Electrolyte additive compounds and related processes for high voltage energy storage devices

Abstract

Provided herein are electrolyte additives and formulations for energy storage devices with improved performance. The improved performance can be realized as improved cycling stability under abuse test conditions. [Figure 1A]

Description

[Technical field]

[0001] [CROSS REFERENCE TO RELATED APPLICATIONS] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 313,109, entitled “ADDITIVE COMPOUNDS FOR HIGH VOLTAGE ENERGY STORAGE DEVICE ELECTROLYTES, AND PROCESSES THEREOF,” filed February 23, 2022, the disclosure of which is incorporated by reference herein in its entirety for all purposes.

[0002] The present disclosure relates generally to energy storage devices, and in particular 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 cells include primary chemical cells, secondary (rechargeable) cells, fuel cells, and various types of capacitors, including ultracapacitors. Increasing the operating voltage and temperature of energy storage devices, including batteries and capacitors, is desirable to improve energy storage, increase power capacity, and expand real-world use cases.

[0004] Lithium-ion batteries have been relied upon as power sources in numerous commercial and industrial applications, for example, in consumer devices, productivity devices, and battery-powered vehicles. However, the demands placed on energy storage devices are continually and rapidly growing. For example, the automotive industry is developing vehicles that rely on small, efficient energy storage, such as plug-in hybrid vehicles and pure electric vehicles. Lithium-ion batteries are suitable to meet future demands, but 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 the electrochemical performance as well as the safety of those batteries, and the compatibility between the electrodes and the electrolyte partially governs the performance of the battery cell.

[0005] In conventional lithium-ion batteries, discharge rates below about C / 5 are typically manageable with higher energy electrode designs, where C / 5 is the discharge current for a cell capacity such that the cell is drained in 5 hours. However, as electrodes become thicker (correlating with higher cell energy), electrolyte formulations become increasingly important to address discharge performance at higher C rates (above 1C) in addition to improving cell life under high voltage and temperature conditions. Summary of the Invention [Problem to be solved by the invention]

[0006] For the purpose 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 or a group of advantages as taught herein, without necessarily achieving other objects or advantages as may be taught or suggested herein. [Means for solving the problem]

[0007] Some embodiments of the present disclosure relate to an electrolyte comprising at least one of a polymeric component comprising units of Formula (A), Formula (B), Formula (C), Formula (D), or Formula (E), or a salt thereof: [ka] (A), [ka] (B) [ka] (C) [ka] (D) [ka] (E), [ka] (F), [ka] (G) and [ka] (H).

[0008] In some embodiments, --- is selected from the group consisting of a single bond and a double bond; R1 is selected from the group consisting of -H, -OLg, and absent; each of R2 and R5 is independently selected from the group consisting of -H and -COOLg; R3 is selected from the group consisting of -COOLg and -CH2COOLg; R4 is selected from the group consisting of -H, -OLg, and -COOLg; X1 is selected from the group consisting of C and N; R6 is N(R 10 ) selected from the group consisting of Lg, -OLg and -NLg; R7 and R 10is independently selected from the group consisting of -H, an aryl group, an alkyl group, -Lg, and absent; each of R8 and R9 is independently selected from the group consisting of -Lg and absent; R 13 is -CH2-, -C(O)-, -C(CH3)2-, -CH2C(O)-, -C(CH3)2CH2-, -C(CH3)2C(O)-, (CHCH) w C(O)-, -(CH2CH2) w C(O)-, and -(C≡C) w C(O)-; R 14 is selected from the group consisting of -H, -OLg and -COOLg; R 15 , R 16 and R 17 each is independently selected from the group consisting of -H, -CN, an alkyl group, and a cyanoalkyl group; X2 is selected from the group consisting of -CN, -NCO, and -NCS; w is an integer ranging from 1 to 10; y is 0 or 1; z is an integer ranging from 1 to 100; and Lg is selected from the group consisting of trimethylsilyl (TMS) and toluenesulfonyl (CH3C6H4SO2).

[0009] In some embodiments, the electrolyte comprises at least two of Formula (A), Formula (B), Formula (C), Formula (D), Formula (F), Formula (G) or Formula (H). In some embodiments, the electrolyte is a salt form of at least one of Formula (A), Formula (B), Formula (C), Formula (D), Formula (F), Formula (G) or Formula (H). In further embodiments, the salt form of at least one of Formula (A), Formula (B), Formula (C), Formula (D), Formula (F), Formula (G) and Formula (H) is selected from the group consisting of LiPF6 salt form, LiBF4 salt form and LiDFOB salt form. In some embodiments, -Lg is TMS.

[0010] In some embodiments of the present disclosure, the electrolyte comprises Formula (A) or a salt thereof. In some embodiments, R1 is -H. In other embodiments, R2 is -COOLg. In some embodiments, R3 is -COOLg. In some embodiments, the electrolyte comprises a salt form of Formula (A). In further embodiments, the salt form of Formula (A) is selected from the group consisting of: [ka] [ka] [ka] [ka] [ka] In some embodiments, R 11 PF6 -1 , BF4 -1 and difluoro(oxalato)borate (DFOB - In some embodiments, n is the number of anionic groups.

[0011] In some embodiments, the compound of formula (A) or salt thereof is selected from the group consisting of: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0012] In some embodiments of the present disclosure, the electrolyte comprises formula (B) or a salt thereof. In some embodiments, R4 is -H. In some embodiments, R5 is -COOLg. In other embodiments, X1 is C. In further embodiments, the compound of formula (B) or a salt thereof is selected from the group consisting of: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0013] In some embodiments of the present disclosure, the electrolyte comprises the formula (C) or a salt thereof. In some embodiments, R6 is -N(R 10 ) Lg. In some embodiments, R 10 is an alkyl group. In some embodiments, R7 is -H. In other embodiments, R8 is absent. In some embodiments, R9 is -Lg. In some embodiments, y is 0. In a further embodiment, the compound of formula (C) or salt thereof is selected from the group consisting of: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0014] In some embodiments, the compound of formula (C) or salt thereof is [ka] It is.

[0015] In some embodiments of the present disclosure, the electrolyte comprises formula (D) or a salt thereof. 13 is -CH2C(O)-. In a further embodiment, the compound of formula (D) or a salt thereof is selected from the group consisting of: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0016] In some embodiments of the present disclosure, the polymer component comprises units of formula (E): In some embodiments, z is an integer ranging from 1 to 10.

[0017] In some embodiments of the present disclosure, the electrolyte comprises Formula (F) or a salt thereof. In some embodiments, R4 is -H. In further embodiments, the compound of Formula (F) or a salt thereof is [ka] is selected from the group consisting of:

[0018] In some embodiments of the present disclosure, the electrolyte comprises formula (G) or a salt thereof. In some embodiments, Lg is TMS. In some embodiments, -Lg is toluenesulfonyl (CH3C6H4SO2). In some embodiments, X2 is -CN. In some embodiments, X2 is -NCO. In some embodiments, X2 is -NCS. In further embodiments, the compound of formula (G) or a salt thereof is TMS-CN, TMS-NCO, TMS-NCS, [ka] and [ka] In some embodiments, the compound of formula (G) or salt thereof is selected from the group consisting of TMS-CN and TMS-NCO.

[0019] In some embodiments of the present disclosure, the electrolyte comprises the formula (H) or a salt thereof. 15 is -H. In some embodiments, R 16 is a cyanoalkyl group. In some embodiments, R 17 is a cyanoalkyl group. In some embodiments, R 15 , R 16 and R 17 is an alkyl group. In a further embodiment, the compound of formula (H) or salt thereof is [ka] [ka] [ka] [ka] and [ka] In some embodiments, the compound of formula (H) or salt thereof is selected from the group consisting of: [ka] and [ka] is selected from the group consisting of:

[0020] In some embodiments of the present disclosure, the electrolyte further comprises a solvent and a lithium salt.

[0021] Some embodiments of the present disclosure relate to an energy storage device, comprising the electrolyte of the present disclosure; a cathode; an anode; and a housing, wherein the electrolyte, the cathode and the anode are disposed within the housing. In some embodiments, the energy storage device is a lithium ion battery. In some embodiments, the energy storage device has a discharge capacity retention of at least about 90% after 50 cycles when cycled at up to 4.4V.

[0022] Some embodiments of the present disclosure relate to a method of preparing an energy storage device, the method comprising preparing an electrolyte of the present disclosure and disposing the electrolyte in a housing comprising a cathode and an anode. In further embodiments, the preparing comprises combining at least one of polymeric components comprising units of Formula (A), Formula (B), Formula (C), Formula (D), Formula (F), Formula (G), Formula (H), and Formula (E), or a salt thereof, with a solvent and a lithium salt to form an electrolyte, and aging the electrolyte prior to disposing the electrolyte in the housing. In some embodiments, the electrolyte is aged for about 2 to 48 hours. [Brief description of the drawings]

[0023] [Figure 1A] 1 is a bar graph showing the number of cycles to reach 160 mAh / g capacity for lithium ion batteries having electrolyte systems including compounds according to some embodiments versus a baseline electrolyte system.

[0024] [Figure 1B] 1 is a bar graph showing the number of cycles to reach 90% of the initial capacity of a lithium ion battery having an electrolyte system including compounds according to some embodiments versus a baseline electrolyte system.

[0025] [Figure 2A]1 is a line graph showing the effect of passivation between 0.5 V and 4.5 V during the formation cycle of cells containing electrolyte systems with various amounts of additive c-D7 (also referred to as "S2-7").

[0026] [Figure 2B] FIG. 2B is an expanded view of the line graph of FIG. 2A showing the effect of passivation between 1.5 V and 3.5 V during the formation cycle of cells containing electrolyte systems with various amounts of additive c-D7 (also referred to as "S2-7").

[0027] [Figure 3A] 1 is a bar graph showing discharge capacity versus cycle number for cells containing electrolyte systems with various amounts of additive c-D7 (also referred to as "S2-7") versus a baseline electrolyte system.

[0028] [Figure 3B] 1 is a bar graph showing average coulombic efficiency versus formation cycle number for cells containing electrolyte systems with various amounts of additive c-D7 (also referred to as "S2-7") versus a baseline electrolyte system.

[0029] [Figure 4] 1 is a plot showing voltage versus specific discharge capacity for cells containing electrolyte systems with various amounts of additive c-D7 (also referred to as "S2-7").

[0030] [Figure 5A] 1 is a plot showing the average specific discharge capacity as a function of cycle number for cells containing electrolyte systems with various amounts of additive c-D7 (also referred to as "S2-7") at high voltage and temperature.

[0031] [Figure 5B] 1 is a plot showing average coulombic efficiency as a function of cycle number for cells containing electrolyte systems with various amounts of additive c-D7 (also referred to as "S2-7") at high voltage and temperature.

[0032] [Figure 6A] 1 is a line graph showing the effect of passivation between 0.5 V and 4.5 V during the formation cycle of cells containing electrolyte systems with various amounts of Additive A4 (also referred to as "S3-2").

[0033] [Figure 6B] FIG. 6B is an expanded view of the line graph of FIG. 6A showing the effect of passivation between 1.5 V and 3.5 V during the formation cycle of cells containing electrolyte systems with various amounts of Additive A4 (also referred to as "S3-2").

[0034] [Figure 7A] 1 is a bar graph showing discharge capacity versus cycle number for cells containing electrolyte systems with various amounts of Additive A4 (also referred to as "S3-2") versus a baseline electrolyte system.

[0035] [Figure 7B] 1 is a bar graph showing average coulombic efficiency versus formation cycle number for cells containing electrolyte systems with various amounts of Additive A4 (also referred to as "S3-2") versus a baseline electrolyte system.

[0036] [Figure 8] 1 is a plot showing voltage versus specific discharge capacity for cells containing electrolyte systems with various amounts of Additive A4 (also referred to as "S3-2").

[0037] [Figure 9A] 1 is a plot showing the average specific discharge capacity as a function of cycle number for cells containing electrolyte systems with various amounts of Additive A4 (also referred to as "S3-2").

[0038] [Figure 9B] 1 is a plot showing average coulombic efficiency as a function of cycle number for cells containing electrolyte systems with various amounts of Additive A4 (also referred to as "S3-2").

[0039] [Figure 10A]1 is a plot showing the average specific discharge capacity as a function of cycle number for cells containing electrolyte systems with various amounts of Additive A1 (also referred to as "S4-1").

[0040] [Figure 10B] 1 is a plot showing average coulombic efficiency as a function of cycle number for cells containing electrolyte systems with various amounts of Additive A1 (also referred to as "S4-1").

[0041] [Figure 11A] 1 is a plot showing the average specific discharge capacity as a function of cycle number for cells containing electrolyte systems with various amounts of Additive A3 (also referred to as "S4-2").

[0042] [Figure 11B] 1 is a plot showing average coulombic efficiency as a function of cycle number for cells containing electrolyte systems with various amounts of Additive A3 (also referred to as "S4-2").

[0043] [Figure 12A] 1 is a plot showing the average specific discharge capacity as a function of cycle number for cells containing electrolyte systems with various amounts of Additive B1 (also referred to as "SP-1").

[0044] [Figure 12B] 1 is a plot showing average coulombic efficiency as a function of cycle number for cells containing electrolyte systems with various amounts of Additive B1 (also referred to as "SP-1").

[0045] [Figure 13A] 1 is a plot showing the average specific discharge capacity as a function of cycle number for cells containing electrolyte systems with various amounts of Additive C3 (also referred to as "DA-1").

[0046] [Figure 13B] 1 is a plot showing average coulombic efficiency as a function of cycle number for cells containing electrolyte systems with various amounts of Additive C3 (also referred to as "DA-1").

[0047] [Figure 14A] 1 is a plot showing average specific discharge capacity as a function of cycle number for cells having an electrolyte system including compounds according to some embodiments relative to a baseline electrolyte system.

[0048] [Figure 14B] 1 is a plot showing average coulombic efficiency as a function of cycle number for cells having an electrolyte system including compounds according to some embodiments relative to a baseline electrolyte system.

[0049] [Figure 15] 1 is a plot showing the average specific discharge capacity as a function of cycle number for cells containing electrolyte systems with various amounts of Additive G1 (also referred to as "N1-8").

[0050] [Figure 16A] 1 shows the 1H NMR spectrum of the conversion of Additive A1 (also referred to as "S4-1") in electrolyte to the final product as a function of time.

[0051] [Figure 16B] 1 shows the 19F NMR spectrum of the conversion of Additive A1 (also referred to as "S4-1") to the final product in the electrolyte as a function of time.

[0052] [Figure 17] 19F NMR spectra of the conversion of Additive A3 (also referred to as "S4-2") to the final product in electrolyte as a function of time.

[0053] [Figure 18] 1 shows the 19F NMR spectrum of the conversion of Additive B1 (also referred to as "SP-1") in electrolyte to the final product as a function of time.

[0054] [Figure 19A]1 shows the 1H NMR spectrum of the conversion of additive C3 (also called "DA-1") to the final product in electrolyte as a function of time.

[0055] [Figure 19B] 1 shows the 19F NMR spectrum of the conversion of additive C3 (also called "DA-1") to the final product in electrolyte as a function of time.

[0056] [Figure 20] 1 shows the 1H NMR spectrum of the conversion of additive c-D7 (also referred to as "S2-7") to the final product in electrolyte as a function of time.

[0057] [Figure 21] 19F NMR spectra of the conversion of additive D4 (also referred to as "S2-3") to the final product in electrolyte as a function of time.

[0058] [Figure 22A] 1 is a test protocol used to evaluate electrolyte additives, according to one embodiment.

[0059] [Figure 22B] 1 is a test protocol used to evaluate electrolyte additives, according to one embodiment.

[0060] [Figure 23] 1 is a chart showing discharge capacity versus cycle number for a lithium ion battery having an electrolyte system including aged compounds according to some embodiments versus a baseline electrolyte system.

[0061] [Figure 24] 1 is a chart showing the discharge capacity and the difference between the average charge voltage and the average discharge voltage versus cycle number for pouch cells having an electrolyte system including compounds according to some embodiments.

[0062] [Figure 25A]1 is a chart showing discharge capacity versus cycle number for pouch cells having an electrolyte system including compounds according to some embodiments.

[0063] [Figure 25B] 1 is a chart showing the difference between average charge voltage and average discharge voltage versus cycle number for pouch cells having an electrolyte system including compounds according to some embodiments. Detailed Description of the Invention

[0064] Electrolyte formulations containing at least one additive or salt thereof are described for high voltage, high energy density energy storage devices (e.g., lithium ion batteries). Such additives may react with lithium salts to improve device performance, such as stabilization of the electrode surface. Such device improvements may advantageously result in improved cycling stability, especially under extreme conditions such as high voltages (e.g., at least 4.4 V) and high temperatures (e.g., about 40-45°C). definition

[0065] As used herein, the term "alkyl" refers to a fully saturated aliphatic hydrocarbon group. The alkyl moiety may be branched or straight-chained. Examples of branched alkyl groups include, but are not limited to, isopropyl, sec-butyl, t-butyl, and the like. Examples of straight-chain alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and the like.

[0066] 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 more than one ring, the rings may be fused and joined together. Cycloalkyl groups may contain 3 to 10 atoms in the ring or 3 to 8 atoms in the ring. Cycloalkyl groups may be unsubstituted or substituted. Exemplary cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.

[0067] As used herein, "cycloalkenyl" refers to a monocyclic or polycyclic hydrocarbon ring system containing one or more double bonds in at least one ring, but if more than one is present, the double bonds cannot form a completely delocalized pi-electron system across all rings (otherwise the group is an "aryl" as defined herein). When composed of more than one ring, the rings may be fused together to be connected. Cycloalkenyl groups may be unsubstituted or substituted.

[0068] 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 more than one triple bond is present, the triple bonds cannot form a completely delocalized pi-electron system throughout all rings. If composed of more than one ring, the rings can be fused together. Cycloalkynyl groups can be unsubstituted or substituted.

[0069] The term "alkoxy" as used herein refers to a straight or branched alkyl radical covalently attached to the parent molecule via an -O- linkage. Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, butoxy, n-butoxy, sec-butoxy, t-butoxy, etc.

[0070] The term "alkenyl," as used herein, refers to a monovalent straight or branched radical of 2 to 20 carbon atoms containing a carbon double bond, including, but not limited to, 1-propenyl, 2-propenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, and the like.

[0071] The term "alkynyl," as used herein, refers to a monovalent straight or branched radical of 2 to 20 carbon atoms containing a carbon triple bond, including, but not limited to, 1-propynyl, 1-butynyl, 2-butynyl, and the like.

[0072] The term "aryl" as used herein refers to a monocyclic aromatic radical, whether one ring or multiple fused rings. Additionally, the term "aryl" includes fused ring systems in which at least two aryl rings or at least one aryl and an ortho-fused bicyclic carbocyclic radical having about 9-10 ring atoms in which at least one ring is aromatic share at least one chemical bond. Examples of "aryl" rings include, but are not limited to, optionally substituted phenyl, biphenyl, naphthalenyl, phenanthrenyl, anthracenyl, tetralinyl, fluorenyl, indenyl, and indanyl.

[0073] The term "heterocycle" or "heterocyclic group" as used herein refers to an optionally substituted monocyclic, bicyclic or tricyclic ring system containing at least one heteroatom in the ring system backbone. The heteroatom is independently selected from oxygen, sulfur and nitrogen. The term "heterocycle" includes multiple fused ring systems. In addition, the term "heterocycle" includes fused ring systems that may have any degree of saturation, as long as at least one ring in the ring system is not aromatic. The monocyclic, bicyclic or tricyclic ring systems may be substituted or unsubstituted and may be attached to other groups through any available valence, preferably any available carbon or nitrogen. Preferred monocyclic ring systems are those with 4, 5, 6, 7 or 8 members. A 6-membered monocyclic ring contains up to 3 heteroatoms, where each heteroatom is independently selected from oxygen, sulfur and nitrogen, and when the ring is 5-membered, the ring preferably has 1 or 2 heteroatoms, where each heteroatom is independently selected from oxygen, sulfur and nitrogen. Preferred bicyclic ring systems are those having 8 to 12 members, including spiro rings.Examples of optional substituents include, but are not limited to, oxo (=O).

[0074] The term "heteroatom" as used herein refers to, for example, oxygen, sulfur and nitrogen.

[0075] The term "amino" as used herein refers to a nitrogen radical substituted with hydrogen, alkyl, aryl, or combinations thereof. Examples of amino groups include, but are not limited to, -NH methyl, -NH2, -N methyl2, -N phenylmethyl, -NH phenyl, -N ethylmethyl, and the like.

[0076] The term "arylalkyl" as used herein refers to one or more aryl groups appended to an alkyl radical. Examples of arylalkyl groups include, but are not limited to, benzyl, phenethyl, phenpropyl, phenbutyl, and the like.

[0077] The term "heteroarylalkyl" as used herein refers to one or more heteroaryl groups appended to an alkyl radical. Examples of heteroarylalkyl include, but are not limited to, pyridylmethyl, furanylmethyl, thiopheneylethyl, and the like.

[0078] The term "aryloxy," as used herein, refers to an aryl radical covalently attached to the parent molecule via an --O-- linkage.

[0079] The term "carbonyl" as used herein refers to C=O (ie, a carbon double bonded to an oxygen).

[0080] The term "oxo" as used herein refers to =O (i.e., a double bond to oxygen). For example, cyclohexane substituted with "oxo" is cyclohexanone.

[0081] The term "alkanoyl" as used herein refers to a "carbonyl" substituted with an "alkyl" group, where the "alkanoyl" group is covalently attached to the parent molecule through the carbon of the "carbonyl" group. Examples of alkanoyl groups include, but are not limited to, methanoyl, ethanoyl, propanoyl, and the like. Methanoyl is commonly known as acetyl.

[0082] 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 of C6 to C7. 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.

[0083] 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, 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 4-14 atoms in the ring, 5-10 atoms in the ring, or 5-6 atoms in the ring. Additionally, 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.

[0084] As used herein, "heterocyclyl" or "heteroalicyclyl" refers to 3, 4, 5, 6, 7, 8, 9, 10, up to 18 membered monocyclic, bicyclic and tricyclic ring systems, in which carbon atoms together with 1-5 heteroatoms make up the ring system. However, heterocycles may optionally contain one or more unsaturated bonds positioned such that a fully delocalized pi-electron system does not occur throughout all rings. Heteroatoms are elements other than carbon, including but not limited to oxygen, sulfur and nitrogen. Heterocycles may further include one or more carbonyl or thiocarbonyl functional groups, to define them as including 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 together. Additionally, any nitrogen in a heteroalicyclic 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-oxathiine, 1,3-oxathiolane, 1,3-dithiole, 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, imidazoline, tetrahydro-1,4-thiazine ... These include, but are not limited to, lysine, 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 benzo-fused analogs thereof (e.g., benzimidazolidinone, tetrahydroquinoline, 3,4-methylenedioxyphenyl).

[0085] As used herein, "aralkyl" and "aryl(alkyl)" refer to an aryl group connected, as a substituent, through a lower alkylene group. The lower alkylene and aryl groups of the aralkyl may be substituted or unsubstituted. Examples include, but are not limited to, benzyl, 2-phenylalkyl, 3-phenylalkyl, and naphthylalkyl.

[0086] As used herein, "heteroaralkyl" and "heteroaryl(alkyl)" refer to a heteroaryl group connected, as a substituent, through a lower alkylene group. The lower alkylene and heteroaryl groups of the heteroaralkyl may 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.

[0087] "(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 (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-thiazinane-4-yl)methyl.

[0088] A "lower alkylene group" is a straight-chain -CH- tethering group that forms bonds connecting molecular fragments through their terminal carbon atoms. Examples include, but are not limited to, methylene (-CH-), ethylene (-CHCH-), propylene (-CHCHCH-) and butylene (-CHCHCHCH-). A lower alkylene group can be substituted by replacing one or more hydrogens of the lower alkylene group with a substituent listed under the definition of "substituted."

[0089] As used herein, "alkoxy" refers to the formula -OR, where R is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, or cycloalkynyl, as defined above. A non-limiting list of alkoxy is methoxy, ethoxy, n-propoxy, 1-methylethoxy (isopropoxy), n-butoxy, iso-butoxy, sec-butoxy, and tert-butoxy. Alkoxy may be substituted or unsubstituted.

[0090] As used herein, "acyl" refers to hydrogen, alkyl, alkenyl, alkynyl, aryl or heteroaryl as a substituent connected through a carbonyl group. Examples include formyl, acetyl, propanoyl, benzoyl and acryl. Acyl may be substituted or unsubstituted.

[0091] As used herein, "acylalkyl" refers to an acyl, as a substituent, connected through a lower alkylene group. Examples include aryl-C(=O)-(CH2). n - and heteroaryl-C(=O)-(CH2) n In the formula, n is an integer ranging from 1 to 6.

[0092] As used herein, "alkoxyalkyl" refers to an alkoxy group connected, as a substituent, through a lower alkylene group. Examples include alkyl-O-(CH2) n In the formula, n is an integer ranging from 1 to 6.

[0093] As used herein, "aminoalkyl" refers to an optionally substituted amino group connected, as a substituent, through a lower alkylene group. Examples include H2N-O-(CH2) n In the formula, n is an integer ranging from 1 to 6.

[0094] As used herein, "hydroxyalkyl" refers to an alkyl group in which one or more of the hydrogen atoms are replaced by a hydroxy group. Exemplary hydroxyalkyl groups include, but are not limited to, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, and 2,2-dihydroxyethyl. Hydroxyalkyl can be substituted or unsubstituted.

[0095] As used herein, "haloalkyl" refers to an alkyl group in which one or more of the hydrogen atoms are replaced by halogen (e.g., monohaloalkyl, dihaloalkyl, and trihaloalkyl). Such groups include, but are not limited to, chloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, and 1-chloro-2-fluoromethyl, 2-fluoroisobutyl. Haloalkyl may be substituted or unsubstituted.

[0096] As used herein, "haloalkoxy" refers to an alkoxy group in which one or more of the hydrogen atoms are replaced with halogen (e.g., mono-haloalkoxy, di-haloalkoxy, and tri-haloalkoxy). Such groups include, but are not limited to, chloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, and 1-chloro-2-fluoromethoxy, 2-fluoroisobutoxy. Haloalkoxy may be substituted or unsubstituted.

[0097] As used herein, "aryloxy" and "arylthio" refer to RO- and RS-, where R is aryl, such as, but not limited to, phenyl. Both aryloxy and arylthio can be substituted or unsubstituted.

[0098] As used herein, "alkylthio" refers to the group "-SR" where R is alkyl. Alkylthio can be substituted or unsubstituted.

[0099] As used herein, "cyanoalkyl" refers to an alkyl group substituted with one or more cyano (-CN) groups. Cyanoalkyls can be substituted or unsubstituted.

[0100] As used herein, a radical refers to a species that has a single unpaired electron such that the species containing the radical 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."

[0101] As used herein, "salt" refers to any substance formed when a leaving group, or hydrogen of an acid form, is replaced by a metal or its equivalent, and which becomes ionized upon dissolution in a solvent with the appropriate pKa (e.g., water or a polar organic solvent). Additives

[0102] Some embodiments described herein generally comprise: [ka] (A), [ka] (B) [ka] (C) [ka] (D) [ka] (E), [ka] (F), [ka] (G), and [ka] (H) The electrolyte additive or its salt selected from at least one of the following: (wherein --- is selected from a single bond and a double bond; R1 is selected from -H, -OLg, and absent; each of R2 and R5 is independently selected from -H and -COOLg; R3 is selected from -COOLg and -CH2COOLg; R4 is selected from -H, -OLg, and -COOLg; X1 is selected from C and N; R6 is N(R 10 ) selected from Lg, -OLg and -NLg; R7 and R 10 is independently selected from -H, an aryl group, an alkyl group, -Lg, and absent; each of R8 and R9 is independently selected from -Lg and absent; R 13 is -CH2-, -C(O)-, -C(CH3)2-, -CH2C(O)-, -C(CH3)2CH2-, -C(CH3)2C(O)-, (CHCH) w C(O)-, -(CH2CH2) w C(O)-, and -(C≡C) w C(O)-; R 14 is selected from the group consisting of -H, -OLg and -COOLg; R 15 , R 16 and R 17 each is independently selected from the group consisting of -H, -CN, an alkyl group, and a cyanoalkyl group; X2 is selected from the group consisting of -CN, -NCO, and -NCS; w is an integer ranging from 1 to 10; y is 0 or 1; z is an integer ranging from 1 to 100; and Lg is selected from trimethylsilyl (TMS) and toluenesulfonyl (CH3C6H4SO2).

[0103] ·Formula (A) In some embodiments, the electrolyte additive comprises Formula (A) having the following structure or a salt thereof: [ka] (A)

[0104] In some embodiments of Formula (A), --- is selected from a single bond and a double bond, R1 is selected from -H, -OLg, and absent, R2 is selected from -H and -COOLg, R3 is selected from -COOLg and -CH2COOLg, and Lg is selected from trimethylsilyl (TMS) and toluenesulfonyl (CH3C6H4SO2).

[0105] In some embodiments of Formula (A), --- is selected from a single bond and a double bond. In any embodiment described herein, --- is a single bond. In any embodiment described herein, --- is a double bond.

[0106] In some embodiments of formula (A), R1 is selected from -H, -OLg, and absent. In some embodiments, R1 is -H. In some embodiments, R1 is -OLg. In some embodiments, R1 is absent.

[0107] In some embodiments of formula (A), R2 is selected from -H and -COOLg. In some embodiments, R2 is -H. In some embodiments, R2 is -COOLg.

[0108] In some embodiments of formula (A), R3 is selected from -COOLg and -CH2COOLg. In some embodiments, R3 is -COOLg. In some embodiments, R3 is -CH2COOLg.

[0109] In any embodiment described herein, Lg is selected from trimethylsilyl (TMS) and toluenesulfonyl (CH3C6H4SO2). In any embodiment described herein, each Lg is TMS.

[0110] In some embodiments, the electrolyte additive is a salt of formula (A). In some embodiments, the salt form of formula (A) has the following structure: [ka] [ka] [ka] [ka] or [ka] (In the formula, R 11 PF6 -1 , BF4 -1 and difluoro(oxalato)borate (DFOB - and n is the number of anionic groups. In some embodiments, the anionic group is PF6 -1 It is. In some embodiments, the anionic group is BF4 -1 It is. In some embodiments, the anionic group is (DFOB - ).

[0111] In some embodiments, the electrolyte additive of formula (A) or a salt thereof is selected from the compounds shown in Table A. [Table A] TIFF2025512612000094.tif121115

[0112] Formula (B) In some embodiments, the electrolyte additive comprises Formula (B) having the following structure or a salt thereof: [ka] (B)

[0113] In some embodiments of formula (B), R4 is selected from -H, -OLg, and -COOLg, R5 is selected from -H and -COOLg, X1 is selected from C and N, and Lg is selected from trimethylsilyl (TMS) and toluenesulfonyl (CH3C6H4SO2).

[0114] In some embodiments of formula (B), R4 is selected from -H, -OLg, and -COOLg. In some embodiments, R4 is -H. In some embodiments, R4 is -OLg. In some embodiments, R4 is -COOLg.

[0115] In some embodiments of formula (B), R5 is selected from -H and -COOLg. In some embodiments, R5 is -H. In some embodiments, R5 is -COOLg.

[0116] In some embodiments of Formula (B), X 1 is selected from C and N. In some embodiments, X 1 is C. In some embodiments, X 1 is N.

[0117] In some embodiments, the electrolyte additive of formula (B) or a salt thereof is selected from the compounds shown in Table B. [Table B]

[0118] Formula (C) In some embodiments, the electrolyte additive comprises Formula (C) having the following structure or a salt thereof: [ka] (C)

[0119] In some embodiments of Formula (C), - is selected from the group consisting of a single bond and a double bond, and R6 is -N(R 10) Lg, -OLg and -NLg; R 10 is selected from -H, an aryl group, an alkyl group, -Lg, and absent, R7 is selected from -H, an aryl group, an alkyl group, -Lg, and absent, R8 is selected from -Lg, and absent, R9 is selected from -Lg, and absent, and y is 0 or 1, and Lg is selected from trimethylsilyl (TMS) and toluenesulfonyl (CH3C6H4SO2).

[0120] In some embodiments of Formula (C), R6 is -N(R 10 In some embodiments, R6 is selected from -N(R 10 In some embodiments, R is -OLg. In some embodiments, R is -NLg. In some embodiments of Formula (C), R 10 is selected from -H, an aryl group, an alkyl group, -Lg, and absent. 10 is -H. In some embodiments, R 10 is an aryl group. In some embodiments, R 10 is an alkyl group. In some embodiments, R 10 In some embodiments, R 10 is non-existent.

[0121] In some embodiments of formula (C), R7 is selected from -H, an aryl group, an alkyl group, -Lg, and absent. In some embodiments, R7 is -H. In some embodiments, R7 is an aryl group. In some embodiments, R7 is an alkyl group. In some embodiments, R7 is -Lg. In some embodiments, R7 is absent.

[0122] In some embodiments of Formula (C), R8 is selected from -Lg and absent. In some embodiments, R8 is -Lg. In some embodiments, R8 is absent.

[0123] In some embodiments of formula (C), R9 is selected from -Lg and absent. In some embodiments, R9 is -Lg. In some embodiments, R9 is absent.

[0124] In some embodiments of Formula (C), y is 0 or 1. In some embodiments, y is 0. In some embodiments, y is 1.

[0125] In some embodiments, the electrolyte additive of formula (C) or a salt thereof is selected from the compounds shown in Table C. [Table C] TIFF2025512612000099.tif140114

[0126] Formula (D) In some embodiments, the electrolyte additive comprises Formula (D) having the following structure or a salt thereof: [ka] (D)

[0127] In some embodiments of Formula (D), R 13 is -CH2-, -C(O)-, -C(CH3)2-, -CH2C(O)-, -C(CH3)2CH2-, -C(CH3)2C(O)-, -(CHCH) w C(O)-, -(CH2CH2) w C(O)-, and -(C≡C) w C(O)-, and Lg is selected from trimethylsilyl (TMS) and toluenesulfonyl (CH3C6H4SO2).

[0128] In some embodiments, R 13 is -CH-. In some embodiments, R 13 is -C(O)-. In some embodiments, R 13 is -C(CH)-. In some embodiments, R 13is -CHC(O)-. In some embodiments, R 13 is -C(CH3)2CH2-. In some embodiments, R 13 is -C(CH3)2C(O)-. In some embodiments, R 13 is -CHCHC(O). In some embodiments, R 13 Ha-(CHCH) w In some embodiments, R 13 Ha-(CH2CH2) w In some embodiments, R 13 HA-(C≡C) w In some embodiments, w is an integer ranging from 1 to 10.

[0129] In some embodiments, the electrolyte additive of formula (D) or a salt thereof is selected from the compounds shown in Table D. [Table D] TIFF2025512612000102.tif76130

[0130] In some embodiments, the electrolyte additive may be one or more of the following compounds or salts thereof: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] or [ka]

[0131] Formula (E) In some embodiments, the electrolyte additive can be a polymeric component that includes units of formula (E), having the following structure: [ka] (E) (wherein z is an integer ranging from 1 to 100). In some embodiments of Formula (E), z is an integer ranging from 1-10. In some embodiments, z is an integer in the range of 5-15. In some embodiments, z is an integer in the range of 1-20.

[0132] Formula (F) In some embodiments, the electrolyte additive comprises Formula (F) having the following structure or a salt thereof: [ka] (F)

[0133] In some embodiments of Formula (F), R 14 is selected from -H, -OLg and -COOLg, and Lg is selected from trimethylsilyl (TMS) and toluenesulfonyl (CH3C6H4SO2).

[0134] In some embodiments, R 14 is -H. In some embodiments, R 14 In some embodiments, R 14 is -COOLg.

[0135] In some embodiments, the electrolyte additive of formula (F) or a salt thereof is selected from the compounds shown in Table E. [Table E]

[0136] Formula (G) In some embodiments, the electrolyte additive comprises Formula (G) having the following structure or a salt thereof: [ka] (G)

[0137] In some embodiments of Formula (G), X2 is selected from the group consisting of -CN, -NCO, and -NCS, and Lg is selected from trimethylsilyl (TMS) and toluenesulfonyl (CH3C6H4SO2).

[0138] In some embodiments, X2 is -CN. In some embodiments, X2 is -NCO. In some embodiments, X2 is -NCS.

[0139] In some embodiments, the electrolyte additive of formula (G) or a salt thereof is selected from the compounds shown in Table F. [Table F]

[0140] Formula (H) In some embodiments, the electrolyte additive comprises Formula (H) having the following structure or a salt thereof: [ka] (H)

[0141] In some embodiments of Formula (H), R 15 , R 16 and R 17 is independently selected from the group consisting of -H, -CN, an alkyl group, and a cyanoalkyl group.

[0142] In some embodiments, R 15 is -H. In some embodiments, R 15 is -CN. In some embodiments, R 15 is an alkyl group. In some embodiments, R 15 is a cyanoalkyl group. In some embodiments, R 16 is -H. In some embodiments, R 16 is -CN. In some embodiments, R 16 is an alkyl group. In some embodiments, R 16 is a cyanoalkyl group. In some embodiments, R 17 is -H. In some embodiments, R 17 is -CN. In some embodiments, R 17 is an alkyl group. In some embodiments, R 17 is a cyanoalkyl group. In some embodiments, R 15 , R 16 and R 17 Each of is an alkyl group.

[0143] In some embodiments, cyanoalkyl groups include linear and branched cyanoalkyl groups, in some embodiments, cyanoalkyl groups include -CHCN, -CHCHCN, -CH(CH)CN, -C(CH)CN, -CH(CHCH)CN, -C(CHCH)CN.

[0144] In some embodiments, the electrolyte additive of formula (H) or a salt thereof is selected from the compounds shown in Table G. [Table G]

[0145] electrolyte The electrolyte formulations described herein may include a lithium salt, an electrolyte solvent, and one or more of the additives discussed herein. In some embodiments, the electrolyte further includes one or more additional additives. In some embodiments, the electrolyte includes about, up to, or up to about 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%, or any range of values ​​therebetween. In some embodiments, the electrolyte comprises a plurality of additives in a range of about, up to, or up to about 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 11% or 12% by weight, in total, or any value therebetween.

[0146] In general, the lithium salt comprises 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 lithium salt can be selected from lithium hexafluorophosphate (LiPF6), lithium tetrafluoroborate (LiBF4), lithium difluoro(oxalato)borate (LiDFOB), and combinations thereof. In some embodiments, the electrolyte can comprise an anion selected from hexafluorophosphate, tetrafluoroborate, and difluoro(oxalato)borate. 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, 4M, 4.1M, 4.2M, 4.3M, 4.4M, 4.5M, 4.6 The salt concentration may be, be about, be up to, or be any range of values ​​therebetween, such as about 0.1 M to about 5 M, about 0.2 M to about 3 M, about 0.3 M to about 2 M, or about 0.7 M to about 1 M.

[0147] In some embodiments, the electrolyte comprises a liquid solvent. The solvents provided herein do not need to dissolve all components, and do not need to completely dissolve each component 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 carbonates, ethers, and / or esters. In some embodiments, the solvent may comprise 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 comprise methyl acetate. In some embodiments, the electrolyte comprises 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97% or 98% by weight, about that %, at least that %, or at least about that %, or any range of values ​​therebetween, of the solvent.

[0148] Energy Storage Devices The energy storage device of the present disclosure comprises an electrolyte, a cathode, an anode, and a housing as discussed herein, wherein the electrolyte, the cathode, and the anode are disposed in the housing.In some embodiments, the energy storage device provided herein is a lithium-ion battery.In some embodiments, the energy storage device provided herein has a discharge capacity retention rate of at least about 90% after 50 cycles when cycled at up to 4.4V.Each of the cathode and the anode comprises an electrode film forming an electrode and a current collector.

[0149] 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.

[0150] In some embodiments, the electrode film includes an anode active material. In some embodiments, the anode active material may include, for example, an intercalation material (such as carbon or graphite), an alloying / dealloying material (such as silicon, silicon oxide, tin, and / or tin oxide), a metal alloy or compound (such as Si-Al and / or Si-Sn), and / or a conversion material (such as manganese oxide, molybdenum oxide, nickel oxide, and / or copper oxide). The anode active materials may be used alone or mixed together to form a multiphase material (such as 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, or Sn-SiOx-SnOx). Positive electrode 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, metallic elements and their compounds, and metal-C composites for the positive electrode.

[0151] In some embodiments, the electrode film includes a negative electrode active material. In some embodiments, the negative electrode active material can include, for example, a metal oxide, a metal sulfide, or a lithium metal oxide. The lithium metal oxide can be, for example, lithium nickel manganese cobalt oxide (NMC), lithium manganese oxide (LMO), lithium iron phosphate (LFP), lithium cobalt oxide (LCO), lithium titanate (LTO), and / or lithium nickel cobalt aluminum oxide (NCA). In some embodiments, the negative electrode active material can be, for example, a layered transition metal oxide (LiCoO2 (LCO), Li(NiMnCo)O2 (NMC) and / or LiNi 0.8 Co 0.15 Al 0.05O2(NCA), spinel-type manganese oxides (LiMn2O4(LMO) and / or LiMn 1.5 Ni 0.5 The negative electrode active material may include sulfur, or a sulfur-containing material such as lithium sulfide (Li2S), or other sulfur-based materials, or mixtures thereof.

[0152] The energy storage device provided herein can be any suitable configuration, such as flat, spirally wound, button-shaped, or pouch.The energy storage device provided herein can be a component of a system, such as a power generation system, an uninterruptible power supply system (UPS), a solar power generation system, an energy recovery system for use in, for example, 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).

[0153] In some embodiments, energy storage devices including the electrolyte formulations provided herein may demonstrate higher discharge rate capabilities as compared to energy storage devices that do not use the electrolyte formulations described herein. Such higher discharge rate capabilities are desirable in high energy, high power applications such as electric vehicle propulsion.

[0154] Energy storage devices comprising 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 cycle performance, including improved storage stability and reduced capacity fade during cycling. In some embodiments, improved cycle performance has also been achieved under aggressive or stress conditions (e.g., long voltage hold at 4.4V).

[0155] 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.

[0156] In some embodiments, the lithium ion battery is configured to operate at about 2.5 to 4.5 V, or 3.0 to 4.2 V. In further embodiments, the lithium ion battery is configured to have a minimum operating voltage of about 2.5 V to about 3 V, respectively. In still further embodiments, the lithium ion battery is configured to have a maximum operating voltage of about 4.1 V to about 4.4 V, respectively.

[0157] 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 including a cathode and an anode. In some embodiments, a method for preparing an electrolyte includes combining at least one of polymer components including units of formula (A), formula (B), formula (C), formula (D), formula (F), formula (G), formula (H), and formula (E), or a salt thereof, a solvent, and a lithium salt to form an electrolyte.

[0158] aging Some embodiments of the present disclosure relate to aging the electrolyte prior to placing it in the 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, 34 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, 5 weeks, 6 weeks, about, at least, or at least about, the period, or any range of values ​​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 2 weeks to about 3 weeks. EXAMPLES

[0159] Exemplary embodiments of the disclosure, including processes, materials and / or resulting products, are described in the following examples.

[0160] Example 1 - Coin Cell Specifications The electrolyte additives were tested for their effectiveness in NMC532 coin cells. The coin cells were fabricated and vacuum sealed in a dry room without electrolyte. Table 1 summarizes the specifications of the coin cells. [Table 1]

[0161] 1M or 1.5M LiPF6% in EC:EMC:DMC in a 25:5:70 weight ratio, containing 0.7 wt% fluoroethylene carbonate (FEC) and 0.25 wt% vinylene carbonate (VC), was used as a control electrolyte ("baseline"). Electrolytes with baseline electrolytes with and without FEC and / or VC but containing various amounts of additives as disclosed herein were also prepared and are described in the Examples below.

[0162] Example 2 - Screening of coin cells Several lithium-ion batteries were tested for discharge and cycling performance under challenge or stress conditions. Figure 1A shows the number of cycles to reach 160 mAh / g capacity for a lithium-ion battery having an electrolyte system including a compound according to some embodiments versus a baseline electrolyte system. Figure 1B shows the number of cycles to reach 90% of the initial capacity for a lithium-ion battery having an electrolyte system including a compound according to some embodiments versus a baseline electrolyte system.

[0163] Example 3 - Passivation effect of additive c-D7 The impact of passivation of coin cells of Example 1 containing electrolyte systems with various amounts of additive c-D7 (also referred to as "S2-7") was tested. For all experiments performed, the cis isomer of additive D7 was used. 100% isomeric purity of the starting material was effective to prevent isomerization while working with the additive. Figure 2A is a line graph showing the impact of passivation between 0.5V and 4.5V during the formation cycle of a cell containing an electrolyte system comprising: (a) 0.7 wt % fluoroethylene carbonate (FEC) and 0.25 wt % vinylene carbonate (VC) ("black line"; "baseline"); (b) 0.5 wt% additive c-D7; 0.7 wt% FEC; and 0.25 wt% VC ("blue line"; "0.5 wt% S2-7"); (c) 1.0 wt% additive c-D7; 0.7 wt% FEC; and 0.25 wt% VC ("red line"; "1.0 wt% S2-7"); (d) 2.0 wt% additive c-D7; 0.7 wt% FEC; and 0.25 wt% VC ("purple line"; "2.0 wt% S2-7"); (e) 1.0 wt% additive c-D7 and 0.7 wt% FEC ("pink line"; "1.0 wt% S2-7(-VC)"); (f) 2.0 wt% additive c-D7 and 0.7 wt% FEC ("green line"; "2.0 wt% S2-7(-VC)"); and (g) 1.0 wt % additive c-D7 ("orange line"; "1.0 wt % S2-7(-VC, -FEC)").

[0164] FIG. 2B is an expanded view of the line graph of FIG. 2A showing the effect of passivation between 1.5 V and 3.5 V. As can be seen in FIG. 2B, the addition of FEC and / or VC to the electrolyte system containing 1.0 wt. % additive c-D7 formed a relatively similar amount of solid electrolyte interface (SEI) compared to the electrolyte system containing 1.0 wt. % additive c-D7 but without VC, and also compared to the electrolyte system containing 1.0 wt. % additive c-D7 but without VC and FEC. Thus, the addition of FEC and / or VC did not adversely affect or did not substantially adversely affect the formation cycle of the electrolyte system containing 1.0 wt. % additive c-D7, as seen by the formation of a similar amount of SEI between 1.5 V and 2.75 V. Even with the addition of as little as 0.5 wt. %, the addition of additive c-D7 to the electrolyte system formed an effective amount of SEI, thus demonstrating improved results compared to the baseline. Surprisingly, the electrolyte system containing 1.0 wt % of additive c-D7 formed a sufficient amount of SEI with or without FEC and / or VC.

[0165] Example 4 - Effect of Additive c-D7 on Average Discharge Capacity and Coulombic Efficiency The average discharge capacity and average coulombic efficiency as a function of cycle number were tested for the coin cells of Example 1 containing electrolyte systems with various amounts of additive c-D7 (also referred to as "S2-7"). Figure 3A shows the average specific discharge capacity versus cycle number for an electrolyte system containing: (a) 0.7 wt % fluoroethylene carbonate (FEC) and 0.25 wt % vinylene carbonate (VC) ("black bars"; "baseline"); (b) 0.5 wt% additive c-D7; 0.7 wt% FEC; and 0.25 wt% VC ("blue bars"; "0.5 wt% S2-7"); (c) wt% additive c-D7; 0.7 wt% FEC; and 0.25 wt% VC ("red bar"; "1.0 wt% S2-7"); (d) 2.0 wt% additive c-D7; 0.7 wt% FEC; and 0.25 wt% VC ("purple bar"; "2.0 wt% S2-7"); (e) wt% additive c-D7 and 0.7 wt% FEC ("green bar"; "1.0 wt% S2-7(-VC)"); (f) 2.0 wt.% additive c-D7 and 0.7 wt.% FEC ("Brown Bar"; "2.0 wt.% S2-7(-VC)"); and (g) wt% of additive c-D7 ("pink bar"; "1.0 wt% S2-7(-VC, -FEC)").

[0166] FIG. 3B shows the average coulombic efficiency versus cycle number for cells utilizing the same electrolyte formulation as in FIG. 3A. As seen in FIG. 3A and FIG. 3B, the addition of FEC and / or VC to an electrolyte system containing 1.0 wt.% of additive c-D7 resulted in relatively similar average specific discharge capacity and average coulombic efficiency compared to an electrolyte system containing 1.0 wt.% of additive c-D7 but without VC, and also compared to an electrolyte system containing 1.0 wt.% of additive c-D7 but without VC and FEC. Thus, the addition of FEC and / or VC did not adversely affect or did not substantially adversely affect the average specific discharge capacity or average coulombic efficiency of the electrolyte system containing 1.0 wt.% of additive c-D7 after four formation cycles. Furthermore, after four cycles, the electrolyte system containing 1.0 wt.% of additive c-D7, FEC and VC resulted in superior discharge capacity compared to the baseline electrolyte system without additive c-D7.

[0167] Example 5 - Effect of Additive c-D7 on Electrochemical Performance The electrochemical performance of the coin cells of Example 1 containing electrolyte systems with various amounts of additive c-D7 (also referred to as "S2-7") was tested. Figure 4 shows the specific discharge capacity versus voltage for an electrolyte system containing: (a) 0.7 wt % fluoroethylene carbonate (FEC) and 0.25 wt % vinylene carbonate (VC) ("black line"; "baseline"); (b) 0.5 wt% additive c-D7; 0.7 wt% FEC; and 0.25 wt% VC ("blue line"; "0.5 wt% S2-7"); (c) wt% additive c-D7; 0.7 wt% FEC; and 0.25 wt% VC ("red line" "1.0 wt% S2-7"); (d) 2.0 wt% additive c-D7; 0.7 wt% FEC; and 0.25 wt% VC ("purple line"; "2.0 wt% S2-7"); (e) wt% additive c-D7 and 0.7 wt% FEC ("pink line"; "1.0 wt% S2-7(-VC)"); (f) 2.0 wt% additive c-D7 and 0.7 wt% FEC ("green line"; "2.0 wt% S2-7(-VC)"); and (g) wt% of additive c-D7 ("orange line"; "1.0 wt% S2-7(-VC, -FEC)").

[0168] As can be seen in Figure 4, the addition of FEC and VC to the electrolyte system with 1.0 wt% additive c-D7 resulted in relatively similar electrochemical performance compared to the electrolyte system with 1.0 wt% additive c-D7 but without FEC and VC. Therefore, the addition of FEC and VC did not adversely affect or did not substantially adversely affect the specific capacity of the electrolyte system with 1.0 wt% additive c-D7.

[0169] Example 6 - Effect of Additive c-D7 on Cycle Performance The cycling performance of coin cells of Example 1 containing electrolyte systems with various amounts of additive c-D7 (also referred to as "S2-7") was tested. Figure 5A shows the average specific discharge capacity of NMC532 cells cycled from 3.0 V to 4.4 V at 40 °C with an electrolyte system containing: (a) 0.7 wt % fluoroethylene carbonate (FEC) and 0.25 wt % vinylene carbonate (VC) ("black squares"; "baseline"); (b) 0.5 wt% additive c-D7; 0.7 wt% FEC; and 0.25 wt% VC ("blue circle"; "0.5 wt% S2-7"); (c) wt% additive c-D7; 0.7 wt% FEC; and 0.25 wt% VC ("red triangle"; "1.0 wt% S2-7"); (d) 2.0 wt% additive c-D7; 0.7 wt% FEC; and 0.25 wt% VC ("purple triangles"; "2.0 wt% S2-7"); (e) wt% additive c-D7 and 0.7 wt% FEC ("green square"; "1.0 wt% S2-7(-VC)"); (f) 2.0 wt% additive c-D7 and 0.7 wt% FEC ("brown triangles"; "2.0 wt% S2-7(-VC)"); and (g) wt% of additive c-D7 ("pink triangles"; "1.0 wt% S2-7(-VC, -FEC)").

[0170] Figure 5B shows the average coulombic efficiency versus cycle number for cells utilizing the same electrolyte formulation as Figure 5A. As can be seen in Figures 5A and 5B, the addition of additive c-D7 as little as 0.5 wt % resulted in substantially superior average specific discharge capacity and average coulombic efficiency compared to the baseline electrolyte system without additive c-D7. Surprisingly, the electrolyte system with additives c-D7 and FEC, but without VC, also provided superior average specific discharge capacity and average coulombic efficiency compared to the baseline electrolyte system. More precisely, the electrolyte system without FEC and VC, but with additive c-D7, provided the best average specific discharge capacity and average coulombic efficiency compared to all other tested electrolyte systems that included the baseline electrolyte system plus additive c-D7.

[0171] Example 7 - Effect of Additive A4 on Passivation The impact of passivation of coin cells of Example 1 containing an electrolyte system with varying amounts of Additive A4 (also referred to as "S3-2") was tested. Figure 6A is a line graph showing the impact of passivation between 0.5V and 4.5V during the formation cycle of a cell containing an electrolyte system including: (a) 0.7 wt % fluoroethylene carbonate (FEC) and 0.25 wt % vinylene carbonate (VC) ("black line"; "baseline"); (b) 0.5 wt% additive A4; 0.7 wt% FEC; and 0.25 wt% VC ("blue line"; "0.5 wt% S3-2"); (c) wt% additive A4; 0.7 wt% FEC; and 0.25 wt% VC ("red line"; "1.0 wt% S3-2"); (d) 2.0 wt% additive A4; 0.7 wt% FEC; and 0.25 wt% VC ("purple line"; "2.0 wt% S3-2"); (e) wt% additive A4 and 0.7 wt% FEC ("orange line"; "1.0 wt% S3-2(-VC)"); (f) 2.0 wt.% Additive A4 and 0.7 wt.% FEC ("brown line"; "2.0 wt.% S3-2(-VC)"); and (g) 3.0 wt% additive A4 and 0.7 wt% FEC ("pink line"; "3.0 wt% S3-2(-VC)").

[0172] FIG. 6B is an expanded view of the line graph of FIG. 6A showing the effect of passivation between 1.5 V and 3.5 V. As can be seen in FIG. 6B, the addition of VC to the electrolyte system containing 1.0 wt. % Additive A4 formed a relatively similar amount of solid electrolyte interface (SEI) compared to the electrolyte system containing 1.0 wt. % Additive A4 but without VC. Therefore, the addition of VC did not adversely affect or did not substantially adversely affect the formation cycle of the electrolyte system containing 1.0 wt. % Additive A4, as a relatively similar amount of SEI was formed between 1.5 V and 2.75 V.

[0173] Example 8 - Effect of Additive A4 on Average Discharge Capacity and Coulombic Efficiency The average discharge capacity and average coulombic efficiency as a function of cycle number were tested for the coin cells of Example 1 containing electrolyte systems with various amounts of Additive A4 (also referred to as "S3-2"). Figure 7A shows the average specific discharge capacity versus cycle number for an electrolyte system containing: (a) 0.7 wt % fluoroethylene carbonate (FEC) and 0.25 wt % vinylene carbonate (VC) ("black bars"; "baseline"); (b) 0.5 wt% additive A4; 0.7 wt% FEC; and 0.25 wt% VC ("blue bars"; "0.5 wt% S3-2"); (c) wt% additive A4; 0.7 wt% FEC; and 0.25 wt% VC ("red bar"; "1.0 wt% S3-2"); (d) 2.0 wt% additive A4; 0.7 wt% FEC; and 0.25 wt% VC ("purple bar"; "2.0 wt% S3-2"); (e) wt% additive A4 and 0.7 wt% FEC ("orange bar"; "1.0 wt% S3-2(-VC)"); (f) 2.0 wt.% Additive A4 and 0.7 wt.% FEC ("Brown Bar"; "2.0 wt.% S3-2(-VC)"); and (g) 3.0 wt.% additive A4 and 0.7 wt.% FEC ("pink bar"; "3.0 wt.% S3-2(-VC)").

[0174] FIG. 7B shows the average coulombic efficiency versus cycle number for cells utilizing the same electrolyte formulation as in FIG. 7A. As seen in FIG. 7A and FIG. 7B, the addition of VC to the electrolyte system containing 1.0 wt. % Additive A4 resulted in relatively similar average specific discharge capacity and average coulombic efficiency compared to the electrolyte system containing 1.0 wt. % Additive A4 but without VC. Thus, the addition of VC did not adversely affect or did not substantially adversely affect the average specific discharge capacity or average coulombic efficiency of the electrolyte system containing 1.0 wt. % Additive A4 after four formation cycles.

[0175] Example 9 - Effect of Additive A4 on Electrochemical Performance The electrochemical performance of coin cells of Example 1 containing electrolyte systems with various amounts of Additive A4 (also referred to as "S3-2") was tested. Figure 8 shows the specific discharge capacity versus voltage for an electrolyte system containing: (a) 0.7 wt % fluoroethylene carbonate (FEC) and 0.25 wt % vinylene carbonate (VC) ("black line"; "baseline"); (b) 0.5 wt% additive A4; 0.7 wt% FEC; and 0.25 wt% VC ("blue line"; "0.5 wt% S3-2"); (c) wt% additive A4; 0.7 wt% FEC; and 0.25 wt% VC ("red line" "1.0 wt% S3-2"); (d) 2.0 wt% Additive A4; 0.7 wt% FEC; and 0.25 wt% VC ("purple line"; "2.0 wt% S3-2"); and (e) wt% additive A4 and 0.7 wt% FEC ("orange line"; "1.0 wt% S3-2(-VC)").

[0176] As can be seen in Figure 8, the addition of VC to the electrolyte system containing 1.0 wt% Additive A4 resulted in relatively similar electrochemical performance compared to the electrolyte system containing 1.0 wt% Additive A4 but no VC, so the addition of VC did not adversely affect or did not substantially adversely affect the specific capacity of the electrolyte system containing 1.0 wt% Additive A4.

[0177] Example 10 - Effect of Additive A4 on Cycling Performance The cycling performance of coin cells of Example 1 containing electrolyte systems with various amounts of Additive A4 (also referred to as "S3-2") was tested. Figure 9A shows the average specific discharge capacity of NMC532 cells cycled from 3.0 V to 4.4 V at 40 °C with an electrolyte system containing: (a) 0.7 wt % fluoroethylene carbonate (FEC) and 0.25 wt % vinylene carbonate (VC) ("black squares"; "baseline"); (b) 0.5 wt% additive A4; 0.7 wt% FEC; and 0.25 wt% VC ("blue circle"; "0.5 wt% S3-2"); (c) wt% additive A4; 0.7 wt% FEC; and 0.25 wt% VC ("red triangle"; "1.0 wt% S3-2"); (d) 2.0 wt% additive A4; 0.7 wt% FEC; and 0.25 wt% VC ("purple triangles"; "2.0 wt% S3-2"); (e) wt% additive A4 ("orange square"; "1.0 wt% S3-2(-VC,-FEC)"); (f) 2.0 wt.% of additive A4 ("brown triangles"; "2.0 wt.% of S3-2(-VC,-FEC)"); and (g) 3.0 wt.% of additive A4 ("pink triangle"; "3.0 wt.% of S3-2(-VC, -FEC)").

[0178] FIG. 9B shows the average coulombic efficiency of an NMC532 cell cycled from 3.0 V to 4.4 V at 40° C. using an electrolyte system containing: (a) 0.7 wt % FEC and 0.25 wt % VC ("black squares"; "baseline"); (b) 0.5 wt% additive A4; 0.7 wt% FEC; and 0.25 wt% VC ("blue circle"; "0.5 wt% S3-2"); (c) wt% additive A4; 0.7 wt% FEC; and 0.25 wt% VC ("red triangle"; "1.0 wt% S3-2"); (d) 2.0 wt% additive A4; 0.7 wt% FEC; and 0.25 wt% VC ("purple triangles"; "2.0 wt% S3-2"); (e) wt% additive A4 and 0.7 wt% FEC ("orange squares"; "1.0 wt% S3-2(-VC)"); (f) 2.0 wt.% additive A4 and 0.7 wt.% FEC ("brown triangles"; "2.0 wt.% S3-2(-VC)"); and (g) 3.0 wt% additive A4 and 0.7 wt% FEC ("pink triangle"; "3.0 wt% S3-2(-VC)").

[0179] As can be seen in Figures 9A and 9B, the addition of Additive A4 resulted in superior average specific discharge capacity and average coulombic efficiency compared to the baseline electrolyte system without Additive A4.

[0180] Example 11 - Effect of Additive A1 on Cycling Performance The cycling performance of coin cells of Example 1 containing electrolyte systems with various amounts of Additive A1 (also referred to as "S4-1") was tested. Figure 10A shows the average specific discharge capacity of NMC532 cells cycled from 3.0 V to 4.4 V at 40 °C with an electrolyte system containing: (a) 0.7 wt % fluoroethylene carbonate (FEC) and 0.25 wt % vinylene carbonate (VC) ("black squares"; "baseline"); (b) 0.5 wt% additive A1; 0.7 wt% FEC; and 0.25 wt% VC ("blue circle"; "0.5 wt% S4-1"); (c) wt% additive A1; 0.7 wt% FEC; and 0.25 wt% VC ("red triangle"; "1.0 wt% S4-1"); (d) 2.0 wt% Additive A1; 0.7 wt% FEC; and 0.25 wt% VC ("purple triangles"; "2.0 wt% S4-1"); and (e) wt% of additive A1 and 0.7 wt% of FEC ("orange squares"; "1.0 wt% of S4-1(-VC)").

[0181] Figure 10B shows the average coulombic efficiency versus cycle number for cells utilizing the same electrolyte formulation as Figure 10A. As can be seen in Figures 10A and 10B, the addition of Additive A1 resulted in superior average specific discharge capacity and average coulombic efficiency compared to the baseline electrolyte system without Additive A1.

[0182] Example 12 - Effect of Additive A3 on Cycling Performance The cycling performance of coin cells of Example 1 containing electrolyte systems with various amounts of Additive A3 (also referred to as "S4-2") was tested. Figure 11A shows the average specific discharge capacity of NMC532 cells cycled from 3.0 V to 4.4 V at 40 °C with an electrolyte system containing: (a) 0.7 wt % fluoroethylene carbonate (FEC) and 0.25 wt % vinylene carbonate (VC) ("black squares"; "baseline"); (b) wt% additive A3; 0.7 wt% FEC; and 0.25 wt% VC ("blue circle"; "0.5 wt% S4-2"); (c) wt% additive A3 and 0.7 wt% FEC ("red triangle"; "1.0 wt% S4-2(-VC)"); (d) 2.0 wt% additive A3 and 0.7 wt% FEC ("purple triangles"; "2.0 wt% S4-2(-VC)"); and (e) 3.0 wt % additive A3 and 0.7 wt % FEC ("orange squares"; "3.0 wt % S4-2(-VC)").

[0183] Figure 11B shows the average coulombic efficiency versus cycle number for cells utilizing the same electrolyte formulation as Figure 11A. As can be seen in Figures 11A and 11B, the addition of Additive A3 resulted in superior average specific discharge capacity and average coulombic efficiency compared to the baseline electrolyte system without Additive A3.

[0184] Example 13 - Effect of Additive B1 on Cycling Performance The cycling performance of coin cells of Example 1 containing electrolyte systems with various amounts of Additive B1 (also referred to as "SP-1") was tested. Figure 12A shows the average specific discharge capacity of NMC532 cells cycled from 3.0 V to 4.4 V at 40 °C with an electrolyte system containing: (a) 0.7 wt % fluoroethylene carbonate (FEC) and 0.25 wt % vinylene carbonate (VC) ("black squares"; "baseline"); (b) 0.5 wt% additive B1; 0.7 wt% FEC; and 0.25 wt% VC ("blue circle"; "0.5 wt% SP-1"); (c) wt% of additive B1; 0.7 wt% of FEC; and 0.25 wt% of VC ("red triangle"; "green triangle"; "1.0 wt% of SP-1"; "repeat"); (d) 2.0 wt% Additive B1; 0.7 wt% FEC; and 0.25 wt% VC ("purple triangles"; "2.0 wt% SP-1"); (e) wt% Additive B1 aged for 4 weeks; 0.7 wt% FEC; and 0.25 wt% VC ("orange squares"; "1.0 wt% SP-1(4w)"); and (f) wt% additive B1 and 0.7 wt% FEC ("brown triangles"; "1.0 wt% SP-1(-VC)").

[0185] Figure 12B shows the average coulombic efficiency versus cycle number for cells utilizing the same electrolyte formulation as Figure 12A. As can be seen in Figures 12A and 12B, the addition of greater than 0.5 wt% Additive B1 resulted in superior average specific discharge capacity and average coulombic efficiency compared to the baseline electrolyte system without Additive B1.

[0186] Example 14 - Effect of Additive C3 on Cycling Performance The cycling performance of coin cells of Example 1 containing electrolyte systems with various amounts of Additive C3 (also referred to as "DA-1") was tested. Figure 13A shows the average specific discharge capacity of NMC532 cells cycled from 3.0 V to 4.4 V at 40 °C with an electrolyte system containing: (a) 0.7 wt % fluoroethylene carbonate (FEC) and 0.25 wt % vinylene carbonate (VC) ("black squares"; "baseline"); (b) 0.5 wt% additive C3; 0.7 wt% FEC; and 0.25 wt% VC ("blue circle"; "0.5 wt% DA-1"); (c) wt% additive C3; 0.7 wt% FEC; and 0.25 wt% VC ("red triangle"; "1.0 wt% DA-1").

[0187] Figure 13B shows the average coulombic efficiency versus cycle number for cells utilizing the same electrolyte formulation as Figure 13A. As can be seen in Figures 13A and 13B, the addition of Additive C3 resulted in better or relatively similar average specific discharge capacity and average coulombic efficiency over 70 cycles compared to the baseline electrolyte system without Additive C3.

[0188] Example 15 - Effect of Additives D2, D4 and D6 on Cycling Performance The cycling performance of coin cells of Example 1 containing an electrolyte system including compounds according to some embodiments was tested. Figure 14A shows the average specific discharge capacity of NMC532 cells cycled from 3.0 V to 4.4 V at 40°C with an electrolyte system including: (a) 0.7 wt % fluoroethylene carbonate (FEC) and 0.25 wt % vinylene carbonate (VC) ("black squares"; "baseline"); (b) wt% additive D2 (also referred to as "S2-1"); 0.7 wt% FEC; and 0.25 wt% VC ("blue circle"; "1.0 wt% S2-1"); (c) wt. % of additive D4 (also referred to as "S2-3"); 0.7 wt. % of FEC; and 0.25 wt. % of VC ("red triangle"; "1.0 wt. % of S2-3"); and (d) wt% additive D6 (also referred to as "S2-5"); 0.7 wt% FEC; and 0.25 wt% VC ("green triangle"; "1.0 wt% S2-5").

[0189] Figure 14B shows the average coulombic efficiency versus cycle number for cells utilizing the same electrolyte formulation as Figure 14A. As can be seen in Figure 14A, the addition of Additive D4 resulted in superior average specific discharge capacity compared to the baseline electrolyte system without Additive D4. Furthermore, as can be seen in FIG. 14B, the addition of additives D2 or D4 resulted in superior coulombic efficiency compared to the baseline electrolyte system without additives D2 or D4.

[0190] Example 16 - Effect of Additive G1 on Cycling Performance The cycling performance of coin cells of Example 1 containing electrolyte systems with various amounts of Additive G1 (also referred to as "N1-8") was tested. Figure 15 shows the discharge capacity of an NMC532 cell cycled from 3.0 V to 4.4 V at 40 °C using an electrolyte system containing: (a) 0.7 wt % fluoroethylene carbonate (FEC) and 0.25 wt % vinylene carbonate (VC) ("black squares"; "baseline"); (b) 0.2 wt% additive G1; 0.7 wt% FEC; and 0.25 wt% VC ("blue circle"; "0.2 wt% N1-8"); (c) 0.5 wt% additive G1; 0.7 wt% FEC; and 0.25 wt% VC ("red triangle"; "0.5 wt% N1-8"); (d) wt% additive G1; 0.7 wt% FEC; and 0.25 wt% VC ("green triangle"; "1.0 wt% N1-8"); and (e) 2.0 wt% additive G1; 0.7 wt% FEC; and 0.25 wt% VC ("orange squares"; "2.0 wt% N1-8").

[0191] As can be seen in FIG. 15, the addition of less than 2 wt % Additive G1 resulted in superior discharge capacity compared to the baseline electrolyte system without Additive G1.

[0192] Example 17 - Aging The electrolyte additives were aged for a period of time to allow for conversion of the additives to their final product forms by reaction with 1.5M LiPF6 salt. The conversion times were determined by NMR measurements. Table 2 summarizes the aged electrolyte additives, their final LiPF6 salt forms, and conversion times. [Table 2]

[0193] Conversion of additives into final products 1 H and 19 The reaction was monitored by F NMR. 1 16A provides the conversion of Additive A1 (also referred to as "S4-1") to the final salt form product in the electrolyte as a function of time by H NMR. 1916A provides the conversion of Additive A1 (also referred to as "S4-1") in electrolyte to the final salt form product as a function of time by F NMR. As shown in Figures 16A and 16B, when the in-situ product is formed, a trimethylfluorosilane by-product is also formed. The reaction is complete in less than 3 weeks.

[0194] FIG. 17 shows the conversion of Additive A3 (also referred to as "S4-2") to the final product in the electrolyte as a function of time. 19 The F NMR spectrum is shown. Scheme 1 proposes a mechanism for the conversion of additive A3 (also called "S4-2") to the final product. The first observation of the final product A3 (also called "S4-2") was observed after one week in electrolyte. After two weeks, small amounts of the parent compound were observed. 1 Present by 1 H NMR. 19 Based on F NMR, complete consumption of the parent compound was observed at 3 weeks, although intermediate species were present. Scheme 1 Proposed mechanism of action of excipient A3 (also called "S4-2") on the final product [ka] (gas)

[0195] cathode FIG. 18 shows the conversion of Additive B1 (also referred to as "SP-1") to the final product in the electrolyte as a function of time. 19 The F NMR spectrum is shown. Scheme 2 proposes a mechanism for the conversion of Additive B1 (also referred to as "SP-1") to the final product. Scheme 2 Proposed mechanism of action of excipient B1 (also called "SP-1") on the end product [ka] CEI or SEI

[0196] Cathode or Anode FIG. 19A shows the conversion of additive C3 (also called "DA-1") to end products in the electrolyte as a function of time. 1The H NMR spectrum is shown in FIG. 19 The conversion of Additive C3 (also called "DA-1") to the final salt form product in electrolyte as a function of time by F NMR is provided. Scheme 3 proposes a mechanism for the conversion of Additive C3 (also called "DA-1") to the final product. Scheme 3 Proposed mechanism for the end product of additive C3 (also called "DA-1") [ka] (gas)

[0197] FIG. 20 shows the conversion of additive c-D7 (also called "S2-7") to the final product in the electrolyte as a function of time. 1 1 H NMR spectrum of additive D4 (also called "S2-3") in the electrolyte as a function of time. 19 As shown in Figure 21, the in-situ product is formed, and the F NMR spectrum of PO2F2 - and carbon suboxide (C3O2) by-product are also formed. Without wishing to be bound by theory, it is believed that formula (E) is produced by the polymerization of carbon suboxide.

[0198] Example 18 - Pouch cell specifications The electrolyte additives were tested for their effectiveness in NMC442 / graphite pouch cells. The pouch cells were fabricated and vacuum sealed in a dry room without electrolyte. Table 3 summarizes the pouch cell specifications. [Table 3]

[0199] 1M or 1.5M LiPF6 in EC:EMC:DMC in a weight ratio of 25:5:70 was used as a control electrolyte ("Comparative Electrolyte 1"). Electrolytes according to Comparative Electrolyte 1 but with 2 wt% fluoroethylene carbonate (FEC) added ("Comparative Electrolyte 2") or 1 wt% 1,3,6-hexanetricarbonitrile (HTCN or additive H2, also referred to as "N3-2") added ("Comparative Electrolyte 3") were also prepared. Electrolytes according to Comparative Electrolyte 1 but with various amounts of additives disclosed herein were also prepared and are described in the examples below.

[0200] The prepared electrolyte was mixed in an argon-filled glove box. After filling with electrolyte, the cells were subjected to a 24 hour wetting period where the cells were held at 1.5 V. The cells were then calibrated at C / 20 (12 mA) to either 4.4 V or 4.5 V depending on which upper cutoff potential was ultimately tested at. After charging to the upper cutoff, the cells were discharged to 3.0 V and charged to 3.8 V and impedance spectra were measured. Additionally, the cells were weighed in water and the weights were recorded. The tested cells were also weighed in water so that the evolved gas volume could be determined using Archimedes' principle.

[0201] Example 19 - Performance of aged electrolyte pouch cells The pouch cells were tested using comparative electrolytes and electrolyte formulations containing additives described herein. The cells were charged and discharged at C / 3 to either 4.4V or 4.5V using the protocols shown in FIG. 22A or FIG. 22B. After two cycles, the cells were held at upper charge limit for 24 hours for extended exposure to high voltage conditions. The actual current used for the C / 3 cycle was 53mA for the 4.4V test and 60mA for the 4.5V test. All tests were performed at 40°C. The cells were tested until their capacity dropped below 100mAh, at which point the test was terminated.

[0202] The test results are shown in FIG. 23, which plots cell capacity versus charge / discharge cycle number for Comparative Electrolyte 1 ("Control"), Comparative Electrolyte 2 ("2% FEC"), Comparative Electrolyte 3 (1 wt% Additive H2 or "1% HTCN"), 1 wt% Additive A1 aged for 2 days, and 1 wt% Additive A1 aged for 14 days. FIG. 23 shows that Additive A1 dramatically improves cell life under these aggressive high voltage, high temperature conditions. Importantly, cells containing Additive A1 outperformed cells containing control electrolytes such as Comparative Electrolyte 1 and Comparative Electrolyte 3 at both 4.4V and 4.5V.

[0203] The cells were also tested to evaluate their cycling performance when additives A1 and A3 were utilized. The number of cycles to reach 100 mA (i.e., 63% initial capacity retention) in FIG. 23 was used as a measure of additive efficacy. The results of the number of cycles to 100 mAh for the cells tested to an upper cutoff of 4.4 V are summarized in Table 3A. The results of the number of cycles to 100 mAh for the cells tested to an upper cutoff of 4.5 V are summarized in Table 3B. The reported results are the average of the data from the two cells tested. [Table 3A] [Table 3B]

[0204] The discharge capacity and the difference between the average charge and discharge voltages versus cycle number of pouch cells having electrolyte systems including compounds according to some embodiments were tested. Figure 24 shows the discharge capacity of an NMC442 pouch cell cycled from 3.0 V to 4.4 V at 40°C with an electrolyte system including: (a) 2 wt. % FEC and 3 wt. % Additive G1 ("3N1-8A-TMSCN"); (b) 2 wt. % FEC and 2 wt. % Additive G1 ("2N1-8A-TMSCN"); (c) 2 wt% FEC and 1 wt% Additive G1 ("1N1-8A-TMSCN"); (d) 2 wt. % FEC and 1 wt. % additive H2 (“1N3-2A-HTCN”); and (e) 2 wt. % fluoroethylene carbonate (FEC) (“2FEC”).

[0205] As seen in Figure 24, the addition of G1 or H2 resulted in improved discharge capacity relative to the baseline electrolyte system containing only 2 wt% FEC. The electrolyte system containing 1 wt% additive H2 resulted in superior average charge and discharge voltages after about 60 cycles compared to the control electrolyte system. Furthermore, the electrolyte system containing 3 wt% additive H2 resulted in superior average charge and discharge voltages after about 80 cycles compared to the control electrolyte system.

[0206] FIG. 25A shows the discharge capacity of an NMC442 pouch cell cycled from 3.0 V to 4.4 V at 40° C. with an electrolyte system containing: (a) 2% by weight fluoroethylene carbonate (FEC) ("2% FEC"); (b) 2 wt% FEC and 1 wt% additive H2 ("1% N3-2-HTCN"); (c) 2 wt% FEC and 1 wt% additive G1 ("1% N1-8-TMSCN"); (d) 2 wt. % FEC and 2 wt. % Additive D4 aged for 40 hours ("2%S2-3-bTMSCN-40 hour aging"); and (e) 2 wt. % FEC and 2 wt. % additive D4 aged for 1 week ("2%S2-3-bTMSCN-1 week aging").

[0207] Figure 25B shows the difference between the average charge voltage and the average discharge voltage versus cycle number for pouch cells utilizing the same electrolyte formulation as in Figure 25A. As can be seen in Figure 25A, the addition of aged Additive D4 resulted in improved discharge capacity relative to the baseline electrolyte system containing only 2 wt% FEC. Furthermore, the electrolyte system containing 2 wt% Additive D4 aged for 1 week resulted in cells with robust average charge and discharge voltages even after over 100 cycles.

[0208] Although certain embodiments of the present invention have been described, these embodiments are presented as examples only and are not intended to limit the scope of the present disclosure. In fact, the novel methods and systems described herein may be embodied in various 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 fall within the scope and spirit of the present disclosure. Therefore, the scope of the present invention is defined only by reference to the appended claims.

[0209] It should be understood that features, substances, properties, or groups described in connection with a particular aspect, embodiment, or example are applicable to any other aspect, embodiment, or example described in this section or elsewhere in this specification, unless they are incompatible. All of the features disclosed in this specification (including the accompanying claims, abstract, and drawings), and / or all of the 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 of the foregoing embodiments. 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.

[0210] Moreover, certain features described in this disclosure in the context of separate embodiments can also be implemented in combination in a single embodiment. Conversely, various features described in the context of a single embodiment can also be implemented separately in multiple embodiments or in any suitable subcombination. Furthermore, although features may be described above as acting in a certain combination, one or more features from the claimed combination may, in some cases, be deleted from the combination, and the combination may be claimed as a subcombination or a variation of the subcombination.

[0211] Furthermore, although 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 all operations need not be performed to achieve desirable results. Other operations not shown or described may be incorporated into the exemplary 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 appreciate 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 steps may be omitted and other steps may be added. Furthermore, the features and attributes of the specific embodiments disclosed above may be combined in different ways to form additional embodiments, all of which fall within the scope of the present disclosure. Also, it should be understood that the separation of the various system components in the above implementations should not be understood to require such separation in all implementations, and 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 system described herein may be provided separately or may be integrated (e.g., packaged together or attached together) to form an energy storage system.

[0212] For the purpose of this disclosure, certain aspects, advantages, and novel features are described herein. Not all such advantages can be achieved according to any particular embodiment. Thus, for example, a person skilled in the art will recognize that the present disclosure can be embodied or implemented to achieve one advantage or group of advantages as taught herein, without necessarily achieving other advantages as taught or suggested herein.

[0213] 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, but other embodiments do not. Thus, such conditional language does not generally imply that the features, elements, and / or steps are in any way required by 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.

[0214] Conjunctive language such as the phrase "at least one of X, Y, and Z" 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, unless otherwise noted. Thus, such conjunctive 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.

[0215] Words of degree used herein, such as "approximately," "about," "generally," and "substantially," as used herein, refer 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 amounts that are 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 result.

[0216] 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 may be defined by the claims, as presented in this section or elsewhere herein, or as presented in the future. The language of the claims should 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 the examples should be interpreted as non-exclusive.

Claims

1. 1. An electrolyte comprising at least one polymeric component comprising units of Formula (A), Formula (B), Formula (C), Formula (D), Formula (F), Formula (G), Formula (H), or Formula (E), or a salt thereof: 【Chemistry 118】 (A), 【Chemical 119】 (B), 【Chemical 120】 (C), 【Chemistry 121】 (D), 【Chemistry 122】 (E), 【Chemical 123】 (F), 【Chemistry 124】 (G), and 【Chemistry 125】 (H), where --- is selected from the group consisting of a single bond and a double bond; R １ is selected from the group consisting of -H, -OLg and absent; R ２ and R ５ each is independently selected from the group consisting of —H and —COOLg; R ３ is -COOLg and -CH ２ COOLg; R ４ is selected from the group consisting of -H, -OLg, and -COOLg; X １ is selected from the group consisting of C and N; R ６ is N(R １０ ) selected from the group consisting of -Lg, -OLg, and -NLg; R ７ and R １０ is independently selected from the group consisting of —H, an aryl group, an alkyl group, -Lg, and absent; R ８ and R ９ each of which is independently selected from the group consisting of -Lg and absent; R １３ is -CH ２ -, -C(O)-, -C(CH ３ ) ２ -, -CH ２ C(O)-, -C(CH ３ ) ２ CH ２ -, -C(CH ３ ) ２ C(O)-, (CHCH) ｗ C(O)-,-(CH ２ CH ２ ) ｗ C(O)-, and -(C≡C) ｗ C(O)—; R １４ is selected from the group consisting of -H, -OLg, and -COOLg; R １５ , R １６ and R １７ each is independently selected from the group consisting of —H, —CN, an alkyl group, and a cyanoalkyl group; X ２ is selected from the group consisting of —CN, —NCO, and —NCS; w is an integer ranging from 1 to 10; y is 0 or 1; z is an integer ranging from 1 to 100; and Lg is trimethylsilyl (TMS) and toluenesulfonyl (CH ３ C ６ H ４ SO ２ ) an electrolyte selected from the group consisting of

2. 10. The electrolyte of claim 1 comprising at least two of Formula (A), Formula (B), Formula (C), Formula (D), Formula (F), Formula (G), or Formula (H).

3. 10. The electrolyte of claim 1, in the salt form of at least one of Formula (A), Formula (B), Formula (C), Formula (D), Formula (F), Formula (G), or Formula (H).

4. The salt form of at least one of formula (A), formula (B), formula (C), formula (D), formula (F), formula (G), and formula (H) is LiPF ６ Salt form, LiBF ４ 4. The electrolyte of claim 3, wherein the electrolyte is selected from the group consisting of a salt form and a LiDFOB salt form.

5. 2. The electrolyte of claim 1, wherein Lg is TMS.

6. 6. The electrolyte of claim 1 comprising formula (A) or a salt thereof:

7. R １ The electrolyte of claim 6 wherein is —H.

8. R ２ The electrolyte of claim 6 wherein is -COOLg.

9. R ３ The electrolyte of claim 6 wherein is -COOLg.

10. 7. The electrolyte of claim 6 comprising a salt form of formula (A):

11. The salt form of formula (A) is 【Chemistry 126】 【Chemistry 127】 【Chemistry 128】 【Chemistry 129】 and 【Chemistry 130】 is selected from the group consisting of During the ceremony, R １１ is PF ６ －１ , B.F. ４ －１ and difluoro(oxalato)borate (DFOB － ) and 11. The electrolyte of claim 10, wherein n is the number of anionic groups.

12. The compound of formula (A) or a salt thereof 【Chemistry 131】 【Chemistry 132】 【Chemistry 133】 【Chemistry 134】 【Chemistry 135】 【Transformation 136】 【Chemistry 137】 【Chemistry 138】 【Chemistry 139】 [Chemistry 140] 【Chemistry 141】 and 【Chemistry 142】 7. The electrolyte of claim 6, selected from the group consisting of:

13. 6. The electrolyte of claim 1 comprising formula (B) or a salt thereof:

14. R ４ The electrolyte of claim 13 wherein is —H.

15. R ５ The electrolyte of claim 13 wherein is -COOLg.

16. X １ The electrolyte of claim 13 wherein is C.

17. The compound of formula (B) or a salt thereof 【Chemistry 143】 【Chemistry 144】 【Chemistry 145】 【Chemistry 146】 【Chemistry 147】 【Chemistry 148】 【Chemistry 149】 [Chemical 150] and 【Chemistry 151】 14. The electrolyte of claim 13 selected from the group consisting of:

18. 6. The electrolyte of claim 1 comprising formula (C) or a salt thereof:

19. R ６ -N (R １０ 20. The electrolyte of claim 18, wherein:

20. R １０ 20. The electrolyte of claim 19, wherein is an alkyl group.

21. R ７ 19. The electrolyte of claim 18, wherein is —H.

22. R ８ 20. The electrolyte of claim 18, wherein is absent.

23. R ９ 19. The electrolyte of claim 18, wherein is -Lg.

24. 19. The electrolyte of claim 18, wherein y is 0.

25. The compound of formula (C) or a salt thereof 【Chemistry 152】 【Chemistry 153】 【Chemistry 154】 【Chemistry 155】 【Chemistry 156】 【Chemistry 157】 【Chemistry 158】 【Chemistry 159】 [Chemical 160] 【Chemistry 161】 【Chemistry 162】 【Chemical 163】 【Chemistry 164】 【Chemistry 165】 【Chemistry 166】 【Chemistry 167】 【Chemical 168】 【Chemistry 169】 【Chemistry 170】 and 【Chemistry 171】 20. The electrolyte of claim 18 selected from the group consisting of:

26. The compound of formula (C) or a salt thereof 【Chemistry 172】 20. The electrolyte of claim 19, wherein:

27. 6. The electrolyte of claim 1 comprising formula (D) or a salt thereof:

28. R １３ Ga-CH ２ 28. The electrolyte of claim 27, which is C(O)-.

29. The compound of formula (D) or a salt thereof 【Chemistry 173】 【Chemistry 174】 【Chemistry 175】 【Chemistry 176】 【Chemistry 177】 【Chemistry 178】 【Chemistry 179】 【Chemistry 180】 【Chemistry 181】 【Chemistry 182】 【Chemistry 183】 【Chemistry 184】 【Chemistry 185】 【Chemical 186】 【Chemistry 187】 and 【Chemical 188】 28. The electrolyte of claim 27 selected from the group consisting of:

30. The compound of formula (D) or a salt thereof 【Chemical 189】 30. The electrolyte of claim 29, wherein:

31. 10. The electrolyte of claim 1 comprising units of formula (E):

32. 32. The electrolyte of claim 31, wherein z is an integer in the range of 1 to 10.

33. 6. The electrolyte of claim 1 comprising formula (F) or a salt thereof:

34. R １４ 34. The electrolyte of claim 33, wherein is —H.

35. The compound of formula (F) or a salt thereof 【Chemistry 190】 34. The electrolyte of claim 33 selected from the group consisting of:

36. 6. The electrolyte of claim 1 comprising formula (G) or a salt thereof:

37. 37. The electrolyte of claim 36, wherein Lg is TMS.

38. Lg is toluenesulfonyl (CH ３ C ６ H ４ SO ２ 37. The electrolyte of claim 36, wherein

39. X ２ 37. The electrolyte of claim 36, wherein is -CN.

40. X ２ 37. The electrolyte of claim 36, wherein is -NCO.

41. X ２ 37. The electrolyte of claim 36, wherein is -NCS.

42. The compound of formula (G) or a salt thereof is TMS-CN, TMS-NCO, TMS-NCS, 【Chemistry 191】 and 【Chemistry 192】 37. The electrolyte of claim 36 selected from the group consisting of:

43. 43. The electrolyte of claim 42, wherein the compound of formula (G) or a salt thereof is selected from the group consisting of TMS-CN and TMS-NCO.

44. 6. The electrolyte of claim 1 comprising formula (H) or a salt thereof:

45. R １５ 45. The electrolyte of claim 44, wherein is —H.

46. R １６ 45. The electrolyte of claim 44, wherein is a cyanoalkyl group.

47. R １７ 45. The electrolyte of claim 44, wherein is a cyanoalkyl group.

48. R １５ , R １６ and R １７ 45. The electrolyte of claim 44, wherein each of is an alkyl group.

49. The compound of formula (H) or a salt thereof 【Chemistry 193】 【Chemistry 194】 【Chemistry 195】 【Chemistry 196】 and 【Chemistry 197】 45. The electrolyte of claim 44, selected from the group consisting of:

50. The compound of formula (H) or a salt thereof 【Chemistry 198】 and 【Chemistry 199】 50. The electrolyte of claim 49 selected from the group consisting of:

51. 6. The electrolyte of claim 1, further comprising a solvent and a lithium salt.

52. The electrolyte of claim 51, wherein the solvent comprises a carbonate.

53. The electrolyte of claim 52, wherein the carbonate is selected from vinylene carbonate (VC), fluoroethylene carbonate (FEC), or a combination thereof.

54. 1. An energy storage device comprising:

6. An electrolyte according to any one of claims 1 to 5. cathode, anode, and a housing, the electrolyte, the cathode, and the anode being disposed within the housing; an energy storage device comprising:

55. 55. The energy storage device of claim 54, wherein the energy storage device is a lithium ion battery.

56. 55. The energy storage device of claim 54, having at least 90% discharge capacity retention after 50 cycles when cycled up to 4.4V.

57. A method for preparing an energy storage device, comprising preparing an electrolyte according to any one of claims 1 to 5; disposing said electrolyte within a housing containing a cathode and an anode; and a method comprising:

58. 58. The method of claim 57, wherein preparing comprises combining at least one of a polymer component comprising units of Formula (A), Formula (B), Formula (C), Formula (D), Formula (F), Formula (G), Formula (H), and Formula (E), or a salt thereof, the solvent, and the lithium salt to form the electrolyte, and aging the electrolyte before disposing the electrolyte in the housing.

59. 58. The method of claim 57, wherein the electrolyte is aged for 2 to 48 hours.

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