WO2018009484A1 - Passivated pre-lithiated micron and sub-micron group iva particles and methods of preparation thereof - Google Patents

Passivated pre-lithiated micron and sub-micron group iva particles and methods of preparation thereof Download PDF

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Publication number
WO2018009484A1
WO2018009484A1 PCT/US2017/040605 US2017040605W WO2018009484A1 WO 2018009484 A1 WO2018009484 A1 WO 2018009484A1 US 2017040605 W US2017040605 W US 2017040605W WO 2018009484 A1 WO2018009484 A1 WO 2018009484A1
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group iva
surface modifier
group
alloy particles
particles
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PCT/US2017/040605
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French (fr)
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Timothy NEWBOUND
Reza KAVIAN
Jeff Norris
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Kratos LLC
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Priority to JP2018569151A priority Critical patent/JP2019520682A/en
Priority to US16/311,988 priority patent/US11522178B2/en
Priority to KR1020197003591A priority patent/KR20190042558A/en
Priority to EP17824762.3A priority patent/EP3482434A4/en
Priority to CN201780041575.XA priority patent/CN109478640B/en
Priority to CA3029244A priority patent/CA3029244A1/en
Priority to BR112019000112-3A priority patent/BR112019000112A2/en
Publication of WO2018009484A1 publication Critical patent/WO2018009484A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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 generally relates to the formation of pre-lithiated micron- and sub-micron Group IVA particles, with surface modifiers applied to passivate lithium from reactions with air and moisture, to the formation of artificial SEI (Solid Electrolyte Interphases) in lithium-ion batteries for improved cycle stability and charge capacity retention, and to methods of preparation and energy storage applications thereof.
  • SEI Solid Electrolyte Interphases
  • Solid Electrolyte Interphase (SEI) formation on an anode during the first charge- discharge cycle can cause high, irreversible capacity loss (ICL) and result in low Coulombic efficiency.
  • ICL irreversible capacity loss
  • Li x Si y alloy crystalline phases
  • Some of these alloys (preferably those with crystalline character) have been prepared as powders by mechanical milling. For example, Iwamura, S. et al. (Sci Rep. 5, 8085;
  • volume expansion upon lithiation of silicon through the formation of multiple Li x Si y phases can reach as high as 400%.
  • This physical property has been the root cause of several detrimental effects that leads to rapid capacity fade upon undergoing multiple charge-discharge cycles.
  • Mechanical stress from volume expansion and contraction during charge/discharge cycles can lead to particle pulverization, loss of electrical contacts, and excessive SEI buildup in the negative electrode composites, with at least 35% of the lithium being consumed in the process.
  • this passivation layer should also function as the SEI layer.
  • compositions and methods for pre-lithiation of Group IVA micron and sub-micron particles by application of surface-modifiers such that reactive lithium-M alloy particles (where M may be Si, Ge, or Sn, for example) are substantially passivated to reactions with air and moisture.
  • the disclosed surface modifiers may serve as an artificial SEI barrier and are impermeable to oxygen and water to an extent such that the particles can be dispersed in aqueous-based slurries typically used to form negative electrodes in existing commercial lithium-ion battery processes.
  • Electrode composites made with these pre-lithiated Group IVA particles may exhibit high first-cycle efficiency (“FCE”) (FCE; at least about 90%) and high subsequent cycle efficiencies.
  • FCE first-cycle efficiency
  • the invention provides a method of producing a negative electrode, including comminuting Li-Group IVA alloy particles in a solvent to a desired particle size distribution range, exposing surfaces of the Li-Group IVA alloy particles to at least one surface modifier present during the comminution process, the at least one surface modifier forming at least one continuous coating on at least one of the exposed surfaces of the Li-Group IVA alloy particles, removing the solvent, and adding the surface-modified Li- Group IVA alloy particles to a negative electrode material by a coating process.
  • FIG. 1 shows a first charge-discharge plot comparison between prelithiated laminate (green) and non-prelithiated laminate (blue).
  • the First Cycle Efficiency (FCE) without prelithiation is about 83.5%, whereas with prelithiation the FCE is about 90%. It can be made to be about 100% with added prelithiated surface-modified silicon.
  • FIG. 2 shows the first 50 charge-discharge cycles after the formation cycle (FCE about 88.5%) full cell with Nickel/Cobalt/ Alumina (NCA) cathode.
  • the anode/cathode ratio is about 1.1.
  • FIG. 3 shows images of laminate made in aqueous binder, (a) About 5% prelithiated surface-modified silicon with protected shell, (b) About 5% prelithiated surface- modified silicon with non-protected shell, (c) Slurry of about 5% prelithiated Si with nonprotected shell. Comparing the panels shows the stability of prelithiated surface-modified silicon product in aqueous binder.
  • FIG. 4 shows a plot of the non-spherical particle size distributions (PSD) of prelithiated surface-modified silicon.
  • D 50 is about 500 nm, and the PSD is narrow.
  • PSD is measured using dynamic light scattering (DLS) particle size analysis is based on Brownian motion light scattering.
  • FIG. 5 shows an SEM image of the non-spherical surface-modified silicon represented in FIG 3.
  • the inactive protective shell allows safe handling of Li x Si y alloy particles in air and aqueous environments. Without this protective shell, Li metal reacts exothermically with water and both Li and Si will quickly oxidize in air to form an oxide shell. While an oxide shell impedes the diffusion of oxygen to the reactive Li x Si y alloy core, it is insufficient to prevent water from reacting violently with Li x Si y alloy.
  • the passivated Li x Si y alloy particles can be combined with binders and other components of the anode composite in common commercial slurry production processes used in conventional LIB manufacturing.
  • the coated Li x Si y alloy may increase the cycle stability of the LIB.
  • Si and other Group IVA elements are known to undergo large volume expansion during
  • This disclosure describes, among other things, how to produce coated Li x Si y alloys designed to enhance the performance of LIB negative electrodes. It should be understood that Ge and Sn or some combination of Si, Ge, and Sn could also be used to form alloys with Li that would function similarly as components of LIB negative electrodes.
  • Li x Si y alloy methods of producing micron or submicron scale Li x Si y alloy with an inactive coating are described.
  • the methods described herein use a Li x Si y alloy as the feedstock for comminution in alkane or cycloalkane solvents, such as hexanes, heptanes, octanes, cyclohexanes, or any saturated alkane solvents.
  • Other Li alloys can also be used with the methods of the present invention, including LiGe, LiSn, or other combinations of Si, Ge, and Sn with Li to form an alloy, for example.
  • One exemplary alloy is L115S14.
  • comminution conditions can be chosen from a combination of parameters that one skilled in the art of comminution will be able to select. Any suitable method of comminution may be used in the process of the present invention, including, but not limited to, milling, wet milling, crushing, grinding, cutting, vibrating, or other processes. If a milling process is used, agitator speeds and other conditions during comminution are chosen depending on the size of the mill, batch size, bead selection, solids loading, solvent selection circulation rate, and secondary reagents employed.
  • Li x Si y alloy is comminuted by a circulating bead mill in an alkane solvent (including, but not limited to, cycloalkane solvents, hexanes, heptanes, octanes, cyclohexanes, or any saturated alkane solvents) with a polymer additive (including, but not limited, to polystyrene, polyacrylonitrile, polyacrylic acid (and its neutral Li salt), and polyaniline).
  • alkane solvent including, but not limited to, cycloalkane solvents, hexanes, heptanes, octanes, cyclohexanes, or any saturated alkane solvents
  • a polymer additive including, but not limited, to polystyrene, polyacrylonitrile, polyacrylic acid (and its neutral Li salt), and polyaniline.
  • polymer coatings may be added post- milling on top of Li x Si y alloy particles with any surface coatings that were
  • the Li x Si y alloy particle size distribution is reduced to the desired PSD range by comminution, preferably about 1,000 - 44,000 nm, or more preferably about 50 - 1,000 nm, and more preferably between about 400 - 600 nm.
  • Highly reactive surfaces of the Li x Si y alloy that are exposed on the fractured Li x Si y alloy particles will form covalent bonds to the polymer and any desired surface modifiers present during the comminution process.
  • the polymer and co-reagents form a continuous coating (protective shell) on the Li x Si y alloy particles, covering all surfaces with an at least 2 nm to about 500 nm lay er.
  • the polymer coating may be thermally processed or crosslinked with added reagents, all part of the protective shell.
  • the milling solvent is then removed by an evaporation process. This could be done by any number of methods known in the art, such as spray drying or evaporation under reduced pressure in a suitable atmosphere.
  • the particle can be heated, for example, to about 150 - 1200 °C for about 30 minutes to about 24 hours under a suitable gas (including, but not limited to, air, Ar, or Ar/H 2 ) or in a vacuum to cure the protective shell. Curing is considered to be partial to complete cross-linking of polymer precursors or carbonization of the hydrocarbon mass on the Li x Si y alloy surfaces.
  • Heating temperatures and durations will depend on what polymer coatings are used to form a protective shell.
  • the resulting coated Li x Si y alloy material can then added to a conventional LIBs negative electrode composite using conventional coating processes (including, but not limited to, the addition of carbon black, graphite, or other additives used with aqueous binder systems in conventional anode slurries, or non-aqueous binder systems, such as NMP/PVdF).
  • 325-mesh Li 15 Si4 (about 48:52 wt%) was prepared thermochemically as the feedstock for wet milling processes in alkane or cycloalkane solvents, such as hexanes, heptanes, octanes, cyclohexanes, or any saturated alkane solvents with a boiling range well above the operation temperature of the milling slurry (typically between about 25 - 60 °C).
  • comminution conditions can be determined. Milling beads and materials are typically selected from hard ceramic materials.
  • Beads range in diameter from about 100 - 1,000 microns, preferably about 300 - 900 microns.
  • the agitator tip-speeds during comminution are typically running between about 2 - 15 m s for about 15 - 1200 minutes, depending on the size of the mill, batch size, bead selection, solids loading, solvent selection circulation rate, and secondary reagents employed.
  • Li 15 Si4 alloy was stirred under Ar for about 48 hours in an about 5% polyacrylonitrile (PAN) solution in dimethylsulfoxide (DMSO).
  • PAN polyacrylonitrile
  • DMSO dimethylsulfoxide
  • the weight equivalent ratio of Li x Si y to PAN was about 7:3.
  • the DMSO was stripped by vacuum distillation, and the remaining solids were dried for about 6 hours under dynamic vacuum at about 80 °C. The remaining solid was heated for about 2 hours under Ar atmosphere to cure the protective coating.
  • dimethylformamide (DMF) is used as the solvent in place of DMSO.
  • monomeric surface modifiers may be added in place of or in addition to polymers.
  • the surface modifiers may be monomers with functional groups that react with the Li x Si y alloy particle surfaces or with the polymer to form chemical bonds. Because Li x Si y alloy is so reactive, almost any organic compound with heteroatoms and/or unsaturated bonds are potential surface modifiers.
  • Reactive monomers could be selected from the group consisting of alkenes, alkynes, aromatics, heteroaromatics, cycloalkenes, alcohols, glycols, polyglycols, ethers, polyethers, thiols, disulfides, amines, amides, pyridines, pyrroles, imides, imidazoles, imidazoline, furans, thiophenes, cyanates, isocyanates, isothiocyanates, ketones, carboxylic acids, esters, amino acids, aldehydes, acrylates, methacrylates, oxylates, organic carbonates, lactones, and gases, such as H 2 , O2, CO2, N 2 0, and HF.
  • Various fluorinated analogs of these compounds can also be used, such as trifluoroacetone, bis(2,2,2-trifluoroethyl) carbonate, 2,2,2-trifluoroethyl acrylate, 2,2,2- trifluoroethyl methacrylate, and 1,3,5-trifluorobenzene.
  • the comminution solvent is then removed by any suitable method, and the coated Li x Si y alloy particle may or may not require heating under a suitable gas to cure the coating and form a protective shell.
  • This protective shell may prevent water or other solvents used to combine elements of the electrode coating process from reacting with the Li x Si y core material.
  • This coated Li x Si y alloy can be added to conventional LIBs negative electrode composite using conventional coating processes.
  • Table 1 shows several mass equivalents of reagents used for comminution, compared with product yields of comminution process and heat processing steps.
  • Table 1 (supplemented by the drawings) demonstrates composition of matter of products after comminution and after heat treatment, as well as the processes disclosed herein.
  • the Li x Si y alloy is comminuted in an inert alkane solvent in the presence of a metal-oxide or a metal-alkoxide reagent.
  • metal oxides are AI2O3, Ti0 2 , Li4Ti 5 0 12 , MgO, NiO, and borates.
  • Metal alkoxides constitute an important class of compounds often used in sol-gel processes. They are characterized by a metal- oxygen-carbon bonding system, including such metals as magnesium, aluminum, titanium, zinc, or lithium. Metal alkoxides in particular have proven to be especially beneficial during comminution as they modify particle surfaces to keep particles well suspended in the slurry with alkane solvents. If required, subsequent curing of the coated Li x Si y particles will form a protective shell comprised of metal oxides that sufficiently impedes ingress of solvents to the Li x Si y alloy particle core.
  • inorganic carbon (non-hydrocarbon) surface modifiers can be added at some stage during or following comminution of Li x Si y alloy and allowed to contact and form covalent bonds on highly reactive sites on newly fractured surfaces of the Li x Si y alloy particles.
  • the surface modifiers can be present at the beginning of the comminution process, or added after most of the particle size reduction has taken place but while surfaces are still very reactive (while there are many non-passivated sites).
  • the progress of the comminution can be monitored by particle size distribution measurements and/or by monitoring slurry temperatures, viscosity, or power input.
  • Inorganic carbon surface modifiers may be comprised from the group: carbon nanotubes (SWCNT, MWCNT), nanospherical carbon, fullerenes, graphene, graphite, or carbon black.
  • other hydrocarbons may be added to help provide complete coverage of the Li x Si y particle surface and provide passivation of the Li x Si y alloy core from reactive solvents.
  • the coated Li x Si y alloy particles are blended with natural flake graphite (NFG). Prolonged blending of these dry powders under inert atmosphere can imbed sub-micron Li x Si y alloy particles into surface pores and crevices of NFG particles (ty pically about 10 - 20 micron). Subsequent coating of the NFG particles with a polymer or polymer precursors to provide a continuous coating on the NFG and over imbedded Li x Si y particles is a means of passivating the Li x Si y alloy while also spacing the Li x Si y particles in a Li-active matrix that will tolerate the expansion and contraction of Li x Si y alloys without breaking critical covalent bonds with its surrounding framework. Subsequent heat treatment may be required, particularly for poly mer precursors to form cross-linked covalent bonds that impart added strength to the electrode composite.
  • NFG natural flake graphite
  • the Li x Si y alloy is comminuted in an inert alkane solvent in the presence of hy drogen, which serves as a forming gas.
  • a forming gas is an industrial gas comprised of inert gas blended with typically about 5% 3 ⁇ 4 or less. Forming gas can be used in the place of purified argon to blanket the slurry during comminution.
  • Molecular hydrogen is reactive toward silicon surfaces. It can also and will migrate into silicon and other metals as atomic hydrogen and will form LiH on the surface of Li x Si y alloy particles.
  • H 2 is also known to cap (passivate) Si surfaces by forming Si-H bonds with "dangling" Si-Si bonds created from fracturing Si particles. This condition may be preferred when it is desired to produce Li x Si y alloy particles with no oxides.
  • comminution of Li x Si y alloy produces submicron or nanoparticle distributions (preferably about 44,000 - 1,000 nm, or more preferably about 50 - 1,000 nm, and more preferably between about 400 - 600 nm).
  • Surface modifiers may be applied to the particles, which induces aggregation of the nanoparticles into micron-sized clusters. Grain structure in the micron-sized clusters is created from the coatings on the nanoparticles. These coatings can be heat-processed (cured) to form tight, porous covalently bonded masses of carbon and metal oxides in grains between the Li x Si y alloy core nanocrystals.
  • the same coating that resides in grains between the Li x Si y alloy nanocrystals form a continuous protective shell around the micron-sized cluster that impedes ingress of solvents, but allows Li + ion mobility and facilitates electrical charge transfer from the Li x Si y alloy particle core to the electrode current collector.
  • the surface modifiers used in this process of making aggregated Li x Si y alloy clusters could be any of the organic reagents, metal oxides, or metal alkoxides disclosed herein.
  • Li salts for example from the group LiF, L12O2, L12CO3, LiBF2(C204), Li2(C204)
  • Li x Si y alloy alone or with other surface modifiers can be heat processed and cured as described above to form a protective shell from a covalently bonded continuous layer of the additives that impedes ingress of solvents, but will allow Li + ion mobility and will facilitate electrical charge transfer from the particle Li x Si y alloy core to the electrode current collector.
  • Li- or Na-organic complexes may be used with any source of Li-active Group IVA elements (e.g., solar grade Si or Ge wafer kerf or metallurgical silicon) to prepare Group IVA particles with partial insertion (prepared in-situ and added during the comminution process) of the alkali metals.
  • Li-active Group IVA elements e.g., solar grade Si or Ge wafer kerf or metallurgical silicon
  • partial insertion prepared in-situ and added during the comminution process
  • the alkali metals e.g., poly cyclic aromatic (PA) compounds, such as pyrene, perylene, and naphthalene, form ion-paired Li + PA " complexes that can deliver Li to the Group IVA particle during comminution.
  • PA poly cyclic aromatic
  • the Li + PA " complexes described above can also function as an electrolyte in an appropriate solvent (such as gamma butyrolactone) whereupon a current is applied to a cell with Li foil as the counter electrode and with a Si/graphite electrode laminated on a Cu current collector as the working electrode.
  • a current is applied to a cell with Li foil as the counter electrode and with a Si/graphite electrode laminated on a Cu current collector as the working electrode.
  • the Si particles in the Si/graphite electrode will undergo Li insertion.
  • This electrode laminate is then partially charged with Li and can be used to make a battery with a partially charged negative electrode.
  • the modifier "about” used in connection with a quantity is inclusive of the stated value and has the meaning dictated by the context (for example, it includes at least the degree of error associated with the measurement of the particular quantity).
  • the modifier “about” should also be considered as disclosing the range defined by the absolute values of the two endpoints. For example, the expression “from about 2 to about 4" also discloses the range “from 2 to 4".
  • the term “about” may refer to plus or minus 10% of the indicated number. For example, “about 10%” may indicate a range of 9% to 11%, and “about 1%” may mean from 0.9-1.1. Other meanings of "about” may be apparent from the context, such as rounding off, so, for example "about 1" may also mean from 0.5 to 1.4.

Abstract

A method of producing a negative electrode, including comminuting Li-Group IVA alloy particles in a solvent to a desired particle size distribution range, exposing surfaces of the Li-Group IVA alloy particles to at least one surface modifier present during the comminution process, the at least one surface modifier forming at least one continuous coating on at least one of the exposed surfaces of the Li-Group IVA alloy particles, removing the solvent, and adding the surface-modified Li-Group IVA alloy particles to a negative electrode material by a coating process.

Description

PASSIVATED PRE-LITHIATED MICRON AND SUB-MICRON GROUP IVA PARTICLES AND METHODS OF PREPARATION THEREOF
Cross-Reference to Related Applications
[0001] This is application claims priority to U.S. Provisional Patent Application No. 62/358,401 filed July 5th, 2016, and U.S. Provisional Patent Application No. 62/479,444 filed March 31st, 2017, both of which are incorporated by reference herein in their entirety.
Technical Field
[0002] The present disclosure generally relates to the formation of pre-lithiated micron- and sub-micron Group IVA particles, with surface modifiers applied to passivate lithium from reactions with air and moisture, to the formation of artificial SEI (Solid Electrolyte Interphases) in lithium-ion batteries for improved cycle stability and charge capacity retention, and to methods of preparation and energy storage applications thereof.
Background of the invention
[0003] Solid Electrolyte Interphase (SEI) formation on an anode during the first charge- discharge cycle can cause high, irreversible capacity loss (ICL) and result in low Coulombic efficiency. This is the primary fate of depleted lithium, which is in limited supply in a full cell where essentially all of the active lithium is supplied initially from the cathode material, and it accounts for a large part of the ICL.
[0004] Typically, nearly all of the lithium used in lithium ion batteries (LIBs) is supplied in its oxidized state as part of the positive electrode (cathode) composite. Supplying lithium in the negative electrode (anode) would require it to be in a reduced state, which is very unstable toward ambient air and, in particular, moisture. Because commercial electrode laminates are typically made from aqueous slurries, pre-lithiation of the active materials in the anode, unless rigorously passivated to avoid reactions with water, has not been successful prior to making the electrode laminate.
[0005] Anode pre-lithiation processes have been developed for after the formation of the electrode laminate. For example, R.W. Grant (US 2014/0310951) discloses an
electrochemical reduction process, and another approach is compressing stabilized Li powder (SLMP) manufactured by FMC (US 7,588,623) into a cured anode laminate. However, both of these processes are not very adaptable to established industry practices and thus, have not been commercialized.
[0006] Other approaches for prelithiation have been published, but none have yet resulted in a viable commercial product or process that could be adapted by LIB manufacturers. There are several stable phases of LixSi (where x is about 1 to about 4.25) that could be synthesized thermochemically to make alloys or crystalline phases (herein generally referred to as LixSiy alloy). Some of these alloys (preferably those with crystalline character) have been prepared as powders by mechanical milling. For example, Iwamura, S. et al. (Sci Rep. 5, 8085;
DOI: 10.1038/srep08085 (2015)) have reported negative electrodes prepared with Li21Si5 alloys by mechanical milling. They assert that Li21Si5 is so reactive that it could not be combined directly with polymer binders without degrading the mixture, unless the alloy was first passivated with carbon. The passivation of Li21Sig particles by carbon black only prevented severe detrimental reactions with polymer binders; it did not passivate the particles toward reactions with water and air.
[0007] Additionally, volume expansion upon lithiation of silicon through the formation of multiple LixSiy phases can reach as high as 400%. This physical property has been the root cause of several detrimental effects that leads to rapid capacity fade upon undergoing multiple charge-discharge cycles. Mechanical stress from volume expansion and contraction during charge/discharge cycles can lead to particle pulverization, loss of electrical contacts, and excessive SEI buildup in the negative electrode composites, with at least 35% of the lithium being consumed in the process. These conditions have impeded commercialization of LIBs with silicon in the anode. For LixSiy to be adaptable to current LIB industry
manufacturing processes, a robust passivation barrier must be applied that is capable of preventing hydrolysis when it is immersed in aqueous-based electrode slurries. Ideally, this passivation layer should also function as the SEI layer.
[0008] Several approaches have been pursued to manage the effects of volume expansion. It is now generally recognized that limiting at least one dimension of Si structures to about 150 nm or less prevents the occurrence of stress fracturing. However, volume expansion and contraction of nanoparticles still occurs with lithiation/'delithiation cycles. Even if Si nanoparticles can be spaced apart from each other to prevent compressive stress fracturing, natural SEI that forms around the lithium-active surfaces is brittle and will continue to fracture, reforming upon electrochemical cycling when active sites are exposed to electrolyte solvents.
[0009] The concept of creating an egg-yolk structure, in which the active Si particle resides inside a rigid shell large enough to accommodate the fully expanded LixSi particle, while also keeping solvent from coming inside the shell, is exemplified by Cui (US
9,231,243). Flexible hydrocarbon shells and various methods of fabricating pyrolyzed carbon shells have been proposed by others. None of these examples has proven commercially viable due to the complexity of the process scale-up, costs of reagents, or lackluster electrochemical performance.
[0010] A prelithiation process asserted by Zhamu et al. (US 8,158,282) to be
economically viable involves galvanic charging of the electrode prior to assembling the cells. However, this process has so far not been adapted by the industry. In summary, no commercially viable processes have yet emerged. Thus, there is a need for a prelithation method that can be applied in commercial production lines for negative electrodes.
Summary of the Invention
[0011] Generally disclosed herein are compositions and methods for pre-lithiation of Group IVA micron and sub-micron particles by application of surface-modifiers, such that reactive lithium-M alloy particles (where M may be Si, Ge, or Sn, for example) are substantially passivated to reactions with air and moisture. The disclosed surface modifiers may serve as an artificial SEI barrier and are impermeable to oxygen and water to an extent such that the particles can be dispersed in aqueous-based slurries typically used to form negative electrodes in existing commercial lithium-ion battery processes. Electrode composites made with these pre-lithiated Group IVA particles may exhibit high first-cycle efficiency ("FCE") (FCE; at least about 90%) and high subsequent cycle efficiencies. With lithiation of the active anode materials, apparent irreversible capacity loss (ICL) from the formation cycles may be mitigated, thus preserving lithium from the cathode that would otherwise be consumed by SEI formation, in addition to the amount that becomes trapped in the Group IVA particles. (First cycle efficiency, expressed in percent (%), defines the ratio of charge that can be accommodated by the anode vs the charge that can be delivered by the anode. The lithium consumed by forming the first SEI deposits in the anode during the first charge/discharge cycle usually accounts for most of the first cycle irreversible capacity loss (ICL). FCE + ICL = 100%.) Additionally, volume expansion of the Group IVA particles has already taken place, thus reducing the severity of volume expansion during the initial charge/discharge cycles. The composition of the passivated pre-lithiated particles and the processes described herein may provide a means of seamless integration of these materials in existing industry electrode manufacturing processes.
[0012] In one embodiment, the invention provides a method of producing a negative electrode, including comminuting Li-Group IVA alloy particles in a solvent to a desired particle size distribution range, exposing surfaces of the Li-Group IVA alloy particles to at least one surface modifier present during the comminution process, the at least one surface modifier forming at least one continuous coating on at least one of the exposed surfaces of the Li-Group IVA alloy particles, removing the solvent, and adding the surface-modified Li- Group IVA alloy particles to a negative electrode material by a coating process.
[0013] Other aspects of the invention will become apparent by consideration of the detailed description and accompanying drawings.
Brief Description of the Drawings
[0014] FIG. 1 shows a first charge-discharge plot comparison between prelithiated laminate (green) and non-prelithiated laminate (blue). The First Cycle Efficiency (FCE) without prelithiation is about 83.5%, whereas with prelithiation the FCE is about 90%. It can be made to be about 100% with added prelithiated surface-modified silicon.
[0015] FIG. 2 shows the first 50 charge-discharge cycles after the formation cycle (FCE about 88.5%) full cell with Nickel/Cobalt/ Alumina (NCA) cathode. The anode/cathode ratio is about 1.1.
[0016] FIG. 3 shows images of laminate made in aqueous binder, (a) About 5% prelithiated surface-modified silicon with protected shell, (b) About 5% prelithiated surface- modified silicon with non-protected shell, (c) Slurry of about 5% prelithiated Si with nonprotected shell. Comparing the panels shows the stability of prelithiated surface-modified silicon product in aqueous binder.
[0017] FIG. 4 shows a plot of the non-spherical particle size distributions (PSD) of prelithiated surface-modified silicon. D50 is about 500 nm, and the PSD is narrow. PSD is measured using dynamic light scattering (DLS) particle size analysis is based on Brownian motion light scattering. [0018] FIG. 5 shows an SEM image of the non-spherical surface-modified silicon represented in FIG 3.
Detailed description
[0019] Before any embodiments of the invention are explained in detail, it is to be understood that the invention is not limited in its application to the details of construction and the arrangement of components set forth in the following description or illustrated in the following drawings. The invention is capable of other embodiments and of being practiced or of being carried out in various ways.
[0020] The inventors of the present application have previously developed a flexible, scalable process (U.S. Patent No. 9,461,304 incorporated herein by reference) to produce sub-micron surface-modified particles of Group IVA elements (U.S. Patent No. 9,461,309 incorporated herein by reference). By employing this general process, it is possible to produce micron or sub-micron LixSiy alloy particles encased with an inactive protective shell. This protective shell may function much like an artificial SEI layer.
[0021] The inactive protective shell allows safe handling of LixSiy alloy particles in air and aqueous environments. Without this protective shell, Li metal reacts exothermically with water and both Li and Si will quickly oxidize in air to form an oxide shell. While an oxide shell impedes the diffusion of oxygen to the reactive LixSiy alloy core, it is insufficient to prevent water from reacting violently with LixSiy alloy. By applying a continuous inactive protective shell that impedes the diffusion of water, the passivated LixSiy alloy particles can be combined with binders and other components of the anode composite in common commercial slurry production processes used in conventional LIB manufacturing.
[0022] The coated LixSiy alloy may increase the cycle stability of the LIB. Si and other Group IVA elements are known to undergo large volume expansion during
lithiation/delithiation (i.e. cycling). The volume expansion causes physical break down of the SEI, which leads to capacity loss as Li is consumed to form new SEI. However, the shell may be inactive and may not undergo significant volume change during cycling. Consequently , much less Li is consumed during lithiation and dehthiation, leading to higher overall Columbic efficiencies and cycle life. [0023] This disclosure describes, among other things, how to produce coated LixSiy alloys designed to enhance the performance of LIB negative electrodes. It should be understood that Ge and Sn or some combination of Si, Ge, and Sn could also be used to form alloys with Li that would function similarly as components of LIB negative electrodes. There are several possible methods in which these materials can be combined to create a composite material with the attributes of each component while also gaining synergies that the individual components lack by themselves. Examples used in the following discussion are intended to be non-limiting with respect to the reagents used in the examples.
[0024] In the present disclosure, methods of producing micron or submicron scale LixSiy alloy with an inactive coating are described. The methods described herein use a LixSiy alloy as the feedstock for comminution in alkane or cycloalkane solvents, such as hexanes, heptanes, octanes, cyclohexanes, or any saturated alkane solvents. Other Li alloys can also be used with the methods of the present invention, including LiGe, LiSn, or other combinations of Si, Ge, and Sn with Li to form an alloy, for example. One exemplary alloy is L115S14. Depending on the desired particle size distribution (PSD) range of the LixSiy alloy product, comminution conditions can be chosen from a combination of parameters that one skilled in the art of comminution will be able to select. Any suitable method of comminution may be used in the process of the present invention, including, but not limited to, milling, wet milling, crushing, grinding, cutting, vibrating, or other processes. If a milling process is used, agitator speeds and other conditions during comminution are chosen depending on the size of the mill, batch size, bead selection, solids loading, solvent selection circulation rate, and secondary reagents employed.
[0025] For example, in some embodiments, LixSiy alloy is comminuted by a circulating bead mill in an alkane solvent (including, but not limited to, cycloalkane solvents, hexanes, heptanes, octanes, cyclohexanes, or any saturated alkane solvents) with a polymer additive (including, but not limited, to polystyrene, polyacrylonitrile, polyacrylic acid (and its neutral Li salt), and polyaniline). Alternately or additionally, polymer coatings may be added post- milling on top of LixSiy alloy particles with any surface coatings that were applied during comminution processing.
[0026] The LixSiy alloy particle size distribution is reduced to the desired PSD range by comminution, preferably about 1,000 - 44,000 nm, or more preferably about 50 - 1,000 nm, and more preferably between about 400 - 600 nm. Highly reactive surfaces of the LixSiy alloy that are exposed on the fractured LixSiy alloy particles will form covalent bonds to the polymer and any desired surface modifiers present during the comminution process. The polymer and co-reagents form a continuous coating (protective shell) on the LixSiy alloy particles, covering all surfaces with an at least 2 nm to about 500 nm lay er. The polymer coating may be thermally processed or crosslinked with added reagents, all part of the protective shell. The milling solvent is then removed by an evaporation process. This could be done by any number of methods known in the art, such as spray drying or evaporation under reduced pressure in a suitable atmosphere. Optionally, the particle can be heated, for example, to about 150 - 1200 °C for about 30 minutes to about 24 hours under a suitable gas (including, but not limited to, air, Ar, or Ar/H2) or in a vacuum to cure the protective shell. Curing is considered to be partial to complete cross-linking of polymer precursors or carbonization of the hydrocarbon mass on the LixSiy alloy surfaces. Heating temperatures and durations will depend on what polymer coatings are used to form a protective shell. The resulting coated LixSiy alloy material can then added to a conventional LIBs negative electrode composite using conventional coating processes (including, but not limited to, the addition of carbon black, graphite, or other additives used with aqueous binder systems in conventional anode slurries, or non-aqueous binder systems, such as NMP/PVdF).
[0027] In one non-limiting example, 325-mesh Li15Si4 (about 48:52 wt%) was prepared thermochemically as the feedstock for wet milling processes in alkane or cycloalkane solvents, such as hexanes, heptanes, octanes, cyclohexanes, or any saturated alkane solvents with a boiling range well above the operation temperature of the milling slurry (typically between about 25 - 60 °C). Depending on the desired PSD range of the LixSiy alloy product, comminution conditions can be determined. Milling beads and materials are typically selected from hard ceramic materials. Beads range in diameter from about 100 - 1,000 microns, preferably about 300 - 900 microns. The agitator tip-speeds during comminution are typically running between about 2 - 15 m s for about 15 - 1200 minutes, depending on the size of the mill, batch size, bead selection, solids loading, solvent selection circulation rate, and secondary reagents employed.
[0028] In another non-limiting example, Li15Si4 alloy was stirred under Ar for about 48 hours in an about 5% polyacrylonitrile (PAN) solution in dimethylsulfoxide (DMSO). The weight equivalent ratio of LixSiy to PAN was about 7:3. The DMSO was stripped by vacuum distillation, and the remaining solids were dried for about 6 hours under dynamic vacuum at about 80 °C. The remaining solid was heated for about 2 hours under Ar atmosphere to cure the protective coating. In an alternate embodiment, dimethylformamide (DMF) is used as the solvent in place of DMSO.
[0029] In some embodiments, monomeric surface modifiers may be added in place of or in addition to polymers. The surface modifiers may be monomers with functional groups that react with the LixSiy alloy particle surfaces or with the polymer to form chemical bonds. Because LixSiy alloy is so reactive, almost any organic compound with heteroatoms and/or unsaturated bonds are potential surface modifiers. Reactive monomers could be selected from the group consisting of alkenes, alkynes, aromatics, heteroaromatics, cycloalkenes, alcohols, glycols, polyglycols, ethers, polyethers, thiols, disulfides, amines, amides, pyridines, pyrroles, imides, imidazoles, imidazoline, furans, thiophenes, cyanates, isocyanates, isothiocyanates, ketones, carboxylic acids, esters, amino acids, aldehydes, acrylates, methacrylates, oxylates, organic carbonates, lactones, and gases, such as H2, O2, CO2, N20, and HF. Various fluorinated analogs of these compounds can also be used, such as trifluoroacetone, bis(2,2,2-trifluoroethyl) carbonate, 2,2,2-trifluoroethyl acrylate, 2,2,2- trifluoroethyl methacrylate, and 1,3,5-trifluorobenzene. The comminution solvent is then removed by any suitable method, and the coated LixSiy alloy particle may or may not require heating under a suitable gas to cure the coating and form a protective shell. This protective shell may prevent water or other solvents used to combine elements of the electrode coating process from reacting with the LixSiy core material. This coated LixSiy alloy can be added to conventional LIBs negative electrode composite using conventional coating processes.
[0030] Table 1 below shows several mass equivalents of reagents used for comminution, compared with product yields of comminution process and heat processing steps. Table 1 (supplemented by the drawings) demonstrates composition of matter of products after comminution and after heat treatment, as well as the processes disclosed herein.
Figure imgf000010_0001
Figure imgf000011_0001
Table 1
[0031] In some embodiments, the LixSiy alloy is comminuted in an inert alkane solvent in the presence of a metal-oxide or a metal-alkoxide reagent. Some examples of metal oxides are AI2O3, Ti02, Li4Ti5012, MgO, NiO, and borates. Metal alkoxides constitute an important class of compounds often used in sol-gel processes. They are characterized by a metal- oxygen-carbon bonding system, including such metals as magnesium, aluminum, titanium, zinc, or lithium. Metal alkoxides in particular have proven to be especially beneficial during comminution as they modify particle surfaces to keep particles well suspended in the slurry with alkane solvents. If required, subsequent curing of the coated LixSiy particles will form a protective shell comprised of metal oxides that sufficiently impedes ingress of solvents to the LixSiy alloy particle core.
[0032] In some embodiments, inorganic carbon (non-hydrocarbon) surface modifiers can be added at some stage during or following comminution of LixSiy alloy and allowed to contact and form covalent bonds on highly reactive sites on newly fractured surfaces of the LixSiy alloy particles. For example, the surface modifiers can be present at the beginning of the comminution process, or added after most of the particle size reduction has taken place but while surfaces are still very reactive (while there are many non-passivated sites). The progress of the comminution can be monitored by particle size distribution measurements and/or by monitoring slurry temperatures, viscosity, or power input. Inorganic carbon surface modifiers may be comprised from the group: carbon nanotubes (SWCNT, MWCNT), nanospherical carbon, fullerenes, graphene, graphite, or carbon black. Optionally, other hydrocarbons (monomers or polymers) may be added to help provide complete coverage of the LixSiy particle surface and provide passivation of the LixSiy alloy core from reactive solvents.
[0033] In some embodiments, the coated LixSiy alloy particles are blended with natural flake graphite (NFG). Prolonged blending of these dry powders under inert atmosphere can imbed sub-micron LixSiy alloy particles into surface pores and crevices of NFG particles (ty pically about 10 - 20 micron). Subsequent coating of the NFG particles with a polymer or polymer precursors to provide a continuous coating on the NFG and over imbedded LixSiy particles is a means of passivating the LixSiy alloy while also spacing the LixSiy particles in a Li-active matrix that will tolerate the expansion and contraction of LixSiy alloys without breaking critical covalent bonds with its surrounding framework. Subsequent heat treatment may be required, particularly for poly mer precursors to form cross-linked covalent bonds that impart added strength to the electrode composite.
[0034] In some embodiments, the LixSiy alloy is comminuted in an inert alkane solvent in the presence of hy drogen, which serves as a forming gas. A forming gas is an industrial gas comprised of inert gas blended with typically about 5% ¾ or less. Forming gas can be used in the place of purified argon to blanket the slurry during comminution. Molecular hydrogen is reactive toward silicon surfaces. It can also and will migrate into silicon and other metals as atomic hydrogen and will form LiH on the surface of LixSiy alloy particles. H2 is also known to cap (passivate) Si surfaces by forming Si-H bonds with "dangling" Si-Si bonds created from fracturing Si particles. This condition may be preferred when it is desired to produce LixSiy alloy particles with no oxides.
[0035] In some embodiments, comminution of LixSiy alloy produces submicron or nanoparticle distributions (preferably about 44,000 - 1,000 nm, or more preferably about 50 - 1,000 nm, and more preferably between about 400 - 600 nm). Surface modifiers may be applied to the particles, which induces aggregation of the nanoparticles into micron-sized clusters. Grain structure in the micron-sized clusters is created from the coatings on the nanoparticles. These coatings can be heat-processed (cured) to form tight, porous covalently bonded masses of carbon and metal oxides in grains between the LixSiy alloy core nanocrystals. The same coating that resides in grains between the LixSiy alloy nanocrystals form a continuous protective shell around the micron-sized cluster that impedes ingress of solvents, but allows Li+ ion mobility and facilitates electrical charge transfer from the LixSiy alloy particle core to the electrode current collector. The surface modifiers used in this process of making aggregated LixSiy alloy clusters could be any of the organic reagents, metal oxides, or metal alkoxides disclosed herein.
[0036] In some embodiments, Li salts (for example from the group LiF, L12O2, L12CO3, LiBF2(C204), Li2(C204)) can be added during comminution of LixSiy alloy alone or with other surface modifiers, which can be heat processed and cured as described above to form a protective shell from a covalently bonded continuous layer of the additives that impedes ingress of solvents, but will allow Li+ ion mobility and will facilitate electrical charge transfer from the particle LixSiy alloy core to the electrode current collector.
[0037] In some embodiments, Li- or Na-organic complexes may be used with any source of Li-active Group IVA elements (e.g., solar grade Si or Ge wafer kerf or metallurgical silicon) to prepare Group IVA particles with partial insertion (prepared in-situ and added during the comminution process) of the alkali metals. For example, poly cyclic aromatic (PA) compounds, such as pyrene, perylene, and naphthalene, form ion-paired Li+PA" complexes that can deliver Li to the Group IVA particle during comminution.
[0038] The Li+PA" complexes described above can also function as an electrolyte in an appropriate solvent (such as gamma butyrolactone) whereupon a current is applied to a cell with Li foil as the counter electrode and with a Si/graphite electrode laminated on a Cu current collector as the working electrode. The Si particles in the Si/graphite electrode will undergo Li insertion. This electrode laminate is then partially charged with Li and can be used to make a battery with a partially charged negative electrode.
[0039] The modifier "about" used in connection with a quantity is inclusive of the stated value and has the meaning dictated by the context (for example, it includes at least the degree of error associated with the measurement of the particular quantity). The modifier "about" should also be considered as disclosing the range defined by the absolute values of the two endpoints. For example, the expression "from about 2 to about 4" also discloses the range "from 2 to 4". The term "about" may refer to plus or minus 10% of the indicated number. For example, "about 10%" may indicate a range of 9% to 11%, and "about 1%" may mean from 0.9-1.1. Other meanings of "about" may be apparent from the context, such as rounding off, so, for example "about 1" may also mean from 0.5 to 1.4.
[0040] For the recitation of numeric ranges herein, each intervening number there between with the same degree of precision is explicitly contemplated. For example, for the range of 6-9, the numbers 7 and 8 are contemplated in addition to 6 and 9, and for the range 6.0-7.0, the number 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, and 7.0 are explicitly contemplated. [0041] Thus, the invention provides, among other things, a method of producing a negative electrode. Various features and advantages of the invention are set forth in the following claims.

Claims

CLAIMS What is claimed is:
1. A method of producing a negative electrode, comprising: a) comminuting Li-Group IVA alloy particles in a solvent to a desired particle size distribution range; b) exposing surfaces of the Li-Group IVA alloy particles to at least one surface modifier present during the comminution process; c) the at least one surface modifier forming at least one continuous coating on at least one of the exposed surfaces of the Li-Group IVA alloy particles; d) removing the solvent; and e) adding the surface-modified Li-Group IVA alloy particles to a negative electrode material by a coating process.
2. The method of claim 1, wherein the comminuting is performed by a circulating bead mill.
3. The method as in any one of claims 1-2, wherein a forming gas comprising H2 is present during the comminution.
4. The method as in any one of claims 1-3, wherein the Li-Group IVA alloy particles in step a) comprise LixSiy, LiGe, LiSn, Li, or any other combination of Si, Ge, and Sn.
5. The method as in any one of claims 1-4, wherein the solvent is selected from the group consisting of cycloalkanes, hexanes, heptanes, octanes, cyclohexanes, and any other saturated alkane.
6. The method as in any one of claims 1-5, wherein the Li-Group IVA alloy particle size distribution is reduced to a range of about 1,000 to about 44,000 nm.
7. The method as in any one of claims 1-5, wherein the Li-Group IVA alloy particle size distribution is reduced to a range of about 50 to about 1,000 nm.
8. The method as in any one of claims 1-5, wherein the Li-Group IVA alloy particle size distribution is reduced to a range of about 400 to about 600 nm.
9. The method as in any one of claims 1-8, wherein the at least one surface modifier comprises a polymer or a monomer additive.
10. The method as in any one of claims 1-9, wherein the at least one surface modifier comprises a polymer additive selected from the group consisting of polystyrene,
polyacrylonitrile, polyacrylic acid, lithium polyacrylate, and polyaniline.
11. The method as in any one of claims 9-10, wherein the polymer additive covalently bonds directly to at least one of the surfaces of the Li-Group IVA particles.
12. The method as in any one of claims 9-111, wherein the continuous coatings comprising the polymer surface modifier are thermally processed or crosslinked with a reagent.
13. The method as in any one of claims 1-12, wherein the at least one surface modifier comprises a monomer additive selected from the group consisting of alkenes, alkynes, aromatics, heteroaromatics, cycloalkenes, alcohols, glycols, polyglycols, ethers, polyethers, thiols, disulfides, amines, amides, pyridines, pyrroles, imides, imidazoles, imidazoline, furans, thiophenes, cyanates, isocyanates, isothiocyanates, ketones, carboxylic acids, esters, amino acids, aldehydes, acrylates, methacrylates, oxylates, organic carbonates, lactones, and the gases H2, <¾, CO2, N20, and HF, and fluorinated analogs thereof when applicable.
14. The method as in any one of claims 1-13, wherein the at least one surface modifier comprises a metal-oxide or a metal-alkoxide.
15. The method as in any one of claims 1-14, wherein the at least one surface modifier comprises a metal-oxide selected from the group consisting of AI2O3, Ti02, Li4Ti50i2, MgO, NiO, and borates.
16. The method as in any one of claims 1-15, wherein the at least one surface modifier comprises a metal alkoxide selected from the group consisting of magnesium alkoxides, aluminum alkoxides, titanium alkoxides, zinc alkoxides, and lithium alkoxides.
17. The method as in any one of claims 1-16, wherein the at least one surface modifier comprises an inorganic carbon surface modifier.
18. The method as in any one of claims 1-17, wherein the at least one surface modifier comprises an inorganic carbon surface modifier selected from the group consisting of single- walled carbon nanotubes (SWCN), multi-walled carbon nanotubes (MWCN), nanospherical carbon, fullerenes, graphene, graphite, and carbon black.
19. The method as in any one of claims 1-18, wherein the at least one surface modifier comprises a Li salt.
20. The method as in any one of claims 1-19, wherein the at least one surface modifier comprises a Li salt selected from the group consisting of LiF, L12O2, L12CO3, LiBF2(C204), and Li2(C204).
21. The method as in any one of claims 1-20, wherein the continuous coatings form protective shells capable of impeding diffusion of oxygen and/or water to cores of the Li-Group IVA alloy particles, wherein the continuous coatings are capable of allowing Li+ ion mobility and/or facilitate electrical charge transfer from the Li-Group IVA alloy particles to an electrode current collector.
22. The method as in any one of claims 1-21, wherein the continuous coatings cover the surfaces of the Li-Group IVA particles with layers greater than or equal to about 2 nm and less than or equal to about 500 nm thick.
23. The method as in any one of claims 1-22, wherein the solvent removal is done by an evaporation process performed by spray drying and/or evaporation under reduced pressure in a suitable atmosphere.
24. The method as in any one of claims 1-23, wherein the Li-Group IVA alloy particles with continuous coatings are heated.
25. The method as in any one of claims 1-24, wherein the Li-Group IVA alloy particles with continuous coatings are heated at about 150 °C to about 1200 °C for about 30 minutes to about 24 hours under a suitable atmosphere.
26. The method as in any one of claims 1-25, wherein a suitable atmosphere for an evaporation process or for heating the Li-Group IVA alloy particles with continuous coatings comprises air, Ar, Ar/H2, and/or vacuum.
27. The method as in any one of claims 1-26, wherein the coating process is performed by addition of carbon black, graphite, or any other additive used with aqueous binder systems in conventional Li ion battery anode slurries.
28. The method as in any one of claims 1-27, wherein the coating process is performed by addition of any additive used with non-aqueous binder systems in conventional Li ion battery production.
29. The method as in any one of claims 1-28, wherein a Li-organic complex or a a-organic complex delivers Li to a Group IVA particle during comminution to form at least one of the Li- Group IVA alloy particles.
30. The method as in any one of claims 1-29, wherein the Li-organic or the Na-organic complex is a poly cyclic aromatic compound.
31. The method as in any one of claims 1-30, wherein the poly cyclic aromatic compound is selected from the group consisting of pyrene, perylene, and naphthalene.
32. The method as in any one of claims 1-31, wherein, when a current is applied with Li foil as a counter electrode and with a Si/graphite electrode laminated on a Cu current collector as a working electrode, the poly cyclic aromatic compound functions as an electrolyte and the laminate becomes partially charged with Li.
33. The method as in any one of claims 1-32, wherein at least one of the Li-Group IVA alloy particles is formed during comminution in step a) from Li-active solar grade Si wafer kerf, Li- active solar grade Ge wafer kerf, and/or Li-active metallurgical silicon.
34. The method as in any one of claims 1-33, further comprising: f) incorporating the negative electrode material into a slurry production process for producing a negative electrode for a battery.
35. The method of as in any one of claims 12-34, wherein the reagent is a monomer additive selected from the group consisting of alkenes, alkynes, aromatics, heteroaromatics,
cycloalkenes, alcohols, glycols, polyglycols, ethers, polyethers, thiols, disulfides, amines, amides, pyridines, pyrroles, imides, imidazoles, imidazoline, furans, thiophenes, cyanates, isocyanates, isothiocyanates, ketones, carboxylic acids, esters, amino acids, aldehydes, acrylates, methacrylates, oxylates, organic carbonates, lactones, and the gases H2, O2, CO2, N20, HF, and fluorinated analogs thereof when applicable.
36. The method as in any one of claims 2-35, wherein the milling bead is a hard ceramic material.
37. The method as in any one of claims 2-36, wherein the milling bead has a diameter from about 100 to about 1,000 microns.
38. The method as in any one of claims 2-37, wherein the milling bead has a diameter from about 300 to about 900 microns.
39. The method as in any one of claims 1-38, wherein an agitator tip-speed during comminution is between about 2 to about 15 m/s for about 15 to about 1200 minutes.
40. A negative electrode produced by the method in any one of claims 1-39.
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