Fluorinated electrolyte additive

Abstract

To provide a fluorinated dialkyl carbonate and a sulfite compound useful for a battery, and to provide a method for producing the same.SOLUTION: The use of fluorinated ethers such as 1,1,1,3,3,3,3, - hexafluoro-2-methoxypropane (HFMOP) as a reaction solvent for preparing fluorinated dialkyl carbonate and sulfite compounds, and battery electrolytes comprising fluorinated dialkyl carbonate and sulfite compounds and low levels of fluorinated ethers such as HFMOP for use in batteries comprising high Ni cathodes and silicon-containing anodes.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application is an international patent application claiming the benefit of U.S. Provisional Patent Application No. 62 / 901,553, filed September 17, 2019, which is incorporated herein by reference in its entirety.

[0002] This disclosure relates to the use of fluorinated ethers, such as 1,1,1,3,3,3,3-hexafluoro-2-methoxypropane (HFMOP), as a reaction solvent to prepare fluorinated dialkyl carbonate and sulfite compounds useful in batteries, and to battery electrolytes comprising fluorinated dialkyl carbonate and sulfite compounds and low levels of fluorinated ethers, such as HFMOP. The use of fluorinated esters, carbonates, and ethers as electrolyte components improves the performance of electrochemical cells containing high-Ni cathodes, such as NMC811, and anodes containing Si. [Background technology]

[0003] Lithium-ion batteries are ubiquitous in our daily lives, and there is a constant need to improve energy density for longer-lasting and safer batteries.

[0004] Carbonate and sulfite compounds are used as electrolyte solvents and additives, respectively, in nonaqueous batteries with cathodes composed of alkali metals, alkaline earth metals, or materials derived from them. For example, lithium-ion batteries commonly use linear or cyclic carbonates, such as dimethyl carbonate or ethylene carbonate. However, at battery voltages above 4.4 V, these compounds decompose, resulting in impaired battery performance. Summary of the Invention

[0005] The present disclosure provides methods for producing fluorinated compounds, including but not limited to fluorinated organic carbonates and fluorinated organic sulfites. In some embodiments, the methods include reacting a first reactant comprising at least one fluorine atom with a second reactant of Formula 20A or 20B, wherein the reactant of Formula 20A or 20B comprises a leaving group L1. [ka]

[0006] The reaction is conducted in the presence of a fluorinated solvent; R1 is selected from optionally substituted alkyl, optionally substituted haloalkyl, optionally substituted alkenyl, optionally substituted haloalkenyl, optionally substituted alkynyl, optionally substituted haloalkynyl, optionally substituted aryl, optionally substituted haloaryl, optionally substituted heteroaryl, and optionally substituted haloheteroaryl; and L2 is a leaving group. In some embodiments, the first reactant is a fluorinated alcohol. In some embodiments, the fluorinated organic carbonate is a fluorinated dialkyl carbonate. In some embodiments, the fluorinated organic sulfite is a fluorinated dialkyl sulfite. In some embodiments, the first reactant comprises one or more groups selected from -CF3, -CHF2, -CH2F, -CHF-, and -CF2-. In some embodiments, the first reactant comprises one or more -CF3 groups. In some embodiments, the first reactant is selected from 2-fluoroethanol, 2,2-difluoroethanol, 2,2,2-trifluoroethanol, 3-fluoro-1-propanol, 3,3-difluoro-1-propanol, 3,3,3-trifluoro-1-propanol, 2,2,3,3,3-pentafluoro-1-propanol, 1,1,1-trifluoro-2-propanol, 1,1,1,3,3-pentafluoro-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 4,4,4-trifluoro-1-butanol, and 5,5,5-trifluoro-1-pentanol. In some embodiments, the first reactant is 1,1,1,3,3,3-hexafluoroisopropanol. In some embodiments, L1 is selected from perfluoroalkylsulfonate, tosylate, mesylate, halogen, nitrate, phosphate, thioether, amine, carboxylate, phenoxide, alkoxide, and amide. In some embodiments, L1 is selected from halogen or -OR2 group. In some embodiments, R2 is alkyl sulfate or aryl sulfate.In some embodiments, L1 is selected from chlorine, iodine, and bromine. In some embodiments, L2 is selected from perfluoroalkylsulfonate, tosylate, mesylate, halogen, nitrate, phosphate, thioether, amine, carboxylate, phenoxide, alkoxide, and amide. In some embodiments, L2 is selected from halogen and -OR3 group. In some embodiments, R3 is an alkyl sulfate or aryl sulfate. In some embodiments, L2 is selected from chlorine, iodine, and bromine. In some embodiments, the compound of Formula 20A is a chloroformate. In some embodiments, the chloroformate is an alkyl chloroformate. In some embodiments, the chloroformate is methyl chloroformate or ethyl chloroformate. In some embodiments, the fluorinated organic carbonate is selected from methyl(2,2,2-trifluoroethyl)carbonate, methyl(1,1,1-trifluoroisopropyl)carbonate, methyl(1,1,1,3,3,3-hexafluoroisopropyl)carbonate, methyl(3,3,3-trifluoropropyl)carbonate, methyl(2-fluoroethyl)carbonate, methyl(2,2-difluoroethyl)carbonate, methyl(3-fluoropropyl)carbonate, methyl(3,3-difluoropropyl)carbonate, methyl(2,2,3,3,3-pentafluoropropyl)carbonate, methyl(4,4,4-trifluorobutyl)carbonate, methyl(1,1,1,3,3-pentafluoroisopropyl)carbonate, and methyl(5,5,5-trifluoropentyl)carbonate. In some embodiments, the compound of Formula 20B is thionyl chloride. In some embodiments, the fluorinated organic sulfite is selected from bis-(2,2,2-trifluoroethyl)sulfite, bis-(1,1,1-trifluoroisopropyl)sulfite, and bis-(1,1,1,3,3,3-hexafluoroisopropyl)sulfite. In some embodiments, the fluorinated solvent comprises one or more groups selected from -CF3, -CHF2, -CH2F, -CHF-, and -CF2-.In some embodiments, the fluorinated solvent comprises one or more -CF3 groups. In some embodiments, the fluorinated solvent comprises two or more -CF3 groups.

[0007] In some embodiments, the fluorinated solvent is an ether or thioether having formula 10: [ka]

[0008] wherein X is O or S, R4 is a partially fluorinated C1-C8 alkyl group; and R5 is an optionally fluorinated C1-C8 alkyl group. In some embodiments, R4 is a partially fluorinated C1-C4 alkyl group; and R5 is an optionally fluorinated C1-C4 alkyl group. In some embodiments, the fluorinated solvent comprises one or more groups selected from 2,2,2-trifluoroethyl, 1,1,1-trifluoroisopropyl, 1,1,1,3,3,3-hexafluoroisopropyl, 3,3,3-trifluoropropyl, 2-fluoroethyl, 2,2-difluoroethyl, 3-fluoropropyl, 3,3-difluoropropyl, 2,2,3,3,3-pentafluoropropyl, 4,4,4-trifluorobutyl, 1,1,1,3,3-pentafluoroisopropyl, and 5,5,5-trifluoropentyl. In some embodiments, the fluorinated solvent is hexafluoroisopropyl methyl ether. In some embodiments, the reaction is carried out in the presence of an amine. In some embodiments, the amine is an alkylamine or pyridine. In some embodiments, the alkylamine is a trialkylamine. In some embodiments, the amine is selected from triethylamine, tripropylamine, tributylamine, diisopropylethylamine, pyridine, dimethylaminopyridine, 2,6-lutidine, and N,N-dimethylaniline. In some embodiments, the reaction is carried out at a temperature of about -40°C to about 80°C. In some embodiments, the reaction is carried out at a temperature of about -40°C to about 70°C. In some embodiments, the reaction is carried out at a temperature of about 0°C to about 35°C. In some embodiments, the reaction is carried out at a temperature of about 10°C to about 35°C.

[0009] The present disclosure also provides a battery including an electrolyte comprising a fluorinated ether or thioether in an amount of about 1 ppm to about 5,000 ppm. In some embodiments, the battery is rechargeable, and the battery has a cycle life of at least 250 cycles. In some embodiments, the fluorinated ether or thioether has Formula 10:

change

[0010] wherein X is O or S, R4 is a partially fluorinated C1-C8 alkyl group; and R5 is an optionally fluorinated C1-C8 alkyl group. In some embodiments, R4 is a partially fluorinated C1-C4 alkyl group; and R5 is an optionally fluorinated C1-C4 alkyl group. In some embodiments, the fluorinated ether or thioether comprises one or more groups selected from -CF3, -CHF2, -CH2F, -CHF-, and -CF2-. In some embodiments, the fluorinated ether or thioether comprises one or more -CF3 groups. In some embodiments, the fluorinated ether or thioether comprises two or more -CF3 groups. In some embodiments, the fluorinated ether or thioether comprises one or more groups selected from 2,2,2-trifluoroethyl, 1,1,1-trifluoroisopropyl, 1,1,1,3,3,3-hexafluoroisopropyl, 3,3,3-trifluoropropyl, 2-fluoroethyl, 2,2-difluoroethyl, 3-fluoropropyl, 3,3-difluoropropyl, 2,2,3,3,3-pentafluoropropyl, 4,4,4-trifluorobutyl, 1,1,1,3,3-pentafluoroisopropyl, and 5,5,5-trifluoropentyl. In some embodiments, the fluorinated ether or thioether is hexafluoroisopropyl methyl ether. In some embodiments, the battery is an alkali metal ion battery. In some embodiments, the battery is a lithium ion battery. In some embodiments, the electrolyte further comprises a fluorinated organic carbonate or fluorinated organic sulfite containing one or more of an optionally substituted alkyl, an optionally substituted haloalkyl, an optionally substituted alkenyl, an optionally substituted haloalkenyl, an optionally substituted alkynyl, an optionally substituted haloalkynyl, an optionally substituted aryl, an optionally substituted haloaryl, an optionally substituted heteroaryl, or an optionally substituted haloheteroaryl. In some embodiments, the fluorinated organic carbonate is a fluorinated dialkyl carbonate.In some embodiments, the fluorinated organic sulfite is a fluorinated dialkyl sulfite. In some embodiments, the fluorinated organic carbonate or the fluorinated organic sulfite comprises one or more groups selected from -CF3, -CHF2, -CH2F, -CHF-, and -CF2-. In some embodiments, the fluorinated organic carbonate or the fluorinated organic sulfite comprises one or more -CF3 groups. In some embodiments, the fluorinated organic carbonate or the fluorinated organic sulfite contains one or more groups selected from 2,2,2-trifluoroethyl, 1,1,1-trifluoroisopropyl, 1,1,1,3,3,3-hexafluoroisopropyl, 3,3,3-trifluoropropyl, 2-fluoroethyl, 2,2-difluoroethyl, 3-fluoropropyl, 3,3-difluoropropyl, 2,2,3,3,3-pentafluoropropyl, 4,4,4-trifluorobutyl, 1,1,1,3,3-pentafluoroisopropyl, and 5,5,5-trifluoropentyl. In some embodiments, the fluorinated organic carbonate or the fluorinated organic sulfite contains one or two 1,1,1,3,3,3-hexafluoroisopropyl groups. In some embodiments, the fluorinated organic carbonate is selected from methyl (2,2,2-trifluoroethyl)carbonate, methyl (1,1,1-trifluoroisopropyl)carbonate, methyl (1,1,1,3,3,3-hexafluoroisopropyl)carbonate, methyl (3,3,3-trifluoropropyl)carbonate, methyl (2-fluoroethyl)carbonate, methyl (2,2-difluoroethyl)carbonate, methyl (3-fluoropropyl)carbonate, methyl (3,3-difluoropropyl)carbonate, methyl (2,2,3,3,3-pentafluoropropyl)carbonate, methyl (4,4,4-trifluorobutyl)carbonate, methyl (1,1,1,3,3-pentafluoroisopropyl)carbonate, and methyl (5,5,5-trifluoropentyl)carbonate.In some embodiments, the fluorinated organic sulfite is selected from bis-(2,2,2-trifluoroethyl) sulfite, bis-(1,1,1-trifluoroisopropyl) sulfite, and bis-(1,1,1,3,3,3-hexafluoroisopropyl) sulfite.

[0011] The present disclosure also provides a battery including an electrolyte comprising a solvent component, the solvent component comprising a fluorinated compound in an amount of from about 1 ppm to about 60%, the fluorinated compound having any of Formula I, Formula II(a), Formula II(b), Formula III, or Formula IV. [ka]

[0012] wherein R10 and R20 are independently selected from C1-C6 alkyl, C1-C8 alkyl, cycloalkyl, aryl, fully or partially fluorinated C1-C6 alkyl, fully or partially fluorinated C1-C8 alkyl, fully or partially fluorinated cycloalkyl, and fully or partially fluorinated aryl. In some embodiments, R20 is fully or partially fluorinated C1-C6 alkyl. In some embodiments, R20 comprises one or more -CF3 groups. In some embodiments, R20 comprises 1 to 3 -CF3 groups. In some embodiments, R20 is selected from trifluoroethyl or hexafluoroisopropyl. In some embodiments, R10 is selected from methyl, ethyl, n-propyl, and 2-propyl. In some embodiments, R10 is selected from fully or partially fluorinated methyl, fully or partially fluorinated ethyl, fully or partially fluorinated n-propyl, and fully or partially fluorinated 2-propyl. In some embodiments, R10 comprises one or more -CF3 groups. In some embodiments, R10 contains 1 to 3 -CF3 groups. In some embodiments, R10 and R20 are the same.

[0013] In some embodiments, the compound of formula IV is a compound of any of formula 400, formula 401, formula 402, or formula 403. [ka]

[0014] In some embodiments, the compound of formula I is a compound of any of formulas 100, 101, 102, or 103. [ka]

[0015] In some embodiments, the compound of Formula II(a) is a compound of any of Formula 200, Formula 201, Formula 202, or Formula 203. [ka]

[0016] In some embodiments, the compound of formula III is a compound of formula 300 or formula 301: [ka]

[0017] In some embodiments, the fluorinated compound is an ether or thioether of Formula 10. [ka]

[0018] In Formula 10, X is O or S, R4 is a partially fluorinated C1-C8 alkyl group; and R5 is an optionally fluorinated C1-C8 alkyl group.

[0019] In some embodiments, R4 is a partially fluorinated C1-C4 alkyl group and R5 is an optionally fluorinated C1-C4 alkyl group. In some embodiments, the fluorinated ether or thioether comprises one or more groups selected from -CF3, -CHF2, -CH2F, -CHF-, and -CF2-. In some embodiments, the fluorinated ether or thioether comprises one or more -CF3 groups. In some embodiments, the fluorinated ether or thioether comprises two or more -CF3 groups. In some embodiments, the fluorinated ether or thioether comprises one or more groups selected from 2,2,2-trifluoroethyl, 1,1,1-trifluoroisopropyl, 1,1,1,3,3,3-hexafluoroisopropyl, 3,3,3-trifluoropropyl, 2-fluoroethyl, 2,2-difluoroethyl, 3-fluoropropyl, 3,3-difluoropropyl, 2,2,3,3,3-pentafluoropropyl, 4,4,4-trifluorobutyl, 1,1,1,3,3-pentafluoroisopropyl, and 5,5,5-trifluoropentyl. In some embodiments, the fluorinated ether or thioether is hexafluoroisopropyl methyl ether.

[0020] In some embodiments, the solvent component contains the fluorinated compound in an amount of about 1 ppm to about 5000 ppm. In some embodiments, the solvent component contains the fluorinated compound in an amount of about 0.0001% to about 5%. In some embodiments, the solvent component contains the fluorinated compound in an amount of about 0.1% to about 2%.

[0021] In some embodiments, the electrolyte is a non-aqueous electrolyte, and the solvent component further comprises one or more of a partially fluorinated organic carbonate and a non-fluorinated organic carbonate. In some embodiments, the non-fluorinated carbonate comprises one or more of EC (ethylene carbonate), EMC (ethyl methyl carbonate), DEC (diethyl carbonate), DMC (dimethyl carbonate), PC (propylene carbonate), and VC (vinylene carbonate or vinylidene carbonate). In some embodiments, the amount of VC in the solvent component is about 0.001% to about 2%. In some embodiments, the partially fluorinated carbonate comprises FEC (fluoroethylene carbonate), and the amount of FEC in the solvent component is about 0.001% to about 10%.

[0022] In some embodiments, the electrolyte further comprises a fluorinated organic carbonate or a fluorinated organic sulfite comprising one or more of an optionally substituted alkyl, an optionally substituted haloalkyl, an optionally substituted alkenyl, an optionally substituted haloalkenyl, an optionally substituted alkynyl, an optionally substituted haloalkynyl, an optionally substituted aryl, an optionally substituted haloaryl, an optionally substituted heteroaryl, or an optionally substituted haloheteroaryl. In some embodiments, the fluorinated organic carbonate is a fluorinated dialkyl carbonate. In some embodiments, the fluorinated organic sulfite is a fluorinated dialkyl sulfite. In some embodiments, the fluorinated organic carbonate or the fluorinated organic sulfite comprises one or more groups selected from -CF3, -CHF2, -CH2F, -CHF-, and -CF2-. In some embodiments, the fluorinated organic carbonate or the fluorinated organic sulfite comprises one or more -CF3 groups. In some embodiments, the fluorinated organic carbonate or the fluorinated organic sulfite comprises one or more groups selected from 2,2,2-trifluoroethyl, 1,1,1-trifluoroisopropyl, 1,1,1,3,3,3-hexafluoroisopropyl, 3,3,3-trifluoropropyl, 2-fluoroethyl, 2,2-difluoroethyl, 3-fluoropropyl, 3,3-difluoropropyl, 2,2,3,3,3-pentafluoropropyl, 4,4,4-trifluorobutyl, 1,1,1,3,3-pentafluoroisopropyl, and 5,5,5-trifluoropentyl. In some embodiments, the fluorinated organic carbonate or the fluorinated organic sulfite comprises one or more 1,1,1,3,3,3-hexafluoroisopropyl groups.

[0023] In some embodiments, the fluorinated organic carbonate is selected from methyl (2,2,2-trifluoroethyl)carbonate, methyl (1,1,1-trifluoroisopropyl)carbonate, methyl (1,1,1,3,3,3-hexafluoroisopropyl)carbonate, methyl (3,3,3-trifluoropropyl)carbonate, methyl (2-fluoroethyl)carbonate, methyl (2,2-difluoroethyl)carbonate, methyl (3-fluoropropyl)carbonate, methyl (3,3-difluoropropyl)carbonate, methyl (2,2,3,3,3-pentafluoropropyl)carbonate, methyl (4,4,4-trifluorobutyl)carbonate, methyl (1,1,1,3,3-pentafluoroisopropyl)carbonate, and methyl (5,5,5-trifluoropentyl)carbonate. In some embodiments, the fluorinated organic sulfite is selected from bis-(2,2,2-trifluoroethyl) sulfite, bis-(1,1,1-trifluoroisopropyl) sulfite, and bis-(1,1,1,3,3,3-hexafluoroisopropyl) sulfite.

[0024] In some embodiments, the fluorinated organic carbonate is selected from ethyl (2,2,2-trifluoroethyl)carbonate, ethyl (1,1,1-trifluoroisopropyl)carbonate, ethyl (1,1,1,3,3,3-hexafluoroisopropyl)carbonate, ethyl (3,3,3-trifluoropropyl)carbonate, ethyl (2-fluoroethyl)carbonate, ethyl (2,2-difluoroethyl)carbonate, ethyl (3-fluoropropyl)carbonate, ethyl (3,3-difluoropropyl)carbonate, ethyl (2,2,3,3,3-pentafluoropropyl)carbonate, ethyl (4,4,4-trifluorobutyl)carbonate, ethyl (1,1,1,3,3-pentafluoroisopropyl)carbonate, and ethyl (5,5,5-trifluoropentyl)carbonate.

[0025] In some embodiments, the fluorinated organic carbonate is n-propyl(2,2,2-trifluoroethyl)carbonate, n-propyl(1,1,1-trifluoroisopropyl)carbonate, n-propyl(1,1,1,3,3,3-hexafluoroisopropyl)carbonate, n-propyl(3,3,3-trifluoropropyl)carbonate, n-propyl(2-fluoroethyl)carbonate, n-propyl(2,2-difluoroethyl)carbonate, ) carbonate, n-propyl(3-fluoropropyl) carbonate, n-propyl(3,3-difluoropropyl) carbonate, n-propyl(2,2,3,3,3-pentafluoropropyl) carbonate, n-propyl(4,4,4-trifluorobutyl) carbonate, n-propyl(1,1,1,3,3-pentafluoroisopropyl) carbonate, and n-propyl(5,5,5-trifluoropentyl) carbonate.

[0026] In some embodiments, the fluorinated organic carbonate is selected from isopropyl(2,2,2-trifluoroethyl)carbonate, isopropyl(1,1,1-trifluoroisopropyl)carbonate, isopropyl(1,1,1,3,3,3-hexafluoroisopropyl)carbonate, isopropyl(3,3,3-trifluoropropyl)carbonate, isopropyl(2-fluoroethyl)carbonate, isopropyl(2,2-difluoroethyl)carbonate, isopropyl(3-fluoropropyl)carbonate, isopropyl(3,3-difluoropropyl)carbonate, isopropyl(2,2,3,3,3-pentafluoropropyl)carbonate, isopropyl(4,4,4-trifluorobutyl)carbonate, isopropyl(1,1,1,3,3-pentafluoroisopropyl)carbonate, and isopropyl(5,5,5-trifluoropentyl)carbonate.

[0027] The present disclosure also provides a battery comprising the electrolyte described herein. In some embodiments, the electrolyte further comprises an alkali salt. In some embodiments, the alkali salt is dissolved in the solvent component, and the concentration of the alkali salt is about 1 M to about 1.5 M. In some embodiments, the alkali salt is dissolved in the solvent component, and the concentration of the alkali salt is about 1 M, about 1.1 M, about 1.2 M, about 1.3 M, about 1.4 M, or about 1.5 M. In some embodiments, the alkali salt is a lithium salt. In some embodiments, the lithium salt is LiPF6.

[0028] The present disclosure also provides a battery comprising the anode and cathode described herein. In some embodiments, the cathode comprises a metal selected from nickel, manganese, and cobalt. In some embodiments, the cathode comprises about 70% to about 90% nickel. In some embodiments, the cathode comprises about 1% to about 15% manganese. In some embodiments, the cathode comprises about 1% to about 15% cobalt. In some embodiments, the cathode comprises about 80% nickel, about 10% manganese, and about 10% cobalt. In some embodiments, the cathode comprises about 90% nickel, about 5% manganese, and about 5% cobalt. In some embodiments, the anode comprises about 2% to about 75% silicon. In some embodiments, the anode comprises about 2% to about 70% silicon oxide-graphite composite. In some embodiments, the anode comprises about 2% to about 70% amorphous silicon graphite composite.

[0029] The present disclosure also provides a battery as described herein, wherein the battery is rechargeable and the battery has a cycle life of about 150 to about 500 cycles. In some embodiments, the battery has a cycle life of at least 200 cycles. In some embodiments, the battery has a cycle life of at least 250 cycles.

[0030] The foregoing summary, as well as the following detailed description of the present disclosure, will be better understood when read in conjunction with the appended drawings. [Brief explanation of the drawings]

[0031] [Figure 1] FIG. 1 shows the improved high temperature performance of a cell containing an NMC811 cathode and a silicon composite anode when using trifluoroethyl methyl carbonate (F3EMC) as the fluorinated component of the electrolyte mixture versus an electrolyte containing fluoroethylene carbonate (FEC).

[0032] [Figure 2] FIG. 2 shows the improved performance at high temperature in a cell containing an NMC811 cathode and a silicon composite anode using an electrolyte containing trifluoroethyl acetate ester versus an electrolyte containing FEC.

[0033] [Figure 3] FIG. 3 shows the improved performance at high temperature for a cell containing an NMC811 cathode and a silicon composite anode using an electrolyte containing hexafluoro-2-methoxypropane (hexafluoro-2-propyl methyl ether) versus an electrolyte containing fluoroethylene carbonate (FEC).

[0034] Detailed Description There is considerable interest in using higher energy density electrodes, such as high-nickel cathodes, such as NMC811, and silicon composite anodes. While batteries fabricated using high-nickel NMC811 and equipped with silicon anodes are commercially important, performance improvements are still needed. The main drawback is the decomposition of the electrolyte in this type of battery, resulting in poor cycling performance. Fluoroethylene carbonate (FEC) is widely used as an electrolyte additive or cosolvent in these systems, helping to create an SEI layer on the Si composite anode. The use of FEC has significant drawbacks due to the large amount of gas evolution within the cell, which poses safety concerns.

[0035] The present disclosure provides for the use of other fluorinated carbonates, ethers, and esters in combination with FEC in the electrolyte to further improve battery cycle life. The present disclosure further provides for the use of trifluoromethylated carbonates in place of and / or in combination with FEC, resulting in significantly improved cycle life.

[0036] In some embodiments, the present disclosure provides an improved process for producing carbonates and sulfites using hexafluoroisopropyl methyl ether as a solvent.

[0037] In some embodiments, the present disclosure provides a battery including an electrolyte comprising a fluorinated ether or thioether. In some embodiments, the amount of fluorinated ether or thioether in the electrolyte is 1 to 5000 ppm. In some embodiments, the amount of fluorinated ether or thioether in the electrolyte is 0.0001% to 2%. In some embodiments, the ethers include hexafluoroisopropyl methyl ether in an amount of 1 to 5000 ppm. In some embodiments, the ethers include hexafluoroisopropyl methyl ether in an amount of 0.0001% to 2%. In some embodiments, the present disclosure provides a battery including an electrolyte comprising bis(1,1,1,3,3,3-hexafluoroisopropyl) sulfite.

[0038] Methods for producing fluorinated carbonates are known in the art. U.S. Patent Application No. 20120141870 discloses the preparation of methyl 2,2,2-trifluoroethyl carbonate in 46% yield by adding methyl chloroformate to a solution of 2,2,2-trifluoroethanol and pyridine in dichloromethane. U.S. Patent Application No. 20180346404 discloses a similar process in which dichloromethane is also used as the solvent. Dichloromethane is disadvantageous for several reasons. For example, traces of chlorine-containing solvents present in the final product can adversely affect battery performance, and dichloromethane is not recommended for large-scale processes due to its toxicity. Furthermore, the yields obtained with dichloromethane are not ideal for large-scale synthesis.

[0039] WO2015083745 and WO2015083747 describe the preparation of methyl 2,2,2-trifluoroethyl carbonate by adding methyl chloroformate to 2,2,2-trifluoroethanol and pyridine in triglyme, where triglyme also remains in the final product and can be detrimental to the battery.

[0040] The preparation of fluorine-containing sulfites has also been reported (Journal of Fluorine Chemistry 6 (1975) 93-104). In this process, a triethylamine adduct of a fluorinated alcohol is reacted with a four-fold excess of thionyl chloride at -78°C. The extremely low temperatures and excess amounts of reactants required make this process both practically and economically undesirable.

[0041] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. All patents and publications referenced herein are incorporated by reference in their entirety.

[0042] definition Unless otherwise stated, chemical structures depicted herein are intended to include compounds that differ only in the presence of one or more isotopically enriched atoms. For example, compounds in which one or more hydrogen atoms are replaced by deuterium or tritium, or one or more carbon atoms are replaced by C- or C-enriched carbon are within the scope of the present disclosure.

[0043] When ranges are used herein to describe physical or chemical properties, such as, for example, molecular weight or chemical formula, all combinations and subcombinations of ranges, and specific embodiments therein, are intended to be included. The use of the term "about" when referring to a numerical value or numerical range means that the stated numerical value or numerical range is approximate within experimental variation (or within statistical experimental error), and thus, the numerical value or numerical range may vary. The variation is typically 0% to 15%, preferably 0% to 10%, and more preferably 0% to 5% of the stated numerical value or numerical range. The term "comprising" (and related terms such as "comprise" or "comprises" or "having" or "including") includes embodiments, such as, for example, any composition, method, or process embodiment that "consists of" or "consists essentially of" the described features.

[0044] "Alkyl" refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing no unsaturation, and having 1 to 10 carbon atoms (e.g., (C1-10) alkyl or C1-10 alkyl). As used herein, a numerical range such as "1 to 10" refers to each integer within the range; for example, "1 to 10 carbon atoms" means that the alkyl group can consist of 1 carbon atom, 2 carbon atoms, 3 carbon atoms, and so on, up to and including 10 carbon atoms. However, the above definition is intended to cover the term "alkyl" where no numerical range is specifically specified. Typical alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butylisobutyl, tertiary butyl, pentyl, isopentyl, neopentyl, hexyl, septyl, octyl, nonyl, and decyl. Alkyl moieties, such as methyl (Me), ethyl (Et), n-propyl (Pr), 1-methylethyl (isopropyl), n-butyl, n-pentyl, 1,1-dimethylethyl (t-butyl), and 3-methylhexyl, can be attached to the rest of the molecule by a single bond.Unless otherwise specified in this specification, the alkyl groups are independently selected from the group consisting of heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, -ORa, -SRa, -OC(O)-Ra, -N(Ra), -C(O)Ra, -C(O)ORa, -OC(O)N(Ra), -C(O)N(Ra), -N(Ra)C(O)ORa, -N(Ra)C(O)Ra, and optionally substituted by one or more substituents which are -N(Ra)C(O)N(Ra)2, N(Ra)C(NRa)N(Ra)2, -N(Ra)S(O)tRa (where t is 1 or 2), -S(O)tORa (where t is 1 or 2), -S(O)tN(Ra)2 (where t is 1 or 2), or PO3(Ra)2 (where each Ra is independently hydrogen, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl).

[0045] "Alkylaryl" means an -(alkyl)aryl radical, where aryl and alkyl are as disclosed herein, optionally substituted with one or more of the substituents described as suitable substituents for aryl and alkyl, respectively.

[0046] "Alkylhetaryl" means a -(alkyl)hetaryl radical, where hetaryl and alkyl are as disclosed herein, optionally substituted with one or more of the substituents described as suitable substituents for aryl and alkyl, respectively.

[0047] "Alkylheterocycloalkyl" means an -(alkyl)heterocyclyl radical, wherein alkyl and heterocycloalkyl are as disclosed herein, optionally substituted by one or more of the substituents described as suitable substituents for heterocycloalkyl and alkyl, respectively.

[0048] An "alkyne" moiety means a group consisting of at least two carbon atoms and at least one carbon-carbon double bond, and an "alkyne" moiety means a group consisting of at least two carbon atoms and at least one carbon-carbon triple bond. The alkyl moiety can be branched, straight-chain, or cyclic, whether saturated or unsaturated.

[0049] "Alkenyl" refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one double bond, and having 2 to 10 carbon atoms (i.e., (C2-10) alkenyl or C2-10 alkenyl). As used herein, whenever a numerical range such as "2 to 10" refers to each integer within the range, for example, "2 to 10 carbon atoms" means that the alkyl group can consist of up to 10 carbon atoms, such as 2 carbon atoms, 3 carbon atoms, etc. The alkenyl moiety can be attached to the remainder of the molecule by a single bond, for example, ethenyl (i.e., vinyl), prop-1-enyl (i.e., allyl), but-1-enyl, pent-1-enyl, and penta-1,4-dienyl. Unless otherwise specified in this specification, the alkenyl groups are independently alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, -ORa, -SRa, -OC(O)-Ra, -N(Ra), -C(O)Ra, -C(O)ORa, -OC(O)N(Ra), -C(O)N(Ra), -N(Ra)C(O)ORa, -N(Ra)C(O)Ra , —N(Ra)C(O)N(Ra)2, N(Ra)C(NRa)N(Ra)2, —N(Ra)S(O)tRa (where t is 1 or 2), —S(O)tORa (where t is 1 or 2), —S(O)tN(Ra)2 (where t is 1 or 2), or PO3(Ra)2 (where each Ra is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl).

[0050] "Alkenyl-cycloalkyl" means an -(alkenyl)cycloalkyl radical, wherein alkenyl and cycloalkyl are as disclosed herein and optionally substituted with one or more of the substituents described as suitable substituents for alkenyl and cycloalkyl, respectively.

[0051] "Alkynyl" refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one triple bond, and having 2 to 10 carbon atoms (i.e., (C2-10)alkynyl or C2-10alkynyl). As used herein, any numerical range such as "2 to 10" refers to each integer within the range; for example, "2 to 10 carbon atoms" means that the alkyl group can consist of up to 10 carbon atoms, such as 2 carbon atoms, 3 carbon atoms, etc. The alkynyl, e.g., ethynyl, propynyl, butynyl, pentynyl, and hexynyl, can be attached to the remainder of the molecule by a single bond. Unless stated otherwise in this specification, alkynyl groups are independently selected from alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, -ORa, -SRa, -OC(O)-Ra, -N(Ra), -C(O)Ra, -C(O)ORa, -OC(O)N(Ra), -C(O)N(Ra), -N(Ra)C(O)ORa, -N(Ra)C(O)Ra, and optionally substituted by one or more substituents which are -N(Ra)C(O)N(Ra)2, N(Ra)C(NRa)N(Ra)2, -N(Ra)S(O)tRa (where t is 1 or 2), -S(O)tORa (where t is 1 or 2), -S(O)tN(Ra)2 (where t is 1 or 2), or PO3(Ra)2 (where each Ra is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl).

[0052] "Alkynyl-cycloalkyl" means an -(alkynyl)cycloalkyl radical, wherein alkynyl and cycloalkyl are as disclosed herein, optionally substituted by one or more of the substituents described as suitable substituents for alkynyl and cycloalkyl, respectively.

[0053] "Carboxaldehyde" means the -(C=O)H radical.

[0054] "Carboxyl" means the --(C.dbd.O)OH radical.

[0055] "Cyano" means the radical --CN.

[0056] "Cycloalkyl" refers to a monocyclic or polycyclic radical containing only carbon and hydrogen and may be saturated or partially unsaturated. Cycloalkyl groups include groups having 3 to 10 ring atoms (i.e., (C3-10)cycloalkyl or C3-10cycloalkyl). As used herein, whenever a numerical range such as "3 to 10" refers to each integer within the range, e.g., "3 to 10 carbon atoms" means that the cycloalkyl group can consist of up to 10 carbon atoms, such as 3 carbon atoms. Illustrative examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, norbornyl, and the like. Unless otherwise stated in the specification, cycloalkynyl groups are independently selected from alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, -ORa, -SRa, -OC(O)-Ra, -N(Ra), -C(O)Ra, -C(O)ORa, -OC(O)N(Ra), -C(O)N(Ra), -N(Ra)C(O)ORa, -N(Ra)C(O)Ra , —N(Ra)C(O)N(Ra)2, N(Ra)C(NRa)N(Ra)2, —N(Ra)S(O)tRa (where t is 1 or 2), —S(O)tORa (where t is 1 or 2), —S(O)tN(Ra)2 (where t is 1 or 2), or PO3(Ra)2 (where each Ra is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl).

[0057] "Cycloalkyl-alkenyl" means a -(cycloalkyl)alkenyl radical, wherein cycloalkyl and alkenyl are as disclosed herein, optionally substituted by one or more of the substituents described as suitable substituents for cycloalkyl and alkenyl, respectively.

[0058] "Cycloalkyl-heterocycloalkyl" means a -(cycloalkyl)heterocycloalkyl radical, wherein cycloalkyl and heterocycloalkyl are as disclosed herein, optionally substituted with one or more of the substituents described as suitable substituents for cycloalkyl and heterocycloalkyl, respectively.

[0059] "Cycloalkyl-heteroaryl" means a -(cycloalkyl)heteroaryl radical, wherein cycloalkyl and heteroaryl are as disclosed herein, optionally substituted with one or more of the substituents described as suitable substituents for cycloalkyl and heteroaryl, respectively.

[0060] The term "alkoxy" refers to the group -O-alkyl, including linear, branched, and cyclic structures and combinations thereof, of from 1 to 8 carbon atoms attached to the parent structure through an oxygen. Examples include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, cyclopropyloxy, and cyclohexyloxy. "Lower alkoxy" refers to an alkoxy group containing 1 to 6 carbons.

[0061] The term "substituted alkoxy" refers to an alkoxy in which the alkyl moiety is substituted (i.e., -O-(substituted alkyl)). Unless otherwise stated in the specification, the alkyl portions of an alkynyl group can independently be alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, -OR, -SR, -OC(O)-Ra, -N(Ra), -C(O)Ra, -C(O)OR, -OC(O)N(Ra), -C(O)N(Ra), -N(Ra)C(O)OR, -N(Ra)C(O) and optionally substituted by one or more substituents which are Ra, —N(Ra)C(O)N(Ra), N(Ra)C(NRa)N(Ra), —N(Ra)S(O)tRa (where t is 1 or 2), —S(O)tORa (where t is 1 or 2), —S(O)tN(Ra) (where t is 1 or 2), or PO3(Ra) (where each Ra is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl).

[0062] The term "alkoxycarbonyl" refers to a group of the formula (alkoxy)(C=O)- attached through the carbonyl carbon, where the alkoxy group has the indicated number of carbon atoms. Thus, a (C1-6)alkoxycarbonyl group is an alkoxy group having from 1 to 6 carbon atoms attached through its oxygen to a carbonyl linker. "Lower alkoxycarbonyl" refers to an alkoxycarbonyl group in which the alkoxy group is a lower alkoxy group.

[0063] The term "substituted alkoxycarbonyl" refers to the group (substituted alkyl)-OC(O)-, which is attached to the parent structure via a carbonyl functionality. Unless otherwise stated in the specification, the alkyl portions of the alkoxycarbonyl group are independently alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, -OR, -SR, -OC(O)-Ra, -N(Ra), -C(O)Ra, -C(O)OR, -OC(O)N(Ra), -C(O)N(Ra), -N(Ra)C(O)OR, -N(Ra)C and optionally substituted by one or more substituents which are (O)Ra, —N(Ra)C(O)N(Ra), N(Ra)C(NRa)N(Ra), —N(Ra)S(O)tRa (where t is 1 or 2), —S(O)tORa (where t is 1 or 2), —S(O)tN(Ra) (where t is 1 or 2), or PO3(Ra)2 (where each Ra is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl).

[0064] "Acyl" refers to the groups (alkyl)-C(O)-, (aryl)-C(O)-, (heteroaryl)-C(O)-, (heteroalkyl)-C(O)-, and (heterocycloalkyl)-C(O)-, which are attached to the parent structure via a carbonyl functionality. When the R radical is heteroaryl or heterocycloalkyl, the heterocycle or chain atoms contribute to the total number of chain or ring atoms. Unless otherwise specified in this specification, the alkyl, acyl, or heteroaryl portion of the acyl group independently represents alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, -ORa, -SRa, -OC(O)-Ra, -N(Ra), -C(O)Ra, -C(O)ORa, -OC(O)N(Ra), -C(O)N(Ra), -N(Ra)C(O)ORa, -N( and optionally substituted by one or more substituents which are: Ra)C(O)Ra, —N(Ra)C(O)N(Ra), N(Ra)C(NRa)N(Ra), —N(Ra)S(O)tRa (where t is 1 or 2), —S(O)tORa (where t is 1 or 2), —S(O)tN(Ra) (where t is 1 or 2), or PO(Ra) (where each Ra is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl).

[0065] "Acyloxy" refers to the R(C=O)O- radical, where R is alkyl, aryl, heteroaryl, heteroalkyl, or heterocycloalkyl as described herein. When the R radical is heteroaryl or heterocycloalkyl, the heterocycle or chain atoms contribute to the total number of chain or ring atoms. Unless otherwise specified in the specification, the R of an acyloxy group is independently alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, -ORa, -SRa, -OC(O)-Ra, -N(Ra), -C(O)Ra, -C(O)ORa, -OC(O)N(Ra), -C(O)N(Ra), -N(Ra)C(O)ORa, -N(Ra)C(O)R and optionally substituted by one or more substituents which are a, —N(Ra)C(O)N(Ra)2, N(Ra)C(NRa)N(Ra)2, —N(Ra)S(O)tRa (where t is 1 or 2), —S(O)tORa (where t is 1 or 2), —S(O)tN(Ra)2 (where t is 1 or 2), or PO3(Ra)2 (where each Ra is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl).

[0066] "Acylsulfonamido" refers to the radical -S(O)-N(Ra)-C(=O)-, where Ra is hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl. Unless otherwise stated in the specification, acylsulfonamido groups are independently alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, -OR, -SR, -OC(O)-Ra, -N(Ra), -C(O)Ra, -C(O)OR, -OC(O)N(Ra), -C(O)N(Ra), -N(Ra)C(O)OR, -N(Ra)C(O)R and optionally substituted by one or more substituents which are a, —N(Ra)C(O)N(Ra)2, N(Ra)C(NRa)N(Ra)2, —N(Ra)S(O)tRa (where t is 1 or 2), —S(O)tORa (where t is 1 or 2), —S(O)tN(Ra)2 (where t is 1 or 2), or PO3(Ra)2 (where each Ra is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl).

[0067] "Amino" or "amine" refers to the radical -N(Ra)2, where, unless otherwise specified herein, each Ra is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl. When an -N(Ra)2 group has two Ra substituents other than hydrogen, they can combine with the nitrogen atom to form a 4-, 5-, 6-, or 7-membered ring. For example, -N(Ra)2 is meant to include, but not be limited to, 1-pyrrolidinyl and 4-morpholinyl. Unless otherwise specified in this specification, amino groups are independently selected from alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, -ORa, -SRa, -OC(O)-Ra, -N(Ra), -C(O)Ra, -C(O)ORa, -OC(O)N(Ra), -C(O)N(Ra), -N(Ra)C(O)ORa, -N(Ra)C(O)Ra, - and optionally substituted by one or more substituents which are N(Ra)C(O)N(Ra), N(Ra)C(NRa)N(Ra), -N(Ra)S(O)tRa (where t is 1 or 2), -S(O)tORa (where t is 1 or 2), -S(O)tN(Ra) (where t is 1 or 2), or PO(Ra) (where each Ra is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl).

[0068] The term "substituted amino" also refers to the N-oxides of the groups -NHRa and NRaRa, respectively, as defined above. The N-oxides can be prepared by treating the corresponding amino group with, for example, hydrogen peroxide or m-chloroperoxybenzoic acid.

[0069] "Amide" or "amido" means a chemical moiety having the formula -C(O)N(R) or NHC(O)R, where R is selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, heteroaryl (bonded through a ring carbon), and heteroalicyclic (bonded through a ring carbon), each of which moieties may itself be optionally substituted. The R of the -N(R) of the amide, together with the nitrogen to which it is attached, may form a 4-, 5-, 6-, or 7-membered ring. Unless otherwise specified herein, an amido group may be independently substituted with one or more of the substituents described herein for alkyl, cycloalkyl, aryl, heteroaryl, or heterocycloalkyl. An amide may be an amino acid or peptide molecule that is attached to a compound disclosed herein to form a prodrug. Procedures and specific groups for forming such amides are known to those of skill in the art and can be readily found in influential sources, such as Greene and Wuts, Protective Groups in Organic Synthesis, 3rd Ed., John Wiley & Sons, New York, NY, 1999, which is incorporated herein by reference in its entirety.

[0070] "Aromatic" or "aryl" or "Ar" refers to an aromatic radical (e.g., C6-C10 aromatic or C6-C10 aryl) having 6 to 10 ring atoms with at least one ring having a conjugated pi-electron system that is carbocyclic (e.g., phenyl, fluorenyl, and naphthyl). Divalent radicals formed from substituted benzene derivatives and having a free valence on a ring atom are referred to as substituted phenylene radicals. Divalent radicals derived from monovalent polycyclic hydrocarbon radicals ending in "-yl" by removing one hydrogen atom from the free valence carbon atom are named by adding "-ydene" to the name of the corresponding monovalent radical. For example, a naphthyl group with two points of attachment is referred to as naphthylidene. As used herein, numerical ranges such as "6 to 10" refer to each integer within the range. For example, "6 to 10 ring atoms" means that the aryl group can consist of up to 10 ring atoms, such as 6 ring atoms, 7 ring atoms, etc. The term includes monocyclic or fused-ring polycyclic (i.e., rings which share adjacent pairs of ring atoms) groups. Unless otherwise stated in the specification, aryl moieties are independently selected from alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, -ORa, -SRa, -OC(O)-Ra, -N(Ra), -C(O)Ra, -C(O)ORa, -OC(O)N(Ra), -C(O)N(Ra), -N(Ra)C(O)ORa, -N(Ra)C(O)Ra, and optionally substituted by one or more substituents which are -N(Ra)C(O)N(Ra)2, N(Ra)C(NRa)N(Ra)2, -N(Ra)S(O)tRa (where t is 1 or 2), -S(O)tORa (where t is 1 or 2), -S(O)tN(Ra)2 (where t is 1 or 2), or PO3(Ra)2 (where each Ra is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl).

[0071] The term "aryloxy" refers to the group -O-aryl.

[0072] The term "substituted aryloxy" refers to an aryloxy in which the aryl substituent is substituted (i.e., -O-(substituted aryl)). Unless otherwise stated in the specification, the aryl portions of the aryloxy group are independently selected from alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, -ORa, -SRa, -OC(O)-Ra, -N(Ra), -C(O)Ra, -C(O)ORa, -OC(O)N(Ra), -C(O)N(Ra), -N(Ra)C(O)ORa, -N(Ra)C(O )Ra, —N(Ra)C(O)N(Ra), N(Ra)C(NRa)N(Ra), —N(Ra)S(O)tRa (where t is 1 or 2), —S(O)tORa (where t is 1 or 2), —S(O)tN(Ra) (where t is 1 or 2), or PO3(Ra) (where each Ra is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl).

[0073] "Aralkyl" or "arylalkyl" means an (aryl)alkyl radical, where aryl and alkyl are as disclosed herein, optionally substituted with one or more of the substituents described as suitable substituents for aryl and alkyl, respectively.

[0074] "Ester" means a chemical radical of the formula -COOR, where R is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl (bonded through a ring carbon), and heteroalicyclic (bonded through a ring carbon). Procedures and specific groups for forming esters are known to those of skill in the art and can be readily found in influential sources, such as Greene and Wuts, Protective Groups in Organic Synthesis, 3rd Ed., John Wiley & Sons, New York, NY, 1999, which is incorporated herein by reference in its entirety. Unless otherwise stated in the specification, ester groups are independently alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, -ORa, -SRa, -OC(O)-Ra, -N(Ra), -C(O)Ra, -C(O)ORa, -OC(O)N(Ra), -C(O)N(Ra), -N(Ra)C(O)ORa, -N(Ra)C(O)Ra, - and optionally substituted by one or more substituents which are N(Ra)C(O)N(Ra), N(Ra)C(NRa)N(Ra), -N(Ra)S(O)tRa (where t is 1 or 2), -S(O)tORa (where t is 1 or 2), -S(O)tN(Ra) (where t is 1 or 2), or PO(Ra) (where each Ra is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl).

[0075] "Fluoroalkyl" means an alkyl radical as defined above that is substituted by one or more fluoro radicals as defined above, e.g., trifluoromethyl, difluoromethyl, 2,2,2-trifluoroethyl, 1-fluoromethyl-2-fluoroethyl, etc. The alkyl portion of the fluoroalkyl radical may be optionally substituted with an alkyl group as defined above.

[0076] The terms "halo," "halide," or "halogen" are intended to mean fluoro, chloro, bromo, or iodo. The terms "haloalkyl," "haloalkenyl," "haloalkynyl," and "haloalkoxy" include alkyl, alkenyl, alkynyl, and alkoxy structures that are substituted with one or more halo groups or combinations thereof. For example, the terms "fluoroalkyl" and "fluoroalkoxy" include haloalkyl and haloalkoxy groups, respectively, where the halo is fluorine.

[0077] "Heteroalkyl," "heteroalkenyl," and "heteroalkynyl" refer to optionally substituted alkyl, alkenyl, and alkynyl radicals having one or more skeletal atoms selected from atoms other than carbon, e.g., oxygen, nitrogen, sulfur, phosphorus, or combinations thereof. Numerical ranges are given, e.g., C1-C4 heteroalkyl, in this example, means a total chain length of 4 atoms. Heteroalkyl groups are independently alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, nitro, oxo, thioxo, trimethylsilanyl, -ORa, -SRa, -OC(O)-Ra, -N(Ra)2, -C(O)Ra, -C(O)ORa, -OC(O)N(Ra)2, -C(O)N(Ra)2, -N(Ra)C(O)ORa, -N(Ra)C(O)Ra, -N(Ra)C(O)N(Ra) 2, N(Ra)C(NRa)N(Ra)2, —N(Ra)S(O)tRa (where t is 1 or 2), —S(O)tORa (where t is 1 or 2), —S(O)tN(Ra)2 (where t is 1 or 2), or PO3(Ra)2 (where each Ra is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl).

[0078] "Heteroalkylaryl" means a -(heteroalkyl)aryl radical, where heteroalkyl and aryl are as disclosed herein, optionally substituted with one or more of the substituents described as suitable substituents for heteroalkyl and aryl, respectively.

[0079] "Heteroalkylheteroaryl" means a -(heteroalkyl)heteroaryl radical, where heteroalkyl and heteroaryl are as disclosed herein, optionally substituted with one or more of the substituents described as suitable substituents for heteroalkyl and heteroaryl, respectively.

[0080] "Heteroalkylheterocycloalkyl" means a -(heteroalkyl)heterocycloalkyl radical, wherein heteroalkyl and heterocycloalkyl are as disclosed herein, optionally substituted with one or more of the substituents described as suitable substituents for heteroalkyl and heterocycloalkyl, respectively.

[0081] "Heteroalkylcycloalkyl" means a -(heteroalkyl)cycloalkyl radical, wherein heteroalkyl and cycloalkyl are as disclosed herein, optionally substituted with one or more of the substituents described as suitable substituents for heteroalkyl and cycloalkyl, respectively.

[0082] "Heteroaryl" or "heteroaromatic" or "HetAr" or "Het" refers to a 5-18-membered aromatic radical (e.g., C5-C13 heteroaryl) containing one or more ring heteroatoms selected from nitrogen, oxygen, and sulfur, and can be a monocyclic, bicyclic, tricyclic, or tetracyclic ring system. As used herein, a numerical range, such as "5-18," refers to each integer within the range. For example, "5-18 ring atoms" means that the heteroaryl group can consist of up to 18 ring atoms, such as 5 ring atoms, 6 ring atoms, and so on. Divalent radicals derived from monovalent heteroaryl radicals ending in "-yl" by removing a hydrogen atom from the atom bearing the free valence are named by adding "-ydene" to the name of the corresponding monovalent radical. For example, a pyridyl group with two points of attachment is called pyridylidene. An N-containing "heteroaromatic" or "heteroaryl" moiety refers to an aromatic group in which at least one of the skeletal atoms of the ring is a nitrogen atom. Polycyclic heteroaryl groups may be fused or unfused. The heteroatoms of the heteroaryl radical may be optionally oxidized. If present, one or more nitrogen atoms may be optionally quaternized. The heteroaryl may be attached to the remainder of the molecule through any atom of the ring. Examples of heteroaryls include, but are not limited to, azepinyl, acridinyl, benzimidazolyl, benzindolyl, 1,3-benzodioxolyl, benzofuranyl, benzoxazolyl, benzo[d]thiazolyl, benzothiadiazolyl, benzo[b][1,4]dioxepinyl, benzo[b][1,4]oxazinyl, 1,4-benzodioxanyl, benzonaphthofuranyl, benzoxazolyl, benzodioxolyl, benzodioxinyl, benzyl, benzo[b][1,4]oxazinyl, 1,4-benzodioxanyl, benzonaphthofuranyl, benzoxazolyl, benzodioxolyl, benzodioxinyl, benzyl, benzo[b][1,4]oxazinyl, benzo[b][1,4]oxazinyl, 1,4-benzodioxanyl, benzo[b]furanyl, benzo[b]thiazolyl, benzo[b]thiadiazolyl, benzo[b][1,4]oxazinyl, benzo[b][ ... Benzoxazolyl, benzopyranyl, benzopyranonyl, benzofuranyl, benzofuranonyl, benzofurazanyl, benzothiazolyl, benzothienyl (benzothiophenyl), benzothieno[3,2-d]pyrimidinyl, benzotriazolyl, benzo[4,6]imidazo[1,2-a]pyridinyl, carbazolyl, cinnolinyl, cyclopenta[d]pyrimidinyl, 6,7-dihydro-5H-cyclopenta[4,5]thieno[2,3-d]pyrimidinyl, 5,6-Dihydrobenzo[h]quinazolinyl, 5,6-dihydrobenzo[h]cinnolinyl, 6,7-dihydro-5H-benzo[6,7]cyclohepta[1,2-c]pyridazinyl, dibenzofuranyl, dibenzothiophenyl, furanyl, furazanyl, furanonyl, furo[3,2-c]pyridinyl, 5,6,7,8,9,10-hexahydrocycloocta[d]pyrimidinyl, 5,6,7,8,9,10-hexahydrocycloocta[d]pyridazinyl, 5,6,7,8,9,10 -Hexahydrocycloocta[d]pyridinyl, isothiazolyl, imidazolyl, indazolyl, indolyl, indazolyl, isoindolyl, indolinyl, isoindolinyl, isoquinolyl, indolizinyl, isoxazolyl, 5,8-methano-5,6,7,8-tetrahydroquinazolinyl, naphthyridinyl, 1,6-naphthyridinonyl, oxadiazolyl, 2-oxoazepinyl, oxazolyl, oxiranyl, 5,6,6a,7,8,9,10,10a-octahydrobenzyl benzo[h]quinazolinyl, 1-phenyl-1H-pyrrolyl, phenazinyl, phenothiazinyl, phenoxazinyl, phthalazinyl, pteridinyl, purinyl, pyranyl, pyrrolyl, pyrazolyl, pyrazolo[3,4-d]pyrimidinyl, pyridinyl, pyrido[3,2-d]pyrimidinyl, pyrido[3,4-d]pyrimidinyl, pyrazinyl, pyrimidinyl, pyridazinyl, pyrrolyl, quinazolinyl, quinoxalinyl, quinolinyl, isoquinolinyl, tetrahydroquinolinyl, 5,6, 7,8-Tetrahydroquinazolinyl, 5,6,7,8-tetrahydrobenzo[4,5]thieno[2,3-d]pyrimidinyl, 6,7,8,9-tetrahydro-5H-cyclohepta[4,5]thieno[2,3-d]pyrimidinyl, 5,6,7,8-tetrahydropyrido[4,5-c]pyridazinyl, thiazolyl, thiadiazolyl, thiapyranyl, triazolyl, tetrazolyl, triazinyl, thieno[2,3-d]pyrimidinyl, thieno[3,2-d]pyrimidinyl, thieno[2,

[0033] Unless otherwise specified in the specification, heteroaryl moieties are independently selected from alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, -ORa, -SRa, -OC(O)-Ra, -N(Ra), -C(O)Ra, -C(O)ORa, -OC(O)N(Ra), -C(O)N(Ra), -N(Ra)C(O)ORa, -N(Ra)C(O)Ra , -N(Ra)C(O)N(Ra)2, N(Ra)C(NRa)N(Ra)2, -N(Ra)S(O)tRa (where t is 1 or 2), -S(O)tORa (where t is 1 or 2), -S(O)tN(Ra)2 (where t is 1 or 2), or PO3(Ra)2 (where each Ra is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl).

[0083] Substituted heteroaryl also includes ring systems substituted with one or more oxide (—O—) substituents, such as, for example, pyridinyl N-oxide.

[0084] "Heteroarylalkyl" means a moiety having an aryl moiety, as described herein, bound to an alkylene moiety, as described herein, wherein the bond to the remainder of the molecule is through the alkylene group.

[0085] "Heterocycloalkyl" refers to a stable 3- to 18-membered non-aromatic ring radical containing 2 to 12 carbon atoms and 1 to 6 heteroatoms selected from nitrogen, oxygen, and sulfur. As used herein, a numerical range, such as "3 to 18," refers to each integer within the range. For example, "3 to 18 ring atoms" means that the heterocycloalkyl group can consist of up to 18 ring atoms, such as 3 ring atoms, 4 ring atoms, and so on. Unless otherwise specified in the specification, the heterocycloalkyl radical is a monocyclic, bicyclic, tricyclic, or tetracyclic ring system, which may include fused or bridged ring systems. The heteroatoms in the heterocycloalkyl radical may be optionally oxidized. One or more nitrogen atoms, if present, may be optionally quaternized. The heterocycloalkyl radical may be partially or fully saturated. The heterocycloalkyl may be attached to the remainder of the molecule through any atom of the ring. Examples of such heterocycloalkyl radicals include, but are not limited to, dioxolanyl, thienyl[1,3]dithianyl, decahydroisoquinolyl, imidazolinyl, imidazolidinyl, isothiazolidinyl, isoxazolidinyl, morpholinyl, octahydroindolyl, octahydroisoindolyl, 2-oxopiperazinyl, 2-oxopiperidinyl, 2-oxopyrrolidinyl, oxazolidinyl, piperidinyl, piperazinyl, 4-piperidonyl, pyrrolidinyl, pyrazolidinyl, quinuclidinyl, thiazolidinyl, tetrahydrofuryl, trithianyl, tetrahydropyranyl, thiomorpholinyl, thiamorpholinyl, 1-oxo-thiomorpholinyl, and 1,1-dioxo-thiomorpholinyl.Unless otherwise stated in the specification, heterocycloalkyl moieties are independently alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, nitro, oxo, thioxo, trimethylsilanyl, -ORa, -SRa, -OC(O)-Ra, -N(Ra)2, -C(O)Ra, -C(O)ORa, -OC(O)N(Ra)2, -C(O)N(Ra)2, -N(Ra)C(O)ORa, -N(Ra)C(O)Ra, -N( and optionally substituted by one or more substituents which are: Ra)C(O)N(Ra)2, N(Ra)C(NRa)N(Ra)2, —N(Ra)S(O)tRa (where t is 1 or 2), —S(O)tORa (where t is 1 or 2), —S(O)tN(Ra)2 (where t is 1 or 2), or PO3(Ra)2, where each Ra is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl.

[0086] "Heterocycloalkyl" also includes bicyclic ring systems in which one non-aromatic ring, typically having 3 to 7 ring atoms, contains at least 2 carbon atoms in addition to 1 to 3 heteroatoms independently selected from oxygen, sulfur, and nitrogen, and combinations comprising at least one of the foregoing heteroatoms, and the other ring, typically having 3 to 7 ring atoms, optionally contains 1 to 3 heteroatoms independently selected from oxygen, sulfur, and nitrogen, and is not aromatic.

[0087] "Nitro" means the -NO2 radical.

[0088] "Oxa" means the -O- radical.

[0089] "Oxo" means the =O radical.

[0090] "Isomers" are different compounds with the same molecular formula. "Stereoisomers" are isomers that differ only in the way their atoms are arranged in space, i.e., their stereochemical makeup. "Enantiomers" are pairs of stereoisomers that are non-superimposable mirror images of each other. A 1:1 mixture of a pair of enantiomers is a "racemic" mixture. "(±)" is used to indicate a racemic mixture where appropriate. "Diastereoisomers" are stereoisomers that have at least two asymmetric atoms but are not mirror images of each other. Absolute stereochemistry is specified according to the Cahn-Ingold-Prelog RS system. When a compound is a pure enantiomer, the stereochemistry at each chiral carbon can be specified as either (R) or (S). Resolved compounds of unknown absolute configuration can be specified as (+) or (-) depending on the direction (dextrorotatory or levorotatory) they rotate plane-polarized light at the wavelength of the sodium D line. Certain compounds described herein contain one or more asymmetric centers and may therefore give rise to enantiomers, diastereomers, and other stereoisomers that can be defined in terms of absolute stereochemistry as (R) or (S). The present chemical compounds, pharmaceutical compositions, and methods are intended to include all such possible isomers, including racemic mixtures, optically pure forms, and intermediate mixtures. Optically active (R)- and (S)-isomers can be prepared using chiral synthons or chiral reagents or resolved using conventional techniques. When a compound described herein contains an olefinic double bond or other center of geometric asymmetry, unless otherwise specified, the compound is intended to include both E- and Z-geometric isomers.

[0091] As used herein, "enantiomeric purity" refers to the relative amount of a particular enantiomer present, expressed as a percentage of the other enantiomer. For example, when a compound that can have either the (R)- or (S)-isomer configuration exists as a racemic mixture, the enantiomeric purity is about 50% with respect to the (R)- or (S)-isomer. When the compound has more of one isomer than the other, e.g., 80% (S)-isomer and 20% (R)-isomer, the enantiomeric purity of the compound with respect to the (S)-isomer is 80%. The enantiomeric purity of a compound can be determined by many methods known in the art, including, but not limited to, chromatography using a chiral support, polarimetry of rotation of polarized light, nuclear magnetic resonance spectroscopy using chiral shift reagents, including, but not limited to, lanthanide-containing chiral complexes or Pirkle's reagent, or derivatization of the compound with a chiral compound such as Mosher's acid followed by chromatography or nuclear magnetic resonance spectroscopy.

[0092] Enantiomers can be isolated from mixtures by methods known to those skilled in the art, such as chiral high-performance liquid chromatography (HPLC) and the formation and crystallization of chiral salts; or preferred enantiomers can be prepared by asymmetric synthesis. See, e.g., Jacques, et al., Enantiomers, Racemates and Resolutions, Wiley Interscience, New York (1981); E.L. Eliel, Stereochemistry of Carbon Compounds, McGraw-Hill, New York (1962); and E.L. Eliel and S.H. Wilen, Stereochemistry of Organic Compounds, Wiley-Interscience, New York (1994).

[0093] As used herein, the terms "enantiomerically enriched" and "non-racemic" refer to a composition in which the weight percent of one enantiomer is greater than the amount of that one enantiomer in a control mixture of racemic composition (e.g., greater than 1:1 by weight). For example, an enantiomerically enriched preparation of the (S)-enantiomer refers to a preparation of that compound in which the (S)-enantiomer is greater than 50% by weight, e.g., at least 75% by weight or at least 80% by weight, relative to the (R)-enantiomer. In some embodiments, the enrichment can be significantly greater than 80% by weight, resulting in a "substantially enantiomerically enriched" or "substantially non-racemic" preparation, which refers to a preparation of a composition in which one enantiomer is at least 85% by weight, e.g., at least 90% by weight or at least 95% by weight, relative to the other enantiomer. The terms "enantiomerically pure" or "substantially enantiomerically pure" refer to a composition that contains at least 98% of one enantiomer and less than 2% of the opposite enantiomer.

[0094] "Moiety" refers to a specific segment or functional group of a molecule. A chemical moiety is often recognized as a chemical substance embedded in or attached to a molecule.

[0095] "Tautomers" are structurally distinct isomers that interconvert via tautomerization. "Tautomerism" is a form of isomerization and includes prototropic or proton shift tautomerization, which are considered a subset of acid-base chemistry. "Prototropic tautomerism" or "proton shift tautomerism" involves the migration of a proton with a change in bond order, often involving the swapping of a single bond with an adjacent double bond. When tautomerization is possible (e.g., in solution), a chemical equilibrium of tautomers can be reached. An example of tautomerization is keto-enol tautomerization. A specific example of keto-enol tautomerization is the interconversion of the tautomers of pentane-2,4-dione and 4-hydroxypent-3-en-2-one. Another example of tautomerization is phenol-keto tautomerization. A specific example of phenol-keto tautomerization is the interconversion of pyridin-4-ol and pyridin-4(1H)-one tautomers.

[0096] A "leaving group or atom" is any group or atom that, under selected reaction conditions, cleaves from a starting material to facilitate reaction at a specific site. Examples of such groups, unless otherwise specified, include halogen atoms and mesyloxy, p-nitrobenzenesulfonyloxy, and tosyloxy groups.

[0097] "Protecting group" is intended to mean a group that selectively blocks one or more reactive sites of a polyfunctional compound so that a chemical reaction can be selectively carried out at an otherwise unprotected reactive site, and then can be easily removed or deprotected after the selected reaction is complete. Various protecting groups are disclosed, for example, in T. H. Greene and P. G. M. Wuts, Protective Groups in Organic Synthesis, Third Edition, John Wiley & Sons, New York (1999).

[0098] "Solvate" means a compound that is physically associated with one or more molecules of a pharmaceutically acceptable solvent.

[0099] "Substituted" means that the referenced group may be bonded with one or more additional groups, radicals, or moieties individually and independently selected from, for example, acyl, alkyl, alkylaryl, cycloalkyl, aralkyl, aryl, carbohydrate, carbonate, heteroaryl, heterocycloalkyl, hydroxy, alkoxy, aryloxy, mercapto, alkylthio, arylthio, cyano, halo, carbonyl, ester, thiocarbonyl, isocyanato, thiocyanato, isothiocyanato, nitro, oxo, perhaloalkyl, perfluoroalkyl, phosphate, silyl, sulfinyl, sulfonyl, sulfonamidyl, sulfoxyl, sulfonate, urea, and amino (including mono- and di-substituted amino groups), and protected derivatives thereof. The substituents themselves may be substituted; for example, a cycloalkyl substituent may itself have a halide substituent on one or more of its ring carbons. The term "optionally substituted" refers to optional substitution with the specified group, radical, or moiety.

[0100] "Sulfanyl" refers to the group including -S-(optionally substituted alkyl), -S-(optionally substituted aryl), -S-(optionally substituted heteroaryl), and -S-(optionally substituted heterocycloalkyl).

[0101] "Sulfinyl" refers to groups including -S(O)-H, -S(O)-(optionally substituted alkyl), -S(O)-(optionally substituted amino), -S(O)-(optionally substituted aryl), -S(O)-(optionally substituted heteroaryl), and -S(O)-(optionally substituted heterocycloalkyl).

[0102] "Sulfonyl" refers to groups including -S(O2)-H, -S(O2)-(optionally substituted alkyl), -S(O2)-(optionally substituted amino), -S(O2)-(optionally substituted aryl), -S(O2)-(optionally substituted heteroaryl), and -S(O2)-(optionally substituted heterocycloalkyl).

[0103] "Sulfonamidyl" or "sulfonamide" refers to the radical -S(=O)2-NRR, where each R is independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, heteroaryl (bonded through a ring carbon), and heteroalicyclic (bonded through a ring carbon). The R groups of -NRR in the -S(=O)2-NRR radical can, together with the nitrogen to which it is attached, form a 4-, 5-, 6-, or 7-membered ring. The sulfonamide group may be optionally substituted with one or more of the substituents described for alkyl, cycloalkyl, aryl, and heteroaryl, respectively.

[0104] "Sulfoxyl" means the -S(=O)2OH radical.

[0105] "Sulfonate" refers to the radical -S(=O)2-OR, where R is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl (bonded through a ring carbon), and heteroalicyclic (bonded through a ring carbon). The sulfonate group may be optionally substituted on R with one or more of the substituents described for alkyl, cycloalkyl, aryl, and heteroaryl, respectively.

[0106] The compounds of the present disclosure also include crystalline and amorphous forms of the compounds, including, for example, polymorphs, pseudopolymorphs, solvates, hydrates, non-solvated polymorphs (including anhydrous forms), conformational polymorphs, and amorphous forms of the compounds, and mixtures thereof. "Crystalline form" and "polymorph" are intended to include all crystalline and amorphous forms of the compounds, including, for example, polymorphs, pseudopolymorphs, solvates, hydrates, non-solvated polymorphs (including anhydrous forms), conformational polymorphs, and amorphous forms, and mixtures thereof, unless a specific crystalline or amorphous form is referenced.

[0107] For the avoidance of doubt, it is intended herein that a specific feature (e.g., an integer, property, value, application, disease, formula, compound, or group) described in connection with a particular aspect, embodiment, or example of the present disclosure is understood to be applicable to any other aspect, embodiment, or example described herein, unless incompatible. Accordingly, such features may be used, where appropriate, with any of the definitions, claims, or embodiments defined herein. Any of the features disclosed herein (including the accompanying claims, abstract, and drawings) and / or any of the steps of any method or process so disclosed may be combined in any combination, except combinations in which at least some of the features and / or steps are mutually exclusive. The disclosure is not limited to the details of the disclosed embodiments. The disclosure extends to any novel one or novel combination of features disclosed herein (including the accompanying claims, abstract, and drawings), or any novel one or novel combination of steps of any method or process so disclosed.

[0108] Furthermore, as used herein, the term "about" means that dimensions, sizes, compositions, parameters, shapes, and other quantities and characteristics are not exact, need not be exact, and may be approximate and / or larger or smaller, as appropriate, and may reflect, for example, tolerances, conversion factors, rounding, measurement error, and other factors known to those skilled in the art. Generally, a dimension, size, composition, parameter, shape, or other quantity or characteristic is "about" or "approximate," whether or not expressly stated as such. It is noted that embodiments of widely different sizes, shapes, and dimensions can employ the described configurations.

[0109] Furthermore, the transitional phrases "comprising," "consisting essentially of," and "consisting of," when used in the appended claims, both verbatim and in modified form, define the scope of the claim in terms of the exclusion from the claim of additional, unrecited claim elements or steps, if any. The term "comprising" is intended to be inclusive or open-ended and does not exclude any additional, unrecited elements, methods, steps, or materials. The term "consisting of" excludes elements, steps, or materials other than the elements, steps, or materials specified in the claim and, in the latter case, impurities ordinarily associated with the specified materials. The term "consisting essentially of" limits the scope of the claim to the specified elements, steps, or materials and to those that do not materially affect the basic and novel characteristics of the claimed embodiment. Alternatively, all embodiments of the present disclosure may be more specifically defined by any of the transitional phrases "comprising," "consisting essentially of," and "consisting of."

[0110] Fluorinated solvents for producing fluorinated compounds The present disclosure provides methods and processes for producing fluorinated dialkyl carbonates, including but not limited to methyl 2,2,2-trifluoroethyl carbonate, methyl 1,1,1-trifluoroisopropyl carbonate, methyl 1,1,1,3,3,3-hexafluoroisopropyl carbonate, bis(2,2,2-trifluoroethyl)carbonate, bis(1,1,1-trifluoroisopropyl)carbonate, bis(1,1,1,3,3,3-hexafluoroisopropyl)carbonate, and fluorinated dialkyl sulfites, including but not limited to bis(2,2,2-trifluoroethyl)sulfite, bis(1,1,1-trifluoroisopropyl)sulfite, and bis(1,1,1,3,3,3-hexafluoroisopropyl)sulfite.

[0111] In the process of preparing fluorochemicals for use as solvents, cosolvents, and additives for high-voltage lithium-ion batteries, several problems have existed in the synthesis, workup, and purification of fluorinated carbonates on a laboratory scale. Without wishing to be bound by any particular theory, it is believed that such problems can be addressed by judicious selection of solvents. In some embodiments, HFMOP was selected, at least in part, for its ability to control the exothermic effects of certain chemical reactions involved, simplify workup, be easily removed, and be harmless in the battery.

[0112] In some embodiments, the present disclosure provides methods for producing fluorinated compounds, including but not limited to fluorinated organic carbonates and fluorinated organic sulfites. In some embodiments, the methods include reacting a first reactant comprising at least one fluorine atom with a second reactant of Formula 20A or 20B, wherein the reactant of Formula 20A or 20B comprises a leaving group L1. [ka]

[0113] The reaction is conducted in the presence of a fluorinated solvent; R1 is selected from optionally substituted alkyl, optionally substituted haloalkyl, optionally substituted alkenyl, optionally substituted haloalkenyl, optionally substituted alkynyl, optionally substituted haloalkynyl, optionally substituted aryl, optionally substituted haloaryl, optionally substituted heteroaryl, and optionally substituted haloheteroaryl; and L2 is a leaving group. In some embodiments, the first reactant is a fluorinated alcohol. In some embodiments, the fluorinated organic carbonate is a fluorinated dialkyl carbonate. In some embodiments, the fluorinated organic sulfite is a fluorinated dialkyl sulfite. In some embodiments, the first reactant comprises one or more groups selected from -CF3, -CHF2, -CH2F, -CHF-, and -CF2-. In some embodiments, the first reactant comprises one or more -CF3 groups. In some embodiments, the first reactant is selected from 2-fluoroethanol, 2,2-difluoroethanol, 2,2,2-trifluoroethanol, 3-fluoro-1-propanol, 3,3-difluoro-1-propanol, 3,3,3-trifluoro-1-propanol, 2,2,3,3,3-pentafluoro-1-propanol, 1,1,1-trifluoro-2-propanol, 1,1,1,3,3-pentafluoro-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 4,4,4-trifluoro-1-butanol, and 5,5,5-trifluoro-1-pentanol. In some embodiments, the first reactant is 1,1,1,3,3,3-hexafluoroisopropanol. In some embodiments, L1 is selected from perfluoroalkylsulfonate, tosylate, mesylate, halogen, nitrate, phosphate, thioether, amine, carboxylate, phenoxide, alkoxide, and amide. In some embodiments, L1 is selected from halogen or -OR2 group. In some embodiments, R2 is alkyl sulfate or aryl sulfate.In some embodiments, L1 is selected from chlorine, iodine, and bromine. In some embodiments, L2 is selected from perfluoroalkylsulfonate, tosylate, mesylate, halogen, nitrate, phosphate, thioether, amine, carboxylate, phenoxide, alkoxide, and amide. In some embodiments, L2 is selected from halogen and -OR3 group. In some embodiments, R3 is an alkyl sulfate or aryl sulfate. In some embodiments, L2 is selected from chlorine, iodine, and bromine. In some embodiments, the compound of Formula 20A is a chloroformate. In some embodiments, the chloroformate is an alkyl chloroformate. In some embodiments, the chloroformate is methyl chloroformate or ethyl chloroformate. In some embodiments, the fluorinated organic carbonate is selected from methyl(2,2,2-trifluoroethyl)carbonate, methyl(1,1,1-trifluoroisopropyl)carbonate, methyl(1,1,1,3,3,3-hexafluoroisopropyl)carbonate, methyl(3,3,3-trifluoropropyl)carbonate, methyl(2-fluoroethyl)carbonate, methyl(2,2-difluoroethyl)carbonate, methyl(3-fluoropropyl)carbonate, methyl(3,3-difluoropropyl)carbonate, methyl(2,2,3,3,3-pentafluoropropyl)carbonate, methyl(4,4,4-trifluorobutyl)carbonate, methyl(1,1,1,3,3-pentafluoroisopropyl)carbonate, and methyl(5,5,5-trifluoropentyl)carbonate. In some embodiments, the compound of Formula 20B is thionyl chloride. In some embodiments, the fluorinated organic sulfite is selected from bis-(2,2,2-trifluoroethyl)sulfite, bis-(1,1,1-trifluoroisopropyl)sulfite, and bis-(1,1,1,3,3,3-hexafluoroisopropyl)sulfite. In some embodiments, the fluorinated solvent comprises one or more groups selected from -CF3, -CHF2, -CH2F, -CHF-, and -CF2-.In some embodiments, the fluorinated solvent comprises one or more -CF3 groups. In some embodiments, the fluorinated solvent comprises two or more -CF3 groups.

[0114] In some embodiments, the fluorinated solvent is an ether or thioether having formula 10: [ka]

[0115] wherein X is O or S, R4 is a partially fluorinated C1-C8 alkyl group; and R5 is an optionally fluorinated C1-C8 alkyl group. In some embodiments, R4 is a partially fluorinated C1-C4 alkyl group; and R5 is an optionally fluorinated C1-C4 alkyl group. In some embodiments, the fluorinated solvent comprises one or more groups selected from 2,2,2-trifluoroethyl, 1,1,1-trifluoroisopropyl, 1,1,1,3,3,3-hexafluoroisopropyl, 3,3,3-trifluoropropyl, 2-fluoroethyl, 2,2-difluoroethyl, 3-fluoropropyl, 3,3-difluoropropyl, 2,2,3,3,3-pentafluoropropyl, 4,4,4-trifluorobutyl, 1,1,1,3,3-pentafluoroisopropyl, and 5,5,5-trifluoropentyl. In some embodiments, the fluorinated solvent is the following: hexafluoroisopropyl methyl ether (or 1,1,1,3,3,3-hexafluoro-2-methoxypropane). [ka]

[0116] In some embodiments, the reaction is carried out in the presence of an amine. In some embodiments, the amine is an alkylamine or pyridine. In some embodiments, the alkylamine is a trialkylamine. In some embodiments, the amine is selected from triethylamine, tripropylamine, tributylamine, diisopropylethylamine, pyridine, dimethylaminopyridine, 2,6-lutidine, and N,N-dimethylaniline. In some embodiments, the reaction is carried out at a temperature of about -40°C to about 80°C. In some embodiments, the reaction is carried out at a temperature of about -40°C to about 70°C. In some embodiments, the reaction is carried out at a temperature of about 0°C to about 35°C. In some embodiments, the reaction is carried out at a temperature of about 10°C to about 35°C.

[0117] As described herein, in some embodiments, the synthesis involves adding methyl chloroformate to a fluorinated alcohol and triethylamine in a solvent, while controlling the exotherm with external cooling water to maintain the internal temperature below 35°C. Initially, tetraglyme (bp: 275-276°C) was used to facilitate purification. This is because, theoretically, low-boiling products would be the first to distill during distillation. However, without wishing to be bound by any particular theory, it is believed that the relatively high heat capacity of tetraglyme makes the exotherm difficult to control, resulting in long (>3 hours) addition times for methyl chloroformate. Using the methods and processes described herein, water cooling is more effective, shortening the addition time to approximately 1 hour.

[0118] As described herein, in some embodiments, workup of the reaction involves neutralizing residual triethylamine and dissolving the triethylamine salt formed during the reaction with a dilute solution of hydrochloric acid. Without wishing to be bound by theory, it is believed that tetraglyme is a miscible solvent with both the aqueous quench and the organic reaction components, making complete removal of water from the organic phase difficult, and a water-free organic phase is important to avoid carbonate hydrolysis during subsequent distillation. Adding a water-immiscible co-solvent, such as HFMOP, improves this. In some embodiments, the reaction itself is carried out in HFMOP, eliminating the need for a secondary solvent and simplifying the workup.

[0119] As described herein, in some embodiments, the purification step is accomplished by fractional distillation at atmospheric pressure. While not wishing to be bound by theory, it is believed that low-boiling HFMOP (bp: 50°C) is much easier to remove for recycling than higher-boiling solvents such as triglyme and tetraglyme. Furthermore, fluorinated ethers such as HFMOP have been shown to provide benefits to the cycle life of lithium-ion batteries. Therefore, while not wishing to be bound by theory, it is believed that any HFMOP remaining in the final product does not impair battery performance, unlike traditional solvents used in the preparation of these chemicals.

[0120] Similarly, HFMOP has been used to synthesize fluorinated alkyl sulfites. The reaction has previously been reported to be carried out under solvent-free conditions by adding thionyl chloride to a mixture of triethylamine and a fluorinated alcohol at -78°C. The use of solvents is mitigated by the fact that the reaction can be carried out at ambient temperature using HFMOP, and the solvent is easily recovered for recycling. The reaction proceeds with the liberation of hydrogen chloride and is highly exothermic, but fluorinated ethers, unlike non-fluorinated ethers, are not acid-labile.

[0121] Battery electrolytes containing fluorine compounds The rapid development of electronic devices has led to an increasing market demand for electrochemical devices such as fuel cells, capacitors, and battery systems. In response to the demand for battery systems in particular, practical rechargeable lithium batteries have been intensively researched. These systems are typically based on the use of lithium metal, lithiated carbon, or lithium alloys as the negative electrode (anode). Lithium batteries are prepared from one or more lithium electrochemical cells. Such cells contain a non-aqueous lithium ion-conducting electrolyte composition interposed between electrically isolated and spaced apart positive and negative electrodes.

[0122] An electrochemical cell includes a housing, an anode and a cathode disposed within the housing and ionic to each other, an electrolyte composition described herein that provides an ionically conductive pathway between the anode and the cathode, and a porous or microporous separator between the anode and the cathode. The housing can be any suitable container for containing electrochemical cell components. The anode and the cathode can comprise any suitable conductive material, depending on the type of electrochemical cell. Suitable examples of anode materials include, but are not limited to, lithium metal, lithium metal alloys, lithium titanate, aluminum, platinum, palladium, graphite, transition metal oxides, and lithiated tin oxide. Suitable examples of cathode materials include, but are not limited to, graphite, aluminum, platinum, palladium, electroactive transition metal oxides containing lithium or sodium, indium tin oxide, and conductive polymers such as polypyrrole and polyvinylferrocene.

[0123] The porous separator helps prevent short circuits between the anode and the cathode. The porous separator typically consists of a single-layer or multi-layer sheet of a microporous polymer, such as polyethylene, polypropylene, or a combination thereof. The pore size of the porous separator is large enough to allow ion transport, but small enough to prevent direct contact between the anode and the cathode, or contact from particle penetration or dendrites that may form on the anode and cathode.

[0124] In one embodiment, the electrochemical cell is a lithium-ion battery, which is a type of rechargeable battery in which lithium ions move from the anode to the cathode during discharge and from the cathode to the anode during charge. Suitable cathode materials for lithium-ion batteries include, but are not limited to, electroactive transition metal oxides containing lithium, such as LiCoO, LiNiO, LiMnO, or LiVO.

[0125] Various lithium composite oxides containing lithium and transition metals can be used as cathode materials. Suitable examples include composite oxides of the general formula LiMO2, where M is any metal element or combination of metal elements, such as cobalt, aluminum, chromium, manganese, nickel, iron, vanadium, magnesium, titanium, zirconium, niobium, molybdenum, copper, zinc, indium, strontium, lanthanum, and cesium. Furthermore, the active material can be made of a material with the formula LiMn2-xMxO4 (where 0≦x≦1) or a material with the general formula LiMPO4 (where M can be any metal element or combination of elements, such as cobalt, aluminum, chromium, manganese, nickel, iron, vanadium, magnesium, titanium, zirconium, niobium, molybdenum, copper, zinc, indium, strontium, lanthanum, and cesium). The battery cathode can include any active material that can be supported on a conductive member, including a metal or another conductive element.

[0126] In one embodiment, the cathode of the lithium-ion battery herein comprises a cathode active material that exhibits a capacity greater than 30 mAh / g in a potential range greater than 4.0 V, preferably (in order of increasing preference) 4.1 V or greater, 4.2 V or greater, 4.3 V or greater, 4.4 V or greater, 4.5 V or greater, 4.25 V or greater, 4.5 V or greater, 4.6 V or greater, or 4.75 V or greater, versus a Li / Li+ reference electrode. One example of such a cathode is a stabilized manganese cathode comprising a lithium-containing manganese composite oxide having a spinel structure as the cathode active material. The lithium-containing manganese composite oxide in the cathode used herein includes an oxide of the formula LixNixMzMn2-y-zO4-d, where x is 0.03 to 1.0; x varies depending on the release and uptake of lithium ions and electrons during charge and discharge; y is 0.3 to 0.6; M includes one or more of Cr, Fe, Co, Al, Ga, Nb, Mo, Ti, Zr, Mg, Zn, V, and Cu; z is 0.01 to 0.18; and d is 0 to 0.3. In one embodiment, in the formula, y is 0.38 to 0.48, z is 0.03 to 0.12, and d is 0 to 0.1. In one embodiment, in the formula, M is one or more of Li, Cl, Fe, Co, and Ga. The stabilized manganese cathode can also include a spinel layered composite that includes a manganese-containing spinel component and a lithium-rich layered structure, as described in US Pat. No. 7,303,840.

[0127] The cathode active material can be prepared using methods such as the hydroxide precursor method described in Liu et al. (J. Phys. Chem., C 13:15073-15079, 2009). In this method, a hydroxide precursor is precipitated from a solution containing the required amounts of manganese, nickel, and other desired metal acetates by the addition of KOH. The resulting precipitate is then dried in an oven and calcined in oxygen with the required amount of LiOH·HO at about 800 to about 950°C for 3 to 24 hours. Alternatively, the cathode active material can be prepared using a solid-state reaction process or a sol-gel process as described in U.S. Pat. No. 5,738,957 (Amine).

[0128] A cathode containing the cathode active material can be prepared by mixing an effective amount (e.g., about 70 wt % to about 97 wt %) of the cathode active material, a polymer binder such as polyvinylidene difluoride, and conductive carbon in a suitable solvent such as N-methylpyrrolidone to form a paste, which is then coated on a current collector such as aluminum foil and dried to form the cathode.

[0129] The lithium-ion battery further includes an anode containing an anode active material capable of storing and releasing lithium ions. Examples of suitable anode active materials include, but are not limited to, lithium alloys such as lithium-aluminum alloys, lithium-lead alloys, lithium-silicon alloys, and lithium-tin alloys; carbon materials such as graphite and mesocarbon microbeads (MCMB); phosphorus-containing materials such as black phosphorus, MnP4, and CoP3; metal oxides such as SnO2, SnO, and TiO2; and lithium titanates such as Li4Ti5O12 and LiTi2O4. In one embodiment, the anode active material is lithium titanate or graphite. The anode can be fabricated by a method similar to that described above for the cathode, for example, by dissolving or dispersing a binder, such as a vinyl fluoride-based copolymer, in an organic solvent or water and then mixing it with a conductive active material to form a paste. The paste is coated onto a metal foil, preferably aluminum or copper foil, used as a current collector. The paste is preferably dried with heat to bond the active mass to the current collector. Suitable anode active materials and anodes are commercially available from companies such as Hitachi NEI Inc. (Somerset, NJ) and Farasis Energy Inc. (Hayward, Calif.).

[0130] The lithium-ion batteries herein also include a porous separator between the anode and the cathode. The porous separator helps prevent short circuits between the anode and the cathode. The porous separator typically consists of a single-layer or multi-layer sheet of a microporous polymer, such as polyethylene, polypropylene, polyamide, or polyimide, or a combination thereof. The separator can also be constructed using a fluorinated polymer. The pore size of the porous separator is large enough to allow ion transport and provide ionically conductive contact between the anode and the cathode, but small enough to prevent direct contact between the anode and the cathode or contact from particle penetration or dendrites that may form on the anode and the cathode. Examples of porous separators suitable for use herein are disclosed in U.S. Patent Application Publication No. 2012 / 0149852.

[0131] The housing of the lithium ion batteries herein can be any suitable container to house the lithium ion battery components. Such containers can be made in the shape of small or large cylinders, prismatic cases, or pouches.

[0132] The lithium-ion batteries herein can be used for any purpose and in any device that can be powered by a lithium-ion battery, non-limiting examples of which include grid storage or as a power source for various electrically powered or electrically assisted devices, such as transportation devices (including motor vehicles, automobiles, trucks, buses, or airplanes), computers, telecommunications equipment, cameras, radios, or power tools.

[0133] In some embodiments, the electrolyte composition is typically a liquid solution of a lithium electrolyte salt in a non-aqueous, aprotic organic electrolyte solvent (often a solvent mixture). The selection of an electrolyte solvent for a rechargeable lithium battery is important for optimal battery performance and involves a variety of factors. However, long-term stability, ionic conductivity, safety, and wetting ability tend to be the most important selection factors for high-volume commercial applications.

[0134] Fluorinated compounds, particularly esters, ethers, and carbonates, are utilized as components of electrolyte solutions used in electrochemical cells, particularly lithium batteries (both primary and secondary batteries). Certain fluorinated compounds may offer several advantages over non-fluorinated compounds, such as reduced flammability, reduced viscosity, improved wettability, improved oxidation / reduction resistance, and / or extended cycle times. These advantages are expected to become even more pronounced at voltages above about 4.0 V, particularly at higher voltages such as 4.3 V or higher, where such non-fluorinated analogs are particularly unstable.

[0135] In some embodiments, the present disclosure provides a battery including an electrolyte containing a fluorinated ether or thioether in an amount of about 1 ppm to about 5,000 ppm. Such amounts can typically be measured using GC or GC / MS. In some embodiments, the amount of the fluorinated ether or thioether in the electrolyte is about 5 ppm to about 500 ppm, about 25 ppm to about 750 ppm, about 50 ppm to about 1,000 ppm, about 100 ppm to about 1,500 ppm, about 250 ppm to about 2,500 ppm, or about 500 ppm to about 5,000 ppm.

[0136] In some embodiments, the battery is rechargeable and has a cycle life of at least 250 cycles. As used herein, cycle life is the number of charge / discharge cycles it takes for a battery to reach 80% of its original capacity. In some embodiments, the battery has a cycle life of at least 250 cycles, at least 500 cycles, at least 750 cycles, or at least 1,000 cycles.In some embodiments, the battery is resistant to at least 250 cycles, at least 300 cycles, at least 350 cycles, at least 400 cycles, at least 450 cycles, at least 500 cycles, at least 550 cycles, at least 600 cycles, at least 650 cycles, at least 700 cycles, at least 750 cycles, at least 800 cycles, at least 850 cycles, at least 900 cycles, at least 950 cycles, at least 1,000 cycles, at least 1,050 cycles, at least 1,100 cycles, at least 1,150 cycles, at least 1,200 cycles, at least 1,250 cycles, at least 1,300 cycles, at least 1,350 cycles, at least 1,400 cycles, at least 1,450 cycles, at least 1,500 cycles, at least 1,550 cycles, at least 1,600 cycles, or at least 1,650 cycles. and / or has a cycle life of at least 1,700 cycles, at least 1,750 cycles, at least 1,800 cycles, at least 1,850 cycles, at least 1,900 cycles, at least 1,950 cycles, at least 2,000 cycles, at least 2,050 cycles, at least 2,100 cycles, at least 2,150 cycles, at least 2,200 cycles, at least 2,250 cycles, at least 2,300 cycles, at least 2,350 cycles, at least 2,400 cycles, at least 2,450 cycles, at least 2,500 cycles, at least 2,550 cycles, at least 2,600 cycles, at least 2,650 cycles, at least 2,700 cycles, at least 2,750 cycles, at least 2,800 cycles, at least 2,850 cycles, at least 2,900 cycles, at least 2,950 cycles, or at least 3,000 cycles.

[0137] In some embodiments, the fluorinated ether or thioether has formula 10: [ka]

[0138] wherein X is O or S, R4 is a partially fluorinated C1-C8 alkyl group; and R5 is an optionally fluorinated C1-C8 alkyl group. In some embodiments, R4 is a partially fluorinated C1-C4 alkyl group; and R5 is an optionally fluorinated C1-C4 alkyl group. In some embodiments, the fluorinated ether or thioether comprises one or more groups selected from -CF3, -CHF2, -CH2F, -CHF-, and -CF2-. In some embodiments, the fluorinated ether or thioether comprises one or more -CF3 groups. In some embodiments, the fluorinated ether or thioether comprises two or more -CF3 groups. In some embodiments, the fluorinated ether or thioether comprises one or more groups selected from 2,2,2-trifluoroethyl, 1,1,1-trifluoroisopropyl, 1,1,1,3,3,3-hexafluoroisopropyl, 3,3,3-trifluoropropyl, 2-fluoroethyl, 2,2-difluoroethyl, 3-fluoropropyl, 3,3-difluoropropyl, 2,2,3,3,3-pentafluoropropyl, 4,4,4-trifluorobutyl, 1,1,1,3,3-pentafluoroisopropyl, and 5,5,5-trifluoropentyl. In some embodiments, the fluorinated ether or thioether is hexafluoroisopropyl methyl ether (or 1,1,1,3,3,3-hexafluoro-2-methoxypropane). [ka]

[0139] In some embodiments, the battery is an alkali metal ion battery. In some embodiments, the battery is a lithium ion battery. In some embodiments, the electrolyte further comprises a fluorinated organic carbonate or fluorinated organic sulfite comprising one or more of an optionally substituted alkyl, an optionally substituted haloalkyl, an optionally substituted alkenyl, an optionally substituted haloalkenyl, an optionally substituted alkynyl, an optionally substituted haloalkynyl, an optionally substituted aryl, an optionally substituted haloaryl, an optionally substituted heteroaryl, or an optionally substituted haloheteroaryl. In some embodiments, the fluorinated organic carbonate is a fluorinated dialkyl carbonate. In some embodiments, the fluorinated organic sulfite is a fluorinated dialkyl sulfite. In some embodiments, the fluorinated organic carbonate or the fluorinated organic sulfite comprises one or more groups selected from —CF 3 , —CHF 2 , —CH 2 F, —CHF—, and —CF 2 —. In some embodiments, the fluorinated organic carbonate or the fluorinated organic sulfite contains one or more -CF groups. In some embodiments, the fluorinated organic carbonate or the fluorinated organic sulfite contains one or more groups selected from 2,2,2-trifluoroethyl, 1,1,1-trifluoroisopropyl, 1,1,1,3,3,3-hexafluoroisopropyl, 3,3,3-trifluoropropyl, 2-fluoroethyl, 2,2-difluoroethyl, 3-fluoropropyl, 3,3-difluoropropyl, 2,2,3,3,3-pentafluoropropyl, 4,4,4-trifluorobutyl, 1,1,1,3,3-pentafluoroisopropyl, and 5,5,5-trifluoropentyl. In some embodiments, the fluorinated organic carbonate or the fluorinated organic sulfite contains one or two 1,1,1,3,3,3-hexafluoroisopropyl groups.In some embodiments, the fluorinated organic carbonate is selected from methyl (2,2,2-trifluoroethyl)carbonate, methyl (1,1,1-trifluoroisopropyl)carbonate, methyl (1,1,1,3,3,3-hexafluoroisopropyl)carbonate, methyl (3,3,3-trifluoropropyl)carbonate, methyl (2-fluoroethyl)carbonate, methyl (2,2-difluoroethyl)carbonate, methyl (3-fluoropropyl)carbonate, methyl (3,3-difluoropropyl)carbonate, methyl (2,2,3,3,3-pentafluoropropyl)carbonate, methyl (4,4,4-trifluorobutyl)carbonate, methyl (1,1,1,3,3-pentafluoroisopropyl)carbonate, and methyl (5,5,5-trifluoropentyl)carbonate. In some embodiments, the fluorinated organic sulfite is selected from bis-(2,2,2-trifluoroethyl) sulfite, bis-(1,1,1-trifluoroisopropyl) sulfite, and bis-(1,1,1,3,3,3-hexafluoroisopropyl) sulfite.

[0140] The following sections describe specific embodiments.

[0141] Item 1. A method for producing a fluorinated organic carbonate or a fluorinated organic sulfite, comprising reacting a first reactant containing at least one fluorine atom with a second reactant of Formula 20A or Formula 20B containing a leaving group L1. [ka]

[0142] The reaction is carried out in the presence of a fluorinated solvent; R1 is selected from optionally substituted alkyl, optionally substituted haloalkyl, optionally substituted alkenyl, optionally substituted haloalkenyl, optionally substituted alkynyl, optionally substituted haloalkynyl, optionally substituted aryl, optionally substituted haloaryl, optionally substituted heteroaryl, and optionally substituted haloheteroaryl; and L2 is a leaving group.

[0143] Item 2. The method of item 1, wherein the first reactant is a fluorinated alcohol.

[0144] Item 3. The method according to Item 1, wherein the fluorinated organic carbonate is a fluorinated dialkyl carbonate.

[0145] Item 4. The method according to Item 1, wherein the fluorinated organic sulfite is a fluorinated dialkyl sulfite.

[0146] Item 5. The method according to any one of items 1 to 4, wherein the first reactant comprises one or more groups selected from -CF3, -CHF2, -CH2F, -CHF-, and -CF2-.

[0147] Item 6. The method of any one of items 1 to 4, wherein the first reactant comprises one or more —CF 3 groups.

[0148] Item 7. The method according to any one of Items 1 to 4, wherein the first reactant is selected from 2-fluoroethanol, 2,2-difluoroethanol, 2,2,2-trifluoroethanol, 3-fluoro-1-propanol, 3,3-difluoro-1-propanol, 3,3,3-trifluoro-1-propanol, 2,2,3,3,3-pentafluoro-1-propanol, 1,1,1-trifluoro-2-propanol, 1,1,1,3,3-pentafluoro-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 4,4,4-trifluoro-1-butanol, and 5,5,5-trifluoro-1-pentanol.

[0149] Item 8. The method according to any one of Items 1 to 4, wherein the first reactant is 1,1,1,3,3,3-hexafluoroisopropanol.

[0150] Item 9. The method according to any one of items 1 to 8, wherein L1 is selected from perfluoroalkylsulfonates, tosylates, mesylates, halogens, nitrates, phosphates, thioethers, amines, carboxylates, phenoxides, alkoxides, and amides.

[0151] Item 10. The method according to any one of items 1 to 8, wherein L1 is selected from halogen or an —OR2 group.

[0152] Item 11. The method according to Item 10, wherein R2 is an alkyl sulfate or an aryl sulfate.

[0153] Item 12. The method according to any one of Items 1 to 8, wherein L1 is selected from chlorine, iodine, and bromine.

[0154] Item 13. The method according to any one of items 1 to 12, wherein L2 is selected from perfluoroalkylsulfonates, tosylates, mesylates, halogens, nitrates, phosphates, thioethers, amines, carboxylates, phenoxides, alkoxides, and amides.

[0155] Item 14. The method according to any one of items 1 to 12, wherein L2 is selected from halogen or an -OR3 group.

[0156] Item 15. The method according to Item 14, wherein R3 is an alkyl sulfate or an aryl sulfate.

[0157] Item 16. The method according to any one of Items 1 to 12, wherein L2 is selected from chlorine, iodine, and bromine.

[0158] Item 17. The method according to any one of Items 1 to 16, wherein the compound of formula 20A is a chloroformate.

[0159] Item 18. The method according to Item 17, wherein the chloroformate is an alkyl chloroformate.

[0160] Item 19. The method according to Item 17, wherein the chloroformate is methyl chloroformate, ethyl chloroformate, n-propyl chloroformate, or 2-propyl chloroformate.

[0161] Item 20. The method of any one of Items 1 to 19, wherein the fluorinated organic carbonate is selected from methyl (2,2,2-trifluoroethyl)carbonate, methyl (1,1,1-trifluoroisopropyl)carbonate, methyl (1,1,1,3,3,3-hexafluoroisopropyl)carbonate, methyl (3,3,3-trifluoropropyl)carbonate, methyl (2-fluoroethyl)carbonate, methyl (2,2-difluoroethyl)carbonate, methyl (3-fluoropropyl)carbonate, methyl (3,3-difluoropropyl)carbonate, methyl (2,2,3,3,3-pentafluoropropyl)carbonate, methyl (4,4,4-trifluorobutyl)carbonate, methyl (1,1,1,3,3-pentafluoroisopropyl)carbonate, and methyl (5,5,5-trifluoropentyl)carbonate.

[0162] Item 21. The method according to any one of Items 1 to 16, wherein the compound of formula 20B is thionyl chloride.

[0163] Item 22. The method according to any one of Items 1 to 19 or Item 21, wherein the fluorinated organic sulfite is selected from bis-(2,2,2-trifluoroethyl) sulfite, bis-(1,1,1-trifluoroisopropyl) sulfite, and bis-(1,1,1,3,3,3-hexafluoroisopropyl) sulfite.

[0164] Item 23. The method according to any one of Items 1 to 22, wherein the fluorinated solvent contains one or more groups selected from -CF3, -CHF2, -CH2F, -CHF-, and -CF2-.

[0165] Item 24. The method of any one of Items 1 to 22, wherein the fluorinated solvent contains one or more -CF3 groups.

[0166] Item 25. The method of any one of Items 1 to 22, wherein the fluorinated solvent contains two or more -CF3 groups.

[0167] Item 26. The method according to any one of Items 1 to 25, wherein the fluorinated solvent is an ether or thioether having formula 10. [ka]

[0168] wherein X is O or S, R4 is a fully or partially fluorinated C1-C8 alkyl group; and R5 is an optionally fluorinated C1-C8 alkyl group.

[0169] Item 27. The method according to Item 26, wherein R4 is a fully or partially fluorinated C1-C4 alkyl group; and R5 is an optionally fluorinated C1-C4 alkyl group.

[0170] Item 28. The method according to any one of Items 1 to 27, wherein the fluorinated solvent comprises one or more groups selected from 2,2,2-trifluoroethyl, 1,1,1-trifluoroisopropyl, 1,1,1,3,3,3-hexafluoroisopropyl, 3,3,3-trifluoropropyl, 2-fluoroethyl, 2,2-difluoroethyl, 3-fluoropropyl, 3,3-difluoropropyl, 2,2,3,3,3-pentafluoropropyl, 4,4,4-trifluorobutyl, 1,1,1,3,3-pentafluoroisopropyl, and 5,5,5-trifluoropentyl.

[0171] Item 28'. The method according to any one of Items 1 to 27, wherein the fluorinated solvent is hexafluoroisopropyl methyl ether.

[0172] Item 29. The method according to any one of Items 1 to 28, wherein the reaction is carried out in the presence of an amine.

[0173] Item 30. The method according to Item 29, wherein the amine is an alkylamine or pyridine.

[0174] Item 31. The method according to Item 30, wherein the alkylamine is a trialkylamine.

[0175] Item 32. The method according to Item 29, wherein the amine is selected from triethylamine, tripropylamine, tributylamine, diisopropylethylamine, pyridine, dimethylaminopyridine, 2,6-lutidine, and N,N-dimethylaniline.

[0176] Item 33. The method according to any one of Items 1 to 32, wherein the reaction is carried out at a temperature of about -40°C to about 80°C.

[0177] Item 34. The method according to any one of Items 1 to 32, wherein the reaction is carried out at a temperature of about -40°C to about 70°C.

[0178] Item 35. The method according to any one of Items 1 to 32, wherein the reaction is carried out at a temperature of about 0°C to about 35°C.

[0179] Item 36. The method according to any one of Items 1 to 32, wherein the reaction is carried out at a temperature of about 10°C to about 35°C.

[0180] Item 37. A battery including an electrolyte containing a solvent component, the solvent component including a fluorinated compound in an amount of about 1 ppm to about 60%, the fluorinated compound having any of Formula I, Formula II(a), Formula II(b), Formula III, or Formula IV. [ka]

[0181] wherein R10 and R20 are independently selected from C1-C6 alkyl, cycloalkyl, aryl, fully or partially fluorinated C1-C6 alkyl, fully or partially fluorinated cycloalkyl, and fully or partially fluorinated aryl.

[0182] Item 38. The battery according to item 37, wherein R20 is a fully or partially fluorinated C1-C6 alkyl.

[0183] Item 39. The battery according to item 37, wherein R20 contains one or more -CF3 groups.

[0184] Item 40. The battery according to item 37, wherein R20 contains 1 to 3 -CF3 groups.

[0185] Item 41. The battery according to item 37, wherein R20 is selected from trifluoroethyl or hexafluoroisopropyl.

[0186] Item 42. The battery according to any of items 37 to 41, wherein R10 is selected from methyl, ethyl, n-propyl, and 2-propyl.

[0187] Item 43. The battery according to any of items 37 to 41, wherein R10 is selected from fully or partially fluorinated methyl, fully or partially fluorinated ethyl, fully or partially fluorinated n-propyl, and fully or partially fluorinated 2-propyl.

[0188] Item 44. The battery of any of items 37 to 41, wherein R10 contains one or more -CF3 groups.

[0189] Item 45. The battery according to any of items 37 to 41, wherein R10 contains 1 to 3 -CF3 groups.

[0190] Item 46. The battery according to item 37, wherein R10 and R20 are the same.

[0191] Item 47. The battery according to item 37, wherein the compound of formula IV is a compound of any of formulas 400, 401, 402, or 403. [ka]

[0192] Item 48. The battery according to item 37, wherein the compound of formula I is a compound of any of formulas 100, 101, 102, or 103. [ka]

[0193] Item 49. The battery of item 37, wherein the compound of formula II(a) is a compound of any of formulas 200, 201, 202, or 203. [ka]

[0194] Item 50. The battery according to item 37, wherein the compound of formula III is a compound of formula 300 or formula 301. [ka]

[0195] Item 51. The battery of item 37, wherein the fluorinated compound is an ether or thioether of formula 10. [ka]

[0196] In Formula 10, X is O or S, R4 is a partially fluorinated C1-C8 alkyl group; and R5 is an optionally fluorinated C1-C8 alkyl group.

[0197] Item 52. The battery of item 51, wherein R4 is a partially fluorinated C1-C4 alkyl group and R5 is an optionally fluorinated C1-C4 alkyl group.

[0198] Item 53. The battery of any of items 51 to 52, wherein the fluorinated ether or thioether contains one or more groups selected from —CF 3 , —CHF 2 , —CH 2 F, —CHF—, and —CF 2 —.

[0199] Item 54. The battery of any of items 51 to 53, wherein the fluorinated ether or thioether contains one or more -CF3 groups.

[0200] Item 55. The battery of any of items 51 to 53, wherein the fluorinated ether or thioether contains two or more -CF3 groups.

[0201] Item 56. The battery of any of items 51 to 55, wherein the fluorinated ether or thioether comprises one or more groups selected from 2,2,2-trifluoroethyl, 1,1,1-trifluoroisopropyl, 1,1,1,3,3,3-hexafluoroisopropyl, 3,3,3-trifluoropropyl, 2-fluoroethyl, 2,2-difluoroethyl, 3-fluoropropyl, 3,3-difluoropropyl, 2,2,3,3,3-pentafluoropropyl, 4,4,4-trifluorobutyl, 1,1,1,3,3-pentafluoroisopropyl, and 5,5,5-trifluoropentyl.

[0202] Item 57. The battery of any of items 51 to 55, wherein the fluorinated ether or thioether is hexafluoroisopropyl methyl ether.

[0203] Item 58. The battery according to any one of Items 37 to 57, wherein the solvent component contains the fluorinated compound in an amount of about 1 ppm to about 5000 ppm. In some embodiments, the solvent component contains the fluorinated compound in an amount of about 1 ppm to about 100 ppm. In some embodiments, the solvent component contains the fluorinated compound in an amount of about 100 ppm to about 500 ppm. In some embodiments, the solvent component contains the fluorinated compound in an amount of about 500 ppm to about 1000 ppm. In some embodiments, the solvent component contains the fluorinated compound in an amount of about 1000 ppm to about 2000 ppm. In some embodiments, the solvent component contains the fluorinated compound in an amount of about 2000 ppm to about 3000 ppm. In some embodiments, the solvent component contains the fluorinated compound in an amount of about 3000 ppm to about 4000 ppm. In some embodiments, the solvent component contains the fluorinated compound in an amount of about 4000 ppm to about 5000 ppm. In some embodiments, the solvent component contains the fluorinated compound in an amount of about 5000 ppm to about 7500 ppm. In some embodiments, the solvent component contains the fluorinated compound in an amount of about 7500 ppm to about 10000 ppm.

[0204] Item 59. The battery according to any one of items 37 to 57, wherein the solvent component comprises the fluorinated compound in an amount of about 0.0001% to about 5%. In some embodiments, the solvent component comprises the fluorinated compound in an amount of about 0.0001% to about 10%. In some embodiments, the solvent component comprises the fluorinated compound in an amount of about 0.0001% to about 15%. In some embodiments, the solvent component comprises the fluorinated compound in an amount of about 0.001% to about 0.01%. In some embodiments, the solvent component comprises the fluorinated compound in an amount of about 0.01% to about 0.1%. In some embodiments, the solvent component comprises the fluorinated compound in an amount of about 0.1% to about 1%. In some embodiments, the solvent component comprises the fluorinated compound in an amount of about 1% to about 2%. In some embodiments, the solvent component contains the fluorinated compound in an amount of about 2% to about 3%. In some embodiments, the solvent component contains the fluorinated compound in an amount of about 3% to about 4%. In some embodiments, the solvent component contains the fluorinated compound in an amount of about 4% to about 5%. In some embodiments, the solvent component contains the fluorinated compound in an amount of about 5% to about 6%. In some embodiments, the solvent component contains the fluorinated compound in an amount of about 6% to about 7%. In some embodiments, the solvent component contains the fluorinated compound in an amount of about 7% to about 8%. In some embodiments, the solvent component contains the fluorinated compound in an amount of about 8% to about 9%. In some embodiments, the solvent component contains the fluorinated compound in an amount of about 9% to about 10%. In some embodiments, the solvent component contains the fluorinated compound in an amount of about 10% to about 20%. In some embodiments, the solvent component contains the fluorinated compound in an amount of about 10% to about 30%. In some embodiments, the solvent component contains the fluorinated compound in an amount of about 30% to about 40%. In some embodiments, the solvent component contains the fluorinated compound in an amount of about 40% to about 50%. In some embodiments, the solvent component contains the fluorinated compound in an amount of about 50% to about 60%.

[0205] Item 60. The battery according to any one of items 37 to 57, wherein the solvent component comprises the fluorinated compound in an amount of about 0.1% to about 2%. In some embodiments, the solvent component comprises the fluorinated compound in an amount of about 0.1% to about 0.5%. In some embodiments, the solvent component comprises the fluorinated compound in an amount of about 0.5% to about 1%. In some embodiments, the solvent component comprises the fluorinated compound in an amount of about 1% to about 1.5%. In some embodiments, the solvent component comprises the fluorinated compound in an amount of about 1.5% to about 2%. In some embodiments, the solvent component comprises the fluorinated compound in an amount of about 2% to about 2.5%. In some embodiments, the solvent component comprises the fluorinated compound in an amount of about 2.5% to about 3%. In some embodiments, the solvent component comprises the fluorinated compound in an amount of about 3% to about 3.5%. In some embodiments, the solvent component contains the fluorinated compound in an amount of about 3.5% to about 4%. In some embodiments, the solvent component contains the fluorinated compound in an amount of about 4% to about 4.5%. In some embodiments, the solvent component contains the fluorinated compound in an amount of about 4.5% to about 5%.

[0206] Item 61. The battery according to any one of items 37 to 60, wherein the electrolyte is a non-aqueous electrolyte and the solvent component further comprises one or more of a partially fluorinated organic carbonate and a non-fluorinated organic carbonate.

[0207] Item 62. The battery of item 58, wherein the non-fluorinated carbonate comprises one or more of EC (ethylene carbonate), EMC (ethyl methyl carbonate), DEC (diethyl carbonate), DMC (dimethyl carbonate), PC (propylene carbonate), and VC (vinylene carbonate and / or vinylidene carbonate).

[0208] Item 63. The battery of item 62, wherein the amount of VC in the solvent component is about 0.001% to about 2%. In some embodiments, the amount of VC in the solvent component is about 0.001% to about 0.01%. In some embodiments, the amount of VC in the solvent component is about 0.01% to about 0.1%. In some embodiments, the amount of VC in the solvent component is about 0.1% to about 0.5%. In some embodiments, the amount of VC in the solvent component is about 0.5% to about 1%. In some embodiments, the amount of VC in the solvent component is about 1% to about 2%. In some embodiments, the amount of VC in the solvent component is about 2% to about 3%. In some embodiments, the amount of VC in the solvent component is about 3% to about 4%. In some embodiments, the amount of VC in the solvent component is about 4% to about 5%.

[0209] Item 64. The battery of item 61, wherein the partially fluorinated carbonate comprises FEC (fluoroethylene carbonate), and the amount of FEC in the solvent component is about 0.001% to about 10%. In some embodiments, the amount of FEC in the solvent component is about 0.001% to about 15%. In some embodiments, the amount of FEC in the solvent component is about 1% to about 25%. In some embodiments, the amount of FEC in the solvent component is about 0.01% to about 10%. In some embodiments, the amount of FEC in the solvent component is about 1% to about 10%. In some embodiments, the amount of FEC in the solvent component is about 0.01% to about 9%. In some embodiments, the amount of FEC in the solvent component is about 0.01% to about 8%. In some embodiments, the amount of FEC in the solvent component is about 0.01% to about 7%. In some embodiments, the amount of FEC in the solvent component is about 0.01% to about 6%. In some embodiments, the amount of FEC in the solvent component is about 0.01% to about 5%. In some embodiments, the amount of FEC in the solvent component is about 5% to about 10%. In some embodiments, the amount of FEC in the solvent component is about 10% to about 15%. In some embodiments, the amount of FEC in the solvent component is about 15% to about 20%. In some embodiments, the amount of FEC in the solvent component is about 20% to about 25%. In some embodiments, the solvent component does not contain FEC.

[0210] Item 65. The battery according to any one of items 37 to 60, wherein the electrolyte further comprises a fluorinated organic carbonate or a fluorinated organic sulfite containing one or more of an optionally substituted alkyl, an optionally substituted haloalkyl, an optionally substituted alkenyl, an optionally substituted haloalkenyl, an optionally substituted alkynyl, an optionally substituted haloalkynyl, an optionally substituted aryl, an optionally substituted haloaryl, an optionally substituted heteroaryl, or an optionally substituted haloheteroaryl.

[0211] Item 66. The battery of item 65, wherein the fluorinated organic carbonate is a fluorinated dialkyl carbonate.

[0212] Item 67. The battery according to item 65, wherein the fluorinated organic sulfite is a fluorinated dialkyl sulfite.

[0213] Item 68. The battery according to any one of items 65 to 67, wherein the fluorinated organic carbonate or the fluorinated organic sulfite contains one or more groups selected from —CF 3 , —CHF 2 , —CH 2 F, —CHF—, and —CF 2 —.

[0214] Item 69. The battery of any of items 65 to 67, wherein the fluorinated organic carbonate or the fluorinated organic sulfite contains one or more -CF3 groups.

[0215] Item 70. The battery according to any one of items 65 to 67, wherein the fluorinated organic carbonate or the fluorinated organic sulfite contains one or more groups selected from 2,2,2-trifluoroethyl, 1,1,1-trifluoroisopropyl, 1,1,1,3,3,3-hexafluoroisopropyl, 3,3,3-trifluoropropyl, 2-fluoroethyl, 2,2-difluoroethyl, 3-fluoropropyl, 3,3-difluoropropyl, 2,2,3,3,3-pentafluoropropyl, 4,4,4-trifluorobutyl, 1,1,1,3,3-pentafluoroisopropyl, and 5,5,5-trifluoropentyl.

[0216] Item 71. The battery according to any one of items 65 to 67, wherein the fluorinated organic carbonate or the fluorinated organic sulfite contains one or two 1,1,1,3,3,3-hexafluoroisopropyl groups.

[0217] Item 72. The battery of item 65, wherein the fluorinated organic carbonate is selected from methyl(2,2,2-trifluoroethyl)carbonate, methyl(1,1,1-trifluoroisopropyl)carbonate, methyl(1,1,1,3,3,3-hexafluoroisopropyl)carbonate, methyl(3,3,3-trifluoropropyl)carbonate, methyl(2-fluoroethyl)carbonate, methyl(2,2-difluoroethyl)carbonate, methyl(3-fluoropropyl)carbonate, methyl(3,3-difluoropropyl)carbonate, methyl(2,2,3,3,3-pentafluoropropyl)carbonate, methyl(4,4,4-trifluorobutyl)carbonate, methyl(1,1,1,3,3-pentafluoroisopropyl)carbonate, and methyl(5,5,5-trifluoropentyl)carbonate.

[0218] Item 73. The battery of item 65, wherein the fluorinated organic sulfite is selected from bis-(2,2,2-trifluoroethyl) sulfite, bis-(1,1,1-trifluoroisopropyl) sulfite, and bis-(1,1,1,3,3,3-hexafluoroisopropyl) sulfite.

[0219] Item 74. The battery according to any one of Items 37 to 73, wherein the electrolyte further contains an alkaline salt.

[0220] Item 75. The battery according to item 74, wherein the alkali salt is dissolved in the solvent component, and the concentration of the alkali salt is about 1 M to about 1.5 M.

[0221] Item 76. The battery of item 74, wherein the alkali salt is dissolved in the solvent component and the concentration of the alkali salt is about 1 M, about 1.1 M, about 1.2 M, about 1.3 M, about 1.4 M, or about 1.5 M. In some embodiments, the concentration of the alkali salt is about 0.5 M. In some embodiments, the concentration of the alkali salt is about 0.6 M. In some embodiments, the concentration of the alkali salt is about 0.7 M. In some embodiments, the concentration of the alkali salt is about 0.8 M. In some embodiments, the concentration of the alkali salt is about 0.9 M. In some embodiments, the concentration of the alkali salt is about 1 M. In some embodiments, the concentration of the alkali salt is about 1.1 M. In some embodiments, the concentration of the alkali salt is about 1.2 M. In some embodiments, the concentration of the alkali salt is about 1.3 M. In some embodiments, the concentration of the alkali salt is about 1.4 M. In some embodiments, the concentration of the alkali salt is about 1.5 M. In some embodiments, the concentration of the alkali salt is about 1.6 M. In some embodiments, the concentration of the alkali salt is about 1.7 M. In some embodiments, the concentration of the alkali salt is about 1.8 M. In some embodiments, the concentration of the alkali salt is about 1.9 M. In some embodiments, the concentration of the alkali salt is about 2 M.

[0222] Item 77. The battery according to any one of items 74 to 76, wherein the alkyl salt is a lithium salt.

[0223] Item 78. The battery of item 77, wherein the lithium salt is LiPF. In some embodiments, the lithium salt is LiFSI (lithium bis(fluorosulfonyl)imide). In some embodiments, the lithium salt is LiTFSI (lithium bis(trifluoromethanesulfonyl)imide). In some embodiments, the lithium salt is LiBOB (lithium bis(oxalato)borate).

[0224] Item 79. The battery of any of items 37 to 78, wherein the cathode comprises a metal selected from nickel, manganese, and cobalt. In some embodiments, the cathode comprises a transition metal.

[0225] Item 80. The battery of any of items 37 to 78, wherein the cathode comprises about 70% to about 90% nickel. In some embodiments, the cathode comprises about 65% nickel. In some embodiments, the cathode comprises about 66% nickel. In some embodiments, the cathode comprises about 67% nickel. In some embodiments, the cathode comprises about 68% nickel. In some embodiments, the cathode comprises about 69% nickel. In some embodiments, the cathode comprises about 70% nickel. In some embodiments, the cathode comprises about 71% nickel. In some embodiments, the cathode comprises about 72% nickel. In some embodiments, the cathode comprises about 73% nickel. In some embodiments, the cathode comprises about 74% nickel. In some embodiments, the cathode comprises about 75% nickel. In some embodiments, the cathode comprises about 76% nickel. In some embodiments, the cathode comprises about 77% nickel. In some embodiments, the cathode comprises about 78% nickel. In some embodiments, the cathode comprises about 79% nickel. In some embodiments, the cathode comprises about 80% nickel. In some embodiments, the cathode comprises about 81% nickel. In some embodiments, the cathode comprises about 82% nickel. In some embodiments, the cathode comprises about 83% nickel. In some embodiments, the cathode comprises about 84% nickel. In some embodiments, the cathode comprises about 85% nickel. In some embodiments, the cathode comprises about 86% nickel. In some embodiments, the cathode comprises about 87% nickel. In some embodiments, the cathode comprises about 88% nickel. In some embodiments, the cathode comprises about 89% nickel. In some embodiments, the cathode comprises about 90% nickel. In some embodiments, the cathode comprises about 91% nickel. In some embodiments, the cathode comprises about 92% nickel. In some embodiments, the cathode comprises about 93% nickel.In some embodiments, the cathode comprises about 94% nickel, hi some embodiments, the cathode comprises about 95% nickel.

[0226] Item 81. The battery of any of items 37 to 78, wherein the cathode comprises about 1% to about 15% manganese. In some embodiments, the cathode comprises about 1% manganese. In some embodiments, the cathode comprises about 2% manganese. In some embodiments, the cathode comprises about 3% manganese. In some embodiments, the cathode comprises about 4% manganese. In some embodiments, the cathode comprises about 5% manganese. In some embodiments, the cathode comprises about 6% manganese. In some embodiments, the cathode comprises about 7% manganese. In some embodiments, the cathode comprises about 8% manganese. In some embodiments, the cathode comprises about 9% manganese. In some embodiments, the cathode comprises about 10% manganese. In some embodiments, the cathode comprises about 11% manganese. In some embodiments, the cathode comprises about 12% manganese, in some embodiments, about 13% manganese, in some embodiments, about 14% manganese, and in some embodiments, about 15% manganese.

[0227] Item 82. The battery of any of items 37 to 78, wherein the cathode comprises about 1% to about 15% cobalt. In some embodiments, the cathode comprises about 1% cobalt. In some embodiments, the cathode comprises about 2% cobalt. In some embodiments, the cathode comprises about 3% cobalt. In some embodiments, the cathode comprises about 4% cobalt. In some embodiments, the cathode comprises about 5% cobalt. In some embodiments, the cathode comprises about 6% cobalt. In some embodiments, the cathode comprises about 7% cobalt. In some embodiments, the cathode comprises about 8% cobalt. In some embodiments, the cathode comprises about 9% cobalt. In some embodiments, the cathode comprises about 10% cobalt. In some embodiments, the cathode comprises about 11% cobalt. In some embodiments, the cathode comprises about 12% cobalt, in some embodiments, about 13% cobalt, in some embodiments, about 14% cobalt, and in some embodiments, about 15% cobalt.

[0228] Item 83. The battery of any of items 37 to 78, wherein the cathode comprises about 80% nickel, about 10% manganese, and about 10% cobalt. In some embodiments, the cathode comprises about 80% nickel, about 1% to about 10% manganese, and about 10% to about 1% cobalt. In some embodiments, the cathode comprises about 65% nickel, and the weight ratio of manganese to cobalt is about 99:1 to about 1:99. In some embodiments, the cathode comprises about 66% nickel, and the weight ratio of manganese to cobalt is about 99:1 to about 1:99. In some embodiments, the cathode comprises about 67% nickel, and the weight ratio of manganese to cobalt is about 99:1 to about 1:99. In some embodiments, the cathode comprises about 68% nickel and a manganese to cobalt weight ratio of about 99:1 to about 1:99. In some embodiments, the cathode comprises about 69% nickel and a manganese to cobalt weight ratio of about 99:1 to about 1:99. In some embodiments, the cathode comprises about 70% nickel and a manganese to cobalt weight ratio of about 99:1 to about 1:99. In some embodiments, the cathode comprises about 71% nickel and a manganese to cobalt weight ratio of about 99:1 to about 1:99. In some embodiments, the cathode comprises about 72% nickel and a manganese to cobalt weight ratio of about 99:1 to about 1:99. In some embodiments, the cathode comprises about 73% nickel and a manganese to cobalt weight ratio of about 99:1 to about 1:99. In some embodiments, the cathode comprises about 74% nickel and a manganese to cobalt weight ratio of about 99:1 to about 1:99. In some embodiments, the cathode comprises about 75% nickel and a manganese to cobalt weight ratio of about 99:1 to about 1:99. In some embodiments, the cathode comprises about 76% nickel and a manganese to cobalt weight ratio of about 99:1 to about 1:99. In some embodiments, the cathode comprises about 77% nickel and a manganese to cobalt weight ratio of about 99:1 to about 1:99. In some embodiments, the cathode comprises about 78% nickel and a manganese to cobalt weight ratio of about 99:1 to about 1:99.In some embodiments, the cathode comprises about 79% nickel and a manganese to cobalt weight ratio of about 99:1 to about 1:99. In some embodiments, the cathode comprises about 80% nickel and a manganese to cobalt weight ratio of about 99:1 to about 1:99. In some embodiments, the cathode comprises about 81% nickel and a manganese to cobalt weight ratio of about 99:1 to about 1:99. In some embodiments, the cathode comprises about 82% nickel and a manganese to cobalt weight ratio of about 99:1 to about 1:99. In some embodiments, the cathode comprises about 83% nickel and a manganese to cobalt weight ratio of about 99:1 to about 1:99. In some embodiments, the cathode comprises about 84% nickel and a manganese to cobalt weight ratio of about 99:1 to about 1:99. In some embodiments, the cathode comprises about 85% nickel and has a manganese to cobalt weight ratio of about 99:1 to about 1:99. In some embodiments, the cathode comprises about 86% nickel and has a manganese to cobalt weight ratio of about 99:1 to about 1:99. In some embodiments, the cathode comprises about 87% nickel and has a manganese to cobalt weight ratio of about 99:1 to about 1:99. In some embodiments, the cathode comprises about 88% nickel and has a manganese to cobalt weight ratio of about 99:1 to about 1:99. In some embodiments, the cathode comprises about 89% nickel and has a manganese to cobalt weight ratio of about 99:1 to about 1:99. In some embodiments, the cathode comprises about 90% nickel and has a manganese to cobalt weight ratio of about 99:1 to about 1:99. In some embodiments, the cathode comprises about 91% nickel and a manganese to cobalt weight ratio of about 99:1 to about 1:99. In some embodiments, the cathode comprises about 92% nickel and a manganese to cobalt weight ratio of about 99:1 to about 1:99. In some embodiments, the cathode comprises about 93% nickel and a manganese to cobalt weight ratio of about 99:1 to about 1:99. In some embodiments, the cathode comprises about 94% nickel and a manganese to cobalt weight ratio of about 99:1 to about 1:99.In some embodiments, the cathode comprises about 95% nickel and a manganese to cobalt weight ratio of about 99:1 to about 1:99. In some embodiments, the cathode comprises about 96% to 99% nickel and a manganese to cobalt weight ratio of about 99:1 to about 1:99.

[0229] Item 84. The battery of any of items 37 to 78, wherein the cathode comprises about 90% nickel, about 5% manganese, and about 5% cobalt.

[0230] Item 85. The battery of any of items 37 to 84, wherein the anode comprises about 2% to about 75% silicon. In some embodiments, the anode comprises about 1% silicon. In some embodiments, the anode comprises about 2% silicon. In some embodiments, the anode comprises about 3% silicon. In some embodiments, the anode comprises about 4% silicon. In some embodiments, the anode comprises about 5% silicon. In some embodiments, the anode comprises about 6% silicon. In some embodiments, the anode comprises about 7% silicon. In some embodiments, the anode comprises about 8% silicon. In some embodiments, the anode comprises about 9% silicon. In some embodiments, the anode comprises about 10% silicon. In some embodiments, the anode comprises about 11% silicon. In some embodiments, the anode comprises about 12% silicon. In some embodiments, the anode comprises about 13% silicon. In some embodiments, the anode comprises about 14% silicon. In some embodiments, the anode comprises about 15% silicon. In some embodiments, the anode comprises about 16% silicon. In some embodiments, the anode comprises about 17% silicon. In some embodiments, the anode comprises about 18% silicon. In some embodiments, the anode comprises about 19% silicon. In some embodiments, the anode comprises about 20% silicon. In some embodiments, the anode comprises about 21% silicon. In some embodiments, the anode comprises about 22% silicon. In some embodiments, the anode comprises about 23% silicon. In some embodiments, the anode comprises about 24% silicon. In some embodiments, the anode comprises about 25% silicon. In some embodiments, the anode comprises about 26% silicon. In some embodiments, the anode comprises about 27% silicon. In some embodiments, the anode comprises about 28% silicon, hi some embodiments, the anode comprises about 29% silicon, hi some embodiments, the anode comprises about 30% silicon.In some embodiments, the anode comprises about 31% silicon. In some embodiments, the anode comprises about 32% silicon. In some embodiments, the anode comprises about 33% silicon. In some embodiments, the anode comprises about 34% silicon. In some embodiments, the anode comprises about 35% silicon. In some embodiments, the anode comprises about 36% silicon. In some embodiments, the anode comprises about 37% silicon. In some embodiments, the anode comprises about 38% silicon. In some embodiments, the anode comprises about 39% silicon. In some embodiments, the anode comprises about 40% silicon. In some embodiments, the anode comprises about 5% to about 10% silicon. In some embodiments, the anode comprises about 10% to about 15% silicon. In some embodiments, the anode comprises about 15% to about 20% silicon. In some embodiments, the anode comprises about 20% to about 25% silicon. In some embodiments, the anode comprises about 25% to about 30% silicon. In some embodiments, the anode comprises about 30% to about 35% silicon. In some embodiments, the anode comprises about 35% to about 40% silicon. In some embodiments, the anode comprises about 40% to about 45% silicon. In some embodiments, the anode comprises about 45% to about 50% silicon. In some embodiments, the anode comprises about 50% to about 55% silicon. In some embodiments, the anode comprises about 55% to about 60% silicon. In some embodiments, the anode comprises about 60% to about 65% silicon. In some embodiments, the anode comprises about 65% to about 70% silicon.

[0231] Item 86. The battery of any of items 37 to 84, wherein the anode comprises about 2% to about 75% silicon oxide graphite composite. In some embodiments, the anode comprises about 1% silicon oxide graphite composite. In some embodiments, the anode comprises about 2% silicon oxide graphite composite. In some embodiments, the anode comprises about 3% silicon oxide graphite composite. In some embodiments, the anode comprises about 4% silicon oxide graphite composite. In some embodiments, the anode comprises about 5% silicon oxide graphite composite. In some embodiments, the anode comprises about 6% silicon oxide graphite composite. In some embodiments, the anode comprises about 7% silicon oxide graphite composite. In some embodiments, the anode comprises about 8% silicon oxide graphite composite. In some embodiments, the anode comprises about 9% silicon oxide graphite composite. In some embodiments, the anode comprises about 10% silicon oxide graphite composite. In some embodiments, the anode comprises about 11% silicon oxide graphite composite. In some embodiments, the anode comprises about 12% silicon oxide graphite composite. In some embodiments, the anode comprises about 13% silicon oxide graphite composite. In some embodiments, the anode comprises about 14% silicon oxide graphite composite. In some embodiments, the anode comprises about 15% silicon oxide graphite composite. In some embodiments, the anode comprises about 16% silicon oxide graphite composite. In some embodiments, the anode comprises about 17% silicon oxide graphite composite. In some embodiments, the anode comprises about 18% silicon oxide graphite composite. In some embodiments, the anode comprises about 19% silicon oxide graphite composite. In some embodiments, the anode comprises about 20% silicon oxide graphite composite. In some embodiments, the anode comprises about 21% silicon oxide graphite composite, hi some embodiments, the anode comprises about 22% silicon oxide graphite composite.In some embodiments, the anode comprises about 23% silicon oxide graphite composite. In some embodiments, the anode comprises about 24% silicon oxide graphite composite. In some embodiments, the anode comprises about 25% silicon oxide graphite composite. In some embodiments, the anode comprises about 26% silicon oxide graphite composite. In some embodiments, the anode comprises about 27% silicon oxide graphite composite. In some embodiments, the anode comprises about 28% silicon oxide graphite composite. In some embodiments, the anode comprises about 29% silicon oxide graphite composite. In some embodiments, the anode comprises about 30% silicon oxide graphite composite. In some embodiments, the anode comprises about 31% silicon oxide graphite composite. In some embodiments, the anode comprises about 32% silicon oxide graphite composite. In some embodiments, the anode comprises about 33% silicon oxide graphite composite. In some embodiments, the anode comprises about 34% silicon oxide graphite composite. In some embodiments, the anode comprises about 35% silicon oxide graphite composite. In some embodiments, the anode comprises about 36% silicon oxide graphite composite. In some embodiments, the anode comprises about 37% silicon oxide graphite composite. In some embodiments, the anode comprises about 38% silicon oxide graphite composite. In some embodiments, the anode comprises about 39% silicon oxide graphite composite. In some embodiments, the anode comprises about 40% silicon oxide graphite composite. In some embodiments, the anode comprises about 5% to about 10% silicon oxide graphite composite. In some embodiments, the anode comprises about 10% to about 15% silicon oxide graphite composite. In some embodiments, the anode comprises about 15% to about 20% silicon oxide graphite composite. In some embodiments, the anode comprises about 20% to about 25% silicon oxide graphite composite.In some embodiments, the anode comprises about 25% to about 30% silicon oxide graphite composite. In some embodiments, the anode comprises about 30% to about 35% silicon oxide graphite composite. In some embodiments, the anode comprises about 35% to about 40% silicon oxide graphite composite. In some embodiments, the anode comprises about 40% to about 45% silicon oxide graphite composite. In some embodiments, the anode comprises about 45% to about 50% silicon oxide graphite composite. In some embodiments, the anode comprises about 50% to about 55% silicon oxide graphite composite. In some embodiments, the anode comprises about 55% to about 60% silicon oxide graphite composite. In some embodiments, the anode comprises about 60% to about 65% silicon oxide graphite composite. In some embodiments, the anode comprises about 65% to about 70% silicon oxide graphite composite. In some embodiments, the anode comprises about 70% to about 75% silicon oxide graphite composite.

[0232] Item 87. The battery of any of items 37 to 84, wherein the anode comprises about 2% to about 75% amorphous silicon graphite composite. In some embodiments, the anode comprises about 1% amorphous silicon graphite composite. In some embodiments, the anode comprises about 2% amorphous silicon graphite composite. In some embodiments, the anode comprises about 3% amorphous silicon graphite composite. In some embodiments, the anode comprises about 4% amorphous silicon graphite composite. In some embodiments, the anode comprises about 5% amorphous silicon graphite composite. In some embodiments, the anode comprises about 6% amorphous silicon graphite composite. In some embodiments, the anode comprises about 7% amorphous silicon graphite composite. In some embodiments, the anode comprises about 8% amorphous silicon graphite composite. In some embodiments, the anode comprises about 9% amorphous silicon graphite composite. In some embodiments, the anode comprises about 10% amorphous silicon graphite composite. In some embodiments, the anode comprises about 11% amorphous silicon graphite composite. In some embodiments, the anode comprises about 12% amorphous silicon graphite composite. In some embodiments, the anode comprises about 13% amorphous silicon graphite composite. In some embodiments, the anode comprises about 14% amorphous silicon graphite composite. In some embodiments, the anode comprises about 15% amorphous silicon graphite composite. In some embodiments, the anode comprises about 16% amorphous silicon graphite composite. In some embodiments, the anode comprises about 17% amorphous silicon graphite composite. In some embodiments, the anode comprises about 18% amorphous silicon graphite composite, hi some embodiments, the anode comprises about 19% amorphous silicon graphite composite, and in some embodiments, the anode comprises about 20% amorphous silicon graphite composite.In some embodiments, the anode comprises about 21% amorphous silicon graphite composite. In some embodiments, the anode comprises about 22% amorphous silicon graphite composite. In some embodiments, the anode comprises about 23% amorphous silicon graphite composite. In some embodiments, the anode comprises about 24% amorphous silicon graphite composite. In some embodiments, the anode comprises about 25% amorphous silicon graphite composite. In some embodiments, the anode comprises about 26% amorphous silicon graphite composite. In some embodiments, the anode comprises about 27% amorphous silicon graphite composite. In some embodiments, the anode comprises about 28% amorphous silicon graphite composite. In some embodiments, the anode comprises about 29% amorphous silicon graphite composite. In some embodiments, the anode comprises about 30% amorphous silicon graphite composite. In some embodiments, the anode comprises about 31% amorphous silicon graphite composite. In some embodiments, the anode comprises about 32% amorphous silicon graphite composite. In some embodiments, the anode comprises about 33% amorphous silicon graphite composite. In some embodiments, the anode comprises about 34% amorphous silicon graphite composite. In some embodiments, the anode comprises about 35% amorphous silicon graphite composite. In some embodiments, the anode comprises about 36% amorphous silicon graphite composite. In some embodiments, the anode comprises about 37% amorphous silicon graphite composite. In some embodiments, the anode comprises about 38% amorphous silicon graphite composite. In some embodiments, the anode comprises about 39% amorphous silicon graphite composite, hi some embodiments, the anode comprises about 40% amorphous silicon graphite composite, hi some embodiments, the anode comprises about 5% to about 10% amorphous silicon graphite composite.In some embodiments, the anode comprises about 10% to about 15% amorphous silicon graphite composite. In some embodiments, the anode comprises about 15% to about 20% amorphous silicon graphite composite. In some embodiments, the anode comprises about 20% to about 25% amorphous silicon graphite composite. In some embodiments, the anode comprises about 25% to about 30% amorphous silicon graphite composite. In some embodiments, the anode comprises about 30% to about 35% amorphous silicon graphite composite. In some embodiments, the anode comprises about 35% to about 40% amorphous silicon graphite composite. In some embodiments, the anode comprises about 40% to about 45% amorphous silicon graphite composite. In some embodiments, the anode comprises about 45% to about 50% amorphous silicon graphite composite. In some embodiments, the anode comprises about 50% to about 55% amorphous silicon graphite composite. In some embodiments, the anode comprises about 55% to about 60% amorphous silicon graphite composite. In some embodiments, the anode comprises about 60% to about 65% amorphous silicon graphite composite. In some embodiments, the anode comprises about 65% to about 70% amorphous silicon graphite composite. In some embodiments, the anode comprises about 70% to about 75% amorphous silicon graphite composite.

[0233] Item 88. The battery according to any one of Items 37 to 87, wherein the battery is rechargeable and has a cycle life of about 150 to about 500 cycles. In some embodiments, the battery has a cycle life of about 150 to about 200 cycles. In some embodiments, the battery has a cycle life of about 200 to about 250 cycles. In some embodiments, the battery has a cycle life of about 250 to about 300 cycles. In some embodiments, the battery has a cycle life of about 300 to about 350 cycles. In some embodiments, the battery has a cycle life of about 350 to about 400 cycles. In some embodiments, the battery has a cycle life of about 400 to about 450 cycles. In some embodiments, the battery has a cycle life of about 450 to about 500 cycles. In some embodiments, the battery has a cycle life of about 500 to about 550 cycles. In some embodiments, the battery has a cycle life of about 550 to about 600 cycles. In some embodiments, the battery has a cycle life of about 600 to about - cycles. In some embodiments, the battery has a cycle life of about to about - cycles. In some embodiments, the battery has a cycle life of about to about - cycles. In some embodiments, the battery has a cycle life of about to about - cycles. In some embodiments, the battery has a cycle life of about to about - cycles. In some embodiments, the battery has a cycle life of about to about - cycles. In some embodiments, the battery has a cycle life of about to about - cycles. In some embodiments, the battery has a cycle life of about to about - cycles. In some embodiments, the battery has a cycle life of about to about - cycles. In some embodiments, the battery has a cycle life of about to about - cycles. In some embodiments, the battery has a cycle life of about to about - cycles. In some embodiments, the battery has a cycle life of about to about - cycles.

[0234] Item 89. The battery of item 88, wherein the battery has a cycle life of at least 200 cycles.

[0235] Item 90. The battery of item 88, wherein the battery has a cycle life of at least 250 cycles. [Example]

[0236] Embodiments encompassed herein will now be described with reference to the following examples, which are provided for illustrative purposes only, and the disclosure encompassed herein should not be construed as being limited to these examples in any way, but rather as including any variations that become evident as a result of the teachings provided herein.

[0237] Example 1: Synthesis of methyl 2,2,2-trifluoroethyl carbonate A 2 L, water-jacketed, 3-neck flask equipped with a mechanical stirrer and an addition funnel was charged with 2,2,2-trifluoroethanol (150 g, 1.50 mol), methyl chloroformate (146 g, 1.55 mol), and hexafluoroisopropyl methyl ether (470 g). Triethylamine (157 g, 1.55 mol) was added slowly to maintain an internal temperature below 30°C (total addition time: 1.5 h). After 2 h, GC showed that 96.1% of the starting alcohol had been converted to methyl 2,2,2-trifluoroethyl carbonate.

[0238] Example 2: Synthesis of methyl 1,1,1-trifluoroisopropyl carbonate A water-jacketed, 1 L, 3-neck flask equipped with a mechanical stirrer and an addition funnel was charged with 1,1,1-trifluoro-2-propanol (114 g, 1.00 mol), methyl chloroformate (94 g, 1.0 mol), and hexafluoroisopropyl methyl ether (200 mL). Triethylamine (102 g, 1.00 mol) was added slowly to maintain an internal temperature below 30°C (total addition time: 2 h). After 2 h, GC showed that 96.4% of the starting alcohol had been converted to methyl 1,1,1-trifluoroisopropyl carbonate.

[0239] Example 3: Synthesis of methyl 1,1,1,3,3,3-hexafluoroisopropyl carbonate A 2 L, water-jacketed, 3-neck flask equipped with a mechanical stirrer and addition funnel was charged with 1,1,1,3,3,3-hexafluoroisopropanol (252 g, 1.50 mol), methyl chloroformate (146 g, 1.55 mol), and hexafluoroisopropyl methyl ether (470 g). Triethylamine (157 g, 1.55 mol) was added slowly to maintain an internal temperature below 30°C (total addition time: 1.5 h). After 2 h, GC indicated that 98.6% of the starting alcohol had been converted to 1,1,1,3,3,3-hexafluoroisopropyl carbonate.

[0240] Example 4: Synthesis of bis(1,1,1,3,3,3-hexafluoroisopropyl) sulfite To 1,1,1,3,3,3-hexafluoroisopropanol (336 g, 2.00 mol) and triethylamine (203 g, 2.00 mol) in hexafluoroisopropyl methyl ether (1.0 kg) was added thionyl chloride (73 mL, 1.0 mol) dropwise at 0° C. (total addition time: 1 h) while maintaining the internal temperature below 15° C. After 2 h, GC showed that 90.6% of the starting alcohol had been converted to bis(1,1,1,3,3,3-hexafluoroisopropyl) sulfite.

[0241] Example 4: Study of Silicon Composite Anodes - Comparison of FEC / FEC Combinations Materials: Cathode: NMC811; Anode: Si-graphite composite, 10% amorphous Si; Baseline electrolyte: 1.2 M LiPF6 in a solvent containing 88% ethylene carbonate / ethyl methyl carbonate (EC / EMC 3:7), 10% FEC, and 2% VC (vinylene carbonate).

[0242] Cycle Life Test: Test vehicle: Single layer pouch cell. Test protocol: Charge at 1C to 4.4V, discharge at 1C to 3.0V (electrode loads: 1.26mAh / cm2 and 1.90mAh / cm2).

[0243] Figure 1 shows the performance improvement of high-temperature silicon anode batteries using electrolytes containing trifluoroethyl methyl carbonate (F3EMC) versus electrolytes containing fluoroethylene carbonate (FEC), with F3EMC and the FEC / F3EMC combination outperforming FEC alone (F3EMC is carbonate CF3CH2OC(O)OCH3; 1C / -1C cycle 4.40 to 3.00 V; cell type - pouch cell, cycled (@45°C) -4.40 V to 3.00 V; cathode - NMC811; anode 10% silicon composite).

[0244] Legend: TIFF2026027447000024.tif517088 1.2 M LiPF6 solution in % EC / EMC (3:7), 10% FEC, and 2% VC TIFF2026027447000025.tif517088% EC / EMC (3:7), 3% FEC, 7% F3EMC, and 2% VC. 1.2 M LiPF6 solution. TIFF2026027447000026.tif517088% EC / EMC (3:7), 10% F3EMC, and 2% VC. 1.2 M LiPF6 solution.

[0245] Figure 2 shows the performance improvement of high-temperature silicon anode batteries using an electrolyte containing trifluoroethyl acetate ester compared to an electrolyte containing FEC, with the FEC / trifluoroethyl acetate ester combination outperforming FEC alone (trifluoroethyl acetate ester is CF3CH2OC(O)CH3; 1C / -1C cycle 4.40 to 3.00 V; cell type—pouch cell, cycle (@45°C) -4.40 V to 3.00 V; cathode—NMC811; anode—10% silicon composite).

[0246] Legend: TIFF2026027447000027.tif517088 1.2 M LiPF6 solution in % EC / EMC (3:7), 10% FEC, and 2% VC (vinylene carbonate) TIFF2026027447000028.tif517083 1.2 M LiPF6 solution in 3% EC / EMC (3:7), 5% FEC, 10% trifluoroethyl acetate ester, and 2% VC (vinylene carbonate) TIFF2026027447000029.tif517088 1.2 M LiPF6 solution in % EC / EMC (3:7), 3% FEC, 7% trifluoroethyl acetate ester, and 2% VC (vinylene carbonate)

[0247] Figure 3 shows the performance improvement of high-temperature silicon anode batteries using an electrolyte containing hexafluoro-2-methoxypropane (hexafluoro-2-propyl methyl ether) versus an electrolyte containing fluoroethylene carbonate (FEC), with hexafluoro-2-methoxypropane without or in combination with FEC exceeding FEC alone by over 80% (hexafluoro-2-methoxypropane is (CF3)2CHOCH3; 1C / -1C cycle 4.40 to 3.00 V; cell type—pouch cell, cycled (at 45°C) −4.40 V to 3.00 V; cathode—NMC811; anode—10% silicon composite).

[0248] Legend: TIFF2026027447000030.tif517088 1.2 M LiPF6 solution in % EC / EMC (3:7), 10% FEC, and 2% VC (vinylene carbonate) TIFF2026027447000031.tif517088 1.2 M LiPF6 solution in % EC / EMC (3:7), 3% FEC, 7% hexafluoro-2-methoxypropane, and 2% VC (vinylene carbonate) TIFF2026027447000032.tif517088 1.2 M LiPF6 solution in 8% EC / EMC (3:7), 10% hexafluoro-2-methoxypropane, and 2% VC (vinylene carbonate)

[0249] Without wishing to be bound by any particular theory, it is believed that in some embodiments, hexafluoro-2-methoxypropane is superior to F3EMC, which is superior to trifluoroethyl acetate ester, which is superior to FEC.

[0250] Several patent and non-patent publications are cited herein to describe the state of the art to which this disclosure pertains, the entire disclosures of each of which are incorporated herein by reference.

[0251] While particular embodiments of the present disclosure have been described and / or illustrated above, various other embodiments will be apparent to those skilled in the art in light of the foregoing disclosure. Accordingly, the present disclosure is not limited to the particular embodiments described and / or illustrated, but is capable of considerable variation and modification without departing from the scope and spirit of the appended claims.

Claims

1. 1. A method for producing a fluorinated organic carbonate or a fluorinated organic sulfite, comprising reacting a first reactant comprising at least one fluorine atom with a second reactant of Formula 20A or 20B comprising a leaving group L1; 【Chemistry 1】 wherein the reaction is carried out in the presence of a fluorinated solvent; R1 is selected from optionally substituted alkyl, optionally substituted haloalkyl, optionally substituted alkenyl, optionally substituted haloalkenyl, optionally substituted alkynyl, optionally substituted haloalkynyl, optionally substituted aryl, optionally substituted haloaryl, optionally substituted heteroaryl, and optionally substituted haloheteroaryl; and L2 is a leaving group.

2. The method of claim 1 , wherein the first reactant is a fluorinated alcohol.

3. The method of claim 1 , wherein the fluorinated organic carbonate is a fluorinated dialkyl carbonate.

4. The method of claim 1 , wherein the fluorinated organic sulfite is a fluorinated dialkyl sulfite.

5. 5. The method of any of claims 1 to 4, wherein the first reactant comprises one or more groups selected from -CF3, -CHF2, -CH2F, -CHF-, and -CF2-.

6. The method of any of claims 1 to 4, wherein the first reactant comprises one or more -CF3 groups.

7. 5. The method of any of claims 1 to 4, wherein the first reactant is selected from 2-fluoroethanol, 2,2-difluoroethanol, 2,2,2-trifluoroethanol, 3-fluoro-1-propanol, 3,3-difluoro-1-propanol, 3,3,3-trifluoro-1-propanol, 2,2,3,3,3-pentafluoro-1-propanol, 1,1,1-trifluoro-2-propanol, 1,1,1,3,3-pentafluoro-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 4,4,4-trifluoro-1-butanol, and 5,5,5-trifluoro-1-pentanol.

8. The method of any of claims 1 to 4, wherein the first reactant is 1,1,1,3,3,3-hexafluoroisopropanol.

9. 9. The method of claim 1, wherein L1 is selected from perfluoroalkylsulfonates, tosylates, mesylates, halogens, nitrates, phosphates, thioethers, amines, carboxylates, phenoxides, alkoxides, and amides.

10. 9. The method of any one of claims 1 to 8, wherein L1 is selected from a halogen or an -OR2 group.

11. 11. The method of claim 10, wherein R2 is an alkyl sulfate or an aryl sulfate.

12. 9. The method of claim 1, wherein L1 is selected from chlorine, iodine, and bromine.

13. 13. The method of any one of claims 1 to 12, wherein L2 is selected from perfluoroalkylsulfonates, tosylates, mesylates, halogens, nitrates, phosphates, thioethers, amines, carboxylates, phenoxides, alkoxides, and amides.

14. 13. The method of any of claims 1 to 12, wherein L2 is selected from a halogen or an -OR3 group.

15. 15. The method of claim 14, wherein R3 is an alkyl sulfate or an aryl sulfate.

16. 13. The method of any one of claims 1 to 12, wherein L2 is selected from chlorine, iodine, and bromine.

17. 17. The method of any of claims 1 to 16, wherein the compound of formula 20A is a chloroformate.

18. 18. The method of claim 17, wherein the chloroformate is an alkyl chloroformate.

19. 18. The method of claim 17, wherein the chloroformate is methyl chloroformate, ethyl chloroformate, n-propyl chloroformate, or 2-propyl chloroformate.

20. 20. The method of any of claims 1 to 19, wherein the fluorinated organic carbonate is selected from methyl(2,2,2-trifluoroethyl)carbonate, methyl(1,1,1-trifluoroisopropyl)carbonate, methyl(1,1,1,3,3,3-hexafluoroisopropyl)carbonate, methyl(3,3,3-trifluoropropyl)carbonate, methyl(2-fluoroethyl)carbonate, methyl(2,2-difluoroethyl)carbonate, methyl(3-fluoropropyl)carbonate, methyl(3,3-difluoropropyl)carbonate, methyl(2,2,3,3,3-pentafluoropropyl)carbonate, methyl(4,4,4-trifluorobutyl)carbonate, methyl(1,1,1,3,3-pentafluoroisopropyl)carbonate, and methyl(5,5,5-trifluoropentyl)carbonate.

21. 17. The method of any of claims 1 to 16, wherein the compound of formula 20B is thionyl chloride.

22. 22. The method of any one of claims 1 to 19 or claim 21, wherein the fluorinated organic sulfite is selected from bis-(2,2,2-trifluoroethyl) sulfite, bis-(1,1,1-trifluoroisopropyl) sulfite, and bis-(1,1,1,3,3,3-hexafluoroisopropyl) sulfite.

23. 23. The method of any of claims 1 to 22, wherein the fluorinated solvent comprises one or more groups selected from -CF3, -CHF2, -CH2F, -CHF-, and -CF2-.

24. 23. The method of any of claims 1 to 22, wherein the fluorinated solvent comprises one or more -CF3 groups.

25. 23. The method of any of claims 1 to 22, wherein the fluorinated solvent contains two or more -CF3 groups.

26. 26. The method of any of claims 1 to 25, wherein the fluorinated solvent is an ether or thioether having formula 10. 【Chemistry 2】 wherein X is O or S, R4 is a fully or partially fluorinated C1-C8 alkyl group, and R5 is an optionally fluorinated C1-C8 alkyl group.

27. 27. The method of claim 26, wherein R4 is a fully or partially fluorinated C1-C4 alkyl group; and R5 is an optionally fluorinated C1-C4 alkyl group.

28. 28. The method of any of claims 1 to 27, wherein the fluorinated solvent comprises one or more groups selected from 2,2,2-trifluoroethyl, 1,1,1-trifluoroisopropyl, 1,1,1,3,3,3-hexafluoroisopropyl, 3,3,3-trifluoropropyl, 2-fluoroethyl, 2,2-difluoroethyl, 3-fluoropropyl, 3,3-difluoropropyl, 2,2,3,3,3-pentafluoropropyl, 4,4,4-trifluorobutyl, 1,1,1,3,3-pentafluoroisopropyl, and 5,5,5-trifluoropentyl, or the fluorinated solvent is hexafluoroisopropyl methyl ether.

29. 29. The method of any of claims 1 to 28, wherein the reaction is carried out in the presence of an amine.

30. 30. The method of claim 29, wherein the amine is an alkylamine or pyridine.

31. 31. The method of claim 30, wherein the alkylamine is a trialkylamine.

32. 30. The method of claim 29, wherein the amine is selected from triethylamine, tripropylamine, tributylamine, diisopropylethylamine, pyridine, dimethylaminopyridine, 2,6-lutidine, and N,N-dimethylaniline.

33. 33. The method of any of claims 1 to 32, wherein the reaction is carried out at a temperature of from about -40°C to about 80°C.

34. 33. The method of any of claims 1 to 32, wherein the reaction is carried out at a temperature of from about -40°C to about 70°C.

35. 33. The method of any of claims 1 to 32, wherein the reaction is carried out at a temperature of from about 0°C to about 35°C.

36. 33. The method of any of claims 1 to 32, wherein the reaction is carried out at a temperature of from about 10°C to about 35°C.

37. 1. A battery comprising an electrolyte including a solvent component, wherein the solvent component comprises a fluorinated compound in an amount of from about 1 ppm to about 60%, the fluorinated compound having any of Formula I, Formula II(a), Formula II(b), Formula III, or Formula IV. 【Transformation 3】 wherein R10 and R20 are independently selected from C1-C6 alkyl, C1-C8 alkyl, cycloalkyl, aryl, fully or partially fluorinated C1-C6 alkyl, fully or partially fluorinated C1-C8 alkyl, fully or partially fluorinated cycloalkyl, and fully or partially fluorinated aryl.

38. 38. The battery of claim 37, wherein R20 is a fully or partially fluorinated C1-C6 alkyl.

39. 38. The battery of claim 37, wherein R20 comprises one or more —CF3 groups.

40. 38. The battery of claim 37, wherein R20 comprises 1 to 3 —CF3 groups.

41. 38. The battery of claim 37, wherein R20 is selected from trifluoroethyl or hexafluoroisopropyl.

42. 42. The battery of any of claims 37 to 41, wherein R10 is selected from methyl, ethyl, n-propyl, and 2-propyl.

43. 42. The battery of any of claims 37 to 41, wherein R10 is selected from fully or partially fluorinated methyl, fully or partially fluorinated ethyl, fully or partially fluorinated n-propyl, and fully or partially fluorinated 2-propyl.

44. 42. The battery of any of claims 37 to 41, wherein R10 comprises one or more -CF3 groups.

45. 42. The battery of any of claims 37 to 41, wherein R10 comprises 1 to 3 -CF3 groups.

46. 38. The battery of claim 37, wherein R10 and R20 are the same.

47. 38. The battery of claim 37, wherein the compound of Formula IV is a compound of any of Formulas 400, 401, 402, or 403. 【Chemistry 4】

48. 38. The battery of claim 37, wherein the compound of Formula I is a compound of any of Formulas 100, 101, 102, or 103. 【Transformation 5】

49. 38. The battery of claim 37, wherein the compound of Formula II(a) is a compound of any of Formulas 200, 201, 202, or 203. 【Transformation 6】

50. 38. The battery of claim 37, wherein the compound of Formula III is a compound of Formula 300 or Formula 301. 【Transformation 7】

51. 38. The battery of claim 37, wherein the fluorinated compound is an ether or thioether of Formula 10. 【Transformation 8】 (In Formula 10, X is O or S, R4 is a partially fluorinated C1-C8 alkyl group; and R5 is an optionally fluorinated C1-C8 alkyl group.)

52. 52. The battery of claim 51, wherein R4 is a partially fluorinated C1-C4 alkyl group and R5 is an optionally fluorinated C1-C4 alkyl group.

53. 53. The battery of any of claims 51-52, wherein the fluorinated ether or thioether comprises one or more groups selected from -CF3, -CHF2, -CH2F, -CHF-, and -CF2-.

54. 54. The battery of any of claims 51 to 53, wherein the fluorinated ether or thioether comprises one or more -CF3 groups.

55. 54. The battery of any of claims 51 to 53, wherein the fluorinated ether or thioether comprises two or more -CF3 groups.

56. 56. The battery of any of claims 51 to 55, wherein the fluorinated ether or thioether comprises one or more groups selected from 2,2,2-trifluoroethyl, 1,1,1-trifluoroisopropyl, 1,1,1,3,3,3-hexafluoroisopropyl, 3,3,3-trifluoropropyl, 2-fluoroethyl, 2,2-difluoroethyl, 3-fluoropropyl, 3,3-difluoropropyl, 2,2,3,3,3-pentafluoropropyl, 4,4,4-trifluorobutyl, 1,1,1,3,3-pentafluoroisopropyl, and 5,5,5-trifluoropentyl.

57. 56. The battery of any of claims 51 to 55, wherein the fluorinated ether or thioether is hexafluoroisopropyl methyl ether.

58. 58. The battery of any of claims 37 to 57, wherein the solvent component comprises the fluorinated compound in an amount of from about 1 ppm to about 5000 ppm.

59. 58. The battery of any of claims 37 to 57, wherein the solvent component comprises the fluorinated compound in an amount of from about 0.0001% to about 5%.

60. 58. The battery of any of claims 37 to 57, wherein the solvent component comprises the fluorinated compound in an amount of from about 0.1% to about 2%.

61. 61. The battery of any of claims 37 to 60, wherein the electrolyte is a non-aqueous electrolyte and the solvent component further comprises one or more of a partially fluorinated organic carbonate and a non-fluorinated organic carbonate.

62. 62. The battery of claim 61 , wherein the non-fluorinated carbonate comprises one or more of EC (ethylene carbonate), EMC (ethyl methyl carbonate), DEC (diethyl carbonate), DMC (dimethyl carbonate), PC (propylene carbonate), and VC (vinylene carbonate and / or vinylidene carbonate).

63. 63. The battery of claim 62, wherein the amount of VC in the solvent component is from about 0.001% to about 2%.

64. 62. The battery of claim 61, wherein the partially fluorinated carbonate comprises FEC (fluoroethylene carbonate), and the amount of FEC in the solvent component is from about 0.001% to about 10%.

65. 61. The battery of any of claims 37 to 60, wherein the electrolyte further comprises a fluorinated organic carbonate or fluorinated organic sulfite containing one or more of an optionally substituted alkyl, an optionally substituted haloalkyl, an optionally substituted alkenyl, an optionally substituted haloalkenyl, an optionally substituted alkynyl, an optionally substituted haloalkynyl, an optionally substituted aryl, an optionally substituted haloaryl, an optionally substituted heteroaryl, or an optionally substituted haloheteroaryl.

66. 66. The battery of claim 65, wherein the fluorinated organic carbonate is a fluorinated dialkyl carbonate.

67. 66. The battery of claim 65, wherein the fluorinated organic sulfite is a fluorinated dialkyl sulfite.

68. 68. The battery of any of claims 65 to 67, wherein the fluorinated organic carbonate or the fluorinated organic sulfite comprises one or more groups selected from -CF3, -CHF2, -CH2F, -CHF-, and -CF2-.

69. 68. The battery of any of claims 65 to 67, wherein the fluorinated organic carbonate or the fluorinated organic sulfite comprises one or more -CF3 groups.

70. 68. The battery of any of claims 65 to 67, wherein the fluorinated organic carbonate or the fluorinated organic sulfite comprises one or more groups selected from 2,2,2-trifluoroethyl, 1,1,1-trifluoroisopropyl, 1,1,1,3,3,3-hexafluoroisopropyl, 3,3,3-trifluoropropyl, 2-fluoroethyl, 2,2-difluoroethyl, 3-fluoropropyl, 3,3-difluoropropyl, 2,2,3,3,3-pentafluoropropyl, 4,4,4-trifluorobutyl, 1,1,1,3,3-pentafluoroisopropyl, and 5,5,5-trifluoropentyl.

71. 68. The battery of any of claims 65 to 67, wherein the fluorinated organic carbonate or the fluorinated organic sulfite contains one or two 1,1,1,3,3,3-hexafluoroisopropyl groups.

72. 66. The battery of claim 65, wherein the fluorinated organic carbonate is selected from methyl(2,2,2-trifluoroethyl)carbonate, methyl(1,1,1-trifluoroisopropyl)carbonate, methyl(1,1,1,3,3,3-hexafluoroisopropyl)carbonate, methyl(3,3,3-trifluoropropyl)carbonate, methyl(2-fluoroethyl)carbonate, methyl(2,2-difluoroethyl)carbonate, methyl(3-fluoropropyl)carbonate, methyl(3,3-difluoropropyl)carbonate, methyl(2,2,3,3,3-pentafluoropropyl)carbonate, methyl(4,4,4-trifluorobutyl)carbonate, methyl(1,1,1,3,3-pentafluoroisopropyl)carbonate, and methyl(5,5,5-trifluoropentyl)carbonate.

73. 66. The battery of claim 65, wherein the fluorinated organic sulfite is selected from bis-(2,2,2-trifluoroethyl) sulfite, bis-(1,1,1-trifluoroisopropyl) sulfite, and bis-(1,1,1,3,3,3-hexafluoroisopropyl) sulfite.

74. 74. The battery of any of claims 37 to 73, wherein the electrolyte further comprises an alkaline salt.

75. 75. The battery of claim 74, wherein the alkali salt is dissolved in the solvent component, and the concentration of the alkali salt is from about 1 M to about 1.5 M.

76. 75. The battery of claim 74, wherein the alkali salt is dissolved in the solvent component, and the concentration of the alkali salt is about 1 M, about 1.1 M, about 1.2 M, about 1.3 M, about 1.4 M, or about 1.5 M.

77. 77. The battery of any of claims 74 to 76, wherein the alkyl salt is a lithium salt.

78. 78. The battery of claim 77, wherein the lithium salt is LiPF6.

79. 79. The battery of any of claims 37-78, wherein the cathode comprises a metal selected from nickel, manganese, and cobalt.

80. 79. The battery of any of claims 37 to 78, wherein the cathode comprises about 70% to about 90% nickel.

81. 79. The battery of any of claims 37 to 78, wherein the cathode comprises from about 1% to about 15% manganese.

82. 79. The battery of any of claims 37 to 78, wherein the cathode comprises from about 1% to about 15% cobalt.

83. 79. The battery of any of claims 37-78, wherein the cathode comprises about 80% nickel, about 10% manganese, and about 10% cobalt.

84. 79. The battery of any of claims 37-78, wherein the cathode comprises about 90% nickel, about 5% manganese, and about 5% cobalt.

85. 85. The battery of any of claims 37 to 84, wherein the anode comprises from about 2% to about 75% silicon.

86. 85. The battery of any of claims 37 to 84, wherein the anode comprises from about 2% to about 70% silicon oxide graphite composite.

87. 85. The battery of any of claims 37-84, wherein the anode comprises from about 2% to about 70% amorphous silicon graphite composite.

88. 88. The battery of any of claims 37 to 87, wherein the battery is rechargeable and has a cycle life of about 150 to about 500 cycles.

89. 89. The battery of claim 88, wherein the battery has a cycle life of at least 200 cycles.

90. 89. The battery of claim 88, wherein the battery has a cycle life of at least 250 cycles.

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