Carbon dioxide saturated electrolyte for energy storage device and method thereof

Abstract

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

Description

[0001] Incorporation by reference to any priority application

[0002] Any and all applications that identify foreign or domestic priority claims in the Application Data Sheet or PCT request filed with this application are incorporated herein by reference pursuant to 37 CFR 1.57 and Regulations 4.18 and 20.6. This application claims priority to U.S. Provisional Patent Application No. 63 / 377,638, filed on September 29, 2022, the disclosure of which is incorporated herein by reference in its entirety and for all purposes. Technical Field

[0003] The present disclosure relates generally to energy storage devices and, more particularly, to improved electrolyte formulations for use in energy storage devices. Background Art

[0004] Energy storage devices are widely used to provide power for electronic, electromechanical, electrochemical, and other useful devices. Such batteries include primary chemical batteries, secondary (rechargeable) batteries, fuel cells, and various kinds of capacitors, including supercapacitors. Improving the operating voltage and temperature of energy storage devices (including batteries and capacitors) is desirable for enhancing energy storage, increasing power capabilities, and broadening real-world use cases.

[0005] Lithium-ion batteries have been relied upon as a power source in numerous commercial and industrial applications, for example, in consumer devices, productivity equipment, and in battery-powered vehicles. However, the demand for energy storage devices continues to grow rapidly. For example, the automotive industry is developing vehicles that rely on compact and efficient energy storage, such as plug-in hybrid vehicles and pure electric vehicles. Lithium-ion batteries are well suited to meet future needs, however, energy density needs to be improved to provide longer-life batteries that can travel farther on a single charge. The electrolyte is a component in conventional lithium-ion batteries that determines the electrochemical performance and safety of these batteries, where the compatibility between the electrodes and the electrolyte determines the battery cell performance to a certain extent. Summary of the invention

[0006] In order to summarize the present invention and the advantages achieved over the prior art, certain objects and advantages of the present invention are described herein. Not all such objects or advantages may be achieved in any particular embodiment of the present invention. Thus, for example, it will be appreciated by those skilled in the art that the present invention may be implemented or performed in a manner that achieves or optimizes an advantage or a group of advantages as taught herein without necessarily achieving other objects or advantages as may be taught or suggested herein.

[0007] All these embodiments are intended to be included within the scope of the invention disclosed herein. These and other embodiments will be apparent to those skilled in the art through the following detailed description of the preferred embodiments in conjunction with the accompanying drawings, and the present invention is not limited to any particular preferred embodiment disclosed.

[0008] One embodiment is a lithium ion battery. The battery may include: a cathode; an anode; and an electrolyte comprising lithium ions and at least one source of carbon dioxide dissolved in a fluorinated solvent.

[0009] In one aspect, an energy storage device is described. The energy storage device comprises: a cathode; an anode; and an electrolyte comprising a lithium salt, a carbon dioxide source, and a fluorinated solvent. In some embodiments, the concentration of the carbon dioxide source in the electrolyte is in the range of 0.1 to 10 weight percent.

[0010] In some embodiments, the carbon dioxide source is selected from gaseous carbon dioxide, dry ice, diethyl pyrocarbonate (DEPC), dimethyl pyrocarbonate (DMPC), diallyl pyrocarbonate (DAPC), bis(tert-butyl) pyrocarbonate (O-Boc2) and combinations thereof. In further embodiments, the carbon dioxide source is diethyl pyrocarbonate. In some embodiments, the concentration of diethyl pyrocarbonate in the electrolyte is in the range of 1 to 6 weight %. In further embodiments, the concentration of diethyl pyrocarbonate in the electrolyte is in the range of 1.5 to 2.5 weight %.

[0011] In some embodiments, the concentration of the fluorinated solvent in the electrolyte is in the range of 5 to 80 weight %. In some embodiments, the concentration of the fluorinated solvent in the electrolyte is in the range of 5 to 20 weight %. In some embodiments, the fluorinated solvent is selected from fluoroethylene carbonate (FEC), difluoroethylene carbonate (diFEC), 2,2,2-trifluoroethyl methyl carbonate (FEMC), bis (2,2,2-trifluoroethyl) carbonate (TFEC), trifluoropropylene carbonate (TFPC), 2,2,3,3-tetrafluoro-1,4-dimethoxybutane (fDMB), bis (2,2,2-trifluoroethyl) ether (BTFE), 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE) and combinations thereof. In certain embodiments, the fluorinated solvent is fluoroethylene carbonate. In some embodiments, the electrolyte is substantially free of ethylene carbonate and dimethyl carbonate.

[0012] In some embodiments, the anode comprises silicon particles. In some embodiments, the silicon particles have a d 50 In a further embodiment, the silicon particles have a d 502-3 microns. In some embodiments, the anode comprises a graphite intercalation material and a silicon alloying / de-alloying material. In some embodiments, the cathode comprises an active material selected from lithium nickel manganese cobalt oxide (NMC), lithium manganese oxide (LMO), lithium nickel dioxide (LNO), lithium iron phosphate (LFP) and lithium nickel cobalt aluminum oxide (NCA). In some embodiments, the lithium salt is selected from lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide and combinations thereof.

[0013] In some embodiments, the energy storage device is configured to retain at least 70% of the initial capacity after 100 cycles between 4.1V and 2.85V at a charge rate of C3:C2. In further embodiments, the energy storage device is configured to retain at least 70% of the initial capacity after 140 cycles between 4.1V and 2.85V at a charge rate of C3:C2. In some embodiments, the energy storage device is a battery pack. In some embodiments, the energy storage device is configured to retain at least 70% of the initial capacity after 225 cycles between 4.2V and 2.85V at a charge rate of C4:C3.

[0014] In another aspect, an electric vehicle with a rechargeable battery pack is described. In some embodiments, the electric vehicle with a rechargeable battery pack includes: a drive motor; a gearbox; electronics; and an energy storage device described herein.

[0015] In another aspect, a method of preparing an electrolyte is described. The method includes: combining a carbon dioxide source, a fluorinated solvent, and a lithium salt to form an electrolyte. In some embodiments, the method also includes aging the electrolyte. In some embodiments, the method also includes filling the electrolyte into an energy storage device. In some embodiments, the electrolyte is positioned within the energy storage device. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 X-ray photoelectron spectroscopy (XPS) characterization of solid electrolyte interphase (SEI) composition resulting from cycling of electrolyte formulations according to some embodiments.

[0017] Figure 2 Included are data graphs of cycle data for an electrolyte system according to some embodiments relative to a baseline electrolyte system.

[0018] Figure 3A X-ray photoelectron spectroscopy (XPS) depth profiling of atomic concentration (%) of solid electrolyte interphase (SEI) constituents resulting from cycling of electrolyte formulations according to some embodiments versus sputtering depth.

[0019] Figure 3BX-ray photoelectron spectroscopy (XPS) characterization of solid electrolyte interphase (SEI) composition resulting from cycling of electrolyte formulations according to some embodiments.

[0020] Figure 4 Included are plots of data showing capacity retention during cycling for electrolyte systems according to some embodiments relative to a baseline electrolyte system.

[0021] Figure 5 is a bar graph showing gas formation for an electrolyte system according to some embodiments relative to a baseline electrolyte system.

[0022] Figure 6 The graph of FIG. 1 shows the discharge capacity versus cycle number for cells having an electrolyte system infused with gaseous carbon dioxide according to some embodiments relative to a baseline electrolyte system.

[0023] Fig. 7A The graph of FIG. 1 shows the discharge capacity versus cycle number relationship for batteries having electrolyte systems including different amounts of solvent blends according to some embodiments.

[0024] Figure 7B Graphs illustrate gas formation for electrolyte systems containing different amounts of solvent blends, according to some embodiments.

[0025] Fig. 8A The graph of FIG. 1 shows the discharge capacity versus cycle number for cells having an electrolyte system including diethyl pyrocarbonate (DEPC) according to some embodiments relative to a baseline electrolyte system.

[0026] Figure 8B The graph of FIG. 1 shows the discharge capacity versus cycle number for cells having an electrolyte system including diethyl pyrocarbonate (DEPC) according to some embodiments relative to a baseline electrolyte system.

[0027] Figure 8C Graphs illustrate gas formation for an electrolyte system including diethyl pyrocarbonate (DEPC), according to some embodiments. DETAILED DESCRIPTION

[0028] The present disclosure may be understood by reference to the following detailed description. It should be noted that, for clarity of illustration, in the various drawings, certain elements may not be drawn to scale, may be represented in a schematic or conceptual manner, or may not exactly correspond to certain physical configurations of the embodiments.

[0029] Electrolyte formulations for high voltage, high energy density energy storage devices (e.g., lithium ion batteries) are described, comprising at least one additive or a salt thereof. In some embodiments, such additives may react with lithium salts to improve device performance, such as stabilizing electrode surfaces. Such device improvements may advantageously provide improved cycle stability. The present disclosure also relates to electrolyte formulations that improve battery cycling by stabilizing a solid electrolyte interphase (SEI).

[0030] Embodiments relate to the use of an electrolyte formulation tailored for high energy anodes that does not include excessive CO 2 CO in gas battery design 2 The saturation and equilibrium fluorinated solvent content are fully optimized. In some embodiments, CO 2 and fluorinated solvents can be used in electrolyte formulations and CO 2 + Fluorinated solvents can extend the life of energy storage devices such as lithium-ion batteries. In some embodiments, the lithium-ion battery comprises a micron silicon anode. In some embodiments, the lithium-ion battery comprises a graphite anode. In addition, additives such as DEPC can be included in the electrolyte formulation and provide favorable results, as discussed below. In some embodiments, the electrolyte does not contain any ethylene carbonate (EC) or dimethyl carbonate (DMC). In some embodiments, the anode is made of an insertion material (such as carbon or graphite) and an alloying / de-alloying material (such as silicon, silicon oxide, tin and / or tin oxide).

[0031] definition

[0032] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. Unless otherwise indicated, all patents, applications, published applications, and other publications cited herein are incorporated by reference in their entirety. If there are multiple definitions for a term in this article, the definition in this section shall prevail unless otherwise indicated.

[0033] Whenever a group is described as "optionally substituted", the group may be unsubstituted or substituted with one or more indicated substituents. Similarly, when a group is described as "unsubstituted or substituted", if substituted, the substituents may be selected from one or more of the indicated substituents. If no substituents are indicated, it means that the indicated "optionally substituted" or "substituted" group may be substituted with one or more groups individually and independently selected from deuterium (D), halogen, hydroxyl, C 1-4 Alkoxy, C 1-8 Alkyl, C 3-20 Cycloalkyl, aryl, heteroaryl, heterocyclic, C 1-6Haloalkyl, cyano, C 2-8 Alkenyl, C 2-8 Alkynyl, C 3-20 Cycloalkenyl, aryl(alkyl), heteroaryl(alkyl), heterocyclyl(alkyl), acyl, thiocarbonyl, C-carboxyl, O-carboxyl, sulfenyl, sulfinyl, sulfonyl, haloalkoxy, amino, monosubstituted amine group and disubstituted amine group.

[0034] As used herein, "C" wherein "a" and "b" are integers a To C b ” refers to the number of carbon atoms in the group. The indicated group can contain from “a” to “b” (including “a” and “b”) carbon atoms. Thus, for example, “C 1 To C 4 "Alkyl" refers to all alkyl groups having 1 to 4 carbons, i.e., CH 3 -、CH 3 CH 2 -、CH 3 CH 2 CH 2 -、(CH 3 ) 2 CH-、CH 3 CH 2 CH 2 CH 2 -、CH 3 CH 2 CH(CH 3 )- and (CH 3 ) 3 C-. If "a" and "b" are not specified, the broadest range described in these definitions shall apply.

[0035] If two "R" groups are described as being "taken together," the R groups and the atoms to which they are attached can form a cycloalkyl, cycloalkenyl, aryl, heteroaryl, or heterocycle. For example, but not limitation, if NR a R b R a and R b When indicated as "taken together", it means that they are covalently bonded to each other either indirectly through an intermediate atom or directly to form a ring, for example:

[0036]

[0037] As used herein, the term "alkyl" refers to a fully saturated aliphatic hydrocarbon group. The alkyl moiety can be branched or straight chain. Examples of branched alkyl groups include, but are not limited to, isopropyl, sec-butyl, tert-butyl, etc. Examples of straight chain alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, etc.

[0038] The term "alkenyl" as used herein refers to a monovalent straight or branched chain group of two to thirty carbon atoms containing one or more carbon double bonds, including but not limited to 1-propenyl, 2-propenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, etc. The alkenyl group may be unsubstituted or substituted.

[0039] The term "alkynyl" as used herein refers to a monovalent straight or branched chain group of two to thirty carbon atoms containing one or more carbon triple bonds, including but not limited to 1-propynyl, 1-butynyl, 2-butynyl, etc. Alkynyl groups can be unsubstituted or substituted.

[0040] As used herein, "cycloalkyl" refers to a fully saturated (no double or triple bonds) monocyclic or polycyclic hydrocarbon ring system. When composed of two or more rings, the rings may be joined together in a fused, bridged or spiro manner. As used herein, the term "fused" refers to two rings that have two atoms and one bond in common. For example, in the following structure, rings A and B are fused As used herein, the term "bridged cycloalkyl" refers to compounds in which the cycloalkyl contains one or more bonds connecting atoms to non-adjacent atoms. is an example of a "bridged" ring. As used herein, the term "spiro" refers to two rings with one atom in common and the two rings are not connected by a bridge. The cycloalkyl group may contain 3 to 30 atoms in one or more rings, 3 to 20 atoms in one or more rings, 3 to 10 atoms in one or more rings, 3 to 8 atoms in one or more rings, or 3 to 6 atoms in one or more rings. The cycloalkyl group may be unsubstituted or substituted. Examples of monocyclic alkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of fused cycloalkyl groups include decahydronaphthyl, dodecahydro-1H-phenazone, and tetrahydroanthracenyl; examples of bridged cycloalkyl groups include bicyclo[1.1.1]pentyl, adamantyl, and norbornyl; examples of spirocycloalkyl groups include spiro[3.3]heptane and spiro[4.5]decane.

[0041] 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 there is more than one, the double bonds cannot form a completely delocalized π-electron system in all rings (otherwise the group would be an "aryl" as defined herein). The cycloalkenyl group may contain 3 to 30 atoms in one or more rings, 3 to 20 atoms in one or more rings, 3 to 10 atoms in one or more rings, 3 to 8 atoms in one or more rings, or 3 to 6 atoms in one or more rings. When composed of two or more rings, the rings may be connected together in a fused, bridged or spiro manner. The cycloalkenyl group may be unsubstituted or substituted.

[0042] 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 there are more than one triple bond, the triple bonds cannot form a completely delocalized π electron system in all rings. The cycloalkynyl group may contain 8 to 30 atoms in one or more rings, 8 to 20 atoms in one or more rings, or 8 to 10 atoms in one or more rings. When composed of two or more rings, these rings may be combined together in a fused, bridged or spiro manner. The cycloalkynyl group may be unsubstituted or substituted.

[0043] 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 π electron system throughout all rings. The number of carbon atoms in an aryl group can vary. For example, an aryl group can be C 6 -C 14 Aryl group, C 6 -C 10 Aryl group or C 6 Aryl groups. Examples of aryl groups include, but are not limited to, benzene, naphthalene, and azulene. Aryl groups may be substituted or unsubstituted.

[0044] As used herein, "heteroaryl" refers to a monocyclic or polycyclic aromatic ring system (a ring system with a completely delocalized π electron system) containing one or more heteroatoms (e.g., 1, 2 or 3 heteroatoms), i.e., non-carbon elements, including but not limited to nitrogen, oxygen and sulfur. The number of atoms in the ring of the heteroaryl group can vary. For example, the heteroaryl group can contain 4 to 14 atoms in one or more rings, 5 to 10 atoms in one or more rings, or 5 to 6 atoms in one or more rings. In addition, the term "heteroaryl" includes fused ring systems in which two rings, such as at least one aryl ring and at least one heteroaryl ring or at least two heteroaryl rings, share at least one chemical bond. 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. The heteroaryl group may be substituted or unsubstituted.

[0045] As used herein, "heterocyclic group" or "heteroalicyclic group" refers to a tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, deca-, up to 18-membered monocyclic, bicyclic and tricyclic ring system, wherein carbon atoms together with 1 to 5 heteroatoms constitute the ring system. The heterocyclic ring may optionally contain one or more unsaturated bonds, however, it is positioned in a manner that a completely delocalized π-electron system does not appear throughout all rings. Heteroatoms are non-carbon elements, including but not limited to oxygen, sulfur and nitrogen. The heterocyclic ring may also contain one or more carbonyl or thiocarbonyl functions, so that the definition includes oxo systems and thio systems, such as lactams, lactones, cyclic imides, cyclic thioimides and cyclic carbamates. When composed of two or more rings, these rings may be combined together in a fused or spiro manner. In addition, any nitrogen in the heteroalicyclic group may be quaternized. The heterocyclic group or heteroalicyclic group may be unsubstituted or substituted. Examples of such "heterocyclyl" or "heteroalicyclic" groups include, but are not limited to, 1,3-dioxine, 1,3-dioxane, 1,4-dioxane, 1,2-dioxolane, 1,3-dioxolane, 1,4-dioxolane, 1,3-oxathiinane, 1,4-oxathiinene, 1,3-oxathiol, 1,3-dithiole, 1,3-dithiolane, 1,4-oxathiinane, tetrahydro-1,4-thiazine, 2H-1,2-oxazine, maleimide, succinimide, barbituric acid, thiobarbituric acid, dioxopiperazine, hydantoin Urea, dihydrouracil, trioxane, hexahydro-1,3,5-triazine, imidazoline, imidazolidine, isoxazoline, isoxazolidine, oxazoline, oxazolidine, oxazolidinone, thiazoline, thiazolidine, morpholine, oxirane, piperidine N-oxide, piperidine, piperazine, pyrrolidine, pyrrolidone, pyrrolidone, 4-piperidone, pyrazoline, pyrazolidine, 2-oxopyrrolidine, tetrahydropyran, 4H-pyran, tetrahydrothiopyran, thiomorpholine, thiomorpholine sulfoxide, thiomorpholine sulfone and their benzo-fused analogs (e.g., benzimidazolidinone, tetrahydroquinoline and / or 3,4-methylenedioxyphenyl).

[0046] As used herein, "aralkyl" and "aryl(alkyl)" refer to an aryl group attached via a lower alkylene group as a substituent. The lower alkylene and aryl groups of the aralkyl group may be substituted or unsubstituted. Examples include, but are not limited to, benzyl, 2-phenylalkyl, 3-phenylalkyl, and naphthylalkyl.

[0047] As used herein, "heteroaralkyl" and "heteroaryl (alkyl)" refer to heteroaryl groups attached via lower alkylene groups as substituents. The lower alkylene and heteroaryl groups of heteroaralkyl can be substituted or unsubstituted. Examples include, but are not limited to, 2-thienylalkyl, 3-thienylalkyl, furanylalkyl, thienylalkyl, pyrrolylalkyl, pyridylalkyl, isoxazolylalkyl and imidazolylalkyl and their benzo-fused analogs.

[0048] "Heteroalicyclic (alkyl)" and "heterocyclyl (alkyl)" refer to a heterocyclic or heteroalicyclic group attached via a lower alkylene group as a substituent. The lower alkylene and heterocyclyl groups of (heteroalicyclic)alkyl can 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-thiazin-4-yl (methyl).

[0049] "Alkylene group" and "lower alkylene group" are straight chain -CH 2 - Anchoring groups, which form bonds through their terminal carbon atoms to connect molecular fragments. Examples include, but are not limited to, methylene (-CH 2 -), ethylene (-CH 2 CH 2 -), propylene (-CH 2 CH 2 CH 2 -) and butylene (-CH 2 CH 2 CH 2 CH 2 -). An alkylene group may be substituted by replacing one or more hydrogen atoms of the alkylene group with one or more of the substituents listed under the definition of "substituted" and / or by replacing one or more hydrogen atoms of the alkylene group with a cycloalkyl group (e.g., ) replaces two hydrogens on the same carbon.

[0050] As used herein, the term "hydroxyl" refers to an -OH group.

[0051] As used herein, "alkoxy" refers to the formula -OR, where R is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, heterocyclyl, cycloalkyl(alkyl), aryl(alkyl), heteroaryl(alkyl) or heterocyclyl(alkyl) as defined herein. A non-limiting list of alkoxy is methoxy, ethoxy, n-propoxy, 1-methylethoxy (isopropoxy), n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, phenoxy and benzyloxy. Alkoxy can be substituted or unsubstituted.

[0052] As used herein, "acyl" refers to hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, aryl(alkyl), heteroaryl(alkyl), and heterocyclyl(alkyl) attached via a carbonyl group as a substituent. Examples include formyl, acetyl, propionyl, benzoyl, and acryloyl. Acyl groups can be substituted or unsubstituted.

[0053] A "cyano" group refers to a "-CN" group.

[0054] As used herein, the term "halogen atom" or "halogen" refers to any of the radioactive stable atoms of column 7 of the periodic table, such as fluorine, chlorine, bromine and iodine.

[0055] A "thiocarbonyl" group refers to a "-C(=S)R" group, wherein R may be the same as defined for O-carboxy. The thiocarbonyl group may be substituted or unsubstituted.

[0056] An "O-carbamyl" group refers to a "-OC(=O)N(R A R B )" group, wherein R A and R B O-carbamoyl may be substituted or unsubstituted.

[0057] An "N-carbamyl" group refers to an "ROC(=O)N(R A )-" group, where R and R A It can be independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, heterocyclyl, cycloalkyl(alkyl), aryl(alkyl), heteroaryl(alkyl) or heterocyclyl(alkyl). N-carbamoyl can be substituted or unsubstituted.

[0058] An "O-thiocarbamyl" group refers to an "-OC(=S)-N(R A R B )" group, wherein R A and R B O-thiocarbamoyl may be substituted or unsubstituted.

[0059] An "N-thiocarbamyl" group refers to an "ROC(=S)N(R A )-" group, where R and R A It can be independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, heterocyclyl, cycloalkyl (alkyl), aryl (alkyl), heteroaryl (alkyl) or heterocyclyl (alkyl). N-thiocarbamoyl can be substituted or unsubstituted.

[0060] A "C-amido" group refers to a "-C(=O)N(R A R B )" group, wherein R A and R BCan be independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, heterocyclyl, cycloalkyl (alkyl), aryl (alkyl), heteroaryl (alkyl) or heterocyclyl (alkyl). C-amide can be substituted or unsubstituted.

[0061] An "N-amido" group refers to an "RC(=O)N(R A )-" group, where R and R A It can be independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, heterocyclyl, cycloalkyl (alkyl), aryl (alkyl), heteroaryl (alkyl) or heterocyclyl (alkyl). N-amide can be substituted or unsubstituted.

[0062] A "C-thioamido" group refers to a "-C(=S)N(R A R B )" group, wherein R A and R B It can be independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, heterocyclyl, cycloalkyl(alkyl), aryl(alkyl), heteroaryl(alkyl) or heterocyclyl(alkyl). C-thioamido can be substituted or unsubstituted.

[0063] An "N-thioamido" group refers to an "RC(=S)N(R A )-" group, where R and R A It can be independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, heterocyclyl, cycloalkyl (alkyl), aryl (alkyl), heteroaryl (alkyl) or heterocyclyl (alkyl). N-thioamide group can be substituted or unsubstituted.

[0064] An "S-sulfonamido" group refers to an "-SO 2 N(R A R B )" group, wherein R A and R B It can be independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, heterocyclyl, cycloalkyl (alkyl), aryl (alkyl), heteroaryl (alkyl) or heterocyclyl (alkyl). S-sulfonylamide can be substituted or unsubstituted.

[0065] The "N-sulfonamide" group refers to the "RSO 2 N(R A )-" group, where R and R AIt can be independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, heterocyclyl, cycloalkyl (alkyl), aryl (alkyl), heteroaryl (alkyl) or heterocyclyl (alkyl). N-sulfonylamide can be substituted or unsubstituted.

[0066] An "O-carboxyl" group refers to a "RC(=O)O-" group, where R can be hydrogen, alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkenyl, aryl, heteroaryl, heterocyclyl, cycloalkyl(alkyl), aryl(alkyl), heteroaryl(alkyl) or heterocyclyl(alkyl), as defined herein. The O-carboxyl group can be substituted or unsubstituted.

[0067] The terms "ester" and "C-carboxy" refer to a "-C(=O)OR" group, where R may be the same as defined for O-carboxy. Esters and C-carboxy may be substituted or unsubstituted.

[0068] A "sulfenyl" group refers to a "-SR" group, where R can be hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, heterocyclyl, cycloalkyl(alkyl), aryl(alkyl), heteroaryl(alkyl) or heterocyclyl(alkyl). The sulfenyl group can be substituted or unsubstituted.

[0069] A "sulfinyl" group refers to a "-S(=O)-R" group, wherein R may be the same as defined for a sulfenyl group. The sulfinyl group may be substituted or unsubstituted.

[0070] A "sulfonyl" group refers to an "SO 2 R" group, wherein R may be the same as defined for p-sulfenyl. The sulfonyl group may be substituted or unsubstituted.

[0071] As used herein, "haloalkyl" refers to an alkyl group in which one or more hydrogen atoms are replaced with a halogen (e.g., monohaloalkyl, dihaloalkyl, and trihaloalkyl). Such groups include, but are not limited to, chloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 1-chloro-2-fluoromethyl, and 2-fluoroisobutyl. Haloalkyl can be substituted or unsubstituted.

[0072] As used herein, "haloalkoxy" refers to an alkoxy group in which one or more hydrogen atoms are replaced with a halogen (e.g., monohaloalkoxy, dihaloalkoxy, and trihaloalkoxy). Such groups include, but are not limited to, chloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 1-chloro-2-fluoromethoxy, and 2-fluoroisobutoxy. Halogenated alkoxy groups may be substituted or unsubstituted.

[0073] As used herein, the term "nitro" refers to -NO 2 Group.

[0074] As used herein, the term "amino" refers to -NH 2 Group.

[0075] A "monosubstituted amine" group refers to a "-NHR" group, where R can be alkyl, alkenyl, alkynyl, haloalkyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, heterocyclyl, cycloalkyl(alkyl), aryl(alkyl), heteroaryl(alkyl) or heterocyclyl(alkyl), as defined herein. The monosubstituted amino group can be substituted or unsubstituted. Examples of monosubstituted amino groups include, but are not limited to, -NH(methyl), -NH(phenyl), and the like.

[0076] A "disubstituted amine" group refers to a "-NR A R B " group, where R A and R B The disubstituted amino groups may be independently alkyl, alkenyl, alkynyl, haloalkyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, heterocyclyl, cycloalkyl(alkyl), aryl(alkyl), heteroaryl(alkyl) or heterocyclyl(alkyl), as defined herein. The disubstituted amino groups may be substituted or unsubstituted. Examples of disubstituted amino groups include, but are not limited to, -N(methyl) 2 , -N(phenyl)(methyl), -N(ethyl)(methyl), etc.

[0077] When the number of substituents is not specified (e.g., haloalkyl), one or more substituents may be present. For example, "haloalkyl" may include one or more halogens that are the same or different. As another example, "C 1 -C 3 The "alkoxyphenyl" group may include one or more identical or different alkoxy groups containing one, two or three atoms.

[0078] As used herein, a radical refers to a species with a single unpaired electron, so that the species containing the radical can be covalently bound to another species. Therefore, in this context, a radical is not necessarily a free radical. On the contrary, a radical represents a specific part of a larger molecule. The term "radical" can be used interchangeably with the term "group".

[0079] It is understood that in any compound described herein having one or more chiral centers, if the absolute stereochemistry is not explicitly indicated, each center can independently be in the R-configuration or S-configuration or a mixture thereof. Thus, the compounds provided herein can be enantiomerically pure, enantiomerically enriched, a racemic mixture, diastereomerically pure, diastereomerically enriched, or a stereoisomeric mixture. In addition, it is understood that in any compound described herein having one or more double bonds that produce geometric isomers that can be defined as E or Z, each double bond can independently be E or Z or a mixture thereof.

[0080] In some embodiments, in any compound described, all tautomeric forms are also intended to be included. For example, but not limited to, for compound References to may be construed to include tautomers

[0081] It is understood that where compounds disclosed herein have unfilled valences, then the valences are filled with hydrogen or an isotope thereof, for example, hydrogen-1 (protium) and hydrogen-2 (deuterium).

[0082] Electrolytes

[0083] The electrolyte formulations described herein may include an alkali metal salt (e.g., a lithium salt and / or a sodium salt) and one or more solvents discussed herein. Typically, the alkali metal salt includes a cation and an anion. In some embodiments, the anion is redox stable. In some embodiments, the anion may be monovalent. In some embodiments, the cation on the alkali metal salt is selected from Li, Na, K and / or Rb. In some embodiments, the sodium salt may be selected from NaPF 6 , NaBF 4 、NaClO 4 、NaN(FSO 2 ) 2 (NaFSI), NaB(C 2 O 4 ) 2 In some embodiments, the lithium salt may be selected from lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium difluoro(oxalato)borate (LiDFOB), lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium hexafluoroarsenate (V) (LiAsF 6 ), lithium perchlorate (LiClO 4) and combinations thereof. In some embodiments, the lithium salt is LiFSI. In some embodiments, the lithium salt may include an anion selected from hexafluorophosphate, tetrafluoroborate, difluoro(oxalato)borate, bis(fluorosulfonyl)imide, bis(trifluoromethanesulfonyl)imide, hexafluoroarsenate (V), and perchlorate. In certain embodiments, the salt concentration of the electrolyte can be, is about, is at most, or is about 0.1 M, 0.2 M, 0.3 M, 0.4 M, 0.5 M, 0.6 M, 0.7 M, 0.8 M, 0.9 M, 1 M, 1.1 M, 1.2 M, 1.3 M, 1.4 M, 1.5 M, 1.6 M, 1.7 M, 1.8 M, 1.9 M, 2 M, 2.1 M, 2.2 M, 2.3 M, 2.4 M, 2.5 M, 2.6 M, 2.7 M, 2.8 M, 2.9 M, 3 M, 3.1 M, 3.2 M, 3.3 In some embodiments, the salt concentration may be 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 1.5 M. In some embodiments, the salt concentration may be 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 1.5 M.

[0084] In some embodiments, the electrolyte further comprises one or more additives. In some embodiments, the additives may be selected from, for example, vinylene carbonate (VC), ethylene sulfate (DTD), lithium difluorophosphate (LFO), fluoroethylene carbonate (FEC), propylene sulfone (PES), phenyl trifluoromethyl sulfide (PTS), lithium bis(oxalate)borate (LiBOB), lithium difluoro(oxalate)borate (LiDFOB), triethyl borate (TEB), trimethyl borate (TMB), tri(trimethylsilyl) borate (TTMSiB), 4-trifluoromethylbenzonitrile (TFMB), tri(trimethylsilyl) phosphite (TTSPi), tri(trimethylsilyl) phosphate (TTSPi), triethyl phosphite (TEPi), lithium ethoxide (EthOLi), lithium methoxide (MeOLi), lithium tetrafluorooxalate phosphate (LiTFOP), lithium difluorobis(oxalate phosphate) (LiDFDOP), and combinations thereof.

[0085] In some embodiments, the electrolyte further comprises one or more additional additives. In some embodiments, the additives may be selected from, for example, diethyl pyrocarbonate (DEPC), dimethyl pyrocarbonate (DMPC), diallyl pyrocarbonate (DAPC), lithium difluoro(oxalate)borate LiDFOB, lithium difluorobis(oxalate)phosphate LiDFBOP, di-tert-butyl dicarbonate (Boc anhydride), and combinations thereof.

[0086] In some embodiments, the electrolyte comprises each additive of 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, and the total amount thereof is 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.

[0087] Solvents

[0088] In some embodiments, the electrolyte comprises a liquid solvent. As provided herein, the solvent does not need to dissolve each component, nor does it need to completely dissolve each component of the electrolyte. In further embodiments, the solvent may include an organic solvent. In some embodiments, the solvent may include one or more functional groups selected from carbonate, dimer carbonate, ether and / or ester. In some embodiments, the electrolyte comprises a solvent. In other embodiments, the electrolyte comprises a variety of solvents. In some embodiments, the solvent may include decarbonated alkyl ester (alkyl decarbonate) compounds and / or dimer compounds (e.g., didecarbonated alkyl ester (alkyl didecarbonate) compounds).

[0089] In some embodiments, the solvent may include carbonate. In further embodiments, carbonate may be selected from cyclic carbonates, such as ethylene carbonate (EC), propylene carbonate (PC), vinyl ethylene carbonate (VEC), vinylene carbonate (VC), fluoroethylene carbonate (FEC) and combinations thereof, or acyclic carbonates, such as dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC) and combinations thereof. In some embodiments, the solvent may include fluoroethylene carbonate (FEC). In some embodiments, the solvent may further include methyl acetate (MA). In some embodiments, the solvent may include ethyl acetate (EA). In some embodiments, the solvent may include propionitrile (PN). In some embodiments, the solvent may include acetonitrile (AN). In some embodiments, the solvent may include gbutyl lactone (GBL). In some embodiments, the solvent does not contain or is substantially free of ethylene carbonate (EC). In some embodiments, the solvent does not contain or is substantially free of dimethyl carbonate (DMC).

[0090] In some embodiments, the solvent includes or is a fluorinated solvent. In some embodiments, the fluorinated solvent is selected from fluoroethylene carbonate (FEC), difluoroethylene carbonate (diFEC), 2,2,2-trifluoroethyl methyl carbonate (FEMC), bis (2,2,2-trifluoroethyl) carbonate (TFEC), trifluoropropylene carbonate (TFPC), 2,2,3,3-tetrafluoro-1,4-dimethoxybutane (fDMB), bis (2,2,2-trifluoroethyl) ether (BTFE), 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE) and combinations thereof.

[0091] In some embodiments, the electrolyte comprises, is about, is at least, or is at least about 70 wt %, 71 wt %, 72 wt %, 73 wt %, 74 wt %, 75 wt %, 76 wt %, 77 wt %, 78 wt %, 79 wt %, 80 wt %, 81 wt %, 82 wt %, 83 wt %, 84 wt %, 85 wt %, 86 wt %, 87 wt %, 88 wt %, 89 wt %, 90 wt %, 91 wt %, 92 wt %, 93 wt %, 94 wt %, 95 wt %, 96 wt %, 97 wt %, or 98 wt % total solvent, or any range of values ​​therebetween. In some embodiments, the electrolyte comprises, is about, is at least, or is at least about 1 wt %, 2 wt %, 3 wt %, 4 wt %, 5 wt %, 6 wt %, 7 wt %, 8 wt %, 9 wt %, 10 wt %, 11 wt %, 12 wt %, 13 wt %, 14 wt %, 15 wt %, 16 wt %, 17 wt %, 18 wt %, 19 wt %, 20 wt %, 21 wt %, 22 wt %, 23 wt %, 24 wt %, 25 wt %, 26 wt %, 27 wt %, 28 wt %, 29 wt %, 30 wt %, 31 wt %, 32 wt %, 33 wt %, 34 wt %, 35 %, 24% by weight, 25% by weight, 26% by weight, 27% by weight, 28% by weight, 29% by weight, 30% by weight, 31% by weight, 32% by weight, 33% by weight, 34% by weight, 35% by weight, 36% by weight, 37% by weight, 38% by weight, 39% by weight, 40% by weight, 41% by weight, 42% by weight, 43% by weight, 44% by weight, 45% by weight, 46% by weight, 47% by weight, 48% by weight, 49% by weight %, 50% by weight, 51% by weight, 52% by weight, 53% by weight, 54% by weight, 55% by weight, 56% by weight, 57% by weight, 58% by weight, 59% by weight, 60% by weight, 61% by weight, 62% by weight, 63% by weight, 64% by weight, 65% by weight, 66% by weight, 67% by weight, 68% by weight, 69% by weight, 70% by weight, 71% by weight, 72% by weight, 73% by weight, 74% by weight, 75% by weight, %, 76 wt%, 77 wt%, 78 wt%, 79 wt%, 80 wt%, 81 wt%, 82 wt%, 83 wt%, 84 wt%, 85 wt%, 86 wt%, 87 wt%, 88 wt%, 89 wt%, 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt%, 95 wt%, 96 wt%, 97 wt% or 98 wt% or any range of values ​​therebetween of each solvent.

[0092] In some embodiments, the electrolyte comprises one or more solvents. In some embodiments, the electrolyte comprises 1, 2, 3, 4, 5 or 6 solvent systems or any value range therebetween. In some embodiments, the electrolyte comprises a first solvent and a second solvent. In some embodiments, the electrolyte solvent system may comprise a volume ratio of about 10: 1, 9: 1, 8: 1, 7: 1, 6: 1, 5: 1, 4: 1, 3: 1, 2: 1, 1: 1, 1: 2, 1: 3, 1: 4, 1: 4, 1: 6, 1: 7, 1: 8, 1: 9, 1: 10 or any range therebetween. For example, in some embodiments, the volume ratio may be about 3: 7, about 1: 1, about 1: 4, about 4: 1, about 3: 2 or about 2: 3.

[0093] Carbon dioxide (CO 2 )source

[0094] In some embodiments, the electrolyte comprises at least one carbon dioxide source. Carbon dioxide source as provided herein can be selected from, for example, gaseous carbon dioxide, dry ice (i.e., solid carbon dioxide) and pyrocarbonate, such as diethyl pyrocarbonate (DEPC) and / or compounds of formula (A) described herein and combinations thereof. For example, in some embodiments, the carbon dioxide source comprises diethyl pyrocarbonate (DEPC).

[0095] Formula (A)

[0096] In some embodiments, the carbon dioxide source comprises or is a compound of formula (A):

[0097]

[0098] In some embodiments, R 1 and R 2 R is independently selected from hydrogen, optionally substituted alkyl, optionally substituted haloalkyl, optionally substituted alkenyl, and optionally substituted alkynyl. 1 and R 2 are independently selected from optionally substituted alkyl and optionally substituted alkenyl.

[0099] In some embodiments, the carbon dioxide source of formula (A) is selected from any one or any combination of the compounds shown in Table A.

[0100] Table A

[0101]

[0102] In some embodiments, the electrolyte comprises at least one source of carbon dioxide at, at least about, at least about 0.01 wt %, 0.05 wt %, 0.1 wt %, 0.2 wt %, 0.3 wt %, 0.4 wt %, 0.5 wt %, 0.6 wt %, 0.7 wt %, 0.8 wt %, 0.9 wt %, 1 wt %, 2 wt %, 3 wt %, 4 wt %, 5 wt %, 6 wt %, 7 wt %, 8 wt %, 9 wt %, 10 wt %, 11 wt %, 12 wt %, 13 wt %, 14 wt %, 15 wt %, 16 wt %, 17 wt %, 18 wt %, 19 wt %, 20 wt %, or any range of values ​​therebetween.

[0103] In some embodiments, the electrolyte formulation will be completely saturated with carbon dioxide. In further embodiments, additional carbon dioxide may be included in the cell.

[0104] Energy storage device

[0105] The energy storage device of the present disclosure includes electrolyte, cathode, anode and shell discussed herein, wherein electrolyte, cathode and anode are arranged in shell. In some embodiments, the energy storage device as provided herein is lithium ion battery and / or sodium ion battery. In some embodiments, the energy storage device as provided herein is configured to retain at least 70% of the initial capacity after 100 cycles between 4.1V and 2.85V at a charging rate of C3:C2. In some embodiments, the energy storage device is configured to retain at least 70% of the initial capacity after 140 cycles between 4.1V and 2.85V at a charging rate of C3:C2. In some embodiments, the energy storage device is a battery pack. In some embodiments, the energy storage device is configured to retain at least 70% of the initial capacity after 225 cycles between 4.2V and 2.85V at a charging rate of C4:C3. Each of the cathode and the anode includes an electrode film and a current collector forming an electrode.

[0106] In some embodiments, an electrode film as provided herein comprises at least one active material. In some embodiments, the electrode film further comprises at least one binder.

[0107] In some embodiments, the electrode film includes an anode active material. In some embodiments, the anode active material may include, for example, an insertion material (such as carbon or graphite), an alloying / de-alloying material (such as silicon, silicon oxide, tin and / or tin oxide), a metal alloy or compound (such as Si-Al and / or Si-Sn), lithium titanate (LTO) and / or a conversion material (such as manganese oxide, molybdenum oxide, nickel oxide and / or copper oxide). The anode active material 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). Anode active materials include common natural graphite, synthetic or artificial graphite, surface-modified graphite, spherical graphite, flake graphite, and blends or combinations of these types of graphite, hard carbon, metal elements and their compounds, and metal-C composite materials for anodes.

[0108] In some embodiments, the anode active material may include, for example, silicon particles. In some embodiments, the silicon particles have a d 50 In some embodiments, the silicon particles have a d 50 In some embodiments, the silicon particles have a d 50 About, at least, or at least about 1 μm, 1.1 μm, 1.2 μm, 1.3 μm, 1.4 μm, 1.5 μm, 1.6 μm, 1.7 μm, 1.8 μm, 1.9 μm, 2 μm, 2.1 μm, 2.2 μm, 2.3 μm, 2.4 μm, 2.5 μm, 2.6 μm, 2.7 μm, 2.8 μm, 2.9 μm, 3 μm, 3.1 μm, 3.2 μm, 3.3 μm, 3.4 μm, 3.5 μm, 3.6 μm, 3.7 μm, 3.8 μm, 3.9 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, or any range of values ​​therebetween.

[0109] In some embodiments, the electrode film comprises an active cathode material. In some embodiments, the cathode active material may comprise, for example, a metal oxide, a metal sulfide, or an alkali metal oxide (e.g., lithium metal oxide and / or sodium metal oxide). The lithium metal oxide may be, for example, lithium nickel manganese cobalt oxide (NMC), lithium manganese oxide (LMO), lithium nickel oxide (LNO), lithium iron phosphate (LFP), lithium cobalt oxide (LCO), and / or lithium nickel cobalt aluminum oxide (NCA). In some embodiments, the cathode active material may comprise, for example, a layered transition metal oxide (such as LiCoO 2(LCO), Li(NiMnCo)O 2 (NMC) and / or LiNi 0.8 Co 0.15 Al 0.05 O 2 (NCA)), spinel manganese oxides (such as LiMn 2 O 4 and / or LiMn 1.5 Ni 0.5 O 4 (LMNO)), olivine (such as LiFePO 4 (LFP), LiMn 1-x Fe x PO 4 The cathode active material may contain sulfur or a material including sulfur, such as lithium sulfide (Li 2 In some embodiments, the sodium metal oxide may be, for example, a layered oxide, a phosphate, and / or a ferrocyanide (e.g., a compound of the Prussian white family). In some embodiments, the sodium metal oxide may be, for example, NaFe 0.5 Mn 0.5 O 2 、NaNi 1 / 3 Fe 1 / 3 Mn 1 / 3 O 2 、NaFe 2 (CN) 6 、Na 2 VOPO 4 F. NaMnO 2 and / or NaFe 0.3 Mn 0.5 Cu 0.2 O 2 .

[0110] Energy storage devices as provided herein can have any suitable configuration, such as plane, spiral winding, button shape or soft bag. Energy storage devices as provided herein can be components of systems such as power generation systems, uninterruptible power supply systems (UPS), photovoltaic power generation systems, energy recovery systems for example in industrial machinery and / or transportation. Energy storage devices as provided herein can be used to power various electronic devices and / or motor vehicles, including hybrid electric vehicles (HEV), plug-in hybrid electric vehicles (PHEV) and / or electric vehicles (EV).

[0111] Energy storage devices including the electrolyte formulations described herein may be characterized by improved capacity retention over the life of the device. Further improvements achievable in various embodiments include improved cycling performance, including improved storage stability and reduced capacity fading during cycling. In some embodiments, improved cycling performance is also achieved under corrosive or stress conditions (e.g., maintained at a long-term constant voltage of 4.4V).

[0112] It should be understood that the electrolyte formulations provided herein can be used in various embodiments with any of a variety 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 described herein or electrolytes containing the additives described herein can be implemented in lithium ion batteries and / or sodium ion batteries.

[0113] 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.

[0114] Preparation method

[0115] The additives, electrolytes, and energy storage devices discussed herein can be synthesized or manufactured. In some embodiments, the method for preparing the energy storage device includes preparing the electrolyte discussed herein and positioning the electrolyte in a housing comprising a cathode and an anode. In some embodiments, the method for preparing the electrolyte includes combining at least one carbon dioxide source, a fluorinated solvent, and a lithium salt to form an electrolyte. In some embodiments, during manufacture, the electrolyte can be pre-saturated with carbon dioxide before the electrolyte of the battery is filled.

[0116] In some embodiments, carbon dioxide can be introduced directly into the cell by placing dry ice in the cell after the electrolyte filling process and before sealing the cell. In some embodiments, carbon dioxide can be introduced directly into the cell by injecting gaseous carbon dioxide through a feed port on the cell. In some embodiments, carbon dioxide can be generated in situ in the electrolyte via the use of a carbon dioxide-generating electrolyte additive. In some embodiments, a carbon dioxide-generating electrolyte additive is mixed directly into the electrolyte before or after the electrolyte is filled into the cell, where carbon dioxide is generated via a chemical and / or electrochemical reaction within the cell (e.g., during cycling).

[0117] aging

[0118] Some embodiments of the present disclosure relate to aging the electrolyte prior to positioning the electrolyte within the housing. In some embodiments, the electrolyte is aged, aged about, aged at least, or aged at least about 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, 2 months, 3 months, 4 months, or any range of values ​​therebetween. For example, in some embodiments, the electrolyte is aged from about 2 hours to about 48 hours, from about 7 days to about 2 weeks, or from 4 weeks to about 3 months.

[0119] In some embodiments, the electrolyte formulations of the present disclosure can be stored at room temperature. In further embodiments, the electrolyte formulations of the present disclosure do not need to be stored at low temperatures to maintain battery performance.

[0120] Example

[0121] Exemplary embodiments of the present disclosure, including methods, materials, and / or resulting products, are described in the following examples.

[0122] Example 1 - XPS Characterization of SEI Composition from Cycling of Cells with Micronized Silicon Anodes

[0123] LiF and polycarbonate species were produced and characterized on the solid electrolyte interphase (SEI) of micrometer-sized silicon anodes using fluorinated electrolyte solvents such as fluoroethylene carbonate (FEC). Figure 1The results of an x-ray photoelectron spectroscopy (XPS) study are shown, which highlights the ratio of LiF content to carbonate species in the SEI on a micron silicon anode cycled in various electrolyte formulations. Sample 1A (also referred to as the "baseline" or "TB baseline") includes an electrolyte comprising 39.7 wt % EC and 7.7 wt % FEC, and sample 1B (also referred to as the "fluorinated TB baseline") includes an electrolyte comprising 34 wt % EC and 20 wt % FEC. The SEI on the micron silicon anode in the electrolytes of sample 1A and sample 1B is similar. Sample 1C includes an electrolyte comprising 20 wt % FEC, 60 wt % 2,2,2-trifluoroethyl methyl carbonate (FEMC) and 20 wt % 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE). Sample ID (also referred to as "TB-156") includes an electrolyte comprising 0 wt% EC and 20 wt% FEC, and exhibits a significantly higher LiF:carbonate ratio than the electrolyte containing EC.

[0124] This high LiF:carbonate ratio is advantageous because LiF has a high band gap (electronic insulator) and is conductive to lithium ions, making it a valuable component in the SEI. Additionally, polymeric carbonate materials such as polyvinyl carbonate (poly-VC) can provide flexibility, which is important for accommodating the expansion and contraction of materials such as silicon. Both LiF and poly-VC are formed via the FEC reduction pathway.

[0125] Example 2 - Cycling performance of soft pack cells with micronized silicon anodes

[0126] Cycling data of soft pack cells with micron silicon anode and NMC811 cathode were also tested at 4.1-2.85V, C3:C2 cycle, and the results were Figure 2 Different amounts of CO were injected into the battery. 2 The performance was compared with the baseline cycle performance. 2 The injection was carried out in a glove box filled with CO 2 This is done by injecting a syringe so that no ambient air can enter the battery. Figure 2 As shown in 2 The content resulted in a 30-40% improvement in cycle life (to 30% energy loss) while reducing catastrophic failure of the battery (i.e., lower slope of the energy loss curve at end of life), as depicted in Sample 2C and Sample 2D. 6mL CO 2 The resulting pouch cell expansion caused by the addition of 39.7 wt % EC and 7.7 wt % FEC may reduce the mechanical integrity of the electrode stack, as depicted in Samples 2E and 2F. In this case, Sample 2A (also referred to as "baseline" or "TB baseline"), which includes an electrolyte containing 39.7 wt % EC and 7.7 wt % FEC, was used to study gas addition. Figure 2 The results shown in the figure confirm the concept that the CO 2 Saturation greatly improves the SEI performance and cycle life using high energy density Si anodes.

[0127] Figure 2 It also shows that 3 mL CO 2 The injection of the gas performed similarly to Sample 2B, which contained 5 wt % DEPC in the electrolyte formulation.

[0128] Example 3 - XPS table of SEI components from cycles of EC-free electrolytes with and without DEPC Levy

[0129] XPS studies comparing EC-free electrolytes with and without DEPC were also tested. The ratio of LiF to other SEI species was compared for electrolytes without DEPC additive and with 5 wt% DEPC additive. Figure 3A The relationship between the atomic percentage of F1s and the sputtering depth is shown. Figure 3A As shown in , sample 3B containing an electrolyte with 5 wt % DEPC provides a higher atomic percentage of F1s than sample 3A containing an electrolyte without DEPC. Figure 3B As shown in , the SEI formed by sample 3A has a significantly higher ratio of LiF: carbonate species. This represents Figure 1 Therefore, by removing EC and adding CO 2 , creating a higher performance SEI. In addition, the use of EC-free CO 2 Saturated electrolyte leads to thinner SEI. After 90% increase in cycle life, the cycle life of the samples with no EC, 20 wt% FEC, CO 2 The thickness of the SEI formed with the saturated electrolyte was about the same as that of the baseline electrolyte at the end of life (defined as 70% energy retention). The fact that the SEI took more cycles to reach the same thickness is consistent with lower lithium-ion inventory loss in the better electrolyte, as SEI formation / reformation consumes lithium ions and can lead to early cell failure.

[0130] Example 4 - Capacity Retention Performance

[0131] The formation of an SEI with a maximum LiF:carbonate ratio leads to a greatly improved cycle life of lithium-ion batteries. This is demonstrated in a pouch cell containing a micronized Si anode and an NMC811 cathode, which was cycled at 4.1-2.85V C3:C2 cycle (>90% depth of discharge).

[0132] Figure 4The cycle life improvement obtained by removing EC, increasing FEC to 20 wt % and then adding increasing amounts of DEPC is highlighted. This is an advantageous high energy density battery design incorporating micron silicon anode technology. Specifically, sample 4A (which includes an electrolyte comprising> 30 wt % EC and 7.7 wt % FEC) is compared to sample 4B (which includes a non-EC, 20 wt % FEC electrolyte formulation). Sample 4C includes a non-EC, 20 wt % FEC electrolyte formulation and LiFSI. Different amounts of DEPC are added to the non-EC, 20 wt % FEC formulation, as depicted in sample 4D and sample 4E.

[0133] like Figure 4 As seen in the Figure 4, by removing the EC and adding 20 wt% FEC, a 40% improvement in cycle life was demonstrated, as depicted in Samples 4B and 4C. By adding only 2.5 wt% DEPC in the no-EC, high-FEC electrolyte, the cycle life was nearly doubled over the baseline, as depicted in Sample 4E. This cycling study showed step-by-step improvements with changes in electrolyte formulation, leading to a 90+% improvement in cycle life in this aggressive cycling test.

[0134] Example 5-CO 2 Gas generation

[0135] Comparison of CO generation from various electrolytes during formation cycles and in pouch cells with micro-Si anode and NMC811 cathode at 4.1–2.85 V, C3:C2 cycling conditions. 2 Gas volume. Figure 5 The effect of DEPC additive on CO in EC-free and high FEC electrolytes is shown. 2 Optimization of gas volume. CO was measured after aging (“Ageing”), immediately after formation (also referred to as “Initial Reference Performance Test” or “RPT-0”), after 100 cycles at 25°C (“100 Cycles at 25C”), after a reference performance test consisting of 100 cycles at 25°C (also referred to as “RPT-100 at 25C”), at end of life (also referred to as “EOL” or 70% energy retention at 25°C), and after a reference performance test at end of life (also referred to as “RPT-EOL at 25C”). 2Gas volume. CO was measured in a pouch cell containing 7.7 wt % FEC and 40 wt % EC (HMC); in a cylindrical cell containing 20 wt % FEC and 0 wt % EC; in a pouch cell containing 20 wt % FEC, 0 wt % EC, and LiFSI; in a cylindrical cell containing 20 wt % FEC, 0 wt % EC, LiFSI, and 1.5 wt % DEPC; and in a cylindrical cell containing 20 wt % FEC, 0 wt % EC, LiFSI, and 2.5 wt % DEPC. 2 Gas volume. Figure 5 As shown in , 1.5-2.5 wt % DEPC was determined to be commercially viable and showed significant improvement in cycle life.

[0136] like Figure 5 As shown in 2 The combination of saturated EC-free, high-FEC electrolytes doubles the cycle life of micronized Si anodes. Based on the SEI characteristics described in this paper, the same electrolyte strategy can be broadly applicable to various lithium-ion and lithium metal battery designs. The same LiF:carbonate ratio in the SEI also improves the cycle life of anodes from graphite to SiC materials to lithium metal.

[0137] Example 6 - Discharge capacity of soft pack battery

[0138] The electrolyte and additives were tested in a soft pack cell format using an NMC-based cathode and a composite micron silicon / graphite anode. The soft pack cells were filled with electrolyte and vacuum sealed inside a glove box. The size of the soft pack bag should allow excess gas to expand into the unconstrained part of the bag. After initial sealing, the battery was not degassed. For cells injected with gaseous carbon dioxide, a feed port was introduced in the soft pack cell construction and the injection of carbon dioxide was performed after the cell was filled with electrolyte and sealed. A soft pack cell fixture was used to apply a constant stacking pressure to the cell throughout the cycle while allowing the gas to expand into the unconstrained part of the soft pack bag.

[0139] Electrochemical cycling tests were performed at 25 °C. All cells were cycled under asymmetric constant current-constant potential (CC-CV) charge-discharge conditions with voltage cutoffs ranging from 4.2 to 2.85 V and charge-discharge rates between C / 20 and C / 2, depending on the experiment. All capacity measurements were normalized to the active material mass loading at the cathode.

[0140] Cycling data showed that direct injection of gaseous carbon dioxide into the pouch cell via the feed port improved lifetime performance. Figure 6The discharge capacity versus cycle number relationship for a cell having an electrolyte system injected with gaseous carbon dioxide is shown. Carbon dioxide was introduced directly into the cell by injecting gaseous carbon dioxide through a feed port on the cell. Figure 6 It is shown that pouch cells such as Sample 6B and Sample 6C injected with 3 mL and 6 mL of gaseous carbon dioxide, respectively, provide superior discharge capacity during cycling compared to a baseline electrolyte system such as Sample 6A that does not contain gaseous carbon dioxide.

[0141] Example 7 - Discharge Capacity and Gas Generation at Different FEC Amounts

[0142] The electrolytes were tested with different amounts of fluoroethylene carbonate (FEC). Fig. 7A The graph shows the discharge capacity-cycle number relationship of cells having electrolyte systems containing different amounts of solvent blends. Fig. 7A Data are shown for sample 7A comprising 2.5 wt % DMPC, 80 wt % EMC and 20 wt % FEC; sample 7B comprising 2.5 wt % DMPC, 82.5 wt % EMC and 17.5 wt % FEC; sample 7C comprising 2.5 wt % DMPC, 85 wt % EMC and 15 wt % FEC; sample 7D comprising 2.5 wt % DMPC, 87.5 wt % EMC and 12.5 wt % FEC; and sample 7E comprising 2.5 wt % DMPC, 90 wt % EMC and 10 wt % FEC.

[0143] Surprisingly, using 10% FEC (such as sample 7E) provided better results than using 20% ​​FEC (such as sample 7A).

[0144] Additionally, the volume change of the pouch cells was measured periodically throughout the cycle life. The measurements presented herein were obtained by removing the cells from the fixture and briefly immersing the cells in deionized water or oil rather than in situ. The buoyancy was determined via a laboratory balance, and the volume change was calculated based on the change in buoyancy, as compared to the initial measurement before cycling.

[0145] At the end of life, the lower FEC content showed a smaller volume of gas compared to the electrolyte with higher FEC content. Specifically, Figure 7B Shown with Fig. 7A Gas formation with the same electrolyte systems as those used in . Again, using 10% FEC provided better results than using 20% ​​FEC.

[0146] Example 8 - Discharge Capacity and Gas Generation of Electrolytes Containing DEPC

[0147] Cycling data showed that the addition of diethylpyrocarbonate (DEPC), an electrolyte additive that generates carbon dioxide in situ, improved the lifetime performance. Fig. 8A Data are shown for Sample 8A (also referred to as the "baseline"), which contained 20 wt % FEC; Sample 8B, which contained 20 wt % FEC and 5 wt % DEPC; and Sample 8C, which contained 20 wt % FEC and 10 wt % DEPC. Figure 8B and 8C Data are shown for Sample 8D (also referred to as the "baseline"), which contained 20 wt % FEC; Sample 8E, which contained 20 wt % FEC and 1.5 wt % DEPC; and Sample 8F, which contained 20 wt % FEC and 2.5 wt % DEPC. Fig. 8A and 8B The discharge capacity versus cycle number relationship of cells having an electrolyte system containing diethyl pyrocarbonate (DEPC) relative to a baseline electrolyte system is shown. Fig. 8A and 8B As shown in , the use of DEPC provides improved results relative to a baseline electrolyte system without DEPC.

[0148] in addition, Figure 8C The gas formation of the electrolyte system containing diethyl pyrocarbonate (DEPC) is shown relative to the baseline electrolyte system without DEPC. Figure 8C As shown in , the use of 1.5% DEPC (such as sample 8E) provides similar results to a baseline electrolyte system without DEPC (such as sample 8D).

[0149] Although certain embodiments of the present invention have been described, these embodiments are presented only by way of example and are not intended to limit the scope of the present disclosure. In fact, the novel methods and systems described herein can be implemented in various other forms. In addition, various omissions, substitutions and changes can be made to the systems and methods described herein without departing from the spirit of the present disclosure. The attached claims and their equivalents are intended to cover such forms or modifications that fall within the scope and spirit of the present disclosure. Therefore, the scope of the present invention is limited only by the attached claims.

[0150] Features, materials, characteristics or groups described in conjunction with a particular aspect, embodiment or example are to be understood to be applicable to any other aspect, embodiment or example described in this section or elsewhere in this specification unless incompatible therewith. All features disclosed in this specification (including any accompanying claims, abstract and drawings) and / or all steps of any method or process so disclosed may be combined in any combination, unless combinations of at least some of such features and / or steps are mutually exclusive. Protection is not limited to the details of any foregoing embodiments. Protection extends to any novel one or any novel combination of the features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any novel one or any novel combination of the steps of any method or process so disclosed.

[0151] In addition, certain features described in the present disclosure in the context of separate embodiments may also be implemented in combination in a single embodiment. Conversely, various features described in the context of a single embodiment may also be implemented individually in multiple embodiments or in any suitable sub-combination. In addition, although features may be described above as functioning in certain combinations, in some cases, one or more features in a claimed combination may be deleted from the combination, and the combination may be claimed as a sub-combination or a variation of a sub-combination.

[0152] In addition, although the operations may be depicted in the drawings or described in the specification in a particular order, such operations do not have to be performed in the particular order shown or in a sequential order, nor do they have to perform all operations to achieve the desired results. Other operations not depicted or described may be incorporated into the example methods and processes. For example, one or more additional operations may be performed before, after, simultaneously, or between any of the described operations. In addition, the operations may be rearranged or reordered in other embodiments. It should be understood by those skilled in the art that in some embodiments, the actual steps taken in the process shown and / or disclosed may be different from those shown in the drawings. Depending on the embodiment, some of the above steps may be removed, and other steps may be added. In addition, the features and attributes of the specific embodiments disclosed above may be combined in different ways to form additional embodiments, all of which are within the scope of the present disclosure. In addition, the separation of various system components in the embodiments described above should not be understood as requiring such separation in all embodiments, and it should be understood that the components and systems described can generally be integrated together into a single product or packaged into multiple products. For example, any component of the energy storage system described herein can be provided separately, or integrated together (e.g., packaged together or attached together) to form an energy storage system.

[0153] For purposes of the present disclosure, certain aspects, advantages, and novel features are described herein. Not all such advantages may be achieved according to any particular embodiment. Thus, for example, one skilled in the art will recognize that the present disclosure may be implemented or performed in a manner that achieves one advantage or a group of advantages as taught herein without necessarily achieving other advantages as may be taught or suggested herein.

[0154] Conditional language, such as "may," "might," "might," or "could," unless expressly stated otherwise or otherwise understood as used in the context, is generally intended to convey that certain embodiments include certain features, elements, and / or steps, while other embodiments do not. Thus, such conditional language is generally not intended to imply that features, elements, and / or steps are in any way required for one or more embodiments, or that one or more embodiments necessarily include logic for determining (with or without user input or prompting) whether such features, elements, and / or steps will be included or performed in any particular embodiment.

[0155] Unless expressly stated otherwise, conjunctive language such as the expression "at least one of X, Y, and Z" should generally be understood with the context as used to convey that an item, term, etc. can be X, Y, or Z. Thus, such conjunctive language is generally not intended to imply that certain embodiments require the presence of at least one of X, at least one of Y, and at least one of Z.

[0156] As used herein, language of degree, such as the terms "approximately," "about," "typically," and "substantially" as used herein, refers to a value, amount, or characteristic that is close to a stated value, amount, or characteristic and still performs the desired function or achieves the desired result. For example, the terms "approximately," "about," "typically," and "substantially" may refer to an amount within less than 10%, less than 5%, less than 1%, less than 0.1%, and less than 0.01% of the stated amount, depending on the desired function or desired result.

[0157] The scope of the disclosure is not intended to be limited by the specific disclosure of preferred embodiments in this section or elsewhere in this specification, but may be defined by the claims as set forth in this section or elsewhere in this specification or as set forth in the future. The language of the claims should be interpreted broadly based on the language employed in the claims and not limited to examples described in this specification or during the prosecution of this application, which examples should be interpreted as non-exclusive.

Claims

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

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

3. The energy storage device according to claim 1 or 2, wherein the carbon dioxide source is selected from gaseous carbon dioxide, dry ice, diethyl pyrocarbonate (DEPC), dimethyl pyrocarbonate (DMPC), diallyl pyrocarbonate (DAPC), bis(tert-butyl) pyrocarbonate (O-Boc2) and combinations thereof. The energy storage device according to claim 3 , wherein the carbon dioxide source is diethyl pyrocarbonate. 5 . The energy storage device according to claim 4 , wherein the concentration of the diethyl pyrocarbonate in the electrolyte is in the range of 1 to 6 wt %. 6 . The energy storage device according to claim 5 , wherein the concentration of the diethyl pyrocarbonate in the electrolyte is in the range of 1.5 to 2.5 wt %.

7. The energy storage device according to any one of claims 1 to 6, wherein the concentration of the fluorinated solvent in the electrolyte is in the range of 5 to 80 wt%.

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

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

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

11. The energy storage device of any one of claims 1-10, wherein the anode comprises silicon particles.

12. The energy storage device according to claim 11, wherein the silicon particles have a d 50 1-5 microns.

13. The energy storage device according to claim 12, wherein the silicon particles have a d 50 2-3 microns.

14. The energy storage device of any one of claims 1-13, wherein the electrolyte is substantially free of ethylene carbonate and dimethyl carbonate.

15. The energy storage device of any one of claims 1-14, wherein the anode comprises a graphite intercalation material and a silicon alloying / de-alloying material.

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

17. The energy storage device according to any one of claims 1 to 16, wherein the lithium salt is selected from lithium hexafluorophosphate, lithium bis(fluorosulfonyl)imide and a combination thereof.

18. The energy storage device of any one of claims 1-17, wherein the energy storage device is configured to retain at least 70% of the initial capacity after 100 cycles between 4.1 V and 2.85 V at a charge rate of C3:C2.

19. The energy storage device of any one of claims 1-17, wherein the energy storage device is configured to retain at least 70% of the initial capacity after 140 cycles between 4.1 V and 2.85 V at a charge rate of C3:C2.

20. The energy storage device of any one of claims 1-17, wherein the energy storage device is configured to retain at least 70% of the initial capacity after 225 cycles between 4.2V and 2.85V at a charge rate of C4:C3.

21. The energy storage device according to any one of claims 1 to 20, wherein the energy storage device is a battery pack.

22. An electric vehicle having a rechargeable battery pack, the electric vehicle comprising: Drive motor; Gearbox; Electronic equipment; and An energy storage device according to any one of claims 1 to 21.

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

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

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

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

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