Carbon dioxide saturated electrolyte for energy storage devices and method thereof

Abstract

Provided herein are electrolyte additives and formulations for energy storage devices with improved performance. The electrolyte comprises at least one carbon dioxide source dissolved in a fluorinated solvent. The improved performance can be realized as improved cycling stability.

Description

[Technical Field]

[0001] [CROSS-REFERENCE TO RELATED APPLICATIONS] All applications for which a foreign or domestic priority claim is identified in an Application Data Sheet or PCT application filed with this application are incorporated herein by reference under 37 CFR 1.57 and Rules 4.18 and 20.6. This application claims priority to U.S. Provisional Patent Application No. 63 / 377,638, filed September 29, 2022, the disclosure of which is incorporated herein by reference in its entirety for all purposes.

[0002] The present disclosure relates generally to energy storage devices, and particularly to improved electrolyte formulations for use in energy storage devices. [Background technology]

[0003] Energy storage devices are widely used to power electronic, electromechanical, electrochemical, and other useful devices. Such batteries include primary chemical batteries, secondary (rechargeable) batteries, fuel cells, and various types of capacitors, including ultracapacitors. Increasing the operating voltage and temperature of energy storage devices, including batteries and capacitors, would be desirable to improve energy storage, increase power capabilities, and broaden real-world use cases.

[0004] Lithium-ion batteries have been relied upon as power sources in numerous commercial and industrial applications, including consumer devices, productivity devices, and battery-powered vehicles. However, the demands placed on energy storage devices are continually and rapidly increasing. For example, the automotive industry is developing vehicles that rely on compact, efficient energy storage, such as plug-in hybrid vehicles and pure electric vehicles. While lithium-ion batteries are suitable for meeting future demands, improvements in energy density are needed to provide longer-lasting batteries that can go further on a single charge. The electrolyte is one component of conventional lithium-ion batteries that determines their electrochemical performance and safety, and the compatibility between the electrodes and the electrolyte partially governs the performance of the battery cell. Summary of the Invention [Problem to be solved by the invention]

[0005] For purposes of summarizing the invention and the advantages achieved over the prior art, certain objects and advantages of the invention are described herein. Not all such objects or advantages may be achieved in any particular embodiment of the invention. Thus, for example, one skilled in the art will recognize that the invention may be embodied or implemented to achieve or optimize one advantage or advantages as taught herein without necessarily achieving other objects or advantages that may be taught or suggested herein. [Means for solving the problem]

[0006] All of these embodiments are intended to be within the scope of the invention disclosed herein. These and other embodiments will become readily apparent to those skilled in the art from the following detailed description of the preferred embodiments, taken in conjunction with the accompanying drawings, and it is to be understood that the invention is not limited to any particular preferred embodiment disclosed.

[0007] One embodiment is a lithium-ion battery. The battery may include a cathode, an anode, an electrolyte including lithium ions dissolved in a fluorinated solvent and at least one source of carbon dioxide.

[0008] In one aspect, an energy storage device is described. The energy storage device includes a cathode; an anode; and an electrolyte including a lithium salt, a carbon dioxide source, and a fluorinated solvent. In some embodiments, the concentration of the carbon dioxide source in the electrolyte is in the range of 0.1 to 10 wt %.

[0009] In some embodiments, the carbon dioxide source is selected from the group consisting of gaseous carbon dioxide, dry ice, diethylpyrocarbonate (DEPC), dimethylpyrocarbonate (DMPC), diallylpyrocarbonate (DAPC), bis(tert-butyl)pyrocarbonate (O-Boc2), and combinations thereof. In further embodiments, the carbon dioxide source is diethylpyrocarbonate. In some embodiments, the concentration of diethylpyrocarbonate in the electrolyte is in the range of 1-6 wt%. In further embodiments, the concentration of diethylpyrocarbonate in the electrolyte is in the range of 1.5-2.5 wt%.

[0010] In some embodiments, the concentration of the fluorinated solvent in the electrolyte is in the range of 5 to 80 wt%. In some embodiments, the concentration of the fluorinated solvent in the electrolyte is in the range of 5 to 20 wt%. In some embodiments, the fluorinated solvent is selected from the group consisting of fluoroethylene carbonate (FEC), difluoroethylene carbonate (diFEC), methyl 2,2,2-trifluoroethyl carbonate (FEMC), bis(2,2,2-trifluoroethyl)carbonate (TFEC), trifluoropropylene carbonate (TFPC), 2,2,3,3-tetrafluoro-1,4-dimethoxybutane (fDMB), bis(2,2,2-trifluoroethyl)ether (BTFE), 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), and combinations thereof. In certain embodiments, the fluorinated solvent is fluoroethylene carbonate. In some embodiments, the electrolyte is substantially free of ethylene carbonate and dimethyl carbonate.

[0011] In some embodiments, the anode comprises silicon particles. In some embodiments, the d of the silicon particles 50 In a further embodiment, the d of the silicon particles is 1 to 5 microns. 50 is 2-3 microns. In some embodiments, the anode comprises a graphite intercalation material and a silicon alloying / dealloying material. In some embodiments, the cathode comprises an active material selected from the group consisting of lithium nickel manganese cobalt oxide (NMC), lithium manganese oxide (LMO), lithium nickel dioxide (LNO), lithium iron phosphate (LFP), and lithium nickel cobalt aluminum oxide (NCA). In some embodiments, the lithium salt is selected from the group consisting of lithium hexafluorophosphate, lithium bis(fluorosulfonyl)imide, and combinations thereof.

[0012] In some embodiments, the energy storage device is configured to have at least 70% retention of its initial capacity after 100 cycles from 4.1 V to 2.85 V at a charge rate of C3:C2. In further embodiments, the energy storage device is configured to have at least 70% retention of its initial capacity after 140 cycles from 4.1 V to 2.85 V at a charge rate of C3:C2. In some embodiments, the energy storage device is a battery. In some embodiments, the energy storage device is configured to have at least 70% retention of its initial capacity after 225 cycles from 4.2 V to 2.85 V at a charge rate of C4:C3.

[0013] In another aspect, an electric vehicle having a rechargeable battery is described. In some embodiments, the electric vehicle having a rechargeable battery includes a drive motor; a gearbox; electronics; and an energy storage device as described herein.

[0014] In another aspect, a method of preparing an electrolyte is described. The method includes combining a carbon dioxide source, a fluorinated solvent, and a lithium salt to form an electrolyte. In some embodiments, the method further includes aging the electrolyte. In some embodiments, the method further includes loading the electrolyte into an energy storage device. In some embodiments, the electrolyte is disposed within the energy storage device. [Brief explanation of the drawings]

[0015] [Figure 1] 1 is an X-ray photoelectron spectroscopy (XPS) characterization of solid electrolyte interface (SEI) components resulting from cycling of electrolyte formulations according to some embodiments.

[0016] [Figure 2] 10 includes data plots of cycling data using an electrolyte system according to some embodiments versus a baseline electrolyte system.

[0017] [Figure 3A] 1 is an X-ray photoelectron spectroscopy (XPS) depth profiling of atomic concentration (%) versus sputtering depth for solid electrolyte interface (SEI) components resulting from cycling of electrolyte formulations according to some embodiments.

[0018] [Figure 3B] 1 is an X-ray photoelectron spectroscopy (XPS) characterization of solid electrolyte interface (SEI) components resulting from cycling of electrolyte formulations according to some embodiments.

[0019] [Figure 4] 10 includes data plots of capacity retention during cycling with an electrolyte system according to some embodiments versus a baseline electrolyte system.

[0020] [Figure 5] 1 is a bar graph showing gas formation in an electrolyte system according to some embodiments relative to a baseline electrolyte system.

[0021] [Figure 6] 1 is a plot showing discharge capacity versus cycle number for a battery having an electrolyte system injected with gaseous carbon dioxide according to some embodiments relative to a baseline electrolyte system.

[0022] [Figure 7A] 1 is a plot showing discharge capacity versus cycle number for batteries having electrolyte systems with various amounts of solvent blends, according to some embodiments.

[0023] [Figure 7B] 1 is a plot showing gas formation for electrolyte systems containing various amounts of solvent blends, according to some embodiments.

[0024] [Figure 8A]1 is a plot showing discharge capacity versus cycle number for a battery having an electrolyte system including diethylpyrocarbonate (DEPC) according to some embodiments, relative to a baseline electrolyte system.

[0025] [Figure 8B] 1 is a plot showing discharge capacity versus cycle number for a battery having an electrolyte system including diethylpyrocarbonate (DEPC) according to some embodiments, relative to a baseline electrolyte system.

[0026] [Figure 8C] 1 is a plot showing gas formation for an electrolyte system including diethylpyrocarbonate (DEPC) according to some embodiments. Detailed Description of the Invention

[0027] The present disclosure may be understood by reference to the following detailed description: It should be noted that for clarity of illustration, certain elements of the various figures may not be drawn to scale and may be represented diagrammatically or conceptually, and may not otherwise precisely correspond to certain physical configurations of embodiments.

[0028] Electrolyte formulations containing at least one additive or its salt are described for high-voltage, high-energy density energy storage devices (e.g., lithium-ion batteries). In some embodiments, such additives can react with lithium salts to improve device performance, such as stabilizing the electrode surface. Such device improvements can advantageously provide improved cycling stability. The present disclosure further relates to electrolyte formulations that improve battery cycling by stabilizing the solid electrolyte interface (SEI).

[0029] Embodiments relate to the application of a uniquely tailored electrolyte formulation to a high-energy anode, fully optimized for CO saturation and equilibrium fluorinated solvent content in a battery design that does not contain excessive CO gas. In some embodiments, CO and fluorinated solvent can be applied to the electrolyte formulation, and the CO + fluorinated solvent combination can extend the life of energy storage devices such as lithium-ion batteries. In some embodiments, the lithium-ion battery includes a micron-silicon anode. In some embodiments, the lithium-ion battery includes a graphite anode. Additionally, additives such as DEPC can be included in the electrolyte formulation, which can provide advantageous results, as discussed below. In some embodiments, the electrolyte does not contain ethylene carbonate (EC) or dimethyl carbonate (DMC). In some embodiments, the anode is made from an intercalation material (e.g., carbon or graphite) and an alloying / dealloying material (e.g., silicon, silicon oxide, tin, and / or tin oxide).

[0030] ·Definition Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art.All patents, applications, published applications and other publications referred to herein are incorporated by reference in their entirety unless otherwise specified.If there are multiple definitions for terms in this specification, the definitions in this section shall prevail unless otherwise specified.

[0031] Whenever a group is described as "optionally substituted," the group may be unsubstituted or substituted with one or more of the indicated substituents. When a group is described as "optionally substituted," the substituents may be selected from one or more of the indicated substituents. If no substituents are indicated, the indicated "optionally substituted" or "substituted" group includes any of the following: deuterium (D), halogen, hydroxy, C 1~4 Alkoxy, C 1~8 Alkyl, C 3~20Cycloalkyl, aryl, heteroaryl, heterocyclyl, C 1~6 Haloalkyl, Cyano, C 2~8 Alkenyl, C 2~8 Alkynyl, C 3~20 It means that each may be substituted with one or more groups independently selected from cycloalkenyl, aryl(alkyl), heteroaryl(alkyl), heterocyclyl(alkyl), acyl, thiocarbonyl, C-carboxy, O-carboxy, sulfenyl, sulfinyl, sulfonyl, haloalkoxy, amino, monosubstituted amine groups, and disubstituted amine groups.

[0032] As used herein, "C" refers to a group of integers where "a" and "b" are integers. a ~C b " refers to the number of carbon atoms in the group. The designated group can contain from "a" to "b" (inclusive) carbon atoms. Thus, for example, a "C1-C4 alkyl" group refers to all alkyl groups having from 1 to 4 carbons, i.e., CH3-, CH3CH2-, CH3CH2CH2-, (CH3)2CH-, CH3CH2CH2CH2-, CH3CH2CH(CH3)-, and (CH3)3C-. When "a" and "b" are not specified, the broadest ranges described by these definitions are assumed.

[0033] When two "R" groups are described as being "together," the R groups and the atoms to which they are attached can form a cycloalkyl, cycloalkenyl, aryl, heteroaryl, or heterocyclic ring. For example, but not limited to, NR a R b Group R a and R b are shown to be "together," it means that they are covalently bonded to each other either indirectly through an intermediate atom or directly to form a ring, for example, as follows: TIFF2025534217000002.tif16114

[0034] As used herein, the term "alkyl" refers to a fully saturated aliphatic hydrocarbon group. The alkyl moiety can be branched or straight-chain. Examples of branched alkyl groups include, but are not limited to, isopropyl, sec-butyl, t-butyl, etc. Examples of straight-chain alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, etc.

[0035] The term "alkenyl," as used herein, refers to a monovalent straight or branched chain radical of 2 to 30 carbon atoms containing a carbon double bond, including, but not limited to, 1-propenyl, 2-propenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, etc. Alkenyl groups can be unsubstituted or substituted.

[0036] The term "alkynyl," as used herein, refers to a monovalent straight or branched chain radical of 2 to 30 carbon atoms containing a carbon triple bond, including, but not limited to, 1-propynyl, 1-butynyl, 2-butynyl, etc. Alkynyl groups can be unsubstituted or substituted.

[0037] As used herein, "cycloalkyl" refers to a monocyclic or polycyclic hydrocarbon ring system that is fully saturated (no double or triple bonds). When composed of two or more rings, the rings may be fused, bridged, or spiro-connected together. As used herein, the term "fused" refers to two rings that share two atoms and one bond. For example, in the following structure, ring A and ring B are fused together: TIFF2025534217000003.tif16114. As used herein, the term "bridged cycloalkyl" refers to a compound in which the cycloalkyl contains a linkage of one or more atoms connecting non-adjacent atoms. TIFF2025534217000004.tif22114 and TIFF2025534217000005.tif26114 is an example of a "bridged" ring. As used herein, the term "spiro" refers to two rings that share one atom in common and are not connected by a bridge. Cycloalkyl groups can contain 3 to 30 atoms in the ring, 3 to 20 atoms in the ring, 3 to 10 atoms in the ring, 3 to 8 atoms in the ring, or 3 to 6 atoms in the ring. Cycloalkyl groups can be unsubstituted or substituted. Examples of monocycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of fused cycloalkyl groups are decahydronaphthalenyl, dodecahydro-1H-phenalenyl, and tetradecahydroanthracenyl; examples of bridged cycloalkyl groups are bicyclo[1.1.1]pentyl, adamantanyl, and norbornanyl; and examples of spirocycloalkyl groups include spiro[3.3]heptane and spiro[4.5]decane.

[0038] As used herein, "cycloalkenyl" refers to a monocyclic or polycyclic hydrocarbon ring system containing one or more double bonds in at least one ring, provided that if more than one is present, the double bonds cannot form a completely delocalized pi-electron system across all rings (otherwise the group would be an "aryl" as defined herein). Cycloalkenyl groups can contain 3 to 30 atoms in the rings, 3 to 20 atoms in the rings, 3 to 10 atoms in the rings, 3 to 8 atoms in the rings, or 3 to 6 atoms in the rings. When composed of more than one ring, the rings may be connected together in a fused, bridged, or spiro fashion. Cycloalkenyl groups can be unsubstituted or substituted.

[0039] As used herein, "cycloalkynyl" refers to a monocyclic or polycyclic hydrocarbon ring system containing one or more triple bonds in at least one ring. If two or more triple bonds are present, the triple bonds cannot form a completely delocalized pi-electron system throughout all rings. Cycloalkynyl groups can contain 8 to 30 atoms in the ring, 8 to 20 atoms in the ring, or 8 to 10 atoms in the ring. When composed of two or more rings, the rings may be joined together in a fused, bridged, or spiro-like fashion. Cycloalkynyl groups can be unsubstituted or substituted.

[0040] As used herein, "aryl" refers to a carbocyclic (all-carbon) monocyclic or polycyclic aromatic ring system (including fused ring systems in which two carbocyclic rings share a chemical bond) having a completely delocalized pi-electron system throughout all rings. The number of carbon atoms in an aryl group can vary. For example, an aryl group can be any group from C6 to C8. 14 Aryl groups, C6-C 10 The aryl group may be an aryl group or a C6 aryl group. Examples of aryl groups include, but are not limited to, benzene, naphthalene, and azulene. The aryl group may be substituted or unsubstituted.

[0041] As used herein, "heteroaryl" refers to a monocyclic or polycyclic aromatic ring system (a ring system having a fully delocalized pi-electron system) containing one or more heteroatoms (e.g., 1, 2, or 3 heteroatoms), i.e., elements other than carbon, including, but not limited to, nitrogen, oxygen, and sulfur. The number of atoms in the rings of a heteroaryl group can vary. For example, a heteroaryl group can contain 4 to 14 atoms in the ring, 5 to 10 atoms in the ring, or 5 to 6 atoms in the ring. Furthermore, the term "heteroaryl" includes fused ring systems in which two rings share at least one chemical bond, such as at least one aryl ring and at least one heteroaryl ring, or at least two heteroaryl rings. Examples of heteroaryl rings include, but are not limited to, furan, furazan, thiophene, benzothiophene, phthalazine, pyrrole, oxazole, benzoxazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, thiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, benzothiazole, imidazole, benzimidazole, indole, indazole, pyrazole, benzopyrazole, isoxazole, benzisoxazole, isothiazole, triazole, benzotriazole, thiadiazole, tetrazole, pyridine, pyridazine, pyrimidine, pyrazine, purine, pteridine, quinoline, isoquinoline, quinazoline, quinoxaline, cinnoline, and triazine. Heteroaryl groups can be substituted or unsubstituted.

[0042] As used herein, "heterocyclyl" or "heteroalicyclyl" refers to 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, and up to 18-membered monocyclic, bicyclic, and tricyclic ring systems, in which the carbon atoms, together with one to five heteroatoms, comprise the ring system. Heterocycles may optionally contain one or more unsaturated bonds positioned so that a fully delocalized pi-electron system does not occur throughout the entire ring. Heteroatoms are elements other than carbon, including, but not limited to, oxygen, sulfur, and nitrogen. Heterocycles may further contain one or more carbonyl or thiocarbonyl functional groups, broadening the definition to include oxo and thio systems, such as lactams, lactones, cyclic imides, cyclic thioimides, and cyclic carbamates. When composed of two or more rings, the rings may be fused or joined together in a spiro fashion. Additionally, any nitrogen in a heteroalicyclic ring may be quaternized. Heterocyclyl or heteroalicyclic groups may be unsubstituted or substituted.Examples of such "heterocyclyl" or "heteroalicyclyl" groups include 1,3-dioxine, 1,3-dioxane, 1,4-dioxane, 1,2-dioxolane, 1,3-dioxolane, 1,4-dioxolane, 1,3-oxathiane, 1,4-oxathiin, 1,3-oxathiolane, 1,3-dithiol, 1,3-dithiolane, 1,4-oxathiane, tetrahydro-1,4-thiazine, 2H-1,2-oxazine, maleimide, succinimide, barbituric acid, thiobarbituric acid, dioxopiperazine, hydantoin, dihydrouracil, trioxane, hexahydro-1,3,5-triazine, imidazoline, and imidazolidine. , isoxazoline, isoxazolidine, oxazoline, oxazolidine, oxazolidinone, thiazoline, thiazolidine, morpholine, oxirane, piperidine N-oxide, piperidine, piperazine, pyrrolidine, pyrrolidone, pyrrolidione, 4-piperidone, pyrazoline, pyrazolidine, 2-oxopyrrolidine, tetrahydropyran, 4H-pyran, tetrahydrothiopyran, thiamorpholine, thiamorpholine sulfoxide, thiamorpholine sulfone and their benzo-fused analogs (e.g., benzimidazolidinone, tetrahydroquinoline and / or 3,4-methylenedioxyphenyl).

[0043] As used herein, "aralkyl" and "aryl(alkyl)" refer to an aryl group connected as a substituent via a lower alkylene group. The lower alkylene and aryl groups of an aralkyl may be substituted or unsubstituted. Examples include, but are not limited to, benzyl, 2-phenylalkyl, 3-phenylalkyl, and naphthylalkyl.

[0044] As used herein, "heteroaralkyl" and "heteroaryl(alkyl)" refer to a heteroaryl group connected as a substituent via a lower alkylene group. The lower alkylene and heteroaryl groups of a heteroaralkyl can be substituted or unsubstituted. Examples include, but are not limited to, 2-thienylalkyl, 3-thienylalkyl, furylalkyl, thienylalkyl, pyrrolylalkyl, pyridylalkyl, isoxazolylalkyl, and imidazolylalkyl, as well as benzo-fused analogs thereof.

[0045] "Heteroalicyclyl(alkyl)" and "heterocyclyl(alkyl)" refer to a heterocyclic or heteroalicyclyl group connected as a substituent via a lower alkylene group. The lower alkylene and heterocyclyl of a (heteroalicyclyl)alkyl may be substituted or unsubstituted. Examples include, but are not limited to, tetrahydro-2H-pyran-4-yl(methyl), piperidin-4-yl(ethyl), piperidin-4-yl(propyl), tetrahydro-2H-thiopyran-4-yl(methyl), and 1,3-thiazinan-4-yl(methyl).

[0046] "Alkylene groups" and "lower alkylene groups" are straight-chain -CH- tethering groups that form bonds connecting molecular fragments through their terminal carbon atoms. Examples include, but are not limited to, methylene (-CH-), ethylene (-CHCH-), propylene (-CHCHCH-), and butylene (-CHCHCHCHCH-). Alkylene groups can be substituted by replacing one or more hydrogens of the alkylene group with a substituent listed under the definition of "substituted," and / or by replacing both hydrogens on the same carbon with a cycloalkyl group (e.g., TIFF2025534217000006.tif16114) can be replaced.

[0047] As used herein, the term "hydroxy" refers to an --OH group.

[0048] As used herein, "alkoxy" refers to the formula -OR, where R is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, heterocyclyl, cycloalkyl(alkyl), aryl(alkyl), heteroaryl(alkyl), or heterocyclyl(alkyl), as defined herein. A non-limiting list of alkoxy is methoxy, ethoxy, n-propoxy, 1-methylethoxy (isopropoxy), n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, phenoxy, and benzoxy. Alkoxy can be substituted or unsubstituted.

[0049] As used herein, "acyl" refers to hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, aryl(alkyl), heteroaryl(alkyl), and heterocyclyl(alkyl) connected as a substituent through a carbonyl group. Examples include formyl, acetyl, propanoyl, benzoyl, and acryl. Acyl may be substituted or unsubstituted.

[0050] A "cyano" group refers to a "-CN" group.

[0051] The term "halogen atom" or "halogen" as used herein means any one of the radiation-stable atoms in column 7 of the periodic table of the elements, such as fluorine, chlorine, bromine and iodine.

[0052] A "thiocarbonyl" group refers to a "-C(=S)R" group where R can be the same as defined for O-carboxy. The thiocarbonyl can be substituted or unsubstituted.

[0053] The "O-carbamyl" group is R A and R Bare independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, heterocyclyl, cycloalkyl(alkyl), aryl(alkyl), heteroaryl(alkyl), or heterocyclyl(alkyl). A R B ) group. O-carbamyl may be substituted or unsubstituted.

[0054] An "N-carbamyl" group is a group consisting of R and R A ROC(═O)N(R) may be independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, heterocyclyl, cycloalkyl(alkyl), aryl(alkyl), heteroaryl(alkyl), or heterocyclyl(alkyl). A )-" group. N-carbamyl may be substituted or unsubstituted.

[0055] The "O-thiocarbamyl" group is R A and R B may independently be hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, heterocyclyl, cycloalkyl(alkyl), aryl(alkyl), heteroaryl(alkyl), or heterocyclyl(alkyl). A R B ) group. O-thiocarbamyl may be substituted or unsubstituted.

[0056] An "N-thiocarbamyl" group is a group consisting of R and R A ROC(═S)N(R) may be independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, heterocyclyl, cycloalkyl(alkyl), aryl(alkyl), heteroaryl(alkyl), or heterocyclyl(alkyl). A )-" group. N-thiocarbamyl may be substituted or unsubstituted.

[0057] A "C-amide" group is R A and R B are independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, heterocyclyl, cycloalkyl(alkyl), aryl(alkyl), heteroaryl(alkyl), or heterocyclyl(alkyl). A R B ) group. C-amides can be substituted or unsubstituted.

[0058] An "N-amido" group is one in which R and R A are independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, heterocyclyl, cycloalkyl(alkyl), aryl(alkyl), heteroaryl(alkyl), or heterocyclyl(alkyl). A )-" group. N-amides can be substituted or unsubstituted.

[0059] A "C-thioamide" group is R A and R B are independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, heterocyclyl, cycloalkyl(alkyl), aryl(alkyl), heteroaryl(alkyl), or heterocyclyl(alkyl). A R B )" group. C-thioamides can be substituted or unsubstituted.

[0060] An "N-thioamido" group is one in which R and R A wherein R C(═S)N(R ) can independently be hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, heterocyclyl, cycloalkyl(alkyl), aryl(alkyl), heteroaryl(alkyl), or heterocyclyl(alkyl). A)-" group. N-thioamides can be substituted or unsubstituted.

[0061] An "S-sulfonamide" group is R A and R B may independently be hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, heterocyclyl, cycloalkyl(alkyl), aryl(alkyl), heteroaryl(alkyl), or heterocyclyl(alkyl). A R B )" group. S-sulfonamides can be substituted or unsubstituted.

[0062] An "N-sulfonamido" group is one in which R and R A may independently be hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, heterocyclyl, cycloalkyl(alkyl), aryl(alkyl), heteroaryl(alkyl), or heterocyclyl(alkyl). A )-" group. N-sulfonamides may be substituted or unsubstituted.

[0063] An "O-carboxy" group refers to an "RC(=O)O-" group, where R can be hydrogen, alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkenyl, aryl, heteroaryl, heterocyclyl, cycloalkyl(alkyl), aryl(alkyl), heteroaryl(alkyl), or heterocyclyl(alkyl), as defined herein. O-carboxy can be substituted or unsubstituted.

[0064] The terms "ester" and "C-carboxy" refer to the group "-C(=O)OR" where R can be the same as defined for O-carboxy. Ester and C-carboxy can be substituted or unsubstituted.

[0065] A "sulfenyl" group refers to the "-SR" group, where R can be hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, heterocyclyl, cycloalkyl(alkyl), aryl(alkyl), heteroaryl(alkyl), or heterocyclyl(alkyl). The sulfenyl can be substituted or unsubstituted.

[0066] A "sulfinyl" group refers to a "-S(=O)-R" group, where R can be the same as defined for sulfenyl. Sulfinyl can be substituted or unsubstituted.

[0067] A "sulfonyl" group refers to a "SOR" group where R can be the same as defined for sulfenyl. The sulfonyl can be substituted or unsubstituted.

[0068] As used herein, "haloalkyl" refers to an alkyl group in which one or more hydrogen atoms are replaced by halogen (for example, monohaloalkyl, dihaloalkyl, and trihaloalkyl). Such groups include, but are not limited to, chloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 1-chloro-2-fluoromethyl, and 2-fluoroisobutyl. Haloalkyl can be substituted or unsubstituted.

[0069] As used herein, "haloalkoxy" refers to an alkoxy group in which one or more hydrogen atoms are replaced by halogen (e.g., mono-haloalkoxy, di-haloalkoxy, and tri-haloalkoxy). Such groups include, but are not limited to, chloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 1-chloro-2-fluoromethoxy, and 2-fluoroisobutoxy. Haloalkoxy can be substituted or unsubstituted.

[0070] The term "nitro," as used herein, refers to the group --NO.sub.2.

[0071] The term "amino," as used herein, refers to the group --NH.sub.2.

[0072] A "monosubstituted amine" group refers to an "-NHR" group, where R can be alkyl, alkenyl, alkynyl, haloalkyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, heterocyclyl, cycloalkyl(alkyl), aryl(alkyl), heteroaryl(alkyl), or heterocyclyl(alkyl), as defined herein. The monosubstituted amino can be substituted or unsubstituted. Examples of monosubstituted amino groups include, but are not limited to, -NH(methyl), -NH(phenyl), and the like.

[0073] A "disubstituted amine" group is R A and R B and "-NR" can be independently alkyl, alkenyl, alkynyl, haloalkyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, heterocyclyl, cycloalkyl(alkyl), aryl(alkyl), heteroaryl(alkyl), or heterocyclyl(alkyl), as defined herein. A R B " group. Disubstituted amino can be substituted or unsubstituted. Examples of disubstituted amino groups include, but are not limited to, -N(methyl), -N(phenyl)(methyl), -N(ethyl)(methyl), and the like.

[0074] Where the number of substituents is not specified (e.g., haloalkyl), one or more substituents may be present. For example, "haloalkyl" can include one or more of the same or different halogens. As another example, "C1-C3 alkoxyphenyl" can include one or more of the same or different alkoxy groups containing 1, 2, or 3 atoms.

[0075] As used herein, a radical refers to a species that has a single unpaired electron, such that the radical-containing species can be covalently bonded to another species. Thus, in this context, a radical is not necessarily a free radical. Rather, a radical refers to a specific portion of a larger molecule. The term "radical" can be used interchangeably with the term "group."

[0076] In any compound described herein having one or more chiral centers, unless the absolute stereochemistry is explicitly indicated, it is understood that each center may independently be in the R or S configuration, or a mixture thereof. Thus, the compounds provided herein may be enantiomerically pure, enantiomerically enriched, racemic, diastereomerically pure, diastereomerically enriched, or a stereoisomeric mixture. Furthermore, in any compound described herein having one or more double bonds that produce geometric isomers that can be defined as E or Z, it is understood that each double bond may independently be E or Z, or a mixture thereof.

[0077] In some embodiments, all tautomeric forms of any compound described are intended to be included. For example, but not limited to, the compound The reference to TIFF2025534217000007.tif19114 refers to the tautomer TIFF2025534217000008.tif17114.

[0078] It is understood that if the compounds disclosed herein have unsatisfied valences, the valences should be filled with hydrogen or an isotope thereof, such as hydrogen-1 (protium) and hydrogen-2 (deuterium).

[0079] ·Electrolyte The electrolyte formulations described herein can include an alkali metal salt (e.g., a lithium salt and / or a sodium salt) and one or more of the solvents discussed herein. Generally, the alkali metal salt includes a cation and an anion. In some embodiments, the anion is redox stable. In some embodiments, the anion can be monovalent. In some embodiments, the cation of the alkali metal salt is selected from Li, Na, K, and / or Rb. In some embodiments, the sodium salt can be selected from NaPF6, NaBF4, NaClO4, NaN(FSO2)2 (NaFSI), NaB(C2O4)2, and combinations thereof. In some embodiments, the lithium salt can be selected from lithium hexafluorophosphate (LiPF), lithium tetrafluoroborate (LiBF), lithium difluoro(oxalato)borate (LiDFOB), lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium hexafluoroarsenate(V) (LiAsF), lithium perchlorate (LiClO), and combinations thereof. In some embodiments, the lithium salt is LiFSI. In some embodiments, the lithium salt can include an anion selected from hexafluorophosphate, tetrafluoroborate, difluoro(oxalato)borate, bis(fluorosulfonyl)imide, bis(trifluoromethanesulfonyl)imide, hexafluoroarsenate(V), and perchlorate.In certain embodiments, the salt concentration of the electrolyte is 0.1M, 0.2M, 0.3M, 0.4M, 0.5M, 0.6M, 0.7M, 0.8M, 0.9M, 1M, 1.1M, 1.2M, 1.3M, 1.4M, 1.5M, 1.6M, 1.7M, 1.8M, 1.9M, 2M, 2.1M, 2.2M, 2.3M, 2.4M, 2.5M, 2.6M, 2.7M, 2.8M, 2.9M, 3M, 3.1M, 3.2M, 3.3M, 3.4M, 3.5M, 3.6M, 3.7M, 3.8M, 3.9M, 4.0M, 4.1M, 4.2M, 4.3M, 4.4M, 4.5M, 4.6M, 4.7M, 4.8M, 4.9M, 5.0M, 5.1M, 5.2M, 5.3M, 5.4M, 5.5M, 5.6M, 5.7M, 5.8M, 5.9M, 6.0M, 6.1M, 6.2M, 6.3M, 6.4M, 6.5M, 6.6M, 6.7M, 6.8M, 6.9M, 7.0M, 7.1M, 7.2M, 7.3M, 7.4M, 7.5M, 7.6M, 7.7M, 7.8M, 7.9M, 8.0M, 8.1M, 8.2M, 8.3M, 8.4M, 8 The salt concentration may be about, up to, or up to about 0.8M, 3.9M, 4M, 4.1M, 4.2M, 4.3M, 4.4M, 4.5M, 4.6M, 4.7M, 4.8M, 4.9M, 5M, 5.1M, 5.2M, 5.3M, 5.4M, 5.5M, 5.6M, 5.7M, 5.8M, 5.9M, 6M, 6.1M, 6.2M, 6.3M, 6.4M, 6.5M, 6.6M, 6.7M, 6.8M, 6.9M, or 7M, or any range therebetween. For example, in some embodiments, the salt concentration may be about 0.1M to about 5M, about 0.2M to about 3M, about 0.3M to about 2M, or about 0.7M to about 1.5M.

[0080] In some embodiments, the electrolyte further comprises one or more additives. In some embodiments, the additive may be selected from, for example, vinylene carbonate (VC), ethylene sulfate (DTD), lithium difluorophosphate (LFO), fluoroethylene carbonate (FEC), propene sulfone (PES), phenyl trifluoromethyl sulfide (PTS), lithium bis(oxalato)borate (LiBOB), lithium difluoro(oxalato)borate (LiDFOB), triethyl borate (TEB), trimethyl borate (TMB), tristrimethylsilyl borate (TTMSiB), 4-trifluoromethylbenzonitrile (TFMB), tristrimethylsilyl phosphite (TTSPi), tristrimethylsilyl phosphate (TTSPi), triethyl phosphite (TEPi), lithium ethoxide (EthOLi), lithium methoxide (MeOLi), lithium tetrafluorooxalate phosphate (LiTFOP), lithium difluorodioxalate phosphate (LiDFDOP), and combinations thereof.

[0081] In some embodiments, the electrolyte further comprises one or more additional additives, which may be selected from, for example, diethylpyrocarbonate (DEPC), dimethylpyrocarbonate (DMPC), diallylpyrocarbonate (DAPC), lithium difluoro(oxalato)borate LiDFOB, lithium difluorobis(oxalato)phosphate LiDFBOP, di-tert-butyldicarbonate (Boc anhydride), and combinations thereof.

[0082] In some embodiments, the electrolyte includes 0.1 wt.%, 0.5 wt.%, 1 wt.%, 1.5 wt.%, 2 wt.%, 2.5 wt.%, 3 wt.%, 3.5 wt.%, 4 wt.%, 4.5 wt.%, 5 wt.%, 5.5 wt.%, 6 wt.%, 7 wt.%, or 8 wt.%, about that value, up to that value, or up to about that value, or any value range therebetween, of each additive. In some embodiments, the electrolyte comprises a plurality of additives that total 0.5 wt.%, 1 wt.%, 1.5 wt.%, 2 wt.%, 2.5 wt.%, 3 wt.%, 3.5 wt.%, 4 wt.%, 4.5 wt.%, 5 wt.%, 5.5 wt.%, 6 wt.%, 6.5 wt.%, 7 wt.%, 7.5 wt.%, 8 wt.%, 8.5 wt.%, 9 wt.%, 9.5 wt.%, 10 wt.%, 11 wt.%, or 12 wt.%, a total of about that value, a total of up to that value, or a total of up to about that value, or any value range therebetween. solvent

[0083] In some embodiments, the electrolyte comprises a liquid solvent. The solvents provided herein need not dissolve all components, and need not completely dissolve the components of the electrolyte. In further embodiments, the solvent may comprise an organic solvent. In some embodiments, the solvent may comprise one or more functional groups selected from carbonate, dimer carbonate, ether, and / or ester. In some embodiments, the electrolyte comprises one solvent. In other embodiments, the electrolyte comprises multiple solvents. In some embodiments, the solvent may comprise an alkyl decarbonate compound and / or a dimerization compound (e.g., an alkyl didecarbonate compound).

[0084] In some embodiments, the solvent may include a carbonate. In further embodiments, the carbonate may be selected from cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), vinyl ethylene carbonate (VEC), vinylene carbonate (VC), fluoroethylene carbonate (FEC), and combinations thereof, or acyclic carbonates such as dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), and combinations thereof. In some embodiments, the solvent may include fluoroethylene carbonate (FEC). In some embodiments, the solvent may further include methyl acetate (MA). In some embodiments, the solvent may include ethyl acetate (EA). In some embodiments, the solvent may include propionitrile (PN). In some embodiments, the solvent may include acetonitrile (AN). In some embodiments, the solvent may include butyrolactone (GBL). In some embodiments, the solvent is free or substantially free of ethylene carbonate (EC). In some embodiments, the solvent is free or substantially free of dimethyl carbonate (DMC).

[0085] In some embodiments, the solvent comprises or is a fluorinated solvent, and the fluorinated solvent is selected from fluoroethylene carbonate (FEC), difluoroethylene carbonate (diFEC), methyl 2,2,2-trifluoroethyl carbonate (FEMC), bis(2,2,2-trifluoroethyl)carbonate (TFEC), trifluoropropylene carbonate (TFPC), 2,2,3,3-tetrafluoro-1,4-dimethoxybutane (fDMB), bis(2,2,2-trifluoroethyl)ether (BTFE), 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), and combinations thereof.

[0086] In some embodiments, the electrolyte comprises 70 wt.%, 71 wt.%, 72 wt.%, 73 wt.%, 74 wt.%, 75 wt.%, 76 wt.%, 77 wt.%, 78 wt.%, 79 wt.%, 80 wt.%, 81 wt.%, 82 wt.%, 83 wt.%, 84 wt.%, 85 wt.%, 86 wt.%, 87 wt.%, 88 wt.%, 89 wt.%, 90 wt.%, 91 wt.%, 92 wt.%, 93 wt.%, 94 wt.%, 95 wt.%, 96 wt.%, 97 wt.%, or 98 wt.%, or about that value, or at least about that value, or any value range therebetween.In some embodiments, the electrolyte contains each solvent individually at 1 wt.%, 2 wt.%, 3 wt.%, 4 wt.%, 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, 10 wt.%, 11 wt.%, 12 wt.%, 13 wt.%, 14 wt.%, 15 wt.%, 16 wt.%, 17 wt.%, 18 wt.%, 19 wt.%, 20 wt.%, 21 wt.%, 22 wt.%, 23 wt.%, 24 wt.%, 25 wt. .%, 26wt.%, 27wt.%, 28wt.%, 29wt.%, 30wt.%, 31wt.%, 32wt.%, 33wt.%, 34wt.%, 35wt.%, 36wt.%, 37wt.%, 38wt.%, 39wt.%, 40wt.%, 41wt.%, 42wt.%, 43wt.%, 44wt.%, 45wt.%, 46wt.%, 47wt.%, 48wt.%, 49wt.%, 50wt.%, 51wt.%, 52w t.%, 53wt.%, 54wt.%, 55wt.%, 56wt.%, 57wt.%, 58wt.%, 59wt.%, 60wt.%, 61wt.%, 62wt.%, 63wt.%, 64wt.%, 65wt.% , 66wt.%, 67wt.%, 68wt.%, 69wt.%, 70wt.%, 71wt.%, 72wt.%, 73wt.%, 74wt.%, 75wt.%, 76wt.%, 77wt.%, 78wt.%, 79 wt.%, 80wt.%, 81wt.%, 82wt.%, 83wt.%, 84wt.%, 85wt.%, 86wt.%, 87wt.%, 88wt.%, 89wt.%, 90wt.%, 91wt.%, 92wt.%, 93wt.%, 94wt.%, 95wt.%, 96wt.%, 97wt.% or 98wt.%, about that value, at least that value, or at least about that value, or any range of values ​​therebetween.

[0087] In some embodiments, the electrolyte comprises one or more solvents. In some embodiments, the electrolyte comprises one, two, three, four, five, or six solvent systems, or any range of solvents therebetween. In some embodiments, the electrolyte comprises a first solvent and a second solvent. In some embodiments, the electrolyte solvent system can comprise a first solvent and a second solvent in a volume ratio of about 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, 1:4, 1:6, 1:7, 1:8, 1:9, 1:10, or any range therebetween. For example, in some embodiments, the volume ratio can be about 3:7, about 1:1, about 1:4, about 4:1, about 3:2, or about 2:3.

[0088] Carbon dioxide (CO2) source In some embodiments, the electrolyte comprises at least one carbon dioxide source. The carbon dioxide source provided herein can be selected from, for example, gaseous carbon dioxide, dry ice (i.e., solid carbon dioxide), and pyrocarbonate, such as diethylpyrocarbonate (DEPC) and / or the compound of formula (A) described herein, and combinations thereof. For example, in some embodiments, the carbon dioxide source comprises diethylpyrocarbonate (DEPC). Formula (A)

[0089] In some embodiments, the carbon dioxide source comprises or is a compound of formula (A): TIFF2025534217000009.tif15114(A)

[0090] In some embodiments, R 1 and R 2 is independently selected from hydrogen, optionally substituted alkyl, optionally substituted haloalkyl, optionally substituted alkenyl, and optionally substituted alkynyl. In some embodiments, R 1 and R 2is independently selected from optionally substituted alkyl and optionally substituted alkenyl.

[0091] In some embodiments, the carbon dioxide source of Formula (A) is selected from any one or any combination of the compounds shown in Table A. [Table A]

[0092] In some embodiments, the electrolyte contains at least one carbon dioxide source at 0.01 wt.%, 0.05 wt.%, 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, 1 wt.%, 2 wt.%, 3 wt.%, 4 wt.%, 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, 10 wt.%, 11 wt.%, 12 wt.%, 13 wt.%, 14 wt.%, 15 wt.%, 16 wt.%, 17 wt.%, 18 wt.%, 19 wt.%, 20 wt.%, 21 wt.%, 22 wt.%, 23 wt.%, 24 wt.%, 25 wt.%, 26 wt.%, 27 wt.%, 28 wt.%, 29 wt.%, 30 wt.%, 31 wt.%, 32 wt.%, 33 wt.%, 34 wt.%, 35 wt.%, 36 wt.%, 37 wt.%, 38 wt.%, 39 wt.%, 40 wt.%, 41 wt.%, 42 wt.%, 43 wt.%, 44 wt.%, 45 wt.%, 46 wt.%, 47 wt.%, 48 wt.%, 49 wt.%, 50 wt.%, 51 wt.%, 52 wt.%, 53 wt.%, 54 wt.%, 55 wt.%, 56 wt.%, 57 wt.%, 58 wt.%, 59 wt.%, 59 %, 6wt.%, 7wt.%, 8wt.%, 9wt.%, 10wt.%, 11wt.%, 12wt.%, 13wt.%, 14wt.%, 15wt.%, 16wt.%, 17wt.%, 18wt.%, 19wt.%, 20wt.%, about that value, at least that value, or at least about that value, or any range of values ​​therebetween.

[0093] In some embodiments, the electrolyte formulation is completely saturated with carbon dioxide. In further embodiments, additional carbon dioxide may be included in the battery.

[0094] Energy storage devices The energy storage device of the present disclosure includes an electrolyte, a cathode, an anode, and a housing as discussed herein, wherein the electrolyte, cathode, and anode are disposed within the housing. In some embodiments, the energy storage device provided herein is a lithium-ion battery and / or a sodium-ion battery. In some embodiments, the energy storage device provided herein is configured to have at least 70% retention of initial capacity after 100 cycles at a C3:C2 charge rate from 4.1 V to 2.85 V. In some embodiments, the energy storage device is configured to have at least 70% retention of initial capacity after 140 cycles at a C3:C2 charge rate from 4.1 V to 2.85 V. In some embodiments, the energy storage device is a battery. In some embodiments, the energy storage device is configured to have at least 70% retention of initial capacity after 225 cycles at a C4:C3 charge rate from 4.2 V to 2.85 V. Each of the cathode and anode includes an electrode film and a current collector forming an electrode.

[0095] In some embodiments, the electrode films provided herein comprise at least one active material. In some embodiments, the electrode films further comprise at least one binder.

[0096] In some embodiments, the electrode film includes an anode active material. In some embodiments, the anode active material can include, for example, an intercalation material (e.g., carbon or graphite), an alloying / dealloying material (e.g., silicon, silicon oxide, tin, and / or tin oxide), a metal alloy or compound (e.g., Si—Al and / or Si—Sn), lithium titanate (LTO), and / or a conversion material (e.g., manganese oxide, molybdenum oxide, nickel oxide, and / or copper oxide). The anode active materials can be used alone or mixed together to form a multiphase material (e.g., Si—C, Sn—C, SiOx—C, SnOx—C, Si—Sn, Si—SiOx, Sn—SnOx, Si—SiOx—C, Sn—SnOx—C, Si—Sn—C, SiOx—SnOx—C, Si—SiOx—Sn, Sn—SiOx—Sn). Anode active materials include common natural graphite, synthetic or artificial graphite, surface-modified graphite, spherical graphite, flake graphite, as well as blends or combinations of these types of graphite, hard carbon, metallic elements and their compounds, and metal-C composites for the anode.

[0097] In some embodiments, the anode active material can include, for example, silicon particles. In some embodiments, the d of the silicon particles 50 In some embodiments, the d of the silicon particles is between about 1 μm and about 10 μm. 50 In some embodiments, the d of the silicon particles is between about 1 μm and about 5 μm. 50 is at or at least about 1 μm, 1.1 μm, 1.2 μm, 1.3 μm, 1.4 μm, 1.5 μm, 1.6 μm, 1.7 μm, 1.8 μm, 1.9 μm, 2 μm, 2.1 μm, 2.2 μm, 2.3 μm, 2.4 μm, 2.5 μm, 2.6 μm, 2.7 μm, 2.8 μm, 2.9 μm, 3 μm, 3.1 μm, 3.2 μm, 3.3 μm, 3.4 μm, 3.5 μm, 3.6 μm, 3.7 μm, 3.8 μm, 3.9 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, or a range of at least about that value, or any value therebetween.

[0098] In some embodiments, the electrode film includes an active cathode material. In some embodiments, the cathode active material can include, for example, a metal oxide, a metal sulfide, or an alkali metal oxide (e.g., lithium metal oxide and / or sodium metal oxide). The lithium metal oxide can be, for example, lithium nickel manganese cobalt oxide (NMC), lithium manganese oxide (LMO), lithium nickel dioxide (LNO), lithium iron phosphate (LFP), lithium cobalt oxide (LCO), and / or lithium nickel cobalt aluminum oxide (NCA). In some embodiments, the cathode active material can be, for example, a layered transition metal oxide (e.g., LiCoO (LCO), Li(NiMnCo)O (NMC), and / or LiNi 0.8 Co 0.15 Al 0.05 O2(NCA)), spinel manganese oxides (e.g., LiMn2O4 and / or LiMn 1.5 Ni 0.5 O4(LMNO)), olivine (e.g., LiFePO4(LFP) or LiMn 1-x Fe x The cathode active material may include sulfur, or a sulfur-containing material such as lithium sulfide (LiS), or other sulfur-based materials, or mixtures thereof. In some embodiments, the sodium metal oxide may be, for example, a layered oxide, a phosphate, and / or a ferricyanide (e.g., a compound in the Prussian White family). In some embodiments, the sodium metal oxide may be, for example, NaFe 0.5 Mn 0.5 O2, NaNi 1 / 3 Fe 1 / 3 Mn 1 / 3 O2, NaFe2(CN)6, Na2VOPO4F, NaMnO2, and / or NaFe 0.3 Mn 0.5 Cu 0.2 It can be O2.

[0099] The energy storage device provided herein can be any suitable configuration, for example, flat, spirally wound, button-shaped, or pouch-shaped.The energy storage device provided herein can be a system component, for example, a power generation system, an uninterruptible power supply system (UPS), a solar power generation system, or an energy recovery system for use in industrial machinery and / or transportation.The energy storage device provided herein can be used to power various electronic devices and / or automobiles, including hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), and / or electric vehicles (EVs).

[0100] Energy storage devices containing the electrolyte formulations described herein may feature improved capacity retention over the life of the device. Further improvements that may be realized in various embodiments include improved cycling performance, including improved storage stability and reduced capacity fade during cycling. In some embodiments, improved cycling performance has also been achieved under aggressive or stress conditions (e.g., long constant voltage holds at 4.4 V).

[0101] It will be understood that the electrolyte formulations provided herein can be used in various embodiments with any of a number of energy storage devices and systems, such as one or more batteries, capacitors, capacitor-battery hybrids, fuel cells, or other energy storage systems or devices and combinations thereof. In some embodiments, the electrolyte additives or electrolytes including the additives described herein can be implemented in lithium-ion batteries and / or sodium-ion batteries.

[0102] In some embodiments, the lithium ion battery is configured to operate between about 2.5 and 4.5 V, or between 3.0 and 4.2 V. In further embodiments, the lithium ion battery is configured to have a minimum operating voltage between about 2.5 V and about 3 V, respectively. In still further embodiments, the lithium ion battery is configured to have a maximum operating voltage between about 4.1 V and about 4.4 V, respectively.

[0103] ·Preparation method The additives, electrolytes, and energy storage devices discussed herein may be synthesized or manufactured. In some embodiments, a method for preparing an energy storage device includes preparing an electrolyte discussed herein and disposing the electrolyte in a housing containing a cathode and an anode. In some embodiments, the method for preparing the electrolyte includes combining at least one carbon dioxide source, a fluorinated solvent, and a lithium salt to form the electrolyte. In some embodiments, the electrolyte may be pre-saturated with carbon dioxide before filling the battery with the electrolyte during manufacture.

[0104] In some embodiments, carbon dioxide can be introduced directly into the battery by placing dry ice into the battery after the e-fill process and before sealing the battery. In some embodiments, carbon dioxide can be introduced directly into the battery by injecting gaseous carbon dioxide through a feedthrough port on the battery. In some embodiments, carbon dioxide can be generated in situ in the electrolyte by the use of a carbon dioxide-generating electrolyte additive. In some embodiments, a carbon dioxide-generating electrolyte additive is mixed directly into the electrolyte before or after filling the electrolyte into the battery, and carbon dioxide is generated via chemical and / or electrochemical reactions within the cell (e.g., during cycling). aging

[0105] Some embodiments of the present disclosure relate to aging the electrolyte before placing it in a housing. In some embodiments, the electrolyte is aged for 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, 25 hours, 26 hours, 27 hours, 28 hours, 29 hours, 30 hours, 31 hours, 32 hours, 33 hours, or 34 hours. The electrolyte may be aged for about, at least, or at least about 2 hours, 35 hours, 36 hours, 37 hours, 38 hours, 39 hours, 40 hours, 41 hours, 42 hours, 43 hours, 44 hours, 45 hours, 46 hours, 47 hours, 48 ​​hours, 3 days, 4 days, 5 days, 6 days, 7 days, 2 weeks, 3 weeks, 4 weeks, 2 months, 3 months, 4 months, about, at least, or at least about 2 hours, or any time range therebetween. For example, in some embodiments, the electrolyte is aged for about 2 hours to about 48 hours, about 7 days to about 2 weeks, or 4 weeks to about 3 months.

[0106] In some embodiments, the electrolyte formulations of the present disclosure can be stored at room temperature, hi further embodiments, the electrolyte formulations of the present disclosure maintain battery performance without being stored at low temperatures. [Example]

[0107] Exemplary embodiments of the present disclosure, including processes, materials and / or resulting products, are described in the following examples.

[0108] Example 1 - XPS characterization of SEI components obtained from cycling a battery with a micron-silicon anode Fluorinated electrolyte solvents, such as fluoroethylene carbonate (FEC), were used to generate and characterize LiF and polymer carbonate species at the solid electrolyte interface (SEI) of micron-silicon anodes. Figure 1 shows the results of an X-ray photoelectron spectroscopy (XPS) study highlighting the ratio of LiF content to carbonate species in the SEI on micron-silicon anodes cycled in various electrolyte formulations. Sample 1A (also known as "baseline" or "TB baseline") contained an electrolyte containing 39.7 wt.% EC and 7.7 wt.% FEC, while Sample 1B (also known as "fluorinated TB baseline") contained an electrolyte containing 34 wt.% EC and 20 wt.% FEC. The SEI on the micron-silicon anodes in the electrolytes of Sample 1A and Sample 1B is similar. Sample 1C contained an electrolyte containing 20 wt.% FEC, 60 wt.% methyl 2,2,2-trifluoroethyl carbonate (FEMC), and 20 wt.% 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE). Sample 1D (also "TB-156") contained an electrolyte containing 0 wt.% EC and 20 wt.% FEC, demonstrating a substantially higher LiF:carbonate ratio compared to the EC-containing electrolyte.

[0109] This high LiF:carbonate ratio is advantageous because LiF has a high bandgap (electronic insulator) and is conductive to lithium ions, making it a valuable component of the SEI. Furthermore, polymeric carbonate species such as polyvinylene carbonate (poly-VC) can offer important flexibility to accommodate the expansion and contraction of materials like silicon. Both LiF and poly-VC are formed by the FEC reduction pathway.

[0110] Example 2: Cycling performance of pouch cells using micron-silicon anodes Cycling data comparing the pouch cell with a micron-silicon anode and NMC811 cathode over a 4.1-2.85 V, C3:C2 cycle was also tested, and the results are shown in Figure 2. Varying amounts of CO2 were injected into the cell and compared to baseline cycling performance. CO2 injection was achieved using a CO2-filled syringe in a glove box to prevent ambient air from entering the cell. As shown in Figure 2, a CO2 content of 3 mL improved cycle life by 30-40% (to a 30% energy loss) and reduced catastrophic battery failure (i.e., a lower slope of the end-of-life energy loss curve), as shown in Samples 2C and 2D. A CO2 content of 6 mL produced swollen pouch cells and, in some cases, reduced the mechanical integrity of the electrode stack, as shown in Samples 2E and 2F. In this case, Sample 2A (also known as "Baseline" or "TB Baseline"), which contains an electrolyte containing 39.7 wt.% EC and 7.7 wt.% FEC, was used to study gas addition. The results, shown in Figure 2, demonstrate the concept that CO saturation of the electrolyte significantly improves SEI characteristics and cycle life using high-energy-density silicon anodes.

[0111] FIG. 2 also shows that an injection of 3 mL of CO 2 gas was performed similarly to Sample 2B, which contained 5 wt. % DEPC in the electrolyte formulation.

[0112] Example 3 - XPS characterization of SEI components obtained from cycling EC-free electrolyte with and without DEPC XPS studies comparing EC-free electrolytes with and without DEPC were also performed. The proportion of LiF was compared to other SEI species for electrolytes without and with a 5 wt.% DEPC additive. Figure 3A shows the atomic percentage of F 1s versus sputter depth. As shown in Figure 3A, Sample 3B, which contained an electrolyte with 5 wt.% DEPC, provided a higher atomic percentage of F 1s compared to Sample 3A, which contained an electrolyte without DEPC. As shown in Figure 3B, Sample 3A formed an SEI with a significantly higher ratio of LiF:carbonate species. This represents a further improvement from the SEI characterized in Figure 1. Thus, both the removal of EC and the addition of CO2 produced a higher-performance SEI. Furthermore, a thinner SEI was obtained using a CO2-saturated electrolyte without EC. After over 90% cycle life, the SEI formed by the EC-free, 20 wt.% FEC, CO2-saturated electrolyte is nearly as thick as the baseline electrolyte at end-of-life (defined as 70% energy retention). Because SEI formation / reformation consumes lithium ions, leading to premature battery failure, the fact that the SEI requires more cycles to achieve the same thickness is consistent with the lower lithium ion inventory loss in the better electrolyte.

[0113] Example 4 - Capacity retention performance Formation of an SEI with the highest LiF:carbonate ratio resulted in a dramatic improvement in cycle life in lithium-ion batteries. This was demonstrated in pouch cells containing a micron-silicon anode and an NMC811 cathode cycled from 4.1 to 2.85 V C3:C2 (>90% depth of discharge).

[0114] Figure 4 highlights the cycle life improvement resulting from removing EC, increasing FEC to 20 wt.%, and then adding increasing amounts of DEPC. This is an advantageous high-energy density battery design incorporating micron-silicon anode technology. Specifically, Sample 4A, containing an electrolyte containing >30 wt.% EC and 7.7 wt.% FEC, was compared with Sample 4B, containing an EC-free, 20 wt.% FEC electrolyte formulation. Sample 4C contained an EC-free, 20 wt.% FEC electrolyte formulation and LiFSI. Varying amounts of DEPC were added to the EC-free, 20 wt.% FEC formulation, as shown in Samples 4D and 4E.

[0115] As can be seen in Figure 4, removing EC and adding 20 wt.% FEC demonstrated a 40% improvement in cycle life, as shown in Samples 4B and 4C. Adding just 2.5 wt.% DEPC to the high-FEC electrolyte without EC nearly doubled the cycle life over the baseline, as shown in Sample 4E. This cycling study demonstrates the incremental improvement provided by the change in electrolyte formulation, resulting in a 90+% improvement in cycle life in this aggressive cycling test.

[0116] Example 5: CO2 gas generation The CO2 gassing volumes generated by various electrolytes were compared in pouch cells with a micron-silicon anode and an NMC811 cathode during the formation cycle and under C3:C2 cycling conditions from 4.1 to 2.85 V. Figure 5 shows the optimization of CO2 gassing volumes in a high-FEC electrolyte without EC containing DEPC additive. CO2 gassing volumes were measured after aging ("After Aging"), immediately after formation (also "Initial Baseline Performance Test" or "RPT-0"), after 100 cycles at 25 °C ("100 cycles at 25 °C"), after a baseline performance test consisting of 100 cycles at 25 °C (also "RPT-100 at 25 °C"), at end-of-life ("EOL" or 70% energy retention at 25 °C), and after a baseline performance test at end-of-life (also "RPT-EOL at 25 °C"). CO gas volume was measured in a pouch cell containing 7.7 wt.% FEC and 40 wt.% EC (HMC); a cylindrical cell containing 20 wt.% FEC and 0 wt.% EC; a pouch cell containing 20 wt.% FEC, 0 wt.% EC, and LiFSI; a cylindrical cell containing 20 wt.% FEC, 0 wt.% EC, LiFSI, and 1.5 wt.% DEPC; and a cylindrical cell containing 20 wt.% FEC, 0 wt.% EC, LiFSI, and 2.5 wt.% DEPC. As shown in Figure 5, concentrations of 1.5 to 2.5 wt.% DEPC were determined to be commercially viable and showed significant improvements in cycle life.

[0117] As shown in Figure 5, the cycle life of the micron-silicon anode was doubled by incorporating an EC-free, high-FEC electrolyte with CO2 saturation. The same electrolyte strategy has broad applicability to various lithium-ion and lithium-metal battery designs based on the SEI properties described herein. The same LiF:carbonate ratio in the SEI also improved the cycle life of anodes ranging from graphite, to SiC materials, to lithium metal.

[0118] Example 6 - Pouch cell discharge capacity The electrolytes and additives were tested in a pouch cell format with an NMC-based cathode and a composite micron-silicon / graphite anode. The pouch cells were filled with electrolyte and vacuum-sealed in a glove box. The pouch bag was sized to allow excess gas to expand into the unrestrained portion of the bag. The cells were not evacuated after initial sealing. For cells injected with gaseous carbon dioxide, a feedthrough port was incorporated into the pouch cell structure, and the carbon dioxide injection occurred after the cell was filled with electrolyte and sealed. A pouch cell fixture was used to apply constant stack pressure to the cells throughout the cycle while allowing the gas to expand into the unrestrained portion of the pouch bag.

[0119] Electrochemical cycling tests were performed at 25° C. All cells were cycled under asymmetric constant current-constant potentiostatic (CC-CV) charge-discharge conditions with voltage cutoffs ranging from 4.2 V to 2.85 V at charge-discharge rates between C / 20 and C / 2, depending on the experiment. All capacity measurements were normalized by the active material mass loading of the cathode.

[0120] The cycling data demonstrated improved life performance with direct injection of gaseous carbon dioxide into the pouch cell through the feed-through port. Figure 6 shows the discharge capacity versus cycle number for a battery with an electrolyte system injected with gaseous carbon dioxide. Carbon dioxide was introduced directly into the battery by injecting gaseous carbon dioxide through the battery's feed-through port. Figure 6 shows that injecting 3 mL and 6 mL of gaseous carbon dioxide into the pouch cell (e.g., Sample 6B and Sample 6C, respectively) resulted in superior discharge capacity during cycling compared to a baseline electrolyte system that did not contain gaseous carbon dioxide, such as Sample 6A.

[0121] Example 7 - Discharge capacity and gas generation with various amounts of FEC Electrolytes were tested using various amounts of fluoroethylene carbonate (FEC). Figure 7A is a plot showing the discharge capacity versus cycle number for batteries with electrolyte systems containing various amounts of solvent blends. Figure 7A shows data for Sample 7A, which contains 2.5 wt.% DMPC, 80 wt.% EMC, and 20 wt.% FEC; Sample 7B, which contains 2.5 wt.% DMPC, 82.5 wt.% EMC, and 17.5 wt.% FEC; Sample 7C, which contains 2.5 wt.% DMPC, 85 wt.% EMC, and 15 wt.% FEC; Sample 7D, which contains 2.5 wt.% DMPC, 87.5 wt.% EMC, and 12.5 wt.% FEC; and Sample 7E, which contains 2.5 wt.% DMPC, 90 wt.% EMC, and 10 wt.% FEC. Surprisingly, the use of 10% FEC, such as in Sample 7E, gave better results than the use of 20% FEC, such as in Sample 7A.

[0122] Additionally, pouch cells were periodically measured for volume change throughout their cycle life. The measurements presented herein were obtained ex situ by removing the cells from the fixture and briefly immersing them in deionized water or oil. Buoyancy was determined by a laboratory balance, and volume change was calculated based on the change in buoyancy compared to the initial measurement before cycling.

[0123] Lower FEC content showed smaller gas volumes at end-of-life compared to electrolytes with higher FEC content. Specifically, Figure 7B shows gas formation for the same electrolyte system used in Figure 7A. Again, using 10% FEC produced better results than using 20% ​​FEC.

[0124] Example 8 - Discharge capacity and gas generation of electrolytes containing DEPC The cycling data showed improved life performance with the addition of diethylpyrocarbonate (DEPC), an electrolyte additive that generates carbon dioxide in situ. Figure 8A shows data for Sample 8A (also "baseline"), which contains 20 wt.% FEC; Sample 8B (also "baseline"), which contains 20 wt.% FEC and 5 wt.% DEPC; and Sample 8C (also "baseline"), which contains 20 wt.% FEC and 10 wt.% DEPC. Figures 8B and 8C show data for Sample 8D (also "baseline"), which contains 20 wt.% FEC; Sample 8E (also "baseline"), which contains 20 wt.% FEC and 1.5 wt.% DEPC; and Sample 8F (also "baseline"), which contains 20 wt.% FEC and 2.5 wt.% DEPC. Figures 8A and 8B show the discharge capacity versus cycle number of a battery with an electrolyte system containing diethylpyrocarbonate (DEPC) compared to the baseline electrolyte system. As shown in Figures 8A and 8B, the use of DEPC resulted in improved results compared to the baseline electrolyte system without DEPC.

[0125] Additionally, Figure 8C shows gas formation in an electrolyte system containing diethylpyrocarbonate (DEPC) relative to a baseline electrolyte system without DEPC. As shown in Figure 8C, the use of 1.5% DEPC, such as Sample 8E, yielded similar results to a baseline electrolyte system without DEPC, such as Sample 8D.

[0126] While certain embodiments of the present invention have been described, these embodiments are presented by way of example only and are not intended to limit the scope of the present disclosure. Indeed, the novel methods and systems described herein may be embodied in a variety of other forms. Furthermore, various omissions, substitutions, and modifications of the systems and methods described herein may be made without departing from the spirit of the present disclosure. The appended claims and their equivalents are intended to cover such forms or modifications as are within the scope and spirit of the present disclosure. Accordingly, the scope of the present invention is defined solely by reference to the appended claims.

[0127] A feature, material, characteristic, or group described in connection with a particular aspect, embodiment, or example should be understood to be applicable to any other aspect, embodiment, or example described in this section or elsewhere in this specification, unless inconsistent therewith. All features disclosed in this specification (including the accompanying claims, abstract, and drawings), and / or all steps of any method or process so disclosed, may be combined in any combination, except combinations in which at least some of such features and / or steps are mutually exclusive. Protection is not limited to the details of any foregoing embodiment. Protection extends to any novel, or any novel combination of, features disclosed in this specification (including the accompanying claims, abstract, and drawings), or any novel, or any novel combination of steps of any method or process so disclosed.

[0128] Furthermore, certain features that are described in this disclosure in the context of separate embodiments can also be implemented in combination in a single embodiment. Conversely, various features that are described in the context of a single embodiment can also be implemented in multiple embodiments separately or in any suitable subcombination. Furthermore, while features may be described above as acting in a particular combination, one or more features from a claimed combination can, in some cases, be deleted from the combination, and the combination can be claimed as a subcombination or a variation of the subcombination.

[0129] Furthermore, while operations may be shown in the figures or described herein in a particular order, such operations need not be performed in the particular order shown, or in sequential order, or even all operations need to be performed to achieve desirable results. Other operations not shown or described may be incorporated into the example methods and processes. For example, one or more additional operations may be performed before, after, simultaneously with, or between any of the described operations. Furthermore, operations may be rearranged or reordered in other implementations. Those skilled in the art will understand that in some embodiments, the actual steps performed in the illustrated and / or disclosed processes may differ from those shown in the figures. Depending on the implementation, certain of the above-described steps may be removed, and other steps may be added. Furthermore, the features and attributes of the specific embodiments disclosed above can be combined in different ways to form additional embodiments, all of which are within the scope of the present disclosure. Also, the separation of the various system components in the above-described implementations should not be understood to require such separation in all implementations, and it should be understood that the described components and systems may generally be integrated together in a single product or packaged in multiple products. For example, any of the components of the energy storage systems described herein may be provided separately or may be incorporated together (e.g., packaged together or attached together) to form an energy storage system.

[0130] For purposes of this disclosure, certain aspects, advantages, and novel features have been described herein. Not necessarily all such advantages may be achieved in accordance with any particular embodiment. Thus, for example, one skilled in the art will recognize that the present disclosure may be embodied or implemented to achieve one advantage or group of advantages as taught herein without necessarily achieving other advantages as may be taught or suggested herein.

[0131] Conditional language such as "can," "could," "might," or "may," unless otherwise specified or understood otherwise within the context in which it is used, is generally intended to convey that certain embodiments include certain features, elements, and / or steps, while other embodiments do not. Thus, such conditional language is generally not intended to imply that the features, elements, and / or steps are somehow required in one or more embodiments, or that one or more embodiments necessarily include logic for determining whether those features, elements, and / or steps should be included in or performed in any particular embodiment, with or without user input or prompting.

[0132] Transitive language such as the phrase "at least one of X, Y, and Z," unless otherwise specified, is understood in the context in which it is generally used to convey that an item, term, etc. can be either X, Y, or Z. Thus, such transitive language is generally not intended to imply that a particular embodiment requires the presence of at least one of X, at least one of Y, and at least one of Z.

[0133] As used herein, language of degree, such as the terms "approximately," "about," "generally," and "substantially," refers to a value, amount, or characteristic that is close to a stated value, amount, or characteristic that still performs a desired function or achieves a desired result. For example, the terms "approximately," "about," "generally," and "substantially" can refer to an amount that is less than 10%, less than 5%, less than 1%, less than 0.1%, and less than 0.01% of the stated amount, depending on the desired function or desired result.

[0134] The scope of the present disclosure is not intended to be limited by the specific disclosure of preferred embodiments in this section or elsewhere herein, but rather may be defined by the claims, as presented in this section or elsewhere herein, or as presented in the future. Claim language is to be interpreted broadly based on the language used in the claims, and not limited to the examples described herein or during the prosecution of this application, and examples are to be construed as non-exclusive.

Claims

1. 1. An energy storage device comprising: a cathode; an anode; an electrolyte comprising a lithium salt, a carbon dioxide source, and a fluorinated solvent; an energy storage device comprising:

2. 10. The energy storage device of claim 1, wherein the concentration of the carbon dioxide source in the electrolyte is in the range of 0.1 to 10 wt %.

3. 3. The energy storage device of claim 1, wherein the carbon dioxide source is selected from the group consisting of gaseous carbon dioxide, dry ice, diethylpyrocarbonate (DEPC), dimethylpyrocarbonate (DMPC), diallylpyrocarbonate (DAPC), bis(tert-butyl)pyrocarbonate (O-Boc2), and combinations thereof.

4. 4. The energy storage device of claim 3, wherein the carbon dioxide source is diethylpyrocarbonate.

5. 5. The energy storage device of claim 4, wherein the concentration of the diethylpyrocarbonate in the electrolyte is in the range of 1 to 6 wt %.

6. 6. The energy storage device of claim 5, wherein a concentration of the diethylpyrocarbonate in the electrolyte is within a range of 1.5 to 2.5 wt %.

7. 7. The energy storage device according to claim 1, wherein the concentration of the fluorinated solvent in the electrolyte is in the range of 5 to 80% by weight.

8. 8. The energy storage device of claim 7, wherein the concentration of the fluorinated solvent in the electrolyte is in the range of 5 to 20 wt %.

9. 9. The energy storage device of any one of claims 1 to 8, wherein the fluorinated solvent is selected from the group consisting of fluoroethylene carbonate (FEC), difluoroethylene carbonate (diFEC), methyl 2,2,2-trifluoroethyl carbonate (FEMC), bis(2,2,2-trifluoroethyl)carbonate (TFEC), trifluoropropylene carbonate (TFPC), 2,2,3,3-tetrafluoro-1,4-dimethoxybutane (fDMB), bis(2,2,2-trifluoroethyl)ether (BTFE), 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), and combinations thereof.

10. 10. The energy storage device of claim 9, wherein the fluorinated solvent is fluoroethylene carbonate.

11. 11. The energy storage device of claim 1, wherein the anode comprises silicon particles.

12. d of the silicon particles ５０ 12. The energy storage device of claim 11, wherein is 1 to 5 microns.

13. d of the silicon particles ５０ 13. The energy storage device of claim 12, wherein is 2-3 microns.

14. 14. The energy storage device of claim 1, wherein the electrolyte is substantially free of ethylene carbonate and dimethyl carbonate.

15. 15. The energy storage device of claim 1, wherein the anode comprises a graphite intercalation material and a silicon alloyed / dealloyed material.

16. 16. The energy storage device of any one of claims 1 to 15, wherein the cathode comprises an active material selected from the group consisting of lithium nickel manganese cobalt oxide (NMC), lithium manganese oxide (LMO), lithium nickel dioxide (LNO), lithium iron phosphate (LFP), and lithium nickel cobalt aluminum oxide (NCA).

17. 17. The energy storage device of claim 1, wherein the lithium salt is selected from the group consisting of lithium hexafluorophosphate, lithium bis(fluorosulfonyl)imide, and combinations thereof.

18. C3: The energy storage device of any one of claims 1 to 17, configured to have at least 70% retention of initial capacity after 100 cycles from 4.1V to 2.85V at a charge rate of C2.

19. C3: The energy storage device of any one of claims 1 to 17, configured to have at least 70% retention of initial capacity after 140 cycles from 4.1V to 2.85V at a charge rate of C2.

20. C4: The energy storage device of any one of claims 1 to 17, configured to have at least 70% retention of initial capacity after 225 cycles from 4.2V to 2.85V at a charge rate of C3.

21. 21. The energy storage device of any one of claims 1 to 20, which is a battery.

22. 1. An electric vehicle having a rechargeable battery, A drive motor; The gearbox and Electronic devices and An energy storage device according to any one of claims 1 to 21; electric vehicles, including

23. A method of preparing an electrolyte comprising combining a carbon dioxide source, a fluorinated solvent, and a lithium salt to form the electrolyte.

24. 24. The method of claim 23, further comprising aging the electrolyte.

25. 25. The method of claim 23 or 24, further comprising loading the electrolyte into an energy storage device.

26. 25. The method of claim 23 or 24, wherein the electrolyte is disposed within an energy storage device.

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