Fluorinated electrolyte additives

Abstract

The present 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 for preparing fluorinated dialkyl carbonate and sulfite compounds useful in batteries, and electrolytes containing the fluorine compounds for use in batteries containing high Ni cathodes and silicon-containing anodes.

Description

[Technical Field]

[0001] Cross-reference of related applications This application is an international patent application claiming the benefits 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 reaction solvents for preparing fluorinated dialkyl carbonate and sulfite compounds useful for batteries, and to battery electrolytes comprising fluorinated dialkyl carbonate and sulfite compounds and low-level fluorinated ethers such as HFMOP. The use of fluorinated esters, carbonates, and ethers as components of the electrolyte improves the performance of electrochemical cells containing a high-Ni cathode such as NMC811 and a Si-containing anode. [Background technology]

[0003] Lithium-ion batteries are ubiquitous in our daily lives. 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 non-aqueous batteries that have cathodes composed of alkali metals, alkaline earth metals, or materials derived therefrom. For example, lithium-ion batteries generally use linear or cyclic carbonates such as dimethyl carbonate or ethylene carbonate. However, at battery voltages exceeding 4.4V, these compounds decompose, resulting in impaired battery performance. [Overview of the Initiative]

[0005] This disclosure provides, but is not limited to, methods for producing fluorinated compounds, including fluorinated organic carbonates and fluorinated organic sulfites. In some embodiments, the method comprises reacting a first reactant containing at least one fluorine atom with a second reactant of formula 20A or formula 20B, wherein the reactant of formula 20A or formula 20B contains a leaving group L 1 Includes. [ka]

[0006] The above reaction is carried out in the presence of a fluorinated solvent; R 1 This 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; L 2is 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, L 1 is selected from perfluoroalkyl sulfonate, tosylate, mesylate, halogen, nitrate, phosphate, thioether, amine, carboxylate, phenoxide, alkoxide, and amide. In some embodiments, L 1 is selected from halogen or -OR 2 group. In some embodiments, R 2 is alkyl sulfate or aryl sulfate. In some embodiments, L 1 is selected from chlorine, iodine, and bromine. In some embodiments, L 2 is selected from perfluoroalkyl sulfonate, tosylate, mesylate, halogen, nitrate, phosphate, thioether, amine, carboxylate, phenoxide, alkoxide, and amide. In some embodiments, L 2Halogen and -OR 3 Selected from the base. In some embodiments, R 3 L is an alkyl sulfate or aryl sulfate. In some embodiments, L 2 This 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 a methyl chloroformate or an 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 a 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 contains one or more groups selected from -CF3, -CHF2, -CH2F, -CHF-, and -CF2-. In some embodiments, the fluorinated solvent contains one or more -CF3 groups. In some embodiments, the fluorinated solvent contains two or more -CF3 groups.

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

[0008] In the formula, X is either O or S, and R 4 R is a partially fluorinated C1-C8 alkyl group; 5 R is a C1-C8 alkyl group which may optionally be fluorinated. In some embodiments, R 4 R is a partially fluorinated C1-C4 alkyl group; 5 The C1-C4 alkyl group is optionally fluorinated. In some embodiments, the fluorinating 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 fluorinating 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 disclosure also provides a battery comprising an electrolyte containing 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 has a cycle life of at least 250 cycles. In some embodiments, the fluorinated ether or thioether has formula 10. [ka]

[0010] In the formula, X is either O or S, and R 4 R5 is a partially fluorinated C1-C8 alkyl group; R5 is a C1-C8 alkyl group that may optionally be fluorinated. In some embodiments, R 4 R is a partially fluorinated C1-C4 alkyl group; 5is a C1-C4 alkyl group which may optionally be fluorinated. 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 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, or 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 fluorinated organic sulfite comprises one or more groups selected from -CF3, -CHF2, -CH2F, -CHF-, and -CF2-. In some embodiments, the fluorinated organic carbonate or fluorinated organic sulfite comprises one or more -CF3 groups. In some embodiments, the fluorinated organic carbonate or 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 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 disclosure also provides a battery comprising an electrolyte containing a solvent component, wherein the solvent component contains a fluorinated compound in an amount of about 1 ppm to about 60%, and the fluorinated compound has any of formulas I, II(a), II(b), III, or IV. [ka]

[0012] In the formula, R 10 and R 20 R is 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, R 20 is a fully or partially fluorinated C1-C6 alkyl group. In some embodiments, R 20 It contains one or more -CF3 groups. In some embodiments, R 20 It contains 1 to 3 -CF3 groups. In some embodiments, R 20 R is selected from trifluoroethyl or hexafluoroisopropyl. In some embodiments, R 10 R is selected from methyl, ethyl, n-propyl, and 2-propyl. In some embodiments, R 10 R 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, R 10 It contains one or more -CF3 groups. In some embodiments, R 10 It contains 1 to 3 -CF3 groups. In some embodiments, R 10 and R 20 They are identical.

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

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

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

[0016] In some embodiments, the compound of formula III is the 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 equation 10, X is either O or S, and R 4 R is a partially fluorinated C1-C8 alkyl group; 5 This is a C1-C8 alkyl group that may optionally be fluorinated.

[0019] In some embodiments, R 4 R is a partially fluorinated C1-C4 alkyl group, 5is a C1-C4 alkyl group which may optionally be fluorinated. 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 a fluorinated compound in an amount of about 1 ppm to about 5000 ppm. In some embodiments, the solvent component contains a fluorinated compound in an amount of about 0.0001% to about 5%. In some embodiments, the solvent component contains a 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 partially fluorinated organic carbonates and non-fluorinated organic carbonates. 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 fluorinated organic sulfite containing one or more 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, or 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 fluorinated organic sulfite contains one or more groups selected from -CF3, -CHF2, -CH2F, -CHF-, and -CF2-. In some embodiments, the fluorinated organic carbonate or fluorinated organic sulfite contains one or more -CF3 groups. In some embodiments, the fluorinated organic carbonate or 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 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) Selected from 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] This disclosure also provides batteries comprising an electrolyte as 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] This disclosure also provides a battery comprising an anode and a cathode as 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] This disclosure also provides a battery as described herein, which is rechargeable and 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 above summary and the following detailed descriptions in this disclosure will be better understood when read in conjunction with the attached drawings. [Brief explanation of the drawing]

[0031] [Figure 1] Figure 1 shows the improved high-temperature performance of a battery containing an NMC811 cathode and a silicon composite anode when trifluoroethyl methyl carbonate (F3EMC) is used as the fluorinating component of the electrolyte mixture, compared to when fluoroethylene carbonate (FEC) is used as the electrolyte.

[0032] [Figure 2] Figure 2 shows the performance improvement at high temperatures in a battery containing an NMC811 cathode and a silicon composite anode when using an electrolyte containing trifluoroethyl acetate ester compared to when using an electrolyte containing FEC.

[0033] [Figure 3] Figure 3 shows the improved high-temperature performance of a battery containing an NMC811 cathode and a silicon composite anode when using an electrolyte containing hexafluoro-2-methoxypropane (hexafluoro-2-propyl methyl ether) compared to when using an electrolyte containing fluoroethylene carbonate (FEC).

[0034] Detailed explanation For example, there is considerable interest in using electrodes with higher energy density, such as high-nickel cathodes like NMC811 and silicon composite anodes. Batteries manufactured using high-nickel NMC811 and equipped with silicon anodes are commercially important, but still require performance improvements. The main drawback is that the electrolyte in this type of battery decomposes, resulting in reduced cycle performance. Fluoroethylene carbonate (FEC) is widely used as an electrolyte additive or cosolvent in these systems and helps to form an SEI layer on the Si composite anode. The use of FEC has a significant drawback: it generates a large amount of gas within the cell, leading to safety issues.

[0035] This disclosure provides the use of other fluorinated carbonates, ethers, and esters in combination with FEC in the electrolyte to further improve battery cycle life. This disclosure further provides the use of trifluoromethylated carbonates in place of and / or in combination with FEC, resulting in a 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 disclosure provides a battery comprising an electrolyte containing a fluorinated ether or a 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, these ethers contain hexafluoroisopropyl methyl ether in an amount of 1 to 5000 ppm. In some embodiments, these ethers contain hexafluoroisopropyl methyl ether in an amount of 0.0001% to 2%. In some embodiments, the disclosure provides a battery comprising an electrolyte containing 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 dichloromethane solution of 2,2,2-trifluoroethanol and pyridine. 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, the presence of trace amounts of chlorine-containing solvent in the final product can adversely affect battery performance, and due to its toxicity, dichloromethane is not recommended for large-scale processes. Furthermore, the yield obtained with dichloromethane is not ideal for large-scale synthesis.

[0039] International Publication Nos. 2015083745 and 2015083747 describe the preparation of methyl 2,2,2-trifluoroethyl carbonate by adding methyl chloroformate to 2,2,2-trifluoroethanol and pyridine in triglycerides. However, triglycerides may remain in the final product, potentially causing disadvantages 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 required extremely low temperatures and excess reactants make this process undesirable both practically and economically.

[0041] Unless otherwise specified, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art to which this disclosure pertains. Any patents and publications referenced herein are incorporated herein by reference in their entirety.

[0042] definition Unless otherwise specified, the chemical structures shown 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 13 C or 14 Compounds in which carbon is replaced with 1C-enriched carbon are within the scope of this disclosure.

[0043] When a range is used herein to describe physical or chemical properties, such as molecular weight or chemical formula, it is intended to include all combinations and subcombinations of the range, as well as any specific embodiments contained therein. The use of the term “approximately” when referring to a numerical value or numerical range means that the numerical value or numerical range mentioned is an approximation within experimental variation (or statistical experimental error), and therefore such numerical value or numerical range may vary. Such 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,” “comprises,” “having,” or “including”) includes embodiments such as any composition, method, or process embodiment that “consist of” or “consist essentially of” the described features.

[0044] "Alkyl" consists only of carbon and hydrogen atoms, does not contain unsaturated atoms, and has 1 to 10 carbon atoms (for example, (C) 1-10 ) Alkyl or C 1-10This refers to a linear or branched hydrocarbon chain radical having an alkyl group. Where used herein, numerical ranges such as "1 to 10" always mean each integer within a given range, for example, "1 to 10 carbon atoms" means that the alkyl group may consist of 1 carbon atom, 2 carbon atoms, 3 carbon atoms, and so on, up to 10 carbon atoms. However, the above definition is intended to cover the term "alkyl" even when a numerical range is not specifically specified. Typical alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butylisobutyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, septyl, octyl, nonyl, and decyl. The alkyl group, for example, 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 herein, the alkyl group is independently a heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, -OR a , -SR a -OC(O)-R a , -N(R a )2, -C(O)R a , -C(O)OR a ,-OC(O)N(R a )2, -C(O)N(R a )2, -N(R a )C(O)OR a , -N(R a )C(O)R a , -N(R a )C(O)N(R a )2, N(R a )C(NR a )N(R a )2, -N(R a )S(O) t Ra (wherein t is 1 or 2), -S(O) t Ure a (wherein t is 1 or 2), -S(O) t N(R a )2 (wherein t is 1 or 2), or PO3(R a )2(each R a , may be independently substituted with one or more substituents (hydrogen, fluoroalkyl, carbocykyl, carbocykylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl).

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

[0046] "Alkylhetalil" means a -(alkyl)hetalil radical in which hetalil and alkyl are as disclosed herein, and optionally substituted with one or more substituents described as preferred substituents for aryl and alkyl, respectively.

[0047] "Alkyl heterocycloalkyl" means an -(alkyl) heterocyclyl radical in which alkyl and heterocycloalkyl are as disclosed herein and optionally substituted with one or more substituents described as preferred substituents for heterocycloalkyl and alkyl, respectively.

[0048] The "alkyne" portion refers to a group consisting of at least two carbon atoms and at least one carbon-carbon double bond, while the "alkyne" portion refers to a group consisting of at least two carbon atoms and at least one carbon-carbon triple bond. The alkyl portion can be branched, linear, or cyclic, whether saturated or unsaturated.

[0049] "Alkenyl" consists of only carbon and hydrogen atoms, contains at least one double bond, and is a straight-chain or branched hydrocarbon chain radical group having 2 to 10 carbon atoms (i.e., (C 2-10 ) alkenyl or C 2-10 alkenyl). When described in this specification, the numerical range such as "2 to 10" always means each integer within the specified range. For example, "2 to 10 carbon atoms" means that the alkyl group can consist of 2 carbon atoms, 3 carbon atoms, etc., up to a maximum of 10 carbon atoms. The alkenyl moiety, for example, ethenyl (i.e., vinyl), prop-1-enyl (i.e., allyl), but-1-enyl, pent-1-enyl, and penta-1,4-dienyl, etc., can be bonded to the rest of the molecule by a single bond. Unless otherwise specified in this specification, the said alkenyl group is independently alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilyl, -OR a , -SR<000007o>, -OC(O)-R a , -N(R a )2, -C(O)R a , -C(O)OR a , -OC(O)N(R a )2, -C(O)N(R a )2, -N(R a )C(O)OR a , -N(R a )C(O)R a , -N(R a )C(O)N(R a )2, N(R a )C(NR a )N(R a )2, -N(R a )S(O) t R a (where t is 1 or 2), -S(O) t OR a (where t is 1 or 2), -S(O) t N(R a It should be noted that in the original text, there is a misspelling in "<000007o> ", which should be " a ". The above translation has been corrected accordingly.)2 (where t is 1 or 2), or PO3(R a )2 (each R a is independently hydrogen, alkyl, fluoroalkyl, carbocyclic, carbocyclic alkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkyl alkyl, heteroaryl, or heteroaryl alkyl) and may be substituted by one or more substituents.

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

[0051] "Alkynyl" consists of only carbon and hydrogen atoms, contains at least one triple bond, and means a straight-chain or branched hydrocarbon chain radical group having 2 to 10 carbon atoms (i.e., (C 2-10 )alkynyl or C 2-10 alkynyl). When described herein, the numerical range such as "2 to 10" always means each integer within the specified range. For example, "2 to 10 carbon atoms" means that the alkyl group can consist of 2 carbon atoms, 3 carbon atoms, etc., up to a maximum of 10 carbon atoms. The alkynyl, such as ethynyl, propynyl, butynyl, pentynyl, and hexynyl, etc., can be bonded to the rest of the molecule by a single bond. Unless otherwise specified herein, the alkynyl group is independently alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilyl, -OR[[ID=1​​​​​​​​​​​​)2, -C(O)N(R a )2, -N(R a )C(O)OR a , -N(R a )C(O)R a , -N(R a )C(O)N(R a )2, N(R a )C(NR a )N(R a )2, -N(R a )S(O) t R a (wherein t is 1 or 2), -S(O) t Ure a (wherein t is 1 or 2), -S(O) t N(R a )2 (wherein t is 1 or 2), or PO3(R a )2(each R a It may be independently substituted with one or more substituents (hydrogen, alkyl, fluoroalkyl, carbocykyl, carbocykylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl).

[0052] "Alkynyl-cycloalkyl" means an -(alkynyl)cycloalkyl radical in which alkynyl and cycloalkyl are as disclosed herein and optionally substituted with one or more substituents described as preferred substituents for alkynyl and cycloalkyl, respectively.

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

[0054] "Carboxyl" refers to the -(C=O)OH radical.

[0055] "Cyano" refers to the -CN radical.

[0056] "Cycloalkyl" refers to a monocyclic or polycyclic radical that contains only carbon and hydrogen and may be saturated or partially unsaturated. A cycloalkyl group is a group having 3 to 10 ring atoms (i.e., (C 3-10 ) Cycloalkyl or C 3-10 Includes cycloalkyl groups. Where described herein, numerical ranges such as "3 to 10" always mean each integer within a given range, for example, "3 to 10 carbon atoms" means that a cycloalkyl group may consist of up to 10 carbon atoms, such as 3 carbon atoms. Exemplary examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, norbornyl. Unless otherwise specified herein, cycloalkynyl groups are independently alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, -OR a , -SR a -OC(O)-R a , -N(R a )2, -C(O)R a , -C(O)OR a ,-OC(O)N(R a )2, -C(O)N(R a )2, -N(R a )C(O)OR a , -N(R a )C(O)R a , -N(R a )C(O)N(R a )2, N(R a )C(NR a )N(R a )2, -N(R a )S(O) t R a (wherein t is 1 or 2), -S(O) t Ure a (wherein t is 1 or 2), -S(O) t N(Ra )2 (wherein t is 1 or 2), or PO3(R a )2(each R a It may be independently substituted with one or more substituents (hydrogen, alkyl, fluoroalkyl, carbocykyl, carbocykylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl).

[0057] "Cycloalkyl-alkenyl" means a -(cycloalkyl)alkenyl radical in which cycloalkyl and alkenyl are as disclosed herein and optionally substituted with one or more substituents described as preferred substituents for cycloalkyl and alkenyl, respectively.

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

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

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

[0061] The term "substituted alkoxy" means an alkoxy in which the alkyl component is substituted (i.e., -O-(substituted alkyl)). Unless otherwise specified herein, the alkyl portion of the alkynyl group is independently alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, -OR a , -SR a -OC(O)-R a , -N(R a )2, -C(O)R a , -C(O)OR a ,-OC(O)N(R a )2, -C(O)N(R a )2, -N(R a )C(O)OR a , -N(R a )C(O)R a , -N(R a )C(O)N(R a )2, N(R a )C(NR a )N(R a )2, -N(R a )S(O) t R a (wherein t is 1 or 2), -S(O) t Ure a (wherein t is 1 or 2), -S(O) t N(R a )2 (wherein t is 1 or 2), or PO3(R a )2(each R a It may be independently substituted with one or more substituents (hydrogen, alkyl, fluoroalkyl, carbocykyl, carbocykylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl).

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

[0063] The term "substituted alkoxycarbonyl" means the group (substituted alkyl)-OC(O)-, where the group is bonded to the parent structure via carbonyl functionality. Unless otherwise specified herein, the alkyl portion of an alkoxycarbonyl group is independently alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, -OR a , -SR a -OC(O)-R a , -N(R a )2, -C(O)R a , -C(O)OR a ,-OC(O)N(R a )2, -C(O)N(R a )2, -N(R a )C(O)OR a , -N(R a )C(O)R a , -N(R a )C(O)N(R a )2, N(R a )C(NR a )N(R a )2, -N(R a )S(O) t R a (wherein t is 1 or 2), -S(O) t Ure a (wherein t is 1 or 2), -S(O) t N(R a )2 (wherein t is 1 or 2), or PO3(Ra )2(each R a It may be independently substituted with one or more substituents (hydrogen, alkyl, fluoroalkyl, carbocykyl, carbocykylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl).

[0064] "Acyl" means the groups (alkyl)-C(O)-, (aryl)-C(O)-, (heteroaryl)-C(O)-, (heteroalkyl)-C(O)-, and (heterocycloalkyl)-C(O)-, where the groups are bonded to the parent structure via a carbonyl functional group. When the R radical is heteroaryl or heterocycloalkyl, the heterocyclic or chain atoms contribute to the total number of chain or ring atoms. Unless otherwise specified herein, the alkyl, acyl, or heteroaryl portion of the acyl group is independently alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, -OR a , -SR a -OC(O)-R a , -N(R a )2, -C(O)R a , -C(O)OR a ,-OC(O)N(R a )2, -C(O)N(R a )2, -N(R a )C(O)OR a , -N(R a )C(O)R a , -N(R a )C(O)N(R a )2, N(R a )C(NR a )N(R a )2, -N(R a )S(O) t R a (wherein t is 1 or 2), -S(O) t Ure a(wherein t is 1 or 2), -S(O) t N(R a )2 (wherein t is 1 or 2), or PO3(R a )2(each R a It may be independently substituted with one or more substituents (hydrogen, alkyl, fluoroalkyl, carbocykyl, carbocykylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl).

[0065] "Acyloxy" means R(C=O)O- radical, where R is an alkyl, aryl, heteroaryl, heteroalkyl, or heterocycloalkyl as described herein. When the R radical is a heteroaryl or heterocycloalkyl, the heterocyclic or chain atoms contribute to the total number of chain or ring atoms. Unless otherwise specified herein, the R of an acyloxy group can independently be alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, or -OR a , -SR a -OC(O)-R a , -N(R a )2, -C(O)R a , -C(O)OR a ,-OC(O)N(R a )2, -C(O)N(R a )2, -N(R a )C(O)OR a , -N(R a )C(O)R a , -N(R a )C(O)N(R a )2, N(R a )C(NR a )N(R a )2, -N(R a )S(O) t R a (wherein t is 1 or 2), -S(O) t Urea (wherein t is 1 or 2), -S(O) t N(R a )2 (wherein t is 1 or 2), or PO3(R a )2(each R a It may be independently substituted with one or more substituents (hydrogen, alkyl, fluoroalkyl, carbocykyl, carbocykylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl).

[0066] "Acyl sulfonamide" is -S(O)2-N(R a )-C(=O)- means radical, R a This group is hydrogen, alkyl, fluoroalkyl, carbocyl, carbocylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl. Unless otherwise specified herein, the acylsulfonamide group is independently alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, -OR a , -SR a -OC(O)-R a , -N(R a )2, -C(O)R a , -C(O)OR a ,-OC(O)N(R a )2, -C(O)N(R a )2, -N(R a )C(O)OR a , -N(R a )C(O)R a , -N(R a )C(O)N(R a )2, N(R a )C(NR a )N(R a )2, -N(R a )S(O) t R a(wherein t is 1 or 2), -S(O) t Ure a (wherein t is 1 or 2), -S(O) t N(R a )2 (wherein t is 1 or 2), or PO3(R a )2(each R a It may be independently substituted with one or more substituents (hydrogen, alkyl, fluoroalkyl, carbocykyl, carbocykylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl).

[0067] "Amino" or "amine" is -N(R a ) means a radical group, and unless otherwise specified herein, each R a These are independently hydrogen, alkyl, fluoroalkyl, carbocyl, carbocylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl. -N(R a ) Two units have two Rs other than hydrogen a If substituents are present, they can combine with the nitrogen atom to form a 4, 5, 6, or 7-membered ring. For example, -N(R a )2 is intended to include, but is not limited to, 1-pyrrolidinyl and 4-morpholinyl. Unless otherwise specified herein, amino groups are independently alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, -OR a , -SR a -OC(O)-R a , -N(R a )2, -C(O)R a , -C(O)OR a ,-OC(O)N(R a )2, -C(O)N(R a )2, -N(R a)C(O)OR a , -N(R a )C(O)R a , -N(R a )C(O)N(R a )2, N(R a )C(NR a )N(R a )2, -N(R a )S(O) t R a (wherein t is 1 or 2), -S(O) t Ure a (wherein t is 1 or 2), -S(O) t N(R a )2 (wherein t is 1 or 2), or PO3(R a )2(each R a It may be independently substituted with one or more substituents (hydrogen, alkyl, fluoroalkyl, carbocykyl, carbocykylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl).

[0068] The term "substituted amino" also refers to the group-NHR, as described above. a and NR a R a This refers to the N-oxide. The N-oxide 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)2 or NHC(O)R, where R is selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, heteroaryl (bonded via a ring carbon), and heteroalicyclic (bonded via a ring carbon) (each of these moieties may be optionally substituted with itself). The R2 of -N(R)2 in the amide, together with the nitrogen to which it is bonded, can form a 4, 5, 6, or 7-membered ring. Unless otherwise specified herein, the amide group may be independently substituted with one or more substituents described herein for alkyl, cycloalkyl, aryl, heteroaryl, or heterocycloalkyl groups. The amide may be an amino acid or peptide molecule that binds to the compounds disclosed herein to form a prodrug. Procedures and specific groups for generating such amides are known to those skilled in the art and are found in influential sources, e.g., Greene and Wuts, Protective Groups in Organic Synthesis, 3 rd This can be readily found in Ed., John Wiley & Sons, New York, NY, 1999 (the entire work is incorporated herein by reference).

[0070] "Aromatic," "aryl," or "Ar" refers to an aromatic radical having 6 to 10 ring atoms having at least one ring with a conjugated pi-electron system that is carbocyclic (e.g., C6-C 10 Aromatic or C6-C 10The term refers to aryl groups (e.g., phenyl, fluorenyl, and naphthyl). Divalent radicals formed from substituted benzene derivatives with free valence on the ring atoms are called substituted phenylene radicals. Divalent radicals derived from monovalent polycyclic hydrocarbon radicals whose names end in "-yl" by removing one hydrogen atom from a free-valence carbon atom are named by adding "-idene" to the name of the corresponding monovalent radical. For example, a naphthyl group with two bond sites is called naphthylidene. Where used herein, numerical ranges such as "6 to 10" always mean each integer within a given range. For example, "6 to 10 ring atoms" means that an aryl group can consist of up to 10 ring atoms, such as 6 ring atoms or 7 ring atoms. The term includes monocyclic or fused polycyclic (i.e., rings sharing adjacent pairs of ring atoms) groups. Unless otherwise specified herein, the aryl moiety is independently alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, -OR a , -SR a -OC(O)-R a , -N(R a )2, -C(O)R a , -C(O)OR a ,-OC(O)N(R a )2, -C(O)N(R a )2, -N(R a )C(O)OR a , -N(R a )C(O)R a , -N(R a )C(O)N(R a )2, N(R a )C(NR a )N(R a )2, -N(R a )S(O) t R a (wherein t is 1 or 2), -S(O) t Ure a (wherein t is 1 or 2), -S(O) tN(R a )2 (wherein t is 1 or 2), or PO3(R a )2(each R a It may be independently substituted with one or more substituents (hydrogen, alkyl, fluoroalkyl, carbocykyl, carbocykylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl).

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

[0072] The term "substituted aryloxy" means an aryloxy in which an aryl substituent is substituted (i.e., -O-(substituted aryl)). Unless otherwise specified herein, the aryl portion of an aryloxy group can independently be alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, -OR a , -SR a -OC(O)-R a , -N(R a )2, -C(O)R a , -C(O)OR a ,-OC(O)N(R a )2, -C(O)N(R a )2, -N(R a )C(O)OR a , -N(R a )C(O)R a , -N(R a )C(O)N(R a )2, N(R a )C(NR a )N(R a )2, -N(R a )S(O) t R a (wherein t is 1 or 2), -S(O) t Ure a (wherein t is 1 or 2), -S(O) tN(R a )2 (wherein t is 1 or 2), or PO3(R a )2(each R a It may be independently substituted with one or more substituents (hydrogen, alkyl, fluoroalkyl, carbocykyl, carbocykylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl).

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

[0074] "Ester" refers to a chemical radical of the formula -COOR, where R is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl (bonded via a ring carbon), and heteroalicyclic (bonded via a ring carbon). Procedures and specific groups for producing esters are known to those skilled in the art and are found in influential sources, such as Greene and Wuts, Protective Groups in Organic Synthesis, 3. rd Ed., John Wiley & Sons, New York, NY, 1999 (the entire work is incorporated herein by reference) can be readily found. Unless otherwise specified herein, ester groups are independently alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, -OR a , -SR a -OC(O)-R a , -N(R a )2, -C(O)R a , -C(O)OR a ,-OC(O)N(R a )2, -C(O)N(Ra )2, -N(R a )C(O)OR a , -N(R a )C(O)R a , -N(R a )C(O)N(R a )2, N(R a )C(NR a )N(R a )2, -N(R a )S(O) t R a (wherein t is 1 or 2), -S(O) t Ure a (wherein t is 1 or 2), -S(O) t N(R a )2 (wherein t is 1 or 2), or PO3(R a )2(each R a It may be independently substituted with one or more substituents (hydrogen, alkyl, fluoroalkyl, carbocykyl, carbocykylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl).

[0075] "Fluoroalkyl" means the defined alkyl radical which is substituted with one or more fluororadicals as defined above, such as trifluoromethyl, difluoromethyl, 2,2,2-trifluoroethyl, 1-fluoromethyl-2-fluoroethyl, etc. The alkyl portion of the fluoroalkyl radical may be substituted with an alkyl group as defined above.

[0076] The terms "halo," "halide," or "halogen" are intended to mean fluoro, chloro, bromo, or iodine. The terms "haloalkyl," "haloalkenyl," "haloalkynyl," and "haloalkoxy" include alkyl, alkenyl, alkynyl, and alkoxy structures 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" mean alkyl, alkenyl, and alkynyl radicals, which may be optionally substituted, and have one or more skeletal chain atoms selected from atoms other than carbon, e.g., oxygen, nitrogen, sulfur, phosphorus, or combinations thereof. A numerical range is given, for example, C1-C4 heteroalkyl means a total chain length of 4 atoms in this example. Heteroalkyls are independently alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, nitro, oxo, thioxo, trimethylsilanyl, -OR a , -SR a -OC(O)-R a , -N(R a )2, -C(O)R a , -C(O)OR a ,-OC(O)N(R a )2, -C(O)N(R a )2, -N(R a )C(O)OR a , -N(R a )C(O)R a , -N(R a )C(O)N(R a )2, N(R a )C(NR a )N(R a )2, -N(R a )S(O) t R a (wherein t is 1 or 2), -S(O) t Ure a (wherein t is 1 or 2), -S(O) t N(R a )2 (wherein t is 1 or 2), or PO3(R a )2(each R aIt may be independently substituted with one or more substituents (hydrogen, alkyl, fluoroalkyl, carbocykyl, carbocykylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl).

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

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

[0080] "Heteroalkyl heterocycloalkyl" means -(heteroalkyl)heterocycloalkyl radical, where heteroalkyl and heterocycloalkyl are as disclosed herein and may optionally be substituted with one or more substituents described as suitable substituents for heteroalkyl and heterocycloalkyl, respectively.

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

[0082] "Heteroaryl," "heteroaromatic," "HetAr," or "Het" refers to a 5-18 member aromatic radical (e.g., C5-C) containing one or more ring heteroatoms selected from nitrogen, oxygen, and sulfur. 13The term "heteroaryl" means a monocyclic, bicyclic, tricyclic, or tetracyclic ring system. Where used herein, numerical ranges such as "5 to 18" always mean each integer within a given range; for example, "5 to 18 ring atoms" means that the heteroaryl group may consist of 5 ring atoms, 6 ring atoms, and so on, up to 18 ring atoms. Divalent radicals derived from monovalent heteroaryl radicals whose names end in "-yl" by removing one hydrogen atom from an atom with free valence are named by adding "-idene" to the name of the corresponding monovalent radical. For example, a pyridyl group with two bond sites is called pyridylidene. The nitrogen-containing "heteroaromatic" or "heteroaryl" moiety means an aromatic group in which at least one of the ring skeleton atoms is a nitrogen atom. Polycyclic heteroaryl groups may or may not be condensed. The heteroatoms of the heteroaryl radical may optionally be oxidized. If present, one or more nitrogen atoms may optionally be quaternized. The heteroaryl can be bonded to the rest of the molecule via any atom in the ring. Examples of heteroaryls, but not limited to, include azepinyl, acridinyl, benzimidazolyl, benzindolyl, 1,3-benzodioxolyl, benzofuranil, benzoxazolyl, benzo[d]thiazolyl, benzothiadiazolyl, benzo[b][1,4]dioxepinyl, benzo[b][1,4]oxazinyl, 1,4-benzodioxanil, benzonaphthofuranil, benzoxazolyl, benzodioxolyl, benzodioxynyl, benzoxazolyl, benzopyranil, benzopyranonil, benzofuranil, and Nzofuranol, benzofuranol, benzothiazolyl, benzothienyl (benzothiophenyl), benzothieno[3,2-d]pyrimidinyl, benzotriazolyl, benzo[4,6]imidazo[1,2-a]pyrimidinyl, 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, isoin Drill, indolinyl, isoindolinyl, isoquinolyl, indolidinyl, isoxazolyl, 5,8-methano-5,6,7,8-tetrahydroquinazolinyl, naphthilidinyl, 1,6-naphthilidinolyl, oxadiazolyl, 2-oxoazepinyl, oxazolyl, oxyranil, 5,6,6a,7,8,9,10,10a-octahydrobenzo[h]quinazolinyl, 1-phenyl-1H-pyrrolyl, phenazinyl, phenothiazinyl, phenoxazinyl, Phthalazinyl, pteridinyl, prinyl, pyranyl, pyrrolyl, pyrazolyl, pyrazolo[3,4-d]pyrimidinyl, pyridinyl, pyrido[3,2-d]pyrimidinyl, pyrido[3,4-d]pyrimidinyl, pyrazinyl, pyrimidinyl, pyridadinyl, pyrrolyl, quinazolinyl, quinoxalinyl, quinolinyl, isoquinolinyl, tetrahydroquinolinyl, 5,6,7,8-tetrahydroquinazolinyl, 5,6,7,8-tetrahydrobenzo[4,5]thieno[ Examples include 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, thiapyranil, triazolyl, tetrazolyl, triazinyl, thieno[2,3-d]pyrimidinyl, thieno[3,2-d]pyrimidinyl, thieno[2,3-c]pyrimidinyl, and thiophenyl (i.e., thienyl). Unless otherwise specified herein, heteroaryl moieties are independently alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, -OR, a, -SR a -OC(O)-R a , -N(R a )2, -C(O)R a , -C(O)OR a ,-OC(O)N(R a )2, -C(O)N(R a )2, -N(R a )C(O)OR a , -N(R a )C(O)R a , -N(R a )C(O)N(R a )2, N(R a )C(NR a )N(R a )2, -N(R a )S(O) t R a (wherein t is 1 or 2), -S(O) t Ure a (wherein t is 1 or 2), -S(O) t N(R a )2 (wherein t is 1 or 2), or PO3(R a )2(each R a It may be independently substituted with one or more substituents (hydrogen, alkyl, fluoroalkyl, carbocykyl, carbocykylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl).

[0083] Substituted heteroaryls also include ring systems substituted with one or more oxide (-O-) substituents, such as pyridinyl N-oxides.

[0084] "Heteroarylalkyl" means a portion having an aryl portion as described herein bonded to an alkylene portion as described herein, with the bond to the rest of the molecule being via an alkylene group.

[0085] "Hypercycloalkyl" means a stable 3-18 member non-aromatic ring radical comprising 2-12 carbon atoms and 1-6 heteroatoms selected from nitrogen, oxygen, and sulfur. Where used herein, numerical ranges such as "3-18" always mean each integer within a given range; for example, "3-18 ring atoms" means that the heterocycloalkyl can consist of 3 ring atoms, 4 ring atoms, and so on, up to 18 ring atoms. Unless otherwise specified herein, the heterocycloalkyl radical is a monocyclic, bicyclic, tricyclic, or tetracyclic ring system, which may include condensed or bridged ring systems. The heteroatoms in the heterocycloalkyl radical may optionally be oxidized. One or more nitrogen atoms, if present, may optionally be quaternized. The heterocycloalkyl radical is partially or completely saturated. The heterocycloalkyl can be bonded to the rest of the molecule via any atom of the ring. Examples of such heterocycloalkyl radicals include, but are not limited to, dioxolanil, thienyl[1,3]dithianil, decahydroisoquinolyl, imidazolinil, imidazolidinil, isothiazolidinil, isoxazolidinil, morpholinil, octahydroindolyl, octahydroisoindolyl, 2-oxopiperazinil, 2-oxopiperidinil, 2-oxopyrrolidinil, oxazolidinil, piperidinil, piperazinil, 4-piperidonyl, pyrrolidinil, pyrazolidinil, quinuclidinil, thiazolidinil, tetrahydrofuryl, trithianil, tetrahydropyranil, thiomorpholinil, thiamorpholinil, 1-oxo-thiomorpholinil, and 1,1-dioxo-thiomorpholinil. Unless otherwise specified herein, the heterocycloalkyl moiety is independently alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, nitro, oxo, thioxo, trimethylsilanyl, -OR a , -SR a -OC(O)-R a , -N(R a )2, -C(O)R a, -C(O)OR a ,-OC(O)N(R a )2, -C(O)N(R a )2, -N(R a )C(O)OR a , -N(R a )C(O)R a , -N(R a )C(O)N(R a )2, N(R a )C(NR a )N(R a )2, -N(R a )S(O) t R a (wherein t is 1 or 2), -S(O) t Ure a (wherein t is 1 or 2), -S(O) t N(R a )2 (wherein t is 1 or 2), or PO3(R a )2(each R a It may be independently substituted with one or more substituents (hydrogen, alkyl, fluoroalkyl, carbocykyl, carbocykylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl).

[0086] "Heterocycloalkyl" also includes non-aromatic 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 a combination of oxygen, sulfur, nitrogen, and at least one of the aforementioned 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.

[0087] "Nitro" refers to the -NO2 radical.

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

[0089] "Oxo" means =O radical.

[0090] "Isomers" are different compounds that have the same molecular formula. "Stereoisomers" are isomers that differ only in the spatial arrangement of their atoms, i.e., in their stereochemical structure. "Enantiomers" are pairs of stereoisomers that are mirror images of each other and cannot be superimposed. A 1:1 mixture of a pair of enantiomers is a "racemic" mixture. "(±)" is used to indicate a racemic mixture as needed. "Diastereoisomers" are stereoisomers that have at least two asymmetric atoms but are not mirror images of each other. Absolute stereochemistry is determined according to the Cahn-Ingold-Prelog RS system. If a compound is a pure enantiomer, the stereochemistry at each chiral carbon can be determined by either (R) or (S). Split compounds with unknown absolute configuration can be determined by either (+) or (-) depending on the direction in which plane polarization is rotated at the wavelength of the sodium D line (dextrorotatory or levorotatory). Certain compounds described herein contain one or more chiral centers and may therefore give rise to enantiomers, diastereomers, and other stereoisomers that can be defined as (R) or (S) from the viewpoint of absolute stereochemistry. The chemicals, pharmaceutical compositions, and methods described herein 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 they can be divided using conventional techniques. Where a compound described herein contains an olefinic double bond or other geometrically asymmetric centers, unless otherwise specified, the compound is intended to include both E and Z geometric isomers.

[0091] As used herein, "enantiomer purity" refers to the relative amount of the presence of a particular enantiomer, expressed as a percentage of other enantiomers. For example, if a compound that may have (R)- or (S)-isomer configurations exists as a racemic mixture, the enantiomer purity is about 50% with respect to the (R)- or (S)-isomer. If the compound has more of one isomer than the other, for example, 80% (S)-isomer and 20% (R)-isomer, the enantiomer purity of the compound with respect to the (S)-isomer is 80%. The enantiomer purity of a compound can be determined by many methods known in the art, including, but not limited to, chromatography using a chiral support, polarization measurement of the rotation of polarization, nuclear magnetic resonance spectroscopy using a chiral shift reagent (the chiral shift reagent is, but not limited to, a lanthanide-containing chiral complex or Pirkle's reagent), or derivatization of the compound using a chiral compound such as Mosher's acid followed by chromatography or nuclear magnetic resonance spectroscopy.

[0092] Enantiomers can be isolated from the mixture 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, for example, Jacques, et al., Enantiomers, Racemates and Resolutions, Wiley Interscience, New York (1981); EL Eliel, Stereochemistry of Carbon Compounds, McGraw-Hill, New York (1962); and EL Eliel and SH Wilen, Stereochemistry of Organic Compounds, Wiley-Interscience, New York (1994).

[0093] As used herein, the terms “enantiomerically concentrated” and “non-racemic” mean a composition in which the weight percentage of one enantiomer is greater than the amount of that enantiomer in a control mixture of racemic compositions (e.g., greater than 1:1 by weight). For example, an enantiomerically concentrated preparation of (S)-enantiomer means a preparation of the compound in which the (S)-enantiomer is greater than 50% by weight relative to the (R)-enantiomer, e.g., at least 75% by weight or at least 80% by weight. In some embodiments, the concentration can significantly exceed 80% by weight, resulting in a “substantially concentrated” or “substantially non-racemic” preparation, which means a preparation of a composition in which one enantiomer is greater than 85% by weight relative to the other enantiomer, e.g., at least 90% by weight or at least 95% by weight, etc. The terms "enantiomerically pure" or "substantially pure in enantiomers" mean a composition containing at least 98% of one enantiomer and less than 2% of the opposite enantiomer.

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

[0095] "Tautomers" are structurally different isomers that are interconverted by tautomerization. "Tautomerism" is a form of isomerization and includes prototropic or proton-shift tautomerism, which is considered a subset of acid-base chemistry. "Prototropic tautomerism" or "proton-shift tautomerism" involves the movement of a proton with a change in bond order and often involves the exchange of a single bond adjacent to a 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 the tautomers of pyridin-4-ol and pyridin-4(1H)-one.

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

[0097] "A 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 another unprotected reactive site and can then be easily removed or deprotected after completion of the selective reaction. 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] "A solvate" means a compound that is physically associated with one or more molecules of a pharmaceutically acceptable solvent.

[0099] "Substituted" means that the group being referred to can be bonded to one or more additional groups, radicals, or moieties independently and individually 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 their protected derivatives. The substituent itself 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" means any substitution by a particular group, radical, or moiety.

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

[0101] "Sulfinyl" means a group 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 a group comprising -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" means a -S(=O)2-NRR radical, where each R is independently selected from groups consisting of hydrogen, alkyl, cycloalkyl, aryl, heteroaryl (bonded via a ring carbon), and heteroalicyclic (bonded via a ring carbon). The -NRR R group of the -S(=O)2-NRR radical, together with the nitrogen to which it is bonded, can form a 4, 5, 6, or 7-membered ring. The sulfonamide group may optionally be substituted with one or more substituents described for alkyl, cycloalkyl, aryl, and heteroaryl groups, respectively.

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

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

[0106] The compounds of this disclosure also include crystalline and amorphous forms of the compounds, including, for example, polymorphs, pseudopolymorphs, solvates, hydrates, non-solvated polymorphs (including anhydrous), conformational polymorphs, and amorphous forms of the compounds, as well as mixtures thereof. Unless a specific crystalline or amorphous form is referred to, “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), conformational polymorphs, and amorphous forms, as well as mixtures thereof.

[0107] To avoid misunderstanding, it is intended that specific features (e.g., integers, properties, values, uses, diseases, formulas, compounds, or groups) described in connection with a particular aspect, embodiment, or example of this disclosure are applicable to other aspects, embodiments, or examples described herein, unless otherwise incompatible. Such features may be used as appropriate in conjunction with any of the definitions, claims, or embodiments defined herein. Any feature disclosed herein (including the accompanying claims, abstract, and drawings), and / or any step of any method or process so thus disclosed, may be combined in any combination, except for any combination in which at least some of the features and / or steps are mutually exclusive. This disclosure is not limited to the details of the disclosed embodiments. This disclosure extends to any novel one or combination of any feature disclosed herein (including the accompanying claims, abstract, and drawings), or any novel one or combination of any step of any method or process so thus disclosed.

[0108] Furthermore, as used herein, the term “approximately” means that dimensions, sizes, compositions, parameters, shapes, and other quantities and characteristics are not, do not need to be, exact, and may be approximate and / or greater or less, as necessary, and may reflect tolerances, conversion factors, rounding, measurement errors, and other factors known to those skilled in the art. In general, dimensions, sizes, compositions, parameters, shapes, or other quantities or characteristics are “approximately” or “roughly,” whether or not they are explicitly stated to be so. It should be noted that very different embodiments of size, shape, and dimensions may adopt the configurations described.

[0109] Furthermore, the transitional phrases “comprising,” “consisting essentially of,” and “consisting of” define the scope of the claims with respect to the exclusion of any additional claimed elements or processes (if any) that are not described, when used in the attached claims in their original and modified forms. The term “comprising” is intended to be inclusive or open-ended and does not exclude any additional, undescribed elements, methods, processes, or materials. The term “consisting of” excludes elements, processes, or materials other than those identified in the claims and, in the latter case, impurities that are not typically associated with the identified materials. The term “consisting essentially of” limits the scope of the claims to those that do not substantially affect the identified elements, processes, or materials and the basic and novel properties of the claimed embodiments. Alternatively, all embodiments of this disclosure can be more specifically defined by any of the following transitional phrases: “comprising,” “consisting essentially of,” and “consisting of.”

[0110] Fluorinating solvents for producing fluorinated compounds This disclosure provides, without limitation, methods and processes for producing fluorinated dialkyl carbonates including 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, and bis(1,1,1,3,3,3-hexafluoroisopropyl) carbonate, as well as, without limitation, fluorinated dialkyl sulfites including 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, co-solvents, and additives in high-voltage lithium-ion batteries, several problems have existed in the laboratory-scale synthesis, workup, and purification of fluorinated carbonates. While we do not wish to be bound by any particular theory, it is believed that such problems can be addressed by a sensible selection of solvents. In some embodiments, HFMOPs have been chosen, at least in part, for their ability to control the exothermic effects of the specific chemical reactions involved, simplify the workup, be easily removed, and be harmless in the battery.

[0112] In some embodiments, the present disclosure provides methods for producing fluorinated compounds, including fluorinated organic carbonates and fluorinated organic sulfites, without limiting them. In some embodiments, the method comprises reacting a first reactant containing at least one fluorine atom with a second reactant of formula 20A or formula 20B, wherein the reactant of formula 20A or formula 20B contains a leaving group L 1 Includes. [ka]

[0113] The above reaction is carried out in the presence of a fluorinated solvent; R 1 This 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; L 2 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, L 1 L is selected from perfluoroalkyl sulfonates, tosylates, mesylates, halogens, nitrates, phosphates, thioethers, amines, carboxylates, phenoxides, alkoxides, and amides. In some embodiments, L 1 is halogen or -OR 2Selected from the base. In some embodiments, R 2 L is an alkyl sulfate or aryl sulfate. In some embodiments, L 1 L is selected from chlorine, iodine, and bromine. In some embodiments, L 2 L is selected from perfluoroalkyl sulfonates, tosylates, mesylates, halogens, nitrates, phosphates, thioethers, amines, carboxylates, phenoxides, alkoxides, and amides. In some embodiments, L 2 Halogen and -OR 3 Selected from the base. In some embodiments, R 3 L is an alkyl sulfate or aryl sulfate. In some embodiments, L 2This 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 a methyl chloroformate or an 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 a 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 contains one or more groups selected from -CF3, -CHF2, -CH2F, -CHF-, and -CF2-. In some embodiments, the fluorinated solvent contains one or more -CF3 groups. In some embodiments, the fluorinated solvent contains two or more -CF3 groups.

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

[0115] In the formula, X is O or S, and R 4 is a partially fluorinated C1-C8 alkyl group; R 5 is an optionally fluorinated C1-C8 alkyl group. In some embodiments, R 4 is a partially fluorinated C1-C4 alkyl group; R 5 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).

Chemical formula

[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 exothermic reaction with external cooling water to maintain an internal temperature below 35°C. First, tetraglyme (bp: 275-276°C) was used to facilitate purification, as the low-boiling point product theoretically distills off first during distillation. However, although we do not wish to be bound by any particular theory, the relatively high heat capacity of tetraglyme is thought to make it difficult to control the exothermic reaction and result in a longer methyl chloroformate addition time (>3 hours). Using the method and process described herein, cooling with water is more effective and the addition time is reduced to approximately 1 hour.

[0118] As described herein, in some embodiments, the work-up of the reaction involves neutralizing any remaining triethylamine and dissolving the triethylamine salt formed during the reaction in a dilute solution of hydrochloric acid. While we do not wish to be bound by any particular theory, tetraglycerides are considered a miscible solvent with both aqueous quench and organic reaction components, making it difficult to completely remove water from the organic phase, and a water-free organic phase is considered important to avoid hydrolysis of carbonates in subsequent distillation. Adding a water-immiscible cosolvent such as HFMOP improves this. In some embodiments, the reaction itself is carried out in HFMOP, eliminating the need for a secondary solvent and allowing for a simplification of the work-up.

[0119] As described herein, in some embodiments, the purification process is achieved by fractional distillation at atmospheric pressure. While we do not wish to be bound by any particular theory, low-boiling point HFMOP (bp: 50°C) is considered to be far easier to remove for recycling than high-boiling point solvents such as triglycerides and tetraglycerides. Furthermore, fluorinated ethers such as HFMOP have been shown to provide advantages in the cycle life of lithium-ion batteries. Therefore, while we do not wish to be bound by any particular theory, HFMOP remaining in the final product is considered not to impair battery performance, unlike conventional solvents used in the preparation of these chemicals.

[0120] Similarly, HFMOP has been used in the synthesis of fluorinated alkyl sulfites. This reaction has been previously 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 a solvent is mitigated by the fact that the reaction can be carried out at ambient temperature using HFMOP, and the solvent is readily recoverable for recycling. The reaction proceeds with the liberation of hydrogen chloride and is highly exothermic, but fluorinated ethers, unlike unfluorinated ethers, are not unstable to acids.

[0121] Battery electrolytes containing fluorine compounds The rapid development of electronic devices has led to increased market demand for electrochemical devices such as fuel cells, capacitors, and battery systems. In particular, to meet the demand for battery systems, practical rechargeable lithium batteries are being actively researched. These systems typically rely on the use of lithium metal, lithium carbon, or lithium alloy as the anode. Lithium batteries are prepared from one or more lithium electrochemical cells. Such cells contain a non-aqueous lithium-ion conductive electrolyte composition inserted between electrically isolated and spaced-apart positive and negative electrodes.

[0122] An electrochemical cell comprises a housing, an anode and a cathode disposed within the housing and ionized to one another, an electrolyte composition according to this specification providing an ion-conducting 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 housing the electrochemical cell components. The anode and the cathode may include 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 lithium tin oxide. Suitable examples of cathode materials include, but are not limited to, graphite, aluminum, platinum, palladium, electroactive transition metal oxides including 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 or multilayer 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 charging. Suitable cathode materials for lithium-ion batteries include, but are not limited to, electroactive transition metal oxides containing lithium, such as LiCoO2, LiNiO2, LiMn2O4, or LiV3O8.

[0125] Various lithium composite oxides containing lithium and transition metals can be used as cathode materials. A preferred example is a composite oxide of the general formula LiMO2, where M is any metallic element or combination of metallic 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 has the chemical formula LiMn 2-x M x It can be made from a material of the formula O4 (wherein 0 ≤ x ≤ 1) or a material of the general formula LiMPO4 (wherein M can be any metallic element or a 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 cathode of the battery may contain any active material that can be held on a conductive member containing a metal or another conductive element.

[0126] In one embodiment, the cathode of the lithium-ion battery described herein is Li / Li + The cathode active material contains a cathode active material exhibiting a capacity of more than 30 mAh / g in a potential range of greater than 4.0 V, preferably (in order of increasing preference) 4.1 V or higher, 4.2 V or higher, 4.3 V or higher, 4.4 V or higher, 4.5 V or higher, 4.25 V or higher, 4.5 V or higher, 4.6 V or higher, or 4.75 V or higher relative to the reference electrode. An example of such a cathode is a stabilized manganese cathode containing 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 is of the formula Li x Ni x M z Mn 2-y-z O 4-dThe stabilized manganese cathode also includes an oxide in the formula, where x is 0.03 to 1.0; x varies depending on the release and incorporation of lithium ions and electrons during charging and discharging; 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 may also include a spinel layered composite comprising a manganese-containing spinel component and a lithium-rich layered structure, as described in U.S. Patent No. 7,303,840.

[0127] The cathode active material can be prepared using methods such as the hydroxide precursor method described by Liu et al. (J. Phys. Chem., C 13:15073-15079, 2009). In this method, the hydroxide precursor is precipitated from a solution containing the required amounts of manganese, nickel, and other desired metal acetates by adding KOH. After drying the resulting precipitate in an oven, it is calcined in oxygen at approximately 800 to 950°C for 3 to 24 hours using the required amount of LiOH·H2O. Alternatively, the cathode active material can be prepared using a solid-phase reaction process or a sol-gel process described in U.S. Patent No. 5,738,957 (Amine).

[0128] A cathode containing the cathode active material can be prepared by mixing an effective amount of the cathode active material (for example, about 70 wt% to about 97 wt%), a polymer binder such as polyvinylidene difluoride, and conductive carbon in a suitable solvent such as N-methylpyrrolidone to produce a paste, then coating it onto a current collector such as aluminum foil and drying it 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 alloy, lithium lead alloy, lithium silicon alloy, and lithium tin alloy; carbon materials such as graphite and mesocarbon microbeads (MCMB); black phosphorus, MnP4, and CoP 3 Phosphorus-containing materials such as; metal oxides such as SnO2, SnO, and TiO2; and Li4Ti5O 12 Examples include lithium titanates such as LiTi2O4. In one embodiment, the anode active material is lithium titanate or graphite. The anode can be prepared by a method similar to that described 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 the conductive active material to obtain a paste. The paste is coated onto a metal foil, preferably aluminum or copper foil, to be used as a current collector. The paste is preferably dried by 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 battery described herein also includes 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 or multilayer sheet of a microporous polymer such as polyethylene, polypropylene, polyamide, or polyimide, or a combination thereof. The separator may also be constructed using a fluorinated polymer. The pore size of the porous separator is large enough to allow ion transport and provide ion-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 lithium-ion battery housing described herein can be any suitable container for housing the lithium-ion battery components. Such containers can be made in the form of small or large cylindrical, prismatic, or pouch-shaped cases.

[0132] The lithium-ion batteries described herein can be used for any purpose and in any device that can be powered by a lithium-ion battery. Non-limiting examples of such purposes / devices include grid storage, or as a power source for various electric or electric assist 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 rechargeable lithium batteries is crucial for optimal battery performance, and various factors are involved. 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 used as components of electrolyte solutions in electrochemical cells, especially lithium batteries (both primary and secondary). Certain fluorinated compounds may offer several advantages over non-fluorinated compounds, including reduced flammability, reduced viscosity, improved wettability, enhanced oxidation / reduction resistance, and / or extended cycle time. These advantages are expected to become even more pronounced at voltages above approximately 4.0V, particularly at higher voltages such as above 4.3V, where such non-fluorinated analogs become particularly unstable.

[0135] In some embodiments, the Disclosure provides a battery comprising an electrolyte containing an amount of fluorinated ether or thioether ranging from about 1 ppm to about 5,000 ppm. Such an amount can typically be measured using GC or GC / MS. In some embodiments, the amount of 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. Cycle life, as defined herein, is the number of charge / discharge cycles it takes for the 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 capable of providing 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, and at least 1,650 cycles. The device 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] In the formula, X is either O or S, and R 4 R is a partially fluorinated C1-C8 alkyl group; 5 R is a C1-C8 alkyl group which may optionally be fluorinated. In some embodiments, R 4 R is a partially fluorinated C1-C4 alkyl group; 5 is a C1-C4 alkyl group which may optionally be fluorinated. 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 containing one or more of 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, or 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 fluorinated organic sulfite contains one or more groups selected from -CF3, -CHF2, -CH2F, -CHF-, and -CF2-. In some embodiments, the fluorinated organic carbonate or fluorinated organic sulfite contains one or more -CF3 groups. In some embodiments, the fluorinated organic carbonate or 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 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 items describe specific embodiments.

[0141] Item 1. A method for producing a fluorinated organic carbonate or fluorinated organic sulfite, comprising a first reactant containing at least one fluorine atom, and a leaving group L 1 This involves reacting with a second reactant of formula 20A or formula 20B that contains [the specified substance]. [ka]

[0142] The above reaction is carried out in the presence of a fluorinated solvent; R 1This 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; L 2 It is a leaving group.

[0143] Item 2. The method according to 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 according to any one of items 1 to 4, wherein the first reactant comprises one or more -CF3 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.L 1 The method according to any one of items 1 to 8, wherein the material is selected from perfluoroalkyl sulfonates, tosylates, mesylates, halogens, nitrates, phosphates, thioethers, amines, carboxylates, phenoxides, alkoxides, and amides.

[0151] Item 10.L 1 However, halogen or -OR 2 A method selected from the base, according to any of items 1 to 8.

[0152] Item 11.R 2 The method according to item 10, wherein the sulfate is an alkyl sulfate or an aryl sulfate.

[0153] Item 12.L 1 However, the method according to any one of items 1 to 8, selected from chlorine, iodine, and bromine.

[0154] Item 13.L 2The method according to any one of items 1 to 12, wherein the material is selected from perfluoroalkyl sulfonates, tosylates, mesylates, halogens, nitrates, phosphates, thioethers, amines, carboxylates, phenoxides, alkoxides, and amides.

[0155] Item 14.L 2 However, halogen or -OR 3 A method selected from the base, using any of items 1 to 12.

[0156] Item 15.R 3 The method according to item 14, wherein the sulfate is an alkyl sulfate or an aryl sulfate.

[0157] Item 16.L 2 However, the method according to any one of items 1 to 12, 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 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 according to 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 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 fluorinating solvent comprises one or more groups selected from -CF3, -CHF2, -CH2F, -CHF-, and -CF2-.

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

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

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

[0168] In the formula, X is either O or S, and R 4 R is a fully or partially fluorinated C1-C8 alkyl group; 5 This is a C1-C8 alkyl group that may optionally be fluorinated.

[0169] Item 27.R 4 However, it is a fully or partially fluorinated C1-C4 alkyl group; R 5 The method according to item 26, wherein the C1-C4 alkyl group may be optionally fluorinated.

[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 fluorinating 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 approximately -40°C to approximately 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 approximately -40°C to approximately 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 approximately 0°C to approximately 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 approximately 10°C to approximately 35°C.

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

[0181] In the formula, R 10 and R 20 These 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.R 20The battery described in item 37, which is a fully or partially fluorinated C1-C6 alkyl group.

[0183] Item 39.R 20 However, the battery described in item 37 includes one or more -CF3 units.

[0184] Item 40.R 20 However, the batteries listed in item 37 include 1 to 3 -CF3 units.

[0185] Item 41.R 20 The battery described in item 37, selected from trifluoroethyl or hexafluoroisopropyl.

[0186] Item 42.R 10 A battery as described in any of items 37 to 41, selected from methyl, ethyl, n-propyl, and 2-propyl.

[0187] Item 43.R 10 The battery according to any of items 37 to 41, wherein the battery 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.R 10 However, a battery as described in any of items 37 to 41, containing one or more -CF3 units.

[0189] Item 45.R 10 However, the batteries listed in any of items 37 to 41 include 1 to 3 -CF3 units.

[0190] Item 46.R 10 and R 20 However, it is the same battery as described in item 37.

[0191] Item 47. The battery according to Item 37, wherein the compound of Formula IV is one of the compounds of Formula 400, Formula 401, Formula 402, or Formula 403. [ka]

[0192] Item 48. The battery described in Item 37, wherein the compound of Formula I is one of the compounds of Formula 100, Formula 101, Formula 102, or Formula 103. [ka]

[0193] Item 49. The battery according to Item 37, wherein the compound of formula II(a) is one of the compounds of formula 200, formula 201, formula 202, or formula 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 according to item 37, wherein the fluorinated compound is an ether or thioether of formula 10. [ka]

[0196] In equation 10, X is either O or S, and R 4 R is a partially fluorinated C1-C8 alkyl group; 5 This is a C1-C8 alkyl group that may optionally be fluorinated.

[0197] Item 52.R 4 However, it is a partially fluorinated C1-C4 alkyl group, R 5 The battery described in item 51, wherein the C1-C4 alkyl group may be optionally fluorinated.

[0198] Item 53. The battery according to any one of items 51 to 52, wherein the fluorinated ether or thioether comprises one or more groups selected from -CF3, -CHF2, -CH2F, -CHF-, and -CF2-.

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

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

[0201] Item 56. A battery according to any one 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 according to any one of items 51 to 55, wherein the fluorinated ether or thioether is hexafluoroisopropyl methyl ether.

[0203] Item 58. A 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. A battery according to any one of items 37 to 57, wherein 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 0.0001% to about 10%. In some embodiments, the solvent component contains the fluorinated compound in an amount of about 0.0001% to about 15%. In some embodiments, the solvent component contains the fluorinated compound in an amount of about 0.001% to about 0.01%. In some embodiments, the solvent component contains the fluorinated compound in an amount of about 0.01% to about 0.1%. In some embodiments, the solvent component contains the fluorinated compound in an amount of about 0.1% to about 1%. In some embodiments, the solvent component contains 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. A battery according to any one of items 37 to 57, wherein the solvent component contains the fluorinated compound in an amount of about 0.1% to about 2%. In some embodiments, the solvent component contains the fluorinated compound in an amount of about 0.1% to about 0.5%. In some embodiments, the solvent component contains the fluorinated compound in an amount of about 0.5% to about 1%. In some embodiments, the solvent component contains the fluorinated compound in an amount of about 1% to about 1.5%. In some embodiments, the solvent component contains the fluorinated compound in an amount of about 1.5% to about 2%. In some embodiments, the solvent component contains the fluorinated compound in an amount of about 2% to about 2.5%. In some embodiments, the solvent component contains the fluorinated compound in an amount of about 2.5% to about 3%. In some embodiments, the solvent component contains 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. A 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 partially fluorinated organic carbonates and non-fluorinated organic carbonates.

[0207] Item 62. The battery according to 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 according to 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 according to Item 61, wherein the partially fluorinated carbonate contains 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. A battery according to any one of items 37 to 60, wherein the electrolyte further comprises a fluorinated organic carbonate or fluorinated organic sulfite containing one or more of 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, or optionally substituted haloheteroaryl.

[0211] Item 66. The battery according to 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 comprises one or more groups selected from -CF3, -CHF2, -CH2F, -CHF-, and -CF2-.

[0214] Item 69. 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 -CF3 groups.

[0215] Item 70. A battery according to any one of items 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.

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

[0217] Item 72. The battery according to 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 according to 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. A battery according to any one of items 37 to 73, wherein the electrolyte further comprises an alkali 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 approximately 1 M to approximately 1.5 M.

[0221] Item 76. 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, 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. A battery according to any one of items 74 to 76, wherein the alkyl salt is a lithium salt.

[0223] Item 78. The battery according to item 77, wherein the lithium salt is LiPF6. 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. A battery according to any one 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. A battery according to any of items 37 to 78, wherein the cathode contains about 70% to about 90% nickel. In some embodiments, the cathode contains about 65% nickel. In some embodiments, the cathode contains about 66% nickel. In some embodiments, the cathode contains about 67% nickel. In some embodiments, the cathode contains about 68% nickel. In some embodiments, the cathode contains about 69% nickel. In some embodiments, the cathode contains about 70% nickel. In some embodiments, the cathode contains about 71% nickel. In some embodiments, the cathode contains about 72% nickel. In some embodiments, the cathode contains about 73% nickel. In some embodiments, the cathode contains about 74% nickel. In some embodiments, the cathode contains about 75% nickel. In some embodiments, the cathode contains about 76% nickel. In some embodiments, the cathode contains about 77% nickel. In some embodiments, the cathode contains about 78% nickel. In some embodiments, the cathode contains about 79% nickel. In some embodiments, the cathode contains about 80% nickel. In some embodiments, the cathode contains about 81% nickel. In some embodiments, the cathode contains about 82% nickel. In some embodiments, the cathode contains about 83% nickel. In some embodiments, the cathode contains about 84% nickel. In some embodiments, the cathode contains about 85% nickel. In some embodiments, the cathode contains about 86% nickel. In some embodiments, the cathode contains about 87% nickel. In some embodiments, the cathode contains about 88% nickel. In some embodiments, the cathode contains about 89% nickel. In some embodiments, the cathode contains about 90% nickel. In some embodiments, the cathode contains about 91% nickel. In some embodiments, the cathode contains about 92% nickel. In some embodiments, the cathode contains about 93% nickel.In some embodiments, the cathode contains about 94% nickel. In some embodiments, the cathode contains about 95% nickel.

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

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

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

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

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

[0231] Item 86. A battery according to any one 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 contains about 10% silicon oxide graphite composite. In some embodiments, the anode contains about 11% silicon oxide graphite composite. In some embodiments, the anode contains about 12% silicon oxide graphite composite. In some embodiments, the anode contains about 13% silicon oxide graphite composite. In some embodiments, the anode contains about 14% silicon oxide graphite composite. In some embodiments, the anode contains about 15% silicon oxide graphite composite. In some embodiments, the anode contains about 16% silicon oxide graphite composite. In some embodiments, the anode contains about 17% silicon oxide graphite composite. In some embodiments, the anode contains about 18% silicon oxide graphite composite. In some embodiments, the anode contains about 19% silicon oxide graphite composite. In some embodiments, the anode contains about 20% silicon oxide graphite composite. In some embodiments, the anode comprises about 21% silicon oxide graphite composite. In some embodiments, the anode comprises about 22% silicon oxide graphite composite.In some embodiments, the anode contains about 23% silicon oxide graphite composite. In some embodiments, the anode contains about 24% silicon oxide graphite composite. In some embodiments, the anode contains about 25% silicon oxide graphite composite. In some embodiments, the anode contains about 26% silicon oxide graphite composite. In some embodiments, the anode contains about 27% silicon oxide graphite composite. In some embodiments, the anode contains about 28% silicon oxide graphite composite. In some embodiments, the anode contains about 29% silicon oxide graphite composite. In some embodiments, the anode contains about 30% silicon oxide graphite composite. In some embodiments, the anode contains about 31% silicon oxide graphite composite. In some embodiments, the anode contains about 32% silicon oxide graphite composite. In some embodiments, the anode contains about 33% silicon oxide graphite composite. In some embodiments, the anode contains about 34% silicon oxide graphite composite. In some embodiments, the anode contains about 35% silicon oxide graphite composite. In some embodiments, the anode contains about 36% silicon oxide graphite composite. In some embodiments, the anode contains about 37% silicon oxide graphite composite. In some embodiments, the anode contains about 38% silicon oxide graphite composite. In some embodiments, the anode contains about 39% silicon oxide graphite composite. In some embodiments, the anode contains about 40% silicon oxide graphite composite. In some embodiments, the anode contains about 5% to about 10% silicon oxide graphite composite. In some embodiments, the anode contains about 10% to about 15% silicon oxide graphite composite. In some embodiments, the anode contains 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 contains about 25% to about 30% silicon oxide graphite composite. In some embodiments, the anode contains about 30% to about 35% silicon oxide graphite composite. In some embodiments, the anode contains about 35% to about 40% silicon oxide graphite composite. In some embodiments, the anode contains about 40% to about 45% silicon oxide graphite composite. In some embodiments, the anode contains about 45% to about 50% silicon oxide graphite composite. In some embodiments, the anode contains about 50% to about 55% silicon oxide graphite composite. In some embodiments, the anode contains about 55% to about 60% silicon oxide graphite composite. In some embodiments, the anode contains about 60% to about 65% silicon oxide graphite composite. In some embodiments, the anode contains about 65% to about 70% silicon oxide graphite composite. In some embodiments, the anode comprises a silicon oxide graphite composite of about 70% to about 75%.

[0232] Item 87. A battery according to any one 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 contains about 9% amorphous silicon graphite composite. In some embodiments, the anode contains about 10% amorphous silicon graphite composite. In some embodiments, the anode contains about 11% amorphous silicon graphite composite. In some embodiments, the anode contains about 12% amorphous silicon graphite composite. In some embodiments, the anode contains about 13% amorphous silicon graphite composite. In some embodiments, the anode contains about 14% amorphous silicon graphite composite. In some embodiments, the anode contains about 15% amorphous silicon graphite composite. In some embodiments, the anode contains about 16% amorphous silicon graphite composite. In some embodiments, the anode contains about 17% amorphous silicon graphite composite. In some embodiments, the anode contains about 18% amorphous silicon graphite composite. In some embodiments, the anode contains about 19% amorphous silicon graphite composite. In some embodiments, the anode contains about 20% amorphous silicon graphite composite.In some embodiments, the anode contains about 21% amorphous silicon graphite composite. In some embodiments, the anode contains about 22% amorphous silicon graphite composite. In some embodiments, the anode contains about 23% amorphous silicon graphite composite. In some embodiments, the anode contains about 24% amorphous silicon graphite composite. In some embodiments, the anode contains about 25% amorphous silicon graphite composite. In some embodiments, the anode contains about 26% amorphous silicon graphite composite. In some embodiments, the anode contains about 27% amorphous silicon graphite composite. In some embodiments, the anode contains about 28% amorphous silicon graphite composite. In some embodiments, the anode contains about 29% amorphous silicon graphite composite. In some embodiments, the anode contains about 30% amorphous silicon graphite composite. In some embodiments, the anode contains about 31% amorphous silicon graphite composite. In some embodiments, the anode contains about 32% amorphous silicon graphite composite. In some embodiments, the anode contains about 33% amorphous silicon graphite composite. In some embodiments, the anode contains about 34% amorphous silicon graphite composite. In some embodiments, the anode contains about 35% amorphous silicon graphite composite. In some embodiments, the anode contains about 36% amorphous silicon graphite composite. In some embodiments, the anode contains about 37% amorphous silicon graphite composite. In some embodiments, the anode contains about 38% amorphous silicon graphite composite. In some embodiments, the anode contains about 39% amorphous silicon graphite composite. In some embodiments, the anode contains about 40% amorphous silicon graphite composite. In some embodiments, the anode contains about 5% to about 10% amorphous silicon graphite composite.In some embodiments, the anode contains about 10% to about 15% amorphous silicon graphite composite. In some embodiments, the anode contains about 15% to about 20% amorphous silicon graphite composite. In some embodiments, the anode contains about 20% to about 25% amorphous silicon graphite composite. In some embodiments, the anode contains about 25% to about 30% amorphous silicon graphite composite. In some embodiments, the anode contains about 30% to about 35% amorphous silicon graphite composite. In some embodiments, the anode contains about 35% to about 40% amorphous silicon graphite composite. In some embodiments, the anode contains about 40% to about 45% amorphous silicon graphite composite. In some embodiments, the anode contains 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. A 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 approximately 600 to approximately . In some embodiments, the battery has a cycle life of approximately ~ to approximately . In some embodiments, the battery has a cycle life of approximately ~ to approximately . In some embodiments, the battery has a cycle life of approximately ~ to approximately . In some embodiments, the battery has a cycle life of approximately ~ to approximately . In some embodiments, the battery has a cycle life of approximately ~ to approximately . In some embodiments, the battery has a cycle life of approximately ~ to approximately . In some embodiments, the battery has a cycle life of approximately ~ to approximately . In some embodiments, the battery has a cycle life of approximately ~ to approximately . In some embodiments, the battery has a cycle life of approximately ~ to approximately . In some embodiments, the battery has a cycle life of approximately ~ to approximately . In some embodiments, the battery has a cycle life of approximately ~ to approximately . In some embodiments, the battery has a cycle life of approximately ~ to approximately . In some embodiments, the battery has a cycle life of approximately ~ to approximately .

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

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

[0236] The embodiments included herein will be described below with reference to the following examples. These examples are provided for illustrative purposes only, and the disclosures included herein should not be construed as being limited in any way to these examples, but rather as including any variations that become apparent as a result of the teachings provided herein.

[0237] Example 1: Synthesis of methyl 2,2,2-trifluoroethyl carbonate 2,2,2-trifluoroethanol (150 g, 1.50 mol), methyl chloroformate (146 g, 1.55 mol), and hexafluoroisopropyl methyl ether (470 g) were added to a 2 L three-necked flask with a cooling water jacket, a mechanical stirrer, and an addition funnel. Triethylamine (157 g, 1.55 mol) was slowly added while maintaining the internal temperature below 30°C (total addition time: 1.5 hours). After 2 hours, GC showed that 96.1% of the starting alcohols had been converted to methyl 2,2,2-trifluoroethyl carbonate.

[0238] Example 2: Synthesis of methyl 1,1,1-trifluoroisopropyl carbonate 1,1,1-trifluoro-2-propanol (114 g, 1.00 mol), methyl chloroformate (94 g, 1.0 mol), and hexafluoroisopropyl methyl ether (200 mL) were added to a 1 L three-necked flask with a cooling water jacket, a mechanical stirrer, and an addition funnel. Triethylamine (102 g, 1.00 mol) was slowly added while maintaining the internal temperature below 30°C (total addition time: 2 hours). After 2 hours, GC showed that 96.4% of the starting alcohols had been converted to methyl 1,1,1-trifluoroisopropyl carbonate.

[0239] Example 3: Synthesis of methyl 1,1,1,3,3,3-hexafluoroisopropyl carbonate 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) were added to a 2 L three-necked flask with a cooling water jacket, a mechanical stirrer, and an addition funnel. Triethylamine (157 g, 1.55 mol) was slowly added while maintaining the internal temperature below 30°C (total addition time: 1.5 hours). After 2 hours, GC showed that 98.6% of the starting alcohols 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 1,1,1,3,3,3-hexafluoroisopropanol (336 g, 2.00 mol) and triethylamine (203 g, 2.00 mol) were added dropwise with thionyl chloride (73 mL, 1.0 mol) at 0°C while maintaining the internal temperature below 15°C (total addition time: 1 hour). After 2 hours, GC showed that 90.6% of the starting alcohols were 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 to 4.4V at 1C and discharge to 3.0V at 1C (electrode load: 1.26mAh / cm²). 2 and 1.90mAh / cm² 2 ).

[0243] Figure 1 shows the performance improvement of high-temperature silicon anode batteries by using an electrolyte containing trifluoroethyl methyl carbonate (F3EMC) instead of an electrolyte containing fluoroethylene carbonate (FEC). Both F3EMC and the FEC / F3EMC combination outperform FEC alone (F3EMC: carbonate CF3CH2OC(O)OCH3; 1C / -1C cycle 4.40~3.00V; cell type - pouch cell, cycle (@45℃) -4.40V~3.00V, cathode - NMC811, anode 10% silicon composite).

[0244] Legend: TIFF0007833400000023.tif41188 1.2M LiPF6 solution in 10%EC / EMC (3:7), 10%FEC, and 2%VC TIFF0007833400000024.tif41288 1.2M LiPF6 solution in 3% EC / EMC (3:7), 3% FEC, 7% F3 EMC, and 2% VC TIFF0007833400000025.tif41188 1.2M LiPF6 solution in 10%EC / EMC (3:7), 10%F3EMC, and 2%VC

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

[0246] Legend: TIFF0007833400000026.tif41188 1.2 M LiPF6 solution in 10% EC / EMC (3:7), 10% FEC, and 2% VC (vinyl carbonate) TIFF0007833400000027.tif41283%EC / EMC (3:7), 5%FEC, 10% trifluoroethyl acetate, and 1.2M LiPF6 solution in 2% VC (vinylene carbonate). TIFF0007833400000028.tif41288 1.2 M LiPF6 solution in 3% EC / EMC (3:7), 3% FEC, 7% trifluoroethyl acetate, and 2% VC (vinylene carbonate)

[0247] Figure 3 shows the performance improvement of high-temperature silicon anode batteries by using an electrolyte containing hexafluoro-2-methoxypropane (hexafluoro-2-propyl methyl ether) compared to an electrolyte containing fluoroethylene carbonate (FEC). Hexafluoro-2-methoxypropane, either without FEC or combined with FEC, exceeded the performance of FEC alone by over 80% (Hexafluoro-2-methoxypropane is (CF3)2CHOCH3; 1C / -1C cycle 4.40~3.00V; Cell type - pouch cell, cycle (@45℃) -4.40V~3.00V, cathode - NMC811, anode 10% silicon composite).

[0248] Legend: TIFF0007833400000029.tif41188 1.2 M LiPF6 solution in 10% EC / EMC (3:7), 10% FEC, and 2% VC (vinyl carbonate) TIFF0007833400000030.tif41288 1.2 M LiPF6 solution in 3% EC / EMC (3:7), 3% FEC, 7% hexafluoro-2-methoxypropane, and 2% VC (vinylene carbonate) TIFF0007833400000031.tif41288 1.2 M LiPF6 solution in 10% EC / EMC (3:7), 10% hexafluoro-2-methoxypropane, and 2% VC (vinylene carbonate).

[0249] While we do not wish to be bound by any particular theory, in some embodiments, hexafluoro-2-methoxypropane is considered superior to F3EMC, F3EMC is considered superior to trifluoroethyl acetate, and trifluoroethyl acetate is considered superior to FEC.

[0250] To describe the current state of the art to which this disclosure relates, several patent and non-patent documents are referenced herein. The entirety of the disclosures of each of these documents is incorporated herein by reference.

[0251] While specific embodiments of the present disclosure are described and / or illustrated above, various other embodiments will be apparent to those skilled in the art from the present disclosure. Therefore, the present disclosure is not limited to the specific embodiments described and / or illustrated, and can be substantially modified and altered without departing from the scope and spirit of the appended claims.

Claims

1. A battery comprising an electrolyte containing a solvent component, wherein the solvent component contains a fluorinated compound in an amount of 1 ppm to 60% by mass, and the fluorinated compound has formula III and contains 2 or more -CF ３ A battery characterized by containing a base. 【Chemistry 1】 (In the formula, R １０ and R ２０ These 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.

2. R ２０ The battery according to claim 1, wherein the C1-C6 alkyl is fully or partially fluorinated.

3. R ２０ However, -CF is 1 or greater ３ The battery according to claim 1, comprising a base.

4. R ２０ However, 1 to 3 units -CF ３ The battery according to claim 1, comprising a base.

5. R ２０ The battery according to claim 1, wherein R is selected from trifluoroethyl or hexafluoroisopropyl.

6. R １０ The battery according to any one of claims 1 to 5, wherein the methyl, ethyl, n-propyl, and 2-propyl propyl propyl propyl propyl propyl methylmethyl propyl propyl methyl propyl methyl propyl propyl methyl propyl methyl

7. R １０ The battery according to any one of claims 1 to 5, wherein the battery 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.

8. R １０ However, -CF is 1 or greater ３ A battery according to any one of claims 1 to 5, comprising a base.

9. R １０ However, 1 to 3 units -CF ３ A battery according to any one of claims 1 to 5, comprising a base.

10. R １０ and R ２０ The battery according to claim 1, which is identical to the battery described in claim 1.

11. The battery according to claim 1, wherein the compound of formula III is a compound of formula 300 or formula 301. 【Chemistry 2】

12. The battery according to any one of claims 1 to 5, wherein the fluorinated compound 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.

13. The battery according to any one of claims 1 to 12, wherein the solvent component contains the fluorinated compound in an amount of 1 ppm to 5000 ppm.

14. The battery according to any one of claims 1 to 12, wherein the solvent component contains the fluorinated compound in an amount of 0.0001% to 40% by mass.

15. The battery according to any one of claims 1 to 12, wherein the solvent component contains the fluorinated compound in an amount of 5% to 30% by mass.

16. The battery according to any one of claims 1 to 15, wherein the electrolyte is a non-aqueous electrolyte, and the solvent component further comprises one or more partially fluorinated organic carbonates and non-fluorinated organic carbonates.

17. The battery according to claim 16, wherein the non-fluorinated organic carbonate comprises one or more of EC (ethylene carbonate), EMC (ethyl methyl carbonate), DEC (diethyl carbonate), DMC (dimethyl carbonate), PC (propylene carbonate), and VC (vinylen carbonate and / or vinylidene carbonate).

18. The battery according to claim 17, wherein the amount of VC in the solvent component is 0.001% by mass to 2% by mass.

19. The battery according to claim 16, wherein the partially fluorinated organic carbonate contains FEC (fluoroethylene carbonate), and the amount of FEC in the solvent component is 0.001% by mass to 10% by mass.

20. The battery according to any one of claims 1 to 15, wherein the electrolyte further comprises a fluorinated organic carbonate or fluorinated organic sulfite containing one or more of 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, or optionally substituted haloheteroaryl.

21. The battery according to claim 20, wherein the fluorinated organic carbonate is a fluorinated dialkyl carbonate.

22. The battery according to claim 20, wherein the fluorinated organic sulfite is a fluorinated dialkyl sulfite.

23. The fluorinated organic carbonate or the fluorinated organic sulfite is -CF ３ ,-CHF ２ ien-CH ２ F, -CHF-, and -CF ２ A battery according to any one of claims 20 to 22, comprising one or more units selected from -.

24. The fluorinated organic carbonate or the fluorinated organic sulfite contains one or more -CF ３ A battery according to any one of claims 20 to 22, comprising a base.

25. The battery according to any one of claims 20 to 22, 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.

26. The battery according to any one of claims 20 to 22, wherein the fluorinated organic carbonate or the fluorinated organic sulfite comprises one or two 1,1,1,3,3,3-hexafluoroisopropyl groups.

27. The battery according to claim 20, 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.

28. The battery according to claim 20, 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.

29. The battery according to any one of claims 1 to 28, wherein the electrolyte further comprises an alkali salt.

30. The battery according to claim 29, wherein the alkali salt is dissolved in the solvent component, and the concentration of the alkali salt is 1 M to 1.5 M.

31. The battery according to claim 29, wherein the alkali salt is dissolved in the solvent component, and the concentration of the alkali salt is 1 M, 1.1 M, 1.2 M, 1.3 M, 1.4 M, or 1.5 M.

32. The battery according to any one of claims 29 to 31, wherein the alkali salt is a lithium salt.

33. The lithium salt is LiPF ６ The battery according to claim 32.

34. The battery according to any one of claims 1 to 33, wherein the cathode of the battery comprises a metal selected from nickel, manganese, and cobalt.

35. The battery according to any one of claims 1 to 34, wherein the anode of the battery contains 2% by mass to 75% by mass of silicon.

36. The battery according to any one of claims 1 to 34, wherein the anode of the battery contains 2% to 70% by mass of silicon oxide graphite composite.

37. The battery according to any one of claims 1 to 34, wherein the anode of the battery contains 5% to 15% by mass of silicon oxide graphite composite.

38. The battery according to any one of claims 1 to 34, wherein the anode of the battery contains 2% to 70% by mass of amorphous silicon graphite composite.

39. The battery according to any one of claims 1 to 34, wherein the anode of the battery contains 5% to 15% by mass of amorphous silicon graphite composite.

40. The battery according to any one of claims 1 to 34, wherein the anode of the battery comprises a metal selected from lithium metal, lithium metal alloy, lithium titanate, and lithium tin oxide.

41. The battery according to any one of claims 1 to 40, wherein the battery is rechargeable and has a cycle life of 150 to 800 cycles.

42. The battery according to claim 41, wherein the battery has a cycle life of at least 200 cycles.

43. The battery according to claim 41, wherein the battery has a cycle life of at least 250 cycles.

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