Electrolytes and electrolyte components, additives, precursors thereof, and methods of manufacture

Abstract

Provided herein are methods and processes useful in producing battery electrolyte precursors and battery electrolytes using metal fluorides.

Description

WSGR Docket No. 64651-711.601ELECTROLYTES AND ELECTROLYTE COMPONENTS, ADDITIVES, PRECURSORS THEREOF, AND METHODS OF MANUFACTURECROSS-REFERENCE

[0001] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 733,093, filed December 12, 2024, which is incorporated by reference herein in its entirety.BACKGROUND OF THE INVENTION

[0002] Use of hazardous and toxic reagents, such as HF, to manufacture and produce battery electrolytes is dangerous and harmful to the environment. Provided herein are processes for manufacturing battery electrolytes and precursors thereof reducing and / or eliminating use of dangerous reagents.SUMMARY OF THE INVENTION

[0003] In some aspects, described herein are methods of manufacturing a battery electrolyte precursor, a battery electrolyte, and / or a salt thereof. In some embodiments, the methods comprise contacting a metal fluoride with a starting reagent in the presence of a polar aprotic compound. In some embodiments, the methods comprise fluorinating the starting reagentto thereby provide a battery electrolyte precursor. In some embodiments, the methods comprise washing a metal fluoride with a solvent. In some embodiments, the methods comprise concentrating the metal fluoride. In some embodiments, the methods comprise contacting the metal fluoride with a starting reagent. In some embodiments, the methods comprise fluorinating the starting reagent in the presence of a polar aprotic compound to provide a battery electrolyte precursor.

[0004] In some embodiments, the polar aprotic compound is comprised in a solvent. In some embodiments, the polar aprotic compound is provided in an amount of at least 1 molar equivalent with respect to the metal fluoride. In some embodiments, the polar aprotic compound is provided in an amount of at least 5 molar equivalents with respect to the metal fluoride. In some embodiments, the polar aprotic compound is provided in an amount of at least 10 molar equivalents with respect to the metal fluoride. In some embodiments, the polar aprotic compound is provided in an amount of at least 20 molar equivalents with respect to the metal fluoride.

[0005] In some embodiments, the polar aprotic compound is provided in an amount of at least 50 molar equivalents with respect to the metal fluoride. In some embodiments, the polar aprotic compound is a polar aprotic solvent which is combined with the battery electrolyte precursor, and / or the metal fluoride. In some embodiments, the polar aprotic compound is added in a catalytic amount.WSGR Docket No. 64651-711.601

[0006] In some embodiments, the polar aprotic compound comprises a nitrile group. In some embodiments, the polar aprotic compound is C1-C6 alkyl-CN. In some embodiments, the polar aprotic compound is acetonitrile. In some embodiments, the polar aprotic compound is propionitrile. In some embodiments, the metal fluoride comprises an alkali metal fluoride.

[0007] In some embodiments, the alkali metal fluoride comprises LiF, NaF, and / or KF. In some embodiments, the alkali metal fluoride comprises LiF. In some embodiments, the alkali metal fluoride comprises NaF. In some embodiments, the alkali metal fluoride comprises KF.

[0008] In some embodiments, the metal fluoride substantially consists of LiF (e.g., has a LiF purity of >80%, 90%, 95%, or 99% prior to the contacting with the polar aprotic compound and / or the battery electrolyte precursor). In some embodiments, the metal fluoride substantially consists of NaF (e.g., has a NaF purity of >80%, 90%, 95%, or 99% prior to the contacting with the polar aprotic compound and / or the battery electrolyte precursor).

[0009] In some embodiments, the metal fluoride substantially consists of KF (e.g., has a KF purity of >80%, 90%, 95%, or 99% prior to contacting with the polar aprotic compound and / or the battery electrolyte precursor). In some embodiments, the metal fluoride consists of a salt having a weight% purity of at least 80% (e.g., 80%, 90%, 95%, or 99%) prior to combination with the polar aprotic compound and / or the battery electrolyte precursor.

[0010] In some embodiments, the metal fluoride is contacted with the starting reagent in an alkyl carbonate solvent (e.g., dimethyl carbonate). In some embodiments, the alkyl carbonate solvent is dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, and / or combinations thereof.

[0011] In some embodiments, the alkyl carbonate solvent is a fluoroalkyl carbonate solvent (e.g., trifluoroethyl carbonate, bis(trifluoroethyl) carbonate, trifluoroethyl methyl carbonate, and / or combinations thereof). In some embodiments, the contacting is performed at a temperature of about 50 to about 150 °C. In some embodiments, the contacting is performed at a temperature of about 80 °C about or more (e.g., about 100 °C or more).

[0012] In some embodiments, the methods further comprise adjusting a pH of a solution comprising the starting reagent (e.g., to a pH of about 6 to about 8) prior to the fluorinating. In some embodiments, the pH of the resultant fluid is adjusted with an acid (e.g., strong acid, weak acid, polyprotic acid, and / or combinations thereof).

[0013] In some embodiments, any of the methods provided herein can comprise reducing a particle size of one or more of: the battery electrolyte precursor, the starting reagent, the electrolyte agent, and / or the metal fluoride prior to, during, or after the contacting of the metal fluoride with the starting reagent. In some embodiments, the size reduction is performed by application of a mechanical force.WSGR Docket No. 64651-711.601

[0014] In certain embodiments, a mechanical force (e.g., a mechanical force provided herein) comprises any suitable mechanical force, such as by using a ball mill, a planetary mill, a mortar and pestle, a twin-screw-extruder, an attritor, a drum mill, an ultrasonic bath, a mechanical press, and / or combinations of one or more thereof. In certain embodiments, a mechanical force is applied using a high-shear mixer, an in-line homogenizer, one or more bead mills, and / or combinations thereof. In certain embodiments, mechanical force provided herein is provided with a ball mill. In some embodiments, a ball mill provided herein comprises a jar and balls (e.g., with a weight of about 1 g to about 20 g). In certain embodiments, a first (e.g., salt) composition provided herein and a second (e.g., salt) composition provided herein are combined in a jar and balls are added. In some embodiments, mechanical force provided herein is provided with a twin screw-extruder, such as by extruding a combination of (e.g., salt) compositions provided herein at varying screw speeds, screw temperatures, residence times, or the like. A twin screw-extruder provided herein is fixed with a gravimetric single screw feeder (e.g., hopper) for programmed addition of (e.g., salt) compositions provided herein.

[0015] In specific embodiments, mechanical force is applied under any suitable condition, such as at a selected or varying frequency, time, temperature, cycles, or the like. In some embodiments, a mechanical force provided herein is applied at a frequency of about 0.5 Hz to about 60 kHz (e.g., about 10 Hz to about 20 kHz). In certain embodiments, a mechanical force provided herein is applied at a frequency of about 5 Hz or more (e.g., about 10 Hz or more, about 20 Hz or more, about 30 Hz or more). In specific embodiments, a mechanical force provided herein is applied at about 35 Hz. In certain embodiments, a mechanical force provided herein is applied for about 1 cycle to about 50 cycles (e.g., about 5 to about 40 cycles, about 10 to about 30 cycles). In some embodiments, a mechanical force provided herein is applied for 1 cycle or more. In specific embodiments, a mechanical force provided herein is applied for 10 cycles. In some embodiments, mechanical force is applied to one or more compositions in solution-phase. In some embodiments, mechanical force is applied to one or more compositions in solid-phase.

[0016] In some embodiments, any step of any method provided herein which involves a solid phase reactant or product may employ one or more of the following to reduce a particle size and increase a surface area of the solid phase reactant or product: mortar and pestle, roller / plate mill, hammer mill, jaw crusher, cone crusher, ball milling, planetary milling, bead milling, stirred media mill, jet milling, cryogenic milling, high-pressure homogenization, ultrasonic cavitation, disc / colloid mill, spray drying, freeze drying, evaporation-condensation (gas-phase condensation), sublimation and recondensation, controlledWSGR Docket No. 64651-711.601 cry stallization / recry stallization, anti-solvent precipitation / flash nanoprecipitation, supercritical fluid micronization, co-crystallization / polymorph control, chemical etching / controlled dissolution, acid / base hydrolysis, enzymatic degradation, laser ablation, plasma synthesis, gasphase condensation, bead milling with dispersants, attrition / abrasive milling, mechanochemical ball milling, twin-screw extrusion, microfluidic / membrane emulsification, spray-freeze-drying, sieving / classification, electrohydrodynamic atomization (electrospray).

[0017] In some embodiments, the acid comprises phosphoric acid, hydrochloric acid, formic acid, acetic acid, benzoic acid, boric acid, silicic acid, oxalic acid, sulfuric acid, sulfurous acid, carbonic acid, and / or combinations thereof. In some embodiments, the acid comprises hydrochloric acid, phosphoric acid, sulfuric acid, and / or combinations thereof.

[0018] In some embodiments, the pH of the solution comprising the starting reagent is adjusted to a pH of about 5 to about 10 (e.g., about 6 to about 9). In some embodiments, the solution comprising the starting reagent has a pH of about ? or more (e.g., about 10 or more).

[0019] In some embodiments, a solution comprising the starting reagent has a pH of about 12 to about 13. In some embodiments, the contacting is at a temperature of about 0 to about 120 °C.

[0020] In some embodiments, the contacting is at a temperature of 80 °C or more. In some embodiments, the contacting is at a temperature of 110 °C or less (e.g., at about 40 °C or less). In some embodiments, the contacting is performed for about 0 hours to about 8 hours. In some embodiments, the contacting is performed for about 1 hour or more.

[0021] In some embodiments, the contacting is performed for about 6 hours or less. In some embodiments, the contacting is performed for about 2 hours.

[0022] In some embodiments, a solvent comprising the contacted metal fluoride and starting reagenthas a boiling point of about 30 °C or more (e.g., about 70 °C or more, about 120 °C or more). In some embodiments, a solvent comprising the contacted metal fluoride and starting reagent has a boiling point of about 240 °C or less. In some embodiments, the contacting is performed at a temperature of about -20 to about 240 °C.

[0023] In some embodiments, the contacting is performed at a temperature of about 80 °C or more. In some embodiments, the contacting is performed at a temperature of about 60 °C. In some embodiments, the contacting is performed at a temperature of about 235 °C or less.

[0024] In some embodiments, the washing and / or concentrating are performed for about 4 hours to about48 hours (e.g., about 8 hours to about 36 hours, about 10 hours to about 28 hours). In some embodiments, the washing is performed for about 8 hours or more. In some embodiments, the washing is performed for about 36 hours or less.WSGR Docket No. 64651-711.601

[0025] In some embodiments, the washing is performed for about 18 hours. In some embodiments, the washing is performed using a solvent having a boiling point of about 30 °C or more (e.g., about 70 °C or more, about 120 °C or more).

[0026] In some embodiments, the washing is performed using a solvent having a boiling point of about 240 °C or less. In some embodiments, the washing is performed with a solvent which is an organic solvent, water, an alcohol, a polar aprotic solvent, a halocarbon, and / or combinations thereof.

[0027] In some embodiments, a solvent comprising the contacted starting reagent is acetonitrile, propionitrile, butyronitrile, toluene, 1,2 -dichlorobenzene, chlorobenzene, fluorobenzene, 1,2 -difluorobenzene, dichloroethane, trifluorotoluene, chloroform, DMF, DMSO, sulfolane, MeTHF, THF, NMP, pyridine, butyl acetate, dioxane, an alcohol (e.g., tert- butanol, tert-amyl alcohol), water, and / or combinations thereof. In some embodiments, a solvent comprising the contacted starting reagent is C1-C6 alkyl-CN, and / or combinations thereof. In some embodiments, a solvent comprising the contacted starting reagent is acetonitrile, propionitrile, butyronitrile, and / or combinations thereof. In certain embodiments, the starting reagent may form a complex with the solvent upon contacting.

[0028] In some embodiments, the contacted starting reagent, polar aprotic compound and metal fluoride form a reaction mixture. In some embodiments, the reaction mixture is at a temperature of about -5 to about 120 °C. In some embodiments, the reaction mixture is at a temperature of about 55 to about 150 °C. In some embodiments, the reaction mixture is at a temperature of about 100 °C or less. In some embodiments, the contacting is for about 0.5 hours to about 40 hours. In some embodiments, the contacting is for about 12 hours or more.

[0029] In some embodiments, the contacting is for about 14 hours to about 22 hours. In some embodiments, the contacting is for about 84 hours or less.

[0030] In some embodiments, the contacting is for about 60 hours to about 80 hours. In some embodiments, the reaction mixture further comprises a phase transfer agent, a base, and / or combinations thereof.

[0031] In some embodiments, the phase transfer agent is a crown ether (e.g., 18 crown 6), a cryptand, an ionic transfer agent (e.g., tetramethylammonium chloride), and / or a hydrogen - bonding phase transfer agent. In some embodiments, the phase transfer agent is a crown ether (e.g., 18 crown 6). In some embodiments, the base is a pyridine derivative (e.g., DMAP).

[0032] In some embodiments, the reaction mixture further comprises a reaction solvent. In some embodiments, the reaction solvent is an organic solvent, water, an alcohol, a polar aprotic solvent, a halocarbon, and / or combinations thereof.WSGR Docket No. 64651-711.601

[0033] In some embodiments, the reaction solvent is a C1 -C6 alkyl-CN. In some embodiments, the reaction solvent is acetonitrile, propionitrile, pyridine, butyronitrile, toluene, 1,2-dichlorobenzene, chlorobenzene, fluorobenzene, 1,2 -difluorobenzene, dichloroethane, trifluorotoluene, chloroform, DMF, DMSO, an alcohol (e.g., tert-butanol, tert-amyl alcohol), water, and / or combinations thereof. In some embodiments, the reaction solvent is acetonitrile, propionitrile, pyridine, butyronitrile, and / or combinations thereof.

[0034] In some embodiments, the reaction solvent is acetonitrile, chloroform, sulfolane, THF, NMP, and / or combinations thereof. In some embodiments, the starting reagent comprises a leaving group. In some embodiments, the leaving group is chlorine, iodine, or bromine.

[0035] In some embodiments, the battery electrolyte precursor comprises at least one additional fluorine (e.g., at least two additional fluorines) compared to the starting reagent. In some embodiments, the battery electrolyte precursor is KPF6, or a salt thereof. In some embodiments, the battery electrolyte precursor is NaPF6, KPF6, or salts thereof.

[0036] In some embodiments, a molar ratio of the phase transfer agent to the starting reagent is about 0 to about 4. In some embodiments, a molar ratio of the base to the starting reagent is about 0 to about 2. In some embodiments, a molar ratio of a fluorine equivalent content in the metal fluoride to the starting reagent is about 0.1 or more.

[0037] In some embodiments, a yield of the battery electrolyte precursor is about 10% or more. In some embodiments, a yield of the battery electrolyte precursor is about 20% to about 80%. In some embodiments, a yield of the battery electrolyte precursor is about 75% to about 95%.

[0038] In some embodiments, a concentration of the starting reagent in the reaction solvent and / or alkyl carbonate solvent is about 0.01 M to about 3 M. In some embodiments, a concentration of the starting reagent in the reaction solvent and / or alkyl carbonate solvent is about 1 M or less.

[0039] In some embodiments, the battery electrolyte precursor is contacted with an electrolyte agent (e.g., lithium salt) to provide a battery electrolyte and / or a salt thereof. In some embodiments, the electrolyte agent is a lithium salt or a sodium salt.

[0040] In some embodiments, the electrolyte agent is lithium perchlorate, lithium sulphate, lithium chloride, lithium bromide, lithium tetrafluoroborate, lithium carbonate, lithium hydroxide, or a combination of two or more thereof.

[0041] In some embodiments, the electrolyte agent is LiCl. In some embodiments, the electrolyte agent is lithium tetrafluoroborate. In some embodiments, the electrolyte agent is lithium perchlorate. In some embodiments, the electrolyte agent is NaCl or NaC104. In someWSGR Docket No. 64651-711.601 embodiments, the starting reagent is PCI3, PCI5, LiPCk, P4O6, P2O5. In some embodiments, the starting reagent is PC13. In some embodiments, the starting reagent is PC15.

[0042] In some embodiments, the battery electrolyte is LiPF6. In some embodiments, the battery electrolyte is NaPF6. In certain embodiments, the battery electrolyte may be prepared as a solvent complex. In further examples, the solvent complex comprises LiPF6and a polar aprotic solvent. In some embodiments, the solvent complex comprises acetonitrile.

[0043] In some embodiments, the battery electrolyte precursor is contacted with the electrolyte agent in a solvent selected from acetonitrile, acetone, THF, ethanol, methanol, dioxane, methyl t-butyl ether, diethyl ether, MEK, dimethyl carbonate, and propylene carbonate, and / or combinations of one or more thereof. In some embodiments, the battery electrolyte precursor is contacted with the electrolyte agent for about 1 hour to about 84 hours (e.g., about 2 hours to about 76 hours, about 3 hours to about 24 hours, about 4 hours to about 12 hours, about 5 hours to about 10 hours). In some embodiments, the battery electrolyte precursor is contacted with the electrolyte agent for about 30 hours or less (e.g., about 24 hours or less, about 18 hours or less, about 12 hours or less, about 8 hours or less).

[0044] In some embodiments, the battery electrolyte precursor is contacted with the electrolyte agent for about 2 hours or more (e.g., about 4 hours or more, about 8 hours or more, about 16 hours or more). In some embodiments, the battery electrolyte precursor is contacted with the electrolyte agent for about 18 hours. In some embodiments, a combination of the battery electrolyte precursor and the electrolyte agent is at a temperature of about 10 to about 80 °C (e.g., about 20 to about 70 °C, about 30 to about 60 °C).

[0045] In some embodiments, a combination of the battery electrolyte precursor and the electrolyte agentis at a temperature of about 10 °C or more (e.g., about 15 °C or more, about 20 °C or more). In some embodiments, a combination of the battery electrolyte precursor and the electrolyte agent is at a temperature of about 60 °C or less (e.g., about 50°C or less, about 40°C or less, about 30°C or less). In some embodiments, a combination of the battery electrolyte precursor and the electrolyte agent is at room temperature.BRIEF DESCRIPTION OF THE DRAWINGS

[0046] The novel features of the invention are set forth with particularity in the appended claims. A better understanding of the features and advantages of the present invention will be obtained by reference to the following detailed description that sets forth illustrative embodiments, in which the principles of the invention are utilized, and the accompanying drawings (also “Figure” and “FIG.” herein), of which:

[0047] FIG.l illustrates an exemplary scheme of fluorinating a starting reagent provided herein.WSGR Docket No. 64651-711.601

[0048] FIG.2 illustrates an exemplary scheme of fluorinating a starting reagent provided herein.

[0049] FIG.3 illustrates an exemplary scheme of fluorinating a starting reagent provided herein.

[0050] FIG.4 illustrates an exemplary scheme of fluorinating a starting reagent provided herein.

[0051] FIG.5 illustrates an exemplary scheme of fluorinating a starting reagent provided herein.

[0052] FIG.6 illustrates an exemplary scheme of fluorinating a starting reagent provided herein.

[0053] FIG.7 illustrates an exemplary scheme of fluorinating a starting reagent provided herein.

[0054] FIG.8 illustrates an exemplary scheme of fluorinating a starting reagent provided herein.

[0055] FIG.9 illustrates an exemplary scheme of fluorinating a starting reagent to produce a battery electrolyte provided herein.

[0056] FIG.10 illustrates an exemplary scheme of fluorinating a starting reagent to produce a battery electrolyte provided herein.

[0057] FIG.ll illustrates an exemplary scheme of fluorinating a starting reagent to produce a battery electrolyte provided herein.

[0058] FIG.12 illustrates an exemplary scheme of fluorinating a starting reagent to produce a battery electrolyte provided herein.

[0059] FIG.13 illustrates an exemplary scheme of fluorinating a starting reagent to produce a battery electrolyte provided herein.

[0060] FIG.14 illustrates an exemplary scheme of preparing a battery electrolyte provided herein.

[0061] FIG.15 illustrates an exemplary scheme of preparing a battery electrolyte provided herein.DETAILED DESCRIPTION OF THE INVENTIONCertain Definitions

[0062] As used herein and in the appended claims, the singular forms "a," "and," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "an agent" includes a plurality of such agents, and reference to "the cell" includes reference to one or more cells (or to a plurality of cells) and equivalents thereof known to those skilled in the art, and so forth. When ranges are used herein for physical properties, suchWSGR Docket No. 64651-711.601 as molecular weight, or chemical properties, such as chemical formulae, all combinations and subcombinations of ranges and specific embodiments therein are intended to be included. The term "about" when referring to a number or a numerical range means that the number or numerical range referred to is an approximation within experimental variability (or within statistical experimental error), and thus the number or numerical range may vary between 1% and 15% of the stated number or numerical range. The term "comprising" (and related terms such as "comprise" or "comprises" or "having" or "including") is not intended to exclude that in other certain embodiments, for example, an embodiment of any composition of matter, composition, method, or process, or the like, described herein, may "consist of" or "consist essentially of" the described features.

[0063] As used herein “ageing” of a solution, product, or reaction mixture generally refers to maintaining the solution, product, or reaction mixture at a temperature for a period of time to allow for completion of a reaction or establishment of an equilibrium. Ageing of a solution can comprise stirring, sonication, and / or recirculation through or over an ion exchange membrane.

[0064] Provided herein are methods and processes useful for synthesizing battery electrolytes. In some instances, such reagents and compositions are useful in producing battery electrolytes in high-yields and / or without using reagents that may be toxic, such as HF, PF3, and / or PF5.

[0065] In some instances, such methods and processes are useful in producing battery electrolyte precursors in high-yields and / or without using toxic reagents, such as HF.

[0066] In some embodiments, provided herein is a method of manufacturing a battery electrolyte precursor (e.g., KPF6). In specific embodiments, any of the methods provided herein can comprise contacting a metal fluoride with a starting reagent to provide a battery electrolyte precursor. In some embodiments, any of the methods provided herein comprises contacting a metal fluoride or a fluorination reagent of PCT / IB2024 / 000280, which is incorporated by reference for disclosure of such reagent, with a starting reagent to provide a battery electrolyte or a battery electrolyte precursor.

[0067] In some embodiments, provided herein is a method of manufacturing a battery electrolyte comprising lithium hexafluorophosphate or a salt thereof. In specific embodiments, any of the methods provided herein can comprise contacting a metal fluoride with a starting reagent (e.g., a starting reagent provided herein) to provide a battery electrolyte.

[0068] Provided herein are methods of using metal fluorides for production of battery electrolyte, battery electrolyte precursors, and / or one or more salts thereof. In some instances,WSGR Docket No. 64651-711.601 such methods and processes are useful in producing fluorinated products in high yield and / or without the need for use of toxic reagents, such as HF.

[0069] In some embodiments, crude metal fluorides are purified at least in part using a filtration process. In some embodiments, a filtrate is concentrated and / or dried during any step or process of any method described herein. In some embodiments, the filtration process comprises passing any solution described herein through the same or a plurality of filtration modules a plurality of times (e.g., by making three or more consecutive passes through the same module and / or by passing once each through three consecutively coupled modules). In some embodiments, a fluorine recovery of a filtration process employed herein is greater than 90% (e.g., greater than 95% or greater than 99%). In some embodiments, a rejection of one or more contaminants by a filtration process employed in any method described herein is greater than 90% (e.g., greater than 95% or greater than 99%). In some embodiments, provided herein is a method of manufacturing a purified metal fluoride, the method comprising washing and concentrating a lower grade (e.g., industrial grade) metal fluoride.

[0070] In certain embodiments, provided herein are methods of providing (e.g., making, manufacturing, or the like) compositions comprising battery electrolytes or battery electrolyte precursors. In specific embodiments, a battery electrolyte provided herein comprises lithium hexafluorophosphate or a salt thereof (e.g., the product of any of the reactions illustrated in FIGs. 10-13). Lithium hexafluorophosphate can also be referred to as lithium phosphohexafluoride, lithium phosphorous hexafluoride, LiPF6, or other equivalent identifiers. In yet more specific embodiments, a battery electrolyte precursor (e.g., as provided herein) is the precursor to lithium hexafluorophosphate, a Li-ion battery electrolyte. In certain embodiments, battery electrolytes or battery electrolyte precursors (e.g., KPF6) are useful for producing battery electrolytes without the use of toxic reagents such as HF.

[0071] In some embodiments, a metal of the metal fluorides may comprise: K+, Na+, Rb+, Ca2+, Mg2+, Fe2+, Fe3+, Cu+, Cu2+, Ag+, Li+, NH4+, Sr+, Ba2+, Zn2+, Cd2+, Al3+, [Co(NH3)6]3+, or Cs+. In still more specific embodiments, (e.g., at least one) metal of the metal fluoride provided herein is K+, Na+, Ca2+, Li+, Co3+, Co2+, U2+, U4+, U6+, Ni2+, and / or Cs.+

[0072] In some embodiments, a solvent provided herein is any suitable solvent, such as a polar aprotic solvent, water, an alcohol, an alkyl carbonate solvent, a halocarbon and / or a combination thereof. In certain embodiments, a solvent provided herein is C1-C6 alkyl-CN, acetonitrile, propionitrile, butyronitrile, toluene, 1,2-dichlorobenzene, chlorobenzene, fluorobenzene, 1,2-difluorobenzene, dichloroethane, trifluorotoluene, chloroform, sulfolane, DMF, DMSO, tert-butanol, dichloromethane (DCM), tert-amyl alcohol, water, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl propylWSGR Docket No. 64651-711.601 carbonate, ethyl propyl carbonate, trifluoroethyl carbonate, bis(trifluoroethyl) carbonate, trifluoroethyl methyl carbonate, THF, MeTHF, NMP, butyl acetate, dioxane, and / or combinations thereof.

[0073] In some embodiments, a solvent provided herein is selected according to its characteristics, such as boiling point, ability to solubilize a composition provided herein, polarity, pH, or the like.

[0074] In certain embodiments, a solvent (e.g., a solvent provided herein) has a boiling point of about 30 °C or more. In some embodiments, a solvent provided herein has a boiling point of about 70 °C or more. In certain embodiments, a solvent or (e.g., fluid) composition provided herein has a boiling point of about 120 °C or more. In some embodiments, a solvent or (e.g., fluid) composition provided herein has a boiling point of about 240 °C or less.

[0075] In some embodiments, provided herein is a method for fluorinating a starting reagent comprising PCh, PCI5, PF5, LiPCk, P4O6, P2O5 or a salt thereof. In some embodiments, provided herein is a method for fluorinating a starting reagent comprising PCI 3, PC15, LiPCl6, P4O6, P2O5 or a salt thereof. In some embodiments, provided herein is a method for fluorinating a starting reagent comprising PCI3, PCI5, or a salt thereof. In certain embodiments, starting reagents provided herein comprise a leaving group (e.g., chlorine, iodine, bromine). In specific embodiments, a leaving group of a starting reagent provided herein is chlorine. In certain embodiments, provided herein are methods for fluorinating a starting reagent (e.g., a starting reagent provided herein) or a salt thereof to provide a battery electrolyte precursor, a battery electrolyte, and / or a salt thereof (e.g., the product of any of the reactions illustrated in FIGs. 1-15). In some embodiments, provided herein are methods for fluorinating a starting reagent (e.g., a starting reagent provided herein) or a salt thereof to provide a battery electrolyte precursor (e.g., KPF6). In specific embodiments, provided herein are methods for fluorinating PCI3. In yet more specific embodiments, provided herein are methods for fluorinating PC15. In still more specific embodiments, provided herein are methods for fluorinating P4O6. In yet more specific embodiments, provided herein are methods for fluorinating LiPCU. In still more specific embodiments, provided herein are methods for fluorinating P2O5. In yet more specific embodiments, the starting reagent is PC15. In still more specific embodiments, the starting reagent is PC13.

[0076] In some instances, a reagent or reagent composition provided herein is used to fluorinate a starting reagent (e.g., a starting reagent provided herein) to provide a high value, high yield battery electrolyte or battery electrolyte precursor without the use of toxic chemicals such as HF.WSGR Docket No. 64651-711.601

[0077] In certain embodiments, provided herein are methods for isolating a battery electrolyte precursor provided herein (e.g., hexafluorophosphate or a salt thereof). In some embodiments, a battery electrolyte precursor provided herein is isolated and / or concentrated (e.g., purified) by any suitable method such as by distillation, crystallization, recrystallization, sublimation, any suitable chromatography method (e.g., column, HPLC, or the like), trituration or the like. In some embodiments, any of the methods provided herein comprise recrystallization after the contacting of the starting reagent and the fluorination reagent. In some embodiments, the recrystallization is performed on one or more of: the battery electrolyte precursor, the starting reagent, the electrolyte agent, and / or the metal fluoride . In some embodiments, the recrystallization is performed on the battery electrolyte, wherein the battery electrolyte is LiPF6. In some embodiments, the recrystallization is performed at a lower temperature than the contacting. In some embodiments, the recrystallization is at a temperature of less than 45 °C. In some embodiments, the recrystallization is at a temperature less than 30 °C (e.g., less than 20 °C, 15 °C, 10 °C, or 5 °C). In some embodiments, the recrystallization is at a temperature of less than 0 °C (e.g., less than -5 °C, -10 °C, -20 °C, or - 30 °C).

[0078] In certain embodiments, an isolation and / or concentration method (e.g., purification) comprises recrystallizing a battery electrolyte precursor provided herein in any suitable solvent (e.g., a solvent provided herein). In certain embodiments, an isolation and / or concentration method (e.g., an isolation or concentration method provided herein) further comprises triturating a battery electrolyte precursor provided herein using any suitable method. In some embodiments, a battery electrolyte precursor provided herein is triturated with any suitable solvent (e.g., a solvent provided herein) to provide a (e.g., isolated) battery electrolyte precursor provided herein. In some embodiments, the triturating comprises crushing a solid in a solvent selected to remove impurities. In certain embodiments, triturating comprises evaporating the solvent from the crushed solid.

[0079] In certain embodiments, provided herein are methods for providing a battery electrolyte provided herein (e.g., lithium hexafluorophosphate). In some embodiments, a battery electrolyte comprises lithium hexafluorophosphate or a salt thereof. In certain embodiments, provided herein is a method comprising contacting a battery electrolyte precursor (e.g., a battery electrolyte precursor provided herein) with an electrolyte agent (e.g., thereby providing a battery electrolyte). In some embodiments, a battery electrolyte precursor (e.g., a battery electrolyte precursor provided herein) contacted with an electrolyte agent (e.g., an electrolyte agent provided herein) provides a battery electrolyte (e.g., a battery electrolyte provided herein). In certain embodiments, an electrolyte agent provided herein is any suitableWSGR Docket No. 64651-711.601 electrolyte salt such as a lithium salt (e.g., lithium perchlorate, lithium sulphate, lithium chloride, lithium bromide, lithium tetrafluoroborate). In some embodiments, an electrolyte agent provided herein is any suitable electrolyte salt such as a lithium salt or a sodium salt (e.g., NaCl, NaC104). In specific embodiments, an electrolyte agent is lithium sulphate. In still more specific embodiments, the electrolyte agent is lithium perchlorate. In yet more specific embodiments, the electrolyte agent is lithium chloride. In still more specific embodiments, the electrolyte agent is lithium bromide. In yet more specific embodiments, the electrolyte salt is lithium tetrafluoroborate. In still more specific embodiments, the electrolyte salt is NaCl. In yet more specific embodiments, the electrolyte salt is NaC104.

[0080] In certain instances, characteristics of the starting reagent (e.g., a starting reagent provided herein), such as reactivity, (e.g., low) solubility provide difficulties for obtaining high yields of a battery electrolyte precursor or battery electrolyte.

[0081] In some embodiments, the battery electrolyte precursor is contacted with the electrolyte agent under any suitable conditions, such as at any selected temperature, with stirring or other agitation, at any selected pH, for any selected period of time, or the like.

[0082] In certain embodiments, an amount of an electrolyte agent (e.g., an electrolyte agent provided herein) is about 0 equivalents to about 5 equivalents of a battery electrolyte precursor (e.g., a battery electrolyte precursor provided herein) (e.g., about 0.5 to about 4 equivalents, about 1 to about 3 equivalents). In some embodiments, the amount of the electrolyte agent is about 0.5 or more (e.g., about 1 or more, about 2 or more, about 4) equivalents of the battery electrolyte precursor. In certain embodiments, the amount of the electrolyte agent is about 4 or less (e.g., about 2 or less, about 1 or less, about 0.5 or less) equivalents of the battery electrolyte precursor. In specific embodiments, the amount of the electrolyte agent is about 1 .1 equivalents of the battery electrolyte precursor. In yet more specific embodiments, the amount of the electrolyte agent is about 2 equivalents of the battery electrolyte precursor. In still more embodiments, the amount of the electrolyte agent is about 1.5 equivalents of the battery electrolyte precursor. In yet more embodiments, the amount of the electrolyte agent is about 1.16 equivalents of the battery electrolyte precursor.

[0083] In certain embodiments, a battery electrolyte precursor (e.g., a battery electrolyte precursor provided herein) is contacted with an electrolyte agent (e.g., an electrolyte agent provided herein) in any suitable solvent (e.g., a solvent provided herein). In certain embodiments, a battery electrolyte precursor (e.g., a battery electrolyte precursor provided herein) is contacted with an electrolyte agent (e.g., an electrolyte agent provided herein) in a selected solvent (e.g., a solvent provided herein). In certain embodiments, a (e.g., selected) solvent is any suitable solvent (e.g., as provided herein). In some embodiments, the selectedWSGR Docket No. 64651-711.601 solvent is an organic solvent. In certain embodiments, the selected solvent is acetonitrile, acetone, tetrahydrofuran (THF), an alcohol (e.g., ethanol, methanol), dioxane, methyl / butyl ether, diethyl ether, methyl ethyl ketone (MEK), an alkyl carbonate (e.g., dimethyl carbonate, propylene carbonate), and / or combinations of one or more thereof. In specific embodiments, a battery electrolyte precursor (e.g., a battery electrolyte precursor provided herein) is contacted with an electrolyte agent (e.g., an electrolyte agent provided herein) in acetonitrile. In yet more specific embodiments, a battery electrolyte precursor (e.g., a battery electrolyte precursor provided herein) is contacted with an electrolyte agent (e.g., an electrolyte agent provided herein) in acetone. In still more specific embodiments, a battery electrolyte precursor (e.g., a battery electrolyte precursor provided herein) is contacted with an electrolyte agent (e.g., an electrolyte agent provided herein) in propylene carbonate and dimethyl carbonate. In yet more specific embodiments, a battery electrolyte precursor (e.g., a battery electrolyte precursor provided herein) is contacted with an electrolyte agent (e.g., an electrolyte agent provided herein) in methanol. In still more specific embodiments, a battery electrolyte precursor (e.g., a battery electrolyte precursor provided herein) is contacted with an electrolyte agent (e.g., an electrolyte agent provided herein) in ethanol. In yet more specific embodiments, a battery electrolyte precursor (e.g., a battery electrolyte precursor provided herein) is contacted with an electrolyte agent (e.g., an electrolyte agent provided herein) in dioxane.

[0084] In certain embodiments, a combination of a battery electrolyte precursor (e.g., a battery electrolyte precursor provided herein) and an electrolyte agent (e.g., an electrolyte agent provided herein) is at a temperature of about 10 to about 80 °C (e.g., about 20 to about 70 °C, about 30 to about 60 °C). In some embodiments, a combination of the battery electrolyte precursor and the electrolyte agent is at a temperature of about l0 °C or more (e.g., about 15 °C or more, about 20 °C or more). In some embodiments, a combination of the battery electrolyte precursor and the electrolyte agent is at a temperature of about 60 °C or less (e.g., about 50°C or less, about 40°C or less, about 30°C or less). In specific embodiments, a combination of the battery electrolyte precursor and the electrolyte agent is at a temperature of about 25 °C. In yet more specific embodiments, a combination of the battery electrolyte precursor and the electrolyte agent is at room temperature.

[0085] In some instances, lowering the temperature (e.g., to about 20 °C or less) of a combination of the battery electrolyte precursor and electrolyte agent after a predetermined amount of time (e.g., about 6 hours to about 48 hours) provides an increased yield of the battery electrolyte.WSGR Docket No. 64651-711.601

[0086] In some embodiments, a battery electrolyte precursor (e.g., a battery electrolyte precursor provided herein) is contacted with an electrolyte agent (e.g., an electrolyte agent provided herein) for about 1 hour to about 84 hours (e.g., about 2 hours to about 76 hours, about 3 hours to about 24 hours, about 4 hours to about 12 hours, about 5 hours to about 10 hours). In some embodiments, the battery electrolyte precursor is contacted with the electrolyte agent for about 30 hours or less (e.g., about 24 hours or less, about 18 hours or less, about 12 hours or less, about 8 hours or less). In certain embodiments, the battery electrolyte precursor is contacted with the electrolyte agent for about 84 hours or less (e.g., about 72 hours or less). In some certain embodiments, the battery electrolyte precursor is contacted with the electrolyte agent for about 2 hours or more (e.g., about 4 hours or more, about 8 hours or more, about 16 hours or more, about 32 hours or more). In certain embodiments, a battery electrolyte precursor (e.g., a battery electrolyte precursor provided herein) is contacted with an electrolyte agent (e.g., an electrolyte agent provided herein) for about 0.5 hours to about 10 hours (e.g., about 1 hours to about 8 hours, about 2 hours to about 6 hours) . In some embodiments, the battery electrolyte precursor is contacted with the electrolyte agent for about 8 hours or less (e.g., about 6 hours or less, about 4 hours or less, about 3 hours or less, about 1 hour or less). In certain embodiments, the battery electrolyte precursor is contacted with the electrolyte agent for about 1 hour or more (e.g., about 2 hours or more, about 4 hours or more, about 8 hours or more). In specific embodiments, the battery electrolyte precursor is contacted with the electrolyte agent for about 2 hours. In yet more specific embodiments, the battery electrolyte precursor is contacted with the electrolyte agent for about 18 hours. In still more specific embodiments, the battery electrolyte precursor is contacted with the electrolyte agent for about 1 hour. In yet more specific embodiments, the battery electrolyte precursor is contacted with the electrolyte agent for about 8 hours. In certain embodiments, the temperature of the combination is changed (e.g., lowered to 0 °C or less) after a period of time.

[0087] In certain embodiments, a drying agent is added to a combination of a battery electrolyte precursor (e.g., a battery electrolyte precursor provided herein) and an electrolyte agent (e.g., an electrolyte agent provided herein). In some embodiments, the drying agent can be any suitable drying agent. In certain embodiments, the drying agent is an organolithium compound (e.g., an alkyl lithium). In specific embodiments, the drying agent is methyl lithium, tert-butyl lithium, lithium hydride, or the like. In yet more specific embodiments, the drying agent is methyl lithium (MeLi). In certain instances, addition of a drying agent improves yield of a battery electrolyte.

[0088] In certain embodiments, a drying agent (e.g., as provided herein) is added to a combination of a battery electrolyte precursor (e.g., a battery electrolyte precursor providedWSGR Docket No. 64651-711.601 herein) and an electrolyte agent (e.g., an electrolyte agent provided herein) after the temperature of the combination of the battery electrolyte precursor and the electrolyte agent (e.g., the combination comprising the battery electrolyte) is lowered to about 20 °C or less (e.g., about 15 °C or less, about 10 °C or less, about 3 °C or less). In specific embodiments, the combination of the battery electrolyte precursor and the electrolyte agent is lowered to about 0 °C prior to addition of the drying agent. In yet more specific embodiments, the combination of the battery electrolyte precursor and the electrolyte agent is lowered to about 5 °C prior to addition of the drying agent.

[0089] In some embodiments, an amount of a drying agent provided herein is about 0.001 equivalents to about 5 equivalents (e.g., about 0.005 to about 1, about 0.01 to about 0.1 ) of a battery electrolyte precursor (e.g., a battery electrolyte precursor provided herein). In certain embodiments, the amount of the drying agent is about 0.005 or more (e.g., about 0.01 or more, about 0.05 or more) equivalents of the battery electrolyte precursor. In some embodiments, the amount of the drying agent is about 5 or less (e.g., about 1 or less, about 0.5 or less, about 0.1 or less, about 0.05 or less) equivalents of the battery electrolyte precursor. In specific embodiments, the amount of the drying agent is about 0.01 to about 0.1 equivalents of the battery electrolyte precursor. In yet more specific embodiments, the amount of the drying agent is about 0.024 equivalents of the battery electrolyte precursor. In certain embodiments, a concentration of a battery electrolyte precursor (e.g., a battery electrolyte precursor provided herein) in a combination provided herein (e.g., a combination of a battery electrolyte precursor and an electrolyte agent in a selected solvent provided herein) is about 0.05 M to about 5 M (e.g., about 0.1 M to about 4 M, about 0.2 M to about 3 M, about 0.5 M to about 1.5 M). In some embodiments, the concentration of the battery electrolyte precursor in the combination is about 0.05 M or more (e.g., about 0.1 M or more, about 0.2 M or more, about 0.8 M or more). In certain embodiments, the concentration of the battery electrolyte precursor in the combination is about 0.4 M or less (e.g., about 3 M or less, about 1 .5 M or less). In specific embodiments, the concentration of the battery electrolyte precursor in the combination is about 1 M. In yet more specific embodiments, the concentration of the battery electrolyte precursor in the combination is about 1.5 M.

[0090] In certain embodiments, provided herein is a composition or a method comprising contacting a starting reagent (e.g., a starting reagent provided herein) with a reagent or reagent composition described herein (e.g., thereby fluorinating the starting reagent and providing a fluorinated product). In some embodiments, a starting reagent provided herein contacted with a reagent or reagent composition provided herein provides a battery electrolyte precursor provided herein. In some embodiments, the starting reagent is contacted with the reagent orWSGR Docket No. 64651-711.601 reagent composition under any suitable conditions, such as at any selected temperature, with stirring or other agitation, at any selected pH, for any selected period of time, or the like.

[0091] In certain embodiments, a combination of a metal fluoride or reagent composition provided herein and a starting reagent provided herein is at a temperature of about -10 to about 150 °C (e.g., about -5 to about 120 °C, about 0 to about 90 °C). In certain embodiments, a combination of a metal fluoride or reagent composition provided herein and a starting reagent provided herein is at a temperature of about 20 to about 200 °C (e.g., about 60 to about 160 °C, about 70 to about 120 °C). In some embodiments, a combination of the metal fluoride or reagent composition and the starting reagent is at a temperature of about 20 °C or more. In certain embodiments, a combination of the metal fluoride or reagent composition and the starting reagent is at a temperature of about 40 °C or more. In some embodiments, a combination of the metal fluoride or reagent composition and the starting reagent is at a temperature of about 60 °C or more. In certain embodiments, a combination of the metal fluoride or reagent composition and the starting reagent is at a temperature of about 80 °C or more. In some embodiments, a combination of the metal fluoride or reagent composition and the starting reagent is at a temperature of about 100 °C or more. In certain embodiments, a combination of the metal fluoride or reagent composition and the starting reagent is at a temperature of about 120 °C or more. In some embodiments, a combination of the metal fluoride or reagent composition and the starting reagent is at a temperature of about 140 °C or more. In specific embodiments, a combination of the metal fluoride or reagent composition and the starting at a temperature of about 0 °C. In yet more specific embodiments, a combination of the metal fluoride or reagent composition and the starting reagent is at room temperature. In still more specific embodiments, a combination of the metal fluoride or reagent composition and the starting reagent is at temperature of about 25 °C. In specific embodiments, a combination of the metal fluoride or reagent composition and the starting reagent is at a temperature of about 75 °C. In still more specific embodiments, a combination of the metal fluoride or reagent composition and the starting reagent is at a temperature of about 80 °C. In yet more specific embodiments, a combination of the metal fluoride or reagent composition and the starting reagent is at a temperature of about 90 °C. In still more specific embodiments, a combination of the metal fluoride or reagent composition and the starting reagent is at a temperature of about 110 °C. In yet more specific embodiments, a combination of the metal fluoride or reagent composition and the starting reagent is at a temperature of about 115 °C. In still more specific embodiments, a combination of the metal fluoride or reagent composition and the starting reagent is at a temperature of about 150 °C.WSGR Docket No. 64651-711.601

[0092] In certain embodiments, a starting reagent provided herein is contacted with a metal fluoride or reagent composition provided herein for about 0.5 hour to about 50 hours (e.g., about 1 hours to about 40 hours, about 1.5 hours to about 20 hours, about 3 hours to about 10 hours). In certain embodiments, a starting reagent provided herein is contacted with a metal fluoride or reagent composition provided herein for about 1 hour to about 84 hours (e.g., about 2 hours to about 76 hours, about 3 hours to about 24 hours, about 4 hours to about 12 hours, about 5 hours to about 10 hours). In some embodiments, the starting reagent is contacted with the metal fluoride or reagent compositionfor about 30 hours or less (e.g., about 24 hours or less, about 18 hours or less, about 12 hours or less, about 8 hours or less). In certain embodiments, the starting reagent is contacted with the metal fluoride or reagent composition for about 84 hours or less (e.g., about 72 hours or less). In some certain embodiments, the starting reagent is contacted with the metal fluoride or reagent composition for about 1 hour or more (e.g., about 4 hours or more, about 16 hours ormore, about 56 hours or more). In specific embodiments, the starting reagent is contacted with the metal fluoride or reagent composition for about 6 hours. In yet more specific embodiments, the starting reagent is contacted with the metal fluoride or reagent composition for about 8 hours. In still more specific embodiments, the starting reagent is contacted with the metal fluoride or reagent composition for about 18 hours. In yet more specific embodiments, the starting reagent is contacted with the metal fluoride or reagent composition for about 66 hours. In yet more specific embodiments, the starting reagent is contacted with the metal fluoride or reagent composition for about 2 hours. In still more specific embodiments, the starting reagent is contacted with the metal fluoride or reagent composition for about 3 hours. In yet more specific embodiments, the starting reagent is contacted with the metal fluoride or reagent composition for about 5 hours. In still more specific embodiments, the starting reagent is contacted with the metal fluoride or reagent composition for about 12 hours.

[0093] In certain instances, contacting a starting reagent with a metal fluoride or reagent composition provided herein under inert conditions provides a greater yield of a battery electrolyte precursor (e.g., a battery electrolyte precursor provided herein) than under conditions without an inert atmosphere. In some instances, contacting a starting reagent with a metal fluoride or reagent composition provided herein under non-inert conditions provides a substantial yield of a battery electrolyte precursor (e.g., about 50% yield or more).

[0094] In some embodiments, an amount of a metal fluoride or reagent composition provided herein is about 0.1 equivalents to about 20 equivalents of a starting reagent provided herein. In certain embodiments, an amount of a metal fluoride or reagent composition provided herein is about 0. 1 equivalents to about 10 equivalents of a starting reagent providedWSGR Docket No. 64651-711.601 herein. In some embodiments, the amount of the metal fluoride or reagent composition is about 1 or more (e.g., about 2 or more, about 3 or more, about 4 or more, about 5 or more, about 6 or more, about 7 or more, about 8 or more, about 9 or more) equivalents of the starting reagent. In certain embodiments, the amount of the metal fluoride or reagent composition is about 20 or less (e.g., about 18 or less, about 15 or less, about 12 or less, about 10 or less) equivalents of the starting reagent. In certain embodiments, the amount of the metal fluoride or reagent composition is about 10 or less (e.g., about 8 or less, about 6 or less, about 4 or less, about 2 or less) equivalents of the starting reagent. In specific embodiments, the amount of the metal fluoride or reagent composition is about 1 equivalent of the starting reagent. In still more specific embodiments, the amount of the metal fluoride or reagent composition is about 2 equivalents of the starting reagent. In yet more specific embodiments, the amount of the metal fluoride or reagent composition is about 3 equivalents of the starting reagent. In still more specific embodiments, the amount of the metal fluoride or reagent composition is about 4 equivalents of the starting reagent. In yet more specific embodiments, the amount of the metal fluoride or reagent composition is about 5 equivalents of the starting reagent. In still more specific embodiments, the amount of the metal fluoride or reagent composition is about 6 equivalents of the starting reagent. In yet more specific embodiments, the amount of the metal fluoride or reagent composition is about 7 equivalents of the starting reagent. In still more specific embodiments, the amount of the metal fluoride or reagent composition is about 8 equivalents of the starting reagent. In yet more specific embodiments, the amount of the metal fluoride or reagent composition is about 9 equivalents of the starting reagent. In still more specific embodiments, the amount of the metal fluoride or reagent composition is about 10 equivalents of the starting reagent.

[0095] In some instances, contacting greater equivalents of an metal fluoride or reagent composition relative to the starting reagent results in high yields of a battery electrolyte precursor provided herein.

[0096] In certain embodiments, a starting reagent provided herein is contacted with a metal fluoride or reagent composition provided herein in a reaction mixture. In some embodiments, a reaction mixture provided herein comprises a starting reagent, a metal fluoride or reagent composition, and a (e.g., reaction) solvent. In certain embodiments, a reaction mixture provided herein comprises a starting reagent, a metal fluoride or reagent composition, and a reaction solvent. In some embodiments, an (e.g., reaction) solvent is any suitable solvent (e.g., as provided herein). In certain embodiments, a reaction solvent is any suitable solvent (e.g., organic solvent) provided herein. In specific embodiments, the reaction solvent is acetonitrile, propionitrile, dimethyl carbonate (DMC), sulfolane, MeTHF, butylWSGR Docket No. 64651-711.601 acetate, dioxane, pyridine, butyronitrile, diethyl carbonate, NMP, and / or DMSO, and / or combinations of one or more thereof. In certain embodiments, the reaction solvent is acetonitrile, propionitrile, pyridine, butyronitrile, toluene, 1,2 -dichlorobenzene, chlorobenzene, fluorobenzene, 1,2 -difluorobenzene, dichloroethane, trifluorotoluene, chloroform, sulfolane, tetrahydrofuran (THF), n-methyl-2 -pyrrolidone (NMP), DMF, DMSO, an alcohol (e.g., tert-butanol, tert-amyl alcohol), water, and / or combinations thereof. In specific embodiments, the reaction solvent is acetonitrile, chloroform, sulfolane, tetrahydrofuran (THF), n-methyl-2 -pyrrolidone (NMP), and / or combinations thereof. In yet more specific, embodiments, the reaction solvent is acetonitrile, propionitrile, pyridine, and / or dimethylcarbonate, and / or combinations of one or more thereof. In still more specific embodiments, the (e.g., reaction) solvent is an alkyl carbonate solvent provided herein. In yet more specific, embodiments, the reaction solvent is acetonitrile. In still more specific embodiments, the (e.g., reaction) solvent is sulfolane. In yet more specific, embodiments, the reaction solvent is chloroform. In still more specific embodiments, the (e.g., reaction) solvent is THF. In yet more specific, embodiments, the reaction solvent is NMP. In still more specific, embodiments, the reaction solvent is propionitrile.

[0097] In certain instances, use of a Cl -C6 alkyl-CN solvent as the reaction solvent, such as acetonitrile or propionitrile, can help facilitate formation of the battery electrolyte or battery electrolyte precursor provided herein. In some instances, C1-C6 alkyl-CN solvent can be readily removed from the battery electrolyte or battery electrolyte precursor, such as under heat and strong vacuum (e.g., under inert conditions).

[0098] In certain embodiments, a reaction mixture provided herein comprises a starting reagent provided herein, a metal fluoride or reagent composition provided herein, a reaction solvent (e.g., a reaction solvent provided herein), a reaction base (e.g., a reaction base provided herein), water (e.g., deionized water), and / or an alcohol (e.g., an alcohol provided herein), and / or combinations of two or more thereof.

[0099] In certain embodiments, a reaction mixture provided herein further comprises a phase transfer agent. In specific embodiments, a reaction mixture provided herein comprises a starting reagent provided herein, a metal fluoride or reagent composition provided herein, a reaction solvent (e.g., a reaction solvent provided herein), and a phase transfer reagent (e.g., a phase transfer agent provided herein). In certain embodiments, a phase transfer agent (e.g., a phase transfer agent provided herein) is any suitable phase transfer agent, such as a crown ether, a cryptand, an ionic transfer agent (e.g., an ammonium salt), a hydrogen -bonding phase transfer agent, and / or a combination thereof. In some embodiments, a phase transfer agent provided herein is Kryptofix 221, Kryptofix 222, 18 -crown-6, (Dibenzo) 18 -crown-6,WSGR Docket No. 64651-711.601(dicyclo)18-crown-6, 12-crown-4, 15-crown-5, 21-crown-7, cryptand-222, 30-crown-10, (dibenzo)30-crown-10, Schreiner’s urea, ammonium sulfate, ammonium bicarbonate, ammonium chloride (e.g., tetramethyl ammonium chloride (TMAC)), ammonium iodide, ammonium benzoate, benzyltrimethyl, ammonium hydroxide, ammonium carbonate, ammonium dichromate, ammonium acetate, ammonium bromide, sodium tetradecyl sulfate, ammonium iodate and / or combinations thereof. In specific embodiments, a phase transfer agent provided herein is 18-crown-6, ammonium chloride, TMAC, and / or combinations thereof.

[0100] In some instances, addition of a phase transfer agent (e.g., a phase transfer agent provided herein) to a reaction mixture provided herein results in high yields of a battery electrolyte precursor provided herein.

[0101] In certain embodiments, an amount of a phase transfer agent (e.g., a phase transfer agent provided herein) is about 0 equivalents to about 8 equivalents of a starting reagent provided herein (e.g., about 0.05 to about 5 equivalents, about 0.1 to about 4 equivalents, about 0.5 to about 3 equivalents). In some embodiments, the amount of the phase transfer agent is about 0.05 or more (e.g., about 0.1 or more, about 0.5 or more, about 1 or more, about 2 or more) equivalents of the starting reagent. In certain embodiments, the amount of phase transfer agent is about 5 or less (e.g., about 3 or less, about 2 or less, about 1 or less, about 0.5 or less, about 0.1 or less) equivalents of the starting reagent. In specific embodiments, the amount of the phase transfer agent is about 1 equivalent of the starting reagent. In still more specific embodiments, the amount of the phase transfer agent is about 2 equivalents of the starting reagent. In yet more specific embodiments, the amount of the phase transfer agent is about 0.2 equivalents of the starting reagent. In still more specific embodiments, the amount of the phase transfer agent is about 0.5 equivalents of the starting reagent. In yet more specific embodiments, the amount of the phase transfer agent is about 0.1 equivalents of the starting reagent. In still more specific embodiments, the amount of the phase transfer agent is about 0.08 equivalents of the starting reagent.

[0102] In certain embodiments, a reaction mixture provided herein further comprises a reaction base (e.g., a reaction base provided herein). In specific embodiments, a reaction mixture provided herein comprises a starting reagent provided herein, a metal fluoride or reagent composition provided herein, a reaction solvent (e.g., a reaction solvent provided herein), and a reaction base (e.g., a reaction base provided herein). In yet more specific embodiments, a reaction mixture provided herein comprises a starting reagent provided herein, a metal fluoride or reagent composition provided herein, a reaction solvent (e.g., a reaction solvent provided herein), a phase transfer agent (e.g., a phase transfer agent provided herein),WSGR Docket No. 64651-711.601 and a reaction base (e.g., a reaction base provided herein). In still more specific embodiments, a reaction mixture provided herein comprises a starting reagent provided herein, a metal fluoride or reagent composition provided herein, a reaction solvent (e.g., a reaction solvent provided herein), a phase transfer agent (e.g., a phase transfer agent provided herein), and one or more reaction bases (e.g., a reaction base provided herein). In certain embodiments, a reaction base (e.g., a reaction base provided herein) is any suitable base, such as an organic base, an amine, a pyridine, and / or a pyridine derivative. In some embodiments, a reaction base provided herein is 4 -dimethylaminop yridine (DMAP), diisopropylethylamine (DIPEA), and / or pyridine. In specific embodiments, a reaction base provided herein is DMAP. In yet more specific embodiments, a reaction base provided herein is DIPEA. In still more specific embodiments, a reaction base provided herein is pyridine.

[0103] In some instances, addition of a reaction base provided herein to a reaction mixture provided herein results in high yields of a battery electrolyte precursor provided herein.

[0104] In certain embodiments, an amount of a reaction base (e.g., a reaction base provided herein) is about 0 equivalents to about 5 equivalents of a starting reagent provided herein (e.g., about 0.1 to about 4 equivalents, about 0.2 to about 3 equivalents, about 0.5 to about 2 equivalents). In some embodiments, the amount of the reaction base is about 0.05 or more (e.g., about 0.1 or more, about 0.5 or more, about 1 or more, about 2 or more) equivalents of the starting reagent. In certain embodiments, the amount of the reaction base is about 3 or less (e.g., about 2 or less, about 1.5 or less, about 1 or less, about 0.5 or less) equivalents of the starting reagent. In specific embodiments, the amount of the reaction base is about 0.2 equivalent of the starting reagent. In still more specific embodiments, the amount of the reaction base is about 1.2 equivalents of the starting reagent. In yet more specific embodiments, the amount of the reaction base is about 1 equivalents of the starting reagent. In still more specific embodiments, the amount of the reaction base is about 2 equivalents of the starting reagent. In yet more specific embodiments, the amount of the reaction base is about 0.5 equivalents of the starting reagent.

[0105] In certain embodiments, a reaction mixture provided herein further comprises (e.g., deionized) water. In specific embodiments, a reaction mixture provided herein comprises a starting reagent provided herein, a metal fluoride or reagent composition provided herein, a reaction solvent (e.g., a reaction solvent provided herein), a reaction base (e.g., a reaction base provided herein), and water.

[0106] In some instances, addition of water to a reaction mixture provided herein results in high yields of a battery electrolyte precursor provided herein.WSGR Docket No. 64651-711.601

[0107] In certain embodiments, an amount of water is about 0 equivalents to about 15 equivalents of a starting reagent provided herein (e.g., about 1 to about 12 equivalents, about 2 to about 9 equivalents, about 3 to about ? equivalents). In some embodiments, the amount of water is about 1 or more (e.g., about 2 or more, about 4 or more, about 6 or more, about 8 or more) equivalents of the starting reagent. In certain embodiments, the amount of water is about 12 or less (e.g., about 10 or less, about 5 or less, about 2 or less) equivalents of the starting reagent. In specific embodiments, the amount of water is about 10 equivalents of the starting reagent. In still more specific embodiments, the amount of water is about 5 equivalents of the starting reagent. In yet more specific embodiments, the amount of water is about 7.5 equivalents of the starting reagent.

[0108] In certain embodiments, a reaction mixture provided herein further comprises an alcohol (e.g., t-amyl alcohol). In specific embodiments, a reaction mixture provided herein comprises a starting reagent provided herein, a metal fluoride or reagent composition provided herein, a reaction solvent (e.g., a reaction solvent provided herein), a reaction base (e.g., a reaction base provided herein), and an alcohol (e.g., an alcohol provided herein). In certain embodiments, an alcohol (e.g., an alcohol provided herein) is any suitable alcohol, such as an alkyl alcohol, a diol, and / or a combination thereof. In some embodiments, an alcohol provided herein is ethyl alcohol, methanol, isopropyl alcohol, t-amyl alcohol, butanol, ethylene glycol, propylene glycol, and / or a combination thereof. In specific embodiments, an alcohol provided herein is isopropyl alcohol, t-amyl alcohol, and / or ethylene glycol.

[0109] In certain embodiments, an amount of alcohol (e.g., an alcohol provided herein) is about 0 equivalents to about 10 equivalents of a starting reagent provided herein (e.g., about 1 to about 9 equivalents, about 2 to about 8 equivalents, about 3 to about 7 equivalents). In some embodiments, the amount of alcohol is about 1 or more (e.g., about 2 or more, about 3 or more, about 4 or more, about 8 or more) equivalents of the starting reagent. In certain embodiments, the amount of alcohol is about 9 or less (e.g., about 8 or less, about 7 or less, about 3 or less) equivalents of the starting reagent. In specific embodiments, the amount of alcohol is about 5 equivalents of the starting reagent.

[0110] In some embodiments, a starting reagent provided herein is contacted with a metal fluoride or reagent composition provided herein with any selected volume of an (e.g., reaction) solvent.[OHl] In certain embodiments, a concentration of a starting reagent provided herein in a reaction mixture provided herein is about 0.05 Mto about 1 M (e.g., about 0.1 Mto about 0.75 M, about 0.2 Mto about 0.5 M). In some embodiments, a concentration of the starting reagent in the reaction mixture is about 0.08 M or more (e.g., about 0.1 M or more, about 0.2 M orWSGR Docket No. 64651-711.601 more, about 0.4 M or more). In certain embodiments, a concentration of the starting reagent in the reaction mixture is about 0.75 M or less (e.g., about 0.5 M or less, about 0.25 M or less). In specific embodiments, a concentration of the starting reagent in the reaction mixture is about 0.25 M. In yet more specific embodiments, a concentration of the starting reagent in the reaction mixture is about 0.33 M. In still more specific embodiments, a concentration of the starting reagent in the reaction mixture is about 0.5 M. In yet more specific embodiments, a concentration of the starting reagent in the reaction mixture is about 0.125 M.

[0112] In some instances, increasing a concentration of a starting reagent provided herein in a reaction mixture provided herein results in high yields of a battery electrolyte precursor provided herein. In certain embodiments, battery electrolytes, battery electrolyte precursors, or salts thereof provided herein, are further purified, such as using any suitable techniques. In some embodiments, the battery electrolytes, battery electrolyte precursors, or salts thereof provided herein, is further purified using chromatography, such as ion-exchange (e.g., chromatography using polymers, resins, semi-permeable membranes, or the like).

[0113] In some embodiments, further purification is used to remove other components, such as trace acids, anions, or cations, solvents, other complexes, and / or combinations thereof. In some embodiments, the chromatography used for purification is an ion -exchange resin. In some embodiments, the ion-exchange resin is a charge basic resin, a chelating resin, a strong acid cation exchange resin, a weak acid cation exchange resin, a strong base anion exchange resin, or a weak base anion exchange resin. In some embodiments, purifying comprises ageing a solution produced by the purification for at least 1 hour (e.g., at least 1, at least 2, at least 4, at least 8, at least 16, or at least 24 hours). In some embodiments the solution is stirred during the ageing process. In some embodiments a temperature of the ageing process may be the same temperature usedin the combination process. In some embodiments, the ageing process is performed at a temperature from 20 °C to 120 °C. In some cases the temperature of the ageing process is about 20 °C, 30 °C, 40 °C, 50 °C, 60 °C, 70 °C, or 80 °C.

[0114] In certain embodiments, battery electrolytes, battery electrolyte precursors, or salts thereof provided herein, are further purified, such as using any suitable techniques. In some embodiments, the battery electrolytes, battery electrolyte precursors, or salts thereof provided herein, are further purified for at least 1, 2, 3, 4, 5, 6, 7, or 8 hours using the chromatography. In some embodiments the purification is performed for at least 12 hours, or at least 1, 2, or 3 days using the chromatography. In some embodiments, chromatography used in methods provided herein comprises a flow rate of at least 1 mL / min, at least 5 mL / min, at least 10 mL / min, at least 25 mL / min, or at least 50 mL / min.WSGR Docket No. 64651-711.601

[0115] In certain embodiments, a starting reagent provided herein contacted with a metal fluoride or reagent composition provided herein provides a battery electrolyte precursor provided herein. In some embodiments, a leaving group (e.g., chlorine, iodine, bromine) of a starting reagent provided herein is replaced with fluorine. In certain embodiments, contacting a starting reagent provided herein with a metal fluoride or reagent composition provided herein provides a battery electrolyte precursor provided herein in a yield of about 10% or more (e.g., about 20% ormore, about 30% or more, about 40% or more, about 50% or more, about 60% or more, about 70% or more, about 80% or more, about 90% or more). In certain embodiments, a yield of a battery electrolyte precursor provided herein is about 10% to about 95% (e.g., about20% to about 80%, about 30% to about 70%, about 40% to about 60%). In certain embodiments, a yield of a battery electrolyte precursor provided herein is about 50% to about 98% (e.g., about 60% to about 97%, about 70% to about 96%, about 80% to about 95%). In some embodiments, a yield of a battery electrolyte precursor provided herein is about 75% to about 95%.

[0116] In some embodiments, a battery electrolyte precursor provided herein comprises PF3, PF5, KPF6or salts thereof. In some embodiments, a battery electrolyte precursor provided herein comprises PF3, PF5, KPF6, NaPF6or salts thereof. In some embodiments, the battery electrolyte precursor is NaPF6, KPF6, or salts thereof. In specific embodiments, the battery electrolyte precursor is KPF6. In yet more specific embodiments, the battery electrolyte precursor is NaPF6.

[0117] In some embodiments, a battery electrolyte provided herein is LiPF6or NaPF6. In specific embodiments, the battery electrolyte is LiPF6. In yet more specific embodiments, the battery electrolyte is NaPF6.

[0118] In certain embodiments, any of the steps provided herein can comprise any of the methods provided herein.

[0119] While preferred embodiments of the present invention have been shown and described herein, it will be obvious to those skilled in the art that such embodiments are provided by way of example only. Numerous variations, changes, and substitutions will now occur to those skilled in the art without departing from the invention. It should be understood that various alternatives to the embodiments of the invention described herein may be employed in practicing the invention. It is intended that the following claims define the scope of the invention and that methods and structures within the scope of these claims and their equivalents be covered thereby.WSGR Docket No. 64651-711.601EXAMPLES

[0120] Example 1: Fluorination of a battery electrolyte precursor and / or a salt thereof using metal fluorides in the presence of a polar aprotic compound.

[0121] Generic Reaction Procedure

[0122] A battery electrolyte precursor was prepared according to the scheme illustrated in FIG. 1. Alkali metal fluoride (6-10 equiv.) was dried for 2-48 h at 150-200 °C under vacuum before allowing to cool and suspending in an organic solvent. Phosphorous pentachloride (1 equiv.) was added. The mixture was allowed to stir for 1-24 hours at -40-80 °C. The suspension was separated and the solids washed with organic solvent and the solvent evaporated to allow a solid alkali metal hexafluorophosphate.

[0123] Synthesis of Potassium Hexafluorophosphate

[0124] Solvent Screen

[0125] A solvent screen was undertaken using the scheme provided in FIG. 2, according to the Generic Reaction Procedure. As shown in Table 1 below, acetonitrile proved to yield the most product. The full results of the solvent screen are detailed below in Table 1.Table 1: Solvent screen for synthesis of KPIS

[0126] Mixed solvent systems

[0127] A mixed solvent screen was undertaken using the scheme of FIG. 3. according to the Generic Reaction ProcedureTable 2: Mixed solvent screen to synthesise KPF^.WSGR Docket No. 64651-711.601

[0128] Reaction Concentration

[0129] A concentration screen was undertaken using the scheme of FIG. 4, according to the Generic Reaction Procedure.Table 3: Reaction concentration screen to synthesise KPF

[0130] Equivalents of Fluoride

[0131] A screening of the equivalents of fluoride added to the reactants was undertaken using the scheme of FIG. 5, according to the Generic Reaction Procedure.Table 4: Equivalents of fluoride screening results.

[0132] Reaction Temperature

[0133] A temperature screen was undertaken using the scheme of FIG. 6 , according to the Generic Reaction Procedure.Table 5: Results for the temperature screen to synthesise KPlf,.WSGR Docket No. 64651-711.601

[0134] Reaction Time

[0135] A time screening was undertaken according using the scheme of FIG. 7, according to the Generic Reaction Procedure.Table 6:Results for the time screenins for the synthesis of KPF^.

[0136] Synthesis of Potassium Hexafluorophosphate

[0137] Synthesis of Potassium Hexafluorophosphate according to the scheme shown in FIG. 8:

[0138] Potassium fluoride (97 g) was dried for 48 h at 180 °C under vacuum before allowing to cool and suspending in acetonitrile (10 vol.). Phosphorous pentachloride (50 g) was added with external cooling. The mixture was allowed to stir for 2 hours at 0 °C. The suspension was separated and the solids washed with acetonitrile. The solvent was evaporated to allow a solid potassium hexafluorophosphate.

[0139] An alternate method for potassium hexafluorophosphate synthesis was further demonstrated, which produced similar results. Acetonitrile was charged to a dry reactor, start stirring at 500 RPM with a temperature control set to 10 °C. Potassium fluoride was then charged through an open port, against a positive flow of inert gas. The potassium fluoride was then stirred in the acetonitrile for 30 min. Phosphorus pentachloride was charged portion -wise through an open port against an adequate flow of an inert gas, ensuring that the internal temperature did not exceed 20 °C. The reaction was monitored by19F NMR. The reaction mixture was then discharged directly into a sinter filter using tubing connected to the drain tap. Wash acetonitrile was charged to the reactor, and the filter cake was resuspended to extract residual product prior to filtering. The pH of the filtrate was adjusted to neutral asWSGR Docket No. 64651-711.601 needed using an ion-exchange resin, subsequently removed by filtration. The filtrate was then charged to a large rotary evaporator, and acetonitrile was evaporated to obtain potassium hexafluorophosphate.

[0140] Sodium Hexafluorophosphate

[0141] Sodium Hexafluorophosphate was synthesized according to the scheme of FIG. 9.

[0142] Sodium fluoride (7 g) was dried for 2 h at 200 °C under vacuum before allowing to cool and suspending in acetonitrile (8 vol.). Phosphorous pentachloride (5 g) was added with external cooling. The mixture was allowed to stir for 2 hours at 0 °C. The suspension was separated and the solids washed with acetonitrile. The solvent was evaporated to allow solid sodium hexafluorophosphate.Table 8: Results of the synthesis of NaPF^

[0143] Lithium hexafluorophosphate

[0144] Lithium hexafluorophosphate was synthesised by replacing the potassium fluoride from above with lithium fluoride, as below:

[0145] Reaction Temperature

[0146] A temperature screen was undertaken according to FIG. 10.Table 9: Results of temperature screen to synthesise LiPF^

[0147] Equivalents of Fluoride

[0148] The equivalents of fluoride were screened according to FIG. 11.Table 10: Results from the equivalents of fluoride screening to synthesise LiPl(r

[0149] Reaction Concentration

[0150] A concentration screening was undertaken according to FIG. 12.WSGR Docket No. 64651-711.601Table 11: Results of the concentration screening to synthesise LiPIh.

[0151] Synthesis of Lithium Hexafluorophosphate

[0152] Synthesis of Lithium Hexafluorophosphate according to FIG. 13:

[0153] Lithium fluoride (16 g) was dried for 18 h at 200 °C under vacuum before allowing to cool and suspending in acetonitrile (85 mL). Phosphorous pentachloride (18 g) was added with external cooling. The mixture was allowed to stir for 2 hours at 40 °C. The suspension was separated and the solids washed with acetonitrile. The solvent was evaporated to allow a solid lithium hexafluorophosphate.Table 12: Results ofLiPI ,, Isolation.

[0154] Mixed solvent systems

[0155] A mixed solvent screen was undertaken using the scheme of FIG. 14.

[0156] In an inert atmosphere, a vial equipped with stirring bar, potassium hexafluorophosphate and lithium chloride (1.2 equiv.) were added. Then acetonitrile and tetrahydrofuran were added according to Table 13.Table 13: Results of THF Effect on reaction.

[0157] Lithium Hexafluorophosphate by cation exchange

[0158] Lithium Hexafluorophosphate by cation exchange according to FIG. 14.

[0159] Under inert and moisture free conditions, lithium chloride (28 g) and potassium hexafluorophosphate (100 g) were suspended in a mixture of acetonitrile and tetrahydrofuranWSGR Docket No. 64651-711.601(4:1 m / m). After the appropriate time, the suspension was filtered and the filtrate concentrated to crystallize the LiPF6-acetonitrile complex;which was dried under high vacuum (< 10 mbar) at 45 °C to yield lithium hexafluorophosphate in 80% yield.

[0160] An additional embodiment of a method provided herein was demonstrated for lithium hexafluorophosphate, which produced similar results. Lithium chloride was dispersed in acetonitrile to minimize particle size. In a separate flask, potassium hexafluorophosphate was dissolved in acetonitrile and was added slowly to the lithium chloride suspension, and additional acetonitrile was used to rinse the KPF6vessel; the suspension was allowed to be stirred for 16 hours at 25-65 °C, after which the reaction was filtered into a separate flask and the crude reaction mixture was pumped through an ion-exchange resin for 7.5 h at 25 mL / min; the mixture was then stirred at 50 °C for 16 h and the solution was transferred to an appropriate vessel where xylene was added and the mixture was heated to 45 °C for 1 hour with stirring; the mixture was filtered and the sample recrystallized from this mixture at -10 °C, after which the crystals were carefully washed, placed under vacuum (0.20 mbar) and were heated to 45 °C for 6-12 hours to isolate lithium hexafluorophosphate.

[0161] Sodium Hexafluorophosphate by cation exchange

[0162] Sodium Hexafluorophosphate by cation exchange according to FIG. 15.

[0163] In a 50 ml 2-necked flask oven dried under nitrogen with stirring bar, sodium chloride was weighed in and suspended in the appropriate solvent, the suspension was stirred for 40 minutes. Potassium hexafluorophosphate (1 equiv.) was added as a solid in one portion and the suspension left stirring for 18 h at room temperature. The suspension was concentrated under nitrogen and filtered. The solid evaporated to dryness overnight. Sodium hexafluorophosphate was isolated.Table 14: Results of isolation of sodium hexafluorophosphate.

Claims

WSGR Docket No. 64651-711.601CLAIMSWHAT IS CLAIMED IS:1 . A method of manufacturing a battery electrolyte precursor, the method comprising: contacting a metal fluoride with a starting reagent in the presence of a polar aprotic compound; and fluorinating the starting reagent to thereby provide a battery electrolyte precursor.

2. A method of manufacturing a battery electrolyte precursor, the method comprising: washing a metal fluoride with a solvent; concentrating the metal fluoride; and contacting the metal fluoride with a starting reagent; and fluorinating the starting reagent in the presence of a polar aprotic compound to provide a battery electrolyte precursor.

3. The method of any one of the preceding claims, wherein the polar aprotic compound is comprised in a solvent.

4. The method of any one of the preceding claims, wherein the polar aprotic compound is provided in an amount of at least 1 molar equivalent with respect to the metal fluoride.

5. The method of any one of the preceding claims, wherein the polar aprotic compound is provided in an amount of at least 5 molar equivalents with respect to the metal fluoride.

6. The method of any one of the preceding claims, wherein the polar aprotic compound is provided in an amount of at least 10 molar equivalents with respect to the metal fluoride.

7. The method of any one of the preceding claims, wherein the polar aprotic compound is provided in an amount of at least 20 molar equivalents with respect to the metal fluoride.

8. The method of any one of the preceding claims, wherein the polar aprotic compound is provided in an amount of at least 50 molar equivalents with respect to the metal fluoride.

9. The method of any one of the preceding claims, wherein the polar aprotic compound is a polar aprotic solvent which is combined with the battery electrolyte precursor, and / or the metal fluoride.

10. The method of any one of claims 1 -2, wherein the polar aprotic compound is added in a catalytic amount.

11. The method of any of the preceding claims, wherein the polar aprotic compound comprises a nitrile group (e.g., C1-C6 alkyl-CN).WSGR Docket No. 64651-711.60112. The method of any of the preceding claims, wherein the polar aprotic compound is acetonitrile.

13. The method of any of the preceding claims, wherein the polar aprotic compound is propionitrile.

14. The method of any of the preceding claims wherein the metal fluoride comprisesan alkali metal fluoride.

15. The method of claim 14, wherein the alkali metal fluoride comprises LiF, NaF, and / or KF.

16. The method of claim 14, wherein the alkali metal fluoride comprises LiF.

17. The method of claim 14, wherein the alkali metal fluoride comprises NaF.

18. The method of claim 14, wherein the alkali metal fluoride comprises KF.

19. The method of any one of claims 1 -14, wherein the metal fluoride substantially consists of LiF (e.g., has a LiF purity of >80%, 90%, 95%, or 99% prior to the contacting with the polar aprotic compound and / or the battery electrolyte precursor).

20. The method of any one of claims 1 -14, wherein the metal fluoride substantially consists of NaF (e.g., has a NaF purity of >80%, 90%, 95%, or 99% prior to the contacting with the polar aprotic compound and / or the battery electrolyte precursor).

21. The method of any one of claims 1 -14, wherein the metal fluoride substantially consists of KF (e.g., has a KF purity of >80%, 90%, 95%, or 99% prior to contacting with the polar aprotic compound and / or the battery electrolyte precursor).

22. The method of any of the preceding claims, wherein the metal fluoride consists of a salt having a weight% purity of at least 80% (e.g., 80%, 90%, 95%, or 99%) prior to combination with the polar aprotic compound and / or the battery electrolyte precursor.

23. The method of any one of the preceding claims, wherein the metal fluoride is contacted with the starting reagent in an alkyl carbonate solvent (e.g., dimethyl carbonate).

24. The method of claim 23, wherein the alkyl carbonate solvent is dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, and / or combinations thereof.

25. The method of any one of claims 23-24, wherein the alkyl carbonate solvent is a fluoroalkyl carbonate solvent (e.g., trifluoroethyl carbonate, bis(trifluoroethyl) carbonate, trifluoroethyl methyl carbonate, and / or combinations thereof).

26. The method of any one of the preceding claims, wherein the contacting is performed at a temperature of about 50 to about 150 °C.

27. The method of any one of the preceding claims, wherein the contacting is performed at a temperature of about 80 °C about or more (e.g., about 100 °C or more).WSGR Docket No. 64651-711.60128. The method of any one of the preceding claims, further comprising adjusting a pH of a solution comprising the starting reagent (e.g., to a pH of about 6 to about 8) prior to the fluorinating.

29. The method of claim 28, wherein the pH of the resultant fluid is adjusted with an acid (e.g, strong acid, weak acid, polyprotic acid, and / or combinations thereof).

30. The method of claim 29, wherein the acid comprises phosphoric acid, hydrochloric acid, formic acid, acetic acid, benzoic acid, boric acid, silicic acid, oxalic acid, sulfuric acid, sulfurous acid, carbonic acid, and / or combinations thereof.

31. The method of any one of claims 29-30, wherein the acid comprises hydrochloric acid, phosphoric acid, sulfuric acid, and / or combinations thereof.

32. The method of any one of claims 28-31, wherein the pH of the solution comprisingthe starting reagent is adjusted to a pH of about 5 to about 10 (e.g., about 6 to about 9).

33. The method of any one of the preceding claims, wherein the solution comprising the starting reagent has a pH of about 7 or more (e.g., about 10 or more).

34. The method of any one of the preceding claims, wherein a solution comprisingthe starting reagent has a pH of about 12 to about 13.

35. The method of any one of the preceding claims, wherein the contacting is at a temperature of about 0 to about 120 °C.

36. The method of any one of the preceding claims, wherein the contacting is at a temperature of 80 °C or more.

37. The method of any one of the preceding claims, wherein the contacting is at a temperature of 110 °C or less (e.g., at about 40 °C or less).

38. The method of any one of the preceding claims, wherein the contacting is performed for about 0 hours to about 8 hours.

39. The method of any one of the preceding claims, wherein the contacting is performed for about 1 hour or more.

40. The method of any one of the preceding claims, wherein the contacting is performed for about 6 hours or less.

41. The method of any one of the preceding claims, wherein the contacting is performed for about 2 hours.

42. The method of any one of the preceding claims, wherein a solvent comprisingthe contacted metal fluoride and starting reagent has a boiling point of about 30 °C or more (e.g., about 70 °C or more, about 120 °C or more).

43. The method of any one of the preceding claims, wherein a solvent comprisingthe contacted metal fluoride and starting reagent has a boiling point of about 240 °C or less.WSGR Docket No. 64651-711.60144. The method of any one of the preceding claims, wherein the contacting is performed at a temperature of about -20 to about 240 °C.

45. The method of any one of the preceding claims, wherein the contacting is performed at a temperature of about 80 °C or more.

46. The method of any one of the preceding claims, wherein the contacting is performed is at a temperature of about 60 °C.

47. The method of any one of the preceding claims, wherein the contacting is performed is at a temperature of about 235 °C or less.

48. The method of any one of claims 2-47, wherein the washing and / or concentrating are performed for about 4 hours to about 48 hours (e.g., about 8 hours to about 36 hours, about 10 hours to about 28 hours).

49. The method of any one of claims 2-48, wherein the washing is performed for about 8 hours or more.

50. The method of any one of claims 2-49, wherein the washing is performed for about 36 hours or less.

51. The method of any one of claims 2-50, wherein the washing is performed for about 18 hours.

52. The method of any one of claims 2-51, wherein the washing is performed using a solvent having a boiling point of about 30 °C or more (e.g., about 70 °C or more, about 120 °C or more).

53. The method of any one of claims 2-52, wherein the washing is performed using a solvent having a boiling point of about 240 °C or less.

54. The method of any one of claims 2-53, wherein the washingis performed with a solvent which is an organic solvent, water, an alcohol, a polar aprotic solvent, a halocarbon, and / or combinations thereof.

55. The method of any one of the preceding claims, wherein a solvent comprisingthe contacted starting reagent is acetonitrile, propionitrile, butyronitrile, toluene, 1,2 -dichlorobenzene, chlorobenzene, fluorobenzene, 1,2-difluorobenzene, dichloroethane, trifluorotoluene, chloroform, DMF, DMSO, sulfolane, MeTHF, THF, NMP, pyridine, butyl acetate, dioxane, an alcohol (e.g., tert-butanol, tert-amyl alcohol), water, and / or combinations thereof.

56. The method of any one of the preceding claims, wherein a solvent comprisingthe contacted starting reagent is acetonitrile, propionitrile, butyronitrile, and / or combinations thereof.

57. The method of any one of the preceding claims, wherein the contacted starting reagent, polar aprotic compound and metal fluoride form a reaction mixture.WSGR Docket No. 64651-711.60158. The method of claim 57, wherein the reaction mixture is at a temperature of about -5 to about 120 °C.

59. The method of any one of claims 57-58, wherein the reaction mixture is at a temperature of about 55 to about 150 °C.

60. The method of any one of claims 57-59, wherein the reaction mixture is at a temperature of about 100 °C or less.

61. The method of any one of claims 57-60, wherein the contacting is for about 0.5 hours to about 40 hours.

62. The method of any one of the preceding claims, wherein the contacting is for about 12 hours or more.

63. The method of any one of the preceding claims, wherein the contacting is for about 14 hours to about 22 hours.

64. The method of any one of the preceding claims, wherein the contacting is for about 84 hours or less.

65. The method of any one of the preceding claims, wherein the contacting is for about 60 hours to about 80 hours.

66. The method of any one of claims 57-65, wherein the reaction mixture further comprises a phase transfer agent, a base, and / or combinations thereof.

67. The method of claim 66, wherein the phase transfer agent is a crown ether (e.g., 18 crown 6), a cryptand, an ionic transfer agent (e.g., tetramethylammonium chloride), and / or a hydrogen-bonding phase transfer agent.

68. The method of claim 67, wherein the phase transfer agent is a crown ether (e.g., 18 crown 6).

69. The method of claim 66, wherein the base is a pyridine derivative (e.g., DMAP).

70. The method of any one of the preceding claims, wherein the reaction mixture further comprises a reaction solvent.

71. The method of any one of the preceding claims, wherein the reaction solvent is an organic solvent, water, an alcohol, a polar aprotic solvent, a halocarbon, and / or combinations thereof.

72. The method of any one of the preceding claims, wherein the reaction solvent is acetonitrile, propionitrile, pyridine, butyronitrile, toluene, 1,2 -dichlorobenzene, chlorobenzene, fluorobenzene, 1,2 -difluorobenzene, dichloroethane, trifluorotoluene, chloroform, DMF, DMSO, an alcohol (e.g., tert-butanol, tert-amyl alcohol), water, and / or combinations thereof.WSGR Docket No. 64651-711.60173. The method of any one of the preceding claims, wherein the reaction solvent is acetonitrile, propionitrile, pyridine, butyronitrile, and / or combinations thereof.

74. The method of any one of the preceding claims, wherein the reaction solvent is acetonitrile, chloroform, sulfolane, THF, NMP, and / or combinations thereof.

75. The method of any one of the preceding claims, wherein the starting reagent comprises a leaving group.

76. The method of any one of the preceding claims, wherein the leaving group is chlorine, iodine, or bromine.

77. The method of any one of the preceding claims, wherein the battery electrolyte precursor comprises at least one additional fluorine (e.g., at least two additional fluorines) compared to the starting reagent.

78. The method of any one of the preceding claims, wherein the battery electrolyte precursor is KPF6, or a salt thereof.

79. The method of any one of the preceding claims, wherein the battery electrolyte precursor is NaPF6, KPF6, or salts thereof.

80. The method of any one of the preceding claims, wherein a molar ratio of the phase transfer agent to the starting reagent is about 0 to about 4.

81. The method of any one of the preceding claims, wherein a molar ratio of the base to the starting reagent is about 0 to about 2.

82. The method of any one of the preceding claims, wherein a molar ratio of a fluorine equivalent content in the metal fluoride to the starting reagent is about 0.1 or more.

83. The method of any one of the preceding claims, wherein a yield of the battery electrolyte precursor is about 10% or more.

84. The method of any one of the preceding claims, wherein a yield of the battery electrolyte precursor is about 20% to about 80%.

85. The method of any one of the preceding claims, wherein a yield of the battery electrolyte precursor is about 75% to about 95%.

86. The method of any one of the preceding claims, wherein a concentration of the starting reagent in the reaction solvent and / or alkyl carbonate solvent is about 0.01 Mto about 3 M.

87. The method of any one of the preceding claims, wherein a concentration of the starting reagent in the reaction solvent and / or alkyl carbonate solvent is about 1 M or less.

88. The method of any one of the preceding claims, wherein the battery electrolyte precursor is contacted with an electrolyte agent (e.g., lithium salt) to provide a battery electrolyte and / or a salt thereof.WSGR Docket No. 64651-711.60189. The method of any one of the preceding claims, wherein the electrolyte agent is a lithium salt or a sodium salt.

90. The method of any one of the preceding claims, wherein the electrolyte agent is lithium perchlorate, lithium sulphate, lithium chloride, lithium bromide, lithium tetrafluoroborate, lithium carbonate, lithium hydroxide, or a combination of two or more thereof.

91. The method of any one of the preceding claims, wherein the electrolyte agent is LiCl.

92. The method of any one of the preceding claims, wherein the electrolyte agent is lithium tetrafluorob orate .

93. The method of any one of the preceding claims, wherein the electrolyte agent is lithium perchlorate.

94. The method of any one of the preceding claims, wherein the electrolyte agent is NaCl or NaC104.

95. The method of any one of the preceding claims, wherein the starting reagent is PCh, PCI5, LiPCIg, P4O6, or P2O5.

96. The method of any one of the preceding claims, wherein the starting reagent is PC15.

97. The method of any one of the preceding claims, wherein the starting reagent is PCI3.

98. The method of any one of the preceding claims, wherein the battery electrolyte is LiPF6.

99. The method of any one of the preceding claims, wherein the battery electrolyte is NaPF6.

100. The method of any one of the preceding claims, wherein the battery electrolyte precursor is contacted with the electrolyte agent in a selected solvent selected from acetonitrile, acetone, THF, ethanol, methanol, dioxane, methyl t-butyl ether, diethyl ether, MEK, dimethyl carbonate, and propylene carbonate, and / or combinations of one or more thereof.

101. The method of any one of the preceding claims, wherein the battery electrolyte precursor is contacted with the electrolyte agent for about 1 hour to about 84 hours (e.g., about 2 hours to about 76 hours, about 3 hours to about 24 hours, about 4 hours to ab out 12 hours, about 5 hours to about 10 hours).

102. The method of any of the preceding claims, further comprising reducing a particle size of one or more of: the battery electrolyte precursor, the starting reagent, the electrolyte agent and / or the metal fluoride (e.g., prior to, during, or after the contacting of the metal fluoride with the starting reagent).

103. The method of claim 102, wherein the size reduction is performed by application of mechanical force.

104. The method of claim 103, wherein the size reduction is performed using one or more of a ball mill, a planetary mill, a bead mill, a mortar and pestle, a twin-screw-extruder, an attritor, a drum mill, an ultrasonic bath, or a mechanical press.WSGR Docket No. 64651-711.601105. The method of any one of claims 102-104, wherein the particle size reduction is performed to reduce a particle size of the electrolyte agent.

106. The method of claim 105, wherein the electrolyte agent is or comprises LiCl.

107. The method of any one of claims 105-106, wherein the size reduction is performed prior to or during the contacting with the battery electrolyte precursor.

108. The method of claim 107, wherein the battery electrolyte precursor is or comprises KPF6.

109. The method of any one of the preceding claims, wherein the battery electrolyte precursor is contacted with the electrolyte agent for about 30 hours or less (e.g., about 24 hours or less, about 18 hours or less, about 12 hours or less, about 8 hours or less).

110. The method of any one of the preceding claims, wherein the battery electrolyte precursor is contacted with the electrolyte agent for about 2 hours or more (e.g., about 4 hours or more, about 8 hours or more, about 16 hours or more).11 l.The method of any one of the preceding claims, further comprising purifying the battery electrolyte or battery electrolyte precursor by using an ion-exchange resin.

112. The method of claim 1 11, wherein the ion exchange resin comprises a weak base anion exchange resin, a weak acid cation exchange resin and / or a strong acid cation exchange resin.

113. The method of any one of the preceding claims, further comprising ageing a solution of battery electrolyte or battery electrolyte precursor at a temperature of at least 25 °C (e.g., at least 25 °C, at least 50 °C, at least 60 °C, at least 70 °C, at least 80 °C).

114. The method of any one of claims 1 11-113, wherein the purifying is performed for at least 1 hour (e.g., at least 1, at least 2, at least 4, at least 8, at least 16, or at least 24 hours).

115. The method of any one of the preceding claims, wherein the battery electrolyte precursor is contacted with the electrolyte agent for about 18 hours.

116. The method of any one of the preceding claims, wherein a combination of the battery electrolyte precursor and the electrolyte agent is at a temperature of about 10 to about 80 °C (e.g., about 20 to about 70 °C, about 30 to about 60 °C).

117. The method of any one of the preceding claims, wherein a combination of the battery electrolyte precursor and the electrolyte agent is at a temperature of about 10 °C or more (e.g., about 15 °C or more, about 20 °C or more).

118. The method of any one of the preceding claims, wherein a combination of the battery electrolyte precursor and the electrolyte agent is at a temperature of about 60 °C or less (e.g., about 50°C or less, about 40°C or less, about 30°C or less).

119. The method of any one of the preceding claims, wherein a combination of the battery electrolyte precursor and the electrolyte agent is at room temperature.

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