Polymer electrolyte containing polyacrylamide and method for producing the same

Abstract

The present invention relates to a polymer electrolyte comprising a polymer backbone derived from dialkylacrylamide monomers that effectively encapsulates deep eutectic solvents (DES) and is compatible with high-potential electrodes. The present invention further relates to composite cathodes and electrochemical cells comprising the polymer electrolyte, and uses thereof.

Description

[Technical Field]

[0001] The present invention relates to a polymer electrolyte comprising a polymer network having a polyacrylamide backbone, which is particularly suitable for use with an electrolyte composition containing a deep eutectic solvent. The present invention further relates to a method for producing the polymer electrolyte, and to the use of the polymer electrolyte in electrochemical cells and the like. [Background technology]

[0002] In recent years, electronic products, electronic devices, and communication devices have become increasingly miniaturized and lightweight. Similarly, electric vehicles, which are emerging as an environmentally friendly means of transportation, are becoming more widespread. These factors have created a demand for higher performance secondary batteries used as power sources for these products. Furthermore, lithium-ion batteries are attracting attention as high-performance batteries due to their high energy density and high reference electrode potential.

[0003] Conventional lithium-ion batteries contain a liquid electrolyte, such as an organic solvent. A major drawback of liquid electrolytes is that the composition, particularly the solvent, is flammable, posing a significant safety risk during normal operation, especially in the event of an accident. Another drawback, inherent to the liquid nature of the electrolyte, is the increased risk of leakage and, in the event of spillage or leakage, the risk of environmental contamination.

[0004] In recent years, efforts have been made to develop solid electrolytes that enable the provision of solid lithium-ion batteries. Such solid batteries significantly reduce EHS (environment, health, and safety) risks. Conventional solid electrolytes may include oxide-based solid electrolytes, polymer-based solid electrolytes, and sulfide-based electrolytes. Polymer-based electrolytes are commonly used because they are less flammable, highly flexible, have excellent thermal stability, and are safer.

[0005] The difficulty in developing solid electrolytes with high ionic conductivity, a broad electrochemical window, and mechanical / thermal stability has led to the concept of solid-liquid composite materials such as solid-composite electrolytes (SCEs).

[0006] These electrolytes include a liquid lithium-ion conductive electrolyte encapsulated within a solid skeleton or network. Examples include ionic liquids confined within an inorganic (e.g., silica) or polymer (e.g., poly(ethylene glycol) diacrylate (PEODA)) solid skeleton.

[0007] A major challenge in the manufacture of solid composite electrolytes is the selection of a polymer skeleton that is stable to sol-gel synthesis and can effectively encapsulate the liquid lithium-ion electrolyte. Furthermore, it is difficult to develop solid composite electrolytes that are compatible with high-potential cathode materials such as NMC622 or NMC811 and exhibit satisfactory anode stability. For example, PEO (polyethylene oxide), the most common solid polymer electrolyte, has anode stability limited to a potential of about 4.0 V vs. Li + / Li.

[0008] Energy Environ.Sci.,2021,14,931-939 contemplates the use of alkali metal bis(trifluoromethane)-sulfonimide (TFSI) salts in polymer electrolytes containing an N-isopropylacrylamide (NIPAM) polymer skeleton.

[0009] Chem.Mater.2020,32,3783-3793 contemplates the use of lithium bis(trifluoromethane)-sulfonimide lithium salt (LiTFSI) and N-methylacetamide (MAc)-based deep eutectic solvents in polymer electrolytes containing an ethylene glycol 4-acryloylmorpholine (AcMo) skeleton.

[0010] U.S. Patent Application Publication No. 2020 / 0343586 (A1) contemplates the use of various deep eutectic solvents in polymer electrolytes containing various polymer skeletons. A polymer electrolyte containing lithium bis(trifluoromethane)-sulfonimide lithium salt (LiTFSI) and an N-methylacetamide (MAc)-based deep eutectic solvent in a polymer network containing an acrylate skeleton is exemplified.

Prior Art Documents

[0011] [Patent Document 1] U.S. Patent Application Publication No. 2020 / 0343586(A1) [Non-patent literature]

[0012] [Non-Patent Document 1] Energy Environ.Sci.,2021,14,931-939 [Non-Patent Document 2] Chem.Mater.2020,32,3783-3793 [Overview of the project] [Problems that the invention aims to solve]

[0013] The object of the present invention is to provide a polymer electrolyte comprising a polymer network compatible with a deep eutectic solvent.

[0014] A further object of the present invention is to provide a polymer electrolyte that is compatible with high-voltage cathode active materials, particularly NMC622.

[0015] A further object of the present invention is to provide a polymer electrolyte having high anodic stability.

[0016] A further object of the present invention is to provide a polymer electrolyte having good mechanical flexibility. [Means for solving the problem]

[0017] [Overview of the prefecture] The inventors have found that polymer electrolytes comprising a polymer network based on specific N-dialkyl(meth)acrylamide monomers effectively encapsulate deep eutectic solvents (DES) and, surprisingly, are compatible with the high-potential electrode active materials described herein. As shown in the accompanying examples, the polymer electrolytes described herein have been found to exhibit excellent cycle stability when combined with high-potential electrode active materials such as NMC622. Furthermore, the inventors have found that while the polymer electrolytes can be conveniently pre-synthesized, they can also be synthesized in the presence of a cathode active material to provide a composite cathode material. One or more of the objects of the present invention are achieved by different embodiments of the present invention described herein.

[0018] Therefore, in a first aspect of the present invention, a polymer electrolyte comprising an electrolyte composition and a polymer network, wherein the electrolyte composition preferably comprises a deep eutectic solvent (DES), and the polymer electrolyte comprises the electrolyte composition and formula (I): [ka] [In the formula, R 1 and R 2 Each of these is independently selected from C1-C6 alkyl groups. R 3 [Selected from H, methyl, or ethyl] Obtained by polymerization of a precursor composition containing a first monomer by However, preferably, a polymer electrolyte is provided in which the monomer according to formula (I) is not N,N-dimethylacrylamide.

[0019] The precursor composition typically further comprises a first crosslinking agent. Preferably, the first crosslinking agent is allyl (-CH3-CH=CH2), oxyranyl (-C2H3O), glycidyl (-CH2-C2H3O), vinyl ether (-O-CH=CH2), vinyl ester (-C(O)-O-CH=CH2), vinylamide (-C(O)-NH-CH=CH2), vinylamine (-NH-CH=CH2), norbornene, maleate, fumarate, itaconate, or alkynyl [ka] The first crosslinking agent is selected from a crosslinking agent comprising two or more functional groups selected from the group consisting of styrene (-Ph-CH=CH2), acrylamide (-NH-C(O)-CH=CH2), methacrylamide (-NH-C(O)-C(CH3)=CH2), acrylate (-OC(O)-CH=CH2), methacrylate (-OC(O)-C(CH3)=CH2), and combinations thereof. Preferably, the first crosslinking agent is selected from a crosslinking agent comprising two or more functional groups selected from acrylamide (-NH-C(O)-CH=CH2), methacrylamide (-NH-C(O)-C(CH3)=CH2), acrylate (-OC(O)-CH=CH2), methacrylate (-OC(O)-C(CH3)=CH2), and combinations thereof.

[0020] In another embodiment, the present invention relates to a method for preparing a polymer electrolyte, (a) A step of preparing a precursor composition comprising an electrolyte composition and a first monomer according to formula (I) described herein, wherein the electrolyte composition preferably comprises a deep eutectic solvent (DES), (b) A preparation method is provided, comprising the step of polymerizing the precursor composition.

[0021] In another embodiment, the present invention provides a composite cathode comprising the polymer electrolyte of the present invention.

[0022] In another embodiment, the present invention provides an electrochemical cell comprising a polymer electrolyte according to the present invention.

[0023] In another aspect of the present invention, the use of a polymer electrolyte according to the present invention as an electrolyte for an electrochemical cell is provided.

[0024] In another aspect of the present invention, a battery, more specifically a lithium-ion battery or a lithium-metal battery, is provided, comprising at least one electrochemical cell containing a polymer electrolyte as described herein, for example, two or more electrochemical cells according to the present invention.

[0025] Another aspect of the present invention provides a method for manufacturing or operating stationary applications such as cars, computers, personal digital assistants, mobile phones, watches, camcorders, digital cameras, thermometers, calculators, laptop BIOSes, communication devices, remote car locks, and energy storage devices for power plants, by using at least one battery or at least one electrochemical cell comprising the polymer electrolyte material described herein.

[0026] Another aspect of the present invention provides the use of an electrochemical cell comprising the polymer electrolyte of the present invention in a motorized vehicle, an electric motor-operated bicycle, a robot, an aircraft (e.g., an unmanned aerial vehicle including a drone), a ship, a satellite, or a fixed energy storage device. [Brief explanation of the drawing]

[0027] [Figure 1] This shows anodic sweep voltammetry performed on the polymer electrolyte of Comparative Example 1. [Figure 2] The anodic sweep voltammetry performed on the polymer electrolyte of Comparative Example 2 is shown. [Figure 3] This shows anodic sweep voltammetry performed on the polymer electrolyte of Example 1. [Figure 4] This shows anodic sweep voltammetry performed on the polymer electrolyte of Example 2. [Figure 5] The EIS characteristics (impedance per 6-hour rest period) of a symmetric cell containing an NMC622 electrode and the polymer electrolyte of Comparative Example 1 are shown. [Figure 6] The EIS characteristics (impedance per 6-hour rest period) of a symmetric cell containing the NMC622 electrode and the polymer electrolyte of Comparative Example 2 are shown. [Figure 7] The EIS characteristics (impedance per 6-hour rest period) of a symmetric cell containing an NMC622 electrode and the polymer electrolyte from Example 1 are shown. [Figure 8] The EIS characteristics (impedance per 6-hour rest period) of a symmetric cell containing an NMC622 electrode and the polymer electrolyte from Example 2 are shown. [Figure 9] The cycle capacities of cells containing NMC622 and Li electrodes, along with the electrolytes of Comparative Examples 1 and 2, are shown. The discharge capacity is the average of the three cells for each C rate. The capacity is normalized with respect to the mass of the positive electrode active material. [Figure 10] The cycle capacities of cells containing NMC622 and Li electrodes, along with the electrolytes of Examples 1 and 2, are shown. The discharge capacity is the average of three cells for each C rate. The capacity is normalized with respect to the mass of the positive electrode active material. [Modes for carrying out the invention]

[0028] The following detailed description details preferred embodiments for realizing the implementation of the present invention. While the present invention is described with reference to these specific preferred embodiments, it will be understood that the present invention is not limited to these preferred embodiments. However, in contrast, the present invention includes a number of substitutes, variations, and equivalents, as will become apparent when considering the modes for carrying out the invention described below.

[0029] The terms “comprise” and its variations thereof, such as “comprises” and “comprising,” as used herein should be interpreted in an open and comprehensive sense, meaning that the embodiments described include the enumerated features but do not exclude the presence of other features insofar as they would render the embodiments unfeasible.

[0030] Expressions used herein such as “one embodiment,” “a particular embodiment,” and “an embodiment” should be interpreted as meaning that the specific features, structures, or characteristics described in relation to that embodiment are included in at least one embodiment. Therefore, the appearance of such expressions in various places throughout this specification does not necessarily all refer to the same embodiment. Furthermore, specific features, structures, or characteristics can be combined in any preferred manner in one or more embodiments. For example, it is expressly assumed that certain features of this disclosure described herein in the context of a separate embodiment may also be combined into a single embodiment.

[0031] As used herein, the singular forms "a," "an," and "the" should be interpreted as referring to multiple objects unless explicitly indicated otherwise. Furthermore, it should be noted that the term "or" is generally used in its broadest sense, meaning "and / or" unless explicitly indicated otherwise.

[0032] As used herein, the term “cathode active material” is also interchangeably referred to as “positive electrode active material.” As those skilled in the art will understand, the cathode polarity can be positive or negative depending on the operating mode of the electrochemical cell containing the cathode active material. As used herein and in the claims, the terms “cathode active material” or “positive electrode active material” are defined as a material that is electrochemically active at the positive electrode or cathode. An active material should be understood as a material that can capture and release Li ions when exposed to a voltage change over a given period of time.

[0033] As used herein, the term "(meth)acrylamide" should be interpreted as "methacrylamide, acrylamide, or a combination thereof." For example, N-dialkyl(meth)acrylamide should be interpreted as "N-dialkylmethacrylamide, N-dialkylacrylamide, or a combination thereof."

[0034] In the context of the composition of the cathode active material, the parameters x, y, z, and a referred to herein are measured by inductively coupled plasma optical emission spectrometry (ICP-OES).

[0035] The ionic conductivity referred to herein is the ionic conductivity determined by electrochemical impedance spectroscopy (EIS) (using Biologic SP-300) of a polymer electrolyte in a symmetric stainless steel|electrolyte|stainless steel swagelok-type cell at a specific temperature by perturbing the open circuit potential with an AC sine wave potential of 10 mV amplitude in the frequency range of 10 kHz to 100 mHz.

[0036] The "anode stability limit" referred to herein is determined by linear sweep voltammetry of a polymer electrolyte sandwiched between a stainless steel working electrode and a lithium metal reference and counter electrode in a coin cell setup (preferably using Bio-Logic, SP-300), and the voltage of the working electrode is swept from the open circuit potential to 6 V with respect to Li -1 / Li at a scan rate of 10 mV s + The stability limit is determined as the onset of oxidation of the electrolyte, which can be observed by a sharp increase in the measured current.

[0037] <The polymer electrolyte of the present invention> In a first aspect of the present invention, a polymer electrolyte comprising an electrolyte composition and a polymer network, wherein the electrolyte composition preferably comprises a deep eutectic solvent (DES), and the polymer electrolyte is obtained by polymerizing a precursor composition comprising the electrolyte composition and a first monomer according to formula (I),

[0038] [Chemical formula] [Wherein, R 1 and R 2 are each independently selected from C1-C6 alkyl, R 3[Selected from H, methyl, or ethyl] However, preferably, a polymer electrolyte is provided in which the monomer according to formula (I) is not N,N-dimethylacrylamide.

[0039] The polymer networks referred to in this disclosure are three-dimensional networks obtained by polymerization of one or more monomers according to formula (I) in the presence of a crosslinking agent. Such three-dimensional polymer networks are also called gels, and the polymer electrolytes of the present invention are also called “gel polymer electrolytes.” For the purposes of this disclosure, a gel polymer refers to a polymer network (i.e., a three-dimensional crosslinking system) that does not exhibit flow in a steady state but allows diffusion of a liquid phase through the polymer network. Preferably, the gel is self-supporting. Such gels typically exhibit a combination of flexibility, mechanical robustness, low vapor pressure, and preferably non-flammability.

[0040] As those skilled in the art will understand based on this disclosure, the electrolyte composition is contained within a polymer network. The electrolyte composition is typically confined within the polymer network, meaning that there is substantially no spontaneous flow of the electrolyte composition from the polymer electrolyte of the present invention when placed on a surface (e.g., a ceramic laboratory bench) without external pressure. In all aspects of the present invention, the electrolyte composition in the absence of a polymer network is very preferably liquid at 20°C.

[0041] In a preferred embodiment, R 1 and R 2 These are the same, preferably R 1 and R 2 The present invention provides a polymer electrolyte in which both are ethyl. In a preferred embodiment, R 3 is selected from H or methyl, preferably R 3 is H. Therefore, in a very preferred embodiment, R 1 and R 2 These are the same, preferably R 1 and R 2 Both are ethyl, R3 is selected from H or methyl, preferably R 3 A polymer electrolyte of the present invention is provided, wherein is H. In all embodiments of the present invention, it is preferable that the monomer according to formula (I) is not N,N-dimethylacrylamide.

[0042] In a preferred embodiment of the present invention, the first monomer constitutes at least 80 mol%, preferably at least 90 mol%, and more preferably at least 95 mol% of all monomers in the precursor composition. In a very preferred embodiment of the present invention, the first monomer constitutes at least 98 mol%, 99 mol%, or about 100 mol% of all monomers in the composition. For the purpose of determining the total amount of monomers in the precursor composition, any compound polymerizable with the first monomer and having a functional value of 1 is considered a monomer, and the functional value is determined based on the acrylamide functional group and the free radical polymerizable functional group of the first monomer.

[0043] <Crosslinking agent> According to a preferred embodiment of the present invention, the precursor composition further comprises a first crosslinking agent. Since the first monomer (acrylamide according to formula (I)) is monofunctional, a three-dimensional polymer network can be formed by including the crosslinking agent in the precursor composition. The crosslinking agent can be selected from any compound that is polymerizable with the first monomer and has a functional value of 2 or more, the functional value being determined based on the acrylamide functional group and the free radical polymerizable functional group of the first monomer.

[0044] The first crosslinking agent is allyl (-CH3-CH=CH2), oxyranyl (-C2H3O), glycidyl (-CH2-C2H3O), vinyl ether (-O-CH=CH2), vinyl ester (-C(O)-O-CH=CH2), vinylamide (-C(O)-NH-CH=CH2), vinylamine (-NH-CH=CH2), norbornene, maleate, fumarate, itaconate, or alkynyl [ka] Preferably, the first crosslinking agent is selected from a crosslinking agent containing two or more functional groups selected from the group consisting of styrene (-Ph-CH=CH2), acrylamide (-NH-C(O)-CH=CH2), methacrylamide (-NH-C(O)-C(CH3)=CH2), acrylate (-OC(O)-CH=CH2), methacrylate (-OC(O)-C(CH3)=CH2), and combinations thereof. In some embodiments of the present invention, the first crosslinking agent comprises two, three, or four functional groups selected from the functional groups described in the preceding sentence, but preferably the first crosslinking agent comprises two of the same or different functional groups selected from the functional groups described in the preceding sentence.

[0045] Examples of preferred, and therefore preferred, embodiments of the first crosslinking agent include allyl methacrylate, allyl acrylate, glycidyl methacrylate, ethylene glycol dicyclopentyl ether methacrylate, ethylene glycol dicyclopentyl ether acrylate, triethylene glycol divinyl ether, poly(ethylene glycol) diacrylamide, poly(ethylene glycol) dimethacrylate, poly(ethylene glycol) diacrylate, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate Triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, propanediol dimethacrylate, propanediol diacrylate, 1,4-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol dimethacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,10-bis(acryloyloxy)decane, 1,12-dodecanediol dimethacrylate, 1,12-Dodecanediol diacrylate, poly(silicone-alt-PEG) dimethacrylate, poly(silicone-alt-PEG) diacrylate, poly(propylene glycol) dimethacrylate, poly(propylene glycol) diacrylate, bisphenol A propoxylate dimethacrylate, bisphenol A propoxylate diacrylate, neopentyl glycol propoxylate dimethacrylate, neopentyl glycol propoxylate diacrylate, glycerol ethoxylate-co-propoxylate dimethacrylate, glycerol ethoxylate -co-propoxylate diacrylate, propylene glycol dimethacrylate, propylene glycol diacrylate, polycaprolactone dimethacrylate, polycaprolactone diacrylate, pentaerythritol propoxylate dimethacrylate, pentaerythritol propoxylate diacrylate, tri(propylene glycol) dimethacrylate, tri(propylene glycol) diacrylate, diurethane dimethacrylate (DUDMA), 1,3,5-trialyl-2,4,6(1H,3H,5H)-trione, 2,4,6-trialyloxy-1,3,5,Triazine, trimethylolpropanepropoxylate trimethacrylate, trimethylolpropanepropoxylate triacrylate, glycerolpropoxylate trimethacrylate, glycerolpropoxylate triacrylate, polycaprolactone trimethacrylate (PCLTMA), polycaprolactone triacrylate, tris-(4-hydroxyphenyl)ethane trimethacrylate, tris-(4-hydroxyphenyl)ethane triacrylate, trimethylolpropaneethoxylate trimethacrylate, trimethylolpropaneethoxylate triacrylate, glycerolethoxylate trimethacrylate, glycerolethoxylate triacrylate, pentaerythritolethoxylate trimethacrylate, pentaerythritolethoxylate triacrylate, ethylenediaminetetrakis(ethoxylate-block-propoxylate)tetramethacrylate Rate, ethylenediaminetetrakis(ethoxylate-block-propoxylate)tetraacrylate, and pentaerythritol propoxylate tetramethacrylate, pentaerythritol propoxylate tetraacrylate, N,N'-methylenebisacrylamide, N,N'-methylenebismethacrylamide, N,N'-ethylenebisacrylamide, N,N'-ethylenebismethacrylamide, N,N'-propylenebisacrylamide, N,N'-Propylenebismethacrylamide, N,N'-Butylenebisacrylamide, N,N'-Butylenebismethacrylamide, N,N'-Pentylenebisacrylamide, N,N'-Pentylenebismethacrylamide, N,N'-Hexylenebisacrylamide, N,N'-Hexylenebismethacrylamide, N,N'-Heptylenebisacrylamide, N,N'-Octylenebisacrylamide, N,N'-octylenebismethacrylamide and combinations thereof are selected. In preferred embodiments of the present invention, the first crosslinking agent is selected from poly(ethylene glycol) dimethacrylate, poly(ethylene glycol) diacrylate, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, propanediol dimethacrylate, propanediol diacrylate, 1,4-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol dimethacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,10-bis(acryloyloxy ) Decane, 1,12-dodecanediol dimethacrylate, 1,12-dodecanediol diacrylate, N,N'-methylenebisacrylamide, N,N'-methylenebismethacrylamide, N,N'-ethylenebismethacrylamide, N,N'-ethylenebismethacrylamide, N,N'-propylenebisacrylamide, N,N'-propylenebismethacrylamide, N,N'-butylenebisacrylamide, N,N'-butyl The first crosslinking agent is selected from ethylene glycol dimethacrylate, ethylene glycol diacrylate, N,N'-methylenebisacrylamide, N,N'-methylenebismethacrylamide, N,N'-hexylenebisacrylamide, N,N'-hexylenebismethacrylamide, N,N'-heptylenebisacrylamide, N,N'-heptylenebismethacrylamide, N,N'-octylenebisacrylamide, N,N'-octylenebismethacrylamide, and combinations thereof. In a very preferred embodiment of the present invention, the first crosslinking agent is selected from ethylene glycol dimethacrylate, ethylene glycol diacrylate, N,N'-methylenebisacrylamide, N,N'-methylenebismethacrylamide, and combinations thereof.

[0046] In some embodiments of the present invention, the first crosslinking agent is selected from a compound according to formula (IIa), a compound according to formula (IIb), or a combination thereof.

[0047] [ka] [In the formula, R 4 , R 5 , R 6 , and R 7 Each is independently selected from H, methyl, or ethyl. R 8 and R 9 Each is independently selected from H or methyl, X is an alkanediyl or polyoxyalkylene, preferably X is (-CH2-) m or -CH2-CH2(-O-CH2-CH2) o -and, Y is an alkanediyl or polyoxyalkylene, preferably Y is (-CH2-) n or -CH2-CH2(-O-CH2-CH2) p -and, m is an integer in the range of 1 to 10. n is an integer in the range of 1 to 10. o is an integer in the range of 1 to 200. p is an integer between 1 and 200.

[0048] As shown in the attached examples, these crosslinking agents were found to have excellent compatibility with the first monomer, resulting in polymer electrolytes with desirable electrochemical and mechanical properties.

[0049] In a preferred embodiment of the present invention, X is (-CH2-) m Selected from the above, where m is in the range of 1 to 6, preferably in the range of 1 to 4, and more preferably m is equal to 2.

[0050] In a preferred embodiment of the present invention, Y is (-CH2-) nSelected from the above, where n is in the range of 1 to 6, preferably in the range of 1 to 4, and more preferably n is equal to 1.

[0051] As those skilled in the art will understand, X is -CH2-CH2(-O-CH2-CH2) o - or Y is -CH2-CH2(-O-CH2-CH2) p -If so, the compounds of formula (IIa) or (IIb) are actually provided in the form of mixtures of compounds with different degrees of ethoxylation and therefore different numbers of o and p. The precursor composition comprises one or more crosslinking agents according to formula (IIa), where X is -CH2-CH2(-O-CH2-CH2) o -If this is the case, the number mean o determined for all compounds of formula (IIa) in the precursor composition is preferably in the range of 1 to 200, more preferably in the range of 2 to 20. Similarly, the precursor composition contains one or more crosslinking agents according to formula (IIb), where Y is -CH2-CH2(-O-CH2-CH2) p -If this is the case, the number mean p determined for all compounds of formula (IIb) in the precursor composition is preferably in the range of 1 to 200, more preferably in the range of 2 to 20.

[0052] The precursor composition may generally contain additional crosslinking agents other than the first crosslinking agent. However, in some preferred embodiments of the present invention, the first crosslinking agent is the only crosslinking agent present. Generally, the average functional value determined across all crosslinking agents in the precursor composition is preferably in the range of 2 to 3, preferably 2 to 2.5, and most preferably 2 to 2.2. For the purpose of determining this average functional value, any compound that is polymerizable with the first monomer and has a functional value of 2 or more is considered a crosslinking agent, and the functional value is determined based on the acrylamide functional group and the free radical polymerizable functional group of the first monomer.

[0053] As those skilled in the art will understand, the amount of crosslinking agent used in the precursor composition affects the mechanical and electrochemical properties of the resulting polymer electrolyte. In preferred embodiments of the present invention, the first crosslinking agent is included in the precursor composition in such an amount that the molar ratio of the total amount of the first monomer to the total amount of the first crosslinking agent in the precursor composition is in the range of 99.5:0.5 to 80:20, preferably in the range of 98:2 to 80:20, and more preferably in the range of 95:5 to 85:15. If the precursor composition contains further additional crosslinking agents other than the first crosslinking agent, the total amount of crosslinking agents in the precursor composition is preferably in the range of 99.5:0.5 to 80:20, preferably in the range of 98:2 to 80:20, and more preferably in the range of 95:5 to 85:15. For the purpose of determining this total amount of crosslinking agent, any compound that is polymerizable with the first monomer and has a functional value of 2 or more is considered a crosslinking agent, and the functional value is determined based on the acrylamide functional group and the free radical polymerizable functional group of the first monomer.

[0054] According to a preferred embodiment of the present invention, the precursor composition further comprises one or more radical initiators, preferably one or more radical initiators selected from thermal initiators, photoinitiators, and combinations thereof.

[0055] Suitable radical thermal initiators include benzoyl peroxide, dibenzoyl peroxide, succinate peroxide, dilauroyl peroxide, didecanoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, di-t-amyl peroxide, α,α'-di(t-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-di-(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di-( t-butylperoxy)hexine-3, t-butylcumyl peroxide, α-cumyl peroxyneodecanoate, α-cumyl peroxyneopeptanoate, t-amyl peroxyneodecanoate, t-butylperoxyneodecanoate, di-(2-ethylhexyl)peroxy-dicarbonate, t-amyl peroxypivalate, t-butyl peroxypivalate, 2,5-dimethyl-2 ,5-bis(2-ethyl-hexanoylperoxy)hexane, dibenzoyl peroxide, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, 1,1-di-(t-amylperoxy)cyclohexane, 1,1-di-(t-butylperoxy)3,3,5-trimethylcyclohexane, 1,1-di-(t-butylperoxy)cyclohexane, OO-t-amyl-O(2-ethylhex Sil) monoperoxycarbonate, OO-t-butyl O-isopropyl monoperoxycarbonate, OO-t-butyl O-(2-ethylhexyl) monoperoxycarbonate, t-amyl peroxybenzoate, t-butyl peroxyacetate, t-butyl peroxybenzoate, ethyl 3,3-di-(t-amyl peroxy)butyrate, ethyl 3,3-di-(t-butyl peroxy)butyrate, dicumyl peroxide;Furthermore, azo compounds, such as 4,4'-azobis(4-cyanovaleric acid), 1,1'-azobis(cyclohexanecarbonitrate), azobisisobutyronitrile (AIBN), and 2,2'-azobis(2-methylpropionamidine)dihydrochloride, 2,2'-azobis[2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propanedisulfate dihydrate, 2,2'-azobis(2-methylpropionamidine)dihydrochloride, and 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]hydrate Examples include, but are not limited to, 2,2'-azobis{2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane}dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis(1-imino-1-pyrrolidino-2-ethylpropane)dihydrochloride, 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide}, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], cumenehydroperoxide, and ammonium persulfate.

[0056] Suitable radical photoinitiators include benzophenone (e.g., "IRGACURE 500"), 3-methylbenzophenone, 2-methylbenzophenone, 3,4-dimethylbenzophenone, 3-hydroxybenzophenone, 4-hydroxybenzophenone, 4,4'-dihydroxybenzophenone, 4-benzoylbenzoic acid, 2-benzoylbenzoic acid, methyl 2-benzoyl benzoate, 4,4'-carbonyl diphthalic anhydride, methylbenzoyl formate (e.g., "DAROCURE MBF"), 1-hydroxycyclohexyl phenyl ketone (e.g., "IRGACURE 184"), 2-hydroxy-2-methyl-1-phenyl-1-propanone (e.g., "DAROCURE 1173"), and 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone (e.g., "IRGACURE 2,2-(2,2-dimethoxy-2-phenylacetoxy-ethoxy)-ethyl ester and 2,2-hydroxy-ethoxy)-ethyl ester (e.g., "IRGACURE 754"), α,α-dimethoxy-α-phenylacetophenone (also known as 2,2-dimethoxy-2-phenylacetophenone (DMPA), e.g., "IRGACURE 651"), 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone (e.g., "IRGACURE 369"), 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl-1-propanone, e.g., "IRGACURE 907"), diphenyl(2,4,6-trimethylbenzoyl)-phosphine oxide (e.g., "IRGACURE 754") TPO"), phosphine oxide, phenylbis(2,4,6-trimethylbenzoyl) (e.g., "IRGACURE 819"), bis(η5-2,4-cyclopentadiene-1-yl)bis[2,6-Difluoro-3-(1H-pyrrole-1-yl)phenyl]titanium (e.g., "IRGACURE 784"), 1-hydroxy-cyclohexyl-phenyl-ketone (e.g., "IRGACURE 184"), 2-hydroxy-2-methyl-1-phenyl-1-propanone (e.g., "DAROCURE 1173"), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one (e.g., "IRGACURE 127"), 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone (e.g., "IRGACURE 2959"), phenylglyoxylate, oxy-phenyl-acetoxyethoxy]ethyl ester, oxy-phenyl-acetoxyethyl ester, phenylglyoxylate methyl ester (e.g., "DAROCUR MBF"), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (e.g., "LUCIRIN TPO"), 2,4,6-trimethylbenzoyl-diphenylphosphine (e.g., "LUCIRIN TPO-L"), liquid blend of acylphosphine oxide (e.g., "IRGACURE 2100"), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (e.g., "IRGACURE 819"), titanocene, bis(η5-2,4-cyclopentadiene-1-yl)bis[2,[6-Difluoro-3-(1H-pyrrole-1-yl)phenyl] (e.g., "IRGACURE 784"), [1-(4-phenylsulfanylbenzoyl)heptylideneamino]benzoate (e.g., "IRGACURE OXE 01"), [1-[9-ethyl-6-(2-methylbenzoyl)carbazole-3-yl]ethylideneamino]acetate (e.g., "IRGACURE OXE 02"), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (e.g., "IRGACURE 907"), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (e.g., "IRGACURE 369"), 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholine-4-ylphenyl)-butan-1-one (e.g., "IRGACURE 379"), benzyldimethylketal, 2,2-dimethoxy-1,2-diphenylethane-1-one (e.g., "IRGACURE 651"), camphorquinone, acetophenone, 4'-hydroxyacetophenone, 3'-hydroxyacetophenone, 4-(dimethylamino)-benzophenone, 4,4'-bis(dimethylamino)-benzophenone, 4,4'-bis(diethylamino)-benzophenone, 4,4'-dichlorobenzophenone, 4-phenylbenzophenone, 1,4-dibenzoylbenzene, 4-(p-tolylthio)-benzophenone, dibenzosverenone, benzyl, p-anisyl, methylbenzoylformate, 9,10-phenanthrenequinone, 2-benzoyl- 2-Propanol, 2-Hydroxy-4'-(2-Hydroxyethoxy)-2-Methylpropiophenone, 1-Benzylcyclohexanol, Benzoin, Anisoin, Benzoin Methyl Ether, Benzoin Ethyl Ether, Benzoin Isopropyl Ether, Benzoin Isobutyl Ether, 2,2-Diethoxyacetophenone, Benzyldimethylketal, 2-Methyl-4'-(Methylthio)-2-Molfolinopropiophenone, 2-Benzyl-2-(Dimethylamino)-4'-Molfolinobylophenone, 2-Isonitrosopropiophenone, 9,Examples include, but are not limited to, 10-phenanthrenequinone, 2-ethylanthraquinone, sodium anthraquinone-2-sulfonate, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthene-9-one, 2,7-dimethyloxythioxanthone, 2,2'-bis(2-chlorophenyl)4,4',5,5'-tetraphenyl-1,2'-biimidazole, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, lithium phenyl-(2,4,6-trimethylbenzoyl)phosphine, and ferrocene.

[0057] In some embodiments of the present invention, the precursor composition further comprises one or more radical initiators selected from 2,2-dimethoxy-2-phenylacetophenone (DMPA), azobisisobutyronitrile (AIBN), and combinations thereof.

[0058] Preferably, one or more radical initiators are used in an amount such that the molar ratio of the total amount of the first monomer in the precursor composition to the total amount of one or more radical initiators in the precursor composition is in the range of 99.8:0.2 to 80:20, preferably in the range of 99:1 to 85:15, and more preferably in the range of 98:2 to 90:10.

[0059] <Electrolyte composition> As those skilled in the art will understand, to obtain a gel-type polymer electrolyte, it is preferable that the polymer is synthesized in the presence of an electrolyte composition, thereby effectively encapsulating the electrolyte composition within the polymer network. However, without being bound by any theory, other methods for obtaining the polymer electrolyte described herein may be realized, for example, by exchanging the electrolyte composition with another liquid composition (e.g., a solvent) encapsulated in the polymer, by absorbing the electrolyte composition into a pre-formed polymer network, or by injecting the electrolyte composition into a pre-formed polymer network. Accordingly, according to the present invention, a polymer electrolyte can be obtained by polymerizing a precursor composition comprising an electrolyte composition and other components (monomers, crosslinkers, initiators, etc.) discussed throughout this disclosure. In all aspects of the present invention, it is very preferable that the electrolyte composition, in the absence of a polymer network, is liquid at 20°C.

[0060] As shown in the attached examples, the inventors have found that deep eutectic solvent (DES)-filled polymer electrolytes exhibit exceptional performance, particularly when combined with high-potential cathode active materials such as NMC622. Therefore, according to a very preferred embodiment of the present invention, the electrolyte composition comprises or consists of a deep eutectic solvent (DES). The deep eutectic solvent is preferably liquid at 20°C.

[0061] It has been found that various relative amounts of DES to the polymer result in functional electrolytes. The precursor composition preferably contains about 45-95 vol% (relative to the total volume of the precursor composition), preferably about 55-90 vol%, and more preferably 70-90 vol% of deep eutectic solvent (DES). It has been found that precursor compositions having about 85 vol% of DES provide excellent ionic conductivity and mechanical properties (increased flexibility). Therefore, in a very preferred embodiment of the present invention, the precursor composition contains about 75-90 vol% (relative to the total volume of the precursor composition), preferably about 80-90 vol%, and most preferably about 83-87 vol% of deep eutectic solvent (DES). The remainder of the precursor composition consists of a first monomer, optionally further monomers, a first crosslinking agent, optionally further crosslinking agents, one or more radical initiators, and optionally further components. In some embodiments, the remainder of the precursor composition essentially consists of a first monomer, optionally further monomers, a first crosslinking agent, optionally further crosslinking agents, and one or more radical initiators.

[0062] The deep eutectic solvent (DES) preferably has a eutectic point of 25°C or lower, preferably 15°C or lower, and more preferably 0°C or lower. In a very preferred embodiment of the present invention, the deep eutectic solvent (DES) has a eutectic point of -15°C or lower, most preferably -25°C or lower. This allows the DES to remain in a liquid state over the typical operating temperature window of electrochemical cells for common applications such as automobiles. The eutectic point referred to herein is determined by a pressure of about 101 kPa.

[0063] The deep eutectic solvent (DES) preferably comprises at least one hydrogen bond acceptor and at least one hydrogen bond donor. The molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is preferably at least 1:1, more preferably at least 1:2, and more preferably at least 1:3. In a preferred embodiment of the present invention, the electrolyte composition comprises or comprises (preferably comprises) a deep eutectic solvent (DES) comprising at least one hydrogen bond acceptor and at least one hydrogen bond donor, and the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is in the range of 1:1 to 1:8, preferably in the range of 1:2 to 1:6, and more preferably in the range of 1:3 to 1:5. A very preferred molar ratio of the hydrogen bond acceptor to the hydrogen bond donor (especially when the hydrogen bond acceptor is lithium bis(trifluoromethanesulfonyl)imide as described elsewhere in this specification, and / or when the hydrogen bond donor is N-methylacetamide as described elsewhere in this specification) is in the range of 1:3.5 to 1:4.5, for example, about 1:4.

[0064] In preferred embodiments of the present invention, the hydrogen bond acceptor comprises a lithium salt, a zinc salt, or a combination thereof, preferably a lithium salt. In a more preferred embodiment, the hydrogen bond acceptor is selected from the group consisting of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium trifluoromethanesulfonate (LiOTf), lithium chloride (LiCl), lithium hexafluorophosphate (LiPF6), lithium polysulfide, lithium perchlorate (LiClO4), lithium bromide (LiBr), lithium iodide (LiI), lithium thiocyanate (LiSCN), lithium tetrafluoroborate (LiBF4), lithium hexafluoroarsenate (LiAsF6), lithium bis(oxalate)borate (LiBOB), lithium fluoroalkyl phosphate (LFAP[LiPF3(CF2CF3)3]), and combinations thereof, preferably lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and / or the hydrogen bond donor is urea, N-methylurea, N,N-dimethylurea, N,N'-di Methylurea, N,N,N'-trimethylurea, thiourea, N-methylthiourea, N,N-dimethylthiourea, N,N'-dimethylthiourea, N,N,N'-trimethylthiourea, ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,4-diol, 1,2,3-propanetriol, acetic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanediic acid, dodeca The substance is selected from the group consisting of benzoic acid, benzoic acid, glycolic acid, citric acid, 2-hydroxypropionic acid, 2-hydroxyisobutyric acid, o-phenylenediamine, corynchloride, acetamide, N-methylacetamide, trifluoroacetamide, N-methyltrifluoroacetamide, benzamide, benzenesulfonic acid, p-toluenesulfonic acid, o-toluenesulfonic acid, m-toluenesulfonic acid, and combinations thereof, and is preferably N-methylacetamide.

[0065] Accordingly, in some embodiments of the present invention, the electrolyte composition comprises a deep eutectic solvent (DES) containing, preferably comprising, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and N-methylacetamide, wherein the molar ratio of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) to N-methylacetamide is in the range of 1:1 to 1:8, preferably in the range of 1:2 to 1:6, more preferably in the range of 1:3 to 1:5, for example, about 1:4.

[0066] The electrolyte composition preferably contains at least 90% by weight (relative to the total weight of the electrolyte composition), preferably at least 95% by weight, and more preferably at least 99% by weight of DES. In some embodiments, the electrolyte composition contains water, for example, 0.1 to 30% by weight (relative to the total weight of the electrolyte composition), or 0.1 to 10% by weight (relative to the total weight of the electrolyte composition). In other preferred embodiments, the electrolyte composition contains less than 5% by weight of water, preferably less than 0.1% by weight, and more preferably less than 0.01% by weight. In some embodiments, the electrolyte composition is substantially water-free. The latter is particularly preferred for use in combination with moisture-sensitive electrodes such as Li or graphite. In all embodiments described herein, the electrolyte composition preferably consists of a deep eutectic solvent (DES).

[0067] As those skilled in the art will understand, in the context of this disclosure, the precursor composition mainly consists of the electrolyte composition described herein in combination with the first monomer, the first crosslinking agent, and one or more initiators described herein. Accordingly, according to preferred embodiments of the present invention, the precursor composition comprises at least 90% by weight (relative to the total weight of the precursor composition), preferably at least 95% by weight (relative to the total weight of the precursor composition), and more preferably at least 99% by weight (relative to the total weight of the precursor composition) of the total amount of the electrolyte composition, the first monomer, optionally further monomers, the first crosslinking agent, optionally further crosslinking agents, and one or more radical initiators. In some embodiments, the precursor composition comprises at least 90% by weight (relative to the total weight of the precursor composition), preferably at least 95% by weight (relative to the total weight of the precursor composition), and more preferably at least 99% by weight (relative to the total weight of the precursor composition) of the total amount of the electrolyte composition, the first monomer, the first crosslinking agent, and one or more radical initiators. As previously described herein, any compound polymerizable with the first monomer and having a functional value of 1 is considered a monomer, and any compound polymerizable with the first monomer and having a functional value of 2 or more is considered a crosslinking agent, the functional value being determined based on the acrylamide functional group and the free radical polymerizable functional group of the first monomer. Accordingly, according to preferred embodiments of the present invention, the polymer electrolyte comprises at least 90% by weight (relative to the total weight of the polymer electrolyte), more preferably at least 98% by weight (relative to the total weight of the polymer electrolyte), and most preferably at least 99% by weight (relative to the total weight of the polymer electrolyte), the total weight of the polymer network and the electrolyte composition. In some embodiments, the polymer electrolyte essentially consists of the polymer network and the electrolyte composition.

[0068] In a preferred embodiment of the present invention, at least Li + 4.6V relative to Li, preferably Li + A polymer electrolyte is provided that has an anodic stability limit of at least 4.7V relative to Li.

[0069] <Method for preparing polymer electrolytes according to the present invention> In another embodiment, the present invention relates to a method for preparing a polymer electrolyte, (i) the step of providing the precursor composition described herein, (ii) A preparation method is provided, comprising the step of polymerizing the precursor composition.

[0070] The embodiments described herein relating to polymer electrolytes are applicable mutatis mutandis to methods for preparing polymer electrolytes. For example, the various embodiments relating to the identification and quantities of monomers, crosslinkers, initiators, and electrolyte compositions described herein in the context of polymer electrolytes are equally applicable to methods for preparing polymer electrolytes.

[0071] In a preferred embodiment of the method for preparing a polymer electrolyte, the precursor composition comprises one or more radical initiators as described herein, and step (ii) comprises activating the radical initiators. Activation is preferably carried out by UV irradiation of the precursor composition or by heating the precursor composition to a temperature of at least 50°C, preferably at least 60°C. Step (ii) is preferably carried out in an inert gas atmosphere, preferably an inert atmosphere such as nitrogen or argon.

[0072] In some embodiments of the present invention, step (ii) includes (ii)a contacting a precursor composition with a cathode active material, and (ii)b polymerizing the precursor composition in the presence of the cathode active material. Step (ii) preferably includes mixing the precursor composition with a cathode active material which is preferably granular, or depositing the precursor composition on the surface of a porous cathode active material. The contact is preferably carried out for at least 1 minute before polymerization so that complete mixing or impregnation can be achieved. In this way, a composite cathode comprising the polymer electrolyte and the cathode active material of the present invention can be obtained.

[0073] The cathode active material may be any cathode active material, preferably a cathode active material suitable for secondary lithium-ion batteries.

[0074] As shown in the attached examples, the inventors have found that polymer electrolytes exhibit surprisingly good electrochemical performance when used in combination with high-potential cathode active materials. Therefore, the cathode active material is preferably Li + At least 4.3V relative to Li, preferably Li + / At least 4.4V relative to Li, more preferably Li + The cathode active material has an upper limit cutoff voltage of at least 4.5V for / Li. The cathode active material is preferably a cathode active material comprising Li, M, and O, where M comprises Ni, and one or both of Mn and Co, preferably M is - Ni with content x such that 50.0 mol% ≤ x ≤ 95.0 mol%, preferably 55.0 mol% ≤ x ≤ 95.0 mol%, - Mn with content y such that 0.0 mol% ≤ y ≤ 40.0 mol%, - Co with a content z such that 0.0 mol% ≤ z ≤ 40.0 mol%, - It contains D with a content of a such that 0.0 mol% ≤ a ≤ 2.0 mol%, where D is at least one element other than Li, Ni, Mn, Co, and O. - x+y+z+a is 100.0 mol%, More preferably, M is - Ni with content x such that 50.0 mol% ≤ x ≤ 85.0 mol%, - Mn with content y such that 7.5 mol% ≤ y ≤ 25.0 mol%, - Co with a content z such that 7.5 mol% ≤ z ≤ 25.0 mol%, - It contains D with a content of a such that 0.0 mol% ≤ a ≤ 2.0 mol%, where D is at least one element other than Li, Ni, Mn, Co, and O. - x+y+z+a is 100.0 mol%, More preferably, M is - Ni with content x such that 55.0 mol% ≤ x ≤ 80.0 mol%, - Mn with content y such that 10.0 mol% ≤ y ≤ 30.0 mol%, - Co with a content z such that 10.0 mol% ≤ z ≤ 30.0 mol%, - It contains D with a content of a such that 0.0 mol% ≤ a ≤ 2.0 mol%, where D is at least one element other than Li, Ni, Mn, Co, and O. - x+y+z+a is 100.0 mol%, More preferably, M is - Ni with content x such that 55.0 mol% ≤ x ≤ 75.0 mol%, - Mn with content y such that 12.5 mol% ≤ y ≤ 22.5 mol%, - Co with a content z such that 12.5 mol% ≤ z ≤ 22.5 mol%, - It contains D with a content of a such that 0.0 mol% ≤ a ≤ 2.0 mol%, where D is at least one element other than Li, Ni, Mn, Co, and O. - x+y+z+a is 100.0 mol%, Most preferably, M is - Ni with content x such that 55.0 mol% ≤ x ≤ 70.0 mol%, - Mn with content y such that 15.0 mol% ≤ y ≤ 22.5 mol%, - Co with a content z such that 15.0 mol% ≤ z ≤ 22.5 mol%, - It contains D with a content of a such that 0.0 mol% ≤ a ≤ 2.0 mol%, where D is at least one element other than Li, Ni, Mn, Co, and O. - x+y+z+a is 100.0 mol%.

[0075] As is known to those skilled in the art, NMC cathode active materials may contain impurities or be doped or coated to result in an overall cathode active material containing one or more elements other than Li, Ni, Mn, Co, and O, which is reflected in the parameter "D" as used herein. In preferred embodiments of the present invention, D is an element selected from the group consisting of Al, B, Ba, Ca, Cr, Fe, Mg, Mo, Nb, S, Si, Sr, Ti, Y, V, W, Zr, and Zn; preferably Al, B, Cr, Nb, S, Si, Ti, Y, Zr, and W; more preferably an element selected from the group consisting of B, Nb, Ti, Zr, and W.

[0076] Suitable cathode active materials include NMC532, NMC622, and NMC811, preferably NMC622 or NMC811, and more preferably NMC622.

[0077] <Composite cathode containing the polymer electrolyte of the present invention> In another aspect of the present invention, a composite cathode is provided comprising a polymer electrolyte as described herein and a cathode active material as described herein.

[0078] The embodiments described herein relating to polymer electrolytes are applicable mutatis mutandis to composite cathodes containing polymer electrolytes. For example, the various embodiments relating to the identification and quantities of monomers, crosslinkers, initiators, and electrolyte compositions described herein in the context of polymer electrolytes are equally applicable to methods for preparing polymer electrolytes.

[0079] The cathode active material contained in the composite cathode may be any cathode active material, preferably a cathode active material suitable for secondary lithium-ion batteries.

[0080] As shown in the attached examples, the inventors have found that polymer electrolytes exhibit surprisingly good electrochemical performance when used in combination with high-potential cathode active materials. Therefore, the cathode active material is preferably Li + At least 4.3V relative to Li, preferably Li + / At least 4.4V relative to Li, more preferably Li + The cathode active material has an upper limit cutoff voltage of at least 4.5V for / Li. The cathode active material is preferably a cathode active material comprising Li, M, and O, where M comprises Ni, and one or both of Mn and Co, preferably M is - Ni with content x such that 50.0 mol% ≤ x ≤ 95.0 mol%, preferably 55.0 mol% ≤ x ≤ 95.0 mol%, - Mn with content y such that 0.0 mol% ≤ y ≤ 40.0 mol%, - Co with a content z such that 0.0 mol% ≤ z ≤ 40.0 mol%, - It contains D with a content of a such that 0.0 mol% ≤ a ≤ 2.0 mol%, where D is at least one element other than Li, Ni, Mn, Co, and O. - x+y+z+a is 100.0 mol%, More preferably, M is - Ni with content x such that 50.0 mol% ≤ x ≤ 85.0 mol%, - Mn with content y such that 7.5 mol% ≤ y ≤ 25.0 mol%, - Co with a content z such that 7.5 mol% ≤ z ≤ 25.0 mol%, - It contains D with a content of a such that 0.0 mol% ≤ a ≤ 2.0 mol%, where D is at least one element other than Li, Ni, Mn, Co, and O. - x+y+z+a is 100.0 mol%, More preferably, M is - Ni with content x such that 55.0 mol% ≤ x ≤ 80.0 mol%, - Mn with content y such that 10.0 mol% ≤ y ≤ 30.0 mol%, - Co with a content z such that 10.0 mol% ≤ z ≤ 30.0 mol%, - It contains D with a content of a such that 0.0 mol% ≤ a ≤ 2.0 mol%, where D is at least one element other than Li, Ni, Mn, Co, and O. - x+y+z+a is 100.0 mol%, More preferably, M is - Ni with content x such that 55.0 mol% ≤ x ≤ 75.0 mol%, - Mn with content y such that 12.5 mol% ≤ y ≤ 22.5 mol%, - Co with a content z such that 12.5 mol% ≤ z ≤ 22.5 mol%, - It contains D with a content of a such that 0.0 mol% ≤ a ≤ 2.0 mol%, where D is at least one element other than Li, Ni, Mn, Co, and O. - x+y+z+a is 100.0 mol%, Most preferably, M is - Ni with content x such that 55.0 mol% ≤ x ≤ 70.0 mol%, - Mn with content y such that 15.0 mol% ≤ y ≤ 25.0 mol%, - Co with a content z such that 15.0 mol% ≤ z ≤ 25.0 mol%, - It contains D with a content of a such that 0.0 mol% ≤ a ≤ 2.0 mol%, where D is at least one element other than Li, Ni, Mn, Co, and O. - x+y+z+a is 100.0 mol%.

[0081] As is known to those skilled in the art, NMC cathode active materials may contain impurities or be doped or coated to result in an overall cathode active material containing one or more elements other than Li, Ni, Mn, Co, and O, which is reflected in the parameter "D" as used herein. In preferred embodiments of the present invention, D is an element selected from the group consisting of Al, B, Ba, Ca, Cr, Fe, Mg, Mo, Nb, S, Si, Sr, Ti, Y, V, W, Zr, and Zn; preferably Al, B, Cr, Nb, S, Si, Ti, Y, Zr, and W; more preferably an element selected from the group consisting of B, Nb, Ti, Zr, and W.

[0082] Suitable cathode active materials include NMC532, NMC622, and NMC811, preferably NMC622 or NMC811, and more preferably NMC622.

[0083] A composite cathode may comprise a homogeneous mixture of cathode active material particles and polymer electrolyte particles. The homogeneous mixture may comprise further components. Alternatively, the composite cathode may comprise a polymer electrolyte coated on and / or at least partially embedded in the cathode active material. Such a composite cathode can be obtained by a polymer electrolyte preparation method described herein earlier, wherein step (ii) comprises (ii)a contacting a precursor composition with a cathode active material and (ii)b polymerizing the precursor composition in the presence of a cathode active material.

[0084] A desired but preferred additional component of the composite cathode of the present invention is a conductive additive, particularly a carbon-based conductive additive. The carbon-based conductive additive may be any carbon-rich material, for example, any material containing at least 95% by weight of carbon, preferably any material containing at least 99% by weight of carbon. Examples of suitable materials are graphite, carbon black, carbon fibers, carbon nanotubes, graphene, and combinations thereof. Carbon black is known to those skilled in the art and includes variants, such as acetylene black or super C65.

[0085] In preferred embodiments, the carbon-based conductive additive described herein is present in the solid composite cathode composition of the present invention in an amount of at least 0.5% by weight (relative to the total weight of the polymer electrolyte and cathode active material), preferably at least 1% by weight (relative to the total weight of the polymer electrolyte and cathode active material), and more preferably at least 3% by weight (relative to the total weight of the polymer electrolyte and cathode active material). Typically, the carbon-based conductive additive is present in an amount of less than 12% by weight (relative to the total weight of the polymer electrolyte and cathode active material), preferably less than 9% by weight (relative to the total weight of the polymer electrolyte and cathode active material), and more preferably less than 7% by weight (relative to the total weight of the polymer electrolyte and cathode active material).

[0086] In another aspect of the present invention, a composite cathode is provided which can be obtained by a polymer electrolyte preparation method described herein earlier, wherein step (ii) comprises the steps of (ii)a contacting a precursor composition with a cathode active material and (ii)b polymerizing the precursor composition in the presence of a cathode active material.

[0087] Another desired but preferred additional component of the composite cathode of the present invention is a binder. In some embodiments of the present invention, the solid composite cathode of the present invention further comprises a binder, for example, a polymer binder. The binder is not particularly limited and may be any suitable polymer binder, such as polyimide (PI), polyvinylidene chloride (PVdC), polyethylene oxide (PEO), polyvinylidene fluoride (PVdF), etc.

[0088] <Electrochemical cell containing the polymer electrolyte of the present invention> In another aspect of the present invention, an electrochemical cell comprising the polymer electrolyte of this specification is provided.

[0089] The embodiments described herein relating to polymer electrolytes are applicable mutatis mutandis to electrochemical cells containing polymer electrolytes. For example, the various embodiments relating to the identification and quantities of monomers, crosslinkers, initiators, and electrolyte compositions described herein in the context of polymer electrolytes are equally applicable to electrochemical cells containing polymer electrolytes.

[0090] The electrochemical cell preferably comprises an anode, a cathode, and an electrolyte.

[0091] The anode comprises an anode active material. Suitable electrochemically active anode materials are known in the art. For example, the anode may include graphite carbon, metallic lithium, or a metallic alloy containing lithium as the anode active material.

[0092] The cathode contains a cathode active material. The cathode active material may be any cathode active material, preferably a cathode active material suitable for secondary lithium-ion batteries.

[0093] As shown in the attached examples, the inventors have found that polymer electrolytes exhibit surprisingly good electrochemical performance when used in combination with high-potential cathode active materials. Therefore, the cathode active material is preferably Li + At least 4.3V relative to Li, preferably Li + / At least 4.4V relative to Li, more preferably Li + The cathode active material has an upper limit cutoff voltage of at least 4.5V for / Li. The cathode active material is preferably a cathode active material comprising Li, M, and O, where M comprises Ni, and one or both of Mn and Co, preferably M is - Ni with content x such that 50.0 mol% ≤ x ≤ 95.0 mol%, preferably 55.0 mol% ≤ x ≤ 95.0 mol%, - Mn with content y such that 0.0 mol% ≤ y ≤ 40.0 mol%, - Co with a content z such that 0.0 mol% ≤ z ≤ 40.0 mol%, - It contains D with a content of a such that 0.0 mol% ≤ a ≤ 2.0 mol%, where D is at least one element other than Li, Ni, Mn, Co, and O. - x+y+z+a is 100.0 mol%, More preferably, M is - Ni with content x such that 50.0 mol% ≤ x ≤ 85.0 mol%, - Mn with content y such that 7.5 mol% ≤ y ≤ 25.0 mol%, - Co with a content z such that 7.5 mol% ≤ z ≤ 25.0 mol%, - It contains D with a content of a such that 0.0 mol% ≤ a ≤ 2.0 mol%, where D is at least one element other than Li, Ni, Mn, Co, and O. - x+y+z+a is 100.0 mol%, More preferably, M is - Ni with content x such that 55.0 mol% ≤ x ≤ 80.0 mol%, - Mn with content y such that 10.0 mol% ≤ y ≤ 30.0 mol%, - Co with a content z such that 10.0 mol% ≤ z ≤ 30.0 mol%, - It contains D with a content of a such that 0.0 mol% ≤ a ≤ 2.0 mol%, where D is at least one element other than Li, Ni, Mn, Co, and O. - x+y+z+a is 100.0 mol%, More preferably, M is - Ni with content x such that 55.0 mol% ≤ x ≤ 80.0 mol%, - Mn with content y such that 12.5 mol% ≤ y ≤ 22.5 mol%, - Co with a content z such that 12.5 mol% ≤ z ≤ 22.5 mol%, - It contains D with a content of a such that 0.0 mol% ≤ a ≤ 2.0 mol%, where D is at least one element other than Li, Ni, Mn, Co, and O. - x+y+z+a is 100.0 mol%, Most preferably, M is - Ni with content x such that 55.0 mol% ≤ x ≤ 70.0 mol%, - Mn with content y such that 15.0 mol% ≤ y ≤ 22.5 mol%, - Co with a content z such that 15.0 mol% ≤ z ≤ 22.5 mol%, - It contains D with a content of a such that 0.0 mol% ≤ a ≤ 2.0 mol%, where D is at least one element other than Li, Ni, Mn, Co, and O. - x+y+z+a is 100.0 mol%.

[0094] As is known to those skilled in the art, NMC cathode active materials may contain impurities or be doped or coated to result in an overall cathode active material containing one or more elements other than Li, Ni, Mn, Co, and O, which is reflected in the parameter "D" as used herein. In preferred embodiments of the present invention, D is an element selected from the group consisting of Al, B, Ba, Ca, Cr, Fe, Mg, Mo, Nb, S, Si, Sr, Ti, Y, V, W, Zr, and Zn; preferably Al, B, Cr, Nb, S, Si, Ti, Y, Zr, and W; more preferably an element selected from the group consisting of B, Nb, Ti, Zr, and W. Suitable cathode active materials include NMC532, NMC622, and NMC811, preferably NMC622 or NMC811, and more preferably NMC622.

[0095] A desired but preferred additional component of the cathode contained in the electrochemical cell of the present invention is a conductive additive, particularly a carbon-based conductive additive. The carbon-based conductive additive may be any carbon-rich substance, for example, any substance containing at least 95% by weight of carbon, preferably any substance containing at least 99% by weight of carbon. Examples of suitable substances are graphite, carbon black, carbon fibers, carbon nanotubes, graphene, and combinations thereof. Carbon black is known to those skilled in the art and includes varieties such as acetylene black or super C65.

[0096] In preferred embodiments, the carbon-based conductive additive described herein is present in the cathode of the electrochemical cell of the present invention in an amount of at least 0.5% by weight (relative to the total weight of the cathode), preferably at least 1% by weight (relative to the total weight of the cathode), and more preferably at least 3% by weight (relative to the total weight of the cathode). Typically, the carbon-based conductive additive is present in an amount of less than 12% by weight (relative to the total weight of the cathode), preferably less than 9% by weight (relative to the total weight of the cathode), and more preferably less than 7% by weight (relative to the total weight of the cathode).

[0097] In some embodiments of the present invention, the cathode contained in the electrochemical cell of the present invention further comprises a binder, such as a polymer binder. The binder is not particularly limited and may be any suitable polymer binder, such as polyimide (PI), polyvinylidene chloride (PVdC), polyethylene oxide (PEO), polyvinylidene fluoride (PVdF), etc.

[0098] In a preferred embodiment of the present invention, the electrochemical cell includes the polymer electrolyte of the present invention, which is arranged in contact with the cathode active material.

[0099] For example, an electrochemical cell may include the polymer electrolyte of the present invention, which is positioned in contact between the anode and the cathode.

[0100] For example, an electrochemical cell may contain the polymer electrolyte of the present invention in the form of a coating on the anode and / or cathode.

[0101] For example, an electrochemical cell may comprise the polymer electrolyte and cathode active material of the present invention in the form of a composite cathode as described earlier herein. In such embodiments, the electrochemical cell preferably comprises a further electrolyte disposed between the composite cathode and the anode, which may be the polymer electrolyte of the present invention or another electrolyte.

[0102] The polymer electrolyte of the present invention, having a gel-like viscosity, is considered a solid electrolyte for the purposes of this disclosure. As will be understood by those skilled in the art, it can also function as a separator in an electrochemical cell.

[0103] The electrochemical cells described herein preferably have Li as the charge transporter. + This is a lithium-ion-containing cell that operates using ions. The electrochemical cell may have a disc-shaped or prismatic shape. The electrochemical cell may include a housing that can be made from steel or aluminum. Multiple electrochemical cells can be combined to form an all-solid-state battery having both solid electrodes and a solid electrolyte.

[0104] In a particularly preferred embodiment, the cathode active material described herein is the only cathode active material contained in the cathode of an electrochemical cell.

[0105] <Method for manufacturing an electrochemical cell according to the present invention> In another aspect, the present invention relates to a method for manufacturing an electrochemical cell, (a) the step of providing a cathode, (b) the step of providing an anode, (c) A step of providing an electrolyte, (d) The step of forming an electrochemical cell by assembling a cathode, anode and polymer electrolyte, The present invention provides a method for producing an electrolyte comprising the polymer electrolyte of the present invention, and / or a cathode provided in the form of a composite cathode comprising the cathode active material and the polymer electrolyte of the present invention.

[0106] Embodiments described herein relating to electrochemical cells or polymer electrolytes are applicable mutatis mutandis to methods for manufacturing electrochemical cells. For example, various embodiments relating to the identification and quantities of monomers, crosslinkers, initiators, and electrolyte compositions described herein in the context of polymer electrolytes are equally applicable to methods for preparing electrochemical cells.

[0107] <Use of polymer electrolytes according to the present invention> In another aspect of the present invention, the use of the polymer electrolyte described herein as an electrolyte for an electrochemical cell is provided.

[0108] The embodiments described herein relating to polymer electrolytes are applicable mutatis mutandis to the use of polymer electrolytes. For example, the various embodiments relating to the identification and quantities of monomers, crosslinkers, initiators, and electrolyte compositions described herein in the context of polymer electrolytes are equally applicable to the use of polymer electrolytes.

[0109] The electrochemical cell is preferably the electrochemical cell described herein in the context of another aspect of the present invention.

[0110] <Battery containing the electrochemical cell of the present invention and its use> Another aspect of the present invention relates to a battery, more specifically a lithium-ion battery or a lithium-metal battery, comprising at least one electrochemical cell containing the gel polymer electrolyte of the present invention, for example, two or more electrochemical cells as described herein.

[0111] The electrochemical cells described herein can be combined with each other, for example, in series or parallel connections. Series connections are preferred. The electrochemical cells or batteries described herein can be used to manufacture or operate stationary applications such as cars, computers, personal digital assistants, mobile phones, watches, camcorders, digital cameras, thermometers, calculators, laptop BIOS, communication equipment, satellites, or remote car locks, and energy storage devices for power plants.

[0112] A further aspect of the present invention is a method for manufacturing or operating stationary applications such as cars, computers, personal digital assistants, mobile phones, watches, camcorders, digital cameras, thermometers, calculators, laptop BIOSes, communication equipment, satellites, remote car locks, and energy storage devices for power plants, by using at least one battery or at least one electrochemical cell as described herein, comprising the polymer electrolyte of the present invention.

[0113] A further aspect of the present invention is the use of an electrochemical cell or battery according to this specification, comprising the polymer electrolyte of the present invention, in a motorized vehicle, an electric motor-operated bicycle, a robot, an aircraft (e.g., an unmanned aerial vehicle including a drone), a ship, a satellite, or a fixed energy storage device.

[0114] A further aspect of the present invention is a method for supplying power to a device, wherein the power is supplied by an electrochemical cell or battery as described herein, comprising the polymer electrolyte of the present invention, wherein the electrochemical cell or battery, preferably the electrochemical cell, operates at a voltage greater than 4.4V, preferably greater than 4.5V, more preferably greater than 4.6V, for example greater than 4.7V. The device may be any battery-powered device, but is preferably selected from stationary applications such as motorized vehicles, computers, personal digital assistants, mobile phones, watches, camcorders, digital cameras, thermometers, calculators, laptop BIOS, communication equipment, satellites, remote car locks, and energy storage devices for power plants, as well as electric motor-driven bicycles, robots, aircraft (e.g., unmanned aerial vehicles including drones), ships, and satellites.

[0115] The present invention further provides a device comprising at least one battery or electrochemical cell as described herein, comprising the polymer electrolyte of the present invention. Preferred are mobile devices such as vehicles, e.g., automobiles, bicycles, aircraft, satellites, or water vehicles, e.g., boats or ships. Other examples of mobile devices are portable devices, e.g., computers, especially laptops, telephones, or power tools from the construction sector, e.g., especially drills, battery-powered screwdrivers, or battery-powered tackers. [Examples]

[0116] 1. Preparation of materials An electrolyte composition consisting of a deep eutectic solvent (DES) was prepared by mixing lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and N-methylacetamide in a molar ratio of 1:4 and vigorously stirring until a homogeneous, clear liquid was obtained. The precursor composition was prepared by mixing the monomers, crosslinking agents, and free radical initiators shown in Table 1 into a premix with a molar ratio of (monomer:crosslinking agent):initiator of (90:10):5, and then adding DES to the premix in a volume ratio of DES:premix of 85:15. The resulting mixture was stirred to obtain a homogeneous blend and polymerized under UV irradiation (365 nm) for 1 hour.

[0117] Cathode containing NMC622 as cathode active material (LiNi 0.6 Mn 0.2 Co 0.2 O2) is 80% by weight LiNi 0.6 Mn 0.2 Co 0.2 The slurry was prepared by mixing O2, 10% by weight of carbon black, and 10% by weight of poly(vinylidene fluoride) (PVDF) in N-methyl-2-pyrrolidone (NMP). The thoroughly mixed slurry was tape-cast onto aluminum foil and dried in air at 110°C to a thickness of approximately 18.7 μm and a yield of 0.622 mg / cm². -2 An electrode with an active material filling amount of 0.109 mAh cm was obtained (0.109 mAh cm). -2 The theoretical capacity of the NMC622 is 175mAh g -1 (Assuming...)

[0118] For use in coin cells, the polymer electrolyte and cathode were cut to the appropriate size using a hollow punch. The Li|polymer electrolyte|NMC622 cell was assembled by placing the positive electrode in front of the Li foil negative electrode, separated by a P-ETG between them.

[0119] [Table 1]

[0120] 2. Determination of electrochemical properties The ionic conductivity was determined by electrochemical impedance spectroscopy (EIS) (using Biologic SP-300) of polymer electrolytes in symmetric stainless steel | electrolyte | stainless steel Swagelok-type cells at specific temperatures by perturbing the open-circuit potential with an AC sinusoidal potential of 10 mV amplitude in the frequency range of 10 kHz to 100 mHz.

[0121] The anode stability limit was determined in a coin cell setup by linear sweep voltammetry (using Bio-Logic, SP-300) of a polymer electrolyte sandwiched between a stainless steel working electrode and lithium metal reference and counter electrodes, with the working electrode voltage set to 10 mV s. -1 With this scan speed, the anode scan will show Li from the open-circuit potential. + The voltage was swept up to 6V for / Li. The stability limit was determined as the onset of electrolyte oxidation, which can be observed by a rapid increase in the measurement current. Although not bound by any theory, the inventors suggest that electrolyte oxidation occurs at TFSI - We believe it may originate from the oxidation of anions.

[0122] The electrochemical compatibility between polymer electrolytes and high-voltage cathode materials was studied using an electrochemical impedance spectrometer (EIS) on an NMC622|polymer electrolyte|NMC622 symmetric cell.

[0123] Cycle performance was determined using a TOYO battery cycler with Li|polymer electrolyte|NMC622 cells prepared as described above. The cells were Li + Before a constant current cycle of 3.0-4.3V for / Li, a 16-hour open-circuit potential (OCP) period was observed. The electrodes were connected to Li + The lithium ( / Li) was activated by two constant-current charge / discharge cycles at 3.0V to 4.3V with a capacitance of 20. The cycle protocol consisted of 5 cycles each at capacitance rates of 20, 10, 5, 2, and 1C, followed by 100 cycles at 10. Capacitance values ​​were normalized to the weight of the cathode active material (NMC), and the results were verified for reproducibility.

[0124] 3.Results The results of the electrochemical property evaluation of the polymer electrolyte of the present invention are shown in Figures 1 to 10 and Table 2.

[0125] Table 2 shows the excellent ionic conductivity of the polymer electrolyte according to the present invention at three different temperatures. Table 2 and Figures 1-4 also show the high anodic stability values ​​measured for the polymer electrolyte of the present invention, indicating that they can operate at high voltages. Table 2 also highlights the compatibility of the polymer electrolyte of the present invention with the NMC622 cathode active material, as can be derived from Figures 5-10.

[0126] Figures 5 to 8 show the EIS results in an NMC622|polymer electrolyte|NMC622 symmetric cell. For the polymer electrolyte of the present invention, there is no significant increase in charge transfer resistance Rct, which indicates that the NMC622|polymer electrolyte interface is chemically stable. Conversely, for the comparative example, it can be seen that the polymer electrolyte is not compatible with NMC622.

[0127] Figures 9 and 10 show the cycle capacity of the Li|polymer electrolyte|NMC622 cell, demonstrating the excellent compatibility of the polymer electrolyte of the present invention with high-potential cathode materials such as NMC622. This finding is particularly surprising considering the poor compatibility between the conventional polymer electrolytes and NMC622 in Comparative Examples 1 and 2.

[0128] [Table 2]

[0129] The polymer electrolytes of Comparative Examples 1 and 2, as well as Examples 1 and 2, were all found to be self-supporting and exhibit good mechanical flexibility.

[0130] Finally, it was found that the formulations of Examples 1 and 2 also yield polymer electrolytes with similar properties to those of Comparative Examples 1 and 2, particularly considering their large electrochemical window and compatibility with high-potential cathode materials such as NMC622.

Claims

1. A polymer electrolyte comprising an electrolyte composition and a polymer network, The electrolyte composition comprises a deep eutectic solvent (DES), The polymer electrolyte is the electrolyte composition and formula (I): 【Chemistry 1】 [In the formula, R １ and R ２ Each of them is independent of C １ ~C ６ Selected from alkyl groups, R ３ [Selected from H, methyl, or ethyl] Obtained by polymerizing a precursor composition containing a first monomer represented by , However, the polymer electrolyte is one in which the monomer represented by formula (I) is not N,N-dimethylacrylamide.

2. The polymer electrolyte according to claim 1, wherein the first monomer constitutes at least 80 mol% of all monomers in the precursor composition.

3. The polymer electrolyte according to claim 1, wherein the precursor composition further comprises a first crosslinking agent.

4. The first crosslinking agent is allyl (—CH ３ —CH═CH ２ ), oxiranyl (—C ２ H ３ O), glycidyl (—CH ２ —C ２ H ３ O), vinyl ether (—O—CH═CH ２ ), vinyl ester (—C(O)—O—CH═CH ２ ), vinyl amide (—C(O)—NH—CH═CH ２ ), vinyl amine (—NH—CH═CH ２ ), norbornene, maleate, fumarate, itaconate, alkynyl 【Chemistry 2】 , styrene (-Ph-CH=CH ２ ), acrylamide (-NH-C(O)-CH=CH ２ ), methacrylamide (-NH-C(O)-C(CH ３ ) = CH ２ ), acrylate (-O-C(O)-CH=CH ２ ), methacrylate (-O-C(O)-C(CH ３ ) = CH ２ The polymer electrolyte according to claim 3, selected from a crosslinking agent comprising two or more functional groups selected from the group consisting of ), and combinations thereof.

5. The polymer electrolyte according to claim 4, wherein the first crosslinking agent is selected from a compound according to the following formula (IIa), a compound according to the following formula (IIb), or a combination thereof: 【Transformation 3】 [In the formula, R ４ , R ５ , R ６ , and R ７ Each is independently selected from H, methyl, or ethyl. R ８ and R ９ Each is independently selected from H or methyl, X is an alkanediyl or polyoxyalkylene. Y is an alkanediyl or polyoxyalkylene. m is an integer in the range of 1 to 10. n is an integer in the range of 1 to 10. o is an integer in the range of 1 to 200. p is an integer between 1 and 200.

6. The polymer electrolyte according to claim 3, wherein the first crosslinking agent is included in the precursor composition in an amount such that the molar ratio of the total amount of the first monomer contained in the precursor composition to the total amount of the first crosslinking agent contained in the precursor composition is in the range of 99.5:0.5 to 80:

20.

7. The polymer electrolyte according to claim 1, wherein the precursor composition further comprises one or more radical initiators.

8. The polymer electrolyte according to claim 1, wherein the deep eutectic solvent (DES) has a eutectic point of 25°C or lower.

9. The polymer electrolyte according to claim 1, wherein the deep eutectic solvent (DES) comprises at least one hydrogen bond acceptor and at least one hydrogen bond donor, and the at least one hydrogen bond acceptor comprises a lithium salt, a zinc salt, or a combination thereof.

10. The at least one hydrogen bond acceptor is lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium trifluoromethanesulfonate (LiOTf), lithium chloride (LiCl), lithium hexafluorophosphate (LiPF) ６ ), lithium polysulfide, lithium perchlorate (LiClO ４ ), lithium bromide (LiBr), lithium iodide (LiI), lithium thiocyanate (LiSCN), lithium tetrafluoroborate (LiBF) ４ ), lithium hexafluoroarsenate (LiAsF ６ ), lithium bis(oxalate) borate (LiBOB), lithium fluoroalkyl phosphate (LFAP [LiPF ３ (CF ２ CF ３ ) ３ A polymer electrolyte according to claim 9, selected from the group consisting of ]), and combinations thereof.

11. The at least one hydrogen bond donor is urea, N-methylurea, N,N-dimethylurea, N,N'-dimethylurea, N,N,N'-trimethylurea, thiourea, N-methylthiourea, N,N-dimethylthiourea, N,N'-dimethylthiourea, N,N,N'-trimethylthiourea, ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,4-diol, 1,2,3-propanetriol, acetic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid A polymer electrolyte according to claim 9, selected from the group consisting of azelaic acid, sebacic acid, undecanediic acid, dodecanediic acid, benzoic acid, glycolic acid, citric acid, 2-hydroxypropionic acid, 2-hydroxyisobutyric acid, o-phenylenediamine, corynchloride, acetamide, N-methylacetamide, trifluoroacetamide, N-methyltrifluoroacetamide, benzamide, benzenesulfonic acid, p-toluenesulfonic acid, o-toluenesulfonic acid, m-toluenesulfonic acid, and combinations thereof.

12. The polymer electrolyte according to claim 1, wherein the precursor composition comprises 45 to 95% by volume (relative to the total volume of the precursor composition) of a deep eutectic solvent (DES).

13. R １ and R ２ and are the same, R ３ The polymer electrolyte according to claim 1, wherein is selected from H or methyl.

14. A method for producing a polymer electrolyte according to any one of claims 1 to 13, (a) the step of preparing the precursor composition according to any one of claims 1 to 13, (b) A method for producing the precursor composition, comprising the step of polymerizing the precursor composition.

15. Use of a polymer electrolyte according to any one of claims 1 to 13 as an electrolyte for an electrochemical cell.

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