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WO2025072959A1 - Particules de silicium revêtues de matériau graphitique, leurs procédés de fabrication et leurs utilisations - Google Patents

Particules de silicium revêtues de matériau graphitique, leurs procédés de fabrication et leurs utilisations Download PDF

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Publication number
WO2025072959A1
WO2025072959A1 PCT/US2024/049312 US2024049312W WO2025072959A1 WO 2025072959 A1 WO2025072959 A1 WO 2025072959A1 US 2024049312 W US2024049312 W US 2024049312W WO 2025072959 A1 WO2025072959 A1 WO 2025072959A1
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WIPO (PCT)
Prior art keywords
graphitic
milling
silicon
particles
silicon particle
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English (en)
Inventor
Yong Lak Joo
Mohammad Abdul AZIZ
Yash JOSHI
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Cornell University
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Cornell University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C19/00—Other disintegrating devices or methods
    • B02C19/06—Jet mills
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure describes, inter alia, graphitic-material-coated silicon particles and compositions thereof and methods of making graphitic-material-coated silicon particles.
  • the present disclosure also provides electrodes and devices comprising graphitic-material-coated silicon particles.
  • a silicon particle which may be an oxidized silicon particle (such as, for example, a partially
  • 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).
  • 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.
  • the composition further comprises one or more active material(s) and/or one or more binder(s).
  • the composition is suitable (or configured) for use in a device (such as, for example, an electrochemical device or the like).
  • 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)).
  • 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).
  • a method comprises in-situ graphitic material (e.g., graphene or the like) coating of silicon particles.
  • a method of making one or more graphitic-material-coated silicon particle(s) comprises one or more milling(s) and/or mixing(s).
  • 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)).
  • the method further comprises forming the mixture prior to the milling.
  • 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
  • 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.
  • 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.
  • the electrode further comprises one or more active material(s).
  • an active material is a conducing material.
  • the electrode further comprises one or more binder(s).
  • the electrode further comprises a current collector.
  • 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)).
  • the present disclosure provides devices.
  • a device comprises one or more electrode(s) of the present disclosure.
  • 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).
  • 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.
  • graphitic material such as, for example, graphene or the like
  • 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 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).
  • FIG. 1 shows a schematic of in situ graphene coating on Si particles during jet milling.
  • FIG. 2 shows average particle size (D50) (left) and DIO, D50, D90, and D99 of milled Si at particles at various milling times (right).
  • 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.
  • 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.
  • EDX energy-dispersive X-ray spectroscopy
  • FIG. 5 shows thermal gravimetric analysis (TGA) of mill coated SiOx and carbon coated SiOx via CVD.
  • 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.
  • FIG. 7 shows TGA of chemical vapor deposition (CVD) grown graphene coated SiOx.
  • 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.%.
  • 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)).
  • 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.
  • FIG. 11 shows a schematic of in situ Si milling, graphene exfoliation, and coating via air jet ball milling.
  • FIG. 12 shows Fourier-Transform Infrared (FT-IR) spectra of metallurgical silicon (MET SI or met Si) (before and after jet milling).
  • FIG. 13 shows Raman spectra of met Si (before and after jet milling).
  • 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).
  • FIG. 15 shows plasma treatment temperature for metallurgical Si (MLSI), milled metallurgical Si (AMSI), solar Si (SSI), and milled solar Si (SMSI).
  • 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).
  • LIB lithium-ion battery
  • ICE initial Coulombic efficiency
  • 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).
  • LIB lithium-ion battery
  • ICE initial Coulombic efficiency
  • FIG. 18 shows Raman spectroscopy characterization of microSi and jet milled microSi.
  • FIG. 19 shows a schematic representation of graphite/graphene coated silicon particles using LabRAM.
  • 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.
  • LIB lithium-ion battery
  • FIG. 24 shows A- an FTIR and B- Raman spectra of met Si, artificial graphite and PAA (before and after jet milling).
  • a given confidence interval e.g., 90%, 95%, or more confidence interval from the mean
  • a given confidence interval e.g. 90%, 95%, or more confidence interval from the mean
  • 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.
  • 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.
  • 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.
  • 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).
  • group also includes radicals (e.g., monovalent radicals and multivalent radicals, such as, for example, divalent radicals, trivalent radicals, and the like).
  • 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.
  • 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.
  • 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.
  • the present disclosure describes, inter alia, graphitic-material-coated silicon particles and compositions thereof and methods of making graphitic-material-coated silicon particles.
  • the present disclosure also provides electrodes and devices comprising graphitic-material-coated silicon particles.
  • 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).
  • 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.
  • 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).
  • 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.
  • a graphitic- material-coated silicon particle further comprises one or more binder(s).
  • 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),
  • a silicon particle
  • 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 linear dimension (e.g., an average linear dimension (e.g.,
  • 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.
  • 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.
  • 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.
  • CVD chemical vapor deposition
  • exGR exfoliated graphene
  • graphite e.g., in the natural form, in an artificial form, in a recycled form, or the like, or any combination thereof
  • petroleum coke structural analogs thereof; and the like; and any combination thereof.
  • a graphitic-material-coated silicon particle can comprise various combinations of silicon particle and graphitic material(s).
  • 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.
  • the exGR coated SiOx particle comprises about 2 wt% carbon.
  • 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.
  • a graphitic-material-coated silicon particle further comprises one or more binder(s).
  • 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.
  • the one or more binder(s) comprise (or is) PAA comprising a molecular weight (M w and/or M n ) of about 4 x 10 6 g/mol.
  • a binder 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.
  • 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).
  • a graphitic-material-coated silicon particle can have various sizes.
  • 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).
  • 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,
  • graphitic material(s) at least partially or completely encapsulate the silicon particle.
  • 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.
  • 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.
  • 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.
  • domain(s) e.g., island(s) or the like
  • 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.
  • 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.
  • a continuous layer e.g., a monolayer or a bilayer or the like or a combination thereof
  • domain(s) e.g., island(s) or the like
  • 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.
  • 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),
  • a graphitic-material-coated silicon particle can comprise various amounts of silicon.
  • 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).
  • a graphitic-material-coated silicon particle may comprise carbon.
  • 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.
  • 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).
  • 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)).
  • 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).
  • 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.
  • a composition is formed by a method of the present disclosure. Non-limiting examples of compositions are provided herein.
  • a composition comprises one or more graphitic-material- coated silicon particle(s).
  • a composition further comprises one or more active material(s) and/or one or more binder(s).
  • 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).
  • 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).
  • a silicon particle size and/or a graphitic material size is/are an average size or average sizes.
  • 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.
  • a composition is suitable (or configured) for use in a device (such as, for example, an electrochemical device or the like).
  • 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)).
  • a method comprises in-situ graphitic material (e.g., graphene or the like) coating of silicon particles.
  • a method comprises forming a mixture and milling the mixture.
  • a method comprises forming a mixture and mixing the mixture.
  • a method comprises forming a mixture, milling the mixture, and mixing the milled mixture.
  • 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.
  • a method of making one or more graphitic-material-coated silicon particle(s) comprises one or more milling(s) and/or mixing(s) described herein.
  • a method of making one or more graphitic-material- coated silicon particle(s) 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).
  • a method of making one or more graphitic-material-coated silicon particle(s) 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).
  • a method further comprises sonication of the milled silicon particle(s) and milled graphitic material(s).
  • a method of making one or more graphitic-material-coated silicon particle(s) 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 graphi
  • resonant acoustic mixing RAM
  • 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 n
  • mixing comprises resonant acoustic mixing or the like (or is carried out using a resonant acoustic mixer or the like).
  • 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).
  • the mixing is blade-less mixing, non-contact mixing, or both.
  • the mixing is carried out with a blade-less and/or non-contact mixer.
  • 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).
  • Vibrational mixing and coating 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.
  • graphite- coated silicon particles formed using a vibrational mixer can provide one or more desirable properties.
  • vibrational mixing and coating such as, for example, resonant acoustic mixing and coating and the like
  • island-like coating which may be achieved by selection of an appropriate starting material concentration.
  • high intensity vibrational mixing and coating such as, for example, resonant acoustic mixing and coating and the like
  • 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.
  • milling and coating processes were combined (e.g., milling resulted in coating) introducing mixture of Si microparticles, graphite (or graphene) and a binder.
  • a binder e.g., boron nitride, boron nitride, 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.
  • 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.
  • a method uses (e.g., in a milling process) one or more silicon microparticle(s) or the like.
  • 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)).
  • one or more silicon particle(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).
  • 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
  • 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 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.
  • one or more silicon particle(s) comprise(s) one or more silicon microparticle(s), one or more silicon nanoparticles, or both.
  • 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.
  • 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)).
  • the one or more graphitic material(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.
  • 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.
  • 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.
  • exGR exfoliated graphene
  • binder(s) can be used in a method of making graphitic-material-coated silicon particles.
  • Non-limiting examples of binders are described herein.
  • Various ratios e.g., weight ratios or the like
  • one or more silicon particle(s), one or more graphitic material(s), and optionally, one or more binder(s) can be used in a method of making graphitic-material-coated silicon particles.
  • 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, 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
  • 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.
  • a mixture is formed prior to a milling or mixing.
  • the mixture is a dry powder.
  • one or more or all of the silicon particle(s), the graphitic material(s), or the binder(s), are dry powder(s).
  • a method can use various amounts of silicon particles, graphenic material(s), and optionally, binder(s).
  • a method 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • the milling process(es) are carried out without heating.
  • 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.
  • 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.
  • 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
  • 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).
  • 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)).
  • 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.
  • a milling can be carried out in (or a milling is performed using various atmospheres).
  • atmospheres include dry air; nitrogen; and argon; and the like; and any combination thereof.
  • 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.
  • a milling provides one or more milled silicon particle(s).
  • 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).
  • 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
  • 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).
  • milled silicon particles comprise decreased crystallinity (as compared with the same silicon particles that have not been milled
  • 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., a diameter, a thickness, or the like), one or more or all
  • milling 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.
  • altered properties such as, for example, altered surface propert(ies)
  • spectroscopy method(s) such as, for example, FTIR spectroscopy, Raman spectroscopy, or the like, or any combination thereof
  • 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.
  • 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.
  • 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.
  • a milling provides one or more milled grapheme material(s).
  • 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).
  • 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).
  • 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
  • a method may comprise sonication.
  • 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).
  • 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).
  • 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.
  • 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).
  • the one or more milled graphitic material(s) independently coat(s) substantially all or all the one or more milled silicon particle(s).
  • a method can produce various graphitic-material-coated silicon particles.
  • graphitic-material-coated silicon particles comprise greater than 95% by weight silicon (based on the total weight of the graphitic-material-coated silicon particles).
  • 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.
  • 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.
  • Graphitic-material-coated silicon particles produced by a method can comprise various sizes.
  • 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).
  • 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)
  • 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).
  • 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)).
  • 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).
  • 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).
  • 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.
  • 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).
  • the one or more graphitic-material-coated silicon particle(s) or one or more composition(s) are additives.
  • one or more graphitic-material-coated silicon particle(s) are an additive or the like.
  • 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)).
  • an electrode such as, for example, an anode or a cathode
  • a reversible electrode such as, for example, a reversible anode or a reversible cathode.
  • an electrode such as, for example, an anode or a cathode further comprises one or more active material(s).
  • 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 PTM and the like), and the like, and any combination thereof).
  • a conducing carbon material e.g., graphene, carbon black (such as, for example, SUPER PTM and the like
  • it is considered conductive carbon blacks (such as, for example, SUPER PTM 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).
  • an electrode (such as, for example, an anode or a cathode) further comprises one or more binder(s).
  • binder(s) are disclosed herein.
  • an electrode or electrodes 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).
  • electrochemical devices such as, for example, secondary batteries or secondary cells, which may be rechargeable batteries, primary batteries or primary cells, or the like.
  • secondary batteries and primary batteries include Li-ion batteries, Li metal batteries, and the like.
  • an electrode (such as, for example, an anode or a cathode) further comprises a current collector.
  • 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.
  • a metal or metal alloy is stainless steel, copper, aluminum, nickel, tantalum, molybdenum, or the like, or an alloy thereof.
  • an electrode (such as, for example, an anode or a cathode) does not comprise a metal current collector.
  • 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.
  • 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).
  • 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).
  • 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)).
  • 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.
  • a device is an electrochemical device or the like.
  • electrochemical devices include, supercapacitors, fuel cells, electrolyzers, electrolytic cells, and the like.
  • 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.
  • 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.
  • a battery is a metal battery, such as, for example, a lithium- metal battery, a sodium-metal battery, magnesium-metal battery, or the like.
  • the device 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).
  • 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.
  • cathodes/cathode materials comprise a conducting carbon aid.
  • a device e.g., a battery or the like
  • 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.
  • 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.
  • a cathode further comprises one or more conducting carbon aid(s) or the like.
  • a cathode is a high-voltage cathode.
  • 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.
  • the device e.g., a battery or the like
  • the device further comprises one or more anode(s), which independently comprise(s) one or more anode material(s).
  • 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.
  • 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).
  • 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.
  • 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).
  • electrolyte(s) e.g., solid-state electrolyte(s), liquid electrolyte(s), or the like, or any combination thereof.
  • liquid electrolyte(s) is/are non-aqueous electrolyte(s).
  • liquid electrolyte(s) is/are aqueous electrolyte(s).
  • 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.
  • one or more electrolyte(s) is/are nonflammable (e.g., non-flammable aqueous electrolyte(s)). Examples of suitable electrolytes are known in the art.
  • liquid electrolytes can be used.
  • 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.
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • EMC ethyl methyl carbonate
  • EMC ethylene carbonate
  • PC propylene carbonate
  • FEC fluoroethylene carbonate
  • VC vinylene carbonate
  • TFEC di-2,2,2-trifluoroethyl carbonate
  • DME dimethoxyethane
  • DOL 1,3-di
  • Solid electrolytes can be used.
  • 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+ x AlxGe 2 x(PO 4 ) 3 (LAGP), Lii +x AlxTi 2 x(PO 4 ) 3 (LATP), lithium phosphorus oxynitride (LiPON), and the like, and any combination thereof).
  • PEO poly(ethylene oxide)
  • PAN poly(acrylonitrile)
  • PC propylene carbonate
  • EC ethylene carbonate
  • ceramic electrolytes e.g. LivLasZnOn (LLZO), Li superionic conductor (LISICON), Lii+ x AlxGe 2 x(PO 4
  • a device comprises bipolar plates, external packaging, and electrical contacts/leads to connect wires, and the like, and any combination thereof.
  • An electrolyte, a cathode, an anode, and, optionally, the current collector may form a cell of a battery.
  • 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.
  • the battery comprises 1 to 500 cells, including all integer number of cells and ranges therebetween.
  • 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.
  • silicon oxide SiOx, where, for example, x is about 0 to about 1.99
  • 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).
  • 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
  • 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.
  • 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.
  • graphene e.g., in the natural form, in an artificial form, in a recycled form, or the like, or any combination thereof
  • CVD chemical vapor deposition
  • exGR exfoliated graphene
  • graphite e.g., in the natural form, in an artificial form, in a recycled form, or the like, or any combination thereof
  • 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.
  • 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)
  • 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)
  • a size such as, for
  • 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.
  • PAA peroxyacetic acids
  • PVDFs polyvinylidene fluorides
  • PVDFs polyvinyl alcohols
  • CMCs carboxymethyl celluloses
  • SBRs styrenebutadiene rubbers
  • 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.
  • 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/
  • 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.
  • 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).
  • 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
  • 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).
  • 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)
  • an average size such as
  • 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).
  • 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
  • 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
  • graphene e.g., in the natural form, in an artificial form, in a recycled form, or the like, or any combination thereof
  • CVD chemical vapor deposition
  • exGR exfoliated graphene
  • graphite e.g., in the natural form, in an artificial form, in a recycled form, or the like, or any combination thereof
  • petroleum coke structural analogs thereof; and the like; and any combination thereof.
  • 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
  • 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.
  • 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).
  • 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.
  • a size or comprise an average size
  • linear dimension(s) e.g., a diameter or the like
  • 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.
  • 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.
  • 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.
  • a method of forming a plurality of graphitic-material-coated silicon particles 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
  • 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.
  • SiOx silicon oxide
  • metallurgical silicon particles recycled metallurgical silicon particles
  • milled metallurgical silicon particles e.g., where x is about 0 to about 1.99
  • 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)
  • 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.
  • graphene e.g., in the natural form, in an artificial form, in a recycled form, or the like, or any combination thereof
  • CVD chemical vapor deposition
  • exGR exfoliated graphene
  • graphite e.g., in the natural form, in an artificial form, in a recycled form
  • 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
  • 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 34-40, 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
  • PAAs polyacrylic acids
  • PVDFs polyvinylidene fluorides
  • PVDFs polyvinyl alcohols
  • CMCs carboxymethyl celluloses
  • SBRs styrenebutadiene rubbers
  • 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.
  • 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.
  • 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).
  • 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
  • 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).
  • a size such as, for example, one or more linear dimension(s) (e.g., an average diameter,
  • 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).
  • 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
  • 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
  • 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 e.g., where x is about 0 to about 1.99
  • solar silicon particles e.g., where x is about 0 to about 1.99
  • graphene e.g., in the natural form, in an artificial form, in a recycled form, or the like, or any combination thereof
  • CVD chemical vapor deposition
  • exGR exfoliated graphene
  • graphite e.g., in the natural form, in an artificial form, in a recycled form, or the like, or any combination thereof
  • petroleum coke structural analogs thereof; and the like; and any combination thereof.
  • 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
  • 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. %).
  • 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
  • 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).
  • 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.
  • a size or comprise an average size
  • linear dimension(s) e.g., a diameter (or average diameter), a thickness (or an average thickness, or the like
  • a thickness or an average thickness, or the like
  • 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.
  • 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.
  • 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.
  • a charge capacity e.g., a lithium-ion conducting batter or the like
  • a method consists essentially of a combination of the steps of the methods disclosed herein. In another embodiment, a method consists of such steps.
  • 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.
  • FIG. 1 shows a schematic of in in situ graphene coating on Si particles during jet milling.
  • 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.
  • the battery performance of resulting Si/graphene hybrids from recycled streams are summarized in FIG. 10.
  • 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.
  • 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.
  • FIG. 11 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.
  • graphene obtained from Advanced Chemicals Supplier (ACS)
  • PAA polyacrylic acid
  • 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.
  • microSi Jet milled micron sized silicon particles
  • FIG. 18 Jet milled micron sized silicon particles
  • 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.
  • 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.
  • Silicon (Si) sources Metallurgical Silicon (Recycled), Milled Metallurgical Silicon, Solar Silicon, Milled Solar Silicon, Silicon oxide
  • Binder Polyacrylic acid (PAA), polyvinylidene fluoride (PVDF), carboxymethyl cellulose (CMC), and styrene-butadiene rubber (SBR)
  • PAA Polyacrylic acid
  • PVDF polyvinylidene fluoride
  • CMC carboxymethyl cellulose
  • SBR styrene-butadiene rubber
  • 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.
  • met Si, CSP and PAA anodes were cycled by using a galvanostatic charge/discharge process to identify their charge/discharge performance.
  • 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.

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
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  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Battery Electrode And Active Subsutance (AREA)
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Abstract

L'invention concerne des particules de silicium revêtues de matériau graphitique et leurs utilisations et des compositions associées et des procédés de fabrication de particules de silicium revêtues de matériau graphitique. Dans divers exemples, un procédé de formation d'une pluralité de particules de silicium revêtues de matériau graphitique comprend le broyage (par exemple, le broyage à billes à jet d'air ou similaire) d'un mélange comprenant une ou plusieurs particules de silicium, un ou plusieurs matériaux graphitiques (par exemple, le graphite, le graphène ou similaire, ou toute combinaison de ceux-ci), et un ou plusieurs liants. Dans divers exemples, une particule de silicium revêtue de matériau graphitique comprend une particule de silicium et un ou plusieurs matériaux graphitiques, le ou les matériaux graphitiques étant disposés sur au moins une partie, sensiblement la totalité ou la totalité d'une ou de plusieurs surfaces de la particule de silicium. Dans divers exemples, une électrode ou un dispositif (tel que, par exemple, un dispositif électrochimique ou similaire) comprend une pluralité de particules de silicium revêtues de matériau graphitique.
PCT/US2024/049312 2023-09-29 2024-09-30 Particules de silicium revêtues de matériau graphitique, leurs procédés de fabrication et leurs utilisations Pending WO2025072959A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020261194A1 (fr) * 2019-06-28 2020-12-30 Talga Technologies Limited Matériau composite contenant du silicium et du graphite et procédé de production associé
US20210114886A1 (en) * 2018-02-15 2021-04-22 The Research Foundation For The State University Of New York Silicon-carbon nanomaterials, method of making same, and uses of same
US20220380223A1 (en) * 2021-05-25 2022-12-01 Ionobell, Inc. Silicon material and method of manufacture

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210114886A1 (en) * 2018-02-15 2021-04-22 The Research Foundation For The State University Of New York Silicon-carbon nanomaterials, method of making same, and uses of same
WO2020261194A1 (fr) * 2019-06-28 2020-12-30 Talga Technologies Limited Matériau composite contenant du silicium et du graphite et procédé de production associé
US20220380223A1 (en) * 2021-05-25 2022-12-01 Ionobell, Inc. Silicon material and method of manufacture

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