WO2024196936A2 - Électrolyte à haute concentration localisé et batterie au lithium-ion le comprenant - Google Patents

Électrolyte à haute concentration localisé et batterie au lithium-ion le comprenant Download PDF

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Publication number
WO2024196936A2
WO2024196936A2 PCT/US2024/020542 US2024020542W WO2024196936A2 WO 2024196936 A2 WO2024196936 A2 WO 2024196936A2 US 2024020542 W US2024020542 W US 2024020542W WO 2024196936 A2 WO2024196936 A2 WO 2024196936A2
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lithium
electrolyte
composition comprises
designs
solvent composition
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WO2024196936A3 (fr
Inventor
Naoki Nitta
Gleb Nikolayevich YUSHIN
Ismael RODRÍGUEZ PÉREZ
William Elliott Gent
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Sila Nanotechnologies Inc
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Sila Nanotechnologies Inc
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/107—Primary casings; Jackets or wrappings characterised by their shape or physical structure having curved cross-section, e.g. round or elliptic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0034—Fluorinated solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • 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

  • a broad range of electrolyte compositions may be utilized in the construction of Li and Li-ion batteries and other metal and metal-ion batteries.
  • improved cell performance e.g., low and stable resistance, high cycling stability, high-rate capability, good thermal stability, long calendar life, etc.
  • an optimal choice of electrolyte needs to be developed for specific types and specific sizes of active particles in both the anode and cathode, specific total battery cell capacities as well as specific operational conditions (e.g., temperature, charge rate, discharge rate, voltage range, capacity utilization, etc.).
  • specific operational conditions e.g., temperature, charge rate, discharge rate, voltage range, capacity utilization, etc.
  • charge storing anodes may comprise silicon (Si)-comprising anode particles with gravimetric capacities in the range from about 800 mAh/g to about 3000 mAh/g (per mass of Si-comprising anode particles in a Li-free state).
  • Si silicon
  • a subset of such anodes includes anodes with the electrode layer exhibiting capacity in the range from about 400 mAh/g to about 2800 mAh/g (per mass of the electrode layer, not counting the mass of the current collector, in a Li-free state).
  • Such a class of charge-storing anodes offers great potential for increasing gravimetric and volumetric energy of rechargeable batteries.
  • Li and Li-ion battery cells with such anodes and conventional electrolytes often require the use of such large amounts of conventional solid-electrolyte interphase (SEI)-building additives to maintain acceptable cycle stability that prevents their use at elevated or low temperatures or undesirably limits their calendar life or does not allow such cells to be charged to high voltages (e.g., above about 4.1-4.3 V). Performance of such battery cells may become particularly poor when the cells are charged to above about 4.3-4.4 V and even more so when the cells are charged to above about 4.5 V. Higher cell voltage, broader operational temperature window, and longer cycle life, however, are advantageous for most applications.
  • SEI solid-electrolyte interphase
  • Such cells may suffer from excessive capacity degradation (e.g., above about 5 %), large volume expansion (e.g., above about 10 %) and significant gassing (e.g., above about 10% thickness change) when exposed to high temperatures (e.g., above about 50-90 °C) in a fully charged state (e.g., state-of-charge (SOC) of about 90 – 100 %) for a prolonged time (e.g., about 12-168 hours). Passing such elevated temperature charging tests is required for most applications. Performance of such cells may also become Attorney Docket No.
  • charge storing anode materials may be produced as high-capacity (nano)composite powders (e.g., at least partially comprised of active material nanomaterials or nanostructures), which exhibit moderately high volume changes (e.g., about 8-180 vol. %) during the first charge-discharge cycle and moderate volume changes (e.g., about 5-50 vol.
  • charge-storing anode particles may include anode particles with an average size (e.g., diameter or thickness) in the range of about 0.2 to about 40 microns (micrometers).
  • average size e.g., diameter or thickness
  • Such a class of charge-storing particles offers great promises for scalable manufacturing and achieving high cell-level energy density and other performance characteristics.
  • Such particles are relatively new and their use in cells using conventional electrolytes may result in relatively poor cell performance characteristics and limited cycle stability. Performance of such battery cells may become particularly poor when the cells are charged to above about 4.1-4.3 V, more so when the cells are charged to above about 4.3-4.4 V and even more so when the cells are charged to above about 4.5 V.
  • High cell voltage, broader operational temperature window and longer cycle life, however, are advantageous for most applications.
  • Such cells may suffer from excessive capacity degradation (e.g., above about 5 %), large volume expansion (e.g., above about 10 %) and significant gassing when exposed to high temperatures (“high-temperature outgassing”) (e.g., about 50-90 °C or higher) in a fully charged state (e.g., state-of-charge, SOC, of about 90-100 %) for a prolonged time (e.g., about 12-168 hours). Passing such elevated temperature charging tests is required for most applications.
  • high-temperature outgassing e.g., about 50-90 °C or higher
  • SOC state-of-charge
  • Cell performance may also become particularly poor when the high- capacity (nano)composite anode capacity loading (areal capacity) becomes moderate (e.g., about 2-4 mAh/cm 2 ) and even more so when the areal capacity becomes high (e.g., about 4-12 mAh/cm 2 ). Higher capacity loading, however, is advantageous for increasing cell energy density and reducing cell manufacturing costs. Similarly, cell performance may degrade when the porosity of such an anode (e.g., the volume occupied by the Attorney Docket No.
  • SN-0076WO spacing between the (nano)composite active anode particles in the electrode and filled with electrolyte, exclusive of closed pores, if any, within the particles themselves that are inaccessible to electrolyte) becomes moderately small (e.g., about 25-35 vol. % after the first charge-discharge cycle) and more so when the porosity of the anode becomes small (e.g., about 5-25 vol. % after the first charge-discharge cycle) or when the amount of a binder and conductive additives in the electrode becomes moderately small (e.g., about 5-15 wt.
  • moderate volume changes e.g., about 5-50 vol.% during the subsequent charge-discharge cycles include (nano)composites comprising so-called conversion-type (which includes both so-called chemical transformation and so-called “true conversion” subclasses) and so-called alloying-type active electrode materials.
  • metal-ion batteries such as Li-ion batteries
  • conversion-type active electrode materials include, but are not limited to, metal fluorides (such as lithium fluoride, iron fluoride, copper fluoride, bismuth fluoride, their mixtures and alloys, etc.), metal chlorides, metal iodides, metal bromides, metal chalcogenides (such as sulfides, including lithium sulfide and other metal sulfides), sulfur, selenium, metal oxides (including but not limited to lithium oxide and silicon oxide), metal nitrides, metal phosphides (including lithium phosphide), metal hydrides, and others.
  • metal fluorides such as lithium fluoride, iron fluoride, copper fluoride, bismuth fluoride, their mixtures and alloys, etc.
  • metal chlorides such as lithium fluoride, iron fluoride, copper fluoride, bismuth fluoride, their mixtures and alloys, etc.
  • metal chlorides such as lithium fluoride,
  • alloying-type electrode materials include, but are not limited to, silicon, germanium, antimony, aluminum, magnesium, zinc, gallium, arsenic, phosphorous, silver, cadmium, indium, tin, lead, bismuth, their alloys, and others. These materials typically offer higher gravimetric and volumetric capacity than so-called intercalation- type electrodes commonly used in commercial metal-ion (e.g., Li-ion) batteries. Alloying-type electrode materials are particularly advantageous for use in certain high- Attorney Docket No. SN-0076WO capacity anodes for Li-ion batteries. Silicon-based alloying-type anodes may be particularly attractive for such applications.
  • high concentrations e.g., about 1.3 M or greater
  • high concentrations may be used to improve the passivation of the anode or cathode by surface passivation layers (SEI or CEI respectively), thereby extending cell lifetime.
  • High concentrations of salt(s) may also be used to reduce the added resistance from the SEI and CEI, thereby reducing the cell resistance, particularly at lower temperatures ( ⁇ 15°C).
  • High concentrations of salt(s) may also be used to reduce the unwanted gas generation at high temperatures (> 40°C), high cell voltages (> 4.0V), and at the end of life.
  • High concentrations of salt(s) may also be used to passivate metal current collector foils against corrosion.
  • high salt concentrations also have many drawbacks. High salt concentration may increase the viscosity of the electrolyte, increasing wetting time during battery cell manufacturing (thereby increasing manufacturing cost) and decreasing conductivity and diffusivity of the electrolyte (thereby decreasing battery rate capability and increasing cell resistance).
  • Some salts are more expensive than other battery materials and compounds, so high salt concentrations may drive up the cost of the battery cell.
  • Some salts are more dense than other battery materials and compounds, so high salt concentrations may increase the density of the electrolyte, thereby decreasing the mass-based gravimetric energy density of the battery.
  • L-HCEs Localized high concentration electrolytes
  • an L-HCE may be referred to as an “electrolyte” for brevity.
  • a diluent is a solvent which does not coordinate the Li + ion of the salt(s).
  • diluents are solvents in which the salt(s) have low- to-negligible solubility. For example, solubility of less than about 0.3 M may be referred to as low-to-negligible solubility.
  • the diluent reduces the viscosity of the electrolyte, while maintaining strong interactions between the salt(s) and the other non-diluent co- solvent(s), in which the salt(s) have high solubility.
  • solubility of greater than about 2 M may be referred to as high solubility.
  • the effect of strong interactions between the salt(s) and/or the other non-diluent co-solvent(s) may be similar to what is observed at high salt concentrations.
  • the diluent may also passivate the anode, Attorney Docket No. SN-0076WO cathode, and/or metal (e.g., current collector metal foil) surfaces against unwanted side reactions.
  • Diluents may also lower the density of the electrolyte.
  • the conductivity of the conventional (or explored in relevant cells or form factors) L-HCEs is typically too low for most practical applications, thereby their applications would lower cell rate capability, require reduced electrode mass loading (and hence reduce volumetric energy density and gravimetric energy density), decrease roundtrip energy efficiency, and increase cell internal resistance and heat generation.
  • careful design and improvement of the electrolyte, battery electrodes, manufacturing processes, and cell usage specifications is necessary.
  • an electrolyte includes a lithium salt composition; a solvent composition; and a diluent composition, wherein: the at least one aromatic compound is Attorney Docket No. SN-0076WO selected from: benzene, fluorobenzene (FB), difluorobenzenes (C 6 H 4 F 2 ), trifluorobenzenes (C 6 H 3 F 3 ), tetrafluorobenzenes (C 6 H 2 F 4 ), pentafluorobenzenes (C 6 H 1 F 5 ), trifluorotoluenes (TFT), bis(trifluoromethyl)benzenes (C 8 H 4 F 6 ), and bis(difluoromethyl)benzenes (C 8 H 6 F 4 ).
  • the at least one aromatic compound is Attorney Docket No. SN-0076WO selected from: benzene, fluorobenzene (FB), difluorobenzenes (C 6 H 4 F 2 ), triflu
  • One aspect is directed to a lithium-ion battery, including an anode current collector, a cathode current collector, an anode disposed on and/or in the anode current collector, a cathode disposed on and/or in the cathode current collector, and an electrolyte ionically coupling the anode and the cathode.
  • the electrolyte includes (1) a lithium salt composition, (2) a solvent composition, and (3) a diluent composition.
  • the anode includes composite particles including carbon and silicon, wherein the composite particles include pores and at least some of the silicon is nanosized silicon in the pores.
  • a lithium-ion battery includes an anode current collector; a cathode current collector; an anode disposed on and/or in the anode current collector; a cathode disposed on and/or in the cathode current collector; and an electrolyte ionically coupling the anode and the cathode, the electrolyte comprising (1) a lithium salt composition and (2) a solvent composition, and (3) a diluent composition, wherein: the anode comprises composite particles comprising carbon and silicon, at least some of the silicon being nanosized silicon in the composite particles; the diluent composition comprises at least one aromatic compound and/or at least one alkane compound; and the at least one alkane compound is selected from (1) non-fluorinated alkane compounds characterized by a first molecular formula C p H 2p+2
  • the at least one aromatic compound is selected from: benzene, fluorobenzene (FB), difluorobenzenes (C 6 H 4 F 2 ), trifluorobenzenes (C 6 H 3 F 3 ), Attorney Docket No. SN-0076WO tetrafluorobenzenes (C 6 H 2 F 4 ), pentafluorobenzenes (C 6 H 1 F 5 ), trifluorotoluenes (TFT), bis(trifluoromethyl)benzenes (C 8 H 4 F 6 ), and bis(difluoromethyl)benzenes (C 8 H 6 F 4 ).
  • the at least one alkane compound comprises two or more of the non-fluorinated alkane compounds and/or the fluorinated alkane compounds.
  • the at least one alkane compound is selected from heptanes (C 7 H 16 ), octanes (C 8 H 18 ), nonanes (C 9 H 20 ), fluoroheptanes (C 7 H 15 F), difluorooctanes (C 8 H 16 F 2 ), and fluorononanes (C 9 H 19 F).
  • a mole fraction of the lithium salt composition in the electrolyte is in a range of 10 mol. % to 20 mol. %.
  • the lithium salt composition comprises a salt compound selected from lithium bis(fluorosulfonyl)imide (LiFSI), LiPF 6 , lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium trifluoromethanesulfonate (LiOTf, LiOSO 2 CF 3 ), LiSO 3 F (LSF), LiClO 4 , LiAsF 6 , LiBF 4 , lithium difluoro(oxalato)borate (LiDFOB), lithium difluoro(bisoxalato)phosphate (LiDFBOP), lithium tetrafluoro(oxalato)phosphate (LiTFOP), lithium trifluoromethanesulfonate (LiOTf), LiSO 3 F (LSF), Li 3 PS 4 , Li 6 PS 5 Cl, lithium tris(fluorosulfonyl)methide (LTFSM), lithium bis(oxalate)
  • LiFSI lithium bis
  • the lithium salt composition comprises two or more salt compounds.
  • the electrolyte comprises at least one non-Li salt compound.
  • the solvent composition comprises vinylene carbonate (VC), a mole fraction of the VC in the electrolyte being in a range of about 0.05 to about 2.00 mol. %. Attorney Docket No. SN-0076WO [0029]
  • the solvent composition comprises fluoroethylene carbonate (FEC), a mole fraction of the FEC in the electrolyte being in a range of about 0.1 to about 20 mol. %.
  • the solvent composition comprises a linear ester, a cyclic ester, and/or a branched ester.
  • the solvent composition comprises a ketone selected from: methyl ethyl ketone (MEK), diethyl ketone (DEK), methyl isopropyl ketone (MiPK), ethyl isopropyl ketone (EiPK), diisopropyl ketone, pinacolone (MtBK), diisobutyl ketone (DiBK), methyl sec-butyl ketone (MsBK), and hexamethylacetone (HMA).
  • MEK methyl ethyl ketone
  • DEK diethyl ketone
  • MiPK methyl isopropyl ketone
  • EiPK ethyl isopropyl ketone
  • HMA hexamethylacetone
  • the solvent composition comprises an ether selected from: diethyl ether, 2-methoxy-2-methylpropane, dipropyl ether, diisopropyl ether, butyl ethyl ether, ethyl tert-butyl ether, 1-propoxybutane, ethyl pentyl ether, butyl isopropyl ether, sec-butyl isopropyl ether, ethylene glycol dimethyl ether (DME), and diethoxyethane.
  • ether selected from: diethyl ether, 2-methoxy-2-methylpropane, dipropyl ether, diisopropyl ether, butyl ethyl ether, ethyl tert-butyl ether, 1-propoxybutane, ethyl pentyl ether, butyl isopropyl ether, sec-butyl isopropyl ether, ethylene glycol dimethyl ether (DME
  • the solvent composition comprises a nitrile selected from acetonitrile (ACN), trimethylacetonitrile (TMAN), 2-oxo-1,3-dioxolane-4-carbonitrile (ECCN), cyclopropylacetonitrile (CPAN), ethylene glycol bis(propionitrile)ether (EGBE), fumaronitrile (FM), succinonitrile, glutaronitrile, adiponitrile (ADN), and 1,3,6- hexanetricarbonitrile (HTCN).
  • ACN acetonitrile
  • TMAN trimethylacetonitrile
  • ECCN 2-oxo-1,3-dioxolane-4-carbonitrile
  • CPAN cyclopropylacetonitrile
  • EGBE ethylene glycol bis(propionitrile)ether
  • FM fumaronitrile
  • ADN 1,3,6- hexanetricarbonitrile
  • the solvent composition comprises an amide selected from dimethylacetamide (DMAc), hexamethylphosphoramide (HMPA), N,N-dimethyl trifluoromethanesulfonamide (DMTMSA), N,N-diethyl trifluoromethanesulfonamide, N,N-dimethyl fluorosulfonamide, and carbamides.
  • DMAc dimethylacetamide
  • HMPA hexamethylphosphoramide
  • DMTMSA N,N-dimethyl trifluoromethanesulfonamide
  • N,N-diethyl trifluoromethanesulfonamide N,N-dimethyl fluorosulfonamide
  • carbamides selected from dimethylacetamide (DMAc), hexamethylphosphoramide (HMPA), N,N-dimethyl trifluoromethanesulfonamide (DMTMSA), N,N-diethyl trifluoromethanesulfonamide, N,N-di
  • the solvent composition comprises a nitroalkane selected from nitromethane (NM), nitroethane (NE), trinitromethane, tetranitromethane, 2- nitropropane (2NP), 1-nitropropane (1-NP), dinitromethane, hexanitroethane (HNE), and heptanitrocubane (HNC).
  • the solvent composition comprises a phosphate selected from trimethyl phosphate (TMP), triethyl phosphate (TEP), tripropyl phosphate (TPrP), triisopropyl phosphate (TIP), triphenyl phosphate (TPP), triallyl phosphate (TAP), tris(2,2,3,3,3-pentafluoropropyl) phosphate (5F-TPrP), tris(1,1,1,3,3,3- hexafluoropropan-2-yl) phosphate (HFiP), and diisopropyl fluorophosphate.
  • the solvent composition comprises a phosphite selected from tris(trimethylsilyl)phosphite (TMSPi), tris(2,2,2-trifluoroethyl) phosphite (TTFPi), triphenyl phosphite (TPPi), tris(1,1,1,3,3,3-hexafluoropropan-2-yl) phosphite (THFPP), and tris(trimethylsilyl) phosphite.
  • the solvent composition comprises a sulfite selected from dimethyl sulfite (DMS), trimethylene sulfite, and ethylene sulfite (ESi).
  • the solvent composition comprises a sulfone selected from ethyl methyl sulfone, ethyl isopropyl sulfone, dimethyl sulfone, ethylmethyl sulfone, ethyl 3-(methylsulfonyl)propanoate, 2-(ethylsulfonyl)aniline, 6-(ethylsulfonyl)-1,3- benzoxazole-2-thiol, ethyl isopropyl sulfone, 4-ethylsulfonylbenzaldehyde, 2- (ethylsulfonyl)ethanamine, 1-(ethanesulfonyl)-4-nitrobenzene, 5-(1-azepanyl)-2- (ethylsulfonyl)aniline, N-(2-(methylsulfonyl)phenyl)acetamide, 3-amin
  • the solvent composition comprises a sulfonamide selected from 2-methyl-5-(methylsulfonyl)benzenesulfonamide, N,N-dimethyl trifluoromethanesulfonamide (DMTMSA), and N,N-dimethyl fluorosulfonamide.
  • the solvent composition comprises a boron (B)-comprising compound selected from pyridine-boron trifluoride (PBF), 3-fluoro pyridine-boron trifluoride (3F-PBF), pyrazine-boron trifluoride, and borate esters.
  • the solvent composition comprises a silicon (Si)-comprising compound selected from siloxanes and silanes.
  • the diluent composition comprises fluorinated ether selected from 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), bis(2,2,2- trifluoroethyl) ether (BTFE), 1,1,2,2-tetrafluoroethyl-2,2,2,3-tetrafluoropropyl ether, tris(2,2-difluoroethyl) orthoformate (TDFEO), bis(2,2-difluoroethyl)ether, tris(2,2,2- trifluoroethyl) orthoformate (TFEO), 2-(2,2-difluoroethoxy)-1,1-difluoroethane, 1-(2,2- Attorney Docket No.
  • the diluent composition comprises one or more amines selected from trimethylamine, triethylamine, tripropylamine, di-isopropylamine, perfluorotriethylamine ((CF 3 CF 2 ) 3 N), perfluoromethyldiethylamine ((CF 3 CF 2 ) 2 CF 3 N), perfluoroethyldimethylamine (CF 3 CF 2 ) 1 (CF 3 ) 2 N), trifluoroethylamine (TFEAm), trifluoropropylamine (TFPAm, C3H6F3N), pentafluoropropylamine (PFPAm, C 3 H 4 F 5 N), trifluoromethylamine (CF 3 NH 2 ), heptafluorobutylamine (HFBAm, C 4 H 4 F 7 N), nonafluoropentylamine (NFPAm, C 5 H 4 F 9 N), 2,2,2-trifluoro-n-(2,
  • the solvent composition comprises one or more amines selected from methylamine, fluoromethylamine, trifluoromethylamine, difluoroethylamine, and diethylamine.
  • the solvent composition comprises one or more sulfonyl fluorides selected from 5-oxooxolane-3-sulfonyl fluoride, methyl 2,2-difluoro-2- (fluorosulfonyl)acetate (MDFA), pyrrolidine-1-sulfonyl fluoride (C 4 H 8 FNO 2 S), N-ethyl- N-methylsulfamoyl fluoride (C 3 H 8 FNO 2 S), (1E)-2-cyanoeth-1-ene-1-sulfonyl fluoride (NC 3 H 2 SO 2 F), trifluoromethylpropane sulfonyl fluoride (C 3 H 6 F 4 SO 2 ), fluoroethane sulf
  • the solvent composition comprises one or more linear carbonates selected from dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC).
  • DMC dimethyl carbonate
  • EMC ethyl methyl carbonate
  • DEC diethyl carbonate
  • a mass of the silicon is in a range of about 10 wt. % to about 90 wt. % of the anode (not counting the anode current collector).
  • the anode additionally comprises graphite particles.
  • the anode additionally comprises carbon nanotubes or carbon black particles.
  • the anode current collector comprises copper.
  • the cathode current collector comprises aluminum.
  • the lithium-ion battery is operated at a temperature in a range of about 40 to about 90 °C, and the lithium-ion battery is configured for propulsion of an automobile.
  • the first integer is between 7 and 20, and the second integer is between 6 and 20.
  • FIG. 1 illustrates an example Li-ion battery in which the electrolytes, components, materials, methods, and other techniques described herein may be implemented.
  • FIG.2 illustrates a few examples of compounds suitable for use in described Li-ion battery electrolytes, including lithium bis(fluorosulfonyl)imide (202), dimethyl carbonate (204), ethyl propionate (206), 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluropropyl ether (208), n-heptane (210), trifluorotoluene (212), and cyclohexane (214).
  • lithium bis(fluorosulfonyl)imide 202
  • dimethyl carbonate 204
  • ethyl propionate ethyl propionate
  • 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluropropyl ether 208
  • n-heptane 210
  • trifluorotoluene 212
  • cyclohexane cyclohexane
  • FIG.3 shows Table 1 with illustrative examples of combinations of primary salts and solvents in which the respective primary salts are soluble in the respective solvents at a molar ratio (primary salt: solvent) of 1:2.
  • FIG.4 shows a Table 2 showing compositions of example electrolytes ELYs #1, #2, and #3.
  • ELY #1 is an example electrolyte that does not contain any diluents.
  • ELYs #2 and #3 are illustrative examples of L-HCE compositions comprising fluorobenzene (FB) and heptane, respectively.
  • FIG.3 shows Table 1 with illustrative examples of combinations of primary salts and solvents in which the respective primary salts are soluble in the respective solvents at a molar ratio (primary salt: solvent) of 1:2.
  • FIG.4 shows a Table 2 showing compositions of example electrolytes ELYs #1, #2, and #3.
  • ELY #1 is an example electrolyte that does not contain any diluent
  • FIG. 5 illustrates the results of high-temperature storage (HT storage) tests performed on ELYs #1-3, including graphical plots of the following battery cell performance characteristics: volume change (502), first-cycle efficiency (FCE) (504), change in internal resistance ( ⁇ R) (506), residual capacity (508), and recoverable capacity (510).
  • FIG.6 shows a Table 3 showing compositions of example electrolytes ELYs #4, #5, #6, #7, #8, #9, and #10, which are illustrative examples of L-HCE compositions and electrolytes comprising respective co-solvents and diluents.
  • FIG. 3 shows compositions of example electrolytes ELYs #4, #5, #6, #7, #8, #9, and #10, which are illustrative examples of L-HCE compositions and electrolytes comprising respective co-solvents and diluents.
  • FIG. 7 illustrates the results of high-temperature storage (HT storage) tests performed on ELYs #4-10, including graphical plots of the following battery cell performance characteristics: volume change (702), first-cycle efficiency (FCE) (704), change in internal resistance ( ⁇ R) (706), residual capacity (708), and recoverable capacity (710).
  • FIG. 8 shows a Table 4 showing the respective additional co-solvents or diluents used in ELYs #11-36.
  • FIG.9 shows the results of cycle life testing on lithium ion battery test cells comprising example electrolytes ELYs #11-31 and #36 including the following battery cell performance characteristics: estimated cycle life (902), discharge voltage (expressed in V) (904), and first-cycle efficiency (FCE) (906).
  • FIG.10 shows a Table 5, showing the conductivities of ELYs #11, #12, #16- 22, #24, and #32-35 at 0 °C and at 25 °C.
  • FIG.11 shows the first-cycle efficiency (FCE) data of lithium ion battery test cells comprising ELY # 37-43, respectively.
  • FCE first-cycle efficiency
  • FIG.12 shows a Table 6 showing the respective boiling points of certain co- solvents or diluents.
  • DETAILED DESCRIPTION [0069] Aspects of the present invention are disclosed in the following description and related drawings directed to specific embodiments of the invention.
  • any numerical range described herein with respect to any embodiment of the present invention is intended not only to define the upper and lower bounds of the associated numerical range, but also as an implicit disclosure of each discrete value within that range in units or increments that are consistent with the level of precision by which the upper and lower bounds are characterized.
  • a numerical distance range from 7 nm to 20 nm encompasses (in nm) a set of [7, 8, 9, 10, ..., 19, 20], as if the intervening numbers 8 through 19 in units or increments of ones were expressly disclosed.
  • a temperature range from about – 120 °C to about – 60 °C encompasses (in °C) a set of temperature ranges from about – 120 °C to about – 119 °C, from about – 119 °C to about – 118 °C, ....
  • a numerical percentage range from 30.92% to 47.44% (i.e., a level of precision in units or increments of hundredths) encompasses (in %) a set of [30.92, 30.93, 30.94, ..., 47.43, 47.44], as if the intervening numbers between 30.92 and 47.44 in units or increments of hundredths were expressly disclosed.
  • any of the intervening numbers encompassed by any disclosed numerical range are intended to be interpreted as if those intervening numbers had been disclosed expressly, and any such intervening number may thereby constitute its own upper and/or lower bound of a sub-range that falls inside of the broader range.
  • Each sub-range e.g., each range that includes at least one Attorney Docket No. SN-0076WO intervening number from the broader range as an upper and/or lower bound
  • a numerical range with upper and lower bounds defined at different levels of precision shall be interpreted in increments corresponding to the bound with the higher level of precision.
  • a numerical percentage range from 30.92% to 47.4% (i.e., levels of precision in units or increments of hundredths and tenths, respectively) encompasses (in %) a set of [30.92, 30.93, 30.94, ..., 47.39, 47.40], as if 47.4% (tenths) was recited as 47.40% (hundredths) and as if the intervening numbers between 30.92 and 47.40 in units or increments of hundredths were expressly disclosed.
  • the level of precision of any particular measurement, threshold or other inexact parameter may vary based on various factors such as measurement instrumentation, environmental conditions, and so on.
  • measurements or thresholds may thereby be interpreted as a respective value assuming a pseudo-exact level of precision (e.g., a threshold of 80% comprises 80.0000...%).
  • reference to such measurements or thresholds may be described via a qualifier that captures pseudo-exact value(s) plus a range that extends above and/or below the pseudo-exact value(s).
  • the above-noted threshold of 80% may be interpreted which encompasses “exactly” 80% (e.g., 80.0000...%) plus some range around 80%.
  • the range encompassed around a measurement or threshold via the “about”, “approximately”, “around” or “ ⁇ ” qualifier may encompass the level of precision for which the respective measurement or threshold is capable of being measured by the most accurate commercially available instrumentation as of the priority date of the subject application.
  • various material properties are described so as to characterize materials (e.g., molecules, particles, powders, slurries, electrodes, separators, electrolytes, battery cells, etc.) in various states. Note that one of ordinary skill in the art is generally capable of selecting (and is herein assumed to select) the most appropriate measurement technique for any particular measurement. Moreover, in some cases, the most appropriate measurement technique may include a combination of techniques. Attorney Docket No.
  • the state of the battery electrode compositions may be in different forms at different stages of manufacture.
  • the battery electrode composition refers to a plurality of active material particles, such as composite active material particles (e.g., Si-C nanocomposite particles), graphite particles, and so on.
  • the active material particles of the battery electrode composition Before being mixed into a slurry, the active material particles of the battery electrode composition may be in the form of a dry powder. After being mixed into the slurry, the active material particles of the battery electrode composition may be suspended in a slurry suspension (e.g., along with other electrode components such as a binder, conductive additives, etc.).
  • the slurry is casted onto a current collector to form an electrode
  • the slurry is dried (solvent evaporation) and the active material particles of the battery electrode composition are bound together via a binder.
  • the active material particles After being sealed in a battery cell with other components such as electrolyte, the active material particles may store/release Li-ions during battery operation.
  • certain parameters are defined in terms of relative terminology such as low, reduced, high, increased, elevated, and so on.
  • temperature unless otherwise stated, this relative terminology may be characterized relative to battery cell storage temperature or battery cell operating temperature, depending on the context of the relevant example.
  • SOC unless otherwise stated, a high SOC may be Attorney Docket No. SN-0076WO defined as higher than about 70% SOC (e.g., in some designs, about 70-80% SOC; in some designs, about 80-90% SOC; in some designs, about 90-100% SOC).
  • preferred battery cell designs may comprise one or more of the following cathodes: lithium cobalt aluminum oxides (LCAO), lithium iron phosphate (LFP), lithium cobalt phosphate (LCP), lithium manganese phosphate (LMP), lithium manganese iron phosphate (LMFP), lithium nickel phosphate (LiNiPO 4 ), lithium vanadium fluoro phosphate (LiVFPO 4 ), lithium iron fluoro sulfate (LiFeSO 4 F), various Li excess materials (e.g., lithium-excess (rocksalt) transition metal oxides and oxy-fluorides such as those comprising Mn, Mo, Cr, Ti, and/or Nb, such as, for example, Li 1.211 Mo 0.467 Cr 0.3 O 2 , Li 1.3 Mn 0.4 Nb 0.3 O 2 , Li 1.2 Mn 0.4 Ti 0.4 O 2 , Li 1.2 Ni 0.333 Ti 0.333 Mo 0.133 O 2 and many others), various high capacity Li-ion based materials
  • cathode active materials e.g., intercalation-type cathode materials, such as LCO, NCM, NCMA, NCA, LMO, LMNO, LFP, LMP, LMFP, etc. or conversion-type active materials comprising S, Li 2 S, metal sulfides, metal fluorides, etc.
  • intercalation-type cathode materials such as LCO, NCM, NCMA, NCA, LMO, LMNO, LFP, LMP, LMFP, etc.
  • conversion-type active materials comprising S, Li 2 S, metal sulfides, metal fluorides, etc.
  • Illustrative examples of a preferred coating material for a preferred active cathode material may include, but are not limited to metal oxides that comprise one or more of the following metals: Ti, Al, Mg, Sr, Li, Si, Sn, Sb, Nb, W, Cr, Mo, Hf, Ta, B, Y, La, Ce, Zn, and Zr.
  • Illustrative examples of a preferred coating material for such cathodes include, but are not limited to, various oxy- fluorides and oxides, such as titanium oxide (e.g., TiO 2 ), aluminum oxide (e.g., Al 2 O 3 ), tungsten oxide (e.g., WO), molybdenum oxide (e.g., MoO or MoO 2 ), chromium oxide (e.g., Cr 2 O 3 ), niobium oxide (e.g., NbO or NbO 2 ) and zirconium oxide (e.g., ZrO 2 ), magnesium oxide (e.g., MgO), silicon oxide (e.g., SiO 2 ), boron oxide (e.g., B 2 O 3 ), lanthanum oxide (La 2 O 3 ), zirconium oxide (e.g., ZrO 2 ) and other suitable metal or mixed metal oxides and their various mixtures and alloys.
  • titanium oxide e.g., Ti
  • such ceramic materials may additionally comprise lithium (Li) - e.g., as lithium titanium oxide (or oxyfluoride), lithium aluminum oxide (or oxyfluoride), lithium tungsten oxide (or oxyfluoride), lithium chromium oxide (or oxyfluoride), lithium niobium oxide (or oxyfluoride), lithium zirconium oxide (or oxyfluoride) and their various alloys, mixtures and combinations.
  • Li lithium titanium oxide (or oxyfluoride), lithium aluminum oxide (or oxyfluoride), lithium tungsten oxide (or oxyfluoride), lithium chromium oxide (or oxyfluoride), lithium niobium oxide (or oxyfluoride), lithium zirconium oxide (or oxyfluoride) and their various alloys, mixtures and combinations.
  • LCO, NCM, NCMA, NCA, LFP, LMFP, LMP, LMO or LMNO may be doped with one or more of Al, Ti, Mg, Nb, Zr, Cr
  • a preferred cathode current collector may comprise aluminum or an aluminum alloy.
  • a preferred battery cell may include a polymer separator, a polymer-ceramic composite separator or Attorney Docket No. SN-0076WO a ceramic separator.
  • such a separator may be stand-alone or may be integrated into an anode or cathode or both.
  • a polymer separator may comprise or be made of polyethylene, polypropylene, or a mixture thereof.
  • a surface of a polymer separator may be coated with a layer of ceramic material.
  • Examples of a preferred coating material for polymer separators may include, but not limited to titanium oxide (TiO 2 ), aluminum oxide (Al 2 O 3 ), aluminum hydroxide or oxyhydroxide, magnesium oxide (MgO) or magnesium hydroxide or oxyhydroxide, silicon oxide (SiO 2 ), zirconium oxide (ZrO 2 ) and their various mixtures and alloys.
  • the cathode may advantageously comprise high Li-capacity materials (e.g., materials with the first cycle specific and/or volumetric de-lithiation capacities higher (e.g., about 10% - about 600% higher) than that of LCO, NCM, NCMA, NCA, LFP, LMFP, LMP, LMO, LMNO or other primary active cathode materials used in the Li-ion battery design), which exhibit high irreversible Li capacity (e.g., in some designs, about 30% or higher irreversible Li capacity; in other designs, 50% or higher irreversible Li capacity; in other designs, 70% or higher irreversible Li capacity; in other designs, 80% or higher irreversible Li capacity) when the Li-ion battery is cycled in a typical voltage range.
  • high Li-capacity materials e.g., materials with the first cycle specific and/or volumetric de-lithiation capacities higher (e.g., about 10% - about 600% higher) than that of LCO, NCM, NCMA, NCA, L
  • Such materials may be added to cathode in order to provide more Li to compensate for irreversible Li losses in the anode during formation cycling.
  • the use of such materials may require a higher charging voltage (e.g., from about 0.1V to about 1V higher - e.g., about 0.1-0.2V higher or 0.2-0.4V higher or about 0.4-0.6V higher or about 0.6-0.8V higher or about 0.8-1 V higher) during the first charge (or any other charge during the so-called “formation”) compared to charging during regular battery use.
  • suitable materials with such high irreversible Li capacity may be produced by combining Li 2 O with a suitable (in some designs, amphoteric; in some designs, Fe or Fe-comprising or Ni or Ni-comprising or Mn or Mn-comprising or Zn or Zn-comprising) metal or metal oxide or by reacting Li 2 O with amphoteric transition metal oxides (e.g., oxides of Fe, Ni, Zn, Al, Mn, Cu, etc.) or oxides of semimetals or nonmetals (e.g., Si, C, P, B, S, Se, etc.) (in other words, with oxides that possess acidic properties when reacted with basic Li 2 O).
  • a suitable transition metal oxides e.g., oxides of Fe, Ni, Zn, Al, Mn, Cu, etc.
  • semimetals or nonmetals e.g., Si, C, P, B, S, Se, etc.
  • suitable materials with such high irreversible Li may comprise carbon (e.g., Li 2 C 2 O 4 ) or sulfur (e.g., Li 2 S) or iron (e.g., Li 5 FeO 4 or Li 4 FeO 3.5 or Li 3 FeO 3.5 or Li 2 FeO 3 , etc.) or nickel (e.g., Li 2 NiO 2 , etc.) or vanadium (e.g., Li 3 V 2 O 5 , etc.) or other lithium transition metal oxides or their various combinations (note - in some designs, these may comprise various dopants).
  • carbon e.g., Li 2 C 2 O 4
  • sulfur e.g., Li 2 S
  • iron e.g., Li 5 FeO 4 or Li 4 FeO 3.5 or Li 3 FeO 3.5 or Li 2 FeO 3 , etc.
  • nickel e.g., Li 2 NiO 2 , etc.
  • vanadium e.g., Li 3 V 2 O 5 , etc.
  • One or more aspects are directed to a battery electrode (e.g., anode) composition comprising a population of Si-comprising particles.
  • suitable Si-comprising active material particles include, but are not limited to: simple (e.g., approximately uniform or relatively low spatial variation) composition of silicon-comprising particles, silicon particles, particles comprising silicon nanoparticles having average size in a range from about 1 nm to about 10 nm or from about 10 nm to about 50 nm or from about 50 nm to about 100 nm or from about 100 nm to about 500 nm, doped or heavily doped silicon comprising particles, particles comprising amorphous material, particles comprising nanocrystalline material, particles comprising amorphous silicon, particles comprising amorphous silicon or silicon-comprising nanoparticles, particles comprising nanocrystalline silicon or silicon-comprising particles, particles comprising silicon nano
  • SN-0076WO comprising particles, silicon-zinc alloy comprising particles, silicon lithium oxide (e.g., with a composition of SiLi y O x ; where 0 ⁇ x ⁇ 7; 0 ⁇ y ⁇ 6; e.g., Li 2 SiO 3 , Li 6 Si 2 O 7 , Li 2 Si 2 O 5 , Li 4 SiO 4 , among others) comprising particles, lithium silicate comprising particles, magnesium silicate comprising particles, silicon magnesium oxide (e.g., with a composition of SiMg y O x ; where 0 ⁇ x ⁇ 4; 0 ⁇ y ⁇ 1.5) comprising particles, aluminum silicon oxide comprising particles, aluminum silicate comprising particles, silicon sulfide comprising particles, oxidized silicon sulfide comprising particles, particles comprising carbon-coated or carbon-decorated silicon, particles comprising silicon carbide-coated or silicon carbide-decorated silicon, particles comprising silicon oxide-coated silicon, particles comprising silicon oxide-decorated silicon, particles comprising silicon
  • nanocomposite particles comprising silicon nanoparticles within carbon pores, particles comprising carbon on their surface, particles comprising polymers on their surface, particles comprising carbon-coated silicon, particles with more than one distinct coatings, particles with more than one distinct coatings on the silicon surface, milled particles, irregularly-shaped particles, spherical or spheroidal particles, round particles, jagged particles, flattened particles, planar particles, elongated particles, fiber-shaped particles and particles with various combinations, variations and mixtures of such compositions, features and properties, among others.
  • a preferred battery cell may include a silicon-comprising nanocomposite (particles) (including, but not limited to the nanocomposite comprising both silicon and carbon) (note that as used herein, a nanocomposite or (nano)composite is at least partially comprised of active material nanomaterials or nanostructures or nanoparticles, irrespective of whether the nanocomposite or (nano)composite itself is a nanomaterial) or silicon oxide (SiO x ) or silicon nitride or natural or synthetic graphite or soft carbon or hard carbon or their various mixtures and combinations in its anode composition.
  • the anode material includes a mixture of silicon-comprising active materials (e.g., Si-C nanocomposite (particles) or other suitable Si-comprising particles) and graphite (e.g., the graphite being separate from the C-part of the Si-C nanocomposite).
  • a Si-C nanocomposite comprises composite particles, which may include Si nanoparticles embedded in pores of a porous carbon or porous carbon-comprising scaffold particle.
  • a porous carbon scaffold particle can comprise graphene material (including, but not limited to highly curved and highly defective graphene) and/or graphite material.
  • a preferred anode current collector may comprise copper or copper alloy.
  • the battery anode composition comprises a population of Si-comprising particles (e.g., nanocomposite particles, among others), in which each of the Si particles comprises silicon (Si) and carbon (C) elements and may comprise other elements, such as nitrogen (N), phosphorus (P), boron (B), oxygen (O), hydrogen (H), sulfur (S), to name a few.
  • the total mass of the Si and the C (on average) may contribute from about 75 wt. % to about 100 wt. % of the total mass of the Si-comprising particles (as in Si-C composites and nanocomposites).
  • the total mass of O may contribute (on average) from about 0 wt. % to about 10 wt. % of the total mass of the Si-comprising particles (in some designs, from about 0 wt. % to about 1 wt. %; in other designs, from about 1 wt. % to about 2.5 wt. %; in other designs, from about 2.5 wt. % to about 5 wt. %; in other designs, from about 5 wt. % to about 10 wt. %;). In some embodiments, the total mass of O may contribute (on average) to less than about 5 wt. % of the total mass of the Si-comprising particles.
  • the total mass of N may contribute (on average) from about 0 wt. % to about 10 wt. % of the total mass of the Si-comprising particles (in some designs, from about 0 wt. % to about 0.1 wt. %; in other designs, from about 0.1 wt. % to about 2 wt. %; in other designs, from about 2 wt. % to about 5 wt. %; in yet other designs, from about 5 wt. % to about 10 wt. %).
  • the total mass of P may contribute (on average) from about 0 wt. % to about 10 wt.
  • the total mass of B may contribute (on average) from about 0 wt. % to about 5 wt. % of the total mass of the Si-comprising particles (in some designs, from about 0 wt. % to about 0.1 wt. %; in other designs, from about 0.1 wt. % to about 1 wt. %; in other designs, from about 1 wt. % to about 5 wt. %; in yet other designs, from about 5 wt. % to about 10 wt. %).
  • the total mass of B may contribute (on average) from about 0 wt. % to about 5 wt. % of the total mass of the Si-comprising particles (in some designs, from about 0 wt. % to about 0.1 wt.
  • the total mass of H may contribute (on average) from about 0 wt. % to about 2 wt. % of the total mass of the Si- comprising particles (in some designs, from about 0 wt. % to about 0.5 wt. %; in other designs, from about 0.5 wt. % to about 1 wt. %; in yet other designs, from about 1 wt. % to about 2 wt. %).
  • the total mass of S may contribute (on average) from about 0 wt. % to about 2.5 wt. % of the total mass of the Si-comprising particles (in Attorney Docket No. SN-0076WO some designs, from about 0 wt. % to about 0.1 wt. %; in other designs, from about 0.1 wt. % to about 0.5 wt. %; in yet other designs, from about 0.5 wt. % to about 2.5 wt. %).
  • a total atomic fraction of the Si and the C may contribute from about 75 at. % to about 100 at. % of the overall Si-C composite particles.
  • such composite particles comprise nano-sized or nanostructured elements (e.g., nano-sized or nanostructured Si, nano-sized or nanostructured C), which may be referred to as nanocomposite particles.
  • nanocomposite particles e.g., nano-sized or nanostructured Si, nano-sized or nanostructured C
  • the Si or Si- comprising material present in such nanocomposites may be in the form of nanoparticles.
  • the mass-average size of Si or Si-comprising material nanoparticles may range from about 1 nm to about 200 nm (in some designs, from about 1 nm to about 10 nm; in other designs, from about 10 nm to about 30 nm; in yet other designs, from about 30 nm to about 100 nm; in yet other designs, from about 100 nm to about 200 nm), as measured using image analysis of electron microscopy (e.g., transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM), scanning electron microscopy (SEM)), X-ray microscopy, X-ray diffraction, neutron scattering and other suitable techniques.
  • TEM transmission electron microscopy
  • STEM scanning transmission electron microscopy
  • SEM scanning electron microscopy
  • An aspect is directed to a battery anode composition
  • a population of Si-comprising particles e.g., nanocomposite particles, among others
  • each of the particles comprises Si and C
  • the Si-comprising particles have certain characteristics.
  • a mass fraction of the silicon in the Si-comprising particles is in a range of about 3 wt. % to about 80 wt. % (in some designs, from about 3 wt. % to about 20 wt. %; in other designs, from about 20 wt. % to about 35 wt. %; in yet other designs, from about 35 wt. % to about 50 wt.
  • a Brunauer-Emmett-Teller (BET) specific surface area (SSA) of the Si-comprising particles is in a range of about 0.5 m 2 /g to about 150 m 2 /g (in some designs, from about 0.5 to about 3 m 2 /g; in other designs, from about 3 m 2 /g to about 12 m 2 /g; in yet other designs, from about 12 m 2 /g to about 18 m 2 /g; in yet Attorney Docket No.
  • the Si-comprising particles e.g., nanocomposite particles, among others
  • about 90 % or more of the Si-comprising particles in the population are characterized by aspect ratios of about 2.3 or less, or aspect ratios of about 2.1 or less.
  • about 50 % or more of the composite particles in the population are characterized by aspect ratios of about 1.25 or more, or aspect ratios of about 1.35 or more.
  • An aspect is directed to a battery electrode composition
  • a population of Si-comprising particles in which the particle population of may be characterized by a particle size distribution (PSD) as determined by laser particle size distribution analysis (LPSA), image analysis of electron microscopy images, or other suitable techniques.
  • PSD particle size distribution
  • the particle size distribution (PSD) that characterizes a particle population may be determined by laser particle size distribution analysis (LPSA) on well- dispersed particle suspensions in one example or by image analysis of electron microscopy images, or by other suitable techniques. While there are diverse processes of measuring PSDs, laser particle size distribution analysis (LPSA) is quite efficient for some applications.
  • LPSA laser particle size distribution analysis
  • particle size parameters of a population’s PSD can be measured, such as: a tenth-percentile volume-weighted particle size parameter (e.g., abbreviated as D 10 ), a fiftieth-percentile volume-weighted particle size parameter (e.g., abbreviated as D 50 ), a ninetieth-percentile volume-weighted particle size parameter (e.g., abbreviated as D 90 ), and a ninety-ninth-percentile volume-weighted particle size parameter (e.g., abbreviated as D 99 ).
  • D 10 tenth-percentile volume-weighted particle size parameter
  • D 50 a fiftieth-percentile volume-weighted particle size parameter
  • D 90 ninetieth-percentile volume-weighted particle size parameter
  • D 99 ninety-ninth-percentile volume-weighted particle size parameter
  • parameters relating to characteristic widths of the PSD may be derived from these particle size parameters, such as D 50 – D 10 (sometimes referred to herein as a left width), D 90 – D 50 (sometimes referred to herein as a right width), and D 90 – D 10 (sometimes referred to herein as a full width).
  • a cumulative volume fraction defined as a cumulative volume of the composite particles with particle sizes of a threshold particle size or less, divided by a total volume of all of the composite particles, may be estimated by LPSA.
  • a fiftieth-percentile volume- weighted particle size parameter (D 50 ) of the PSD of Si-comprising particles may advantageously be in a range of about 0.5 ⁇ m to about 25.0 ⁇ m, or in a range of about 0.5 to about 4.0 ⁇ m, or in a range of about 4.0 to about 6.0 ⁇ m, or in a range of about 6.0 to Attorney Docket No. SN-0076WO about 8.0 ⁇ m or in a range of about 8.0 to about 16.0 ⁇ m or in a range of about 16.0 to about 25.0 ⁇ m.
  • a cumulative volume fraction defined as a cumulative volume of the composite particles with particle sizes of a threshold particle size or less, divided by a total volume of all of the composite particles, may be estimated by LPSA.
  • the cumulative volume fraction, with the threshold particle size at about 5 ⁇ m may advantageously be about 99 vol. % or less, or about 95 vol. % or less, or about 90 vol. % or less, or about 85 vol. % or less, or about 80 vol. % or less.
  • the cumulative volume fraction, with the threshold particle size at about 7 ⁇ m may advantageously be about 99 vol. % or less, or about 95 vol. % or less, or about 90 vol. % or less, or about 85 vol. % or less, or about 80 vol. % or less.
  • the cumulative volume fraction, with the threshold particle size at about 10 ⁇ m may advantageously be about 99 vol. % or less, or about 95 vol. % or less, or about 90 vol.
  • the cumulative volume fraction, with the threshold particle size at 2 about 0 ⁇ m may advantageously be about 99 vol. % or less, or about 95 vol. % or less, or about 90 vol. % or less, or about 85 vol. % or less, or about 80 vol. % or less.
  • the cumulative volume fraction, with the threshold particle size at about 30 ⁇ m may advantageously be about 99 vol.
  • Si-comprising particles e.g., Si-C nanocomposite particles, among others
  • cell performance characteristics e.g., reduce cell stability, increase its impedance, reduce rate performance, reduce packing density, reduce electrode smoothness or uniformity, reduce electrode mechanical properties, reduce volumetric capacity, increase (e.g., localized) volume expansion, etc.
  • the cumulative volume fraction, with the threshold particle size at about 10 ⁇ m may advantageously be about 80 vol. % or more, or about 85 vol. % Attorney Docket No. SN-0076WO or more, or (in some designs) even about 90 vol. % or more.
  • the cumulative volume fraction, with the threshold particle size at about 12 ⁇ m may advantageously be about 90 vol. % or more, or about 95 vol. % or more, or (in some designs) even about 98 vol.
  • the cumulative volume fraction, with the threshold particle size at about 15 ⁇ m may advantageously be about 80 vol. % or more, or about 85 vol. % or more, or (in some designs) even about 90 vol. % or more.
  • the cumulative volume fraction, with the threshold particle size at about 25 ⁇ m may advantageously be about 90 vol. % or more, or about 95 vol. % or more, or (in some designs) even about 98 vol. % or more.
  • the cumulative volume fraction, with the threshold particle size at about 18 ⁇ m may advantageously be about 80 vol. % or more, or about 85 vol. % or more, or (in some designs) even about 90 vol. % or more.
  • the cumulative volume fraction, with the threshold particle size at about 35 ⁇ m may advantageously be about 90 vol. % or more, or about 95 vol. % or more, or (in some designs) even about 98 vol. % or more.
  • the cumulative volume fraction, with the threshold particle size at about 40 ⁇ m may advantageously be about 80 vol. % or more, or about 85 vol. % or more, or (in some designs) even about 90 vol. % or more.
  • the cumulative volume fraction, with the threshold particle size at about 50 ⁇ m may advantageously be about 90 vol. % or more, or about 95 vol. % or more, or (in some designs) even about 98 vol. % or more.
  • Si-comprising active material (composite) particles may exhibit true density (e.g., as measured by using an argon gas pycnometer) in the range from about 1.1 g/cc to about 2.8 g/cc (in some designs, from about 1.1 g/cc to about 1.5 g/cc; in other designs, from about 1.5 g/cc to about 1.8 g/cc; in other designs, from about 1.8 g/cc to about 2.1 g/cc; in other designs, from about 2.1 g/cc to about 2.4 g/cc; in yet other designs, from about 2.4 g/cc to about 2.8 g/cc).
  • true density e.g., as measured by using an argon gas pycnometer
  • Si-comprising active material (composite) particles may comprise internal pores.
  • the open (e.g., to nitrogen gas at 77K) pore volume e.g., as measured by nitrogen sorption/desorption isotherm measurement technique and including the pores in the range from about 0.4 nm to about 100 nm
  • the open (e.g., to nitrogen gas at 77K) pore volume may range from about 0.00 cc/g to about 0.50 cc/g (assuming theoretical density of the individual material components present in Si- comprising particles) – in some designs, from about 0.00 cc/g to about 0.10 cc/g; in other designs, from about 0.10 cc/g to about 0.20 cc/g; in other designs, from about 0.20 cc/g to about 0.30 cc/g; in other designs, from about 0.30 cc/g to about 0.40 cc/g; in other designs, from about 0.40 cc/g to
  • the closed (e.g., to nitrogen gas at 77K) pore volume may range from about 0.00 cc/g to about 1.00 cc/g – in some designs, from about 0.00 cc/g to about 0.10 cc/g; in other designs, from about 0.10 cc/g to about 0.20 cc/g; in other designs, from about 0.20 cc/g to about 0.30 cc/g; in other designs, from about 0.30 cc/g to about 0.40 cc/g; in other designs, from about 0.40 cc/g to about 0.50 cc/g; in other designs, from about 0.50 cc/g to about 0.60 cc/g; in other designs, from about 0.60 cc/g to about 0.70 cc/g
  • the volume-average size of the open (e.g., to nitrogen gas at 77K) pores may range from about 0.5 nm to about 100 nm – in some designs, from about 0.5 nm to about 5 nm; in other designs, from about 5 nm to about 20 nm; in other designs, from about 20 nm to about 50 nm; in yet other designs, from about 50 nm to about 100 nm.
  • the volume-average size of the closed (e.g., to nitrogen gas at 77K) pores may range from about 0.5 nm to about 200 nm – in some designs, from about 0.5 nm to about 5 nm; in other designs, from about 5 nm to about 20 nm; in other designs, from about 20 nm to about 50 nm; in other designs, from about 50 nm to about 100 nm; in yet other designs, from about 100 nm to about 200 nm.
  • Si-comprising active material (composite) particles may exhibit moderate (e.g., about 7-120 vol. %) or high (e.g., about 120-200 vol. %) volume changes during initial lithiation (e.g., down to around 0.01 V vs. Li/Li + ). In some designs, Si-comprising active material (composite) particles may exhibit volume changes in the range from about 8 vol. % to about 180 vol. % during one or more charge-discharge cycles of the battery cell.
  • Si-comprising active material (composite) particles may exhibit moderately small (e.g., about 3-7 vol. %) or moderate (e.g., about 7-120 vol. %) volume changes during electrochemical battery cycling from about 0-5 % state of charge (SOC) to about 90-100 % SOC and back during battery operation.
  • Si-comprising active material (composite) particles may exhibit reversible capacity for Li storage in the range from about 1400 to about 2800 mAh/g (e.g., about 1400-1600 mAh/g or about 1600-1800 mAh/g or about 1800-2000 mAh/g or about 2000-2400 mAh/g or about 2400-2800 mAh/g), as measured at room temperature in half cells using a suitable charge-discharge protocol (e.g., when lithiated to about 0.01 V vs.
  • a suitable charge-discharge protocol e.g., when lithiated to about 0.01 V vs.
  • a constant current e.g., C/10
  • Si-comprising active material (composite) particles may exhibit first cycle lithiation capacity in the range from about 1600 to about 3000 mAh/g (e.g., about 1600-1800 mAh/g or about 1800-2000 mAh/g or about 2000-2200 mAh/g or about 2200-2400 mAh/g or about 2400-2600 mAh/g or about 2600-3000 mAh/g), as measured at room temperature in half cells using a suitable charge-discharge protocol (e.g., when lithiated to about 0.01 V vs.
  • a suitable charge-discharge protocol e.g., when lithiated to about 0.01 V vs.
  • Si-comprising active material (composite) particles may exhibit first cycle “formation” losses in the range from about 6 % to about 15 % (e.g., about 6-8% or about 8-10% or about 10-12% or about 12-15%), as measured at room temperature in half cells using a suitable charge-discharge protocol (e.g., when lithiated to about 0.01 V vs.
  • a constant current e.g., C/10
  • a preferred battery cell may comprise a relatively high areal capacity loading in its electrodes (anodes and cathodes), such as from around 2.0 mAh/cm 2 to around 12 mAh/cm 2 (in some implementations, from about 2 to about 3.5 mAh/cm 2 ; in other implementations, from about 3.5 to about 4.5 mAh/cm 2 ; in other implementations, from about 4.5 to about 6.5 mAh/cm 2 ; in other implementations, from about 6.5 to about 8 mAh/cm 2 ; in other implementations, from about 8 to about 12 mAh/cm 2 ).
  • a relatively high areal capacity loading in its electrodes such as from around 2.0 mAh/cm 2 to around 12 mAh/cm 2 (in some implementations, from about 2 to about 3.5 mAh/cm 2 ; in other implementations, from about 3.5 to about 4.5 mAh/cm 2 ; in other implementations, from about 4.5 to about 6.5 mAh/cm 2 ; in other implementations, from
  • Li-containing electrodes and active materials for example, partially or fully lithiated Si-comprising anodes or partially or fully lithiated Si-comprising anode particles, partially or fully lithiated metal fluoride comprising cathodes (such as a mixture of LiF and metals such as Cu, Fe, Ni, Bi, and various other metals and metal alloys and mixtures of such and other metals, etc.) or partially or fully lithiated metal halide comprising cathode particles, partially or fully lithiated chalcogenides (such as Li 2 S, Li 2 S/metal mixtures, Li 2 Se, Li 2 Se/metal mixtures, Li 2 S- Li 2 Se mixtures, various other
  • various material properties may change based on whether active material particle(s) are in a Li-free state, a partially lithiated state, or a fully lithiated state.
  • Such Li-dependent material properties may include particle pore volume, electrode pore volume, and so on.
  • reference to such Li-dependent material properties e.g., at particle level, at inter-particle level, at electrode level, etc.
  • some examples below are characterized at the electrode level (e.g., as opposed to particle level or interparticle level or cell level, etc.).
  • an Li-free state is used to refer to a material that is free of electrochemically active Li, and other types of Li such as in electrochemically inactive compounds may (optionally) be part of such an Li-free material.
  • conversion materials change (convert) from one crystal structure to another (hence the name “conversion”- type, e.g., an electrochemical reaction). This process is also accompanied by breaking chemical bonds and forming new ones.
  • conversion e.g., an electrochemical reaction
  • Li ions are inserted into alloying type materials forming lithium alloys (hence the name “alloying”- type).
  • alloying type materials forming lithium alloys.
  • alloying forming lithium alloys
  • “alloying”-type electrode materials are considered to be a subclass of “conversion”-type electrode materials.
  • a preferred anode for a battery cell may comprise a mixture of Si-C nanocomposite (particles) (or, in some designs, other Si-comprising anode particles) and graphite (particles) as the anode active material, a so-called blended anode.
  • an anode may comprise inactive material (separate from any inactive material that is made part of active material-comprising composite particles), such as binder(s) (e.g., polymer binder) and other functional additives (e.g., surfactants, electrically conductive additives).
  • the anode active material can be in a range of about 90 wt. % to about 98 wt. % of the anode.
  • suitable intercalation-type graphites to be used in combination with Si-C nanocomposite or other Si-comprising particles in a blend
  • various aspects of this disclosure may be applicable to soft-type synthesis graphite, hard-type synthesis graphite, and pitch coat natural graphite; including but not limited to those which exhibit discharge capacity from about 350 to about 362 mAh/g; including but not limited to those which exhibit low, moderate and high swelling; including but not limited to those which exhibit good and poor compression, including but not limited to those which exhibit Brunauer- Emmett-Teller (BET) surface area of about 1 to about 4 m 2 /g; including but not limited Attorney Docket No.
  • BET Brunauer- Emmett-Teller
  • SN-0076WO to those which exhibit lithiation efficiency of about 90 % and more; including but not limited to those which exhibit particle sizes from about 8 ⁇ m to about 18 ⁇ m; including but not limited to those which exhibit densities ranging from about 1.5 g/cm 3 to about 1.8 g/cm 3 ; including but not limited to those which exhibit poor, moderate, or good cycle life; including but not limited to those which are coated and comprise coatings with coating thickness to appreciably improve compression and springing during cycling, or any combination thereof.
  • intercalation-type cathodes including high voltage cathodes
  • suitable intercalation-type cathodes in the context of lithium nickel cobalt aluminum oxides (NCA), lithium nickel cobalt manganese aluminum oxides (NCMA), lithium nickel oxides (LNO), lithium manganese oxides (LMO), lithium nickel manganese cobalt oxides (NCM), lithium nickel manganese oxide (LNMO), lithium cobalt oxide (LCO), lithium cobalt aluminum oxides (LCAO), lithium iron phosphate (LFP), lithium manganese phosphate (LMP), lithium cobalt phosphate (LCP), lithium nickel phosphate (LNP), lithium manganese iron phosphate (LMFP), and other lithium transition metal (TM) oxide or phosphate or sulfate (or mixed) cathodes that rely on the intercalation of lithium (Li) and changes in the TM oxidation state (including, but not limited to those that may be doped or heavily doped; including, but not limited to those that
  • the example battery 100 includes a negative anode 102, a positive cathode 103, a separator 104 interposed between the anode 102 and the cathode 103, an electrolyte (shown implicitly) impregnating the separator 104, a battery case 105, and a sealing member 106 sealing the battery case 105.
  • battery 100 also includes an anode current collector and a cathode current collector.
  • the anode is disposed on and/or in the anode current collector and the cathode is disposed on and/or in the cathode current collector.
  • Li-ion battery electrolyte salts that are readily commercially available at scale include lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), SO 2 FN ⁇ (Li + )SO 2 F (LiFSI), CF 3 SO 2 N ⁇ (Li + )SO 2 CF 3 (LiTFSI), lithium trifluoromethanesulfonate (LiOTf), lithium bis(oxalato)borate (LiB(C 2 O 4 ) 2 ) (LiBOB), lithium difluorophosphate (LFO), and lithium difluoro(oxalato)borate (LiBF 2 (C 2 O 4 )) (LiDFOB).
  • LiPF 6 lithium hexafluorophosphate
  • LiBF 4 lithium tetrafluoroborate
  • LiFSI SO 2 FN ⁇ (Li + )SO 2 F
  • LiTFSI CF 3 SO 2
  • lithium perchlorate LiClO 4
  • Li fluorosulfate LSF
  • lithium tris(fluorosulfonyl)methanide LPFSM
  • lithium hexafluoroantimonate LiSbF 6
  • lithium hexafluorosilicate Li 2 SiF 6
  • lithium hexafluoroaluminate Li 3 AlF 6
  • various imides CF 3 CF 2 SO 2 N ⁇ (Li + )SO 2 CF 3 , CF 3 CF 2 SO 2 N ⁇ (Li + )SO 2 CF 2 CF 3 , CF 3 SO 2 N ⁇ (Li + )SO 2 CF 2 OCF 3 , CF 3 OCF 2 SO 2 N ⁇ (Li + )SO 2 CF 2 OCF 3 , C 6 F 5 SO 2 N ⁇ (Li + )SO 2 CF 3 , C 6 F 5 SO 2 N ⁇ (Li + )SO 2 CF 3 , C 6 F 5 SO 2 N
  • Electrodes utilized in Li-ion batteries are typically produced by (i) formation of a slurry comprising active materials, conductive additives, binder solutions and, in some cases, surfactant or other functional additives; (ii) casting the slurry onto and/or into a metal current collector foil (e.g., Cu foil for most anodes and Al foil for most cathodes); and (iii) drying the casted electrodes to completely evaporate the solvent.
  • a metal current collector foil e.g., Cu foil for most anodes and Al foil for most cathodes
  • Conventional anode materials utilized in Li-ion batteries are of an intercalation-type, whereby metal ions are intercalated into and occupy interstitial positions of such materials during the charge or discharge of a battery. Such anodes experience small or very small volume changes when used in electrodes.
  • Polyvinylidene Attorney Docket No. SN-0076WO fluoride also known as polyvinylidene difluoride (PVDF), and carboxymethyl cellulose (CMC) are the two most common binders used in these electrodes. Carbon black is the most common conductive additive used in these electrodes, followed by flakes of artificial graphite.
  • PVDF polyvinylidene difluoride
  • CMC carboxymethyl cellulose
  • Such anodes exhibit relatively small gravimetric and volumetric capacities (typically less than about 370 mAh/g rechargeable specific capacity in the case of graphite- or hard carbon-based anodes and less than about 600 mAh/cm 3 rechargeable volumetric capacity at the electrode level without considering the volume of the current collector foils).
  • Alloying-type (or, more broadly, conversion-type) anode materials for use in Li-ion batteries offer higher gravimetric and volumetric capacities compared to intercalation-type anodes.
  • Earth-abundant silicon (Si) offers approximately 10 times higher gravimetric capacity and approximately 3 times higher volumetric capacity compared to an intercalation-type graphite (or graphite-like) anode.
  • Si suffers from significant volume expansion during Li insertion (up to approximately 300 vol. %) and thus may induce thickness changes and mechanical failure of Si-comprising anodes.
  • Si (and some Li-Si alloy compounds that may form during lithiation of Si) suffer from relatively low electrical conductivity and relatively low ionic (Li-ion) conductivity. Electronic and ionic conductivity of Si is lower than that of graphite.
  • Si-comprising particles including, but not limited to Si- carbon composites, Si-metal composites, Si-polymer composites, Si-ceramic composites, composites comprising various combinations of nanostructured Si, carbon, polymer, ceramic and metal or other types of porous composites comprising nanostructured Si or nanostructured or nano-sized Si particles of various shapes and forms
  • Si may be doped or heavily doped with nitrogen (N), phosphorous (P), boron (B) or other elements or be allowed with metals.
  • Si-comprising anode particles may exhibit high gravimetric Attorney Docket No. SN-0076WO capacities in the range from about 800 mAh/g to about 3000 mAh/g (per mass of Si- comprising anode particles in a Li-free state). Such high specific capacity is advantageous for attaining lighter batteries.
  • Li-ion battery cells with anodes comprising high- capacity anode particles may exhibit undesirably fast degradation in conventional electrolytes, particularly at elevated temperatures (e.g., at or above battery operating temperature, e.g., above about 50-80 °C) or when charged to high voltages (e.g., above about 4-4.3 V).
  • a subset of anodes with Si-comprising anode particles may include anodes with an electrode layer exhibiting capacity in the range from about 400 mAh/g to about 2800 mAh/g (per mass of the electrode layer, not counting the mass of the current collector, in a Li-free state).
  • Li-ion battery cells with anodes comprising high-capacity anode particles may exhibit undesirably fast degradation in conventional electrolytes, particularly at elevated temperatures (e.g., at or above battery operating temperatures, e.g., above about 50-80 °C) or when charged to high voltages (e.g., above about 4-4.3 V).
  • anodes comprising alloying-type (or, more broadly, conversion-type) active materials include, but are not limited to, those that comprise germanium, antimony, aluminum, magnesium, zinc, gallium, arsenic, phosphorous, silver, cadmium, indium, tin, lead, bismuth, their alloys, and others.
  • anodes comprising active materials in a metallic form
  • other interesting types of high-capacity (including nanocomposite) anodes may comprise metal oxides (including silicon oxide, lithium oxide, etc.), metal nitrides (including silicon nitride, etc.), metal oxy-nitrides (including silicon oxy-nitride, etc.), metal phosphides (including lithium phosphide), metal hydrides, and others.
  • Li-ion cells with alloying-type (or, more broadly, conversion-type) active anode materials may exhibit undesirably fast degradation in conventional electrolytes, particularly at elevated temperatures (e.g., at or above battery operating temperatures, e.g., above about 50-80 °C) or when charged to high voltages (e.g., above about 4-4.3 V) and stored at such voltages at elevated temperatures (e.g., above about 50-80 °C).
  • degradation of Li-ion cells with alloying-type (or, more broadly, conversion- type) active anode materials may become particularly undesirably fast for large cells (e.g., Attorney Docket No.
  • SN-0076WO cells with cell capacity in the range from about 10 Ah to about 40 Ah or ultra-large cells (e.g., cells with cell capacity in the range from about 40 Ah to about 400 Ah) or gigantic cells (e.g., cells with cell capacity in the range from about 400 Ah to about 4,000 Ah or even more).
  • ultra-large cells e.g., cells with cell capacity in the range from about 40 Ah to about 400 Ah
  • gigantic cells e.g., cells with cell capacity in the range from about 400 Ah to about 4,000 Ah or even more.
  • large, or ultra-large or gigantic cells may be particularly attractive for use in some electric transportation or grid storage applications.
  • degradation of Li-ion cells with alloying-type (or, more broadly, conversion-type) active anode materials may become particularly undesirably fast for cells comprising medium (e.g., about 3-4 g/Ah) or small (e.g., about 2-3 g/Ah) amount of electrolyte when normalized by total cell capacity.
  • medium e.g., about 3-4 g/Ah
  • small e.g., about 2-3 g/Ah
  • electrolyte when normalized by total cell capacity.
  • using a medium or a small amount of electrolyte may be particularly attractive for reducing cell fabrication costs or certain side reactions and for maximizing energy density of cells.
  • One or more aspects of the present disclosure enables one to mitigate or overcome some or all of such limitations and substantially enhance performance of such Li-ion cells by using certain disclosed electrolyte compositions.
  • High-capacity (nano)composite anode powders including, but not limited to those that comprise Si
  • which exhibit moderately high volume changes e.g., about 8 – about 180 vol. %) during the first charge-discharge cycle
  • moderate volume changes e.g., about 4 – about 50 vol.% during the subsequent charge-discharge cycles
  • an average size in the range from about 0.2 to about 40 microns for some applications, more preferably from about 0.4 to about 20 microns
  • electrodes with electrode areal capacity loading from moderate (e.g., from about 2 to about 4 mAh/cm 2 ) to high (e.g., from about 4 to about 12 mAh/cm 2 ) and ultra-high (e.g., above about 12 mAh/cm 2 ) are also particularly attractive for use in cells.
  • a near-spherical or a spheroidal or an ellipsoid (inc. oblate spheroid) shape of these composite particles may additionally be very attractive for increasing rate performance and volumetric capacity (density) of the electrodes. Note that such high-capacity Attorney Docket No.
  • SN-0076WO (nano)composite anode “powders” may be in the form of a “dry” powder (e.g., before being mixed into or suspended in a slurry), in the slurry itself (e.g., in a suspended state), or in a casted electrode (e.g., casted into an electrode, bound together with a suitable binder and/or conductive additives and/or functional additives, and dried).
  • moderate volume changes e.g., about 4 - about 50 vol.% during the subsequent charge- discharge cycles, an average size in the range from about 0.2 to about 40 microns and relatively low density (e.g., about 0.5 - 3.8 g/cc), are relatively new and their performance characteristics and limited cycle stability are typically relatively poor, particularly if electrode areal capacity loading is moderate (e.g., from about 2 to about 4 mAh/cm 2 ) and even more so if electrode areal capacity loading is high (e.g., from about 4 to about 12 mAh/cm 2 ) or ultra-high. Higher capacity loading, however, is advantageous in some designs for increasing cell energy density and reducing cell manufacturing costs.
  • the cell performance may suffer when such an electrode (e.g., anode) porosity (e.g., volume occupied by the spacing between the (nano)composite active anode particles in the electrode and filled with electrolyte, exclusive of closed pores, if any, within the particles themselves that are inaccessible to electrolyte) becomes moderately small (e.g., about 25 - about 35 vol. %) and more so when the electrode (e.g., anode) porosity becomes small (e.g., about 5 - about 25 vol. %) or when the amount of the binder and conductive additives in the electrode (e.g., anode) becomes moderately small (e.g., about 6 - about 15 wt.
  • an electrode porosity e.g., volume occupied by the spacing between the (nano)composite active anode particles in the electrode and filled with electrolyte, exclusive of closed pores, if any, within the particles themselves that are inaccessible to electrolyt
  • Li and Li-ion battery cells with such anodes and conventional electrolytes often require the use of such large amounts of conventional SEI-building additives to maintain acceptable cycle stability that prevents their use at elevated or low temperatures or undesirably limits their calendar life or does not allow such cells to be charged to high voltages (e.g., above about 4.1-4.3 V). In some designs, performance of such battery cells may become particularly poor when the cells are charged to above about 4.3-4.4 V and even more so when the cells are charged to above about 4.5 V. [00107] Higher cell voltage, broader operational temperature window, and longer cycle life, however, are advantageous for most applications.
  • such cells may suffer from excessive capacity degradation (e.g., above about 5%), large volume expansion (e.g., above about 10%) and significant gassing when exposed to high temperatures (e.g., above about 50-90 °C) in a fully charged state (e.g., state-of-charge, SOC, of about 90-100 %) for a prolonged time (e.g., about 12-168 hours). Passing such elevated temperature charging tests is often required for most applications.
  • excessive capacity degradation e.g., above about 5%
  • large volume expansion e.g., above about 10%
  • significant gassing when exposed to high temperatures (e.g., above about 50-90 °C) in a fully charged state (e.g., state-of-charge, SOC, of about 90-100 %) for a prolonged time (e.g., about 12-168 hours). Passing such elevated temperature charging tests is often required for most applications.
  • degradation of Li- ion cells comprising high-capacity (nano)composite anode powders, which exhibit moderately high volume changes during the first charge-discharge cycle, moderate volume changes during the subsequent charge-discharge cycles and an average size in the range from about 0.2 to about 40 microns may become particularly undesirably fast for large cells (e.g., cells with cell capacity in the range from about 10 Ah to about 40 Ah) or ultra-large cells (e.g., cells with cell capacity in the range from about 40 Ah to about 400 Ah) or gigantic cells (e.g., cells with cell capacity in the range from about 400 Ah to about 4,000 Ah or even more).
  • large cells e.g., cells with cell capacity in the range from about 10 Ah to about 40 Ah
  • ultra-large cells e.g., cells with cell capacity in the range from about 40 Ah to about 400 Ah
  • gigantic cells e.g., cells with cell capacity in the range from about 400 Ah to about 4,000 Ah or even more.
  • Li-ion cells with such volume changing anode particles may become particularly undesirably fast for cells comprising medium (e.g., about 2-4 mL/Ah) or small (e.g., about 1-2 mL/Ah) amount of electrolyte when normalized by total cell capacity.
  • medium e.g., about 2-4 mL/Ah
  • small e.g., about 1-2 mL/Ah
  • One or more embodiments of the present disclosure Attorney Docket No. SN-0076WO enables one to mitigate or overcome some or all of such limitations and substantially enhance performance of such Li-ion cells by using certain disclosed electrolyte compositions.
  • One or more embodiments of the present disclosure overcome some of the above-discussed challenges of various types of metal-ion (e.g., Li-ion) cells comprising high-capacity nanocomposite anode materials (for example, materials comprising conversion-type or alloying-type active materials) that may comprise Si in their composition, may experience certain volume changes during cycling (for example, moderately high volume changes (e.g., about 8 - about 160 or about 180 vol. %) during the first charge-discharge cycle and moderate volume changes (e.g., about 4 - about 50 vol.
  • Li-ion metal-ion
  • Electrode porosity filled with electrolyte in the range from about 5 to about 35 vol.
  • relatively low binder content may comprise moderate or small amount of electrolyte per cell capacity (e.g., less than about 2 mL/Ah), may be charged to moderately high (e.g., above about 4.1-4.3 V) or high (e.g., above about 4.3-4.4 V) or very high (e.g., above about 4.5-4.8 V) voltages, may be exposed to temperatures above about 40 °C at high state of charge (e.g., SOC of about 70 – 100%) during testing or operation, may be produced as large cells (e.g., cells with cell capacity in the range from about 10 Ah to about 40 Ah) or ultra-large cells (e.g., cells with cell capacity in the range from about 40 Ah to about 400 Ah) or gigantic cells (e.g., cells with cell capacity in the range from about 400 Ah to about 4,000 Ah or even more).
  • moderately high e.g., above about 4.1-4.3 V
  • high e.g., above about 4.3-4.4 V
  • very high e.
  • cathode materials utilized in Li-ion batteries are of an intercalation-type and commonly crystalline and polycrystalline. Such cathodes typically exhibit a highest charging potential of less than about 4.3 V vs. Li/Li + , reversible gravimetric capacity of less than about 190 mAh/g (based on the mass of active material) Attorney Docket No. SN-0076WO and reversible volumetric capacity of less than about 800 mAh/cm 3 (based on the volume of the electrode and not counting the volume occupied by the current collector foil). For given anodes, higher energy density in Li-ion batteries may be achieved either by using high-voltage cathodes (cathodes with a highest charging potential from about 4.3 V vs.
  • Some high-voltage intercalation-type cathodes may comprise nickel (Ni). Some high-voltage intercalation-type cathodes may comprise manganese (Mn). Some high-voltage intercalation-type cathodes may comprise iron (Fe). Some high-voltage intercalation-type cathodes may comprise cobalt (Co). Some high-voltage intercalation- type cathodes may comprise aluminum (Al).
  • high-voltage intercalation-type cathodes may comprise, as a dopant, silicon (Si), tin (Sn), antimony (Sb), or germanium (Ge) or their various combinations.
  • high-voltage intercalation-type cathode particles may comprise fluorine (F) as a dopant in their structure or the surface layer.
  • Some high-voltage intercalation-type cathodes may comprise phosphorous (P) as a dopant.
  • Some high-voltage intercalation-type cathodes may comprise sulfur (S) as a dopant.
  • Some high-voltage intercalation-type cathodes may comprise selenium (Se) as a dopant.
  • Some high-voltage intercalation-type cathodes may comprise tellurium (Te) as a dopant. Some high-voltage intercalation-type cathodes may comprise magnesium (Mg). Some high-voltage intercalation-type cathodes may comprise zirconium (Zr). Combination of such (or similar) types of higher energy density cathodes with high- capacity (e.g., Si-comprising) anodes may result in high cell-level energy density. Unfortunately, the cycle stability and other performance characteristics of such cells may not be sufficient for some applications, at least when used in combination with conventional electrolytes.
  • One or more embodiments of the present disclosure are thereby directed to electrolyte compositions that work well for a combination of high voltage intercalation cathodes (cathodes with the highest charging potential in the range from about 4.0-4.2 V to about 4.5 V vs. Li/Li + and, in some cases, from about 4.5 V vs. Li/Li + to about 5.1 V vs. Li/Li + ) with a subclass of high-capacity moderate volume changing anodes (e.g., anodes comprising (nano)composite anode powders, which exhibit moderately high Attorney Docket No. SN-0076WO volume changes (e.g., about 8 - about 160 or about 180 vol.
  • high voltage intercalation cathodes cathodes with the highest charging potential in the range from about 4.0-4.2 V to about 4.5 V vs. Li/Li + and, in some cases, from about 4.5 V vs. Li/Li + to about 5.1 V
  • moderate volume changes e.g., about 4 - about 50 vol.%) during the subsequent charge-discharge cycles
  • an average particle size e.g., average diameter
  • specific surface area in the range from about 0.5 to about 50 m 2 /g (when normalized by the mass of the composite electrode particles) and, in the case of Si-comprising anodes, specific capacities in the range from about 400 to about 2800 mAh/g (when normalized by the total mass of all the anode particles, conductive or other additives and binders, but does not include the weight of the current collectors) or in the range from about 650-800 to about 3000 mAh/g (when normalized by the mass of the Si-comprising anode particles only).
  • a particular electrolyte composition may be selected based on the value of the highest cathode charge potential or the highest operating temperature or the longest cycle or calendar life requirement.
  • One or more embodiments of the present disclosure are also directed to electrolyte compositions that work well for a combination of (i) a subclass of moderate capacity (e.g., about 150-260 mAh/g per mass of active materials, in some design), high- voltage intercalation-type cathodes (which may be layered cathodes in some designs; which may comprise Ni or Co or Mn or a combination of some of such metals in some designs, such as, for example, LCO (lithium cobalt oxides), NCA (lithium nickel cobalt aluminum oxides), NCMA (lithium nickel cobalt manganese aluminum oxides), LNO (lithium nickel oxides), LMO (lithium manganese oxides), NCM (lithium nickel cobalt manganese oxides, also known as NMC), LCAO (lithium cobalt
  • Li/Li + during full cell battery cycling (in some designs, above about 4.2 V vs. Li/Li + ; in other designs, above 4.3 V vs. Li/Li + ; in yet other designs, above about 4.4 V vs. Li/Li + ; in yet other designs, above about 4.5 V vs. Li/Li + ; in yet other designs, above about 4.6 V vs.
  • Li/ Li + with (ii) a subclass of high-capacity moderate volume changing anodes: anodes comprising about 5 - about 100 wt.% of (nano)composite anode powders (e.g., Si-C nanocomposites), which exhibit moderately high volume changes (e.g., about 8 - about 160 or about 180 vol. %) during Attorney Docket No.
  • anodes comprising about 5 - about 100 wt.% of (nano)composite anode powders (e.g., Si-C nanocomposites), which exhibit moderately high volume changes (e.g., about 8 - about 160 or about 180 vol. %) during Attorney Docket No.
  • the first charge-discharge cycle moderate volume changes (e.g., about 4 - about 50 vol.%) during the subsequent charge-discharge cycles, an average size (e.g., average diameter) in the range from about 0.2 to about 40 microns and specific surface area in the range from about 0.5 to about 50 m 2 /g normalized by the mass of the (nano)composite anode particles and, in the case of Si-comprising anodes, specific reversible capacities in the range from about 400 to about 2800 mAh/g (when normalized by the total mass of all the active electrode particles, conductive additives and binders) or in the range from about 800 to about 3000 mAh/g (when normalized by the mass of the composite anode particles only).
  • an average size e.g., average diameter
  • specific surface area in the range from about 0.5 to about 50 m 2 /g normalized by the mass of the (nano)composite anode particles and, in the case of Si-compri
  • cells comprising anode electrodes based on high-capacity nanocomposite anode particles or powders (comprising conversion- or alloying-type active anode materials) that experience certain volume changes during cycling (moderately high volume changes (e.g., an increase by about 8 - about 180 vol. % or a reduction by about 8 – about 70 vol. %) during the first charge- discharge cycle and moderate volume changes (e.g., about 4 - about 50 vol.
  • the addition of some known SEI-forming additives may improve SEI stability during cycling but may induce undesirable electrolyte oxidation on the cathode (particularly at higher voltages or elevated temperature), resulting in gassing, cell swelling and reduced cycle and calendar life.
  • the addition of some known cathode solid electrolyte interphase (CEI)-forming additives may induce Attorney Docket No. SN-0076WO protective film formation on the cathode, reducing further electrolyte oxidation and gassing, but often at the expense of reduced SEI stability on the anode or other undesirable effects.
  • L-HCEs may improve the stability of the SEI without inducing undesirable electrolyte oxidation on the cathode.
  • L-HCEs may reduce the rate of undesirable electrolyte oxidation on the cathode, and in some designs may increase desirable electrolyte oxidation reactions on the cathode which prevent other gas generating electrolyte reactions from happening, for example, by forming a CEI.
  • cells comprising anode electrodes based on Si-nanocomposite and graphite particles or powders, may benefit from electrolytes which exhibit moderate to minimal fluoroethylene carbonate (FEC) mole concentration, moderate to none ethylene carbonate (EC), and low-to-none vinylene carbonate (VC) concentration, wherein low to minimal is about 5 mol % to 0.5 mol %, low to none is about 5 mol % to 0 mol %, and moderate to none is about 20 mol % to 0 mol %.
  • FEC, VC, and EC are examples of cyclic carbonates.
  • some electrolytes with lower concentrations of FEC and VC may exhibit longer cycle life, reduced high-temperature outgassing on the cathode, decreased voltage hysteresis, reduced SEI resistance, higher energy throughput (i.e., total energy stored by the battery cell during its lifetime), and decreased battery self-heating during operation.
  • swelling of binder(s) in electrolyte(s) depends not just on the binder composition(s), but may also depend on the electrolyte composition(s). Furthermore, in some designs, such swelling (and the resulting performance reduction) often correlates with the reduction in elastic modulus upon exposure of binders to electrolytes.
  • the reduction in binder modulus by over about 15-20 % may result in a noticeable reduction in performance.
  • the reduction in the binder modulus by about two times (2x) may result in a substantial performance reduction.
  • the reduction in modulus by about five or more times e.g., about 5x-500x
  • selecting an electrolyte composition that does not induce significant binder swelling may Attorney Docket No. SN-0076WO be highly preferential for certain applications.
  • an electrolyte composition that reduces the binder modulus by less than about 30 % (more preferably, by no more than about 10 %) when exposed to electrolyte.
  • anodes which comprise more than one binder composition in some designs, it may be preferred to select an electrolyte composition where at least one binder does not reduce the modulus by over about 30 % (more preferably, by no more than about 10 %) when exposed to electrolyte.
  • binders with functional groups which do not chemically or electrochemically interact with the electrolyte components such as Li salts, FEC, VC, co-solvents, Li salt additives, and HT storage additives.
  • the inventors have found that in some designs the presence of carboxylic acid groups in the binders can cause excessive outgassing during the HT storage test. It may be advantageous in some designs to use a greater amount of branched esters in ELY formulations to cut HT outgassing. In some implementations, it may be desirable to have a branched ester composition in a range of about 10-30 mol. %, about 20-50 mol. %, or about 40-70 mol. % of the ELY formulation. [00117] In one or more embodiments of the present disclosure, it may be advantageous to have a total salt concentration in the electrolyte in the range from about 8 mol. % to about 22 mol.
  • Salt concentrations in the electrolyte that are too low may lead to excessive HT outgassing, reduced ELY conductivity, increased charge-transfer resistance in some designs (e.g., when high- capacity anode materials are used).
  • Higher salt concentration in the electrolyte may lead to reduced cycle life stability.
  • Such reduced cycle life stability characteristics may be related to reduced mobility of Li + cations in the electrolyte in some designs and, in some designs, the formation of poor SEI.
  • Higher salt concentration may also lead to increased electrolyte density, increased viscosity, decreased conductivity, and increased cost in some designs, which may be undesirable for some applications including low temperature performance. Higher salt concentrations may also lead to faster charging and discharging rates, which may be beneficial for some applications. Such improved rate performance may be related to the reduced anode and cathode charge-transfer resistance despite low Attorney Docket No. SN-0076WO electrolyte conductivity. Such improved rate performance may be beneficial for low temperature applications. Higher salt concentration may also lead to reduced high- temperature (HT) outgassing during the HT storage test.
  • HT high- temperature
  • Such improved outcome of the HT storage test may be related to the higher concentration of salt and formation of fluoride protective layer on the surface of the cathode, which may impede other chemicals from the oxidative decomposition.
  • improved HT storage outcome may be due to better the formation of an SEI that is more resistant to high-temperature outgassing reactions.
  • the optimal salt concentration may depend on the particular cell design and electrolyte composition.
  • One aspect of the present disclosure is directed to an electrolyte for a lithium- ion battery.
  • the electrolyte comprises a lithium salt composition, a solvent composition, and a diluent composition.
  • the lithium salt composition may preferably comprise lithium bis(fluorosulfonyl)imide (LiFSI) (shown as 202 in FIG.2) as a primary lithium salt.
  • a mole fraction of the primary lithium salt (e.g., LiFSI) in the electrolyte may preferably be in a range of approximately 8 mol. % to approximately 22 mol. % (e.g., in some designs, in a range of about 10 mol. % to about 20 mol. %).
  • a mole fraction (concentration) of the primary lithium salt in the electrolyte may preferably be in a range of approximately 4 mol.
  • the electrolyte may comprise one or more additional salts with a total salt mole fraction of approximately 8 mol. % to approximately 22 mol. % (e.g., in some designs, in a range of about 10 mol. % to about 20 mol. %.
  • a higher molarity (or a higher mole fraction) of certain salt(s) such as LiFSI
  • a higher molarity (or a higher mole fraction) of salt(s) may be advantageous to use to improve the operation of electrolyte at low temperatures, such as from about -30 o C to about +10 o C.
  • a higher molarity (or a higher mole fraction) of certain salts may lead to poor charge and discharge rate capability.
  • the molarity (or mole fraction) of the salt is too high, the operation of the electrolyte at lower Attorney Docket No. SN-0076WO temperatures may be degraded.
  • the primary salt may be one of the following: lithium bis(fluorosulfonyl)imide (LiFSI), LiPF 6 , lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium trifluoromethanesulfonate (LiOTf, LiOSO 2 CF 3 ), LiSO 3 F (LSF), LiClO 4 , LiAsF 6 , LiBF 4 , and lithium difluoro(oxalato)borate (LiDFOB).
  • LiFSI lithium bis(fluorosulfonyl)imide
  • LiPF 6 lithium bis(trifluoromethanesulfonyl)imide
  • LiTFSI lithium trifluoromethanesulfonate
  • LiOTf lithium trifluoromethanesulfonate
  • LSF LiSO 3 F
  • LiClO 4 LiAsF 6 , LiBF 4
  • LiDFOB lithium difluoro(oxalato)
  • the primary salt has a major contribution (e.g., about 15-20% or more of the total current carried by the salt’s cations and anions) to the conductivity of the electrolyte, and/or comprises about 8-20 mol. % of the electrolyte, or about 10 to about 20 mol. % of the electrolyte.
  • the electrolyte may also comprise a total of 0.01-9 mol. % of one, two or more secondary salts.
  • These secondary salts may comprise one or more of LiPF 6 , LiFSI, LiTFSI, lithium difluoro(oxalato)borate (LiDFOB), lithium difluoro(bisoxalato)phosphate (LiDFBOP), lithium tetrafluoro(oxalato)phosphate (LiTFOP), lithium trifluoromethanesulfonate (LiOTf), LiSO 3 F (LSF), Li 3 PS 4 , Li 6 PS 5 Cl, lithium tris(fluorosulfonyl)methide (LTFSM), LiBF 4 , lithium bis(oxalate)borate (LiBOB), lithium tetracyanoborate (LiBison), lithium dicyano-trifluoromethyl-imidazole (LiTDI), lithium dicyano-(pentafluoroethyl)imidazole (LiPDI), lithium bis(fluoromalanoto)borate (LiBFMB), lithium di
  • the primary salt does not provide sufficient ionic conductivity or does not form sufficiently stable anode SEI or cathode CEI or does not form sufficiently ionically conductive anode SEI or cathode CEI at low or room temperature or does not Attorney Docket No. SN-0076WO provide sufficient thermal stability of the SEI or CEI or does not offer other important benefits, an additional salt may be added at relatively high concentrations (> about 3 mol. %) to improve the electrolyte conductivity or SEI or CEI properties.
  • the primary salt composition preferably does not contain LiPF 6 , due to its thermal decomposition at high temperatures, reducing the battery cell’s high-temperature stability and calendar life.
  • the electrolyte may comprise ⁇ about 1 mol. % of one, two, three or more non-Li alkali metal cation (e.g., Na), alkaline earth (e.g., Mg), Yttrium (Y), lanthanum (La) and lanthanide metal variants of the discussed above lithium primary or secondary salts, even if the electrolyte is intended for a Li-ion battery.
  • non-Li alkali metal cation e.g., Na
  • alkaline earth e.g., Mg
  • Yttrium Y
  • La lanthanum
  • the electrolyte may additionally include additives (additive compounds) such as charge-transfer additives which may reduce the charge- transfer resistance at the anode and/or cathode.
  • Li salt additives as well as some other compounds may function as charge-transfer additives.
  • suitable Li salt additives may include but not limited to: lithium difluorophosphate (LiPO 2 F 2 or LFO), lithium tetrafluoroborate (LiBF 4 ), lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium fluorosulfate (LiSO 3 F), lithium difluoro(oxalato)borate (LiDFOB), and lithium bis(oxalato)borate (LiBOB).
  • LiPFI lithium tetrafluoroborate
  • LiFSI lithium bis(fluorosulfonyl)imide
  • LiTFSI lithium bis(trifluoromethanesulfonyl)imide
  • LiSO 3 F lithium fluorosulfate
  • LiDFOB lithium difluoro(oxalato)borate
  • charge-transfer additives that are not Li salts are methyl 2,2-difluoro-2- (fluorosulfonyl)acetate (MDFA), dimethyl sulfite (DMS), and triisopropyl phosphate (TIP).
  • MDFA 2,2-difluoro-2- (fluorosulfonyl)acetate
  • DMS dimethyl sulfite
  • TIP triisopropyl phosphate
  • additives that function as high-temperature storage additives which may suppress high-temperature outgassing (e.g., caused by electrolyte components such as VC) may be employed as well.
  • high-temperature storage additives are: 1,3,2-dioxathiolane 2,2-dioxide (DTD) and methylene methanedisulfonate (MMDS), to name a few.
  • DTD 1,3,2-dioxathiolane 2,2-dioxide
  • MMDS methylene methanedisulf
  • a mole fraction (concentration) of the additives may be in a range of approximately 0.1 mol. % to approximately 6 mol. %.
  • a mole fraction (concentration) of the additives may be in Attorney Docket No. SN-0076WO a range of approximately 0.5 mol. % to approximately 1.5 mol. %.
  • a mole fraction (concentration) of the additive lithium salt(s) in the electrolyte may preferably be in a range of approximately 0.05 M to approximately 0.15 M.
  • secondary salts used as charge-transfer additives can also comprise Na or other alkali metal cations or Mg or other alkaline earth metal cations instead of a Li cation, even if the electrolyte is intended for use in a Li-ion battery.
  • High-temperature outgassing (HT gassing) in a battery cell is an undesirable phenomenon that is observed to result from a heat treatment (also referred to as high- temperature storage treatment) of the battery cell after it has been charged to a high state- of-charge (SOC).
  • the temperature of the heat treatment can vary depending on the specific heat treatment implementation, e.g., about 80 o C, about 72 oC, about 60 oC, and other temperatures in a range of about 50 oC to about 90 oC.
  • the duration of the heat treatment can also vary depending on the specific heat treatment implementation, e.g., about 10 days, about 7 days, about 3 days, about 2.5 days, about 2 days, and other durations. [00125] A measurement of the volume of the gases formed in the cell constitutes a metric for the high-temperature outgassing test.
  • the volume of the gases in the cell at atmospheric pressure (“gas volume”) is compared to the initial volume of the cell before the high- temperature storage treatment under a high state-of-charge (SOC).
  • the gas volume preferably does not exceed about 20 vol. % of the initial volume of the cell.
  • the gas volume preferably does not exceed about 12 vol. % of the initial volume of the cell.
  • the gas volume preferably does not exceed about 3 vol. % of the initial volume of the cell.
  • the gas volume preferably does not exceed about 1 vol.
  • the solvent composition includes one or more compounds that help to solvate the lithium salt composition.
  • a compound that is employed in the solvent composition may be referred to as a "main co-solvent” (alternatively referred to as a “primary solvent”) when the mole fraction of that compound is greater than each Attorney Docket No. SN-0076WO of the other compounds in the solvent composition.
  • the solubility of a primary salt in the solvent composition may preferably be equal or higher than about 1.5 M.
  • co-solvents that more strongly coordinate salts are preferable due to higher conductivity (leading to higher rate capability).
  • the compounds of the solvent composition preferably do not vaporize from the electrolyte mixture at temperatures below about 60 to about 80 °C. In some implementations, some vaporization of electrolyte components may be permitted if the cell container is able to withstand the high pressure from gases inside the cell. In some implementations, the compounds of the solvent composition preferably do not solidify or precipitate from the electrolyte mixture at temperatures above about -30 to about -10 °C.
  • a higher mole fraction of the co-solvents will increase the conductivity of the electrolyte, and may increase the rate capability of the battery cell.
  • a preferred solvent composition for a Li-ion battery electrolyte may include at least one linear carbonate (LC).
  • linear carbonates include: dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC).
  • DMC dimethyl carbonate
  • EMC ethyl methyl carbonate
  • DEC diethyl carbonate
  • a preferred solvent composition for a lithium-ion battery electrolyte may include DMC as a main co-solvent.
  • the molecular weights of these linear carbonate compounds are about 90.08 g/mol (DMC), about 104.10 g/mol (EMC), and about 118.13 g/mol (DEC), respectively.
  • DMC linear carbonate dimethyl carbonate
  • EMC electrolyzed carbonate
  • DEC linear carbonate dimethyl carbonate
  • the solvent composition includes a linear carbonate dimethyl carbonate (DMC), shown as 204 in FIG.2.
  • DMC may constitute at least about 60 wt. % (e.g., about 60 - about 70 wt. %, about 70 - about 80 wt. Attorney Docket No. SN-0076WO %, about 80 - about 90 wt. %, about 90 - about 95 wt. %, about 95 - about 99 wt. %, or about 99 - about 100 wt. %) of the solvent composition.
  • the mole fraction (concentration) of the DMC in the electrolyte may be in a range of about 35 mol. % to about 65 mol. % (e.g., in a range of about 35 mol.
  • the solvent composition of the preferable L-HCE may include one, two or more ester compound(s) selected from the following: (i) linear esters such as ethyl propionate (EP), ethyl acetate (EA), methyl butyrate (MB), methyl propionate (MP), methyl acetate (MA), propyl acetate (PA), methyl formate (MF), butyl formate (BF), butyl acetate (BA), amyl formate, methyl caproate, ethyl valerate, propyl butyrate, butyl propionate, amyl acetate, hexyl formate, propyl propionate, methyl propionat
  • the total mole fraction (concentration) of all the ester compounds in the electrolyte may be in a range of about 5 mol. % to about 75 mol. % (e.g., in a range of about 1 mol. % to about 5 mol. %, or in a range of about 5 mol. % to about 15 mol. %, or Attorney Docket No. SN-0076WO in a range of about 15 mol. % to about 25 mol. %, or in a range of about 25 mol. % to about 45 mol.
  • the total wt. fraction (concentration) of all the ester compounds of the solvent composition may range from about 30 wt. % to about 100 wt. % (in some designs, from about 30 wt. % to about 50 wt. %; in other designs, from about 50 wt.
  • a suitable composition of ester compounds in the L-HCE may contribute to better ionic conductivity in the electrolyte, better discharge rate capability, better fast charge performance, reduced HT outgassing, reduced end-of-life outgassing, better calendar life, and/or better low-temperature performance.
  • a mole fraction of esters may be in the range of about 1 mol. % to about 75 mol. %.
  • EP shown as 206 in FIG.2 may offer a good balance of stability, solubility, and rate capability.
  • EP may constitute at least about 60 wt. % (e.g., about 60 - 70 wt. %, about 70 - 80 wt. %, about 80 - 90 wt. %, about 90 - 95 wt. %, about 95 - 99 wt. %, or about 99 - 100 wt. %) of the solvent composition.
  • the mole fraction (concentration) of the EP in the electrolyte may be in a range of about 40 mol. % to about 70 mol. % (e.g., in a range of about 40 mol. % to about 50 mol. %, or in a range of about 50 mol. % to about 60 mol. %, or in a range of about 60 mol. % to about 70 mol. %). In some implementations in which EP is employed in the solvent composition, the mole fraction (concentration) of the EP in the electrolyte may be in a range of about 35 mol. % to about 40 mol. %.
  • the mole fraction (concentration) of the EP in the electrolyte may be in a range of about 60 mol. % to about 70 mol. %.
  • Attorney Docket No. SN-0076WO [00132]
  • the solvent composition in a suitable L-HCE may comprise one or more cyclic carbonates (in some designs, in addition to other suitable co- solvents, such as esters) such as: vinylene carbonate (VC), vinylene ethylene carbonate (VEC), fluoroethylene carbonate (FEC), ethylene carbonate (EC), and propylene carbonate (PC).
  • a mole fraction (concentration) of the VC in the electrolyte may be in a range of about 0.05 mol. % to about 2.00 mol. % (e.g., from about 0.05 mol. % to about 0.5 mol.%; or from about 0.5 mol.% to about 1 mol. %; or from about 1 mol. % to about 2 mol.%).
  • a mole fraction (concentration) of the FEC in the electrolyte may be in a range of about 0.1 mol. % to about 20 mol. % (e.g., from about 0.1 mol.
  • % to about 0.5 mol. % or from about 0.5 mol. % to about 1 mol. %; or from about 1 mol. % to about 2 mol. %; or from about 2 mol. % to about 4 mol. %; or from about 4 mol. % to about 6 mol. %; or from about 6 mol. % to about 8 mol. %; from about 8 mol. % to about 10 mol. %; from about 10 mol. % to about 15 mol. %; from about 15 mol. % to about 20 mol. %).
  • a mole fraction (concentration) of the EC in the electrolyte may be in a range of 1 mol. % to 5 mol. %.
  • a mole fraction (concentration) of the PC in the electrolyte may be in a range of about 1 mol. % to about 20 mol. %.
  • a total mole fraction of the cyclic carbonates in the electrolyte may be in a range of about 0.05 to about 6 mol. %.
  • the cyclic carbonates may be considered as being present in the electrolyte at additive-level concentrations.
  • a total mole fraction of the cyclic carbonates in the electrolyte may be in a range of about 6 to about 12 mol. %.
  • a total mole fraction of the cyclic carbonates in the electrolyte may be in a range of about 12 to 20 mol. %.
  • a total mole fraction of the cyclic carbonates in the electrolyte may be in a range of about 20 to 30 mol. %.
  • a concentration of FEC in the electrolyte may be in a range of approximately 0.1 mol. % to approximately 30 mol. %.
  • concentration of FEC in the electrolyte is too low (e.g., in some implementations, less Attorney Docket No. SN-0076WO than approximately 1 mol. % or, in other implementations, about 0.1 to about 1 mol. % or, in other implementations, below about 0.1 mol. %)
  • the cycle life may degrade undesirably fast because of insufficient amount of suitable SEI builders.
  • FEC concentrations may undesirably be accompanied by increased high-temperature outgassing, as well as lower discharge voltages (due to the overly resistive SEI formation) and/or increased viscosity of the electrolyte (due to the high viscosity of FEC).
  • Lower discharge voltages typically result in lower volumetric energy densities (VEDs), and higher viscosities result in lower ionic conductivities.
  • the FEC concentration should preferably be set to below a certain threshold (e.g., mol. % threshold) in some designs.
  • the FEC concentration should preferably not exceed approximately 30 mol. %.
  • the FEC concentration preferably does not exceed approximately 6 mol.
  • the L-HCE solvent composition includes VC, and the mole fraction of VC in the electrolyte is in the range of about 0.1 to about 4 mol. %. In some implementations, the mole fraction of VC is preferably in the range of about 0.1-1 mol. %. In some implementations, the mole fraction of VC is preferably in the range of about 1-4 mol. %. In some designs, within a preferred concentration range (e.g., mole fraction in a range of about 0.1 mol. % to about 1 mol. %, or mole fraction in a range of about 1 mol.
  • the presence of VC in the electrolyte may contribute to a preferable balance of good cycle life, good ionic conductivity, and high discharge voltage.
  • the electrolyte comprises a low composition of VC (e.g., about 0.1-1 mol.%) to improve the calendar life, High T stability of the electrolyte, and charge-transfer resistance (which reduces rate capability, especially at lower temperatures).
  • EC ethylene carbonate
  • EC can be used as an SEI "builder” to build SEI, which helps to improve cycle life.
  • EC may provide better cycle life by being used in combination with Attorney Docket No. SN-0076WO other SEI “builder” compounds. In some implementations, EC may be more suitable as a SEI “builder” when graphite particles are blended into the anode. In some implementations, a good balance between cycle life, ionic conductivity, discharge voltage, and low-temperature performance can be achieved when the mole fraction of EC in the electrolyte is about 0.5 mol. % to about 1 mol. %, about 1 mol. % to about 5 mol. %, or about 5 mol. % to 15 mol. %.
  • the solvent composition comprises non-fluorinated ethers (e.g., dimethoxyethane (also referred to as ethylene glycol dimethyl ether, DME), diethoxyethane, and dipropyl ether).
  • ethers including non- fluorinated ethers
  • ethers may be preferable as co-solvents due to their electrochemical stability to reduction at the anode, especially when oxidation reactions at the cathode are passivated by other means.
  • non-fluorinated ethers may not be preferable due to their electrochemical instability to oxidation at the cathode.
  • an electrolyte comprises about 10-20 mol.
  • an electrolyte comprises about 20-50 mol. % of non-fluorinated ethers. In yet other implementations, an electrolyte comprises about 50-70 mol. % of non- fluorinated ethers.
  • the L-HCE solvent composition may comprise one, two or more ethers (including non-fluorinated ethers), such as: diethyl ether, 2-methoxy-2-methylpropane, dipropyl ether, diisopropyl ether, butyl ethyl ether, ethyl tert-butyl ether, 1-propoxybutane, ethyl pentyl ether, butyl isopropyl ether, sec-butyl isopropyl ether, ethylene glycol dimethyl ether (also referred to as dimethoxyethane, DME), and diethoxyethane, to name a few.
  • ethers including non-fluorinated ethers
  • Ethers exhibit very low density, very low melting point and very low viscosity, which may enhance cell performance at high rates or low temperatures or may help reduce electrolyte mass and thus increase gravimetric energy density (specific energy) of batteries. Ethers, however, may exhibit reduced stability at high electrochemical potentials and thus may be more suitable for cells comprising lower voltage cathodes or when cathode surface is well passivated with other co-solvent molecules.
  • Attorney Docket No. SN-0076WO [00138]
  • a total weight fraction of ether co-solvents in the L-HCE may range from about 1 wt. % to about 2 wt. %; in other designs, the total weight fraction may range from about 2 wt.
  • the total weight fraction may range from about 3 wt. % to about 5 wt. %; in other designs, the total weight fraction may range from about 5 wt. % to about 10 wt. %; in other designs, the total weight fraction may range from about 10 wt. % to about 20 wt. %; in other designs, the total weight fraction may range from about 20 wt. % to about 40 wt. %; in other designs, the total weight fraction may range from about 40 wt. % to about 60 wt. %; in other designs, the total weight fraction may range from about 60 wt. % to about 70 wt. %.
  • the L-HCE solvent composition may comprise one, two or more ketones, such as: methyl ethyl ketone (MEK), diethyl ketone (DEK), methyl isopropyl ketone (MiPK), ethyl isopropyl ketone (EiPK), diisopropyl ketone, pinacolone (MtBK), diisobutyl ketone (DiBK), methyl sec-butyl ketone (MsBK), and hexamethylacetone (HMA).
  • ketones such as: methyl ethyl ketone (MEK), diethyl ketone (DEK), methyl isopropyl ketone (MiPK), ethyl isopropyl ketone (EiPK), diisopropyl ketone, pinacolone (MtBK), diisobutyl ketone (DiBK), methyl sec-butyl ketone (M
  • ketones also have low viscosity, resulting in fast Li + diffusion and high conductivity which leads to high rate capability.
  • ketones are often not used as electrolyte solvents due to their instability with the electrodes and/or salts.
  • the mole fraction of ketones in the electrolyte may be limited to about 0.1-5 mol. % or about 5-20 mol. % because they may excessively swell or dissolve one or more electrode binder polymers, such as polyvinylidene difluoride (PVDF).
  • PVDF polyvinylidene difluoride
  • ketones may contribute higher than additive amounts (e.g., greater than about 5 mol. %) to the electrolyte composition.
  • ketones may reduce HT gassing and improve the ionic conductivity of the salt, improving rate capability.
  • ketones may not be compatible with some graphite anodes because the strong association with the Li + ion causes the solvents to co-intercalate, causing the graphite particles to degrade via co- intercalation.
  • an electrolyte preferably comprises ketones at a mole fraction in a range of about 0.01-5 mol. %. In other implementations, an electrolyte preferably comprises ketones at a mole fraction in a range of about 5-20 mol. %. In yet Attorney Docket No.
  • an electrolyte preferably comprises ketones at a mole fraction in a range of about 20-50 mol. %. In yet other implementations, an electrolyte preferably comprises ketones at a mole fraction in a range of about 50-75 mol. %.
  • the L-HCE solvent composition may advantageously comprise one, two or more nitriles or other nitrogen (N) - comprising solvents (with one, two, three, four or more N atoms per molecule), including but not limited to: nitriles (e.g., acetonitrile (ACN), trimethylacetonitrile (TMAN), 2-oxo-1,3-dioxolane-4-carbonitrile (ECCN), cyclopropylacetonitrile (CPAN), ethylene glycol bis(propionitrile)ether (EGBE), fumaronitrile (FM), succinonitrile, glutaronitrile, adiponitrile (ADN), 1,3,6- hexanetricarbonitrile (HTCN)), pyridine-boron trifluoride (PBF), 3-fluoro pyridine-boron trifluoride (3F-PBF), pyrazine-boron trifluoride, triethylamine, tri
  • N nitrogen
  • Nitriles tend to have strong dipole moments and high dielectric constants, and often make great solvents for salts.
  • nitriles tend to be used in limited quantities in Li-ion batteries due to instability to reduction at the anode, often destabilizing the SEI, and instability to oxidation at the cathode. Yet, some of such effects may be mitigated.
  • nitriles a present in an electrolyte at only additive levels (e.g., about 0.01-5 mol. %) to prevent HT gassing reactions from occurring or to protect against overcharging the cathode to too high of a voltage.
  • nitriles may be used at higher mole fractions (concentrations) if surface and/or salt reactions are passivated.
  • an electrolyte may comprise nitrile molecules at a mole fraction of about 0.01-5 mol. % as an additive.
  • an electrolyte may comprise nitrile molecules at a mole fraction of about 5-20 mol. %.
  • an electrolyte may comprise nitrile molecules at a mole fraction of about 20-50 mol. %.
  • an electrolyte may comprise nitrile molecules at a mole fraction of about 50-70 mol. %.
  • the L-HCE solvent composition may comprise one, two, three or more of other types of N-containing solvents, such as amides.
  • suitable amides may include, but are not limited to: dimethylacetamide (DMAc), hexamethylphosphoramide (HMPA), N,N-dimethyl trifluoromethanesulfonamide (DMTMSA), N,N-diethyl-trifluoromethanesulfonamide, Attorney Docket No. SN-0076WO N,N-dimethyl fluorosulfonamide, and carbamides (also referred to as ureas) (e.g., tetramethylurea).
  • DMAc dimethylacetamide
  • HMPA hexamethylphosphoramide
  • DMTMSA N,N-dimethyl trifluoromethanesulfonamide
  • SN-0076WO N,N-dimethyl fluorosulfonamide and carbamides (also referred to as ureas)
  • the solvent composition preferably comprises HMPA as it dissolves Li metal and delays cell short circuiting from Li dendrites.
  • an electrolyte may comprise amides at a mole fraction in a range of about 0.1-5 mol. % as an additive. In other implementations, an electrolyte may comprise amides at a mole fraction in a range of about 5-20 mol. %. In yet other implementations, an electrolyte may comprise amides at a mole fraction in a range of about 20-50 mol. %. In yet other implementations, an electrolyte may comprise amides in a range of about 50- 70 mol. %.
  • the L-HCE solvent composition may comprise one, two, or more nitroalkanes, such as: nitromethane (NM), nitroethane (NE), trinitromethane, tetranitromethane, 2-nitropropane (2NP), 1-nitropropane (1-NP), dinitromethane, hexanitroethane (HNE), heptanitrocubane (HNC), and trifluoro- nitrobenzenes (C 6 H 2 F 3 NO 2 ), to provide a few illustrative examples.
  • the L-HCE solvent composition may also comprise hydrazinium nitroformate (HNF).
  • nitroalkanes have high dielectric constants, improving the conductivity of the electrolyte and thus improving the rate capability. Nitroalkanes may release very large amounts of energy when oxidized however, thus commonly limiting their use to additive quantities (e.g., about 0.001-5.000 mol.%) in many embodiments.
  • a solvent composition may preferably comprise nitroalkanes to form a more stable SEI.
  • an electrolyte may comprise nitroalkane molecules at a mole fraction in a range of about 0.001-0.1 mol. %, about 0.1-1 mol. %, about 1-2 mol. %, or about 2-5 mol. %.
  • an electrolyte may comprise nitroalkanes at a mole fraction in a range of about 5-20 mol. %, about 20-50 mol. %, or about 50-70 mol. %.
  • a total weight fraction of N-containing solvents in the L-HCE may range from about 0.05 wt. % to about 0.2 wt.%; in other designs, a total weight fraction may range from about 0.2 wt. % to about 0.4 wt. %; in other designs, a total weight fraction may range from about 0.4 wt. % to about 0.8 wt. %; in other designs, a total weight fraction may range from about 0.8 wt.
  • a total weight fraction may range from about 2 wt. % to about 3 wt. %; in other designs, a total weight fraction may range from about 3 wt. % to about 5 wt. %; in other designs, Attorney Docket No. SN-0076WO a total weight fraction may range from about 5 wt. % to about 10 wt. %; in other designs, a total weight fraction may range from about 10 wt. % to about 20 wt. %; in other designs, a total weight fraction may range from about 20 wt. % to about 40 wt. %; in other designs, a total weight fraction may range from about 40 wt.
  • the L-HCE solvent composition may advantageously comprise one, two, or more P-comprising co-solvents, such as phosphites and/or phosphates, for example.
  • Suitable phosphates include trimethyl phosphate (TMP), triethyl phosphate (TEP), tripropyl phosphate (TPrP), triisopropyl phosphate (TIP), triphenyl phosphate (TPP), triallyl phosphate (TAP), tris(2,2,3,3,3- pentafluoropropyl) phosphate (5F-TPrP), tris(1,1,1,3,3,3-hexafluoropropan-2-yl) phosphate (HFiP), and diisopropyl fluorophosphate, to name a few.
  • Suitable phosphites include tris(trimethylsilyl)phosphite (TMSPi), tris(2,2,2- trifluoroethyl) phosphite (TTFPi), triphenyl phosphite (TPPi), tris(1,1,1,3,3,3- hexafluoropropan-2-yl) phosphite (THFPP), and tris(trimethylsilyl) phosphite, to name a few.
  • phosphates may be preferable due to their endothermic decomposition reactions, because they reduce the cell self-heating from decomposition at high temperatures.
  • phosphorus-containing co-solvents are preferable due to flammability suppression via radical neutralization.
  • carbonate-based solvents produce hydrogen radicals upon heating, which further react with oxygen to produce oxygen free radicals. This triggers the generation of more free radicals, leading to a self sustaining fire.
  • phosphorus radicals which are part of the electrolyte decomposition products, can react with hydrogen radicals and inhibit the radical linear chain reaction, suppressing the combustion of the electrolyte solvent by acting as radical scavengers.
  • Some phosphates are some of the most inexpensive and widely used flame retardant compounds (e.g., TEP (triethyl phosphate), TPP (triphenyl phosphate), TPrP (tripropyl phosphate), and DMMP (dimethyl methylphosphonate)).
  • TEP triethyl phosphate
  • TPP triphenyl phosphate
  • TPrP tripropyl phosphate
  • DMMP dimethyl methylphosphonate
  • alkyl phosphates have been known as fire- retardants when studied as co-solvents (typically around 40% vol for non-flammability) due to their high Li salt solvability and the wide range of operating temperatures, reducing the flammability of conventional electrolytes.
  • phosphates may not be preferable due to their low stability to reduction at the anode.
  • phosphates may comprise a major fraction of the solvent composition if the anode has been sufficiently stabilized.
  • phosphates (such as TIP, fluorophosphates, etc.) may preferably comprise the electrolyte to reduce the charge- transfer resistance of the anode anode/or cathode of the Li-ion battery, thus improving the rate capability especially at low temperatures.
  • an electrolyte may comprise phosphates at a mole fraction in a range of about 0.01-5.00 mol.
  • an electrolyte may comprise phosphates at a mole fraction in a range of about 5-20 mol. % of the electrolyte. In other implementations, an electrolyte may comprise phosphates at a mole fraction in a range of about 20-40 mol. % of the electrolyte. In yet other implementations, an electrolyte may comprise phosphates at a mole fraction in a range of about 40-70 mol. % of the electrolyte. [00145] In some designs, a total weight fraction of P-containing solvents in L-HCE may range from about 0.01 wt.
  • a total weight fraction may range from about 0.1 wt. % to about 0.2 wt. %; in other designs, a total weight fraction may range from about 0.2 wt. % to about 0.4 wt. %; in other designs, a total weight fraction may range from about 0.4 wt. % to about 0.8 wt. %; in other designs, a total weight fraction may range from about 0.8 wt. % to about 2 wt. %; in other designs, a total weight fraction may range from about 2 wt. % to about 3 wt. %; in other designs, a total weight fraction may range from about 3 wt.
  • the solvent composition comprises one, two or more sulfur (S) - containing molecules.
  • Some of such molecules may be liquid at room temperature. Some of such molecules may be solid at room temperature (thus typically used in smaller amounts in batteries operating at room temperatures). Some of such molecules may additionally comprise P, B or N, in some designs. Illustrative examples of Attorney Docket No.
  • SN-0076WO suitable S-containing molecules include, but are not limited to: sulfites (e.g., dimethyl sulfite (DMS), trimethylene sulfite, ethylene sulfite(ESi)), sulfones (e.g., ethyl methyl sulfone, ethyl isopropyl sulfone (EIS), dimethyl sulfone, ethylmethyl sulfone, ethyl 3- (methylsulfonyl)propanoate, 2-(ethylsulfonyl)aniline, 6-(ethylsulfonyl)-1,3- benzoxazole-2-thiol, ethyl isopropyl sulfone, 4-ethylsulfonylbenzaldehyde, 2- (ethylsulfonyl)ethanamine, 1-(ethanesulfonyl)-4-
  • sulfur-containing molecules may be preferable to form polymeric SEI and/or CEI to stabilize the anode and/or cathode respectively for improved cycle life and/or reduced HT gassing.
  • an electrolyte comprises sulfur-containing molecules at a mole fraction in a range of about 0.01-5 mol. % of the electrolyte. In other implementations, an electrolyte comprises sulfur-containing molecules at a mole fraction in a range of about 20-50 mol. % of the electrolyte. In yet other implementations, an electrolyte comprises sulfur-containing molecules at a mole fraction in a range of about 50-70 mol. % of the electrolyte.
  • a total weight fraction of S-containing solvents in the L-HCE may range from about 0.01 wt. % to about 0.1 wt.%; in other designs, a total weight fraction may range from about 0.1 wt. % to about 0.2 wt. %; in other designs, a total Attorney Docket No. SN-0076WO weight fraction may range from about 0.2 wt. % to about 0.4 wt. %; in other designs, a total weight fraction may range from about 0.4 wt. % to about 0.8 wt. %; in other designs, a total weight fraction may range from about 0.8 wt. % to about 2 wt.
  • a total weight fraction may range from about 2 wt. % to about 3 wt. %; in other designs, a total weight fraction may range from about 3 wt. % to about 5 wt. %; in other designs, a total weight fraction may range from about 5 wt. % to about 10 wt. %; in other designs, a total weight fraction may range from about 10 wt. % to about 20 wt. %; in other designs, a total weight fraction may range from about 20 wt. % to about 40 wt. %; in other designs, a total weight fraction may range from about 40 wt. % to about 60 wt.
  • the solvent composition comprises one, two or more boron (B) - containing molecules. Some of such molecules may be liquid at room temperature. Some of such molecules may be solid at room temperature (thus typically used in smaller amounts in batteries operating at room temperatures). In some designs, B-containing molecules may comprise N, P, S, F or Si.
  • pyridine-boron trifluoride PPF
  • 3-fluoro pyridine-boron trifluoride 3F-PBF
  • pyrazine-boron trifluoride pyrazine-boron trifluoride
  • borate esters e.g., trimethyl borate, triethyl borate, triisopropyl borate, tri-tert-butyl borate, etc.
  • B- comprising co-solvents may enhance SEI or CEI stability, particularly at high temperatures, in some designs.
  • a total weight fraction of B-containing solvents in the L-HCE may range from about 0.01 wt.
  • a total weight fraction may range from about 0.1 wt. % to about 0.2 wt. %; in other designs, a total weight fraction may range from about 0.2 wt. % to about 0.4 wt. %; in other designs, a total weight fraction may range from about 0.4 wt. % to about 0.8 wt. %; in other designs, a total weight fraction may range from about 0.8 wt. % to about 2 wt. %; in other designs, a total weight fraction may range from about 2 wt. % to about 3 wt. %; in other designs, a total weight fraction may range from about 3 wt.
  • the solvent composition comprises one, two or more silicon (Si) - containing molecules.
  • Si silicon
  • Illustrative examples of such molecules may include Attorney Docket No. SN-0076WO but are not limited to: (i) siloxanes (e.g., hexamethyldisiloxane, octamethyltrisiloxane, etc.); (ii) silanes (e.g., diphenyl silane, etc.).
  • a total weight fraction of Si-containing solvents in the L- HCE may range from about 0.1 wt. % to about 0.2 wt.
  • a total weight fraction may range from about 0.2 wt. % to about 0.4 wt. %; in other designs, a total weight fraction may range from about 0.4 wt. % to about 0.8 wt. %; in other designs, a total weight fraction may range from about 0.8 wt. % to about 2 wt. %; in other designs, a total weight fraction may range from about 2 wt. % to about 3 wt. %; in other designs, a total weight fraction may range from about 3 wt. % to about 5 wt. %; in other designs, a total weight fraction may range from about 5 wt. % to about 10 wt.
  • a mole fraction (concentration) of the solvent composition in the electrolyte may be in a range of about 25 mol. % to about 75 mol. % (e.g., in a range of about 25 mol.
  • a molar ratio of the solvent composition to the LiPF 6 salt may be in a range of about 0.1 to about 5 (e.g., about 0.1 to about 0.5; or about 0.5 to about 1; or about 1 to about 2, or about 2 to about 3, or about 3 to about 4 or about 4 to about 5).
  • a molar ratio of the solvent composition to the LiTFSI may be in a range of about 0.1 about to about 5 (e.g., about 0.1 to about 0.5; or Attorney Docket No. SN-0076WO about 0.5 to about 1; or about 1 to about 2, or about 2 to about 3, or about 3 to about 4 or about 4 to about 5).
  • a molar ratio of the solvent composition to the LiFSI may be in a range of about 0.1 to about 5 (e.g., about 0.1 to about 0.5; or about 0.5 to about 1; or about 1 to about 2, or about 2 to about 3, or about 3 to about 4 or about 4 to about 5).
  • the L-HCE includes a diluent composition.
  • the diluent composition preferably includes compounds in which the electrolyte’s salt(s) (e.g., LiFSI, among many others listed herein) have solubility of less than about 0.3 M.
  • the compounds of the diluent composition are preferably sufficiently stable against reduction at the anode and oxidation at the cathode, either by being unreactive or by undergoing passivation reactions.
  • the compounds of the diluent composition preferably do not vaporize from the electrolyte mixture at temperatures below about 60 to about 80 °C. In some cases, some vaporization of electrolyte components may be acceptable if the cell container is able to withstand the high pressure from gases formed inside the cell.
  • the compounds of the diluent composition preferably do not solidify or precipitate from the electrolyte mixture at temperatures above about -30 to about -10 °C.
  • At least half (by weight) of the diluent composition exhibit a melting point or a glass transition temperature below about - 30 °C (in some designs, from about -120 °C to about -90 °C; in other designs, from about -90 °C to about -70 °C; in other designs, from about -70 °C to about -50 °C; in other designs, from about -50 °C to about -30 °C).
  • the diluent composition may comprise a fluorinated ether (e.g., 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), melting point of about -94 °C), or an alkane (e.g., heptane, melting point of about -90.6 °C).
  • TTE 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether
  • an alkane e.g., heptane, melting point of about -90.6 °C
  • the diluent composition in the L-HCE electrolyte
  • the diluent composition in the L-HCE may be in the range of about 5-75 mol. % (e.g., in the range of about 5-15 mol. %, about 15-25 mol. % or about 25-35 mol.
  • the diluent composition may include one, two or more fluorinated ethers.
  • fluorinated ethers include, but are not limited to: 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), bis(2,2,2-trifluoroethyl) ether (BTFE), 1,1,2,2-tetrafluoroethyl-2,2,2,3-tetrafluoropropyl ether (an isomer of TTE), tris(2,2-difluoroethyl) orthoformate (TDFEO), bis(2,2- difluoroethyl)ether, tris(2,2,2-trifluoroethyl) orthoformate (TFEO), 2-(2,2- difluoroethoxy)-1,1-difluoroethane, 1-(2,2-difluoroethoxy)-1,1-difluoroethane, 1-(2,2- difluoroethoxy)-1,1-difluoroethane, 1,1,1,2,2-tetra
  • Illustrative examples of chemical formulas for the suitable fluorinated ethers may include, but are not limited to: CHF 2 CF 2 -O-CH 3 , CHF 2 CF 2 -O-CH 2 CH 3 , CHF 2 CF 2 CH 2 -O-CH 3 , CF 3 CF 2 CF 2 -O-CH 3 , CF 3 CF 2 CH 2 -O-CHF 2 , CHF 2 CF 2 CH 2 -O- CHF 2 , CF 3 CHFCF 2 -O-CH 2 CH 3 , CF 3 CHFCF 2 -O-CH 2 CF 3 , CF 3 CHFCF 2 -O-CH 2 CF 3 , CF 3 CHFCF 2 -O-CHFCF 3 , CF 3 CHFCF 2 -O-CH 2 CF 2 CH 2 F, or CF 3 CHFCF 2 -O-CH 2 CF 2 CH 2 F, to name a few.
  • fluorinated ethers such as TTE may be preferable due to chemical and electrochemical stability at both the anode and the cathode.
  • a mole fraction of the fluorinated ether(s) in the electrolyte is in a range of about 20-35 mol. %. In other implementations, a mole fraction of the fluorinated ether(s) in the electrolyte is in a range of about 5-20 mol. %.
  • the diluent composition includes 1,1,2,2- tetrafluoroethyl-2,2,3,3-tetrafluropropyl ether (TTE), shown as 208 in FIG. 2.
  • TTE may constitute at least about 90 wt. % (e.g., about 90 - about 95 wt. %, about 95 - about 99 wt. %, or about 99 - about 100 wt. %) of the diluent composition.
  • the mole fraction (concentration) of the TTE in the electrolyte may be in a range of about 15 mol. % to about 40 mol. % (e.g., in a range of about 15 mol. % to about 25 mol. %, or in a range of about 25 mol. % to about 40 mol. %).
  • the mole fraction (concentration) Attorney Docket No. SN-0076WO of the TTE in the electrolyte may be in a range of about 40 mol. % to about 55 mol. %.
  • a molar ratio of solvent composition to the TTE is in a range of about 1 to about 5 (e.g., about 1 to about 2, about 2 to about 3, about 3 to about 4, or about 4 to about 5).
  • the diluent composition may comprise one, two or more amines (including fluorinated amines).
  • fluorinated amines include, but are not limited to: trimethylamine, triethylamine, tripropylamine, di- isopropylamine, perfluorotriethylamine ((CF 3 CF 2 ) 3 N) (and other similarly structured amines (e.g., perfluoromethyldiethylamine (CF 3 CF 2 ) 2 CF 3 N), perfluoroethyldimethylamine (CF3CF2)1(CF3)2N), among others)), trifluoroethylamine (TFEAm), trifluoropropylamine (TFPAm, C 3 H 6 F 3 N), pentafluoropropylamine (PFPAm, C 3 H 4 F 5 N), trifluoromethylamine (CF 3 NH 2 ), heptafluorobutylamine (HFBAm, C 4 H 4 F 7 N), nonafluoropentylamine (NFPAm, C 5 H 4 F 9 N), 2,2,
  • the solvent composition may comprise one, two, or more amines.
  • suitable fluorinated amines include, but are not limited to: methylamine, fluoromethylamine, trifluoromethylamine, difluoroethylamine, and diethylamine, among others.
  • a mole fraction of the fluorinated amine(s) in the L- HCE (electrolyte) is in a range of about 0.1-75 mol. % (in some implementations, in a range of about 0.1-5 mol. %; in other implementations, in a range of about 5-15 mol.
  • the solvent composition may comprise one, two, or more sulfonyl fluorides. Sulfonyl fluorides may have the added benefit of forming a stable Attorney Docket No. SN-0076WO SEI on the anode and/or CEI on the cathode.
  • Suitable sulfonyl fluorides include, but are not limited to: 5-oxooxolane-3-sulfonyl fluoride, methyl 2,2- difluoro-2-(fluorosulfonyl)acetate (MDFA), pyrrolidine-1-sulfonyl fluoride (C 4 H 8 FNO 2 S), N-ethyl-N-methylsulfamoyl fluoride (C 3 H 8 FNO 2 S), (1E)-2-cyanoeth-1- ene-1-sulfonyl fluoride (NC 3 H 2 SO 2 F), trifluoromethylpropane sulfonyl fluoride (C 3 H 6 F 4 SO 2 ), fluoroethane sulfonyl fluoride (C 2 H 4 F 2 O 2 S), perfluorobutane sulfonyl fluorides, perfluorohexane sulfonyl fluorides, perflufluorobut
  • fluorinated sulfonyl fluorides may be advantageous because of their exceptional inertness against the cathode for any reaction other than the CEI forming reaction.
  • an electrolyte comprises about 1-10 mol. % of sulfonyl fluorides. In other implementations, an electrolyte comprises about 10-20 mol. % of sulfonyl fluorides. In yet other implementations, an electrolyte comprises about 20-50 mol. % of sulfonyl fluorides. In yet other implementations, an electrolyte comprises about 50-70 mol.
  • the diluent composition of L-HCE may comprise one, two or more alkanes, including fluorinated alkanes.
  • alkanes include, but are not limited to: heptanes (C 7 H 16 ), octanes (C 8 H 18 ), nonanes (C 9 H 20 ), fluoroheptanes, difluorooctanes (C 8 H 16 F 2 ), fluorononanes (C 9 H 19 F), other alkanes with the general formula C p H 2p+2 , where p is an integer between 7 and 20 (e.g., in some implementations, between 5 and 20); and other fluorinated alkanes with the general formula C q H q1 F q2 , in which q is an integer between 6 and 20 (e.g., in some implementations,
  • alkanes may reduce undesirable high-temperature (HT) outgassing (especially on charged cells) and minimize the undesirable increase in cell internal resistance due to exposure to high temperature.
  • non-fluorinated alkanes may be advantageous compared to fluorinated diluents due to their relative chemical and electrochemical stability, low density (allowing high gravimetric energy density), better long-term environmental impact (e.g., no C-F bonds) and lower cost.
  • alkanes may be preferable due to their weak intermolecular forces, decreasing the electrolyte viscosity and increasing the rate capability through faster diffusion and conductivity.
  • a mole fraction of the alkane(s) (including fluorinated alkane(s)) in the L-HCE (electrolyte) is in a range of about 0.1-75 mol. % (in some implementations, in a range of about 0.1-5 mol. %; in other implementations, in a range of about 5-15 mol. %; in other implementations, in a range of about 15-25 mol. %; in yet other implementations, in a range of about 25-35 mol. %; in yet other implementations, in a range of about 35-50 mol. %; in yet other implementations, in a range of about 50-75 mol. %).
  • alkanes may have limited solubility (miscibility) with the other components of the electrolyte, and may make up a relatively small fraction (e.g., mole fraction) of the electrolyte.
  • a relatively small fraction e.g., mole fraction
  • the maximum miscibility of heptane in this electrolyte is about 17 mol. %.
  • one, two, or more aromatics may be employed in the electrolyte.
  • the respective aromatic may function as a diluent or a solvent.
  • the diluent (or solvent) composition may comprise one, two or more aromatics.
  • such aromatics suitable for use in electrolytes may comprise side groups.
  • at least some of the suitable aromatics are liquid at room temperature.
  • at least some of the suitable aromatics are solid at room temperature.
  • the suitable aromatics include heteroaromatic compounds.
  • suitable aromatics may comprise Si, B, P, N and/or O.
  • Suitable aromatics compounds include, but are not limited to: benzene, fluorobenzene (FB), difluorobenzenes (C 6 H 4 F 2 ), Attorney Docket No. SN-0076WO trifluorobenzenes (C 6 H 3 F 3 ), tetrafluorobenzenes (C 6 H 2 F 4 ), pentafluorobenzenes (C 6 H 1 F 5 ), trifluorotoluenes (TFT), bis(trifluoromethyl)benzenes (C 8 H 4 F 6 ), and bis(difluoromethyl)benzenes (C 8 H 6 F 4 ).
  • one or more of the foregoing aromatics may be used in a diluent composition.
  • one or more of certain aromatics that are ring-fluorinated pyridines e.g., fluoropyridines (C 5 H 4 FN), difluoropyridines (C 5 H 3 F 2 N), trifluoropyridines (C 5 H 2 F 3 N), tetrafluoropyridines (C 5 HF 4 N), etc.
  • ring-fluorinated pyridines e.g., fluoropyridines (C 5 H 4 FN), difluoropyridines (C 5 H 3 F 2 N), trifluoropyridines (C 5 H 2 F 3 N), tetrafluoropyridines (C 5 HF 4 N), etc.
  • aromatics may be effectively used for overcharge protection of the cathode because they can be oxidized at the cathode.
  • aromatics may help to reduce HT gassing and the increase in cell internal resistance due to exposure to high temperature.
  • aromatics may be used at higher mole fractions in the electrolyte.
  • fluorinated aromatics may be preferable due to their greater electrochemical stability towards oxidation reactions at the cathode that generate gas, especially at higher temperatures (e.g., > about 40 °C).
  • a mole fraction of aromatic molecules in an electrolyte may be in a range of about 0-5 mol. %, about 5-15 mol. %, about 15-35 mol. %, about 35-50 mol. %, or about 50-75 mol. %.
  • Many good candidate molecules for the diluent composition are fluorinated. Fluorinated organics have the performance advantage of forming a very stable C-F bond (in particular against oxidation at the cathode), while fluorine is the lightest halide element, minimizing the increase in solvent density (an increase in solvent density would lead to a decrease in the gravimetric energy density of the cell).
  • Fluorinated organic molecules may have higher boiling points due to higher molar mass. Solvents which do not dissolve salt tend to have intermolecular forces dominated by dispersion forces and have low dielectric constant (i.e., only weakly shield the electric field between the salt anion and cation). Apart from aromatics and alkanes, molecules with slightly higher dielectric constants may be modified by fluorination to reduce the dielectric constant and be used as a diluent, such as in the case of ethers. Attorney Docket No.
  • the presence of certain surface passivating salts (e.g., LiFSI or LiDFOB, among many others) and/or diluents (e.g., TTE, among many others) in a L-HCE (electrolyte) may reduce the need for other SEI builders, enabling electrolytes that comprise FEC, VC, and/or EC at relatively low mole fractions while attaining high cycle life.
  • the electrolyte comprises LiFSI at a mole fraction in a range of about 10 mol. % to about 25 mol. % (e.g., in a range of about 10 to about 15 mol.
  • the primary salt e.g., LiTFSI, LiOTf, or LiFSI in certain cases, or others
  • the primary salt may cause corrosion of the Al current collector of the cathode, if the total salt mole fraction (concentration) is too low and the diluent mole fraction (concentration) is not sufficiently high.
  • the electrolyte may comprise one or more aluminum passivating salts (e.g., LiPF 6 ) as a secondary salt at sufficiently high concentrations (e.g., in some implementations, such as the examples shown in FIG.11, a concentration of about 0.6 M of LiPF 6 in the electrolytes was found to be sufficient to obtain significant beneficial effects on performance characteristics such as first-cycle efficiency; in other implementations, concentrations higher than or lower than about 0.6 M may be needed) to passivate the aluminum current collector against the primary salt.
  • one or more aluminum passivating salts e.g., LiPF 6
  • sufficiently high concentrations e.g., in some implementations, such as the examples shown in FIG.11, a concentration of about 0.6 M of LiPF 6 in the electrolytes was found to be sufficient to obtain significant beneficial effects on performance characteristics such as first-cycle efficiency; in other implementations, concentrations higher than or lower than about 0.6 M may be needed
  • the electrolyte of the lithium-ion battery may suffer from low rate capability and high cell resistance when cycled at room (or lower) temperatures, which may result in one or more of the following battery characteristics: low discharge voltage, low cycle life, low calendar life, high HT gassing, and inferior low-temperature performance.
  • a cell may induce a high voltage on the cathode, causing unwanted oxidation reactions such as those that cause non-Li metals to be removed from the cathode active material, unwanted gases to be evolved, and/or current collector corrosion.
  • the anode and/or cathode may degrade more rapidly due to some particles Attorney Docket No. SN-0076WO undergoing more volume change than others.
  • the cell may degrade through the plating of Li metal at the anode. As such, an L-HCE composition needs to be carefully optimized for a particular cell design and battery operating conditions.
  • L-HCE conductivity larger than about 3 mS/cm at (e.g., typical) operating temperatures (in some designs, larger than about 4 mS/cm; in other designs, larger than about 5 mS/cm; in other designs, larger than about 6 mS/cm; in other designs, larger than about 7 mS/cm; in other designs, larger than about 8 mS/cm; in other designs, larger than about 9 mS/cm; in other designs, larger than about 10 mS/cm; in other designs, larger than about 12 mS/cm; in other designs, larger than about 15 mS/cm).
  • typical operating temperatures in some designs, larger than about 4 mS/cm; in other designs, larger than about 5 mS/cm; in other designs, larger than about 6 mS/cm; in other designs, larger than about 7 mS/cm; in other designs, larger than about 8 mS/cm; in other designs, larger than about 9 mS
  • a lithium-ion battery may include an anode current collector, a cathode current collector, an anode disposed on and/or in the anode current collector, a cathode disposed on and/or in the cathode current collector, and any one of the electrolytes as described herein ionically coupling the anode and the cathode.
  • anode current collector e.g., in a range of about 20 °C to about 30 °C.
  • the anode can comprise (A) Si-comprising particles (e.g., Si-C nanocomposite particles comprising carbon and silicon which contribute to about 75-100 wt. % of such particles (e.g., (1) with the silicon part being arranged as active material particles and the carbon forming an inactive or substantially inactive part of scaffolding matrix with pores (sometimes referred to as porous carbon) in which the silicon active material is disposed therein, and/or (2) with the silicon part being arranged as active materials particles in the composite particles and a carbon coating or a carbon shell being arranged around the composite particles) and/or (B) graphitic carbon particles comprising carbon (e.g., with carbon-comprising graphite as an active material) and being substantially free of silicon.
  • Si-comprising particles e.g., Si-C nanocomposite particles comprising carbon and silicon which contribute to about 75-100 wt. % of such particles (e.g., (1) with the silicon part being arranged as active material particles and the carbon
  • the silicon may be present in the composite particles as nanosized silicon and/or nanostructured silicon.
  • the anode may contain a mixture of (A) silicon-carbon nanocomposite particles and (B) graphitic carbon particles.
  • the anode is Attorney Docket No. SN-0076WO sometimes referred to as a blended anode herein.
  • a mass of the silicon may be in a range of about 10 wt. % to about 90 wt. % of a total mass of the anode (not counting the weight of the current collector).
  • the anode may additionally include carbon nanotubes (e.g., single-wall carbon nanotubes or double- wall carbon nanotubes or multi-wall carbon nanotubes) at a concentration of less than about 1 wt. % of the anode (not counting the weight of the current collector).
  • the anode may include carbon black particles at a concentration of more than about 1 wt. % of the anode (not counting the weight of the current collector).
  • the anode may include graphene (e.g., multi-layered / multi-walled graphene), graphene oxide (e.g., multi-layered / multi-walled graphene) or exfoliated graphite particles at a concentration of more than about 1 wt. % of the anode (not counting the weight of the current collector).
  • the diluent composition may improve the rate capability, reduce HT gassing, improve low temperature performance, improve calendar life, and reduce the cost. Rate capability and low temperature performance may be improved through the lowering of the viscosity of the electrolyte and the reduction of the charge-transfer resistance at the anode and cathode.
  • the diluent composition may be inert to reduction at the anode, oxidation at the cathode, and chemical decomposition through interaction with a salt or other organic and inorganic components.
  • TTE is one such example of a diluent compound that exhibits beneficial effects.
  • the diluent can promote self-passivating reactions, forming stable SEI at the anode and CEI at the cathode to prevent undesirable reactions.
  • a test pouch-type Li-ion battery cell with capacity of about 0.22 Ah may comprise: (i) an anode with Si-C nanocomposite active material particles (with specific reversible capacity of about 1500 mAh/g when normalized to the mass of the anode without the current collector foil) casted on Cu current collector foil from a water-based suspension comprising a polyacrylic acid Attorney Docket No.
  • LCO LiCoO 2
  • a test pouch-type Li-ion battery cell with capacity of about 0.54 Ah may comprise: (i) an anode with Si-C nanocomposite active material particles (with specific reversible capacity of about 1500 mAh/g when normalized to the mass of the anode without the current collector foil) casted on Cu current collector foil from a water-based suspension comprising a polyacrylic acid based binder and a carbon black conductive additive, (ii) a cathode with single crystalline high-Ni NCM (approximately LiNi 0.8 Co 0.1 Mn 0.1 O 2 ) active material particles casted on Al current collector foil from an organic solvent suspension comprising a polyvinylidene fluoride (PVDF)
  • PVDF polyvinylidene fluoride
  • a test pouch-type Li-ion battery cell with capacity of about 0.155 Ah may comprise: (i) an anode with Si-C nanocomposite active material particles (with specific reversible capacity of about 1500 mAh/g when normalized to the mass of the anode without the current collector foil) casted on Cu current collector foil from a water-based suspension comprising a poly(vinyl alcohol) based binder and a carbon black conductive additive, (ii) a cathode with LCO (LiCoO 2 ) active material particles casted on Al current collector foil from an organic solvent suspension comprising a polyvinylidene fluoride (PVDF)-based binder and a carbon black conductive additive, anode:cathode areal capacity ratio of about 1.1:1 and cycle start areal capacity loading of about 2.7 mAh/cm 2 , charge voltage of about 4.2V, (iii) a polyethylene separator, and (i
  • a test pouch-type Li-ion battery cell with capacity of about 0.165 Ah may comprise: (i) an anode with Si-C nanocomposite active material particles (with specific reversible capacity of about 1500 mAh/g when normalized to the mass of the anode without the current collector foil) casted on Cu current collector foil from a water-based suspension comprising a poly(vinyl alcohol) based binder and a carbon black conductive additive, (ii) a cathode with LCO (LiCoO 2 ) active material particles casted on Al current collector foil from an organic solvent suspension comprising a polyvinylidene fluoride (PVDF)-based binder and a carbon black conductive additive, anode:cathode areal capacity ratio of about 1.1:1 and cycle start areal capacity loading of about 2.7 mAh/cm 2 , charge voltage of about 4.4V, (ii)
  • Table 1 shows some illustrative combinations of salt and solvent that were found to be soluble at a molar ratio of about 1:2 respectively, when mixed at room temperature ( ⁇ 25°C). The ratio of moles salt to liters of solvent is shown as a rough estimate of the molar concentration of the resulting mixture. Solvents were added to salts and left to mix for approximately 16 hours in a bench top automatic rocking platform shaker. The electrolytes were then observed for results (solubility) using a flashlight to make sure that all of the salt had fully dissolved. The salt composition was deemed soluble if no visible salt was seen or no reflections from the salts were seen while using the flashlight, and the liquid was clear.
  • FIGS. 5 and 7 show the results of HT storage testing with various example electrolytes in Cell Designs A and B, respectively.
  • the cells underwent a first charge- discharge cycle with a 0.1 C current, with the ratio of discharge/charge capacity defined as the first-cycle efficiency (504, 704).
  • Cells of Cell Design A were charged to an upper cutoff voltage of 4.4 V and then discharged to 2.5 V, while cells of Cell Design B were charged to an upper cutoff voltage of 4.2 V and then discharged to 2.5 V.
  • the cells were then charged at 0.2C to an intermediate voltage of 4.0 V or 3.5 V for cell Designs A and B, respectively, degassed under vacuum, and resealed.
  • the cells then underwent a second cycle at 0.2C, including a constant voltage hold after the 0.2C charge at their respective upper cutoff voltages until the current fell to 0.05C (referred to as a 0.2C ⁇ 0.05C charge).
  • Attorney Docket No. SN-0076WO The discharge capacity of this cycle is defined as the “initial capacity.”
  • the cells were then finally charged a third time at 0.2C ⁇ 0.05C to their respective upper cutoff voltages.
  • the cells AC resistances were then measured and their internal volumes were measured using the Archimedes method.
  • Cells of Cell Design A were then stored at 72 ⁇ C for 60h, while cells of Cell Design B were stored at 60 ⁇ C for 72h.
  • the AC resistances and cell volumes were then measured after the storage period – the change in internal resistance ( ⁇ R) (506, 706) and volume change metrics (502, 702) in FIGS.5 and 7 are defined as the change in these values between the pre- and post-storage measurements.
  • the cells were then discharged to 2.5 V at 0.2C – the ratio of this discharge capacity to the initial capacity is defined as the “residual capacity” (508, 708) in FIGS.5 and 7.
  • the cells then underwent another 0.2C ⁇ 0.05C charge to their upper cutoff voltages and a 0.2C discharge to 2.5V.
  • the ratio of this discharge capacity to the initial capacity is defined as the “recoverable capacity” (510, 710) in FIGS.5 and 7.
  • Factors such as L-HCE composition, the so-called “formation protocol” (temperature, charge and discharge rates, constant current vs. pulsed current vs. oscillating current during initial charging, etc.), anode particle surface chemistry, binder chemistry, etc., affect the composition and properties of the SEI on the anode particle surfaces and the CEI on the cathode particle surfaces.
  • L-HCE composition in particular, may have a significant impact on the SEI and CEI composition and be selected to tune SEI composition and microstructure to be more favorable.
  • inorganic Li-containing nanoparticles in the suitable or preferable Si-comprising anode particles commonly leads to higher cell stability and better cell performance characteristics.
  • higher volume and mass fractions of LiF (e.g., in the form of LiF nanoparticles) in the suitable or preferable Si-comprising anode particles’ SEI commonly leads to higher cell stability and better cell performance characteristics (e.g., higher calendar life, higher cycle stability, better performance at elevated temperatures, better performance at room or low temperatures, etc.).
  • LiF LiF
  • Si-comprising anode particles SEI commonly leads to higher cell stability and better cell performance characteristics.
  • More uniform distribution of LiF (e.g., in the form of LiF nanoparticles) in the SEI on suitable or preferable Si-comprising Attorney Docket No. SN-0076WO anode particles may lead to higher cell stability and better cell performance characteristics. For example, formation of a high fraction of LiF on the outer surface of the SEI with prolonged cycling (e.g., after about 500 full charge-discharge cycles) may be undesirable.
  • the SEI on the suitable or preferable Si-comprising anode particles may comprise Li 2 O (e.g., in the form of Li 2 O nanoparticles) (e.g., to attain higher calendar life, higher cycle stability, better performance at elevated temperatures, better performance at room or low temperatures, etc.).
  • Li 2 O e.g., in the form of Li 2 O nanoparticles
  • Higher volume and mass fractions of Li 2 O (e.g., in the form of Li 2 O nanoparticles) in the near-particle fraction of the SEI on suitable or preferable Si-comprising anode particles SEI may lead to higher cell stability and better cell performance characteristics.
  • Li 2 O e.g., in the form of Li 2 O nanoparticles
  • the SEI on the suitable or preferable Si-comprising anode particles may comprise Li 2 S or Li 2 Se or both (e.g., in the form of Li 2 S or Li 2 Se or mixed nanoparticles) (e.g., to attain higher calendar life, higher cycle stability, better performance at elevated temperatures, better performance at room or low temperatures, etc.).
  • Li 2 S or Li 2 Se or both e.g., in the form of Li 2 S or Li 2 Se or mixed nanoparticles
  • SEI near-particle fraction of the SEI on suitable or preferable Si-comprising anode particles SEI
  • More uniform distribution of Li 2 S or Li 2 Se or both (e.g., in the form of Li 2 S or Li 2 Se or mixed nanoparticles) in the SEI on suitable or preferable Si-comprising anode particles may lead to higher cell stability and better cell performance characteristics.
  • the SEI on the suitable or preferable Si-comprising anode particles may comprise both LiF and at least one other Li-comprising inorganic component (e.g., Li 2 O or Li 2 S or Li 2 Se or Li 3 N or their various mixtures and combinations; in the Li 2 O case in the form of Li 2 O and LiF nanoparticles; in some designs, with Li 2 O and LiF having an intimate contact with each other; in some designs, in the form of composite or intermixed Li 2 O-LiF nanoparticles; in the Li 2 S case in the form of Li 2 S and LiF nanoparticles; in some designs, with an intimate contact with each other; in some designs, in the form of composite or intermixed Li 2 S-LiF nanoparticles, etc.).
  • Li 2 O or Li 2 S or Li 2 Se or Li 3 N or their various mixtures and combinations e.g., Li 2 O or Li 2 S or Li 2 Se or Li 3 N or their various mixtures and combinations; in the Li 2 O
  • the SEI formed within the first about 50 cycles may comprise about 10-75 wt. % inorganic components (in some designs, from about 10 to about 20 wt.%; in other designs, from about 20 to about 30 wt.%; in other designs, from about 30 to about 40 wt.%; in other designs, from about 40 to about 50 wt.%; in other designs, from about 50 to about 60 wt.%; in other designs, from about 60 to about 75 wt.%). In some designs, it may be preferable for the SEI formed within the first 50 cycles to comprise about 2-50 wt.
  • the SEI formed within the first about 50 cycles may comprise about 2-50 wt. % Li 2 O (in some designs, from about 2 to about 5 wt.%; in other designs, from about 5 to about 10 wt.%; in other designs, from about 10 to about 20 wt.%; in other designs, from about 20 to about 50 wt.%).
  • the SEI formed within the first about 50 cycles may comprise about 2-50 wt. % Li 2 O (in some designs, from about 2 to about 5 wt.%; in other designs, from about 5 to about 10 wt.%; in other designs, from about 10 to about 20 wt.%; in other designs, from about 20 to about 50 wt.%).
  • the SEI composition may be estimated from X-ray photoelectron spectroscopy (XPS), secondary emission mass spectrometry (SIMS) and many other suitable techniques (e.g., including those by using synchrotron measurements).
  • FIG. 5 shows the results of HT storage testing in Cell Design A pouch cells with electrolytes ELY #1, ELY #2, and ELY #3.
  • the molar composition of the electrolytes is shown in Table 2 (FIG. 4).
  • ELY #1 is an example of an ester-based (comprising EI) electrolyte.
  • ELY #2 is an example of an electrolyte containing fluorobenzene (FB).
  • ELY #3 is an example of an electrolyte containing heptane.
  • Both ELY #2 and ELY #3 are examples of electrolytes containing weakly coordinating electrolyte molecules (i.e., diluents). Both ELY #2 and ELY #3 show slightly improved FCE over ELY #1, which could be due to the altered Li-ion solvation structure, increased contact ion pairs, and/or increased salt anion reduction at the anode increasing the LiF content in the anode SEI and improving the passivation of the anode parasitic reactions. ELY #2 shows a larger volume change (502, FIG. 5) than the other electrolytes during Attorney Docket No.
  • FIG. 7 shows the results of HT storage testing in Cell Design B pouch cells with electrolytes comprising ELYs #4 to #10.
  • the compositions of the electrolytes are shown in Table 3 (FIG.4).
  • the ELYs #4 to #9 are of the following general composition: about 0.95 M LiPF 6 and about 0.19 M LiFSI, dissolved in about 12 vol. % FEC, about 42.25 vol.
  • ELYs #4 to #9 the other co-solvents are hexamethylacetone (HMA) (ELY #5), trimethylacetonitrile (TMAN) (ELY #6), EP (ELY #7), and DMC (ELY #8); and the diluents are trifluorotoluene (TFT) (ELY #4), and FB (ELY #9) respectively.
  • ELY # 10 comprises about 0.95 M LiPF 6 and about 0.19 M LiFSI, dissolved in about 12 vol. % FEC, about 64.5 vol. % EP, about 1.5 vol. % VC, about 2.0 vol. % ADN, and about 20 vol. % n- heptane as diluent.
  • the compositions of the electrolytes ELY #4 - ELY #10 are also listed in Table 3 (FIG.6).
  • Example ELYs #4, #9, and #10 contain diluents (TFT, FB, and n-heptane, respectively).
  • the weakly coordinating diluents are able to reduce the total gas generation (as measured by cell volume change, 702) and internal resistance change ⁇ R during HT storage (706) compared to ELY #7 (EP) and ELY #8 (DMC), which could be due to the altered Li-ion solvation structure, increased contact ion pairs, and reduced salt anion oxidation at the cathode.
  • diluents are able to give high FCEs comparable to ELY #7 (EP) and ELY #8 (DMC), which may be due to the altered Li-ion solvation structure and increased contact ion pairs leading to reduced salt anion oxidation at the cathode and increased salt anion reduction at the anode, which could lead to the formation of a robust, passivating, mechanically stable anode SEI and/or cathode CEI containing a higher fraction of LiF, and/or other inorganic species such as Li 2 O and/or Li 2 CO 3 in electrolytes with weakly coordinating co-solvents.
  • Example ELY #5 contains HMA (a ketone), which reduces the total gas generation (as measured by cell volume change, 702), increases the residual capacity after HT storage (708), and gives comparable FCE (704) compared to ELY #7 (EP, a linear ester) and ELY #8 (DMC, a linear carbonate), which could be due to the formation of a robust, passivating cathode CEI in electrolytes containing ketones through oxidation of the ketone to insoluble products such as Li 2 CO 3 , Li 2 O, and organic polymers, which may reduce the rate of oxidation of other ELY components at high voltage.
  • HMA a ketone
  • Example ELY #6 contains a TMAN (a nitrile), which reduces the total gas generation (as measured by cell volume change, 702) and internal resistance change ⁇ R during HT storage (706), and gives comparable FCE (704) compared to ELY #7 (EP) and ELY #8 (DMC), which could be due to the formation of a robust, passivating, ionically conductive cathode CEI in electrolytes containing nitriles through decomposition of the nitrile to form insoluble products such as Li 3 N and organic polymers, which may reduce the rate of oxidation of other ELY components at high voltage and reduce buildup of resistive byproducts at the anode and cathode interfaces during HT storage.
  • TMAN a nitrile
  • FIG.9 shows the results of cycle life testing in example Cell Design C pouch cells with electrolytes comprising ELYs #11 to #31 and #36.
  • the cells underwent a first charge-discharge cycle with a 0.1 C current, with the ratio of discharge/charge capacity defined as the first-cycle efficiency (FCE) (906 in FIG.9).
  • the cells were charged to an upper cutoff voltage of 4.2 V and then discharged to 2.5 V.
  • the cells were then charged at 0.2C to an intermediate voltage of 4.0 V, degassed under vacuum, and resealed.
  • the cells then underwent a capacity check cycle with a 1C ⁇ 0.5C charge to 3.8V, followed by a 0.5C ⁇ 0.05C charge to 4.2V, followed by a 0.2C discharge to 2.5V.
  • the cells then underwent repeated cycling with the same charge protocol but followed by a 0.5C discharge to 2.5V.
  • the capacity-weighted average of the discharge voltage in the first 0.5C discharge cycle is plotted as the discharge voltage (expressed in V) (904) in FIG.9. For every 20th cycle, the cells were discharged at 0.2C to check the low-rate discharge Attorney Docket No. SN-0076WO capacity.
  • Example ELYs #11 to #35 are of the following generalized composition: about 1.15 M LiPF 6 dissolved in about 39 vol. % EP, about 2 vol. % VC, about 20 vol. % FEC, and about 39 vol. % of one other co-solvent/diluent.
  • ELYs #11 to #35 the other co-solvents/diluents are EI (ELY #11), HMA (ELY #12), 2-nitropropane (2NP) (ELY #13), diethyl ketone (DEK) (ELY #14), TMAN (ELY #15), EP (ELY #16), DMC (ELY #17), ethyl isopropyl sulfone (EIS) (ELY #18), sulfolane (Sl) (ELY #19), DMS (ELY #20), triethyl phosphate (TEP) (ELY #21), triisopropyl phosphate (TIP) (ELY #22), FB (ELY #23), TFT (ELY #24), ethylene sulfite (ESi) (ELY #25), pinacolone (MtBK) (ELY #26), diisobutyl ketone (DiBK) (ELY #27), ethyl
  • ELY #36 comprises about 1.15 M LiPF 6 dissolved in about 58 vol. % EP, about 2 vol. % VC, about 20 vol. % FEC, and about 20 vol. % heptane.
  • a summary of the additional co-solvent or diluent employed in ELYs #11-36 can be found in Table 4 (FIG.8).
  • Example ELYs #12 (HMA), #14 (DEK), #26 to #30 (MtBK, DiBK, EiPK, MiPK, MsBK, respectively), and #34 (MEK) contain ketones.
  • electrolytes containing the respective ketone co-solvents exhibit high cycle life characteristics (902) comparable to or greater than those of ELY #17 (DMC, a linear carbonate).
  • electrolytes containing the respective ketone co-solvents give high FCE values (906) comparable to those of ELY #16 (EP, a linear ester) and ELY #17 (DMC, a linear carbonate).
  • These properties may be due to the generation of passivating decomposition products in the anode SEI and/or cathode CEI such as Li 2 CO 3 , Li 2 O, and Attorney Docket No. SN-0076WO organic polymers in electrolytes containing ketones due to the reduction of the ketone at the anode and/or oxidation of the ketone at the cathode.
  • electrolytes containing the respective ketone co-solvents show high discharge voltage values (904) comparable to or greater than those of ELY #16 (EP, a linear ester) and ELY #17 (DMC, a linear carbonate). This may be due to the high dielectric constant and dipole moment of ketone co-solvents, which could increase ion dissociation in solution and increase ionic conductivity.
  • Example ELYs #13 (2NP) and #35 (NM) contain nitroalkane co-solvents, which show higher discharge voltage and much higher ionic conductivity compared to ELY #16 (EP, a linear ester) and ELY #17 (DMC, a linear carbonate).
  • Example ELYs #15 (TMAN) and #31 (CPAN) contain nitrile co-solvents and show high discharge voltages (904) comparable to or greater than those of ELY #16 (EP, a linear ester) and ELY #17 (DMC, a linear carbonate).
  • Example ELYs #18 (EIS) and #19 (Sl) contain sulfone co-solvents and show high cycle life characteristics (902) comparable to or greater than those of ELY #16 (EP, a linear ester) and ELY #17 (DMC, a linear carbonate).
  • Example ELYs #20 (DMS) and #25 (ESi) contain sulfite co-solvents and show much higher discharge voltages (904) and, in the case of DMS, higher ionic conductivities (Table 5, FIG.10) than those of ELY #16 (EP, a linear ester) and ELY #17 (DMC, a linear carbonate).
  • These properties may be due to the high dielectric constant and dipole moment of sulfite co-solvents, which may increase ion dissociation in solution and increase ionic conductivity. This may also be due to reduced interfacial resistance in sulfite-containing electrolytes, which may be due to the high ionic conductivity of the decomposition products in the anode SEI and/or cathode CEI such as Li 2 SO 3 , Li 2 SO 4 , Li 2 S, and polysulfides.
  • ELYs #20 (DMS) and #25 (ESi) show high cycle life characteristics (902) comparable to or greater than those of ELY #16 (EP, a linear ester) and ELY #17 (DMC, a linear carbonate). This may be due to the generation of passivating decomposition products in the anode SEI and/or cathode CEI such as Li 2 SO 3 , Li 2 SO 4 , Li 2 S, polysulfides, and organic polymers in electrolytes containing sulfites due to the reduction of the sulfite at the anode and/or oxidation of the sulfite at the cathode.
  • passivating decomposition products in the anode SEI and/or cathode CEI such as Li 2 SO 3 , Li 2 SO 4 , Li 2 S, polysulfides, and organic polymers in electrolytes containing sulfites due to the reduction of the sulfite at the anode and/or oxidation of the
  • Example ELYs #21 (TEP), #22 (TIP), and #33 (TMP) contain phosphate co- solvents.
  • TEP ELY #21
  • the cycle life 902 is high and comparable to that of ELY #17 (DMC, a linear carbonate)
  • TIP ELY #22
  • the FCE Attorney Docket No. SN-0076WO 906 is higher than those of ELY #16 (EP, a linear ester) and ELY #17 (DMC, a linear carbonate).
  • passivating decomposition products in the anode SEI and/or cathode CEI such as Li 3 PO 4 , Li 3 P, polyphosphates, and organic polymers in electrolytes containing phosphates due to the reduction of the phosphate at the anode and/or oxidation of the phosphate at the cathode.
  • Example ELYs #23 (FB), #24 (TFT), and #36 (heptane) contain diluents. These electrolytes exhibit high cycle life characteristics (902) and FCE values (906) comparable to or greater than those of ELY #16 (EP, a linear ester) and ELY #17 (DMC, a linear carbonate).
  • These properties may be due to the altered Li-ion solvation structure and increased concentration of contact ion pairs in solution, which may reduce the salt anion oxidation at the cathode and increase the anion reduction at the anode.
  • Increased anion reduction at the anode may increase the LiF content in the anode SEI, which may increase the mechanical stability of the SEI, reduce the reduction of other electrolyte components, and reduce capacity fade.
  • the weakly coordinating co-solvents (diluents) themselves may also contribute beneficial reduction and oxidation products to the anode SEI and cathode CEI upon their decomposition, such as LiF and organic polymers, which may further increase the passivation of the electrodes and reduce capacity fade.
  • FIG.11 shows the first-cycle efficiency (FCE) data of cells of Cell Design D, charged at 0.1C to 4.4V and discharged at 0.1C to 2.5V, filled with respective example electrolytes ELYs #37 to #43.
  • Example ELYs #37 to #43 are of the following general composition: about 11 mol.
  • the salt compositions for ELYs #37 to #43 were: about 11 mol. % LiPF 6 (ELY #37), about 11 mol. % LiFSI (ELY #38), about 5.5 mol. % LiPF 6 and about 5.5 mol. % LiFSI (ELY #39), about 11 mol. % lithium trifluoromethanesulfonate (LiOTf) (ELY #40), about 5.5 mol. % LiPF 6 and about 5.5 mol.
  • % LiOTf (ELY #41), about 11 mol. % LiTFSI (ELY #42), about 5.5 mol. % LiPF6 and about 5.5 mol. % LiTFSI (ELY #43).
  • the L-HCE may be preferable for the L-HCE to exhibit room- temperature density in a range from about 0.8 g/cc to about 1.8 g/cc (in some designs, from about 0.8 to about 1.2 g/cc; in other designs, from about 1.2 to about 1.4 g/cc; in other designs, from about 1.4 to about 1.6 g/cc; in yet other designs, from about 1.6 to about 1.8 g/cc).
  • Too low or too high density may undesirably limit various Li-ion battery cell characteristics (e.g., stability, high-rate performance, low temperature performance, charge rate, specific energy, etc.).
  • the L-HCE may be preferable for the L-HCE to exhibit room- temperature dynamic viscosity ( ⁇ ) in a range from about 0.5 cP to about 30 cP (in some designs, from about 0.5 cP to about 2.5 cP; in other designs, from about 2.5 cP to about 3.5 cP; in other designs, from about 3.5 cP to about 5 cP; in other designs, from about 5 cP to about 7.5 cP; in other designs, from about 7.5 cP to about 10 cP; in other designs, from about 10 cP to about 12.5 cP; in other designs, from about 12.5 cP to about 15 cP; Attorney Docket No.
  • SN-0076WO in other designs, from about 15 cP to about 20 cP; in other designs, from about 20 cP to about 25 cP; in other designs, from about 25 cP to about 30 cP).
  • selecting L-HCE composition to exhibit lower viscosity in some designs, by using lower salt fractions or higher fraction of lower viscosity co-solvents, etc. may generally be beneficial.
  • Room temperature viscosity that is too high may induce premature cell failure if charging at faster rates (e.g., by inducing uncontrolled or undesirable Li plating, SEI damages by nonuniform lithiation or delithiation of anodes, CEI or cathode particle damages by nonuniform lithiation or delithiation of cathodes or by other mechanisms, etc.).
  • higher L-HCE viscosity may enhance calendar life, reduce gassing, improve cycle stability and provide other performance benefits for cells with lower area capacity loadings or cells that operate at higher temperatures or cells that charge slower, etc.
  • An L-HCE viscosity that is too low (e.g., below about 0.5 cP) (which may be achieved, for example, by using very low viscosity co-solvents or diluents or by reducing salt concentration or by selecting specific salts and attaining low solvation size or low solvation energy, etc.) may also lead to undesirable cell performance characteristics (e.g., lower than desired calendar life or cycle life, worse than desired performance at high voltages or high temperatures, etc.).
  • the optimum L-HCE viscosity may depend on the particular anode and cathode chemistry, anode and cathode properties (e.g., active material particle size and specific surface area, active material crystal structure and grain size, electrode porosity, electrode tortuosity, binder chemistry and distribution, etc.), electrode areal capacity loadings, N-P ratio, typical charging or discharging rates, cell operating conditions (including temperature) and other factors.
  • anode and cathode properties e.g., active material particle size and specific surface area, active material crystal structure and grain size, electrode porosity, electrode tortuosity, binder chemistry and distribution, etc.
  • electrode areal capacity loadings
  • N-P ratio typical charging or discharging rates
  • cell operating conditions including temperature
  • the L-HCE may be preferable for the L-HCE to exhibit room- temperature conductivity (e.g., as determined by electrochemical impedance spectroscopy or other suitable measurements) in the range from about 2 to about 25 mS/cm (in some designs, from about 2 to about 5 mS/cm; in other designs, from about 5 to about 8 mS/cm; in other designs, from about 8 to about 11 mS/cm; in other designs, from about 11 to about 14 mS/cm; in other designs, from about 14 to about 18 mS/cm; in other designs, from about 18 to about 21 mS/cm; in other designs, from about 21 to about Attorney Docket No.
  • Both too high and too low conductivity may correlate with poor cell performance in cells comprising suitable L-HCE compositions.
  • the optimum conductivity may depend on the cell composition, design and operating conditions.
  • elevated operating temperature may be desirable for applications such as for propulsion of automobiles (e.g., cars, vans, buses, and trucks); stationary storage for residential, commercial, industrial, or grid use; or propulsion of manned/unmanned aircrafts or seacrafts.
  • elevated operating temperature may be achieved by means of a heat pump, resistive heating elements, self-heating, waste heat (e.g. from a hot process fluid or motor), or passive heating from the ambient environment.
  • the operating temperature may be in the range of about 40 to about 90 °C (e.g., about 40-45 °C, about 45-50 °C, about 50-55 °C, about 55-60 °C, about 60-65 °C, about 65-70 °C, about 70-75 °C, about 75-80 °C, about 80-85 °C, or about 85-90 °C).
  • the L-HCE may have a sufficiently high (at least about 10 °C above the operating temperature) boiling point to enable operation at elevated temperatures (about 40-90 °C) without the cell case rupturing due to vaporization of the electrolyte, and without a rigid enclosure to pressurize the electrolyte.
  • FIG. 12 shows a Table 6 listing the boiling points of certain compounds, which may function as co-solvents and/or diluents, ordered from low to high, as an illustrative example.
  • electrolytes with lower boiling points at atmospheric pressure may be acceptable if a rigid cell casing such as a cylindrical (e.g., 18650 cells, 21700 cells, 46xx format cells such as 4680 cells, etc.) or prismatic cell design (e.g., 40Ah, 80Ah, 150Ah, etc.) is used to allow the cell to operate at elevated pressures without the cell case rupturing.
  • the acceptable maximum internal pressure generated by the electrolyte may be elevated pressures in the range of about 1-1.2 bar, about 1.2-5 bar, about 5-10 bar, or about 10-20 bar in absolute terms.
  • the above-described exemplary particles may generally be of any shape (e.g., near-spherical or a spheroidal or an ellipsoid (e.g., including oblate spheroid), cylindrical, plate-like, have a random shape, etc.) and of any size.
  • the maximum size of the particle may depend on the rate performance requirements, on the rate of the ion diffusion into the partially filled particles, and/or on other parameters.
  • the average diffusion distance from the solid- electrolyte interphase (e.g., from the surface of the composite particles) to the inner core of the composite particles may be smaller than about 10 microns for the optimal performance.
  • Some aspects of this disclosure may also be applicable to cells with conventional intercalation-type electrodes (e.g., cathodes with no nickel or relatively small amounts of nickel, anodes with no silicon or relatively small amounts of silicon) and provide benefits of improved rate performance or improved stability or improved calendar life, particularly for electrodes with medium and high-capacity loadings (e.g., greater than about 3-4 mAh/cm 2 ).
  • medium and high-capacity loadings e.g., greater than about 3-4 mAh/cm 2
  • each dependent clause can refer in the clauses to a specific combination with one of the other clauses, the aspect(s) of that dependent clause are not limited to the specific combination. It will be appreciated that other example clauses can also include a combination of the dependent clause aspect(s) with the subject matter of any other dependent clause or independent clause or a Attorney Docket No. SN-0076WO combination of any feature with other dependent and independent clauses.
  • the various aspects disclosed herein expressly include these combinations, unless it is explicitly expressed or can be readily inferred that a specific combination is not intended (e.g., contradictory aspects, such as defining an element as both an electrical insulator and an electrical conductor).
  • a lithium-ion battery comprising: an anode current collector; a cathode current collector; an anode disposed on and/or in the anode current collector; a cathode disposed on and/or in the cathode current collector; and an electrolyte ionically coupling the anode and the cathode, the electrolyte comprising (1) a lithium salt composition and (2) a solvent composition, and (3) a diluent composition, wherein: the anode comprises composite particles comprising carbon and silicon, at least some of the silicon being nanosized silicon in the composite particles; the diluent composition comprises at least one aromatic compound and/or at least one alkane compound; and the at least one alkane compound is selected from (1) non-fluorinated alkane
  • the at least one aromatic compound is selected from: benzene, fluorobenzene (FB), difluorobenzenes (C 6 H 4 F 2 ), trifluorobenzenes (C 6 H 3 F 3 ), tetrafluorobenzenes (C 6 H 2 F 4 ), pentafluorobenzenes (C 6 H 1 F 5 ), trifluorotoluenes (TFT), bis(trifluoromethyl)benzenes (C 8 H 4 F 6 ), and bis(difluoromethyl)benzenes (C 8 H 6 F 4 ).
  • FB fluorobenzene
  • C 6 H 4 F 2 difluorobenzenes
  • C 6 H 3 F 3 trifluorobenzenes
  • tetrafluorobenzenes C 6 H 2 F 4
  • pentafluorobenzenes C 6 H 1 F 5
  • trifluorotoluenes TFT
  • the at least one alkane compound is selected from heptanes (C 7 H 16 ), octanes (C 8 H 18 ), nonanes (C 9 H 20 ), fluoroheptanes (C 7 H 15 F), difluorooctanes (C 8 H 16 F 2 ), and fluorononanes (C 9 H 19 F).
  • the at least one alkane compound is selected from heptanes (C 7 H 16 ), octanes (C 8 H 18 ), nonanes (C 9 H 20 ), fluoroheptanes (C 7 H 15 F), difluorooctanes (C 8 H 16 F 2 ), and fluorononanes
  • a mole fraction of the lithium salt composition in the electrolyte is in a range of 10 mol. % to 20 mol. %.
  • the lithium salt composition comprises a salt compound selected from lithium bis(fluorosulfonyl)imide (LiFSI), LiPF6, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium trifluoromethanesulfonate (LiOTf, LiOSO 2 CF 3 ), LiSO 3 F (LSF), LiClO 4 , LiAsF 6 , LiBF 4 , lithium difluoro(oxalato)borate (LiDFOB), lithium difluoro(bisoxalato)phosphate (LiDFBOP), lithium tetrafluoro(oxalato)phosphate (LiTFOP),
  • LiFSI lithium bis(fluorosulfonyl)imide
  • LiPF6 lithium bis(trifluoromethanesulfony
  • the solvent composition comprises fluoroethylene carbonate (FEC), a mole fraction of the FEC in the electrolyte being in a range of about 0.1 to about 20 mol. %.
  • FEC fluoroethylene carbonate
  • Clause 11 The lithium-ion battery of any of clauses 1 to 10, wherein: the solvent composition comprises a linear ester, a cyclic ester, and/or a branched ester.
  • the solvent composition comprises a ketone selected from: methyl ethyl ketone (MEK), diethyl ketone (DEK), methyl isopropyl ketone (MiPK), ethyl isopropyl ketone (EiPK), diisopropyl ketone, pinacolone (MtBK), diisobutyl ketone (DiBK), methyl sec-butyl ketone (MsBK), and hexamethylacetone (HMA).
  • a ketone selected from: methyl ethyl ketone (MEK), diethyl ketone (DEK), methyl isopropyl ketone (MiPK), ethyl isopropyl ketone (EiPK), diisopropyl ketone, pinacolone (MtBK), diisobutyl ketone (DiBK), methyl sec-butyl ketone (MsBK), and
  • the solvent composition comprises an ether selected from: diethyl ether, 2-methoxy-2- methylpropane, dipropyl ether, diisopropyl ether, butyl ethyl ether, ethyl tert-butyl ether, 1-propoxybutane, ethyl pentyl ether, butyl isopropyl ether, sec-butyl isopropyl ether, ethylene glycol dimethyl ether (DME), and diethoxyethane.
  • the solvent composition comprises an ether selected from: diethyl ether, 2-methoxy-2- methylpropane, dipropyl ether, diisopropyl ether, butyl ethyl ether, ethyl tert-butyl ether, 1-propoxybutane, ethyl pentyl ether, butyl isopropyl ether, sec-butyl isopropyl ether, ethylene glycol
  • the solvent composition comprises a nitrile selected from acetonitrile (ACN), trimethylacetonitrile (TMAN), 2-oxo-1,3-dioxolane-4-carbonitrile (ECCN), cyclopropylacetonitrile (CPAN), ethylene glycol bis(propionitrile)ether (EGBE), fumaronitrile (FM), succinonitrile, glutaronitrile, adiponitrile (ADN), and 1,3,6- hexanetricarbonitrile (HTCN).
  • ACN acetonitrile
  • TMAN trimethylacetonitrile
  • ECCN 2-oxo-1,3-dioxolane-4-carbonitrile
  • CPAN cyclopropylacetonitrile
  • EGBE ethylene glycol bis(propionitrile)ether
  • FM fumaronitrile
  • ADN 1,3,6- hexanetricarbonitrile
  • HTCN 1,3,6- hexanetricarbonitrile
  • the solvent composition comprises an amide selected from dimethylacetamide (DMAc), hexamethylphosphoramide (HMPA), N,N-dimethyl trifluoromethanesulfonamide (DMTMSA), N,N-diethyl trifluoromethanesulfonamide, N,N-dimethyl fluorosulfonamide, and carbamides.
  • DMAc dimethylacetamide
  • HMPA hexamethylphosphoramide
  • DMTMSA N,N-dimethyl trifluoromethanesulfonamide
  • N,N-diethyl trifluoromethanesulfonamide N,N-dimethyl fluorosulfonamide
  • carbamides carbamides
  • the solvent composition comprises a nitroalkane selected from nitromethane (NM), nitroethane (NE), trinitromethane, tetranitromethane, 2-nitropropane (2NP), 1- nitropropane (1-NP), dinitromethane, hexanitroethane (HNE), and heptanitrocubane (HNC).
  • the solvent composition comprises a phosphate selected from trimethyl phosphate (TMP), triethyl phosphate (TEP), tripropyl phosphate (TPrP), triisopropyl phosphate (TIP), triphenyl phosphate (TPP), triallyl phosphate (TAP), tris(2,2,3,3,3-pentafluoropropyl) phosphate (5F-TPrP), tris(1,1,1,3,3,3-hexafluoropropan-2-yl) phosphate (HFiP), and diisopropyl fluorophosphate.
  • TMP trimethyl phosphate
  • TTPrP tripropyl phosphate
  • TIP triisopropyl phosphate
  • TPP triphenyl phosphate
  • TPP triallyl phosphate
  • TPP tris(2,2,3,3,3-pentafluoropropyl) phosphate
  • HFiP tris(1,1,1,3,3,3-hexafluor
  • the solvent composition comprises a phosphite selected from tris(trimethylsilyl)phosphite (TMSPi), tris(2,2,2-trifluoroethyl) phosphite (TTFPi), triphenyl phosphite (TPPi), tris(1,1,1,3,3,3-hexafluoropropan-2-yl) phosphite (THFPP), and tris(trimethylsilyl) phosphite.
  • TMSPi tris(trimethylsilyl)phosphite
  • TTFPi tris(2,2,2-trifluoroethyl) phosphite
  • TPPi triphenyl phosphite
  • THFPP tris(1,1,1,3,3,3-hexafluoropropan-2-yl) phosphite
  • THFPP tris(trimethylsilyl) phosphite
  • the solvent composition comprises a sulfite selected from dimethyl sulfite (DMS), trimethylene sulfite, and ethylene sulfite (ESi).
  • DMS dimethyl sulfite
  • ESi ethylene sulfite
  • the solvent composition comprises a sulfone selected from ethyl methyl sulfone, ethyl isopropyl sulfone, dimethyl sulfone, ethylmethyl sulfone, ethyl 3- (methylsulfonyl)propanoate, 2-(ethylsulfonyl)aniline, 6-(ethylsulfonyl)-1,3- benzoxazole-2-thiol, ethyl isopropyl sulfone, 4-ethylsulfonylbenzaldehyde, 2- (ethylsulfonyl)ethanamine, 1-(ethanesulfonyl)-4-nitrobenzene, 5-(1-azepanyl)-2- (ethylsulfonyl)aniline, N-(2-(methylsulfonyl)pheny
  • a sulfone selected from ethyl
  • Clause 21 The lithium-ion battery of any of clauses 1 to 20, wherein: the solvent composition comprises a sulfonamide selected from 2-methyl-5- (methylsulfonyl)benzenesulfonamide, N,N-dimethyl trifluoromethanesulfonamide (DMTMSA), and N,N-dimethyl fluorosulfonamide.
  • the solvent composition comprises a sulfonamide selected from 2-methyl-5- (methylsulfonyl)benzenesulfonamide, N,N-dimethyl trifluoromethanesulfonamide (DMTMSA), and N,N-dimethyl fluorosulfonamide.
  • DMTMSA N,N-dimethyl trifluoromethanesulfonamide
  • the solvent composition comprises a boron (B)-comprising compound selected from pyridine-boron trifluoride (PBF), 3-fluoro pyridine-boron trifluoride (3F-PBF), pyrazine- boron trifluoride, and borate esters.
  • B boron
  • the solvent composition comprises a silicon (Si)-comprising compound selected from siloxanes and silanes.
  • the diluent composition comprises fluorinated ether selected from 1,1,2,2-tetrafluoroethyl- 2,2,3,3-tetrafluoropropyl ether (TTE), bis(2,2,2-trifluoroethyl) ether (BTFE), 1,1,2,2- tetrafluoroethyl-2,2,2,3-tetrafluoropropyl ether, tris(2,2-difluoroethyl) orthoformate (TDFEO), bis(2,2-difluoroethyl)ether, tris(2,2,2-trifluoroethyl) orthoformate (TFEO), 2- (2,2-difluoroethoxy)-1,1-difluoroethane, 1-(2,2-difluoroethoxy)-1,1-difluoroethane, 1- (2,2-difluoroethoxy)-1,1-difluoroethane,1-difluoroethane,
  • the diluent composition comprises one or more amines selected from trimethylamine, triethylamine, tripropylamine, di-isopropylamine, perfluorotriethylamine ((CF 3 CF 2 ) 3 N), perfluoromethyldiethylamine ((CF 3 CF 2 ) 2 CF 3 N), perfluoroethyldimethylamine (CF 3 CF 2 ) 1 (CF 3 ) 2 N), trifluoroethylamine (TFEAm), trifluoropropylamine (TFPAm, C 3 H 6 F 3 N), pentafluoropropylamine (PFPAm, C 3 H 4 F 5 N), trifluoromethylamine (CF 3 NH 2 ), heptafluorobutylamine (HFBAm, C 4 H 4 F 7 N), nonafluoropentylamine (NFPAm, C 5 H
  • Clause 26 The lithium-ion battery of any of clauses 1 to 25, wherein: the solvent composition comprises one or more amines selected from methylamine, fluoromethylamine, trifluoromethylamine, difluoroethylamine, and diethylamine.
  • the solvent composition comprises one or more amines selected from methylamine, fluoromethylamine, trifluoromethylamine, difluoroethylamine, and diethylamine.
  • the solvent composition comprises one or more sulfonyl fluorides selected from 5- oxooxolane-3-sulfonyl fluoride, methyl 2,2-difluoro-2-(fluorosulfonyl)acetate (MDFA), pyrrolidine-1-sulfonyl fluoride (C 4 H 8 FNO 2 S), N-ethyl-N-methylsulfamoyl fluoride (C 3 H 8 FNO 2 S), (1E)-2-cyanoeth-1-ene-1-sulfonyl fluoride (NC 3 H 2 SO 2 F), trifluoromethylpropane sulfonyl fluoride (C 3 H 6 F 4 SO 2 ), fluoroethane sulfonyl fluoride (C 2 H 4 F 2 O 2 S), perfluorobutane sulfonyl fluorides, perfluorohexane
  • MDFA 2,2-difluoro-2-(fluoros
  • Clause 28 The lithium-ion battery of any of clauses 1 to 27, wherein: the solvent composition comprises one or more linear carbonates selected from dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC).
  • DMC dimethyl carbonate
  • EMC ethyl methyl carbonate
  • DEC diethyl carbonate
  • Clause 29 The lithium-ion battery of any of clauses 1 to 28, wherein: a mass of the silicon is in a range of about 10 wt. % to about 90 wt. % of the anode (not counting the anode current collector).
  • Clause 30 The lithium-ion battery of any of clauses 1 to 29, wherein: the anode additionally comprises graphite particles. [00241] Clause 31.
  • Clause 32 The lithium-ion battery of any of clauses 1 to 31, wherein: the anode current collector comprises copper.
  • Clause 33 The lithium-ion battery of any of clauses 1 to 32, wherein: the cathode current collector comprises aluminum.
  • Clause 34 The lithium-ion battery of any of clauses 1 to 33, wherein the lithium-ion battery is operated at a temperature in a range of about 40 to about 90 °C, and the lithium-ion battery is configured for propulsion of an automobile. [00245] Clause 35.
  • Additional Clause 2 The electrolyte of Additional Clause 1, wherein: the at least one alkane compound comprises two or more of the non-fluorinated alkane compounds and/or the fluorinated alkane compounds.
  • Additional Clause 3 The electrolyte of any of Additional Clauses 1 to 2, wherein: the at least one alkane compound is selected from heptanes (C 7 H 16 ), octanes (C 8 H 18 ), nonanes (C 9 H 20 ), fluoroheptanes (C 7 H 15 F), difluorooctanes (C 8 H 16 F 2 ), and fluorononanes (C 9 H 19 F).
  • the lithium salt composition comprises a salt compound selected from lithium bis(fluorosulfonyl)imide (LiFSI), LiPF 6 , lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium trifluoromethanesulfonate (LiOTf, LiOSO 2 CF 3 ), LiSO 3 F (LSF), LiClO 4 , LiAsF 6 , LiBF 4 , lithium difluoro(oxalato)borate (LiDFOB), lithium difluoro(bisoxalato)phosphate (LiDFBOP), lithium tetrafluoro(oxalato)phosphate (LiTFOP), lithium trifluoromethanesulfonate (LiOTf), LiSO 3 F (LSF), Li 3 PS 4 , Li 6 PS 5 Cl, lithium tris(fluorosulfonyl)methide (LTF
  • LiFAP lithium phosphate
  • Li 3 PO 4 lithium fluorophosphate
  • LiPO 2 F 2 or LFO lithium difluorophosphate
  • LiClO 4 Li 2 SO 4 , LiNO 3 , lithium hexafluorosilicate (Li 2 SiF 6 ), lithium hexafluoroaluminate (Li 3 AlF 6 ), lithium iodide (LiI), LiAsF 6 , lithium cyclo-difluoromethane-1,1- bis(sulfonyl)imide (Li DMSI), and lithium cyclo-hexafluoropropane-1,1- bis(sulfonyl)imide (Li HPSI).
  • Additional Clause 6 The electrolyte of any of Additional Clauses 1 to 5, wherein the lithium salt composition comprises two or more salt compounds.
  • Additional Clause 7. The electrolyte of any of Additional Clauses 1 to 6, wherein the electrolyte comprises at least one non-Li salt compound.
  • Additional Clause 8. The electrolyte of any of Additional Clauses 1 to 7, wherein: the solvent composition comprises vinylene carbonate (VC), a mole fraction of the VC in the electrolyte being in a range of about 0.05 to about 2.00 mol. %.
  • FEC fluoroethylene carbonate
  • the solvent composition comprises a linear ester, a cyclic ester, and/or a branched ester.
  • the solvent composition comprises a ketone selected from: methyl ethyl ketone (MEK), diethyl ketone (DEK), methyl isopropyl ketone (MiPK), ethyl isopropyl ketone (EiPK), diisopropyl ketone, pinacolone (MtBK), diisobutyl ketone (DiBK), methyl sec- butyl ketone (MsBK), and hexamethylacetone (HMA).
  • MEK methyl ethyl ketone
  • DEK diethyl ketone
  • MiPK methyl isopropyl ketone
  • EiPK ethyl isopropyl ketone
  • HMA hexamethylacetone
  • the solvent composition comprises an ether selected from: diethyl ether, 2- methoxy-2-methylpropane, dipropyl ether, diisopropyl ether, butyl ethyl ether, ethyl tert- butyl ether, 1-propoxybutane, ethyl pentyl ether, butyl isopropyl ether, sec-butyl isopropyl ether, ethylene glycol dimethyl ether (DME), and diethoxyethane.
  • ether selected from: diethyl ether, 2- methoxy-2-methylpropane, dipropyl ether, diisopropyl ether, butyl ethyl ether, ethyl tert- butyl ether, 1-propoxybutane, ethyl pentyl ether, butyl isopropyl ether, sec-butyl isopropyl ether, ethylene glycol dimethyl ether (DME
  • the solvent composition comprises a nitrile selected from acetonitrile (ACN), Attorney Docket No. SN-0076WO trimethylacetonitrile (TMAN), 2-oxo-1,3-dioxolane-4-carbonitrile (ECCN), cyclopropylacetonitrile (CPAN), ethylene glycol bis(propionitrile)ether (EGBE), fumaronitrile (FM), succinonitrile, glutaronitrile, adiponitrile (ADN), and 1,3,6- hexanetricarbonitrile (HTCN).
  • ACN acetonitrile
  • TMAN 2-oxo-1,3-dioxolane-4-carbonitrile
  • CPAN cyclopropylacetonitrile
  • EGBE ethylene glycol bis(propionitrile)ether
  • FM fumaronitrile
  • ADN 1,3,6- hexanetricarbonitrile
  • HTCN 1,3,6- hexanetricarbonitrile
  • the solvent composition comprises an amide selected from dimethylacetamide (DMAc), hexamethylphosphoramide (HMPA), N,N-dimethyl trifluoromethanesulfonamide (DMTMSA), N,N-diethyl trifluoromethanesulfonamide, N,N-dimethyl fluorosulfonamide, and carbamides.
  • DMAc dimethylacetamide
  • HMPA hexamethylphosphoramide
  • DMTMSA N,N-dimethyl trifluoromethanesulfonamide
  • N,N-diethyl trifluoromethanesulfonamide N,N-dimethyl fluorosulfonamide
  • carbamides carbamides
  • the solvent composition comprises a nitroalkane selected from nitromethane (NM), nitroethane (NE), trinitromethane, tetranitromethane, 2-nitropropane (2NP), 1- nitropropane (1-NP), dinitromethane, hexanitroethane (HNE), and heptanitrocubane (HNC).
  • NM nitromethane
  • NE nitroethane
  • N-NP 2-nitropropane
  • HNE 1- nitropropane
  • HNC heptanitrocubane
  • the solvent composition comprises a phosphate selected from trimethyl phosphate (TMP), triethyl phosphate (TEP), tripropyl phosphate (TPrP), triisopropyl phosphate (TIP), triphenyl phosphate (TPP), triallyl phosphate (TAP), tris(2,2,3,3,3- pentafluoropropyl) phosphate (5F-TPrP), tris(1,1,1,3,3,3-hexafluoropropan-2-yl) phosphate (HFiP), and diisopropyl fluorophosphate.
  • TMP trimethyl phosphate
  • TTPrP tripropyl phosphate
  • TIP triisopropyl phosphate
  • TPP triphenyl phosphate
  • TPP triallyl phosphate
  • TPP tris(2,2,3,3,3- pentafluoropropyl) phosphate
  • HFiP tris(1,1,1,3,3,3-hexafluor
  • the solvent composition comprises a phosphite selected from tris(trimethylsilyl)phosphite (TMSPi), tris(2,2,2-trifluoroethyl) phosphite (TTFPi), triphenyl phosphite (TPPi), tris(1,1,1,3,3,3-hexafluoropropan-2-yl) phosphite (THFPP), and tris(trimethylsilyl) phosphite.
  • TMSPi tris(trimethylsilyl)phosphite
  • TTFPi tris(2,2,2-trifluoroethyl) phosphite
  • TPPi triphenyl phosphite
  • THFPP tris(1,1,1,3,3,3-hexafluoropropan-2-yl) phosphite
  • THFPP tris(trimethylsilyl) phosphite
  • the solvent composition comprises a sulfite selected from dimethyl sulfite (DMS), trimethylene sulfite, and ethylene sulfite (ESi).
  • DMS dimethyl sulfite
  • ESi ethylene sulfite
  • Additional Clause 19 The electrolyte of any of Additional Clauses 1 to 18, wherein: the solvent composition comprises a sulfone selected from ethyl methyl sulfone, ethyl isopropyl sulfone, dimethyl sulfone, ethylmethyl sulfone, ethyl 3- Attorney Docket No.
  • Additional Clause 20 The electrolyte of any of Additional Clauses 1 to 19, wherein: the solvent composition comprises a sulfonamide selected from 2-methyl-5- (methylsulfonyl)benzenesulfonamide, N,N-dimethyl trifluoromethanesulfonamide (DMTMSA), and N,N-dimethyl fluorosulfonamide.
  • DMTMSA N,N-dimethyl trifluoromethanesulfonamide
  • Additional Clause 21 Additional Clause 21.
  • the solvent composition comprises a boron (B)-comprising compound selected from pyridine-boron trifluoride (PBF), 3-fluoro pyridine-boron trifluoride (3F-PBF), pyrazine-boron trifluoride, and borate esters.
  • B boron
  • the solvent composition comprises a silicon (Si)-comprising compound selected from siloxanes and silanes.
  • the diluent composition comprises fluorinated ether selected from 1,1,2,2- tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), bis(2,2,2-trifluoroethyl) ether (BTFE), 1,1,2,2-tetrafluoroethyl-2,2,2,3-tetrafluoropropyl ether, tris(2,2-difluoroethyl) orthoformate (TDFEO), bis(2,2-difluoroethyl)ether, tris(2,2,2-trifluoroethyl) orthoformate (TFEO), 2-(2,2-difluoroethoxy)-1,1-difluoroethane, 1-(2,2- difluoroethoxy)-1,1-difluoroethane, 1-(2,2-difluoroethoxy)-1,1-difluoroethane,1-difluor
  • the diluent composition comprises one or more amines selected from trimethylamine, triethylamine, tripropylamine, di-isopropylamine, perfluorotriethylamine ((CF 3 CF 2 ) 3 N), perfluoromethyldiethylamine ((CF 3 CF 2 ) 2 CF 3 N), perfluoroethyldimethylamine (CF 3 CF 2 ) 1 (CF 3 ) 2 N), trifluoroethylamine (TFEAm), trifluoropropylamine (TFPAm, C 3 H 6 F 3 N), pentafluoropropylamine (PFPAm, C 3 H 4 F 5 N), trifluoromethylamine (CF 3 NH 2 ), heptafluorobutylamine (HFBAm, C 4 H 4 F 7 N), nonafluoropentylamine (NFPAm, C5H4F9N), 2,2,
  • Additional Clause 25 The electrolyte of any of Additional Clauses 1 to 24, wherein: the solvent composition comprises one or more amines selected from methylamine, fluoromethylamine, trifluoromethylamine, difluoroethylamine, and diethylamine.
  • the solvent composition comprises one or more amines selected from methylamine, fluoromethylamine, trifluoromethylamine, difluoroethylamine, and diethylamine.
  • the solvent composition comprises one or more sulfonyl fluorides selected from 5-oxooxolane-3-sulfonyl fluoride, methyl 2,2-difluoro-2-(fluorosulfonyl)acetate (MDFA), pyrrolidine-1-sulfonyl fluoride (C 4 H 8 FNO 2 S), N-ethyl-N-methylsulfamoyl fluoride (C 3 H 8 FNO 2 S), (1E)-2-cyanoeth-1-ene-1-sulfonyl fluoride (NC 3 H 2 SO 2 F), trifluoromethylpropane sulfonyl fluoride (C 3 H 6 F 4 SO 2 ), fluoroethane sulfonyl fluoride (C 2 H 4 F 2 O 2 S), perfluorobutane sulfonyl fluorides, perfluorohexane
  • MDFA 2,2-difluoro-2-(fluorosul
  • Additional Clause 27 The electrolyte of any of Additional Clauses 1 to 26, wherein: the solvent composition comprises one or more linear carbonates selected from dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC).
  • DMC dimethyl carbonate
  • EMC ethyl methyl carbonate
  • DEC diethyl carbonate
  • a lithium-ion battery comprising: an anode current collector; a cathode current collector; an anode disposed on and/or in the anode current collector; a cathode disposed on and/or in the cathode current collector; and the electrolyte of Additional Clause 1 ionically coupling the anode and the cathode, wherein: the anode comprises composite particles comprising carbon and silicon, at least some of the silicon being nanosized silicon in the composite particles.
  • Additional Clause 29 The lithium-ion battery of Additional Clause 28, wherein: a mass of the silicon is in a range of about 10 wt. % to about 90 wt. % of the anode excluding the anode current collector.
  • Additional Clause 30 The lithium-ion battery of any of Additional Clauses 28 to 29, wherein: the anode additionally comprises graphite particles.
  • Additional Clause 31 The lithium-ion battery of any of Additional Clauses 28 to 30, wherein: the anode additionally comprises carbon nanotubes and/or carbon black particles.
  • the anode current collector comprises copper.
  • the cathode current collector comprises aluminum.
  • the lithium-ion battery of any of Additional Clauses 28 to 33 wherein: the lithium-ion battery is operated at a temperature in a range of about 40 to about 90 °C; and the lithium-ion battery is configured to supply an electromotive force for propulsion of an automobile.
  • Additional Clause 35 The electrolyte of any of Additional Clauses 1 to 34, wherein: the first integer is between 7 and 20, and the second integer is between 6 and 20.
  • Additional Clause 36 The electrolyte of any of Additional Clauses 1 to 35, wherein: the diluent composition additionally comprises at least one aromatic compound.
  • Additional Clause 37 Additional Clause 37.
  • the at least one aromatic compound is selected from: benzene, fluorobenzene (FB), difluorobenzenes (C 6 H 4 F 2 ), trifluorobenzenes (C 6 H 3 F 3 ), tetrafluorobenzenes (C 6 H 2 F 4 ), pentafluorobenzenes (C 6 H 1 F 5 ), trifluorotoluenes (TFT), bis(trifluoromethyl)benzenes (C 8 H 4 F 6 ), and bis(difluoromethyl)benzenes (C 8 H 6 F 4 ).
  • FB fluorobenzene
  • C 6 H 4 F 2 difluorobenzenes
  • C 6 H 3 F 3 trifluorobenzenes
  • tetrafluorobenzenes C 6 H 2 F 4
  • pentafluorobenzenes C 6 H 1 F 5
  • trifluorotoluenes TFT
  • An electrolyte comprising: a lithium salt composition; a solvent composition; and a diluent composition, wherein: the diluent composition comprises at least one aromatic compound, and the at least one aromatic compound is selected from: benzene, fluorobenzene (FB), difluorobenzenes (C 6 H 4 F 2 ), trifluorobenzenes (C 6 H 3 F 3 ), tetrafluorobenzenes (C 6 H 2 F 4 ), pentafluorobenzenes (C 6 H 1 F 5 ), trifluorotoluenes (TFT), bis(trifluoromethyl)benzenes (C 8 H 4 F 6 ), and bis(difluoromethyl)benzenes (C 8 H 6 F 4 ).
  • FB fluorobenzene
  • difluorobenzenes C 6 H 4 F 2
  • trifluorobenzenes C 6 H 3 F 3
  • Additional Clause 39 The electrolyte of Additional Clause 38, wherein: a mole fraction of the lithium salt composition in the electrolyte is in a range of about 10 mol. % to about 20 mol. %. [00286] Additional Clause 40.
  • the lithium salt composition comprises a salt compound selected from lithium bis(fluorosulfonyl)imide (LiFSI), LiPF 6 , lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium trifluoromethanesulfonate (LiOTf, LiOSO 2 CF 3 ), LiSO 3 F (LSF), LiClO 4 , LiAsF 6 , LiBF 4 , lithium difluoro(oxalato)borate (LiDFOB), lithium difluoro(bisoxalato)phosphate (LiDFBOP), lithium tetrafluoro(oxalato)phosphate (LiTFOP), lithium trifluoromethanesulfonate (LiOTf), LiSO 3 F (LSF), Li 3 PS 4 , Li 6 PS 5 Cl, lithium tris(fluorosulfonyl)methide (LT)
  • LiFSI lithium bis(fluorosulfonyl)
  • Additional Clause 41 The electrolyte of any of Additional Clauses 38 to 40, wherein the lithium salt composition comprises two or more salt compounds.
  • Additional Clause 42 The electrolyte of any of Additional Clauses 38 to 41, wherein the electrolyte comprises at least one non-Li salt compound.
  • Attorney Docket No. SN-0076WO Attorney Docket No. SN-0076WO
  • Additional Clause 43 The electrolyte of any of Additional Clauses 38 to 42, wherein: the solvent composition comprises vinylene carbonate (VC), a mole fraction of the VC in the electrolyte being in a range of about 0.05 to about 2.00 mol. %.
  • Additional Clause 44 The solvent composition comprises vinylene carbonate (VC), a mole fraction of the VC in the electrolyte being in a range of about 0.05 to about 2.00 mol. %.
  • FEC fluoroethylene carbonate
  • Additional Clause 45 The electrolyte of any of Additional Clauses 38 to 44, wherein: the solvent composition comprises a linear ester, a cyclic ester, and/or a branched ester.
  • the solvent composition comprises a ketone selected from: methyl ethyl ketone (MEK), diethyl ketone (DEK), methyl isopropyl ketone (MiPK), ethyl isopropyl ketone (EiPK), diisopropyl ketone, pinacolone (MtBK), diisobutyl ketone (DiBK), methyl sec- butyl ketone (MsBK), and hexamethylacetone (HMA).
  • MEK methyl ethyl ketone
  • DEK diethyl ketone
  • MiPK methyl isopropyl ketone
  • EiPK ethyl isopropyl ketone
  • HMA hexamethylacetone
  • the solvent composition comprises an ether selected from: diethyl ether, 2- methoxy-2-methylpropane, dipropyl ether, diisopropyl ether, butyl ethyl ether, ethyl tert- butyl ether, 1-propoxybutane, ethyl pentyl ether, butyl isopropyl ether, sec-butyl isopropyl ether, ethylene glycol dimethyl ether (DME), and diethoxyethane.
  • ether selected from: diethyl ether, 2- methoxy-2-methylpropane, dipropyl ether, diisopropyl ether, butyl ethyl ether, ethyl tert- butyl ether, 1-propoxybutane, ethyl pentyl ether, butyl isopropyl ether, sec-butyl isopropyl ether, ethylene glycol dimethyl ether (DME
  • the solvent composition comprises a nitrile selected from acetonitrile (ACN), trimethylacetonitrile (TMAN), 2-oxo-1,3-dioxolane-4-carbonitrile (ECCN), cyclopropylacetonitrile (CPAN), ethylene glycol bis(propionitrile)ether (EGBE), fumaronitrile (FM), succinonitrile, glutaronitrile, adiponitrile (ADN), and 1,3,6- hexanetricarbonitrile (HTCN).
  • ACN acetonitrile
  • TMAN trimethylacetonitrile
  • ECCN 2-oxo-1,3-dioxolane-4-carbonitrile
  • CPAN cyclopropylacetonitrile
  • EGBE ethylene glycol bis(propionitrile)ether
  • FM fumaronitrile
  • ADN 1,3,6- hexanetricarbonitrile
  • HTCN 1,3,6- hexanetricarbonitrile
  • the solvent composition comprises an amide selected from dimethylacetamide (DMAc), hexamethylphosphoramide (HMPA), N,N-dimethyl trifluoromethanesulfonamide (DMTMSA), N,N-diethyl trifluoromethanesulfonamide, N,N-dimethyl fluorosulfonamide, and carbamides.
  • DMAc dimethylacetamide
  • HMPA hexamethylphosphoramide
  • DMTMSA N,N-dimethyl trifluoromethanesulfonamide
  • N,N-diethyl trifluoromethanesulfonamide N,N-dimethyl fluorosulfonamide
  • carbamides carbamides
  • the solvent composition comprises a nitroalkane selected from nitromethane (NM), nitroethane (NE), trinitromethane, tetranitromethane, 2-nitropropane (2NP), 1- nitropropane (1-NP), dinitromethane, hexanitroethane (HNE), and heptanitrocubane (HNC).
  • the solvent composition comprises a phosphate selected from trimethyl phosphate (TMP), triethyl phosphate (TEP), tripropyl phosphate (TPrP), triisopropyl phosphate (TIP), triphenyl phosphate (TPP), triallyl phosphate (TAP), tris(2,2,3,3,3- pentafluoropropyl) phosphate (5F-TPrP), tris(1,1,1,3,3,3-hexafluoropropan-2-yl) phosphate (HFiP), and diisopropyl fluorophosphate.
  • TMP trimethyl phosphate
  • TEP triethyl phosphate
  • TPrP tripropyl phosphate
  • TIP triisopropyl phosphate
  • TPP triphenyl phosphate
  • TPP triphenyl phosphate
  • TPP triallyl phosphate
  • TPP tris(2,2,3,3,3- pentafluoropropyl)
  • the solvent composition comprises a phosphite selected from tris(trimethylsilyl)phosphite (TMSPi), tris(2,2,2-trifluoroethyl) phosphite (TTFPi), triphenyl phosphite (TPPi), tris(1,1,1,3,3,3-hexafluoropropan-2-yl) phosphite (THFPP), and tris(trimethylsilyl) phosphite.
  • TMSPi tris(trimethylsilyl)phosphite
  • TTFPi tris(2,2,2-trifluoroethyl) phosphite
  • TPPi triphenyl phosphite
  • THFPP tris(1,1,1,3,3,3-hexafluoropropan-2-yl) phosphite
  • THFPP tris(trimethylsilyl) phosphite
  • the solvent composition comprises a sulfite selected from dimethyl sulfite (DMS), trimethylene sulfite, and ethylene sulfite (ESi).
  • DMS dimethyl sulfite
  • ESi ethylene sulfite
  • the solvent composition comprises a sulfone selected from ethyl methyl sulfone, ethyl isopropyl sulfone, dimethyl sulfone, ethylmethyl sulfone, ethyl 3- (methylsulfonyl)propanoate, 2-(ethylsulfonyl)aniline, 6-(ethylsulfonyl)-1,3- benzoxazole-2-thiol, ethyl isopropyl sulfone, 4-ethylsulfonylbenzaldehyde, 2- (ethylsulfonyl)ethanamine, 1-(ethanesulfonyl)-4-nitrobenzene, 5-(1-azepanyl)-2- (ethylsulfonyl)aniline, N-(2-(methylsulfonyl)
  • Additional Clause 55 The electrolyte of any of Additional Clauses 38 to 54, wherein: the solvent composition comprises a sulfonamide selected from 2-methyl-5- (methylsulfonyl)benzenesulfonamide, N,N-dimethyl trifluoromethanesulfonamide (DMTMSA), and N,N-dimethyl fluorosulfonamide.
  • DMTMSA dimethyl trifluoromethanesulfonamide
  • Additional Clause 56 Additional Clause 56.
  • the solvent composition comprises a boron (B)-comprising compound selected from pyridine-boron trifluoride (PBF), 3-fluoro pyridine-boron trifluoride (3F-PBF), pyrazine-boron trifluoride, and borate esters.
  • B boron
  • the solvent composition comprises a silicon (Si)-comprising compound selected from siloxanes and silanes.
  • the diluent composition comprises fluorinated ether selected from 1,1,2,2- tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), bis(2,2,2-trifluoroethyl) ether (BTFE), 1,1,2,2-tetrafluoroethyl-2,2,2,3-tetrafluoropropyl ether, tris(2,2-difluoroethyl) orthoformate (TDFEO), bis(2,2-difluoroethyl)ether, tris(2,2,2-trifluoroethyl) orthoformate (TFEO), 2-(2,2-difluoroethoxy)-1,1-difluoroethane, 1-(2,2- difluoroethoxy)-1,1-difluoroethane, 1-(2,2-difluoroethoxy)-1,1-difluoroethoxy)-1,1-difluoroethane
  • the diluent composition comprises one or more amines selected from trimethylamine, triethylamine, tripropylamine, di-isopropylamine, perfluorotriethylamine ((CF 3 CF 2 ) 3 N), perfluoromethyldiethylamine ((CF 3 CF 2 ) 2 CF 3 N), perfluoroethyldimethylamine (CF 3 CF 2 ) 1 (CF 3 ) 2 N), trifluoroethylamine (TFEAm), trifluoropropylamine (TFPAm, C 3 H 6 F 3 N), pentafluoropropylamine (PFPAm, C 3 H 4 F 5 N), trifluoromethylamine (CF 3 NH 2 ), heptafluorobutylamine (HFBAm, C 4 H 4 F 7 N), Attorney Docket No.
  • Additional Clause 60 The electrolyte of any of Additional Clauses 38 to 59, wherein: the solvent composition comprises one or more amines selected from methylamine, fluoromethylamine, trifluoromethylamine, difluoroethylamine, and diethylamine.
  • the solvent composition comprises one or more sulfonyl fluorides selected from 5-oxooxolane-3-sulfonyl fluoride, methyl 2,2-difluoro-2-(fluorosulfonyl)acetate (MDFA), pyrrolidine-1-sulfonyl fluoride (C 4 H 8 FNO 2 S), N-ethyl-N-methylsulfamoyl fluoride (C 3 H 8 FNO 2 S), (1E)-2-cyanoeth-1-ene-1-sulfonyl fluoride (NC 3 H 2 SO 2 F), trifluoromethylpropane sulfonyl fluoride (C 3 H 6 F 4 SO 2 ), fluoroethane sulfonyl fluoride (C 2 H 4 F 2 O 2 S), perfluorobutane sulfonyl fluorides, 5-oxooxolane-3-sulfonyl fluoride, methyl 2,2-di
  • Additional Clause 62 The electrolyte of any of Additional Clauses 38 to 61, wherein: the solvent composition comprises one or more linear carbonates selected from dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC).
  • DMC dimethyl carbonate
  • EMC ethyl methyl carbonate
  • DEC diethyl carbonate
  • a lithium-ion battery comprising: an anode current collector; a cathode current collector; an anode disposed on and/or in the anode current collector; a cathode disposed on and/or in the cathode current collector; and the electrolyte of Additional Clause 38 ionically coupling the anode and the cathode, wherein: the anode comprises composite particles comprising carbon and silicon, at least some of the silicon being nanosized silicon in the composite particles.
  • Additional Clause 64 The lithium-ion battery of Additional Clause 63, wherein: a mass of the silicon is in a range of about 10 wt. % to about 90 wt. % of the anode excluding the anode current collector.
  • Additional Clause 65 The lithium-ion battery of any of Additional Clauses 63 to 64, wherein: the anode additionally comprises graphite particles.
  • Additional Clause 66 The lithium-ion battery of any of Additional Clauses 63 to 65, wherein: the anode additionally comprises carbon nanotubes and/or carbon black particles.
  • Additional Clause 67 The lithium-ion battery of any of Additional Clauses 63 to 66, wherein: the anode current collector comprises copper.
  • Additional Clause 68 The lithium-ion battery of any of Additional Clauses 63 to 67, wherein: the cathode current collector comprises aluminum.
  • Additional Clause 69 The lithium-ion battery of any of Additional Clauses 63 to 68, wherein: the lithium-ion battery is operated at a temperature in a range of about 40 to about 90 °C; and the lithium-ion battery is configured to supply an electromotive force for propulsion of an automobile.
  • This description is provided to enable any person skilled in the art to make or use embodiments of the present invention. It will be appreciated, however, that the present invention is not limited to the particular formulations, process steps, and materials disclosed herein, as various modifications to these embodiments will be readily apparent to those skilled in the art. That is, the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention.

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Abstract

Un électrolyte comprend (1) une composition de sel de lithium, (2) une composition de solvant et (3) une composition de diluant. Dans certains modes de réalisation, la composition de diluant comprend au moins un composé alcane. Dans certains modes de réalisation, le ou les composés alcanes sont choisis parmi (1) des composés alcanes non fluorés caractérisés par une première formule moléculaire CpH2p+2, dans laquelle p est un premier nombre entier compris entre 5 et 20, et (2) des composés alcanes fluorés caractérisés par une seconde formule moléculaire CqHq1Fq2, q étant un deuxième nombre entier compris entre 4 et 20, q1 étant un troisième nombre entier positif, et q2 étant un quatrième nombre entier positif, q, q1 et q2 étant liés par q1 + q2 = 2q + 2. Une batterie au lithium-ion comprenant un tel électrolyte est également divulguée.
PCT/US2024/020542 2023-03-20 2024-03-19 Électrolyte à haute concentration localisé et batterie au lithium-ion le comprenant Ceased WO2024196936A2 (fr)

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US202363491234P 2023-03-20 2023-03-20
US63/491,234 2023-03-20
US202363612748P 2023-12-20 2023-12-20
US63/612,748 2023-12-20
US18/608,268 US20240322244A1 (en) 2023-03-20 2024-03-18 Localized high concentration electrolyte and lithium-ion battery comprising the same
US18/608,268 2024-03-18

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Cited By (1)

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CN119695274A (zh) * 2024-12-11 2025-03-25 惠州亿纬锂能股份有限公司 一种锂离子电池用电解液、应用其的锂离子电池

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JP2006210022A (ja) * 2005-01-25 2006-08-10 Toyota Motor Corp 電解質およびその利用
WO2014065246A1 (fr) * 2012-10-22 2014-05-01 旭硝子株式会社 Solution d'électrolyte non aqueux pour batteries secondaires et batterie secondaire au lithium-ion
EP3176129A4 (fr) * 2014-07-31 2018-02-28 Kanto Denka Kogyo Co., Ltd. Procédé de production de difluorophosphate
DE102016210562A1 (de) * 2016-06-14 2017-12-14 Bayerische Motoren Werke Aktiengesellschaft Verfahren zur erhöhung der sicherheit in lithiumionen-batterien und lithiumionen-batterie mit erhöhter sicherheit
US20240204253A1 (en) * 2022-11-29 2024-06-20 Sila Nanotechnologies, Inc. Compounds for enhancing the solid-electrolyte interphase (sei) of silicon-based anode materials in lithium-ion batteries, and electrolytes, batteries, and methods relating thereto

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119695274A (zh) * 2024-12-11 2025-03-25 惠州亿纬锂能股份有限公司 一种锂离子电池用电解液、应用其的锂离子电池

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