” or “the like,” whether or not expressly stated to be such. It is understood that where “about,” is used before a quantitative value, the parameter also includes the specific quantitative value itself, unless specifically stated otherwise.

[0037] Ranges of values are disclosed herein. The ranges set out a lower limit value and an upper limit value. Unless otherwise stated, the ranges include the lower limit value, the upper limit value, and all values between the lower limit value and the upper limit value, including, but not limited to, all values to the magnitude of the smallest value (either the lower limit value or the upper limit value) of a range. It is to be understood that such a range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. To illustrate, a numerical range of “0.1% to 5%” should be interpreted to include not only the explicitly recited values of 0.1% to 5%, but also, unless otherwise stated, include individual values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.5% to 1.1%; 0.5% to 2.4%; 0.5% to 3.2%, and 0.5% to 4.4%, and other possible sub-ranges) within the indicated range. It is also understood (as presented above) that there are a number of values disclosed herein, and that each value is also herein disclosed as “about” that particular value in addition to the value itself. For example, if the value “10” is disclosed, then “about 10” is also disclosed. Ranges can be expressed herein as from “about” one particular value, and/or to “about” another particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms a further disclosure. For example, if the value “about 10” is disclosed, then “10” is also disclosed.

[0038] As used herein, unless otherwise stated, the term “group” refers to a chemical entity that is monovalent (i.e., has one terminus that can be (is) covalently bonded to other chemical species), divalent, or polyvalent (i.e., has two or more termini that can be (are) covalently bonded to other chemical species). The term “group” also includes radicals (e.g., monovalent radicals and multivalent radicals, such as, for example, divalent radicals, trivalent radicals, and the like). Illustrative examples of groups include:

the like.

[0039] As used herein, unless otherwise stated, the term “structural analog” refers to any silicon particle, graphitic material, polymer, or the like, or any portion thereof (such as, for example, one or more group(s) thereof or the like) or group if one atom or group of atoms, functional group or functional groups, or substructure or substructures is/are replaced with another atom or group of atoms, functional group or functional groups, substructure or substructures, or the like. In various examples, the term “structural analog” refers to any group that is derived from an original silicon particle, graphitic material, polymer, or the like or portion thereof (such as, for example, one or more group(s) thereof or the like) or the like by a chemical reaction, where the silicon particle, graphitic material, polymer, or the like or portion thereof (such as, for example, one or more group(s) thereof or the like) or the like is modified or partially substituted such that at least one structural feature of the silicon particle, graphitic material, polymer, or the like or portion thereof (such as, for example, one or more group(s) thereof or the like) or the like is retained.

[0040] The present disclosure describes, inter alia, graphitic-material-coated silicon particles and compositions thereof and methods of making graphitic-material-coated silicon particles. In various examples, the present disclosure also provides electrodes and devices comprising graphitic-material-coated silicon particles.

[0041] In an aspect, the present disclosure provides graphitic-material-coated silicon particles. In various examples, a graphitic-material-coated silicon particle comprises one or more graphitic material(s) disposed on at least a portion or all of the exterior surface(s) of a silicon particle, and optionally, one or more binder(s). In various examples, graphitic- material-coated silicon particle or graphitic-material-coated silicon particles is/are formed by a method of the present disclosure. Non-limiting examples of graphitic-material-coated silicon particles are provided herein.

[0042] In various example, a graphitic-material-coated silicon particle comprises: a silicon particle of the present disclosure (e.g., a milled silicon particle or the like) and one or more graphitic material(s) of the present disclosure (e.g., milled graphitic material(s) or the like). In various examples, the one or more graphitic material(s) is/are disposed on (such as, for example, coated on or the like) at least a portion, substantially all, or all of one or more surface(s) (e.g., exterior surface(s)) of the silicon particle. In various examples, a graphitic- material-coated silicon particle further comprises one or more binder(s).

[0043] In various example, a graphitic-material-coated silicon particle comprises: a silicon particle (e.g., a milled silicon particle or the like) comprising a size (such as, for example, one or more linear dimension(s) (e.g., a diameter or the like), which may be longest linear dimension(s), or the like) of about 10 nm to about 5 pm, including all 0.1 nm values and ranges therebetween (e.g., about 10 nm to 2 pm, about 100 nm to about 500 nm, or about 300 nm to about 700 nm, or about 300 nm to about 700 nm, or about 100 nm to about 3 pm); and one or more graphitic material(s) (e.g., milled graphitic material(s) or the like) comprising a size (such as, for example, one or more linear dimension(s) (e.g., a diameter, a thickness, or the like), which may be longest linear dimension(s), or the like) of about 2 nm (or a monolayer, bilayer, trilayer, or the like) to about 3 pm, including all 0.1 nm values and ranges therebetween (e.g., about 2 nm to about 50 nm, about 10 nm to about 100 nm, about 100 nm to about 3 pm), where the one or more graphitic material(s) is/are disposed on (such as, for example, coated on or the like) at least a portion, substantially all, or all of one or more surface(s) (e.g., exterior surface(s)) of the silicon particle. In various examples, a graphitic- material-coated silicon particle further comprises one or more binder(s).

[0044] In various examples, at least a portion, substantially all, or all of the graphitic material(s) comprise a size (such as, for example, one or more linear dimension(s) (e.g., a diameter, a thickness, or the like), one or more or all of which may be longest linear dimension(s), or the like) (which may be an average size, such as, for example, an average linear dimension (e.g., an average diameter, and average thickness, or the like), which may be an average longest linear dimension, or the like) that is smaller (e.g., about 80% or more smaller, about 50% or more smaller, about 20% or more smaller, about 10% or more smaller, or about 5% or more smaller) than the size (such as, for example, one or more linear dimension(s) (e.g., a diameter, a thickness, or the like), one or more or all of which may be longest linear dimension(s), or the like) (which may be an average size, such as, for example, an average linear dimension (e.g., an average diameter, an average thickness, or the like), which may be an average longest linear dimension, or the like) of the silicon particle.

[0045] A graphitic-material-coated silicon particle can comprise various silicon particles. A silicon particle may be an oxidized silicon particle (such as, for example, a partially oxidized silicon particle or completely oxidized silicon particle). Non-limiting examples of silicon particles include silicon oxide particles (SiOx, where, for example, x is 0.01 to 1.99) particles; metallurgical silicon particles; recycled metallurgical silicon particles; milled metallurgical silicon particles; solar silicon particles; and milled solar silicon particles; structural analogs thereof; and the like; and any combination thereof.

[0046] A graphitic-material-coated silicon particle can comprise various graphitic materials. The graphitic materials of a graphitic-material-coated silicon particle can be the same. In the case where a graphitic-material-coated silicon particle comprises two or more graphitic materials, two or more of the graphitic materials are different (e.g., structurally different, compositionally different, or the like, or any combination thereof). Non-limiting examples of graphitic materials include graphene (e.g., in the natural form, in an artificial form, in a recycled form, or the like, or any combination thereof); chemical vapor deposition (CVD) grown graphene; exfoliated graphene (exGR); graphite (e.g., in the natural form, in an artificial form, in a recycled form, or the like, or any combination thereof); and petroleum coke; structural analogs thereof; and the like; and any combination thereof.

[0047] A graphitic-material-coated silicon particle can comprise various combinations of silicon particle and graphitic material(s). In various examples, the silicon particle is a SiOx particle and/or at least a portion or all the one or more graphitic material(s) is/are exGR. In various examples, the exGR coated SiOx particle comprises about 2 wt% carbon. In various examples, the silicon particle is a SiOx particle and/or at least a portion or all the one or more graphitic material(s) is CVD grown graphene.

[0048] In various examples, a graphitic-material-coated silicon particle further comprises one or more binder(s). In various examples, the one or more binder(s) is/are chosen from: polyacrylic acids; peroxyacetic acids (PAA); poly vinylidene fluorides (PVDFs); polyvinyl alcohols (PVAs), carboxymethyl celluloses (CMCs), styrene-butadiene rubbers (SBRs); and acrylic polymers; structural analogs thereof; and the like; and any combination thereof. In various examples, the one or more binder(s) comprise (or is) PAA comprising a molecular weight (M_w and/or M_n) of about 4 x 10⁶ g/mol. Without intending to be bound by any particular theory, it is considered the binder(s) bond(s) the active substance(s) (e.g., silicon particle(s)), the conductive agent(s) (e.g., graphitic material(s)), and the current collector, if present, to maintain the stability of the electrode structure in the process of charge and/or discharge. In various examples, a binder is a polymer that can interact with Si through its functional groups, such as, for example, -COOH, -OH, and the like (e.g., polyacrylic acids (PAAs), polyvinyl alcohols (PVAs), carboxymethyl celluloses (CMCs), and the like, and any combination thereof).

[0049] A graphitic-material-coated silicon particle can have various sizes. In various examples, a graphitic-material-coated silicon particle comprises a size (such as, for example, one or more linear dimension(s) (e.g., a diameter or the like), which may be longest linear dimension(s), or the like) of about 10 nm to about 8 pm, including all 0.1 nm values and ranges therebetween (e.g., about 10 nm to about 1 pm, about 10 nm to about 2 pm, about 10 nm to less than about 1 pm, about 10 nm to less than about 2 pm, about 100 nm to about 3 pm).

[0050] In various examples, graphitic material(s) at least partially or completely encapsulate the silicon particle. In various examples, graphitic material(s) form a monolayer or a bilayer or the like or a combination thereof at least partially or completely encapsulating the silicon particle. In various examples, graphitic material(s) form a continuous layer (e.g., a monolayer or a bilayer or a combination thereof) disposed on at least a portion, substantially all, or all of one or more or all of the surfaces of the silicon particle. In various examples, graphitic material(s) form one or more domain(s) (e.g., island(s) or the like) independently comprising a monolayer or a bilayer or the like or a combination thereof) (e.g., at least a portion, substantially all, or all of the domain(s) is/are discontinuous domain(s)) disposed on a surface of the silicon particle. In various examples, graphitic material(s) form a continuous layer (e.g., a monolayer or a bilayer or the like or a combination thereof) or one or more domain(s) (e.g., island(s) or the like) independently comprising a monolayer or a bilayer or the like or a combination thereof) disposed on about 90% or more, about 95% or more, about 98% or more, about 99% or more, about 99.9% or more, or about 100% of one or more or all of the surfaces of the silicon particle. In various examples, graphitic material(s) form a continuous layer (e.g., a monolayer or a bilayer or the like or a combination thereof) or one or more domain(s) (e.g., island(s) or the like) independently comprising a thickness of 2 nm or a monolayer (or a bilayer, trilayer, or the like) to about 100 nm, including all 0.1 nm values and ranges therebetween.

[0051] In various examples, the thickness of the graphitic material(s) encapsulating or the layer of graphitic material(s) disposed on the silicon particle does not substantially change (e.g., over the entire area of the silicon particle coated by the graphitic material(s)). In various examples, the thickness of the graphitic material(s) encapsulating or the layer of graphitic material(s) disposed on the silicon particle does not change by more than 10%, more than 5%, more than 1%, more than 0.1% (e.g., over the entire area of the silicon particle coated by the graphitic material(s)). The thickness or change in thickness of the graphitic material(s) can be determined by methods known in the art. In various examples, the thickness or change in thickness of the graphitic material(s) is determined by one or more electron microscopy methods (such as, for example, scanning electron microscopy (SEM), transmission electron microscopy (TEM), or the like),

[0052] A graphitic-material-coated silicon particle can comprise various amounts of silicon. In various examples, graphitic-material -coated silicon particles comprise about 60% or greater, about 70% or greater, about 80% or greater, about 90% or greater, or 95% or greater by weight silicon (based on the total weight of the graphitic-material-coated silicon particles).

[0053] A graphitic-material-coated silicon particle may comprise carbon. In various examples, a graphitic-material-coated silicon particle comprises carbon at about 1 wt.% to about 40 wt.% (based on the total weight of the particle), including all 0.1 wt.% values and ranges therebetween.

[0054] In various examples, a graphitic-material-coated silicon particle or graphitic- material-coated silicon particles is/are suitable (or configured) for use in a device (such as, for example, an electrochemical device or the like). In various examples, a graphitic-material- coated silicon particle or graphitic-material-coated silicon particles is/are suitable (or configured) for use in an (or as an) electrode (such as, for example, an anode or a cathode of a device (such as, for example, an electrochemical device or the like)).

[0055] In an aspect, the present disclosure provides compositions. In various examples, a composition comprises one or more graphitic-material-coated silicon particle(s) (such as, for example one or more graphitic-material-coated silicon particle(s) of the present disclosure). In various examples, a composition comprises at least two or more different (e.g., structurally different, compositionally different, or the like, or any combination thereof) graphitic- material-coated silicon particles. In various examples, a composition is formed by a method of the present disclosure. Non-limiting examples of compositions are provided herein.

[0056] In various examples, a composition comprises one or more graphitic-material- coated silicon particle(s). In various examples, a composition further comprises one or more active material(s) and/or one or more binder(s). [0057] A composition can comprise various graphitic-material-coated silicon particles. The graphitic-material-coated silicon particles of a composition may be substantially the same or the same or two more of the graphitic-material-coated silicon particles are different (e.g., structurally different, compositionally different, or the like, or any combination thereof). In various examples, the graphitic-material-coated silicon particles of a composition independently comprise a size (or comprise an average size) (such as, for example, one or more linear dimension(s) (e.g., a diameter or the like), which may be longest linear dimension(s), or the like) of about 10 nm to about 8 pm, including all 0.1 nm values and ranges therebetween (e.g., about 10 nm to about 1 pm, about 10 nm to about 2 pm, about 10 nm to less than about 1 pm, about 10 nm to less than about 2 pm, about 100 nm to about 3 pm). In various examples, a silicon particle size and/or a graphitic material size is/are an average size or average sizes. In various examples, the graphitic-material-coated silicon particles of a composition independently comprise carbon at (or comprise carbon at an average of) about 1 wt.% to about 40 wt.% (based on the total weight of the particles), including all 0.1 wt.% values and ranges therebetween.

[0058] In various examples, a composition is suitable (or configured) for use in a device (such as, for example, an electrochemical device or the like). In various examples, a composition is suitable (or configured) or use in an (or as an) electrode (such as, for example, an anode or a cathode of a device (such as, for example, an electrochemical device or the like)).

[0059] In an aspect, the present disclosure provides methods of making one or more graphitic-material -coated silicon particle(s). In various examples, a method comprises in-situ graphitic material (e.g., graphene or the like) coating of silicon particles. In various examples, a method comprises forming a mixture and milling the mixture. In various examples, a method comprises forming a mixture and mixing the mixture. In various examples, a method comprises forming a mixture, milling the mixture, and mixing the milled mixture. In various examples, a method produces one or more graphitic-material-coated silicon particle(s) or composition(s) of the present disclosure. Non-limiting examples of methods are provided herein.

[0060] In various examples, a method of making one or more graphitic-material-coated silicon particle(s) (such as, for example, one or more graphitic-material-coated silicon particle(s) of the present disclosure) comprises one or more milling(s) and/or mixing(s) described herein. In various examples, a method of making one or more graphitic-material- coated silicon particle(s) (such as, for example, one or more graphitic-material-coated silicon particle(s) of the present disclosure) comprises (prior to the milling(s) and/or mixing(s)) forming a mixture comprising: one or more silicon particle(s), one or more graphitic material(s), and optionally, one or more binder(s).

[0061] In various examples, a method of making one or more graphitic-material-coated silicon particle(s) (such as, for example, one or more graphitic-material-coated silicon particle(s) of the present disclosure) comprises forming a mixture comprising: one or more silicon particle(s), one or more graphitic material(s), and one or more binder(s), and milling the mixture in a milling device, where milled silicon particle(s) and/or milled graphitic material(s) are formed (e.g., at least a portion of, substantially all, or all the one or more silicon particle(s) and the one or more graphitic material(s) are reduced in size during the milling). In various examples, a method further comprises sonication of the milled silicon particle(s) and milled graphitic material(s).

[0062] In various examples, a method of making one or more graphitic-material-coated silicon particle(s) (such as, for example, one or more graphitic-material-coated silicon particle(s) of the present disclosure) comprises reducing the size (e.g., of at least a portion, substantially all, or all) of one or more silicon particle(s) and/or one or more graphitic material(s) (e.g., milling, such as, for example, planetary ball milling, vertical ball milling, or the like, or any combination thereof) of one or more silicon particle(s) and/or one or more graphitic material(s) (e.g., where at least a portion of, substantially all, or all the one or more silicon particle(s) and the one or more graphitic material(s) are reduced in size during the milling), and mixing (e.g., resonant acoustic mixing (RAM), ball milling, or the like) the one or more silicon particle(s) and/or one or more graphitic material(s) that have been reduced in size (e.g., milled or the like, or any combination thereof) and optionally, one or more binder(s), wherein the graphitic-material-coated silicon particles are formed (e.g., the one or more silicon particle(s) are coated by the one or more graphitic material(s)). In various other examples, a method of making one or more graphitic-material-coated silicon particle(s) (such as, for example, one or more graphitic-material-coated silicon particle(s) of the present disclosure) mixing (e.g., resonant acoustic mixing, ball milling, or the like) the one or more silicon particle(s) comprising a size (such as, for example, one or more linear dimension(s) (e.g., a diameter or the like), one or more or all of which may be longest linear dimension(s), or the like) (which may be an average size, such as, for example, an average linear dimension (e.g., an average diameter), which may be an average longest linear dimension or the like) of 10 nm to about 5 pm, including all 0.1 nm values and ranges therebetween (e.g., about 10 nm to 2 pm, about 100 nm to about 500 nm, or about 300 nm to about 700 nm, or about 300 nm to about 700 nm, or about 100 nm to about 3 pm), and one or more graphitic material(s) comprising a size (such as, for example, one or more linear dimension(s) (e.g., a diameter, a thickness, or the like), one or more or all of which may be longest linear dimension(s), or the like) (which may be an average size, such as, for example, an average linear dimension (e.g., an average diameter, and average thickness, or the like), which may be an average longest linear dimension, or the like) of about 2 nm or a monolayer (or a bilayer, trilayer, or the like) to about 3 pm, including all 0.1 nm values and ranges therebetween (e.g., 2 nm to about 2 pm, about 10 nm to about 2 pm, about 50 nm to about 100 nm, or about 100 nm to about 3 pm), and optionally, one or more binder(s) or the like, wherein the graphitic-material-coated silicon particles are formed (e.g., the one or more silicon particle(s) are coated by the one or more graphitic material(s)).

[0063] In various examples, mixing comprises resonant acoustic mixing or the like (or is carried out using a resonant acoustic mixer or the like). In various examples, the mixing comprises resonant acoustic mixing at a vibration intensity of about 10 to about 100 G, including all 0.1 G values and ranges therebetween, and/or for a desired time (such as, for example, about 10 seconds to about 1 hour, including all integer second values and ranges therebetween (e.g., about 30 seconds to about 30 minutes). In various examples, the mixing is blade-less mixing, non-contact mixing, or both. In various examples, the mixing is carried out with a blade-less and/or non-contact mixer. In various examples, the mixing does not result in a substantial (e.g., 5% or more, 1% or more, 0.5% or more) or observable (e.g., by optical microscopy, electron microscopy, or the like) decrease in size of the one or more milled silicon particle(s) or one or more silicon particle(s) and/or one or more milled graphitic material(s) or one or more graphitic material(s).

[0064] Vibrational mixing and coating (such as, for example, resonant acoustic mixing and coating and the like) can be an efficient process for forming graphitic-material-coated silicon particles. Vibrational mixing and coating (such as, for example, resonant acoustic mixing and coating and the like) may be carried out without solvent. In this case, it is expected the solvent-free methods can be used for diverse materials and applications to prepare graphitic-material-coated silicon particles.

[0065] Without intending to be bound by any particular theory, it is considered graphite- coated silicon particles formed using a vibrational mixer (such as, for example, LabRAM (described herein) can provide one or more desirable properties. In various examples, vibrational mixing and coating (such as, for example, resonant acoustic mixing and coating and the like) provides “island-like” coating (which may be achieved by selection of an appropriate starting material concentration. In various examples, high intensity vibrational mixing and coating (such as, for example, resonant acoustic mixing and coating and the like) provided desirable conductivity and improved structural stability and provided protection of milled Si particles from the electrolyte. The resulting graphitic-material-coated silicon particles can have desirable Si content (e.g., 60 to 90 wt%) and can be a cost-effective additive for the graphite anodes for high-capacity Li-ion batteries.

[0066] In various examples, milling and coating processes were combined (e.g., milling resulted in coating) introducing mixture of Si microparticles, graphite (or graphene) and a binder. Without intending to be bound by any particular theory it is considered bombardment of particles in the milling device (e.g., air jet ball milling device or the like), Si particles are fractured into submicron size particles and graphite (or graphene) get sheared and broken into small sizes. The continuous bombardment of milled Si and fractured graphene in the presence of a binder leads to the effective coating of graphitic materials on milled Si particles. The effective coating of graphene on the surface of milled Si provides desirable conductivity, improves the structural stability and provides a protection of milled Si particles from the electrolyte. Also, the graphite is exfoliated during jet ball milling operation, which reduced the system cost. The resulting graphene coated Si particles will have very high Si content (greater than 95 wt%) and can be a cost-effective additive for the graphite anodes for high capacity Li-ion batteries.

[0067] Various silicon particle(s) can be used in a method of making graphitic-material- coated silicon particles. Non-limiting examples of silicon particles are described herein. In various examples, a method uses (e.g., in a milling process) one or more silicon microparticle(s) or the like.

[0068] Silicon particles used in a method of making graphitic-material-coated silicon particles can have various sizes (e.g., prior to milling(s) and/or mixing(s)). In various examples, one or more silicon particle(s) (e.g., prior to milling(s) and/or mixing(s)) independently comprise a size (such as, for example, one or more linear dimension(s), which may be longest linear dimension(s) (e.g., a diameter or the like), or the like) (which may be an average size, such as, for example, an average linear dimension, which may be an average longest linear dimension (e.g., an average diameter) or the like) of about 1 pm to about 100 pm, including all 0.1 pm values and ranges therebetween (e.g., about 10 pm to about 100 pm). In various examples, the size (such as, for example, a longest linear dimension (e.g., a diameter or the like) or the like) of SiOx particles is independently from about 2 pm to about 4 pm. In various examples, one or more silicon particle(s) comprise(s) one or more silicon microparticle(s), one or more silicon nanoparticles, or both.

[0069] Various grapheme material(s) can be used in a method of making graphitic- material-coated silicon particles. Combinations of grapheme materials may be used. Nonlimiting examples of grapheme materials are described herein. In various examples, at least a portion or all the one or more graphitic material(s) is/are an aqueous suspension of the one or more graphitic material(s), one or more dry form(s) of the one or more graphitic material(s), or the like, or any combination thereof.

[0070] Grapheme materials used in a method of making graphitic-material-coated silicon particles can have various sizes (e.g., prior to milling(s) and/or mixing(s)). In various examples, the one or more graphitic material(s) (e.g., prior to milling(s) and/or mixing(s)) independently comprise a size (such as, for example, one or more linear dimension(s), which may be longest linear dimension(s), or the like) (which may be an average size, such as, for example, an average linear dimension, which may be an average longest linear dimension or the like) of about 10 pm to about 100 pm, including all 0.1 pm values and ranges therebetween. In various examples, one or more or all of the grapheme materials is/are chemical vapor deposition (CVD) grown graphene or the like (e.g., CVD grown graphene or the like independently comprising a size (such as, for example, a linear dimension, which may be a longest linear dimension or the like) of about 1 pm. In various examples, one or more or all of the grapheme materials is/are exfoliated graphene (exGR) or the like (e.g., exGr or the like independently comprising a size (such as, for example, a linear dimension, which may be a longest linear dimension or the like) of about 6 pm.

[0071] Various binder(s) can be used in a method of making graphitic-material-coated silicon particles. Non-limiting examples of binders are described herein.

[0072] Various ratios (e.g., weight ratios or the like) of one or more silicon particle(s), one or more graphitic material(s), and optionally, one or more binder(s) (which may be referred to as the starting materials of a mixing and/or milling) can be used in a method of making graphitic-material-coated silicon particles. In various examples, a ratio (e.g., weight ratio or the like) or percentage range (e.g., weight percentage range or the like) of the one or more silicon particle(s), the one or more graphitic material(s), and one or more binder(s), if present, (which may be collectively referred to as the starting materials of the mixing) is about 60 to about 98:about 2.5 to about 35:about 1 to about 20 (where the ratios or percentage ranges total 100 or 100%, respectively), including all 0.1 values for each component ratio or percentage therebetween (e.g., about 60:20:20, about 60:25: 15, about 60:35:5, about 70:25:5, about 80: 15:5, about 80: 17:3, about 85:7.5:7.5, about 85: 10:5, about 85: 12:3, about 90:5:5, about 90:8:2, about 95:4: 1, about 95:2.5:2.5, or about 98: 1 : 1, (e.g., for silicon:graphene:polyacrylic acid or the like as the starting materials/components). In various examples, a ratio (e.g., weight ratio or the like) or percentage range (e.g., weight percentage range or the like) of the one or more silicon particle(s), the one or more graphitic material(s), and one or more binder(s), if present, used in a method of making graphitic-material-coated silicon particles is or corresponds to the ratio (e.g., weight ratio or the like) or percentage range (e.g., weight percentage range or the like) of the one or more silicon particle(s), the one or more graphitic material(s), and one or more binder(s), if present, in the graphitic-material- coated silicon coated particles produced in the method.

[0073] In various examples, a mixture is formed prior to a milling or mixing. In various examples, the mixture is a dry powder. In various examples, one or more or all of the silicon particle(s), the graphitic material(s), or the binder(s), are dry powder(s).

[0074] A method can use various amounts of silicon particles, graphenic material(s), and optionally, binder(s). In various examples, a method (or a mixture) comprises about 60 weight percent (wt.%) to about 98 wt.% (based on the total weight of the mixture) of the one or more silicon particle(s), including all 0.1 wt.% values and ranges therebetween and/or about 1 wt.% to about 40 wt.% (based on the total weight of the mixture) of the one or more graphitic material(s), including all 0.1 wt.% values and ranges therebetween and/or about 1 wt.% to about 20 wt.% (based on the total weight of the mixture) of the one or more binder(s), including all 0.1 wt.% values and ranges therebetween.

[0075] A method can comprise various milling processes and/or use of various milling machines. Combinations of milling processes and/or milling machines can be used. In various examples, the one or more silicon particle(s) is/are fractured into submicron scale silicon particles or the like (e.g., forming the one or more milled silicon particle(s)) and/or the one or more graphitic material(s) is/are broken into smaller sizes of graphitic materials or the like (e.g., forming the one or more milled graphitic material(s) or the like) during the milling.

[0076] Non-limiting examples of milling processes and/or milling machines are described herein. In various examples, a milling is ball milling (such as, for example, a planetary ball milling or the like) or the like and/or the milling device is a ball milling device (such as, for example, a planetary ball milling device or the like) or the like, the milling is jet milling (such as, for example, jet ball milling, air jet milling, air jet ball milling, or the like) or the like and/or the milling device is a jet milling device (such as, for example, a jet ball milling device, an air jet milling device, an air jet ball milling device, or the like) or the like, the milling is hammer milling or the like and/or the milling device is a hammer milling device or the like, the milling is pin milling or the like and/or the milling device is a pin milling device or the like, the milling is screen milling (such as, for example, conical screen milling or the like) or the like and/or the milling device is a screen milling device (such as, for example, conical screen milling device or the like) or the like. Without intending to be bound by any particular theory, it is considered these milling processes and/or milling machines provide impact, attrition, shear compression, or the like, or any combination thereof, which are significant forces for size reduction. In various examples, a milling device, system, or the like is operated a vibration/frequency range of milling about 40 to about 120 Hz, including all 0.1 Hz values and ranges therebetween. In various examples, the milling process(es) are carried out without heating.

[0077] In various examples, milling comprises or is only air jet ball milling. Without intending to be bound by any particular theory, it is considered air jet ball milling technique is an efficient process to reduce the particle size to ~1 pm or less. Also, in certain examples, the graphite is exfoliated during jet ball milling operation, which ultimately reduced cost. In various examples, air jet milling provides substantially no or no observable contamination. [0078] In various examples, reducing the size (e.g., at least a portion of, substantially all, or all of one or more silicon particle(s) and/or one or more graphitic material(s) (e.g., milling, such as, for example, planetary ball milling, vertical ball milling, or the like, or any combination thereof, one or more silicon particle(s) and/or one or more graphitic material(s) (e.g., at least a portion of, substantially all, or all the one or more silicon particle(s) and the one or more graphitic material(s) are reduced in size during the milling) is carried out independently or simultaneously.

[0079] A milling can be carried out for various times. In various examples, a milling is carried out for about 10 minutes to about 5 hours, including all 0.1 hour values and ranges therebetween (e.g., 1 hour to about 4 hours).

[0080] A milling or milling device can apply pressure to the silicon particle(s), the grapheme material(s), and optionally, the binder(s) (or a mixture comprising the silicon particle(s), the grapheme material(s), and optionally, the binder(s)). In various examples, a milling device applies a pressure to the mixture from about 0.6 MPa to about 1 MPa, including all 0.1 MPa values and ranges therebetween.

[0081] A milling can be carried out in (or a milling is performed using various atmospheres). Non-limiting examples of atmospheres include dry air; nitrogen; and argon; and the like; and any combination thereof. In various examples, a milling atmosphere is inert (e.g., an inert gas or a mixture or combination thereof) and/or a milling is performed using an inert gas or a combination or mixture thereof.

[0082] A milling provides one or more milled silicon particle(s). In various examples, one or more of the milled silicon particle(s) independently comprise(s) a size (such as, for example, one or more linear dimension(s) (e.g., a diameter or the like), which may be longest linear dimension(s), or the like) (or comprise an average size, such as, for example, an average linear dimension, which may be an average longest linear dimension (e.g., an average diameter) or the like)) of 10 nm to about 5 pm, including all 0.1 nm values and ranges therebetween (e.g., about 10 nm to 2 pm, about 100 nm to about 500 nm, or about 300 nm to about 700 nm, or about 300 nm to about 700 nm, or about 100 nm to about 3 pm). In various examples, 80% or more, 85% or more, 90% or more, 95% or more, 99% or more, 99.9% or more, or all of the one or more milled silicon particle(s) independently comprise a size (such as, for example, one or more linear dimension(s) (e.g., a diameter or the like), which may be longest linear dimension(s), or the like) (or comprise an average size, such as, for example, an average linear dimension, which may be an average longest linear dimension (e.g., an average diameter) or the like)) of 10 nm to about 5 pm, including all 0.1 nm values and ranges therebetween (e.g., about 10 nm to 2 pm, about 100 nm to about 500 nm, or about 300 nm to about 700 nm, or about 300 nm to about 700 nm, or about 100 nm to about 3 pm). In various examples, milled silicon particles comprise decreased crystallinity (as compared with the same silicon particles that have not been milled). In various examples, milled silicon particles are substantially amorphous or amorphous.

[0083] In various examples, at least a portion, substantially all, or all of the milled graphitic material(s) comprise a size (such as, for example, one or more linear dimension(s) (e.g., a diameter, a thickness, or the like), one or more or all of which may be longest linear dimension(s), or the like) (which may be an average size, such as, for example, an average linear dimension (e.g., an average diameter, and average thickness, or the like), which may be an average longest linear dimension, or the like) that is smaller (e.g., about 80% or more smaller, about 50% or more smaller, about 20% or more smaller, about 10% or more smaller, or about 5% or more smaller) than the size (such as, for example, one or more linear dimension(s) (e.g., a diameter, a thickness, or the like), one or more or all of which may be longest linear dimension(s), or the like) (which may be an average size, such as, for example, an average linear dimension (e.g., an average diameter, an average thickness, or the like), which may be an average longest linear dimension, or the like) of the milled silicon particle(s). [0084] In various examples, milling (e.g., jet milling or the like) provides one or more silicon particle(s), one or more graphitic material(s), or one or more binder(s) (collectively referred to as an “additive sample”), or any combination thereof with one or more altered properties (such as, for example, altered surface propert(ies), decreased (e.g., as determined by one or more spectroscopy method(s), such as, for example, FTIR spectroscopy, Raman spectroscopy, or the like, or any combination thereof) relative the silicon particle(s), graphitic material(s), or binder(s), or any combination thereof prior to milling or that have not been milled. In various examples, at least a portion or all of the oxygen-containing functional groups (such as, for example, silicon-oxygen functional groups or the like or any combination thereof) of at least a portion or all of the silicon particle(s) were absent after milling (e.g., were removed by the milling), at least a portion or all of the silicon particle(s) exhibited increased amorphousness and/or decreased crystallinity), or the like, or any combination thereof. For example, FIG. 24A shows the absorption band around 1074 cm ¹ is stretching mode of the intertetrahedral oxygen atoms in the Si-O-Si linkage before jet milling. However, in the FTIR spectra of met Si/Graphite/PAA composite, all oxygen-containing functional groups vanished, indicating the oxygen-containing functional groups were almost removed in the high speed jet milling process. FIG. 24B shows the Raman spectra of met Si/Graphite/PAA composite. From this figure, the strong peak located at 482 cm ¹ correspond to the characteristic Raman shift of crystalline Si. However, the peak intensity of silicon also decreases and shift to 485 cm ¹ correspond to the characteristic Raman shift of an amorphous Si after jet milling.

[0085] A milling provides one or more milled grapheme material(s). In various examples, one or more milled graphitic material(s) independently comprise(s) a size (such as, for example, one or more linear dimension(s), which may be longest linear dimension(s), or the like) (or comprise an average size, such as, for example, an average linear dimension, which may be an average longest linear dimension or the like) of about 2 nm (or a monolayer, bilayer, trilayer, or the like) to about 3 pm, including all 0.1 nm values and ranges therebetween (e.g., about 2 nm to about 50 nm, about 10 nm to about 100 nm, about 100 nm to about 3 pm). In various examples, 80% or more, 85% or more, 90% or more, 95% or more, 99% or more, 99.9% or more, or all of the one or more milled graphitic material(s) independently comprise a size (such as, for example, one or more linear dimension(s) (e.g., a diameter or the like), which may be longest linear dimension(s), or the like) (or comprise an average size, such as, for example, an average linear dimension, which may be an average longest linear dimension (e.g., an average diameter) or the like)) of about 2 nm (or a monolayer, bilayer, trilayer, or the like) to about 3 m, including all 0.1 nm values and ranges therebetween (e.g., about 2 nm to about 50 nm, about 10 nm to about 100 nm, about 100 nm to about 3 pm).

[0086] A method may comprise sonication. In various examples, a method further comprises sonicating (such as, for example, ultrasonicating or the like) or the like the milled silicon particle(s) and/or the milled graphitic material(s).

[0087] In various examples, one or more graphitic material(s) and/or milled graphitic material(s) coat(s) (e.g., in situ coat(s)) one or more silicon particle(s) and/or milled silicon particle(s), optionally, in the presence of the binder(s). In various examples, one or more milled graphitic material(s) coat(s) (e.g., in situ coat(s)) the one or more milled silicon particle(s), optionally, in the presence of the binder.

[0088] In various examples, the one or more graphitic material(s) and/or milled graphitic material(s) is/are disposed on at least a portion, substantially all, or all of one or more or all of the surface(s) of the silicon particle(s). In various examples, the one or more milled graphitic material(s) independently coat(s) substantially all or all the one or more milled silicon particle(s).

[0089] A method can produce various graphitic-material-coated silicon particles. In various examples, graphitic-material-coated silicon particles comprise greater than 95% by weight silicon (based on the total weight of the graphitic-material-coated silicon particles). In various examples, at least a portion or all the one or more silicon particle(s) is/are SiOx particles and/or at least a portion or all the one or more graphitic material(s) is CVD grown graphene. In various examples, at least a portion or all the one or more silicon particle(s) is/are SiOx particles and/or at least a portion or all the one or more graphitic material(s) is/are exGR. In various examples, the exGR coated SiOx particles comprises about 2 wt% (wt% = weight percent) carbon.

[0090] Graphitic-material-coated silicon particles produced by a method can comprise various sizes. In various examples, graphitic-material-coated silicon particles produced by a method independently comprise a size (such as, for example, one or more linear dimension(s) (e.g., a diameter or the like), which may be longest linear dimension(s), or the like) (which may be an average size, such as, for example, an average linear dimension, which may be an average longest linear dimension (e.g., an average diameter) or the like) of about 10 nm to about 8 pm, including all 0.1 nm values and ranges therebetween (e.g., about 10 nm to about 1 pm, about 10 nm to about 2 pm, about 10 nm to less than about 1 pm, about 10 nm to less than about 2 pm, about 100 nm to about 3 pm). [0091] In various examples, a graphitic-material-coated silicon particle or graphitic- material-coated silicon particles produced by a method is/are suitable for use in a device (such as, for example, an electrochemical device or the like). In various examples, a graphitic-material -coated silicon particle or graphitic-material-coated silicon particles produced by a method is/are suitable for use in an (or as an) electrode (such as, for example, an anode or a cathode of a device (such as, for example, an electrochemical device or the like)).

[0092] In various examples, a method does not comprise one or more or all of a thermal treatment, a plasma treatment, microwave treatment, infrared treatment, or the like. In various examples, a method does not comprise exfoliation of the graphitic material(s) (such, as, for example, graphene).

[0093] In an aspect, the present disclosure provides electrodes. An electrode comprises one or more graphitic-material-coated silicon particle(s) (such as, for example one or more graphitic-material -coated silicon particle(s) of the present disclosure). In various examples, an electrode comprises at least two or more different (e.g., structurally different, compositionally different, or the like, or any combination thereof) graphitic-material-coated silicon particles. Non-limiting examples of electrodes are provided herein.

[0094] In various examples, an electrode (such as, for example, an anode or a cathode) comprises one or more graphitic-material-coated silicon particle(s) or one or more composition(s) comprising one or more graphitic-material-coated silicon particle(s) (e.g., at least two or more different (e.g., structurally different, compositionally different, or the like, or any combination thereof) graphitic-material-coated silicon particles). In various examples, the one or more graphitic-material-coated silicon particle(s) or one or more composition(s) are additives. In various examples, one or more graphitic-material-coated silicon particle(s) are an additive or the like. Without intending to be bound by any particular theory, it is considered the one or more graphitic-material-coated silicon particle(s) can be an additive that increases the energy density of an anode (relative to an anode comprising the same components, materials, etc., but without the one or more graphitic-material-coated silicon particle(s)). In various examples, an electrode (such as, for example, an anode or a cathode) is a reversible electrode (such as, for example, a reversible anode or a reversible cathode).

[0095] In various examples, an electrode (such as, for example, an anode or a cathode) further comprises one or more active material(s). In various examples, an active material is a conducing material (such as, for example, a conducing carbon material (e.g., graphene, carbon black (such as, for example, SUPER P™ and the like), and the like, and any combination thereof). Without intending to be bound by any particular theory, it is considered conductive carbon blacks (such as, for example, SUPER P™ conductive carbon blacks and the like) with a desirable (e.g., high to very high) void volume allow the retention of a carbon network (e.g., at low to very low filler content).

[0096] In various examples, an electrode (such as, for example, an anode or a cathode) further comprises one or more binder(s). Non-limiting examples of binders are disclosed herein.

[0097] In various examples, an electrode or electrodes (such as, for example, an anode or anodes or a cathode or cathodes) are part of electrochemical devices (such as, for example, secondary batteries or secondary cells, which may be rechargeable batteries, primary batteries or primary cells, or the like). Non-limiting examples of secondary batteries and primary batteries include Li-ion batteries, Li metal batteries, and the like.

[0098] In various examples, an electrode (such as, for example, an anode or a cathode) further comprises a current collector. In various examples, a current collector is a metal current collector, a metal alloy current collector, or the like. Non-limiting examples of current collectors are known in the art. In various examples, a metal or metal alloy is stainless steel, copper, aluminum, nickel, tantalum, molybdenum, or the like, or an alloy thereof. In various examples, an electrode (such as, for example, an anode or a cathode) does not comprise a metal current collector. In various examples, the one or more graphitic-material-coated silicon particle(s) is/are disposed on at least a portion of an exterior surface of a current collector. In various examples, an electrode (such as, for example, an anode or a cathode) is free of other conducting materials (e.g., free of carbon-based conducting materials and the like).

[0099] In various examples, an electrode (such as, for example, an anode or a cathode) is suitable for (or configured for) use in a device (such as, for example, an electrochemical device or the like). In various examples, an electrode is suitable for (or configured for) use in a device (such as, for example, as an anode or a cathode of a device (such as, for example, an electrochemical device or the like)).

[0100] In an aspect, the present disclosure provides devices. A device comprises one or more electrode(s) of the present disclosure. Non-limiting examples of devices are provided herein.

[0101] In various examples, a device is an electrochemical device or the like. Nonlimiting examples of electrochemical devices include, supercapacitors, fuel cells, electrolyzers, electrolytic cells, and the like. [0102] A device can be various batteries. A device may be a solid-state battery or a liquid electrolyte battery. Non-limiting examples of batteries include secondary/rechargeable batteries, primary batteries, and the like. In various examples, a battery is an ion-conducting battery. Non-limiting examples of ion-conducting batteries include lithium-ion conducting batteries, potassium-ion conducting batteries, sodium-ion conducting batteries, magnesium- ion conducting batteries, aluminum-ion conducting batteries, iron-ion conducting batteries, and the like. In various examples, a battery is a metal battery, such as, for example, a lithium- metal battery, a sodium-metal battery, magnesium-metal battery, or the like.

[0103] In various examples, in the case where a device comprises an anode or anodes of the present disclosure, the device (e.g., a battery or the like) further comprises one or more cathode(s), which comprise(s) one or more cathode material(s). Examples of suitable cathode materials are known in the art. In various examples, the cathode material(s) is/are one or more lithium-containing cathode material(s) or the like. Non-limiting examples of lithium- containing cathode materials include lithium nickel manganese cobalt oxides, LiCoCh, LiNii/3Coi/3Mm/3O2, LiNio.5Coo.2Mno.3O2, lithium manganese oxides (LMOs), lithium iron phosphates (LFPs), LiMnPO4, LiCoPO4, and Li2MMn30s, where M is chosen from Fe, Co, and the like, and any combination thereof, and the like, and any combination thereof. In various examples, cathodes/cathode materials comprise a conducting carbon aid. In various examples, a device (e.g., a battery or the like) comprises a conversion-type cathode. Nonlimiting examples of conversion-type cathode materials include air, oxygen, iodine, sulfur, sulfur composite materials, polysulfides, metal sulfides, such as, for example, M0S2, FeS2, TiS2, and the like, and any combination thereof. In various examples, a cathode comprises a carbon material/carbon materials, a lithium-containing material/lithium-containing materials, air, oxygen, iodine, sulfur, sulfur composite material/sulfur composite materials, polysulfide/polysulfides, metal sulfide/metal sulfides, or the like. In various examples, a cathode further comprises one or more conducting carbon aid(s) or the like. In various examples, a cathode is a high-voltage cathode. Non-limiting examples of high-voltage cathodes include a cathode comprising one or more NMC ternary cathode material(s) independently comprising nickel, manganese, and cobalt (e.g., LiNio.8Mno.1Coo.1O2 (NMC811), LiNio.6Mno.2Coo.2O2 (NMC622), or the like), and the like.

[0104] In various examples, in the case where a device comprises a cathode of the present disclosure, the device (e.g., a battery or the like) further comprises one or more anode(s), which independently comprise(s) one or more anode material(s). Examples of suitable anode materials are known in the art. Non-limiting examples of anode material(s) include metals, such as, for example, lithium metal, potassium metal, sodium metal, magnesium metal, aluminum metal, and the like, lithium-ion conducting anode materials, sodium-ion conducting anode materials, magnesium-ion conducting anode materials, aluminum-ion conducting anode materials, and the like. Non-limiting examples of lithium containing anode materials include lithium carbide, LieC, lithium titanates (LTOs), and the like, and combinations thereof), and combinations thereof. Non-limiting examples of sodium-ion conducting anode material include Na2CsH4O4 and Nao.66Lio.22Tio.78O2, and the like, and combinations thereof. Non-limiting examples of magnesium-containing anode materials include Mg2Si, and the like, and combinations thereof. The device, which may be a battery, may comprise a material chosen from silicon-containing materials, tin and its alloys, tin/carbon, phosphorus, and the like.

[0105] A device, which may be a battery, may comprise a conversion-type electrode (e.g., anode or cathode, depending on which electrode (e.g., anode or cathode) of the present disclosure is used). Non-limiting examples of conversion-type electrode materials include air (e.g., oxygen), iodine, sulfur, sulfur composite materials, polysulfides, metal sulfides, such as, for example, M0S2, FeS2, TiS2, and the like, and combinations thereof.

[0106] In various examples, a device (e.g., a battery or the like) further comprises one or more electrolyte(s) (e.g., solid-state electrolyte(s), liquid electrolyte(s), or the like, or any combination thereof). In various examples, liquid electrolyte(s) is/are non-aqueous electrolyte(s). In various examples, liquid electrolyte(s) is/are aqueous electrolyte(s). In various examples, liquid electrolyte(s) comprise(s) one or more carbonate-based electrolyte(s) (e.g., such as, for example, alkyl carbonates, cyclic carbonates, and the like, and any combination thereof), ether-based electrolyte(s), ionic liquid-based electrolyte(s), or like, or any combination thereof. In various examples, one or more electrolyte(s) is/are nonflammable (e.g., non-flammable aqueous electrolyte(s)). Examples of suitable electrolytes are known in the art.

[0107] Various liquid electrolytes can be used. Non-limiting examples of liquid electrolytes include dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), ethylene carbonate (EC), propylene carbonate (PC), fluoroethylene carbonate (FEC), vinylene carbonate (VC), di-2,2,2-trifluoroethyl carbonate (TFEC), dimethoxyethane (DME), 1,3-dioxolane (DOL), diglyme, triglyme, tetraglyme, and the like, and any combination thereof.

[0108] Various solid electrolytes can be used. Non-limiting examples of solid electrolytes include polymer electrolytes (e.g. poly(ethylene oxide) (PEO), poly(acrylonitrile) (PAN), propylene carbonate (PC), ethylene carbonate (EC), and the like, and any combination thereof), ceramic electrolytes (e.g. LivLasZnOn (LLZO), Li superionic conductor (LISICON), Lii+_xAlxGe₂ x(PO₄)₃ (LAGP), Lii_+xAlxTi₂ x(PO₄)₃ (LATP), lithium phosphorus oxynitride (LiPON), and the like, and any combination thereof).

[0109] In various examples, a device comprises bipolar plates, external packaging, and electrical contacts/leads to connect wires, and the like, and any combination thereof.

[0110] An electrolyte, a cathode, an anode, and, optionally, the current collector may form a cell of a battery. In various examples, a battery comprises a plurality of the cells and each adjacent pair of the cells is separated by a bipolar plate. The number of cells in the battery is determined by the performance requirements (e.g., voltage output and the like) of the battery and is limited only by fabrication constraints. For example, the battery comprises 1 to 500 cells, including all integer number of cells and ranges therebetween.

[OHl] The following Statements describe various examples of graphitic-material-coated silicon particles and compositions, uses thereof, methods of making graphitic-material-coated silicon particles, electrodes, and devices of the present disclosure and are not intended to be in any way limiting:

Statement 1. A method of forming a plurality of graphitic-material-coated silicon particles comprising: milling (e.g., milling a mixture comprising) one or more silicon particle(s), one or more graphitic material(s), and optionally, one or more binder(s) (e.g., in a milling device), where milled silicon particle(s) and/or milled graphitic material(s) are formed (e.g., at least a portion of, substantially all, or all the one or more silicon particle(s) and the one or more graphitic material(s) are reduced in size during the milling), where the graphitic-material- coated silicon particles are formed.

Statement 2. A method according to Statement 1, where the one or more silicon parti cle(s) comprise(s) one or more silicon microparticle(s).

Statement 3. A method according to Statement 1 or 2, where the one or more silicon particle(s) is/are chosen from: silicon oxide (SiOx, where, for example, x is about 0 to about 1.99) particles; metallurgical silicon particles; recycled metallurgical silicon particles; milled metallurgical silicon particles; solar silicon particles; and milled solar silicon particles; structural analogs thereof, and the like; and any combination thereof.

Statement 4. A method according to any one of Statements 1-3, where the one or more silicon particle(s) independently comprise a size (such as, for example, one or more linear dimension(s) (e.g., a diameter or the like), which may be longest linear dimension(s), or the like) (which may be an average size, such as, for example, an average linear dimension, which may be an average longest linear dimension (e.g., an average diameter or the like) or the like) of about 1 gm to about 100 gm, including all 0.1 gm values and ranges therebetween (e.g., about 10 gm to about 100 gm).

Statement 5. A method according to any one of Statements 1-4, where the mixture comprises about 60 weight percent (wt.%) to about 98 wt.% (based on the total weight of the mixture) of the one or more silicon particle(s), including all 0.1 wt.% values and ranges therebetween. Statement 6. A method according to any one of Statements 1-5, where the one or more graphitic material(s) is/are chosen from: graphene (e.g., in the natural form, in an artificial form, in a recycled form, or the like, or any combination thereof); chemical vapor deposition (CVD) grown graphene; exfoliated graphene (exGR); graphite (e.g., in the natural form, in an artificial form, in a recycled form, or the like, or any combination thereof); and petroleum coke; structural analogs thereof; and the like; and any combination thereof.

Statement 7. A method according to any one of Statements 1-6, where the one or more graphitic material(s) independently comprise a size (such as, for example, one or more linear dimension(s) (e.g., a diameter, a thickness, or the like), which may be longest linear dimension(s), or the like) (which may be an average size, such as, for example, an average linear dimension (e.g., an average diameter, an average thickness or the like), which may be an average longest linear dimension or the like) of about 10 pm to about 100 pm, including all 0.1 pm values and ranges therebetween.

Statement 8. A method according to any one of Statements 1-7, where the mixture comprises about 1 wt.% to about 40 wt.% (based on the total weight of the mixture) of the one or more graphitic material(s), including all 0.1 wt.% values and ranges therebetween.

Statement 9. A method according to any one of Statements 1-8, where at least a portion or all the one or more graphitic material(s) is/are an aqueous suspension of the one or more graphitic material(s), one or more dry form(s) of the one or more graphitic material(s), or the like, or any combination thereof.

Statement 10. A method according to any one of Statements 1-9, where the one or more binder(s) is/are chosen from: polyacrylic acids; peroxyacetic acids (PAA); polyvinylidene fluorides (PVDFs); polyvinyl alcohols (PVAs), carboxymethyl celluloses (CMCs), styrenebutadiene rubbers (SBRs); and acrylic polymers; structural analogs thereof; and the like; and any combination thereof.

Statement 11. A method according to any one of Statements 1-10, where the mixture comprises about 1 wt.% to about 20 wt.% (based on the total weight of the mixture) of the one or more binder(s), including all 0.1 wt.% values and ranges therebetween. Statement 12. A method according to any one of Statements 1-11, where the milling is ball milling (such as, for example, a planetary ball milling or the like) or the like and/or the milling device is a ball milling device (such as, for example, a planetary ball milling device or the like) or the like, the milling is jet milling (such as, for example, jet ball milling, air jet milling, air jet ball milling, or the like) or the like and/or the milling device is a jet milling device (such as, for example, a jet ball milling device, an air jet milling device, an air jet ball milling device, or the like) or the like, the milling is hammer milling or the like and/or the milling device is a hammer milling device or the like, the milling is pin milling or the like and/or the milling device is a pin milling device or the like, the milling is screen milling (such as, for example, conical screen milling or the like) or the like and/or the milling device is a screen milling device (such as, for example, conical screen milling device or the like) or the like.

Statement 13. A method according to any one of Statements 1-12, where the milling is carried out for about 10 minutes to about 5 hours, including all 0.1 hour values and ranges therebetween (e.g., 1 hour to about 4 hours).

Statement 14. A method according to any one of Statements 1-13, where the milling device applies a pressure to the mixture from about 0.6 MPa to about 1 MPa, including all 0.1 MPa values and ranges therebetween.

Statement 15. A method according to any one of Statements 1-14, where the milling atmosphere is (or comprises or the milling is performed using) a gas chosen from: dry air; nitrogen; and argon; and the like; and any combination thereof.

Statement 16. A method according to any one of Statements 1-15, where the one or more milled silicon particle(s) independently comprise a size (such as, for example, one or more linear dimension(s) (e.g., a diameter or the like), which may be longest linear dimension(s), or the like) (or comprise an average size, such as, for example, an average linear dimension, which may be an average longest linear dimension (e.g., an average diameter) or the like)) of about 10 nm to about 5 pm, including all 0.1 nm values and ranges therebetween (e.g., about 10 nm to 2 pm, about 100 nm to about 500 nm, or about 300 nm to about 700 nm, or about 300 nm to about 700 nm, or about 100 nm to about 3 pm).

Statement 17. A method according to any one of Statements 1-16, where the one or more milled graphitic material(s) independently comprise a size (such as, for example, one or more linear dimension(s) (e.g., a diameter, a thickness, or the like), which may be longest linear dimension(s), or the like) (or comprise an average size, such as, for example, an average linear dimension (e.g., an average diameter, an average thickness, or the like), which may be an average longest linear dimension or the like) of about 2 nm (or a monolayer, bilayer, trilayer, or the like) to about 3 gm, including all 0.1 nm values and ranges therebetween (e.g., about 2 nm to about 50 nm, about 10 nm to about 100 nm, about 100 nm to about 3 gm). Statement 18. A method according to any one of Statements 1-17, where the graphitic- material-coated silicon particles independently comprise a size (such as, for example, one or more linear dimension(s) (e.g., a diameter or the like), which may be longest linear dimension(s), or the like) (which may be an average size, such as, for example, an average linear dimension, which may be an average longest linear dimension (e.g., an average diameter) or the like) of about 10 nm to about 8 gm, including all 0.1 nm values and ranges therebetween (e.g., about 10 nm to about 1 gm, about 10 nm to about 2 gm, about 10 nm to less than about 1 gm, about 10 nm to less than about 2 gm, about 100 nm to about 3 gm). Statement 19. A graphitic-material-coated silicon particle comprising: a silicon particle (e.g., a milled silicon particle or the like) comprising a size (such as, for example, one or more linear dimension(s) (e.g., a diameter or the like), which may be longest linear dimension(s), or the like) of 10 nm to about 5 pm, including all 0.1 nm values and ranges therebetween (e.g., about 10 nm to 2 pm, about 100 nm to about 500 nm, or about 300 nm to about 700 nm, or about 300 nm to about 700 nm, or about 100 nm to about 3 gm); and one or more graphitic material(s) (e.g., milled graphitic material(s) or the like) comprising a size (such as, for example, one or more linear dimension(s) (e.g., a diameter, a thickness, or the like), which may be longest linear dimension(s), or the like) of about 2 nm (or a monolayer, bilayer, trilayer, or the like) to about 3 gm, including all 0.1 nm values and ranges therebetween (e.g., about 2 nm to about 50 nm, about 10 nm to about 100 nm, about 100 nm to about 3 gm), where the one or more graphitic material(s) is/are disposed on (such as, for example, coated on or the like) at least a portion, substantially all, or all of one or more surface(s) (e.g., exterior surfaces(s)) of the silicon particle.

Statement 20. A graphitic-material-coated silicon particle according to Statement 19, where the one or more silicon particle(s) is/are chosen from: silicon oxide (SiOx) particles; metallurgical silicon particles; recycled metallurgical silicon particles; milled metallurgical silicon particles; solar silicon particles; and milled solar silicon particles; structural analogs thereof; and the like; and any combination thereof.

Statement 21. A graphitic-material-coated silicon particle according to Statement 19 or 20, where the one or more graphitic material(s) is/are chosen from: graphene (e.g., in the natural form, in an artificial form, in a recycled form, or the like, or any combination thereof); chemical vapor deposition (CVD) grown graphene; exfoliated graphene (exGR); graphite (e.g., in the natural form, in an artificial form, in a recycled form, or the like, or any combination thereof); and petroleum coke; structural analogs thereof; and the like; and any combination thereof.

Statement 22. A graphitic-material-coated silicon particle according to any one of Statements 19-21, where the graphitic-material-coated silicon particle comprises a size (such as, for example, one or more linear dimension(s) (e.g., a diameter or the like), which may be longest linear dimension(s), or the like) of about 10 nm to about 8 pm, including all 0.1 nm values and ranges therebetween (e.g., about 10 nm to about 1 pm, about 10 nm to about 2 pm, about 10 nm to less than about 1 pm, about 10 nm to less than about 2 pm, about 100 nm to about 3 pm).

Statement 23. A graphitic-material-coated silicon particle according to any one of Statements 19-22, where the graphitic-material-coated silicon particle comprises carbon at about 1 wt.% to about 40 wt.% (based on the total weight of the particle), including all 0.1 wt.% values and ranges therebetween.

Statement 24. A composition comprising one or more graphitic-material-coated silicon particle(s) of the present disclosure (such as, for example, one or more graphitic-material- coated silicon parti cle(s) according to any one of Statements 19 to 23).

Statement 25. A composition according to Statement 24, where the graphitic-material-coated silicon particles independently comprise a size (or comprise an average size) (such as, for example, one or more linear dimension(s) (e.g., a diameter or the like), which may be longest linear dimension(s), or the like) of about 100 nm to about 3 pm, including all 0.1 nm values and ranges therebetween.

Statement 26. A composition according to Statement 24 or 25, where the graphitic-material- coated silicon particles independently comprise carbon at (or comprise carbon at an average of) about 1 wt.% to about 40 wt.% (based on the total weight of the particles), including all 0.1 wt.% values and ranges therebetween.

Statement 27. An electrode (such as, for example, an anode or a cathode) comprising one or more graphitic-material-coated silicon parti cle(s) of any one of Statements 19 to 23, one or more graphitic-material-coated silicon particle(s) made by a method of any one of Statements 1 to 22, or one or more composition(s) of any one of Statements 24 to 26, or any combination thereof.

Statement 28. An electrode according to Statement 27, the electrode (such as, for example, the anode or the cathode) further comprising an active material or the like and, optionally, a binder. Statement 29. A device comprising one or more electrode(s) (such as, for example, anode(s), cathode(s), or any combination thereof) of Statement 27 or 28.

Statement 30. A device according to Statement 29, where the device is an electrochemical device or the like.

Statement 31. A device according to Statement 30, where the electrochemical device is a battery, a supercapacitor, a fuel cell, an electrolyzer, or an electrolytic cell, or the like. Statement 32. A device according to Statement 31, where the battery is a metal ionconducting battery or the like.

Statement 33. A device according to Statement 32, where the ion-conducting battery is a lithium-ion conducting battery, a potassium-ion conducting battery, a sodium-ion conducting battery, a calcium-ion conducting battery, a magnesium-ion conducting battery, a zinc-ion conducting battery, an aluminum-ion conducting battery, or an iron-ion conducting battery, or the like.

Statement 34. A method of forming a plurality of graphitic-material-coated silicon particles (such as, for example, graphitic-material-coated silicon particles independently according to any one of Statements 52-56 or a composition according to any one of Statements 57- 59) comprising: A - reducing the size (e.g., of at least a portion, substantially all, or all) of one or more silicon particle(s) and/or one or more graphitic material(s) (e.g., milling, such as, for example, planetary ball milling, vertical ball milling, or the like, or any combination thereof) of one or more silicon particle(s) and/or one or more graphitic material(s) (e.g., where at least a portion of, substantially all, or all the one or more silicon particle(s) and the one or more graphitic material(s) are reduced in size during the milling), and mixing (e.g., resonant acoustic mixing or the like) the one or more silicon particle(s) and/or one or more graphitic material(s) that have been reduced in size (e.g., milled or the like, or any combination thereof) and optionally, one or more binder(s), where the graphitic-material-coated silicon particles are formed (e.g., the one or more silicon particle(s) are coated by the one or more graphitic material(s)); or B - mixing (e.g., resonant acoustic mixing, ball milling, or the like) the one or more silicon particle(s) comprising a size (such as, for example, one or more linear dimension(s) (e.g., a diameter or the like), one or more or all of which may be longest linear dimension(s), or the like) (which may be an average size, such as, for example, an average linear dimension (e.g., an average diameter), which may be an average longest linear dimension or the like) of 10 nm to about 5 pm, including all 0.1 nm values and ranges therebetween (e.g., about 10 nm to 2 pm, about 100 nm to about 500 nm, or about 300 nm to about 700 nm, or about 300 nm to about 700 nm, or about 100 nm to about 3 pm), and one or more graphitic material(s) comprising a size (such as, for example, one or more linear dimension(s) (e.g., a diameter, a thickness, or the like), one or more or all of which may be longest linear dimension(s), or the like) (which may be an average size, such as, for example, an average linear dimension (e.g., an average diameter, and average thickness, or the like), which may be an average longest linear dimension, or the like) of about 2 nm or a monolayer (or a bilayer, trilayer, or the like) to about 3 pm, including all 0.1 nm values and ranges therebetween (e.g., 2 nm to about 2 pm, about 10 nm to about 2 pm, about 50 nm to about 100 nm, or about 100 nm to about 3 pm), and optionally, one or more binder(s) or the like, where the graphitic-material-coated silicon particles are formed (e.g., the one or more silicon particle(s) are coated by the one or more graphitic material(s)).

Statement 35. A method according to Statement 34, where the one or more silicon parti cle(s) comprise(s) one or more silicon microparticle(s), one or more silicon nanoparticles, or both. Statement 36. A method according to Statement 34 or 35, where the one or more silicon particle(s) is/are chosen from: silicon oxide (SiOx (e.g., where x is about 0 to about 1.99) particles; metallurgical silicon particles; recycled metallurgical silicon particles; milled metallurgical silicon particles; solar silicon particles; and milled solar silicon particles; structural analogs thereof, and the like; and any combination thereof.

Statement 37. A method according to any one of Statements 34-36, where the one or more silicon particle(s) (e.g., prior to size reduction, such as, for example, milling or the like) independently comprise a size (such as, for example, one or more linear dimension(s) (e.g., a diameter or the like), one or more or all of which may be longest linear dimension(s), or the like) (which may be an average size, such as, for example, an average linear dimension, which may be an average longest linear dimension (e.g., an average diameter) or the like) of about 1 pm to about 100 pm, including all 0.1 pm values and ranges therebetween (e.g., about 10 pm to about 100 pm); and/or the one or more silicon parti cle(s) after the size reduction (e.g., milling) independently comprise a size (such as, for example, one or more linear dimension(s) (e.g., a diameter or the like), one or more or all of which may be longest linear dimension(s), or the like) (which may be an average size, such as, for example, an average linear dimension (e.g., an average diameter or the like), which may be an average longest linear dimension, or the like) of about 10 nm to about 5 pm, including all 0.1 nm values and ranges therebetween 10 nm to about 5 pm, including all 0.1 nm values and ranges therebetween (e.g., about 10 nm to 2 pm, about 100 nm to about 500 nm, or about 300 nm to about 700 nm, or about 300 nm to about 700 nm, or about 100 nm to about 3 pm). Statement 38. A method according to any one of Statements 34-37, where the mixture comprises about 60 weight percent (wt.%) to about 98 wt.% (based on the total weight of the mixture) of the one or more silicon particle(s), including all 0.1 wt.% values and ranges therebetween.

Statement 39. A method according to any one of Statements 34-38, where the one or more graphitic material(s) is/are chosen from: graphene (e.g., in the natural form, in an artificial form, in a recycled form, or the like, or any combination thereof); chemical vapor deposition (CVD) grown graphene; exfoliated graphene (exGR); graphite (e.g., in the natural form, in an artificial form, in a recycled form, or the like, or any combination thereof); and petroleum cokes (such as, for example, natural petroleum cokes, artificial petroleum cokes, recycled petroleum cokes, and the like, and any combination thereof); structural analogs thereof; and the like; and any combination thereof.

Statement 40. A method according to any one of Statements 34-39, where the one or more graphitic material(s) (e.g., prior to size reduction, such as, for example, milling or the like) independently comprise a size (such as, for example, one or more linear dimension(s), one or more or all of which may be longest linear dimension(s), or the like) (which may be an average size, such as, for example, an average linear dimension (e.g., an average diameter, an average thickness, or the like), which may be an average longest linear dimension or the like, of about 10 pm to about 100 pm, including all 0.1 pm values and ranges therebetween (e.g., about 10 pm to about 100 pm); and/or the one or more graphitic material(s) after the size reduction (e.g., milling) independently comprise a size (such as, for example, one or more linear dimension(s), one or more or all of which may be longest linear dimension(s), or the like) (which may be an average size, such as, for example, an average linear dimension (e.g., an average diameter, an average thickness, or the like), which may be an average longest linear dimension or the like, of about 2 nm or a monolayer (or a bilayer, trilayer, or the like) to about 3 pm, including all 0.1 nm values and ranges therebetween (e.g., 2 nm to about 2 pm, about 10 nm to about 2 pm, about 50 nm to about 100 nm).

Statement 41. A method according to any one of Statements 34-40, where the mixture comprises about 1 wt.% to about 40 wt.% (based on the total weight of the mixture) of the one or more graphitic material(s), including all 0.1 wt.% values and ranges therebetween. Statement 42. A method according to any one of Statements 34-41, where at least a portion or all the one or more graphitic material(s) is/are an aqueous suspension of the one or more graphitic material(s), one or more dry form(s) of the one or more graphitic material(s), or the like, or any combination thereof. Statement 43. A method according to any one of Statements 34-42, where the one or more binder(s) is/are chosen from: polyacrylic acids (PAAs); peroxyacetic acids; polyvinylidene fluorides (PVDFs); polyvinyl alcohols (PVAs), carboxymethyl celluloses (CMCs), styrenebutadiene rubbers (SBRs); and acrylic polymers; structural analogs thereof; and the like; and any combination thereof.

Statement 44. A method according to any one of Statements 34-43, where the binder(s), if present, is/are present at about 1 wt.% to about 20 wt.% (based on the total weight of the silicon particle(s) and graphitic material(s)), including all 0.1 wt.% values and ranges therebetween.

Statement 45. A method according to any one of Statements 34-44, where the milling is ball milling (such as, for example, a planetary ball milling or the like) or the like and/or the milling device is a ball milling device (such as, for example, a planetary ball milling device or the like) or the like, the milling is vertical bead milling or the like and/or the milling device is a vertical bead milling device or the like, the milling is hammer milling or the like and/or the milling device is a hammer milling device or the like, the milling is pin milling or the like and/or the milling device is a pin milling device or the like, the milling is screen milling (such as, for example, conical screen milling or the like) or the like and/or the milling device is a screen milling device (such as, for example, conical screen milling device or the like) or the like.

Statement 46. A method according to any one of Statements 34-45, where the milling is carried out for about 10 minutes to about 5 hours, including all 0.1 hour values and ranges therebetween (e.g., 1 hour to about 4 hours) and/or the mixing is carried out for about 10 seconds to about 1 hour, including all 0.1 hour values and ranges therebetween (e.g., about 0.5 minute to about 0.5 hour).

Statement 47. A method according to any one of Statements 34-46, where the milling device applies a pressure to the mixture from about 0.6 MPa to about 1 MPa, including all 0.1 MPa values and ranges therebetween.

Statement 48. A method according to any one of Statements 34-47, where the milling atmosphere is (or the milling is performed using) a gas chosen from: dry air; nitrogen; and argon; and the like; and any combination thereof.

Statement 49. A method according to any one of Statements 34-48, where the one or more milled silicon particle(s) independently comprise a size (such as, for example, one or more linear dimension(s) (e.g., a diameter or the like), one or more or all of which may be longest linear dimension(s), or the like) (or comprise an average size, such as, for example, an average linear dimension (e.g., an average diameter), which may be an average longest linear dimension or the like)) of 10 nm to about 5 gm, including all 0.1 nm values and ranges therebetween (e.g., about 10 nm to 2 gm, about 100 nm to about 500 nm, or about 300 nm to about 700 nm, or about 300 nm to about 700 nm, or about 100 nm to about 3 gm).

Statement 50. A method according to any one of Statements 34-49, where the one or more milled graphitic material(s) independently comprise a size (such as, for example, one or more linear dimension(s) (e.g., an average diameter, an average thickness, or the like), one or more or all of which may be longest linear dimension(s), or the like) (or comprise an average size, such as, for example, an average linear dimension (e.g., an average diameter, an average thickness, or the like), which may be an average longest linear dimension or the like) of about 2 nm or a monolayer (or a bilayer, trilayer, or the like) to about 3 pm, including all 0.1 nm values and ranges therebetween (e.g., 2 nm to about 2 pm, about 10 nm to about 2 pm, about 50 nm to about 100 nm, or about 100 nm to about 3pm).

Statement 51. The method of Statements 34-50, where the graphitic-material-coated silicon particles independently comprise a size (such as, for example, one or more linear dimension(s) (e.g., a diameter or the like), one or more or all of which may be longest linear dimension(s), or the like) (which may be an average size, such as, for example, an average linear dimension (e.g., an average diameter, an average thickness, or the like), which may be an average longest linear dimension or the like) of about 10 nm to about 10 pm, including all 0.1 nm values and ranges therebetween (e.g., about 50 nm to about 3 pm or about 100 nm to about 3 pm).

Statement 52. A graphitic-material-coated silicon particle (which may be made by a method of any one of claims 34-51) comprising: a silicon particle (e.g., a milled silicon particle or the like) comprising a size (such as, for example, one or more linear dimension(s) (e.g., a diameter or the like), one or more or all of which may be longest linear dimension(s), or the like) of 10 nm to about 5 pm, including all 0.1 nm values and ranges therebetween (e.g., about 10 nm to 2 pm, about 100 nm to about 500 nm, or about 300 nm to about 700 nm, or about 300 nm to about 700 nm, or about 100 nm to about 3 pm); and one or more graphitic material(s) (e.g., milled graphitic material(s) or the like) comprising a size (such as, for example, one or more linear dimension(s), one or more or all of which may be longest linear dimension(s), or the like) of about 2 nm or a monolayer (or a bilayer, trilayer, or the like) to about 3 pm, including all 0.1 nm values and ranges therebetween (e.g., 2 nm to about 2 pm, about 10 nm to about 2 pm, about 50 nm to about 100 nm, or about 100 nm to about 3pm), where the one or more graphitic material(s) is/are disposed on (such as, for example, coated on or the like) at least a portion, substantially all, or all of one or more surface(s) (e.g., exterior surfaces(s)) of the silicon particle.

Statement 53. A graphitic-material-coated silicon particle according to Statement 52, where the one or more silicon particle(s) is/are chosen from: silicon oxide (SiOx (e.g., where x is about 0 to about 1.99) particles; metallurgical silicon particles; recycled metallurgical silicon particles; milled metallurgical silicon particles; solar silicon particles; and milled solar silicon particles; structural analogs thereof; and the like; and any combination thereof.

Statement 54. A graphitic-material-coated silicon particle according to Statement 52 or 53, where the one or more graphitic material(s) is/are chosen from: graphene (e.g., in the natural form, in an artificial form, in a recycled form, or the like, or any combination thereof); chemical vapor deposition (CVD) grown graphene; exfoliated graphene (exGR); graphite (e.g., in the natural form, in an artificial form, in a recycled form, or the like, or any combination thereof); and petroleum coke; structural analogs thereof; and the like; and any combination thereof.

Statement 55. A graphitic-material-coated silicon particle according to any one of Statements 52-54, where the graphitic-material-coated silicon particle comprises a size (such as, for example, one or more linear dimension(s) (e.g., a diameter or the like), one or more or all of which may be longest linear dimension(s), or the like) of about 10 nm to about 8 pm, including all 0.1 nm values and ranges therebetween (e.g., about 10 nm to about 1 pm, about 10 nm to about 2 pm, about 10 nm to less than about 1 pm, about 10 nm to less than about 2 pm, about 100 nm to about 3 pm).

Statement 56. A graphitic-material-coated silicon particle according to any one of Statements 52-55, where the graphitic-material-coated silicon particle comprises carbon at about 1 wt.% to about 40 wt.% (based on the total weight of the particle), including all 0.1 wt.% values and ranges therebetween (e.g., about 10 wt. % to about 40 wt. %) and/or comprises silicon at about 60 wt.% to about 99 wt.% (based on the total weight of the particle), including all 0.1 wt.% values and ranges therebetween (e.g., about 60 wt. % to about 90 wt. %).

Statement 57. A composition comprising one or more graphitic-material-coated silicon particle(s) of the present disclosure (such as, for example, one or more graphitic-material- coated silicon particle(s) according to any one of Statements 52 to 56).

Statement 58. A composition according to Statement 57, where the graphitic-material-coated silicon particles independently comprise a size (or comprise an average size) (such as, for example, one or more linear dimension(s) (e.g., a diameter (or average diameter), a thickness (or an average thickness, or the like), one or more or all of which may be longest linear dimension(s), or the like) of about 100 nm to about 3 m, including all 0.1 nm values and ranges therebetween.

Statement 59. A composition according to Statement 57 or 58, where the graphitic-material- coated silicon particles independently comprise carbon at (or comprise carbon at an average of) about 1 wt.% to about 40 wt.% (based on the total weight of the particles), including all 0.1 wt.% values and ranges therebetween.

Statement 60. An electrode (such as, for example, an anode or a cathode) comprising one or more graphitic-material-coated silicon particle(s) of any one of Statements 52 to 56, one or more graphitic-material-coated silicon particle(s) made by a method of any one of Statements 34 to 51, or one or more composition(s) of any one of Statements 57 to 59, or any combination thereof.

Statement 61. An electrode according to Statement 60, the electrode further comprises an active material or the like and, optionally, a binder.

Statement 62. A device comprising one or more electrode(s) of Statement 60 or 61.

Statement 63. A device according to Statement 62, where the device is an electrochemical device or the like.

Statement 64. A device according to Statement 63, where the electrochemical device is a battery, a supercapacitor, a fuel cell, an electrolyzer, or an electrolytic cell, or the like. Statement 65. A device according to Statement 64, where the battery is a metal ionconducting battery or the like.

Statement 66. A device according to Statement 65, where the ion-conducting battery is a lithium-ion conducting battery, a potassium-ion conducting battery, a sodium-ion conducting battery, a calcium-ion conducting battery, a magnesium-ion conducting battery, a zinc-ion conducting battery, an aluminum-ion conducting battery, or an iron-ion conducting battery, or the like.

Statement 67. A device according to any one of Statements 64-66, where the device (which may be a battery, such as for example, an ion conducting battery (e.g., a lithium-ion conducting batter or the like) or the like) exhibits a charge capacity (mAh g'¹) decrease of about 30% or less, about 20% or less, about 10% or less, or about 5% or less after about 500 cycles or more or about 1,000 cycles or more.

[0112] The steps of the methods described in the various embodiments and examples disclosed herein are sufficient to produce one or more graphitic-material-coated silicon particles of the present disclosure. Thus, in various examples, a method consists essentially of a combination of the steps of the methods disclosed herein. In another embodiment, a method consists of such steps.

[0113] The following Examples are presented to illustrate the present disclosure. The Examples are not intended to be limiting in any manner.

EXAMPLE 1

[0114] This Example describes graphitic-material-coated silicon particles, compositions, anodes, methods of making graphitic-material-coated silicon particles, and uses thereof of the present disclosure.

[0115] In-situ graphene coating of electrode materials. Two processes (i.e., milling and coating) were combined by introducing mixture of silicon (Si) microparticles, graphite (or graphene) and a binder. During the bombardment of particles in the milling device (either ball milling or jet milling), Si particles get fractured into submicron size particles, while graphite (or graphene) get sheared and broken into small sizes. The continuous bombardment of milled Si and fractured graphene in the presence of a binder leads to the effective coating of graphitic materials on milled Si particles. Graphene on the surface of milled Si not only ensures excellent conductivity, but also improves the structural stability and provides a protection of milled Si particles from the electrolyte. The resulting graphene coated Si particles (from recycled battery graphite and solar cells) and will have very high Si content (greater than 95 wt%) and can be a cost-effective additive for the graphite anodes for high capacity Li-ion batteries. FIG. 1 shows a schematic of in in situ graphene coating on Si particles during jet milling.

[0116] Experimental. Ball Milling of Si Microparticles. Using the 4.0 L KM MILL (Model : KM-1) with Zirconia Ceramic balls (mixture of 0.1mm & 0.3mm), 10 wt% metallurgical Si microparticles (size : 2.0 jUffl) in water were fed to the 4.0L mixing tank at 200ml/min, and milled to submicron particles at milling speed of 1,700 rpm. FIG. 2 shows the milled Si particle sizes at various milling times, showing that the average Si particle size goes down below 250 nm after 60 minutes of milling.

[0117] In situ Graphene Coating of Si particles. To prove the concept of in situ graphene coating of silicon particles during the milling, grapheme materials (exfoliated graphene (lateral dimension: 6 Z/m) from graphite or CVD grown graphene from ACS materials (lateral dimension: 1 Z/m)) with a binder (polyacrylic acid, PAA (Mw = 4 x 106) were added to a ball mill together with Si microparticles (SiOx, size: 2- 4 jt/m). [0118] In FIG. 3, SEM images of ball milled Si particles, and graphene only, and Si particles with Gr (5 wt%) for 1 hour, 2 hours, 3 hours and 4 hours are shown. As demonstrated in the Figure, Si particles with graphene after 1-hour ball milling leads to a similar morphology of graphene only, and thus 1 hour was used as balling time.

[0119] In situ exGr coating on SiOx particles. SiOx particles and exfoliated graphene with a binder were fed to the ball mill machine to coat exGr on SiOx particles during the milling process. EDX mapping of exGr coated SiOx (combined, Si (in green) only and C (in red) only) are shown in FIG. 4, and those of carbon coated SiOx via CVD are also shown for comparison. As seen in the figure, carbon (graphene) is uniformly distributed throughout the SiOx particles.

[0120] The TGA plot of exfoliated graphene (exGr) coated SiOx during the ball mill is shown in FIG. 5. TGA results confirm that both mill coated SiOx and carbon coated SiOx via CVD have about 2 wt% of carbon.

[0121] In-situ CVD grown Gr coating SiOx. SiOx particles and CVD grown graphene (CVD Gr) with a binder were fed to the ball mill machine to coat CVD Gr on SiOx particles during the milling process. EDX mapping of CVD Gr coated SiOx (combined, Si (in green) only and C (in red) only) are shown in FIG. 6, and those of exGr coated SiOx are also shown for comparison. As seen in the figure, a larger amount of carbon (graphene) is uniformly distributed throughout the SiOx particles for both CVD grown Gr coating.

[0122] The TGA plot of CVD grown graphene (CVD Gr) coated SiOx during the ball mill is shown in FIG. 7. TGA results confirm that both CVD grown GR coated SiOx have about 4 wt% of graphene, which is higher than 2 wt% of graphene for exGr coated SiOx particles. These results also confirm that CVD grown Gr with smaller lateral dimension can provide better coating compared to larger exfoliated graphene.

[0123] Li-ion Coin Cell Performance. Graphene coated SiOx anodes. To evaluate the effectiveness of in-situ graphene coating of Si particles during the milling process, anodes of Gr coated SiOx with conductive carbon and binder were fabricated via conventional slurry casting using the NMP as the solvent, and the initial discharge/charge profiles and initial Coulombic efficiency (ICE) of the 2032 coin cells were measured, and the results were summarized in FIG. 8. In the Figure and table, those of carbon coated SiOx via CVD are also shown for comparison. The carbon content in both coated SiOx particles was kept the same at 2 wt%. As demonstrated in the Figure, In-situ coating of graphene on SiOx particles is able to achieve the virtually the same ICE and capacity as carbon coated SiOx particles via CVD. [0124] To confirm the adaptability of graphene coated Si particles to various slurry casting systems, NMP and water was used as a solvent in two different slurry casting systems with PVDF and CMC/SBR as binders, respectively, and the cells were made with two anodes from different slurry cast systems. The first cycle discharge/charge curves and initial Coulombic efficiency (ICE) for two CVD Gr coated SIOx anodes are summarized in FIG. 9. As shown in the Figure, both capacity and ICE vary significantly, depending on the choice of solvent. The performance of water slurry cast anode of graphene coated SIOx was much higher than that of NMP slurry cast anode. For graphene that is suspended in water for use as in both exfoliated graphene and CVD grown graphene, using the water-based slurry certainly helps to minimize the side reactions associated with residual water during the milling coating and the solvent in the cell.

[0125] Milled Si/graphene hybrid anodes from recycled streams. The ultimate goal of this invention is to fabricate cost-effective Si/graphene hybrids for Li-ion anode applications from recycled streams. We milled Si particles from the waste stream of solar cell processes and exfoliated graphite into graphene from consumed anodes of Li-ion batteries. The battery performance of resulting Si/graphene hybrids from recycled streams are summarized in FIG. 10. As demonstrated in the Figure, silicon/Gr hybrid anodes from waste solar cell and recycled graphite exhibit superior performance, yielding over 1,500 mAh/g capacity and over 1,000 mAh/g capacity even after 300 cycles.

EXAMPLE 2

[0126] This Example describes graphitic-material-coated silicon particles, compositions, anodes, methods of making graphitic-material-coated silicon particles, and uses thereof of the present disclosure.

[0127] A schematic of in situ Si milling, graphene exfoliation, and coating via air jet ball milling is shown in FIG. 11. Metallurgical Silicon (Met Si) had an average size of approximately 300 nm to 3 pm before jet milling and an average size of approximately 300 nm to 2.5 pm after jet milling. Metallurgical Silicon (Met Si) from jet milling showed less oxidation peak of Si-0 (FIG. 12). The crystalline nature of Met Si showed less crystallinity and shift to amorphous nature after air jet milling (FIG. 13). Met Si from jet milling was mixed with graphene (obtained from Advanced Chemicals Supplier (ACS)) and polyacrylic acid (PAA) (60:20:20) to prepare an anode. MetSi from jet milling was collected and mixed with ACS Gr and PAA of using the ratio of 60 : 20 : 20. An anode (target 0.6mg) was prepared by air-controlled electrospray. The anode was dried in vacuum. TGA was used to confirm the amount of silicon (60%) and graphene (18%). A cell was prepared using the dried anode. TGA results showed target combination of Jet. Met Si, ACS Gr and PAA (60:20:20). Battery results showed an improved ICE of 86.6% and comparable capacity (FIG. 14). Anode of Met Si from Jet Milling showed improved battery performance than the met Si (plasma treated with different temperature). The crystallinity of Micro-silica also checked before and after Air Jet Milling operation, where Micro-silica showed amorphous nature after Air Jet Milling.

[0128] Battery performance of jet milled Met Si was compared with other Si sources (FIGS. 15-17). The metallurgical Si (MLSI - plasma treated at 660 °C and 880 °C), milled metallurgical Si (AMSI - plasma treated at 660 °C (particle size approximately 150 to 200 nm) and 880 °C (particle size 200 to 250 nm)), and milled solar Si (SMSI - plasma treated at 660 °C (particle size approximately 150 to 200 nm) and 880 °C (particle size 200 to 250 nm)) was characterized by SEM.

[0129] Jet milled micron sized silicon particles (microSi) was evaluated (FIG. 18). The microSi was characterized by SEM and Raman spectroscopy before and after jet milling. The crystalline nature of micro Si showed less crystallinity and shift to amorphous nature after air jet milling.

EXAMPLE 3

[0130] This Example describes graphitic-material-coated silicon particles, compositions, anodes, methods of making graphitic-material-coated silicon particles, and uses thereof of the present disclosure.

[0131] Acoustic mixer for coating graphite onto silicon particles.

[0132] Materials and LabRAM operation parameters:

Silicon (Si) sources: Metallurgical Silicon (Recycled), Milled Metallurgical Silicon, Solar Silicon, Milled Solar Silicon, Silicon oxide

Silicon size: 10 nm to 5 pm

Graphite sources: Natural, Artificial, and Recycled, and Petroleum coke

Graphite size: 10 nm to 2 pm

Binder: Polyacrylic acid (PAA), polyvinylidene fluoride (PVDF), carboxymethyl cellulose (CMC), and styrene-butadiene rubber (SBR)

Coating time at LabRAM: 30 seconds to 30 minutes Vibration intensity at LabRAM: 10 to 100 g [0133] Milling and mixing processes were combined by introducing a mixture of different sizes of Si microparticles and graphite (or graphene) with and without a binder polyacrylic acid (PAA). During the high-intensity vibration of particles in the LabRAM device, Si particles are coated by graphite (or graphene). The repeated collisions of the host particles (milled Si) lead to the transfer/dispersion of the guest particles (graphene) in the presence of a binder leading to the effective coating of graphitic materials on milled Si particles (FIG. 19). Cost-effective metallurgical Si and graphite from recycled sources were used to produce anode materials. The metallurgical Si and graphite were processed by high- intensity vibrational mixing (using LabRAM) to minimize interfacial resistance by coating and depositing the nanosized particles on the surface of the anode, and finally to minimize volume expansion of Si particles by coating the direct contact of the graphite/graphene species. The specific focus of was to improve the interfacial resistance and electrochemical performance in Li-ion batteries.

[0134] First, 50-80 wt% of micro silica (typical size: 50 pm) was mixed with 20-30 wt% graphene (typical size: 2-3 pm) and PAA using the hand mixer. Then the mixture was transferred to an exclusive polycarbonate container, filled up to 20-50%, and installed in a ResonantAcoustic® Mixer (LabRAM II, Resodyn Inc.). The resonant acoustic mixer started to accelerate the container by using the acoustic wave and vibration energy up to 60 G and operation was run for 5 minutes. SEM images show that the graphene deposited nicely on the surface of the micro silica as shown in (FIG. 20A,B). In addition, Si and C elements of graphene-coated micro-Si were measured by EDS mapping. It was realized that the C element’s existence is confirmed successfully, and mapping data is shown in in (FIG. 20C- E).

[0135] Secondly, 50-80 wt% of metallurgical silicon (typical size: 2-3 pm) was mixed with 20-30 wt% nano-size conducting carbon (CSP) and PAA using the hand mixer. The resonant acoustic mixer again started to accelerate the container by using the acoustic wave and vibration energy up to 60 G and operation was run for 5 minutes. (FIG. 21 A, B) showed the insufficient coating dispersion or inhomogeneous distribution on the surface of the silicon particles.

[0136] For the optimization of 20-30 wt% conducting carbon-coated metallurgical silicon (50-80 wt%) without binder at different times tests were carried out for 5, 15, and 30 minutes (FIG. 22A-F), and an excessive energy condition was attempted at 60 G. 5 minutes of the conducting carbon coating of metallurgical silicon are shown the comparatively uniform coating of conducting carbon. However, as the application time increased, the effect, efficiency, and dispersion of the coating agent carbon began to become more perfect at 20 minutes.

[0137] On the other hand, 60 G and 30 minutes in the condition of conducting carbon coating are not uniform or sufficient, which shows that more acceleration energy is necessary to disperse the carbon nanoparticles evenly.

[0138] The battery cells containing either resonant mixer of met Si, CSP and PAA or met Si and CSP anodes were cycled by using a galvanostatic charge/discharge process to identify their charge/discharge performance. As seen in the initial charge (delithiation)/discharge (lithiation) curves in FIG. 23 A, B, met Si, CSP and PAA anode exhibit a higher charge capacity of 1481 mAh g'¹ and efficiency of 86% than met Si and CSP anodes (1197 mAh g’¹, 84%, respectively). The cell with met Si and CSP anodes shows comparatively lower performance because low binder amount, which was added after LabRAM operation.

[0139] Although the present disclosure has been described with respect to one or more particular embodiments and/or examples, it will be understood that other embodiments and/or examples of the present disclosure may be made without departing from the scope of the present disclosure.

Claims

CLAIMS:

1. A method of forming a plurality of graphitic-material-coated silicon particles comprising: milling a mixture comprising one or more silicon particle(s), one or more graphitic material(s), and one or more binder(s), wherein milled silicon particle(s) and/or milled graphitic material(s) are formed, wherein the graphitic-material-coated silicon particles are formed.

2. The method of claim 1, wherein the one or more silicon particle(s) comprise(s) one or more silicon microparticle(s).

3. The method of claim 1, wherein the one or more silicon particle(s) is/are chosen from: silicon oxide (SiOx) particles; metallurgical silicon particles; recycled metallurgical silicon particles; milled metallurgical silicon particles; solar silicon particles; milled solar silicon particles; structural analogs thereof; and any combination thereof.

4. The method of claim 1, wherein the one or more silicon parti cle(s) independently comprise a size of about 1 pm to about 100 pm.

5. The method of claim 1, wherein the mixture comprises about 60 weight percent (wt.%) to about 98 wt.% (based on the total weight of the mixture) of the one or more silicon particle(s).

6. The method of claim 1, wherein the one or more graphitic material(s) is/are chosen from: graphene; chemical vapor deposition (CVD) grown graphene; exfoliated graphene (exGR); graphite; and petroleum coke; structural analogs thereof; and any combination thereof.

7. The method of claim 1, wherein the one or more graphitic material(s) independently comprise a size of about 10 pm to about 100 pm.

8. The method of claim 1, wherein the mixture comprises about 1 wt.% to about 40 wt.% (based on the total weight of the mixture) of the one or more graphitic material(s).

9. The method of claim 1, wherein at least a portion or all the one or more graphitic material(s) is/are an aqueous suspension of the one or more graphitic material(s), one or more dry form(s) of the one or more graphitic material(s), or any combination thereof.

10. The method of claim 1, wherein the one or more binder(s) is/are chosen from: polyacrylic acids; peroxyacetic acids (PAA); polyvinylidene fluorides; and acrylic polymer; structural analogs thereof; and any combination thereof.

11. The method of claim 1, wherein the mixture comprises about 1 wt.% to about 20 wt.% (based on the total weight of the mixture) of the one or more binder(s).

12. The method of claim 1, wherein the milling is ball milling and/or the milling device is a ball milling device, the milling is jet milling and/or the milling device is a jet milling device, the milling is hammer milling and/or the milling device is a hammer milling device, the milling is pin milling and/or the milling device is a pin milling device, the milling is screen milling and/or the milling device is a screen milling device.

13. The method of claim 1, wherein the milling is carried out for about 10 minutes to about 5 hours.

14. The method of claim 1, wherein the milling device applies a pressure to the mixture from about 0.6 MPa to about 1 MPa.

15. The method of claim 1, wherein the milling atmosphere is a gas chosen from: dry air; nitrogen; and argon; and any combination thereof.

16. The method of claim 1, wherein the one or more milled silicon parti cle(s) independently comprise a size of about 10 nm to about 5 pm.

17. The method of claim 1, wherein the one or more milled graphitic material(s) independently comprise a size of about 2 nm to about 3 pm.

18. The method of claim 1, wherein the graphitic-material-coated silicon particles independently comprise a size of about 10 nm to about 8 pm.

19. A graphitic-material-coated silicon particle comprising: a silicon particle comprising a size of about 10 nm to about 5 pm; and one or more graphitic material(s) comprising a size of about 2 nm to about 3 pm, wherein the one or more graphitic material(s) is/are disposed on at least a portion, substantially all, or all of one or more surface(s) of the silicon particle.

20. The graphitic-material-coated silicon particle of claim 19, wherein the one or more silicon parti cle(s) is/are chosen from: silicon oxide (SiOx) particles; metallurgical silicon particles; recycled metallurgical silicon particles; milled metallurgical silicon particles; solar silicon particles; and milled solar silicon particles; structural analogs thereof; and any combination thereof.

21. The graphitic-material-coated silicon particle of claim 19, wherein the one or more graphitic material(s) is/are chosen from: graphene ; chemical vapor deposition (CVD) grown graphene; exfoliated graphene (exGR); graphite; and petroleum coke; structural analogs thereof; and any combination thereof.

22. The graphitic-material-coated silicon particle of claim 19, wherein the graphitic-material - coated silicon particle comprises a size of about 10 nm to about 8 pm.

23. The graphitic-material-coated silicon particle of claim 19, wherein the graphitic-material - coated silicon particle comprises carbon at about 1 wt.% to about 40 wt.% (based on the total weight of the particle).

24. A composition comprising one or more graphitic-material-coated silicon particle(s) of claim 19.

25. The composition of claim 24, wherein the graphitic-material-coated silicon particles independently comprise a size of about 10 nm to about 8 pm.

26. The composition of claim 24, wherein the graphitic-material-coated silicon particles independently comprise carbon at about 1 wt.% to about 40 wt.% (based on the total weight of the particles).

27. An electrode comprising one or more composition(s) of claim 24.

28. The electrode of claim 27, the electrode further comprising an active material and, optionally, a binder.

29. A device comprising one or more electrode(s) of claim 27.

30. The device of claim 29, wherein the device is an electrochemical device.

31. The device of claim 30, wherein the electrochemical device is a battery, a supercapacitor, a fuel cell, an electrolyzer, or an electrolytic cell.

32. The device of claim 31, wherein the battery is a metal ion-conducting battery.

33. The device of claim 32, wherein the ion-conducting battery is a lithium-ion conducting battery, a potassium-ion conducting battery, a sodium-ion conducting battery, a calcium-ion conducting battery, a magnesium-ion conducting battery, a zinc-ion conducting battery, an aluminum-ion conducting battery, or an iron-ion conducting battery.