Electrolyte composition and its electrochemical device

Abstract

This specification provides electrolyte compositions suitable for electrochemical devices such as batteries, energy storage devices, sensors, capacitors, electrochromic elements, and photoelectric conversion elements.

Description

Description of related applications

[0001] This application claims priority to U.S. Provisional Patent Application No. 63 / 493124, filed on March 30, 2023, which is entirely referenced herein. [Technical Field]

[0002] This disclosure relates to an electrolyte composition suitable for electrochemical devices such as batteries, energy storage devices, sensors, capacitors, electrochromic elements, and photoelectric conversion elements. [Background technology]

[0003] Battery technology has undergone a dramatic transformation over the past 50 years. As the field of electrical energy storage continues to grow and gains widespread applications, the demands on lithium-ion batteries (LIBs) are increasing. Cycle life has been pushed up from thousands to millions of cycles, energy density has improved to nearly 500 Wh / kg, and the cost of high-performance batteries is gradually decreasing, approaching a low level of $100 / Wh. Under these high demands, the performance limits of current LIB systems—namely, the combination of lithium metal oxide cathode and graphite anode in a liquid carbonate electrolyte—are nearing their limits, and further performance improvements are only expected to be minimal. However, as the energy density of LIBs increases, the failure of LIBs filled with high energy in a given space will pose more serious safety concerns.

[0004] As the energy density and scale of lithium-ion batteries (LIBs) increase, finding solutions to safety concerns related to LIBs has become increasingly important. Safety issues in LIBs can stem from the use of flammable solvent mixtures such as carbonates / ethers, which can lead to serious accidents such as ignition, combustion, and even explosion of LIBs in cases of overcharging, short circuits, or overheating. [Overview of the project]

[0005] This disclosure broadly relates to various electrolyte compositions. The subject matter of this disclosure includes, in some cases, interrelated products, alternative solutions to specific problems, and / or multiple different uses of one or more systems and / or articles.

[0006] In one embodiment, the present invention relates to an electrolyte composition comprising an electrolyte salt, a polymer, and a solvent containing a fluorinated ether and a non-fluorinated ether.

[0007] In one embodiment, the electrolyte composition comprises an electrolyte salt, a polymer, and a solvent containing a non-fluorinated ether, wherein the electrolyte salt is present in an amount of about 30% to about 75% by mass based on the total mass of the electrolyte composition.

[0008] In one embodiment, the electrolyte composition comprises an electrolyte salt and a solvent containing a fluorinated ether and a non-fluorinated ether, wherein the fluorinated ether has a boiling point of at least 100°C.

[0009] In one embodiment, the present disclosure features an electrochemical device comprising the electrolyte composition of this disclosure.

[0010] In one embodiment, an electrochemical device comprising a negative electrode, a positive electrode, and an electrolyte composition of the present disclosure, characterized in that the electrochemical device exhibits a capacity retention rate of at least 70% at a temperature in the range of -10°C to -20°C for at least 6 hours.

[0011] In one embodiment, an electrochemical device comprising a negative electrode, a positive electrode, and an electrolyte composition of the present disclosure, wherein the electrochemical device passes a hotbox test in which it is held at a temperature of 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, and 190°C for 10 minutes in a 100% charged state, with a European Automotive Research and Development Council (EUCAR) hazard level of 4 or less.

[0012] In one embodiment, an electrochemical device comprising a negative electrode, a positive electrode, and an electrolyte composition of the present disclosure, wherein the electrochemical device, when fully charged, emits 3 mA / cm² over 1 hour. 2 It features an electrochemical device that, when overcharged with a charging current or when it reaches 8.5V, passes an overcharge test with a European Automotive Research and Development Council (EUCAR) hazard level of 4 or less.

[0013] In one embodiment, an electrochemical device comprising a negative electrode, a positive electrode, and the electrolyte composition of the present disclosure, wherein the electrolyte is approximately 10.5 mAh / cm². 2 Approximately 16.5mAh / cm³ 2 The electrochemical device is characterized by having a charging current density in the range of [range]. In some embodiments, the electrolyte composition further comprises a polymer.

[0014] The term "mass percent" or "mass percentage" refers to a specific component or the proportion of a component, where the percentage is calculated as the mass percentage of all components excluding water, unless otherwise specified.

[0015] The term "alkyl" refers to a saturated acyclic hydrocarbon group that contains a specific number of carbon atoms and may be linear or branched. For example, C 1-10 This indicates that the group may have 1 to 10 (inclusive) carbon atoms. Non-limiting examples include methyl, ethyl, isopropyl, tert-butyl, and n-hexyl. As used in this context, the term “saturated” means that only single bonds exist between the constituent carbon atoms and the other available valencies occupied by hydrogen and / or other substituents as defined herein.

[0016] The term "halogen" refers to fluoro(F), chloro(Cl), bromo(Br), or iodine(I).

[0017] The term "oxo" refers to a divalent double-bonded oxygen atom (i.e., "=O"). As used here, the oxo group bonds to a carbon atom to form a carbonyl group.

[0018] The term "alkoxy" refers to an -O-alkyl group (e.g., -OCH3).

[0019] The term "hydroxyalkyl" refers to an alkyl group in which one or more hydrogen atoms are exchanged with hydroxyl atoms.

[0020] The term "haloalkyl" refers to an alkyl group in which one or more hydrogen atoms are independently replaced by a halogen of a chosen type.

[0021] The term "fluoroalkyl" refers to an alkyl group in which one or more hydrogen atoms are exchanged for fluorine. The term "aryl" refers to a 6- to 20-membered whole-carbocyclic system (e.g., a 6-carbon monocyclic, 10-carbon bicyclic, or 14-carbon tricyclic aromatic ring system) in which at least one ring of the system is aromatic. Examples of aryl groups include phenyl, naphthyl, and tetrahydronaphthyl.

[0022] The term "carbocyryl" as used herein refers to a cyclic saturated hydrocarbon group having, for example, 3 to 20 ring carbons, preferably 3 to 16 ring carbons, more preferably 3 to 12 ring carbons, or 3 to 10 ring carbons or 3 to 6 ring carbons. Examples of cycloalkyl groups include, without limitation, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Cycloalkyl groups may contain multiple condensed and / or crosslinked rings. Non-limiting examples of condensed / crosslinked cycloalkyls include bicyclo[1.1.0]butane, bicyclo[2.1.0]pentane, bicyclo[1.1.1]pentane, bicyclo[3.1.0]hexane, bicyclo[2.1.1]hexane, bicyclo[3.2.0]heptane, bicyclo[4.1.0]heptane, bicyclo[2.2.1]heptane, bicyclo[3.1.1]heptane, bicyclo[4.2.0]octane, bicyclo[3.2.1]octane, and bicyclo[2.2.2]octane. Cycloalkyls also include spiro rings (for example, spiro dirings in which two rings are connected by only one atom). Non-limiting examples of spirocyclic cycloalkyl groups include spiro[2.2]pentane, spiro[2.5]octane, spiro[3.5]nonane, spiro[3.5]nonane, spiro[4.4]nonane, spiro[2.6]nonane, spiro[4.5]decane, spiro[3.6]decane, and spiro[5.5]undecane. In this context, the term "saturated" means that only single bonds exist between the constituent carbon atoms.

[0023] The term "heteroaryl" as used herein refers to a ring system having 5 to 20 ring atoms, such as 5, 6, 9, 10, or 14 ring atoms, wherein at least one ring in the system contains one or more heteroatoms independently selected from the group consisting of N, O, S, Si, and B, and at least one ring in the system is aromatic (however, it does not have to be a ring containing heteroatoms, e.g., tetrahydroisoquinolinyl). Heteroaryl groups can include monocyclic, bridging, condensed, and spirocyclic systems, as long as one of the rings in the system is aromatic. Examples of heteroaryls include thienyl, pyridinyl, furyl, oxazolyl, oxadiazolyl, pyrrolyl, imidazolyl, triazolyl, thiodiazolyl, pyrazolyl, isoxazolyl, thiadiazolyl, pyranyl, pyrazinyl, pyrimidinyl, pyridadinyl, triazinyl, thiazolyl, benzothienyl, benzooxadiazolyl, benzofuranil, benzimidazolyl, benzotriazolyl, sinnolinyl, indazolyl, indolyl, isoquinolinyl, isothiazolyl, naphthylidinyl, prinyl, thienopyridinyl, pyrido[2, Examples include [3-d]pyrimidinyl, pyrrolo[2,3-b]pyrimidinyl, quinazolinyl, quinolinyl, thieno[2,3-c]pyrimidinyl, pyrazolo[3,4-b]pyrimidinyl, pyrazolo[3,4-c]pyrimidinyl, pyrazolo[4,3-c]pyridine, pyrazolo[4,3-b]pyrimidinyl, tetrazolyl, chroman, 2,3-dihydrobenzo[b][1,4]dioxin, benzo[d][1,3]dioxol, 2,3-dihydrobenzofuran, tetrahydroquinoline, 2,3-dihydrobenzo[b][1,4]oxathiin, and isoindoline. In some embodiments, the heteroaryl is selected from thienyl, pyridinyl, furyl, pyrazolyl, imidazolyl, isoindolinyl, pyranyl, pyrazinyl, and pyrimidinyl.For clarification, heteroaryls also include aromatic lactams, aromatic cyclic ureas, or their vinyl analogs, where each ring nitrogen adjacent to the carbonyl is tertiary (i.e., all three valencies are occupied by non-hydrogen substituents), such as one or more pyridines where each ring nitrogen adjacent to the carbonyl is tertiary (i.e., the oxo group (i.e., "=O") as used herein is a component of the heteroaryl ring).

[0024] The term "heterocyclyl" refers to a saturated or partially unsaturated ring system having 3 to 16 ring atoms, each having at least one heteroatom selected from O, N, S, Si, and B (e.g., a 3 to 8-membered monocyclic, a 5 to 12-membered dicyclic, or a 10 to 14-membered tricyclic), where, as far as the valency allows, one or more ring atoms may be substituted with 1 to 3 oxos (e.g., forming a lactam), and one or more N or S atoms may be substituted with 1 to 2 oxides (e.g., forming an N-oxide, S-oxide, or S,S-dioxide). Heterocyclyl groups include monocyclic, bridging, condensed, and spirocyclic systems. Examples of heterocyclyl groups include piperazinyl, pyrrolidinyl, dioxanyl, morpholinyl, tetrahydrofuranyl, tetrahydropyridyl, dihydropyridine, dihydropyridyl, dihydropyrrolyl, dihydrofuranyl, and dihydrothiophenyl. Heterocyclyls may contain multiple fused and crosslinked rings. Non-limiting examples of fused / crosslinked heterocyclyls include 2-azabicyclo[1.1.0]butane, 2-azabicyclo[2.1.0]pentane, 2-azabicyclo[1.1.1]pentane, 3-azabicyclo[3.1.0]hexane, 5-azabicyclo[2.1.1]hexane, 3-azabicyclo[3.2.0]heptane, octahydrocyclopenta[c]pyrrole, 3-azabicyclo[4.1.0]heptane, 7-azabicyclo[2.2.1]heptane, 6-azabicyclo[3.1.1]heptane, 7-azabicyclo[4.2.0]octane, 2-azabicyclo[2.2.2]octane, 3-azabicyclo Examples include [3.2.1]octane, 2-oxabicyclo[1.1.0]butane, 2-oxabicyclo[2.1.0]pentane, 2-oxabicyclo[1.1.1]pentane, 3-oxabicyclo[3.1.0]hexane, 5-oxabicyclo[2.1.1]hexane, 3-oxabicyclo[3.2.0]heptane, 3-oxabicyclo[4.1.0]heptane, 7-oxabicyclo[2.2.1]heptane, 6-oxabicyclo[3.1.1]heptane, 7-oxabicyclo[4.2.0]octane, 2-oxabicyclo[2.2.2]octane, and 3-oxabicyclo[3.2.1]octane.Heterocyclines also include spiro rings (e.g., spiro dirings, where two rings are connected by only one atom). Non-restrictive examples of spiro ring heterocyclines include 2-azaspiro[2.2]pentane, 4-azaspiro[2.5]octane, 1-azaspiro[3.5]nonane, 2-azaspiro[3.5]nonane, 7-azaspiro[3.5]nonane, 2-azaspiro[4.4]nonane, 6-azaspiro[2.6]nonane, 1,7-diazaspiro[4.5]decane, 7-azaspiro[4.5]decane, 2,5-diazaspiro[3.6]decane, 3-azaspiro[5.5]undecane, and 2-oxaspiro[2.2] Examples include pentane, 4-oxaspiro[2.5]octane, 1-oxaspiro[3.5]nonane, 2-oxaspiro[3.5]nonane, 7-oxaspiro[3.5]nonane, 2-oxaspiro[4.4]nonane, 6-oxaspiro[2.6]nonane, 1,7-dioxaspiro[4.5]decane, 2,5-dioxaspiro[3.6]decane, 1-oxaspiro[5.5]undecane, 3-oxaspiro[5.5]undecane, and 3-oxa-9-azaspiro[5.5]undecane.

[0025] Details of one or more embodiments of the subject matter of this disclosure are described in the accompanying drawings and description. Other features, aspects, and advantages of the subject matter of this disclosure will become apparent from the description, drawings, and claims. [Brief explanation of the drawing]

[0026] Non-limiting embodiments of this disclosure are described by example with reference to the accompanying drawings. The drawings are schematic and not drawn to scale. In the drawings, each of the identical or substantially identical components is usually indicated by a single number. For clarity, not all components are labeled in all drawings, and not all components of each embodiment of this disclosure are shown in illustrations that are unnecessary for a person skilled in the art to understand this disclosure. [Figure 1] Graph of the number of cycles against capacity retention of the battery of this disclosure during asymmetric cycle testing. [Figure 2]Graphs of cycle count against capacity retention for various batteries in this disclosure [Figure 3] Graphs showing the number of cycles against capacity retention for various batteries of this disclosure during charging speed tests at various charging current densities. [Modes for carrying out the invention]

[0027] This disclosure relates broadly to electrolyte compositions suitable for various electrochemical devices. In some embodiments, the electrolyte composition comprises an electrolyte salt, a polymer, and a solvent. In other embodiments, the electrolyte composition does not contain a polymer. The solvent may comprise a non-fluorinated ether or a non-fluorinated ether and a fluorinated ether.

[0028] The electrolyte compositions of this disclosure have one or more non-limiting beneficial properties, such as: The electrolyte compositions of this disclosure can be stable (e.g., pass safety tests such as the safety tests described in the examples below) when contained in an electrochemical device (e.g., a battery) equipped with a lithium metal anode. The electrolyte compositions of this disclosure can have improved wetting performance (e.g., wetting rate, contact angle, etc.) when contained in an electrochemical device. The electrolyte compositions of this disclosure can exhibit at least 70% capacity retention at low temperatures (e.g., 0°C, -10°C, or -20°C) when contained in an electrochemical device (e.g., a battery). The electrolyte compositions of this disclosure can be thermally stable when contained in an electrochemical device (e.g., a battery) because none of the components of the electrolyte composition have a boiling point below 100°C. The electrolyte compositions of this disclosure can be used to obtain safer and longer-lasting lithium batteries. The electrolyte compositions may exhibit better ionic conductivity. These properties would be beneficial to charge / discharge rate performance. In some embodiments, the electrolyte composition further comprises a polymer.

[0029] In some embodiments, the electrolyte composition of the present disclosure includes a solvent, and the solvent is a non-fluorinated ether. In some embodiments, the non-fluorinated ether is of formula (I): R 1a -O-R 2a (I), where R 1a is C1-C 10 alkyl, R 2a is -(CH2) n -O-(C1-C 10 alkyl) or C1-C 10 alkyl, or R 1a and R 2a together with the oxygen atom to which they are attached form a 4- to 7-membered heterocyclyl, and n is an integer and is 1 or 2.

[0030] In some embodiments, R 1a is C1-C6 alkyl. In some embodiments, R 1a is methyl, ethyl, or propyl.

[0031] In some embodiments, R 2a is C1-C6 alkyl. In some embodiments, R 2a is methyl, ethyl, or propyl.

[0032] In some embodiments, R 2a is -(CH2) n -O-(C1-C 10 alkyl). In some embodiments, R 2a is -(CH2) n -O-(C1-C6 alkyl). In some embodiments, R 2a is -(CH2) n -O-(C1-C3 alkyl). In some embodiments, R 2a is -(CH2) n -O-(C1 alkyl), -(CH2) n -O-(C2 alkyl), or -(CH2) n -O-(C3 alkyl).

[0033] In some embodiments, R 1a and R 2a These, together with the oxygen atoms to which they are bonded, form a 4- to 7-membered ring heterocycline. In some embodiments, R 1a and R 2a These, together with the oxygen atoms to which they are bonded, form a 4- to 7-membered ring heterocycline, where this heterocycline contains one or two oxygen heteroatoms. In some embodiments, n is 1. In some embodiments, n is 2.

[0034] In some embodiments, the non-fluorinated ether may include 2-ethoxyethanol, dimethoxymethane, dimethoxyethane, 1,2-diethoxyethane, 1,1-diethoxyethane, 1,1-dipropoxyethane, 1,2-dipropoxyethane, diethylene glycol, 2-(2-ethoxyethoxy)ethanol, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol, tri(ethylene glycol) monomethyl ether, tri(ethylene glycol) monoethyl ether, tri(ethylene glycol) monobutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, diethylene glycol dibutyl ether, tetraethylene glycol, tetra(ethylene glycol) monomethyl ether, tetra(ethylene glycol) monoethyl ether, tetra(ethylene glycol) monobutyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, and the like.

[0035] For example, non-fluorinated ethers may include one or more of 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dibutoxyethane, diethyl ether, dibutyl ether, di-tert-butyl ether, tert-butyl ethyl ether, tert-butyl methyl ether, 1,3-dioxolane, 1,4-dioxane, and di(propylene glycol)methyl ether. In some embodiments, the non-fluorinated ether includes 1,2-diethoxyethane.

[0036] In some embodiments, the solvent is substantially free of 1,2-dimethoxyethane. As used herein, the term “substantially free” of a component, as provided throughout this disclosure, is intended to mean that the composition or device contains that component in amounts less than about 0.1% by mass (as a mass percentage of the total mass of the composition or device), or in small or insignificant amounts, unless otherwise specified. In some embodiments, the compositions or devices of this disclosure are substantially free of 1,2-dimethoxyethane, meaning that the composition or device contains less than about 0.1% by mass of 1,2-dimethoxyethane.

[0037] In some embodiments, the electrolyte composition disclosed herein comprises a solvent, wherein the solvent comprises a fluorinated ether. In some embodiments, the fluorinated ether is of formula (II):

[0038] [ka]

[0039] It is a compound of which, in the formula, R 3a H, C1-C 10 Alkyl, C1-C 10 Fluoroalkyl, -O-(C1-C 10 Alkyl) or -O-(C1-C 10 Fluoroalkyl) and R 4a and R 5a Each of these is independently C1-C10 Alkyl, C1-C 10 Fluoroalkyl, -O-(C1-C 10 Alkyl) or -O-(C1-C 10 Fluoroalkyl) and R 3a , R 4a , and R 5a At least one of them is -O-(C1-C 10 Alkyl) or -O-(C1-C 10 Fluoroalkyl) and R 3a , R 4a , and R 5a At least one of them is C1-C 10 Contains fluoroalkyl substances.

[0040] In some embodiments, R 3a is H. In some embodiments, R 3a C1-C 10 It is alkyl. In some embodiments, R 3a is a C1-C6 alkyl group. In some embodiments, R 3a These are methyl, ethyl, or propyl.

[0041] In some embodiments, R 3a is -O-(C1-C 10 It is alkyl. In some embodiments, R 3a is -O-(C1-C6 alkyl). In some embodiments, R 3a It is -O-(C1-C3 alkyl).

[0042] In some embodiments, R 3a is -O-(C1-C 10 It is a fluoroalkyl. In some embodiments, R 3a is -O-(C1-C6 fluoroalkyl). In some embodiments, R 3a is -O-(C1-C3 fluoroalkyl). In some embodiments, R 3a It is either -O-(CF3) or -O-(CHF2).

[0043] In some embodiments, R 4a C1-C 10 It is alkyl. In some embodiments, R 4a is a C1-C6 alkyl group. In some embodiments, R 4a These are methyl, ethyl, or propyl.

[0044] In some embodiments, R 4a C1-C 10 It is a fluoroalkyl. In some embodiments, R 4a is a C1-C6 fluoroalkyl group. In some embodiments, R 4a These are -CF3, -CH2-CHF2, or -CF2-CH3.

[0045] In some embodiments, R 4a is -O-(C1-C 10 It is alkyl. In some embodiments, R 4a is -O-(C1-C6 alkyl). In some embodiments, R 4a It is -O-(C1-C3 alkyl).

[0046] In some embodiments, R 4a is -O-(C1-C 10 It is a fluoroalkyl. In some embodiments, R 4a is -O-(C1-C6 fluoroalkyl). In some embodiments, R 4a It is -O-(C1-C3 fluoroalkyl).

[0047] In some embodiments, R 5a C1-C 10 It is alkyl. In some embodiments, R 5a is a C1-C6 alkyl group. In some embodiments, R 5a These are methyl, ethyl, or propyl.

[0048] In some embodiments, R 5a is C1-C 10 fluoroalkyl. In some embodiments, R 5a is C1-C6 fluoroalkyl. In some embodiments, R 5a is -CF3, -CH2-CHF2 or -CF2-CH3.

[0049] In some embodiments, R 5a is -O-(C1-C 10 alkyl). In some embodiments, R 5a is -O-(C1-C6 alkyl). In some embodiments, R 5a is -O-(C1-C3 alkyl).

[0050] In some embodiments, R 5a is -O-(C1-C 10 fluoroalkyl). In some embodiments, R 5a is -O-(C1-C6 fluoroalkyl). In some embodiments, R 5a is -O-(C1-C3 fluoroalkyl).

[0051] For example, fluorinated ethers include bis(2,2,2-trifluoroethoxy)methane (BTFM), 1,1,1,3,3,3-hexafluoro-2-(1,1,1,3,3,3-hexafluoropropane-2-yloxymethoxy)propane, bis(3,3,3-trifluoropropoxy)methane, 1,1,1-trifluoro-3-[(2,2,2-trifluoroethoxy)methoxy]propane, bis(2,2,3,3,3-pentafluoropropoxy)methane, and The fluorinated ether comprises one or more of the following: 1,1,1,2,2-pentafluoro-3-((2,2,2-trifluoroethoxy)methoxy)propane, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), 1H,1H,5H-octafluoropentyl-1,1,2,2-tetrafluoroethyl ether (OTE), bis(2,2,2-trifluoroethyl) ether, 1H,1H,2'H-perfluorodipropyl ether, 2,2,2-trifluoroethyl 1,1,2,2-tetrafluoroethyl ether, 1,2-(1,1,2,2-tetrafluoroethoxy)ethane (TFEE), and tris(2,2,2-trifluoroethyl) orthoformate (TFEO). In some embodiments, the fluorinated ether is BTFM.

[0052] In some embodiments, in formula (II), R 3a is -O-(C1-C 10 Alkyl) or -O-(C1-C 10 Fluoroalkyl) and R 4a and R 5a Each of these independently is -O-(C1-C 10 Alkyl) or -O-(C1-C 10 It is a fluoroalkyl compound. For example, fluorinated ethers may include bis(2,2,2-trifluoroethoxy)methane (BTFM) or tris(2,2,2-trifluoroethyl) orthoformate (TFEO).

[0053] The solvent may contain a non-fluorinated ether in an amount ranging from 0.1% to about 100% by mass. For example, the solvent may contain a non-fluorinated ether in an amount ranging from 0.1% to about 99% by mass, about 10% to about 90% by mass, about 20% to about 80% by mass, about 25% to about 70% by mass, about 25% to about 45% by mass, or about 50% to about 80% by mass. In some embodiments, the solvent may contain a non-fluorinated ether in an amount ranging from about 25% to about 45% by mass or about 30% to about 40% by mass.

[0054] The solvent may contain fluorinated ether in amounts ranging from 0.1% to about 99% by mass. For example, the solvent may contain fluorinated ether in amounts ranging from 0.1% to about 99% by mass, about 10% to about 90% by mass, about 20% to about 80% by mass, about 25% to about 75% by mass, or about 55% to about 75% by mass. In some embodiments, the solvent may contain fluorinated ether in amounts ranging from about 55% to about 75% by mass or about 60% to about 70% by mass.

[0055] In some embodiments, the non-fluorinated ether and the fluorinated ether exist in mass ratios of 1:20 to 20:1, 1:10 to 10:1, 1:5 to 10:1, 1:3 to 8:1, or 1:1 to 3:1. In some embodiments, the non-fluorinated ether and the fluorinated ether exist in mass ratios ranging from 1:3 to 8:1, or 1:1 to 3:1.

[0056] In some embodiments, the solvent has a boiling point of at least 100°C at 1 atmosphere (approximately 101 Pa). In some embodiments, the solvent has a boiling point of at least 110°C, at least 120°C, at least 130°C, or at least 140°C at 1 atmosphere (approximately 101 Pa). In some embodiments, the fluorinated ether and / or non-fluorinated ether has a boiling point of at least 100°C at 1 atmosphere (approximately 101 Pa). In some embodiments, the solvent has a boiling point of at least 110°C, at least 120°C, at least 130°C, or at least 140°C at 1 atmosphere (approximately 101 Pa).

[0057] The solvent may be present in the electrolyte composition in an amount of at least 15% by mass, based on the total mass of the electrolyte composition. For example, the solvent may be present in the electrolyte composition in an amount of at least 15% by mass, at least 20% by mass, at least 30% by mass, at least 40% by mass, at least 50% by mass, at least 60% by mass, at least 70% by mass, at least 80% by mass, at least 85% by mass, at least about 90% by mass, at least about 95% by mass, or at least about 98% by mass. In another example, the solvent may be present in the electrolyte composition in an amount ranging from about 15% to about 95% by mass, about 25% to about 95% by mass, about 50% to about 95% by mass, about 75% to about 90% by mass, about 85% to about 99.5% by mass, about 85% to about 99% by mass, about 90% to about 99% by mass, about 30% to about 60% by mass, or about 40% to about 55% by mass, based on the total mass of the electrolyte composition. In some embodiments, the solvent is present in the electrolyte composition in an amount ranging from 40% to about 55% by mass, or from about 75% to about 90% by mass, based on the total mass of the electrolyte composition.

[0058] Electrolyte salts may be present in the electrolyte composition in amounts ranging from about 5% to about 85% by mass, based on the total mass of the electrolyte composition. For example, electrolyte salts may be present in the electrolyte composition in amounts ranging from about 5% to about 75% by mass, or from about 15% to about 75% by mass, or from about 25% to about 75% by mass, or from about 30% to about 70% by mass, or from about 40% to about 60% by mass, or from about 15% to about 50% by mass, or from about 10% to about 30% by mass, based on the total mass of the electrolyte composition. In some embodiments, electrolyte salts may be present in the electrolyte composition in amounts ranging from about 40% to about 60% by mass, based on the total mass of the electrolyte composition. In some embodiments, electrolyte salts may be present in the electrolyte composition in amounts ranging from about 10% to about 30% by mass, based on the total mass of the electrolyte composition.

[0059] The polymer may be present in the electrolyte composition of this disclosure in an amount of about 0.1% to about 15% by mass, based on the total mass of the electrolyte composition. For example, the polymer may be present in the electrolyte composition of this disclosure in an amount of about 0.1% to about 10% by mass, about 0.5% to about 5% by mass, or about 0.5% to about 2.5% by mass, based on the total mass of the electrolyte composition.

[0060] In some embodiments, the electrolyte composition of the present disclosure comprises, based on the total mass of the electrolyte composition, about 15% to about 95% by mass of solvent, about 5% to about 85% by mass of electrolyte salt, and about 0.1% to about 15% by mass of polymer. In some embodiments, the electrolyte composition of the present disclosure comprises, based on the total mass of the electrolyte composition, about 40% to about 60% by mass of solvent, about 40% to about 60% by mass of electrolyte salt, and about 0.5% to about 2.5% by mass of polymer. In some embodiments, the electrolyte composition of the present disclosure comprises, based on the total mass of the electrolyte composition, about 70% to about 90% by mass of solvent, about 10% to about 30% by mass of electrolyte salt, and about 0.5% to about 2.5% by mass of polymer.

[0061] Certain embodiments include polymers, solvents, and electrolyte salts. In some cases, the electrolyte composition is crosslinked and may include polymers having a heterogeneous polymer network structure obtained by a crosslinking reaction of a composition containing one or more crosslinking agents. In some embodiments, the polymer is synthesized from one or more crosslinking agents, and at least one crosslinking agent has three or more polymerizable or crosslinkable ends. In some embodiments, at least one of the one or more crosslinking agents has three or more polymerizable or crosslinkable ends.

[0062] In one embodiment, a crosslinking agent having three or more polymerizable or crosslinkable ends has the following formula:

[0063] [ka]

[0064] The formula comprises, where X is C, Si, N, P, B, or a cyclic structure, and R1, R2, and R3 are polymerizable or crosslinkable ends that are directly or covalently bonded to X by spacer chains or groups. R1, R2, R3 and their spacer chains or groups may be the same or different from one another.

[0065] In one embodiment, three or more polymerizable or crosslinkable ends (R1, R2, R3, and R4) are C 2-20 Alkenil, C 2-20 Independently selected from the group consisting of alkynyl, epoxy, amino, hydroxyl, carboxylic acid, or any substituted form thereof.

[0066] In one embodiment, the crosslinking agent having three or more polymerizable or crosslinkable ends is a triacrylate, tetraacrylate, modified triacrylate, modified tetraacrylate, silane, siloxane, or triazinan-trione (triazine-trione).

[0067] In one embodiment, a crosslinking agent having three or more terminals is

[0068] [ka]

[0069] The formula is selected from the group consisting of, where R4 and R5 are

[0070] [ka]

[0071] Independently selected from the group consisting of, where each of R1, R2, R3, and R6 is independently selected from the group consisting of hydrogen, methyl, ethyl, phenyl, methylphenyl, benzyl, acrylic, epoxyethyl, isocyanate, cyclic carbonate, lactone, lactam, and vinyl, and n is an integer between 0 and 50,000. * This indicates a connection point.

[0072] In one embodiment, the crosslinking agent is

[0073] [ka]

[0074] It has the formula:

[0075] In one embodiment, the modified triacrylate and tetraacrylate include triacrylate and tetraacrylate having substituents such as -CN, -SO2H, -CO2H, -CO2-, F, Cl, Br, or I.

[0076] In one embodiment, the crosslinking agent having three or more terminals is a silane or siloxane.

[0077] In some embodiments, one or more crosslinking agents or spacer chains or groups are, but are not limited to, -O-, -NR c-, -S-, -C(=O)-, -C(=O)O-, -C(=O)NR c -, -C(=O)S-, -OC(=O)O-, -NR c C(=O)O-, -NR c C(=O)NR c -, -S(=O)-, -S(=O)2-, -OS(=O)2-, -OS(=O)2O-, -NR c S(=O)²⁻, -NR c S(=O)2NR c -, -OS(=O)2NR c -, C 1-6 Alkirenyl, C 2-6 Alkenylenyl, C 2-6 Alkinylenyl, C 6-14 Alyrenyl, 5-14 membered ring heteroallyrenyl, C 3-10 Contains a structure comprising carbocyclenyl or a 3-10 membered heterocyclenyl ring; alkylenyl, alkenylenyl, alkynylenyl, aryrenyl, heteroaryrenyl, carbocyclenyl, or heterocyclenyl may be halogen, -CN, -NO2, C 1-6 Alkyl, C 1-6 Haloalkyl, C 16 Hydroxyalkyl, C 16 Aminoalkyl, C 2-6 Alkenil, C 2-6 Alkinyl, C 6-14 Aryl, 5-14 membered ring heteroaryl, C 3-10 Carbocyclyl, 3-10 membered ring heterocyclyl, -SR b -S(=O)R a -S(=O)2R a -S(=O)2OR b -S(=O)2NR c R d , -NR c R d , -NR c S(=O)2R a , -NR c S(=O)2R a , -NR c S(=O)2OR b , -NR c S(=O)2NR c R d , -NRb C(=O)NR c R d , -NR b C(=O)R a , -NR b C(=O)OR b , -OR b -OS(=O)2R a -OS(=O)2OR b -OS(=O)2NR c R d -OC(=O)R a , -OC(=O)OR b -OC(=O)NR c R d -C(=O)R a , -C(=O)OR b , or -C(=O)NR c R d It is replaced as needed; R a , R b , R c , and R d Independently, C 1-6 Alkyl, C 1-6 Haloalkyl, C 16 Hydroxyalkyl, C 16 Aminoalkyl, C 2-6 Alkenil, C 2-6 Alkinyl, C 3-10 Carbocyclyl, 3-10 membered ring heterocyclyl, C 6-14 Aryl, or 5-14 membered ring heteroaryl; alkyl, haloalkyl, hydroxyalkyl, aminoalkyl, alkenyl, alkynyl, carbocykrill, heterocyclyl, aryl, and heteroaryl are one or more oxo, halogen, -CN, -OH, -OMe, -NH2, -C(=O)Me, -C(=O)OH, -C(=O)OMe, C 16 Alkyl, or C 16 Haloalkyl groups are substituted as needed.

[0078] In some embodiments, R c and R dIt forms a 3-10 membered heterocycline ring with heteroatoms (such as N, O, S, and P), and this heterocycline contains one or more oxo, halogen, -CN, -OH, -OMe, -NH2, -C(=O)Me, -C(=O)OH, -C(=O)OMe, and C 16 Alkyl, or C 16 Haloalkyl groups are substituted as needed.

[0079] In one embodiment, one of the crosslinking agent or spacer chain or group is -XC(=O)CR 3 =C(R 4 )Includes the structure of 2, where X is independently O or NR e And R e H or C 1-6 It is alkyl, and each R 3 and R 4 H or C 1-6 It is alkyl.

[0080] In one embodiment, one of the crosslinking agents is not limited to,

[0081] [ka]

[0082] It has one or more functional groups, including

[0083] In one embodiment, the crosslinking agent having one or more functional groups is not limited to,

[0084] [ka]

[0085] Includes,

[0086] [ka]

[0087] That is the case.

[0088] In some embodiments, the crosslinking agent having one or more functional groups is a monomer for ring-opening polymerization and has the following formula:

[0089] [ka]

[0090] The expression has any of the following substitution forms, where x is an integer ranging from 1 to 1000.

[0091] In some embodiments, the monomer for ring-opening polymerization is:

[0092] [ka]

[0093] Includes.

[0094] In some embodiments, the monomers for ring-opening polymerization include unsubstituted or substituted oxirane rings, oxetane rings, furan rings, aziridine rings, and azetidine rings.

[0095] In addition, one embodiment relates to a composition for use in a polymer solid electrolyte, a battery or other electrochemical device containing the same, and a method for manufacturing the same. In some cases, incorporating vinyl and / or allyl functional groups and performing UV crosslinking or thermal crosslinking can improve various electrochemical properties, and the electrochemical properties can be more clearly improved if the crosslinking agent has polymerizable or crosslinkable ends such as vinyl and allyl in at least three directions of the chemical structure of the crosslinking agent (i.e., the crosslinking agent has three crosslinkable ends).

[0096] In one embodiment, the present disclosure relates broadly to electrochemical cells, such as batteries, comprising the polymer electrolyte compositions disclosed herein. In one embodiment, the battery is a LIB, such as a lithium-ion solid-state battery. The electrochemical cell may include a negative electrode, a positive electrode, and / or a separator. Many of these are commercially available. In some embodiments, the polymer electrolyte compositions of the present disclosure may be used alone and / or in combination with other electrolyte materials as electrolytes in electrochemical cells.

[0097] In some embodiments, polymerizable and crosslinkable ends (or groups) are not limited to C 2-20 Alkenil, C 2-20 This includes alkynyl, epoxy, amino, hydroxyl, carboxylic acid, or any substituted form thereof. In some embodiments, they are vinyl and / or allyl.

[0098] In addition, in one embodiment, the ends or groups of vinyl and / or allyl may be crosslinked together. For example, such functional groups may be crosslinked using ultraviolet light, at high temperatures (e.g., between 20°C and 100°C), in the presence of an initiator, or by other methods including those described herein. In some cases, incorporating three crosslinkable ends results in a disordered or irregular network structure, improving electrochemical properties such as relatively high ionic conductivity and decomposition voltage.

[0099] The electrolyte compositions of this disclosure may include an electrolyte salt. The electrolyte salt may be, for example, a lithium salt, or other salts such as sodium, potassium, magnesium, or calcium salts.

[0100] In some embodiments, the electrolyte salt includes a lithium salt. In some embodiments, the electrolyte salt includes lithium perchlorate (LiClO4), lithium nitrate (LiNO3), lithium hexafluoride phosphate (LiPF6), lithium borofluoride (LiBF4), lithium arsenide hexafluoride (LiAsF6), lithium trifluoromethanesulfonate (LiCF3SO3), lithium bisperfluoroethylsulfonylimide (LiBETI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethanesulfonyl)imide (LiN(CF3SO2)2, LiTFSI), lithium bis(oxalate)borate (LiBOB), lithium difluoro(oxalate)borate (LiBF2C2O4, LiDFOB), and lithium fluoroalkyl phosphate (Li[PF x (C y F 2y+1-z H z ) 6-x ])(1≦x≦5, 1≦y≦8, and 0≦z≦2y-1), comprising one or more of lithium fluoride phosphate (Li2PO3F), lithium difluorophosphate (LiDFP), lithium difluoro(bisoxalate) phosphate (LiC4PO8F2), and lithium tetrafluorooxalate phosphate (LiC2PO4F4), lithium tris(trifluoromethanesulfonyl)methide (LiC(CF3SO2)3), LiF, LiCl, LiBr, LiI, Li2SO4, Li3PO4, Li2CO3, LiOH, lithium acetate, lithium trifluoromethylacetate, and lithium oxalate. In some embodiments, the electrolyte salt comprises one or more of LiFSI and LiTFSI.

[0101] An electrochemical device comprising an electrolyte composition described herein is provided herein.

[0102] In some embodiments, the electrochemical device either does not include a negative electrode or includes one. In some embodiments, the electrochemical device includes a negative electrode.

[0103] In some embodiments, the negative electrode is a carbon negative electrode, a Li negative electrode, a Si negative electrode, an alloy negative electrode, or Li4Ti5O 12 It is either made from a conversion anode material. In some embodiments, the carbon anode includes graphite, soft carbon, hard carbon, or a combination thereof. In some embodiments, the Li anode includes Li metal foil, Cu, Ni, or Li metal on stainless steel. In some embodiments, the Si anode includes Si, Si / carbon composite, SiO x (0≦x<2), SiO x (0≦x<2) / Includes carbon composites or combinations thereof. In some embodiments, the alloy anode includes Sn, SnO2, Sb, Al, Mg, Bi, In, As, Zn, Ga, B, or combinations thereof. In some embodiments, the conversion anode material is M a X b The material comprises M, where M is Mn, Fe, Co, Ni, or Cu, X is O, S, Se, F, N, or P, and a and b are each 1 to 4. In some embodiments, the negative electrode is a Li metal foil, or Li metal on Cu, Ni, or stainless steel.

[0104] In some embodiments, the electrochemical device includes a positive electrode. In some embodiments, the positive electrode is made from an electroactive material comprising one or more of the following: lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, lithium titanate, metallic lithium, lithium metal oxide, lithium manganese oxide, lithium cobalt oxide, and lithium iron phosphate.

[0105] In some embodiments, the electrochemical device disclosed herein is capable of measuring 3 mA / cm² over 1 hour when fully charged. 2When overcharged with a charging current of 4 or less, or when the voltage reaches 8.5V, the device passes the overcharge test with a European Automotive Research and Development Council (EUCAR) hazard level of 4 or less. EUCAR hazard levels can be seen in Table 1. In some embodiments, the electrochemical device is a LIB, and the electrochemical device, at 100% charge, receives 3mA / cm over 1 hour. 2 When overcharged with a charging current or when the voltage reaches 8.5V, it passes the overcharge test with a EUCAR hazard level of 4 or less.

[0106] [Table 1]

[0107] In some embodiments, the electrochemical device passes a high-temperature constant-temperature chamber test in which the electrochemical device is held at the following temperatures for 10 minutes in a 100% charged state: 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, and 190°C, with an EUCAR hazard level of 4 or less. In some embodiments, the electrochemical device is a lithium-ion solid-state battery, and the electrochemical device passes a high-temperature constant-temperature chamber test in which the electrochemical device is held at the following temperatures for 10 minutes in a 100% charged state: 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, and 190°C, with an EUCAR hazard level of 4 or less. In some embodiments, the LIB is a lithium-ion solid-state battery.

[0108] In some embodiments, the electrochemical device maintains a specific capacity of at least 160 mAh / g over at least 200 asymmetric cycles, or at least 220 asymmetric cycles, or at least 250 asymmetric cycles, with a charging current of 1 mA / cm². 2 The discharge current is 3 mA / cm². 2In some embodiments, the electrochemical device is a LIB, which maintains a specific capacitance of at least 160 mAh / g over at least 200 asymmetric cycles, or at least 220 asymmetric cycles, or at least 250 asymmetric cycles, and has a charging current of 1 mA / cm². 2 The discharge current is 3 mA / cm². 2 In some embodiments, the electrochemical device is a LIB, which maintains a specific capacitance of at least 160 mAh / g over at least 220 asymmetric cycles, and has a charging current of 1 mA / cm². 2 The discharge current is 3 mA / cm². 2 In some embodiments, the electrochemical device is a LIB, which maintains a specific capacitance of at least 160 mAh / g over at least 250 asymmetric cycles, and has a charging current of 1 mA / cm². 2 The discharge current is 3 mA / cm². 2 That is the case.

[0109] In some embodiments, the electrochemical device maintains a specific capacity of at least 140 mAh / g over at least 120 symmetrical cycles, or at least 130 symmetrical cycles, or at least 135 symmetrical cycles, with charging and discharging currents of 1 mA / cm². 2 In some embodiments, the electrochemical device is a LIB, maintaining a specific capacitance of at least 140 mAh / g over at least 120 symmetrical cycles, or at least 130 symmetrical cycles, or at least 135 symmetrical cycles, with a charging current and a discharging current of 1 mA / cm². 2 In some embodiments, the electrochemical device is a LIB, maintaining a specific capacitance of at least 140 mAh / g over at least 130 symmetrical cycles, with a charging current and a discharging current of 1 mA / cm². 2 In some embodiments, the electrochemical device is a LIB, maintaining a specific capacitance of at least 140 mAh / g over at least 135 symmetrical cycles, with a charging current and a discharging current of 1 mA / cm². 2 That is the case.

[0110] In some embodiments, the electrochemical device has a current of at least about 10 mA / cm². 2 at least approximately 15mA / cm² 2 at least approximately 18 mA / cm² 2 , or approximately 10mA / cm² 2 From approximately 18mA / cm² 2 It has a charging current density of at least about 10 mA / cm². In some embodiments, the electrochemical device is a LIB and has a charging current density of at least about 10 mA / cm². 2 at least approximately 15 mA / cm² 2 at least approximately 18 mA / cm² 2 , or approximately 10mA / cm² 2 From approximately 18mA / cm² 2 It has a charging current density of approximately 10 mA / cm². In some embodiments, the electrochemical device is a LIB and has a charging current density of approximately 10 mA / cm². 2 From approximately 18mA / cm² 2 It has a charging current density of approximately 12 mA / cm². In some embodiments, the electrochemical device is a LIB and has a charging current density of approximately 12 mA / cm². 2 From approximately 18mA / cm² 2 It has a charging current density of .

[0111] In some embodiments, the electrochemical device has a current of at least about 6 mA / cm². 2 It has a charging current density of at least about 9 mA / cm². For example, an electrochemical device has a charging current density of at least about 9 mA / cm². 2 at least approximately 10.5 mA / cm² 2 at least approximately 12 mA / cm² 2 at least approximately 13.5 mA / cm² 2 at least approximately 15mA / cm² 2 , or at least about 16.5 mA / cm² 2 It has a charging current density of at least about 9 mA / cm². In some embodiments, the electrochemical device is a LIB and has a charging current density of at least about 9 mA / cm². 2 at least approximately 10.5 mA / cm² 2 at least approximately 12 mA / cm² 2 at least approximately 13.5 mA / cm² 2 at least approximately 15 mA / cm²2 , or at least about 16.5 mA / cm² 2 It has a charging current density of at least about 13.5 mA / cm². In some embodiments, the electrochemical device has a charging current density of at least about 13.5 mA / cm². 2 Or approximately 16.5 mA / cm² 2 It has a charging current density of .

[0112] In some embodiments, the electrochemical device exhibits a capacity retention rate of at least 50% (e.g., 50% to 100%) at temperatures ranging from 0°C to -20°C for at least 3 hours. For example, the electrochemical device is a LIB and exhibits a capacity retention rate of at least 50%, at least 60%, at least 70%, or at least 80% at temperatures ranging from 0°C to -20°C or from -10°C to -20°C for at least 3 hours, at least 6 hours, or at least 12 hours. In some embodiments, the electrochemical device is a LIB and exhibits a capacity retention rate of at least 80% at temperatures ranging from -20°C for at least 6 hours. In some embodiments, the electrochemical device is a LIB and exhibits a capacity retention rate of at least 80% at temperatures ranging from -20°C for at least 12 hours.

[0113] Electrochemical devices comprising a negative electrode, a positive electrode, and a polymer electrolyte composition of the Disclosure, wherein the polymer electrolyte composition comprises an electrolyte salt disclosed herein, a polymer disclosed herein, and a solvent comprising a non-fluorinated ether, and the electrochemical device exhibits a capacity retention rate of at least 70% at a temperature in the range of -10°C to -20°C for at least 6 hours, are also provided herein. In some embodiments, the electrochemical device is a LIB. In some embodiments, the solvent further comprises a fluorinated ether. In some embodiments, the electrochemical device exhibits a capacity retention rate of at least 70% at a temperature in the range of -10°C to -20°C for at least 12 hours.

[0114] Electrochemical devices comprising a negative electrode, a positive electrode, and a polymer electrolyte composition of the Disclosure, wherein the polymer electrolyte composition comprises an electrolyte salt, a polymer, and a solvent comprising a non-fluorinated ether, and the electrochemical device passes a high-temperature constant-temperature chamber test in which the electrochemical device is held at 10 minutes at each of the following temperatures: 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, and 190°C, with a hazard level of 4 or less EUCAR, in a 100% charged state. In some embodiments, the electrochemical device is a LIB. In some embodiments, the solvent further comprises a fluorinated ether. In some embodiments, the LIB is a lithium-ion solid-state battery.

[0115] An electrochemical device comprising a negative electrode, a positive electrode, and a polymer electrolyte composition of the present disclosure, wherein the polymer electrolyte composition comprises an electrolyte salt, a polymer, and a solvent comprising a non-fluorinated ether, wherein the electrochemical device, when fully charged, exhibits a current of 3 mA / cm² over 1 hour. 2 Electrochemical devices are also provided herein that, when overcharged with a charging current or when the voltage reaches 8.5V, pass an overcharge test with an EUCAR hazard level of 4 or less. In some embodiments, the electrochemical device is a LIB. In some embodiments, the solvent further comprises a fluorinated ether.

[0116] An electrochemical device comprising a negative electrode, a positive electrode, and a polymer electrolyte composition of the present disclosure, wherein the polymer electrolyte composition comprises an electrolyte salt, a polymer, and a solvent comprising a non-fluorinated ether, and the electrochemical device has a capacitance of about 10.5 mA / cm². 2 From approximately 16.5 mA / cm² 2 Electrochemical devices having a charging current density in the range of are also provided herein. In some embodiments, the electrochemical device is a LIB. In some embodiments, the solvent further comprises a fluorinated ether. In some embodiments, the electrochemical device has a charging current density of about 12 mA / cm². 2From approximately 16.5 mA / cm² 2 It has a charging current density in the range of . In some embodiments, the electrochemical device has a charging current density of at least about 15 mA / cm². 2 It has a charging current density. In some embodiments, LIB is a lithium-ion solid-state battery.

[0117] In some embodiments, the polymer electrolyte compositions of the present disclosure may further include additives. In some embodiments, the additives may provide improved processability and / or controlled ionic conductivity and mechanical strength. For example, the additives may be polymers, small molecules (i.e., having a molecular weight of less than 1 kDa), nitriles, cyclic carbonates, ionic liquids, and the like. Potentially suitable additives, though not limited to these examples, include ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, propylene carbonate, fluoroethylene carbonate, vinylene carbonate, succinonitrile, glutalonitrile, hexonitrile, malononitrile, dimethyl sulfoxide, propane-1-ene-1,3-sultone, sulfolane, ethyl vinyl sulfone, tetramethylene sulfone, vinyl sulfone, methyl vinyl sulfone, phenyl vinyl sulfone, N-propyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide, 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide, trimethyl phosphate, triethyl phosphate, and poly(ethylene oxide). In some other cases, the additive may function as a plasticizer.

[0118] In some embodiments, the additive may be present in a mass percentage of about 1% to about 10% by mass, or about 0.01% to about 5% by mass, based on the total mass of the polymer electrolyte composition.

[0119] In some embodiments, the polymer electrolyte composition may further include initiators. Specific non-limiting examples of initiators include photoinitiators, 2,2'-azobis(2-methylpropionitrile), benzoyl peroxide, cumene hydroperoxide, dicumyl peroxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, ammonium persulfate, anisoin, anthraquinone, benzophenone, benzoin methyl ether, 2-isopropylthioxanthone, 9,10-phenanthrenequinone, 3'-hydroxyacetophenone, and 3,3',4,4'-benzo Examples include phenonetetracarboxylic dianhydride, 2-benzoylbenzoic acid, (±)-camphorquinone, 2-ethylanthraquinone, 2-methylbenzophenone, 4-hydroxybenzophenone, 2-hydroxy-2-methylpropiophenone, benzoin isobutyl ether, 4,4'-bis(dimethylamino)benzophenone, 4,4'-dihydroxybenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, ferrocene, dibenzosverenone, benzoin ethyl ether, benzyl, methylbenzoyl formate, and 4-benzoylbenzoic acid. In some cases, the initiator has a mass fraction (mass percent) between 0.01% and 5% by mass, based on the total mass of the polymer solid electrolyte, or other suitable mole fractions for initiating crosslinking. In some embodiments, the mass fraction is 5.0% by mass or less, 4.0% by mass or less, 3.0% by mass or less, 2.0% by mass or less, or 1.0% by mass or less. In some embodiments, the mass fraction is 1.0% by mass or less, 0.8% by mass or less, 0.6% by mass or less, 0.4% by mass or less, 0.2% by mass or less, 0.1% by mass or less, or 0.05% by mass or less.

[0120] Some aspects of this disclosure relate more broadly to systems and methods for producing any of the polymer electrolyte compositions described herein. For example, polymers may be produced by reacting various crosslinking agents together.

[0121] In some cases, during the curing process, at least some of the crosslinking agents may crosslink, for example, as described herein, and in some cases, this may improve various electrochemical properties. For example, exposure to ultraviolet light may accelerate the crosslinking process.

[0122] This disclosure broadly relates to devices having the polymer electrolyte compositions disclosed herein. These devices may be batteries, LIBs, i.e., lithium-ion solid-state batteries. Batteries may be configured for applications such as portable device applications, transportation applications, and stationary energy storage applications. Non-limiting examples of ion-conducting batteries include lithium-ion conductive batteries. These devices may also be batteries comprising one or more lithium-ion electrochemical cells.

[0123] In various examples, the battery includes a polymer electrolyte composition, a negative electrode, and a positive electrode having an electroactive material.

[0124] In various examples, the negative electrode includes carbon negative electrodes, Li negative electrodes, Si negative electrodes, alloy negative electrodes, and / or conversion negative electrode materials. Carbon negative electrodes may include graphite, soft carbon, hard carbon, or a combination thereof. Li negative electrodes may include Li metal foil, Li metal on Cu (or on other current collectors such as stainless steel or Ni). Si negative electrodes include Si, Si / carbon composite negative electrodes, and SiO x (0≦x<2), SiO x (0≦x<2) / May include a carbon composite anode. The alloy anode may include Sn, SnO2, Sb, Al, Mg, Bi, In, As, Zn, Ga, and B. In various embodiments, the battery does not include a anode (it only includes a current collector).

[0125] The conversion negative electrode material is M a X b It may include, where M is Mn, Fe, Co, Ni, Cu, and X is O, S, Se, F, N, P. In addition, a and b are each from 1 to 4.

[0126] In various embodiments, the negative electrode is Li4Ti5O 12 Includes.

[0127] In various embodiments, examples of electroactive materials include lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, lithium titanate, metallic lithium, lithium metal oxide, lithium manganese oxide, lithium cobalt oxide, and lithium iron phosphate.

[0128] In some embodiments, the electrochemical device is 1 mA / cm² at 25°C. 2 Using a discharge current of 1 mA / cm² at a rate of 250 cycles, it has a capacity retention rate of approximately 90% to 100% after 250 cycles, or 1 mA / cm² at 25°C. 2 Using a discharge current at this rate, it has a capacity retention rate of at least 90% after 150 cycles.

[0129] In some embodiments, the electrochemical device has a capacity retention rate of about 50% to about 99%, or about 70% to about 99%, or about 80% to about 99%, or about 90% to about 99%, or at least 50%, at least 75%, and at least 80% when a discharge current rate of 0.33C is used at -20°C.

[0130] Several crosslinking agents, electrolyte salts, additives, and other materials, as described in International Publication No. 2020 / 096632A1 and U.S. Patent Application Publications No. 2020 / 0144665A1 and 2020 / 0144667A1, are all incorporated herein by reference.

[0131] The following examples are intended to illustrate certain embodiments of the present disclosure, but are not intended to illustrate the entire scope of the present disclosure.

[0132] The preceding description and the following examples detail specific embodiments of the present disclosure and describe the best-case scenario envisioned by the inventors. However, it should be recognized that, no matter how detailed the preceding description may seem, the present disclosure is implementable in various ways and should be interpreted in accordance with the appended claims and their equivalents.

[0133] While the disclosed teachings have described various uses, methods, compounds, compositions, and materials, it will be understood that various changes and modifications thereto can be made without departing from the teachings herein. The following examples are provided to illustrate the disclosed teachings more clearly and are not intended to limit the scope of the teachings presented herein. Although the teachings describe these exemplary embodiments, those skilled in the art will readily understand that numerous variations and modifications of these exemplary embodiments are possible without requiring excessive experimentation. All such variations and modifications are within the scope of the teachings of this disclosure. [Examples]

[0134] Example 1A - Preparation of an electrochemical device Preparation of a pouch-type cell containing a high concentration of ether electrolyte (Battery A) A basic solution was prepared by mixing 53% by mass of LiFSI and 47% by mass of 1,2-diethoxyethane. 1.5% by mass of pentaerythritol tetraacrylate and 0.1% by mass of AIBN were added to this basic solution. The basic solution was thoroughly mixed for 30 minutes to form a homogeneous solution. This homogeneous solution was poured into a pouch-type cell and allowed to stand at room temperature for 48 hours to allow the homogeneous solution to be uniformly distributed within the pouch-type cell. Next, the pouch-type cell was placed in a 65°C oven for 2 hours to allow for thermal crosslinking. The pouch-type cell used LiNi as the positive electrode. 0.8 Co 0.1 Mn 0.1 It contained O2 (NMC811), Li laminated on a Cu foil as the negative electrode, and a polyolefin film as a separator.

[0135] Preparation of a pouch-type cell containing a high concentration of ether-fluorinated ether electrolyte (Battery B) A basic solution was prepared by mixing 19% by mass of LiFSI, 17% by mass of 1,2-diethoxyethane, and 64% by mass of bis(2,2,2-trifluoroethoxy)methane (BTFM). To this homogeneous solution, 1.5% by mass of pentaerythritol tetraacrylate and 0.1% by mass of AIBN were added. The basic solution was thoroughly mixed for 30 minutes to form a homogeneous solution. This homogeneous solution was poured into a pouch-type cell and allowed to stand at room temperature for 48 hours to allow the homogeneous solution to be uniformly distributed in the pouch-type cell. Next, the pouch-type cell was placed in a 65°C oven for 2 hours to allow for thermal crosslinking.

[0136] Example 1B - Preparation of an electrochemical device Preparation of a pouch-type cell containing an ether electrolyte (Battery X) Mix 40% by mass of LiFSI and 60% by mass of 1,2-dibutoxyethane to prepare the basic solution. Add 5% by mass of poly(ethylene glycol) diacrylate (M) to this basic solution. n Add 700 ml of 2,2'-azobis(2-methylpropionitrile) (AIBN) and 0.1% by mass. Mix the base solution thoroughly for 30 minutes to form a homogeneous solution. Pour this homogeneous solution into a pouch cell and allow it to stand at room temperature for 48 hours to allow the homogeneous solution to be uniformly distributed in the pouch cell. Next, place the pouch cell in a 65°C oven for 2 hours to allow it to be thermally crosslinked. The pouch cell has LiNi as the positive electrode. 0.8 Co 0.1 Mn 0.1 It contained O2 (NMC811), Li laminated on a Cu foil as the negative electrode, and a polyolefin film as a separator.

[0137] Battery X is expected to function similarly to battery A.

[0138] Preparation of a pouch-type cell containing a high concentration of ether electrolyte (Battery Y) A basic solution is prepared by mixing 25% by mass of LiFSI, 25% by mass of 1,2-dibutoxyethane, and 50% by mass of 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE). 5% by mass of tris[2-(acryloyloxy)ethyl]isocyanurate and 0.1% by mass of AIBN are added to this homogeneous solution. The basic solution is thoroughly mixed for 30 minutes to form a homogeneous solution. This homogeneous solution is poured into a pouch-type cell and allowed to stand at room temperature for 48 hours to allow the homogeneous solution to be uniformly distributed within the pouch-type cell. Next, the pouch-type cell is placed in a 65°C oven for 2 hours to allow for thermal crosslinking. The pouch-type cell uses LiNi as the positive electrode. 0.8 Co 0.1 Mn 0.1 It contained O2 (NMC811), Li laminated on a Cu foil as the negative electrode, and a polyolefin film as a separator.

[0139] Battery Y is expected to function similarly to battery B.

[0140] Example 2 - Testing of Electrochemical Devices The previously disclosed batteries, namely batteries A and B, were tested as follows.

[0141] Cycle Performance: Batteries with positive electrode, negative electrode, separator, and electrolyte were charged and discharged at room temperature between various voltage ranges using Neware test measures at various current rates. Cycle life is determined by the number of cycles (capacity retention rate) at which the battery cell reaches 80% of its original capacity.

[0142] Asymmetric Cycle Test: Each battery is charged and discharged from 2.8V to 4.25V (0% to 100% State of Charge (SOC)) until it has effectively degraded to the point where it can deliver only 80% of its initial capacity. The number of cycles is then measured. The charging current used in this test was 1 mA / cm². 2 The discharge current used in this test was 3 mA / cm². 2Table 2 and Figure 1 below show the asymmetric cycle data from battery A. As can be seen from Table 2 and Figure 1 below, battery B showed more than 300 cycles before reaching an 80% capacity retention rate.

[0143] Symmetrical Cycle Test: Each battery is charged and discharged from 2.8V to 4.25V (0% to 100% State of Charge (SOC)) until it has effectively degraded to the point where it can deliver only 80% of its initial capacity. The number of cycles is then measured. The charging current used in this test was 1 mA / cm². 2 The discharge current used in this test was 1 mA / cm². 2 Table 2 and Figure 2 below show the symmetrical cycle data from each of the tested batteries. As can be seen from Table 2 and Figure 2 below, batteries A and B showed more than 130 cycles before reaching an 80% capacity retention rate.

[0144] Low-temperature test: Each battery was tested for capacity retention at temperatures ranging from 25°C to -20°C. The batteries were tested for a capacity retention rate of 0.3 mA / cm². 2 The batteries were charged to 100% SOC at 25°C at a charging speed of 1 mA / cm², then left at 25°C, 10°C, 0°C, -10°C, and -20°C for 12 hours before being discharged, and the capacity retention rate of each battery was recorded. The discharge rate was 1 mA / cm². 2 Table 3 shows that both batteries A and B retained more than 70% of their capacity at -10°C. At -20°C, battery B unexpectedly showed a capacity retention rate higher than 70%, while battery A showed a capacity retention rate of only 1%. This clearly demonstrated the effectiveness of adding the fluorinated ether solvent.

[0145] Speed ​​Test: Each battery was tested for charging speed capability and capacity retention. Table 2 and Figure 3 below show the speed test data from each of the tested batteries. As can be seen from Table 2 and Figure 3 below, batteries A and B were 10 mA / cm². 2 We demonstrated that even at higher current densities, a high capacity retention rate of at least 60% can be maintained.

[0146] [Table 2]

[0147] [Table 3]

[0148] Example 3: Safety Test Overcharge Test: Batteries A and B were tested for safety based on the overcharge of each battery, according to the hazard levels of the European Automotive Research and Development Council (EUCAR) shown in Table 1 above. To overcharge the batteries, each battery was charged to 100% SOC and subjected to 3 mA / cm² for 1 hour. 2 Charge the battery further with a current of 0, or up to 8.5V (whichever happens first). Table 4 below shows the results of the overcharge test for each battery.

[0149] High-Temperature Chamber Test: Batteries A and B were tested for safety based on the overheating of each battery, according to the EUCAR hazard levels shown in Table 1 above. To overheat the batteries, each battery was heated from room temperature to 193°C at a rate of 5°C / min, and then rested for 10 minutes at temperatures of 133°C, 143°C, 153°C, 163°C, 173°C, 183°C, and 193°C. Table 4 below shows the results of the high-temperature chamber test for each battery.

[0150] [Table 4]

[0151] A battery was considered to have passed the safety test if its EUCAR hazard level was 4 or less (e.g., 0, 1, 2, 3, or 4). An EUCAR hazard level of 5 or higher was considered a failure in the safety test. The results of the battery safety tests are shown in Table 4. Both Battery A and Battery B showed an EUCAR hazard level of 4 or less in the high-temperature constant-temperature chamber test and the overcharge test.

[0152] Example 4: Study of Concentration Preparation of Coin Cells with Different Concentrations of Ether Electrolytes LiFSI and 1,2 - diethoxyethane were mixed to form a basic solution. 1.5 wt% of pentaerythritol tetraacrylate (PETA) and 0.1 wt% of AIBN were added to this basic solution. The basic solution was thoroughly mixed for 30 minutes to form a homogeneous solution. This homogeneous solution was injected into the coin cell and left standing at room temperature for 48 hours to uniformly distribute the homogeneous solution in the coin cell. Next, the coin cell was placed in an oven at 65 °C for 2 hours to enable thermal cross - linking. The mass percentages of LiFSI and 1,2 - diethoxyethane were different for Cells 4 - 1 to 4 - 7 shown in Table 5. The coin cell contained LiNi 0.8 Co 0.1 Mn 0.1 O2 (NMC811) as the positive electrode, Li laminated on a Cu foil as the negative electrode, and a polyolefin film as the separator.

[0153]

Table 5

[0154] As shown in Table 6 below, it was found that all cells exhibited a capacity of over 160 mAh / g at a discharge rate of 1.5 mA / cm 2 . It was also found that a higher concentration (e.g., 5 M or more) of LiFSI in 1,2 - diethoxyethane showed an improvement in the Coulombic efficiency (CE) in Li - Cu, and thus would have better stability when in contact with lithium metal.

[0155]

Table 6

[0156] Example 5: Study of the Ratio of Non - fluorinated Ether to Fluorinated Ether A number of coin cells were prepared according to the procedure of Example 4. However, each coin cell was prepared with different amounts of fluorinated ether: bis(2,2,2-trifluoroethoxy)methane (BTFM) and non-fluorinated ether: 1,2-diethoxyethane (DEE). The polymer electrolyte composition of each coin cell is shown in Table 7 below. Each coin cell was tested for viscosity, ionic conductivity (IC), Coulomb efficiency (CE), and capacity. As shown in Table 8 below, the coin cells were found to function with fluorinated ether percentages ranging from 0% to at least 90%.

[0157] [Table 7]

[0158] [Table 8]

[0159] Viscosity measurement: Dynamic viscosity was measured using a viscometer at 150 rpm. Viscosity decreased as the proportion of BTFM increased. Low viscosity may be beneficial for the electrolyte in order to wet the positive electrode and separator.

[0160] Measurement of Contact Angle: A drop of the polymer electrolyte composition from batteries 1 to 6 of Example 5 was placed on the positive electrode or separator. Subsequently, the contact angle was measured. The contact angle decreased as the proportion of BTFM increased, demonstrating the effectiveness of BTFM in improving wetting.

[0161] [Table 9]

[0162] Over a BTFM proportion ranging from 0% to at least 90%, the electrolyte of the DEE-BTFM mixture exhibits high ionic conductivity (IC) greater than 1.5 mS / cm at 25°C, high IC greater than 0.5 mS / cm at -20°C, high CE greater than 99%, and 1.5 mA / cm 2showed a specific capacity of more than 160 mAh / g at the discharge rate of

[0163] Example 6: Example of fluorinated ether A number of coin cells were prepared according to the procedure of Example 4, except that a different fluorinated ether: tris(2,2,2-trifluoroethyl) orthoformate (TFEO) was used. The electrolyte compositions of each coin cell are shown in Table 10 below. Each coin cell was tested for ionic conductivity and Coulombic efficiency. The results are shown in Table 11 below.

[0164]

Table 10

[0165]

Table 11

[0166] Example 7: Example of fluorinated ether A number of coin cells were prepared according to the procedure of Example 4, except that a different fluorinated ether: 1,2-(1,1,2,2-tetrafluoroethoxy)ethane (TFEE) was used. The polymer electrolyte compositions of each coin cell are shown in Table 12 below. Each coin cell was tested for IC and CE. The results are shown in Table 13 below.

[0167]

Table 12

[0168]

Table 13

[0169] Example 8: Study on the ratio of initiators Numerous coin cells were prepared according to the procedure of Example 4, except that different amounts of AIBN were used. The polymer electrolyte composition of each coin cell is shown in Table 14, while the IC and CE results are shown in Table 15.

[0170] [Table 14]

[0171] [Table 15]

[0172] Example 9: Study of Li salts Numerous coin cells were prepared according to the procedure of Example 4, except that a mixture of LiFSI and LiTFSI was used as the Li salt. The polymer electrolyte composition of each coin cell is shown in Table 16 below, and the ICs of the coin cells were tested, with the results shown in Table 17 below.

[0173] [Table 16]

[0174] [Table 17]

[0175] Example 10 Preparation of coin cell batteries with high concentration ether electrolyte (Battery 10-1) A homogeneous solution was formed by mixing 46% by mass of LiFSI, 8% by mass of LiTFSI, and 46% by mass of 1,2-diethoxyethane for 30 minutes. This homogeneous solution was injected into a coin cell and left to stand at room temperature for 48 hours to allow the homogeneous solution to be uniformly distributed within the coin cell. The coin cell used LiNi as the positive electrode. 0.8 Co 0.1 Mn 0.1It contained O2 (NMC811), Li laminated on a Cu foil as the negative electrode, and a polyolefin film as a separator.

[0176] Preparation of coin cell batteries with high concentration ether-fluorinated ether electrolyte (Battery 10-2) A homogeneous solution was prepared by mixing 13% by mass of LiFSI, 12% by mass of 1,2-diethoxyethane, and 75% by mass of 1,1,1,3,3,3-hexafluoro-2-{[(1,1,1,3,3,3-hexafluoro-2-propanyl)oxy]methoxy}propane for 30 minutes. This homogeneous solution was injected into a coin cell and left to stand at room temperature for 48 hours to allow the homogeneous solution to be uniformly distributed within the coin cell. The coin cell used LiNi as the positive electrode. 0.8 Co 0.1 Mn 0.1 It contained O2 (NMC811), Li laminated on a Cu foil as the negative electrode, and a polyolefin film as a separator.

[0177] [Table 18]

[0178] Table 18 shows that the viscosity decreased and the Coulomb efficiency increased when fluorinated ether was added to the electrolyte. The decreased ionic conductivity is likely due to the reduced concentration of lithium salt. Battery 10-2 is predicted to exhibit improved thermal stability and flame retardancy compared to battery 10-1.

[0179] Various embodiments of the features of the present disclosure are described herein. However, it should be understood that such embodiments are given only as examples, and various modifications, alterations, and substitutions can be conceived by those skilled in the art without departing from the scope of the present disclosure. It should also be understood that various alternatives to the specific embodiments described herein are also included within the scope of the present disclosure.

[0180] manner In a first aspect of this disclosure, the polymer electrolyte composition comprises an electrolyte salt, a polymer, and a solvent comprising a fluorinated ether and a non-fluorinated ether.

[0181] In a second aspect of the present disclosure, the polymer electrolyte composition comprises an electrolyte salt, a polymer, and a solvent containing a non-fluorinated ether, wherein the electrolyte salt is present in an amount of about 30% to about 75% by mass, based on the mass of the non-fluorinated ether.

[0182] In a third aspect of the present disclosure, the electrolyte composition comprises an electrolyte salt and a solvent comprising a fluorinated ether and a non-fluorinated ether, wherein the fluorinated ether has a boiling point of at least 100°C at 1 atmosphere (about 10¹ Pa).

[0183] In a fourth embodiment according to any of the preceding embodiments, the non-fluorinated ether is a compound of formula (I):R 1a -OR 2a (I) is a compound in which R 1a C1-C 10 It is alkyl, R 2a is, -(CH2) n -O-(C1-C 10 Alkyl) or C1-C 10 It is alkyl, or R 1a and R 2a These, along with the oxygen atom to which they are bonded, form a 4- to 7-membered ring heterocycline, where n is an integer, either 1 or 2.

[0184] In a fifth embodiment according to any prior aspect, the non-fluorinated ether includes one or more of 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dibutoxyethane, diethyl ether, dibutyl ether, di-tert-butyl ether, tert-butyl ethyl ether, tert-butyl methyl ether, 1,3-dioxolane, 1,4-dioxane, and di(propylene glycol)methyl ether.

[0185] In a sixth embodiment according to any prior aspect, the non-fluorinated ether includes 1,2-diethoxyethane.

[0186] In the seventh embodiment according to the first or third to sixth aspects, the fluorinated ether is of formula (II):

[0187] [ka]

[0188] It is a compound of which, in the formula, R 3a H, C1-C 10 Alkyl, C1-C 10 Fluoroalkyl, -O-(C1-C 10 Alkyl) or -O-(C1-C 10 Fluoroalkyl) and R 4a and R 5a Each of these is independently C1-C 10 Alkyl, C1-C 10 Fluoroalkyl, -O-(C1-C 10 Alkyl) or -O-(C1-C 10 Fluoroalkyl) and R 3a , R 4a , and R 5a At least one of them is -O-(C1-C 10 Alkyl) or -O-(C1-C 10 Fluoroalkyl) and R 3a , R 4a , and R 5a At least one of them is C1-C 10 Contains fluoroalkyl substances.

[0189] In the eighth aspect according to the seventh aspect, the fluorinated ether is bis(2,2,2-trifluoroethoxy)methane (BTFM), 1,1,1,3,3,3-hexafluoro-2-(1,1,1,3,3,3-hexafluoropropane-2-yloxymethoxy)propane, bis(3,3,3-trifluoropropoxy)methane, 1,1,1-trifluoro-3-[(2,2,2-trifluoroethoxy)methoxy]propane, bis(2,2,3,3,3-pentafluoropropoxy) The mixture comprises methane, and one or more of the following: 1,1,1,2,2-pentafluoro-3-((2,2,2-trifluoroethoxy)methoxy)propane, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), 1H,1H,5H-octafluoropentyl-1,1,2,2-tetrafluoroethyl ether (OTE), bis(2,2,2-trifluoroethyl) ether, 1H,1H,2'H-perfluorodipropyl ether, 2,2,2-trifluoroethyl 1,1,2,2-tetrafluoroethyl ether, 1,2-(1,1,2,2-tetrafluoroethoxy)ethane (TFEE), and tris(2,2,2-trifluoroethyl) orthoformate (TFEO).

[0190] In the ninth embodiment according to the first or third to sixth aspects, the fluorinated ether is of formula (II):

[0191] [ka]

[0192] It is a compound of which, in the formula, R 3a H, -O-(C1-C 10 Alkyl) or -O-(C1-C 10 Fluoroalkyl) and R 4a and R 5a Each of these independently is -O-(C1-C 10 Alkyl) or -O-(C1-C 10 It is a fluoroalkyl group.

[0193] In the tenth embodiment according to the ninth aspect, the fluorinated ether comprises one or more bis(2,2,2-trifluoroethoxy)methane (BTFM) or tris(2,2,2-trifluoroethyl) orthoformate (TFEO).

[0194] In the eleventh embodiment according to the first or third to tenth aspects, the solvent contains a fluorinated ether in an amount ranging from 0.1% to about 99% by mass, or from about 10% to about 90% by mass, from about 20% to about 80% by mass, from about 25% to about 75% by mass, or from about 55% to about 75% by mass.

[0195] In the twelfth embodiment according to the first or third to eleventh aspects, the solvent contains a non-fluorinated ether in an amount ranging from 0.1% to about 99% by mass, or from about 10% to about 90% by mass, from about 20% to about 80% by mass, from about 25% to about 70% by mass, or from about 25% to about 45% by mass.

[0196] In the thirteenth embodiment according to the first or third to twelfth aspects, the non-fluorinated ether and the fluorinated ether exist in mass ratios of 1:20 to 20:1, 1:10 to 10:1, 1:5 to 10:1, 1:3 to 8:1, or 1:1 to 3:1.

[0197] In the fourteenth embodiment according to the second aspect, the non-fluorinated ether in the solvent is 1,2-diethoxyethane.

[0198] In a 15th embodiment according to any prior aspect, the solvent is present in an amount ranging from at least 85% by mass, at least about 90% by mass, at least about 95% by mass, or at least about 98% by mass, or from about 85% by mass to about 99% by mass, or from about 90% by mass to about 99% by mass, based on the total mass of the electrolyte composition.

[0199] In any sixteenth embodiment according to the preceding model, the solvent is substantially free of 1,2-dimethoxyethane.

[0200] In a 17th embodiment according to any prior aspect, the solvent has a boiling point of at least 100°C at 1 atmosphere (about 10¹ Pa).

[0201] In the 18th embodiment according to any prior aspect, the electrolyte salt is lithium perchlorate (LiClO4), lithium nitrate (LiNO3), lithium hexafluoride phosphate (LiPF6), lithium borofluoride (LiBF4), lithium hexafluoride arsenide (LiAsF6), lithium trifluoromethanesulfonate (LiCF3SO3), lithium bisperfluoroethylsulfonylimide (LiBETI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethanesulfonyl)imide (LiN(CF3SO2)2, LiTFSI), lithium bis(oxalate)borate (LiBOB), lithium difluoro(oxalate)borate (LiBF2C2O4, LiDFOB), lithium fluoroalkyl phosphate (Li[PF x (C y F 2y+1-z H z ) 6-x ])(1≦x≦5, 1≦y≦8, and 0≦z≦2y-1), comprising one or more of the following: lithium fluoride phosphate (Li2PO3F), lithium difluorophosphate (LiDFP), lithium difluoro(bisoxalate) phosphate (LiC4PO8F2), and lithium tetrafluorooxalate phosphate (LiC2PO4F4), lithium tris(trifluoromethanesulfonyl)methide (LiC(CF3SO2)3), LiF, LiCl, LiBr, LiI, Li2SO4, Li3PO4, Li2CO3, LiOH, lithium acetate, lithium trifluoromethylacetate, and lithium oxalate.

[0202] In the 19th embodiment according to the 18th embodiment, the electrolyte salt comprises one or more of bis(fluorosulfonyl)imide lithium (LiFSI), trifluoromethanesulfonimide lithium (LiTFSI), and lithium difluorophosphate.

[0203] In a 20th embodiment according to any earlier aspect, the electrolyte salt is present in the polymer electrolyte composition in an amount of about 5% to about 75% by mass, or about 15% to about 75% by mass, or about 25% to about 75% by mass, or about 30% to about 70% by mass, or about 40% to about 60% by mass, or about 15% to about 50% by mass, based on the total mass of the polymer electrolyte composition.

[0204] In a 21st embodiment according to any prior aspect, the polymer is crosslinked and has a heterogeneous polymer network structure obtained by a crosslinking reaction of a composition containing one or more crosslinking agents.

[0205] In the 22nd embodiment according to the 21st embodiment, at least one of the one or more crosslinking agents has three or more polymerizable or crosslinkable ends.

[0206] In a 23rd embodiment according to any prior aspect, the polymer is present in an amount of about 0.1% to about 10% by mass, about 0.5% to about 5% by mass, or about 0.5% to about 2.5% by mass.

[0207] In a 24th embodiment, an electrochemical device comprising a polymer electrolyte composition according to any of the preceding embodiments is disclosed.

[0208] In the 25th embodiment according to the 24th aspect, the electrochemical device further includes a negative electrode, the negative electrode being a carbon negative electrode, a Li negative electrode, a Si negative electrode, an alloy negative electrode, or Li4Ti5O 12 It is either made from a conversion anode material or manufactured from a conversion anode material.

[0209] In the 26th embodiment according to the 25th aspect, the carbon anode includes graphite, soft carbon, hard carbon, or a combination thereof.

[0210] In the 27th embodiment according to the 25th aspect, the Li anode includes Li metal foil, Cu, Ni, or Li metal on stainless steel.

[0211] In the 28th embodiment according to the 25th aspect, the Si negative electrode is Si, Si / carbon composite, SiO x (0≦x<2), SiO x (0 ≤ x < 2) / Includes carbon composites or combinations thereof.

[0212] In the 29th embodiment according to the 25th aspect, the alloy negative electrode includes Sn, SnO2, Sb, Al, Mg, Bi, In, As, Zn, Ga, B, or a combination thereof.

[0213] In the 30th embodiment according to the 25th aspect, the conversion anode material is M a X b It includes M, where M is Mn, Fe, Co, Ni, or Cu, and X is O, S, Se, F, N, or P, and each of a and b is independently in the range of 1 to 4.

[0214] In the 31st embodiment according to the 25th aspect, the negative electrode is a Li metal foil, or Li metal on Cu, Ni, or stainless steel.

[0215] In the 32nd embodiment according to any of the 24th to 31st embodiments, the electrochemical device is such that, when fully charged, it emits 3 mA / cm² over a period of 1 hour. 2 When overcharged with a charging current or when the voltage reaches 8.5V, it passes the overcharge test with a European Automotive Research and Development Council (EUCAR) hazard level of 4 or less.

[0216] In a 33rd embodiment according to any of the 24th to 32nd embodiments, the electrochemical device passes a high-temperature constant-temperature chamber test in which the electrochemical device is held at 10 minutes at each of the following temperatures: 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, and 190°C, with a European Automotive Research and Development Council (EUCAR) hazard level of 4 or less.

[0217] In the 34th embodiment according to any of the 24th to 33rd embodiments, the electrochemical device maintains a specific capacity of at least 160 mAh / g over at least 200 asymmetric cycles, or at least 220 asymmetric cycles, or at least 250 asymmetric cycles, and the charging current is 1 mA / cm². 2 The discharge current is 3 mA / cm². 2 That is the case.

[0218] In a 35th embodiment according to any of the 24th to 34th embodiments, the electrochemical device maintains a specific capacity of at least 140 mAh / g over at least 120 symmetrical cycles, or at least 130 symmetrical cycles, or at least 135 symmetrical cycles, with charging and discharging currents of 1 mA / cm². 2 That is the case.

[0219] In the 36th embodiment according to any of the 24th to 35th embodiments, the electrochemical device has a current of at least about 10 mA / cm². 2 at least approximately 15 mA / cm² 2 at least approximately 18 mA / cm² 2 , or approximately 10mA / cm² 2 From approximately 18mA / cm² 2 It has a charging current density of .

[0220] In the 37th embodiment according to any of the 24th to 36th embodiments, the electrochemical device has a capacity retention rate of at least 50%, at least 60%, at least 70%, or at least 80% at a temperature in the range of 0°C to -20°C or -10°C to -20°C for at least 3 hours, at least 6 hours, or at least 12 hours.

[0221] In a 38th aspect, an electrochemical device is disclosed comprising an electrolyte composition including a negative electrode; a positive electrode; and an electrolyte salt, and a solvent containing a non-fluorinated ether, wherein the electrochemical device has a capacity retention rate of at least 70% at a temperature in the range of -10°C to -20°C for at least 6 hours.

[0222] In the 39th embodiment according to the 38th aspect, the solvent further comprises a fluorinated ether.

[0223] In the 40th embodiment according to the 38th or 39th aspect, the electrolyte further comprises a polymer.

[0224] In a forty-first embodiment, an electrochemical device is disclosed comprising an electrolyte composition comprising a negative electrode; a positive electrode; and an electrolyte salt and a solvent containing a non-fluorinated ether, wherein the electrochemical device passes a high-temperature constant-temperature chamber test in which the device is held at 10 minutes in a 100% charged state at the following temperatures: 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, and 190°C, each at a hazard level of 4 or less of the European Automotive Research and Development Council (EUCAR).

[0225] In the 42nd embodiment according to the 41st aspect, the solvent further comprises a fluorinated ether.

[0226] In the 43rd embodiment according to the 41st or 42nd aspect, the electrolyte further comprises a polymer.

[0227] In a 44th aspect, an electrochemical device comprising an electrolyte composition including a negative electrode; a positive electrode; and an electrolyte salt and a solvent containing a non-fluorinated ether, wherein the electrochemical device, when fully charged, exhibits a capacitance of 3 mA / cm² over 1 hour. 2 An electrochemical device is disclosed that, when overcharged with a charging current or when it reaches 8.5V, passes an overcharge test with a European Council for Automotive Research and Development (EUCAR) hazard level of 4 or less.

[0228] In the 45th embodiment according to the 44th aspect, the solvent further comprises a fluorinated ether.

[0229] In the 46th embodiment according to the 44th or 45th aspect, the electrolyte further comprises a polymer.

[0230] In the 47th aspect, an electrochemical device comprising an electrolyte composition including a negative electrode; a positive electrode; and an electrolyte salt and a solvent containing a non-fluorinated ether, wherein the capacitance is about 10.5 mA / cm². 2 From approximately 16.5 mA / cm² 2 An electrochemical device having a charging current density in the range of is disclosed.

[0231] In the 48th embodiment according to the 47th aspect, the solvent further comprises a fluorinated ether.

[0232] In the 49th embodiment according to the 47th or 48th aspect, the electrolyte further comprises a polymer.

[0233] In the 50th embodiment according to any of the 38th to 49th embodiments, the fluorinated ether has a boiling point of at least 100°C at 1 atmosphere (approximately 10¹ Pa).

[0234] In the 51st embodiment according to the 50th aspect, the fluorinated ether is of formula (II):

[0235] [ka]

[0236] It is a compound of which, in the formula, R 3a H, -O-(C1-C 10 Alkyl) or -O-(C1-C 10 Fluoroalkyl) and R 4a and R 5a Each of these independently is -O-(C1-C 10 Alkyl) or -O-(C1-C 10 It is a fluoroalkyl group.

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