By-product-free method for solid hybrid electrolytes

Abstract

The present disclosure relates to a hybrid electrolyte composition comprising an ion-conducting inorganic material and an in situ cross-linked matrix. Methods and devices comprising such compositions are also described herein. The hybrid electrolyte composition comprises about 60 wt % to about 95 wt % of the ion-conducting inorganic material and about 5 wt % to about 40 wt % of an in situ cross-linked matrix, the in situ cross-linked matrix having a binder and a plurality of cross-linking agents, the cross-linking agents forming thermally reversible bonds within the in situ cross-linked matrix, and the thermally reversible bonds do not produce by-products.

Description

[Technical Field]

[0001] (Integrated by reference) The PCT application is filed concurrently with this application as part of this application. Each application identified in the concurrently filed PCT application for which this application claims benefit or priority is incorporated herein by reference in its entirety for any purpose.

[0002] This disclosure relates to a hybrid electrolyte composition comprising an ion-conducting inorganic material and an in situ crosslinking matrix. Methods and apparatus comprising such compositions are also described herein. [Background technology]

[0003] Solid electrolytes offer various advantages over liquid electrolytes in primary and secondary batteries. For example, in lithium-ion secondary batteries, inorganic solid electrolytes may be less flammable than conventional liquid organic electrolytes. Solid electrolytes can also facilitate the use of lithium metal electrodes by suppressing dendrite formation. Solid electrolytes can also offer advantages such as high energy density, good cycle stability, and electrochemical stability under various conditions. However, there are various challenges to the large-scale commercialization of solid electrolytes. One challenge is maintaining contact between the electrolyte and the electrode. For example, inorganic materials such as inorganic sulfide glass and ceramics have high ionic conductivity (10) at room temperature. -4While they possess resistances greater than S / cm, these do not function as efficient electrolytes due to poor adhesion to electrodes during battery cycling. Another challenge is that glass and ceramic solid conductors are too brittle to be fabricated on a large scale into high-density thin films. This can result in high bulk electrolyte resistance due to excessive film thickness and dendrite formation due to the presence of voids that allow for dendrite penetration. Even relatively ductile sulfide glasses have mechanical properties that are not sufficient to fabricate glass into high-density thin films. Techniques to improve adhesion, such as the addition of solid polymer binders, tend to reduce ionic conductivity, making it particularly challenging to improve these mechanical properties without sacrificing ionic conductivity. It is not uncommon to observe a decrease in conductivity to less than one-tenth with the introduction of just 1 wt% of binder. Solid polymer electrolyte systems may have improved mechanical properties that facilitate adhesion and formation into thin films, but they may have low ionic conductivity at room temperature or insufficient mechanical strength.

[0004] For the large-scale production and commercialization of solid-state batteries, a material is needed that possesses high ionic conductivity at room temperature and is flexible enough to be processed into thin, high-density films without sacrificing ionic conductivity. [Overview of the Initiative]

[0005] This disclosure relates to a hybrid electrolyte composition. In a first embodiment, the composition comprises about 60 wt% to about 95 wt% of an ion-conducting inorganic material and about 5 wt% to about 40 wt% of an in situ crosslinked matrix.

[0006] In some embodiments, the ion-conducting inorganic material has lithium. In other embodiments, the ion-conducting inorganic material is a sulfide-based material.

[0007] In some embodiments, the in situ crosslinking matrix comprises a binder and a plurality of crosslinking agents. Non-limiting binders include polymer backbones, copolymer backbones, or graft copolymer backbones. Other non-limiting binders include perfluoroethers, epoxy, polybutadiene, poly(styrene-β-butadiene), polyolefins, polysiloxanes, polytetrahydrofuran, polystyrene, polyethylene, polybutylene, poly(styrene-butadiene-styrene) (SBS), poly(styrene-ethylene-butylene-styrene) (SEBS), poly(styrene-isoprene-styrene) (SIS), acrylonitrile butadiene rubber, ethylene propylene diene monomer polymers, and copolymers thereof.

[0008] In other embodiments, the binder includes a plurality of inorganic cages. Non-limiting inorganic cages include silica, silsesquioxane, hydride silsesquioxane, or partially condensed silsesquioxane. In some embodiments, the plurality of inorganic cages are (SiO 1.5 ) n This includes n being an integer of 8, 10, or 12. In certain embodiments, the crosslinking agent is (SiO 1.5 ) n Bonded to a silicon atom in the first inorganic cage containing (SiO 1.5 ) n It bonds to another silicon atom in the second inorganic cage, which contains it.

[0009] An in situ crosslinking matrix may have multiple crosslinking agents. In some embodiments, the crosslinking agents form thermoreversible bonds within the matrix, and these thermoreversible bonds do not produce byproducts. In certain embodiments, the thermoreversible bonds are formed by Diels-Alder cycloaddition, Huisgen cycloaddition, thiol-ene reactions, Michael addition, ring-opening reactions, or click chemistry reactions.

[0010] In another embodiment, the crosslinking agent is -L 1 -X1 -L 2 -,-L 1 -X 1 -L 2 -X 2 -L 3 - or (-L 1 )(-L 1a )X 1 -L 2 -X 2 (L 3 -)(L 3a -) has a structure of, L 1 L, 1a L, 2 L, 3 L, and 3a each of L independently includes an optionally substituted alkylene, an optionally substituted heteroalkylene, or an optionally substituted arylene, X 1 or X 2 each of which independently includes a Diels - Alder cycloaddition product, a Huisgen cycloaddition product, a thiol - ene reaction product, a Michael addition product, or a ring - opening reaction product.

[0011] In some embodiments, each of L 1 L, 1a L, 2 L, 3 L, and 3a each of L independently is an optionally substituted alkylene, an optionally substituted heteroalkylene, or an optionally substituted arylene. In other embodiments, each of L 1 L, 1a L, 2 L, 3 L, and 3a each of L independently is -Cy-, -Ak - Cy-, -Het - Cy-, -Cy - Ak-, -Cy - Het-, -Ak - Cy - Ak, -Het - Cy - Het-, -(Ar) a -, -(Ak) b -(O - Ak) a -, or -(Ak - O) b -(Ak) a-, where Cy is a divalent linker containing a heterocyclic or carbocyclic ring, Ak is an optionally substituted alkylene, Het is an optionally substituted heteroalkylene, Ar is an optionally substituted arylene, a is an integer from 1 to 10, and b is 0 or 1.

[0012] In other technologies, X 1 or X 2 Each of these independently contains a divalent linker comprising a thio, heterocyclic, or carbocyclic ring. In certain embodiments, X 1 or X 2 Each of them is independent, [ka] It is a part selected from the group consisting of X a is -C(R 1 )2-, -NR 1 -, -O-, or -S-, X b is =CR 1 -or -N-, X c is-[C(R 1 )2] c1 -, -NR 1 -, -O-, -S-, or -C(O)-O-, R 1 c1 is H or an optionally substituted alkyl group, c1 is an integer from 1 to 3, and the portion may be substituted with cyano, hydroxyl, halo, nitro, carboxyaldehyde, carboxyl, alkoxy, oxo, or alkyl groups.

[0013] In a second embodiment, the disclosure relates to a membrane comprising a hybrid electrolyte composition (e.g., any of those described herein). In some embodiments, the elastic modulus of the membrane is about 0.2 GPa to about 3 GPa.

[0014] In a third aspect, the present disclosure relates to a method for forming a hybrid electrolyte composition (for example, any of those described herein), comprising the steps of: preparing a mixture having a binder component bonded to a first linker containing a first reactive group and an ion-conductive inorganic material; and reacting the binder component with a binder to form an in situ crosslinked matrix.

[0015] In some embodiments, the method further comprises the steps of casting the hybrid electrolyte composition as a film and optionally repairing the film by heating it to a temperature of about 100°C to about 190°C.

[0016] In some embodiments, the binder includes a second reactant configured to react with the first reactant to form a thermoreversible bond within the matrix, the thermoreversible bond not producing byproducts. In certain embodiments, the first reactant and the second reactant react together to form a Diels-Alder cycloaddition product, a Huisgen cycloaddition product, a thiol-ene reaction product, a Michael addition product, or a ring-opening reaction product.

[0017] In other embodiments, the first reactive group and the second reactive group are selected from one of the following: a diene-dienophile pair, a 1,3-dipole-parent dipole pair, a thiol-and-optionally-substituted alkene pair, a thiol-and-optionally-substituted alkyne pair, a nucleophile-and-strained heterocyclyl electrophile pair, a nucleophile-and-optionally-substituted α,β-unsaturated carbonyl compound pair, or a nucleophile-and-optionally-substituted strained cyclic compound pair. In yet another embodiment, the first and second reactive groups are selected from the group consisting of optionally substituted 1,3-butadiene, optionally substituted alkene, optionally substituted alkyne, optionally substituted α,β-unsaturated aldehyde, optionally substituted unsaturated α,β-thioaldehyde, optionally substituted α,β-unsaturated ketone, optionally substituted azide, optionally substituted thiol, optionally substituted unsaturated cycloalkyl, optionally substituted unsaturated heterocyclyl, optionally substituted α,β-unsaturated imine, optionally substituted aldehyde, optionally substituted imine, optionally substituted nitroso compound, optionally substituted diazene, optionally substituted thioketone, optionally substituted α,β-unsaturated ketone, optionally substituted α,β-unsaturated aldehyde, optionally substituted anionic nucleophile, and optionally substituted strained epoxy.

[0018] The binder component can provide any useful binder and may contain any useful monomer. In some embodiments, the binder component contains a monomer bonded to the first linker containing the first reactive group. In other embodiments, the binder component is -[R M -(L * -R 1* )] n -Includes the structure, R M L is the monomer, * It is a divalent linker, R 1* is the first reactive group, and n is 1 to 10.

[0019] In other embodiments, the monomer may include a substituted styrene monomer, a substituted ethylene monomer, a substituted propylene monomer, a substituted butylene monomer, a substituted butadiene monomer, a substituted perfluoroalkane monomer, a substituted perfluoroether monomer, a substituted isoprene monomer, a substituted ethylidene norbornene monomer, or a substituted diene monomer.

[0020] In some embodiments, the binder component is -[R M1 ] n1 -[R M2 ] n2 -[R M3 -(L * -R 1* )] n3 -[R M4 ] n4 -Includes the structure, R M1 is the first monomer, R M2 is the second monomer, R M3 is the third monomer, R M4 is the fourth monomer, L * It is a divalent linker, R 1* is the first reactive group, where each of n1, n2, n3, and n4 is independently between 0 and 10, and at least one of n1, n2, n3, and n4 is not 0. In certain embodiments, the first monomer, the second monomer, the third monomer, and the fourth monomer include an optionally substituted styrene monomer, an optionally substituted ethylene monomer, an optionally substituted propylene monomer, an optionally substituted butylene monomer, an optionally substituted butadiene monomer, an optionally substituted perfluoroalkane monomer, an optionally substituted perfluoroether monomer, an optionally substituted isoprene monomer, an optionally substituted ethylidene norbornene monomer, or an optionally substituted diene monomer.

[0021] In other embodiments, the binder component includes an inorganic cage bonded to the first linker including the first reactive group. In certain embodiments, the binder component is R C -(L * -R 1* ) n having the structure of, where R C is the inorganic cage, L * is a divalent linker, R 1* is the first reactive group, and n is 8, 10, or 12. In some embodiments, R C is (SiO 1.5 ) n .

[0022] In any of the embodiments herein (e.g., in the binder component), at least one L * (divalent linker) is independently -Cy-, -Ak-Cy-, -Het-Cy-, -Cy-Ak-, -Cy-Het-, -Ak-Cy-Ak, -Het-Cy-Het-, -(Ar) a (-), -(Ak) b -(O-Ak) a (-), or -(Ak-O) b -(Ak) a (-), where Cy is a divalent linker including a heterocyclic or carbocyclic ring, Ak is an optionally substituted alkylene, Het is an optionally substituted heteroalkylene, Ar is an optionally substituted arylene, a is an integer from 1 to 10, and b is 0 or 1.

[0023] In any of the embodiments herein, R 1* (e.g., the first reactive group in the binder component) is selected from an optionally substituted diene, an optionally substituted unsaturated heterocyclyl, an optionally substituted α,β-unsaturated aldehyde, an optionally substituted α,β-unsaturated thioaldehyde, an optionally substituted α,β-unsaturated imine, an optionally substituted azide, or an optionally substituted thiol.

[0024] Any useful binder can be used to form an in situ crosslinked matrix. In some embodiments, the binder further comprises a third reactive group, where at least one of the first and second reactive groups reacts together to form a thermoreversible bond in the matrix, and another first reactive group and the third reactive group react together to form another thermoreversible bond. In certain embodiments, the second and third reactive groups are the same.

[0025] In some embodiments, the binder is R 2* -L * -R 3* It has a structure, R 2* is the second reactive group, L * It is a divalent linker, R 3* is the third reactive group. In a particular embodiment, R 2* and R 3* Each of these is independently selected from the group consisting of optionally substituted alkenes, optionally substituted alkynes, optionally substituted unsaturated cycloalkyls, optionally substituted heterocyclyls, optionally substituted imines, optionally substituted nitroso compounds, optionally substituted azo compounds, optionally substituted thioketones, optionally substituted thiophosphates, and optionally substituted thion oxide compounds.

[0026] In any embodiment of this specification (for example, in a binder), L * are independently -Cy-, -Ak-Cy-, -Het-Cy-, -Cy-Ak-, -Cy-Het-, -Ak-Cy-Ak, -Het-Cy-Het-, -(Ar) a -,-(Ak) b -(O-Ak) a -, or -(Ak-O) b -(Ak) a-, where Cy is a divalent linker containing a heterocyclic or carbocyclic ring, Ak is an optionally substituted alkylene, Het is an optionally substituted heteroalkylene, Ar is an optionally substituted arylene, a is an integer from 1 to 10, and b is 0 or 1.

[0027] In any embodiment of this specification, the thermoreversible bond is formed by a Diels-Alder cycloaddition reaction, a Huisgen cycloaddition reaction, a thiol-ene reaction, a Michael addition reaction, a ring-opening reaction, or a click chemistry reaction. In certain embodiments, the thermoreversible bond comprises a Diels-Alder cycloaddition product, a Huisgen cycloaddition product, a thiol-ene reaction product, a Michael addition product, or a ring-opening reaction product. In other embodiments, the thermoreversible bond comprises a thio, an optionally substituted heterocyclyl, or an optionally substituted cycloalkyl. In yet another embodiment, the thermoreversible bond is [ka] Includes a portion selected from the group consisting of X a is -C(R 1 )2-, -NR 1 -, -O-, or -S-, X b is =CR 1 -or -N-, X c is-[C(R 1 )2] c1 -, -NR 1 -, -O-, -S-, or -C(O)-O-, R 1 c1 is H or an optionally substituted alkyl group, c1 is an integer from 1 to 3, and the portion may be substituted with cyano, hydroxyl, halo, nitro, carboxyaldehyde, carboxyl, alkoxy, oxo, or alkyl groups.

[0028] In a fourth embodiment, the disclosure includes a battery comprising any composition or any membrane described herein.

[0029] In a fifth embodiment, the disclosure includes electrodes comprising any composition or film described herein.

[0030] In a sixth embodiment, the disclosure includes an electrode comprising an in situ crosslinked matrix, an electrochemically active material, and ion-conducting particles. In one embodiment, the electrode optionally comprises a carbon additive. In a particular embodiment, the carbon additive is an electron-conducting carbon-based additive (e.g., activated carbon, carbon nanotubes, graphene, graphite, carbon fibers, carbon black, or any of those described herein). In another embodiment, the electrode is an anode or a cathode. In yet another embodiment, the carbon additive is provided for the anode, the cathode, or both.

[0031] In some embodiments, the in situ crosslinking matrix comprises a binder and a plurality of crosslinking agents, the crosslinking agents forming thermoreversible bonds within the matrix, and the thermoreversible bonds do not generate byproducts.

[0032] In a seventh embodiment, the disclosure includes a composition comprising a separator having an ion-conducting inorganic material and a first in situ crosslinking matrix, and an electrode. In some embodiments, the electrode has a second in situ crosslinking matrix, and the first matrix and the second matrix comprise a binder and a plurality of crosslinking agents, the crosslinking agents forming thermally reversible bonds between the matrices, the thermally reversible bonds not producing byproducts.

[0033] In an eighth embodiment, the disclosure includes a method comprising the steps of preparing an electrode and a separator composition, and reacting the binder components of the electrode and the separator composition with a linker to form an in situ crosslinked matrix between the electrode and the separator composition. In some embodiments, the electrode and the separator composition each have a binder component bonded to a first linker containing a first reactant. In other embodiments, the linker includes a second reactant configured to react with the first reactant to form a thermoreversible bond in the matrix, the thermoreversible bond not producing byproducts. Further details are as follows: [Brief explanation of the drawing]

[0034] [Figure 1] A schematic diagram is shown providing non-limiting examples of crosslinking agents containing compounds (I-1) to (I-8). Such compounds may be thiols and alkenes / alkynes used in thiol-ene polymerization.

[0035] [Figure 2A] A schematic diagram is shown providing non-limiting examples of all-carbon dienes, including compounds (II-1) to (II-10), that can undergo the Diels-Alder reaction. [Figure 2B] A schematic diagram is shown providing non-limiting examples of heteroatom dienes, including compounds (II-11) to (II-14), that can undergo the Diels-Alder reaction.

[0036] [Figure 3A] A schematic diagram is shown providing non-limiting examples of all-carbon dienophiles, including compounds (III-1) to (III-11), that can undergo the Diels-Alder reaction. [Figure 3B] A schematic diagram is shown providing non-limiting examples of heteroatom dienophiles, including compounds (III-12) to (III-19) that can undergo the Diels-Alder reaction.

[0037] [Figure 4A]A schematic diagram is shown providing non-limiting examples of polymers having dienes / dienophiles as terminal groups in the polymer backbone. [Figure 4B] A schematic diagram is shown providing non-limiting examples of polymers having dienes / dienophiles in the main chain of the polymer backbone. [Figure 4C] A schematic diagram is shown providing a non-limiting example of a polymer having a diene / dienophile in a chain graft extending from the polymer backbone, in which the diene / dienophile can be directly incorporated during polymerization. [Figure 4D] A schematic diagram is shown providing non-limiting examples of polymers that can be post-functionalized to include dienes / dienophiles that modify the reactive groups.

[0038] [Figure 5] A schematic diagram is shown providing non-limiting examples of monomers and crosslinking agents containing compounds (V-1) to (V-7).

[0039] [Figure 6] This graph shows the thermogravimetric analysis (TGA) results for polystyrene-β-poly(ethylene-ran-butylene)-β-polystyrene-g-maleic anhydride (SEBS-gMA).

[0040] [Figure 7] This graph shows the Fourier transform infrared (FTIR) spectra of SEBS-gMA and furfuryl-modified SEBS (SEBS-gFA).

[0041] [Figure 8] This graph shows the proton nuclear magnetic resonance (1H NMR) spectra of SEBS-gMA (black) and SEBS-gFA (gray) obtained in CDCl3 using a 700MHz instrument.

[0042] [Figure 9]This graph shows the stress-strain curves of SEBS film (thick black line), SEBS-gMA film (thin black line), SEBS-gFA film (dashed line), and SEBS-gFA+0.5BMI film (gray line) tested at a speed of 0.05 in / min (1.27 mm / min).

[0043] [Figure 10] This graph shows the stress-strain analysis of an unrestricted hybrid electrolyte composition prepared using a 75:25=Li2S:P2S5 conductor and 20 wt% SEBS (gray line), SEBS-gMA (dashed line), SEBS-gFA (thick black line), and BMI-bridged SEBS-gFA (thin black line) binders, tested at a speed of 0.05 in / min (1.27 mm / min).

[0044] [Figure 11A] A schematic diagram of a non-limiting cell described in a particular embodiment of the present invention is shown. A cell is provided comprising an anode 104 positioned between a current collector 102 and an electrolyte / separator 106. [Figure 11B] A schematic diagram of a non-limiting cell described in a particular embodiment of the present invention is shown. A cell is provided comprising a current collector 102 adjacent to an electrolyte / separator 106. [Figure 11C] A schematic diagram of a non-limiting cell described in a particular embodiment of the present invention is shown. A cell is provided comprising an anode 104 positioned between a current collector 102 and an electrolyte / cathode double layer 112.

[0045] [Figure 12] A schematic diagram of the crosslinking components that provide the crosslinked film 1206 is shown. [Modes for carrying out the invention]

[0046] One aspect of the present invention relates to an ion-conductive solid composition comprising ion-conductive inorganic particles in a matrix of organic material. The resulting composite material has high ion conductivity and mechanical properties that facilitate processing. In certain embodiments, the ion-conductive solid composition is flexible and can be cast as a film.

[0047] Another aspect of the present invention relates to a battery comprising an ion-conducting solid composition as described herein. In some embodiments of the present invention, a solid electrolyte having an ion-conducting solid composition is provided. In some embodiments of the present invention, an electrode having an ion-conducting solid composition is provided.

[0048] Certain embodiments of the subject matter described herein may have the following advantages: In some embodiments, the ion-conducting solid composition can be processed into various shapes using manufacturing techniques that are easily scaled up. The manufactured composite is flexible, allowing for good adhesion to other components of batteries or other devices. The solid composition has high ion conductivity, allowing the composition to be used as an electrolyte or electrode material. In some embodiments, the ion-conducting solid composition allows for the use of lithium metal anodes by suppressing dendrites. In some embodiments, the ion-conducting solid composition does not dissolve polysulfides, allowing for the use of sulfur cathodes.

[0049] Further details of the ion-conducting solid composition, solid electrolyte, electrode, and battery described in embodiments of the present invention are described below.

[0050] Ion-conducting solid compositions may be referred to as hybrid compositions herein. The term "hybrid" is used herein to describe composite materials comprising an inorganic phase and an organic phase. The term "composite material" is used herein to describe composite materials of inorganic and organic materials.

[0051] In some embodiments, the composite material is formed from a precursor that is polymerized in situ after being mixed with inorganic particles. Polymerization may be carried out under pressure to induce interparticle contact. Once polymerized, the pressure can be removed while the particles remain fixed by the polymer matrix. In some implementations, the organic material includes a crosslinked polymer network. This network can restrain the inorganic particles and prevent them from migrating during operation of a battery or other device incorporating the composite material.

[0052] In some embodiments, polymerization can induce interparticle contact without the application of external pressure. For example, certain polymerization reactions involving crosslinking can produce sufficient shrinkage to achieve interparticle contact and high conductivity without pressurization during polymerization.

[0053] Polymer precursors and polymer matrices are compatible with solid ion-conducting particles, are non-volatile, and are inactive with battery components such as electrodes. Polymer precursors and polymer matrices may further be characterized by being non-polar or having low polarity. Polymer precursors and polymer matrices may interact with the inorganic phase to ensure that the components are sufficiently mixed uniformly and microscopically without affecting the bulk composition of at least the inorganic phase. Interactions may include one or both physical and chemical interactions. Examples of physical interactions include hydrogen bonding, van der Waals bonding, electrostatic interactions, and ionic bonding. Chemical interactions refer to covalent bonding. A polymer matrix that is generally inactive with the inorganic phase may nevertheless form bonds with the particle surfaces, but without decomposing or altering the bulk composition of the inorganic phase. In some embodiments, the polymer matrix may mechanically interact with the inorganic phase.

[0054] The "number-average molecular weight" or "M" is related to a specific component of a solid composition (e.g., a high molecular weight polymer binder). nThe term "number-average molecular weight" refers to the statistical average molecular weight of all molecules of a component, expressed in units of g / mol. Number-average molecular weight can be measured, for example, in gel permeation chromatography (where M is the number average molecular weight). n The number-average molecular weight can be calculated based on known criteria based on online detection systems such as refractive index, ultraviolet light, or other detectors, viscometery, mass spectrometry, or techniques known in the art such as colligative methods (e.g., vapor pressure osmosis, end group determination, or proton NMR). The number-average molecular weight is given by the formula

number

[0055] "Weight-average molecular weight" or "M" is a term related to a specific component of a solid composition (e.g., a high molecular weight polymer binder). w The term "statistical average molecular weight" refers to the statistical average molecular weight of all molecules in a component, expressed in units of g / mol, taking into account the weight of each molecule in determining its contribution to the molecular weight average. The larger the molecular weight of a given molecule, the greater its M value. w The weight-average molecular weight contributes to the value. The weight-average molecular weight can be calculated by techniques known in the art that are highly sensitive to molecular size, such as static light scattering, small-angle neutron scattering, X-ray scattering, and sedimentation velocity methods. The weight-average molecular weight is given by the formula

number

[0056] "Alkoxy" means -OR (wherein R is an optionally substituted alkyl group as described herein). Examples of alkoxy groups include trihaloalkoxys such as methoxy, ethoxy, butoxy, and trifluoromethoxy. The alkoxy group may be substituted or unsubstituted. For example, the alkoxy group may be substituted with one or more substituents as described herein in relation to alkyl. Examples of unsubstituted alkoxy groups include C 1~3 , C 1~6 , C 1~12 , C 1~16 , C 1~18 , C 1~20 , or C 1~24 An example is an alkoxy group.

[0057] The term "alkyl," when used herein alone or as part of another group, refers to a straight-chain or branched-chain hydrocarbon containing any number of carbon atoms and having no double or triple bonds in its main chain. "Lower alkyl," as used herein, refers to a subset of alkyl groups containing 1 to 6 carbon atoms and being a straight-chain or branched-chain hydrocarbon group. Unless otherwise indicated, the terms "alkyl" and "lower alkyl" include both substituted and unsubstituted alkyl or lower alkyl groups. Examples of lower alkyl groups include methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, and tert-butyl.

[0058] Alkyl groups can also be substituted or unsubstituted. For example, an alkyl group may be (1)C 1~6 Alkoxy (for example, -O-Ak(where Ak may be substituted)) 1~6 (1) Alkyl)), (2)C 1~6 Alkyl sulfinyl (for example, -S(O)-Ak(wherein Ak may be substituted C)) 1~6 (3)C 1~6 Alkylsulfonyl (for example, -SO2-Ak(wherein Ak may be substituted)) 1~6 (4) Alkyl (for example, -NR) N1 R N2(In the formula, R N1 and R N2 Each of them independently is either H or an optionally substituted alkyl, or R N1 and R N2 (1) (1) (2) (3) (3) (4 3~8 Cycloalkyl (e.g., monovalent saturated or unsaturated non-aromatic cyclic C 3~8 (1) Hydrocarbon group), (12) Halo (e.g., F, Cl, Br, or I), (13) Heterocyclyl (e.g., unless otherwise specified, a 5, 6, or 7-membered ring containing 1, 2, 3, or 4 non-carbon heteroatoms, e.g., nitrogen, oxygen, phosphorus, sulfur, or halo), (14) Heterocyclyloxy (e.g., -O-Het (wherein Het is a heterocyclyl as described herein)), (15) Heterocyclyloil (e.g., -C(O)-Het (wherein Het is a heterocyclyl as described herein)), (16) Hydroxyl (e.g., -OH), (17) N-protected amino, (18) Nitro (e.g., -NO2), (19) Oxo (e.g., =O), (20) C 3~8 Spirocyclyl (e.g., alkylene or heteroalkylenedi radical in which both ends are bonded to the same carbon atom of the parent group), (21)C 1~6 Thioalkoxy (for example, -S-Ak(wherein Ak may be substituted C)) 1~6 (Alkyl), (22)thiol (e.g., -SH), (23)-CO2R A (In the formula, R A (a) hydrogen, (b) C 1~6 Alkyl, (c)C 4~18 Aryl, and (d)(C 4~18 Ariel)C 1~6Alkyl (for example, selected from the group consisting of -L-Ar (wherein L is the divalent form of an optionally substituted alkyl group and Ar is an optionally substituted aryl)), (24)-C(O)NR B R C (In the formula, R B and R C Each of them is (a) hydrogen, (b) C 1~6 Alkyl, (c)C 4~18 Aryl, and (d)(C 4~18 Ariel)C 1~6 Alkyl (for example, independently selected from the group consisting of -L-Ar (wherein L is the divalent form of an optionally substituted alkyl group and Ar is an optionally substituted aryl)), (25)-SO2R D (In the formula, R D (a)C 1~6 Alkyl, (b)C 4~18 Aryl, and (c)(C 4~18 Ariel)C 1~6 Alkyl (for example, selected from the group consisting of -L-Ar (wherein L is the divalent form of an optionally substituted alkyl group and Ar is an optionally substituted aryl)), (26)-SO2NR E R F (In the formula, R E and R F Each of them is (a) hydrogen, (b) C 1~6 Alkyl, (c)C 4~18 Aryl, and (d)(C 4~18 Ariel)C 1~6 Alkyl (for example, independently selected from the group consisting of -L-Ar (wherein L is the divalent form of an optionally substituted alkyl group and Ar is an optionally substituted aryl)), and (27)-NR G R H (In the formula, R G and R H Each of these is (a) hydrogen, (b) N-protecting group, (c) C 1~6 Alkyl, (d)C 2~6 Alkenyl (e.g., an optionally substituted alkyl having one or more double bonds), (e)C 2~6Alkynyl (e.g., an optionally substituted alkyl having one or more triple bonds), (f)C 4~18 Aryl, (g)(C 4~18 Ariel)C 1~6 Alkyl (e.g., L-Ar (wherein L is the divalent form of an optionally substituted alkyl group and Ar is an optionally substituted aryl group)), (h)C 3~8 Cycloalkyl, and (i)(C 3~8 Cycloalkyl)C 1~6 Alkyl alkyl groups may be substituted with 1, 2, 3, or 4 substituents in the case of 2 or more carbon alkyl groups, independently selected from the group consisting of alkyl groups (e.g., -L-Cy (wherein L is the divalent form of an optionally substituted alkyl group, and Cy is an optionally substituted cycloalkyl group as described herein)), and in one embodiment, two groups are not bonded to the nitrogen atom via a carbonyl or sulfonyl group). The alkyl group may be a primary, secondary, or tertiary alkyl group substituted with one or more substituents (e.g., one or more halo or alkoxy groups). In some embodiments, the unsubstituted alkyl group is C 1~3 , C 1~6 , C 1~12 , C 1~16 , C 1~18 , C 1~20 , or C 1~24 It is an alkyl group.

[0059] "Alkylene" means the polyvalent (e.g., divalent) form of an alkyl group as described herein. Examples of alkylene groups include methylene, ethylene, propylene, and butylene. In some embodiments, the alkylene group is C 1~3 , C 1~6 , C 1~12 , C 1~16 , C 1~18 , C 1~20 , C 1~24 , C 2~3 , C 2~6 , C 2~12 , C 2~16 , C 2~18 , C 2~20 , or C2~24 The alkylene group is branched or unbranched. The alkylene group is also substituted or unsubstituted. For example, the alkylene group may be substituted with one or more substituents as described herein in relation to alkyl groups.

[0060] As used herein, the term "aryl" refers to a group containing monocyclic and bicyclic aromatic groups. An example is condensed benzo-C (as defined herein). 4~8 Examples of aryl groups include phenyl, benzyl, anthracenyl, anthryl, benzocyclobutenyl, benzocyclooctenyl, biphenylyl, crisenyl, dihydroindenyl, fluorantenyl, indacenyl, indenyl, naphthyl, phenanthryl, phenoxybenzyl, picenyl, pyrenyl, and terphenyl, among others, including cycloalkyl radicals such as indanyl, tetrahydronaphthyl, and fluorenyl. The term aryl also includes heteroaryls, which are defined as groups containing an aromatic group in which at least one heteroatom is incorporated into the ring of the aromatic group. Examples of heteroatoms, but not limited to these, include nitrogen, oxygen, sulfur, and phosphorus. Similarly, the term nonheteroaryl (which is also included in the term aryl) defines groups containing an aromatic group that does not contain a heteroatom. Aryl groups can be substituted or unsubstituted. Aryl groups are (1)C 1~6 Alkanoyl (for example, -C(O)-Ak(where Ak may be substituted) 1~6 (1) Alkyl)), (2)C 1~6 Alkyl, (3)C 1~6 Alkoxy (for example, -O-Ak(where Ak may be substituted)) 1~6 (4)C 1~6 Alkoxy-C 1~6 Alkyl (for example, -LO-Ak(wherein L is the divalent form of an optionally substituted alkyl group, and Ak is an optionally substituted C) 1~6 (5)C 1~6 Alkyl sulfinyl (for example, -S(O)-Ak(wherein Ak may be substituted C)) 1~6(6)C 1~6 Alkylsulfinyl-C 1~6 Alkyl (for example, -LS(O)-Ak(wherein L is the divalent form of an optionally substituted alkyl group, and Ak is an optionally substituted C) 1~6 (7)C 1~6 Alkylsulfonyl (for example, -SO2-Ak(wherein Ak may be substituted)) 1~6 (8)C 1~6 Alkylsulfonyl-C 1~6 Alkyl (for example, -L-SO2-Ak(wherein L is the divalent form of an optionally substituted alkyl group, and Ak is an optionally substituted C) 1~6 (9) alkyl, (10) amino (e.g., -NR) N1 R N2 (In the formula, R N1 and R N2 Each of them independently is either H or an optionally substituted alkyl, or R N1 and R N2 (11)C 1~6 Aminoalkyl (e.g., one or more -NRs as described herein) N1 R N2 (1) an alkyl group as defined herein, substituted with a group; (12) heteroaryl (e.g., a subset of aromatic heterocyclyl groups (e.g., a 5, 6, or 7-membered ring containing 1, 2, 3, or 4 noncarbon heteroatoms unless otherwise specified); (13) (C 4~18 Ariel)C 1~6 (14) Alkyl (e.g., -L-Ar (wherein L is the divalent form of an optionally substituted alkyl and Ar is an optionally substituted aryl)), (15) Allyroyl (e.g., -C(O)-Ar (wherein Ar is an optionally substituted aryl)), (16) Azide (e.g., N3 or -N=N-), (17) Cyano (e.g., -CN), (18) C 1~6(18) Azidoalkyl (e.g., alkyl groups as defined herein, substituted with one or more azide groups as described herein), (19) Carboxaldehyde (e.g., -C(O)H), (12) Carboxaldehyde-C 1~6 Alkyl (for example, an alkyl group as defined herein, substituted with one or more carboxyaldehyde groups as described herein), (20)C 3~8 Cycloalkyl (e.g., monovalent saturated or unsaturated non-aromatic cyclic C 3~8 (Hydroxide group), (21)(C 3~8 Cycloalkyl)C 1~6 (22) Alkyl (e.g., alkyl groups as defined herein, substituted by one or more cycloalkyl groups as described herein), (23) Halo (e.g., F, Cl, Br, or I), (24) C 1~6 (24) Haloalkyl (e.g., an alkyl group as defined herein, substituted by one or more halo groups as described herein), (25) Heterocyclyl (e.g., a 5, 6, or 7-membered ring containing 1, 2, 3, or 4 noncarbon heteroatoms, e.g., nitrogen, oxygen, phosphorus, sulfur, or halo, unless otherwise specified), (26) Heterocyclyloxy (e.g., -O-Het (wherein Het is a heterocyclyl as described herein)), (27) Hydroxyl (e.g., -OH), (28) C 1~6 (29) Hydroxyalkyl (e.g., alkyl groups as defined herein, substituted with one or more hydroxyls as described herein), (29) Nitro (e.g., -NO2), (30) C 1~6 Nitroalkyl (for example, alkyl groups as defined herein, substituted with one or more nitros as described herein), (31) N-protected amino, (32) N-protected amino-C 1~6 (33) Alkyl (e.g., alkyl groups as defined herein, substituted with one or more N-protected amino groups), (34) Oxo (e.g., =O), (35) C 1~6Thioalkoxy (for example, -S-Ak(wherein Ak may be substituted C)) 1~6 (35) thio-C 1~6 Alkoxy-C 1~6 Alkyl (for example, -LS-Ak(wherein L is the divalent form of an optionally substituted alkyl and Ak is the optionally substituted C) 1~6 (It is alkyl)), (36)-(CH2) r CO2R A (In the formula, r is an integer from 0 to 4, R A (a) hydrogen, (b) C 1~6 Alkyl, (c)C 4~18 Aryl, and (d)(C 4~18 Ariel)C 1~6 Alkyl (for example, selected from the group consisting of -L-Ar (wherein L is the divalent form of an optionally substituted alkyl and Ar is an optionally substituted aryl)), (37)-(CH2) r CONR B R C (In the formula, r is an integer from 0 to 4, and each R B and R C (a) hydrogen, (b) C 1~6 Alkyl, (c)C 4~18 Aryl, and (d)(C 4~18 Ariel)C 1~6 Alkyl (for example, independently selected from the group consisting of -L-Ar (wherein L is the divalent form of an optionally substituted alkyl and Ar is an optionally substituted aryl)), (38)-(CH2) r SO2R D (In the formula, r is an integer from 0 to 4, R D (a)C 1~6 Alkyl, (b)C 4~18 Aryl, and (c)(C 4~18 Ariel)C 1~6 Alkyl (for example, selected from the group consisting of -L-Ar (wherein L is the divalent form of an optionally substituted alkyl and Ar is an optionally substituted aryl)), (39)-(CH2) r SO2NR E R F(In the formula, r is an integer from 0 to 4, R E and R F Each of them is (a) hydrogen, (b) C 1~6 Alkyl, (c)C 4~18 Aryl, and (d)(C 4~18 Ariel)C 1~6 Alkyl (for example, independently selected from the group consisting of -L-Ar (wherein L is the divalent form of an optionally substituted alkyl and Ar is an optionally substituted aryl)), (40)-(CH2) r NR G R H (In the formula, r is an integer from 0 to 4, R G and R H Each of these is (a) hydrogen, (b) N-protecting group, (c) C 1~6 Alkyl, (d)C 2~6 Alkenyl (e.g., an optionally substituted alkyl having one or more double bonds), (e)C 2~6 Alkynyl (e.g., an optionally substituted alkyl having one or more triple bonds), (f)C 4~18 Aryl, (g)(C 4~18 Ariel)C 1~6 Alkyl (e.g., -L-Ar (wherein L is the divalent form of an optionally substituted alkyl and Ar is an optionally substituted aryl)), (h)C 3~8 Cycloalkyl, and (i)(C 3~8 Cycloalkyl)C 1~6 (41) Alkyl (e.g., -L-Cy (wherein L is the divalent form of an optionally substituted alkyl and Cy is an optionally substituted cycloalkyl as described herein)) independently selected from the group consisting of alkyls, (42) -L-Cy (wherein L is the divalent form of an optionally substituted alkyl and Cy is an optionally substituted cycloalkyl as described herein), (43) -L-Cy (wherein L is the divalent form of an optionally substituted alkyl and Cy is an optionally substituted cycloalkyl as described herein), (45) -L-Cy (wherein L is the divalent form of an optionally substituted alkyl and Cy is an optionally substituted cycloalkyl as described herein), (46) -L-Cy (wherein L is the divalent form of an optionally substituted alkyl and Cy is an optionally substituted cycloalkyl as described herein), (47) -L-Cy (wherein L is the divalent form of an optionally substituted alkyl and Cy is an optionally substituted cycloalkyl as described herein), (48) -L-Cy (wherein L is the divalent form of an optionally substituted alkyl and Cy is an optionally substituted cycloalkyl as described herein), (49) -L-Cy (wherein L is the divalent form of an optionally substituted alkyl and Cy is an optionally substituted cycloalkyl as described herein), (41) -L-Cy (e.g., -L-Cy (wherein L is the divalent form of an optionally substituted alkyl and Cy is an optionally substituted cycloalkyl as described herein), (42) -L-Cy (wherein L is the divalent form of an optionally substituted alkyl and Cy is an optionally substituted cycloalkyl as described herein), (43) -L-Cy (e.g., -L-Cy (wherein L f (In the formula, R f(44) aryloxy (e.g., -OAr (wherein Ar is an optionally substituted aryl)), (45) cycloalkoxy (e.g., -O-Cy (wherein Cy is an optionally substituted cycloalkyl)), (46) cycloalkylalkoxy (e.g., -OL-Cy (wherein L is a divalent form of an optionally substituted alkyl and Cy is an optionally substituted cycloalkyl)), and (47) arylalkoxy (e.g., -OL-Ar (wherein L is a divalent form of an optionally substituted alkyl and Ar is an optionally substituted aryl)) can be substituted with one, two, three, four, or five substituents independently selected from the group consisting of (47) arylalkoxy (e.g., -OL-Ar (wherein L is a divalent form of an optionally substituted alkyl and Ar is an optionally substituted aryl)). In certain embodiments, the unsubstituted aryl group is C 4~18 , C 4~14 , C 4~12 , C 4~10 , C 6~18 , C 6~14 , C 6~12 , or C 6~10 It is an aryl group.

[0061] "Arylene" means the polyvalent (e.g., divalent) form of the aryl group described herein. Exemplary arylene groups include phenylene, naphthylene, biphenylene, triphenylene, diphenyl ether, acenaphthenylene, anthrylene, or phenanthrylene. In some embodiments, the arylene group is C 4~18 , C 4~14 , C 4~12 , C 4~10 , C 6~18 , C 6~14 , C 6~12 , or C 6~10 The arylene group may be branched or unbranched. The arylene group may also be substituted or unsubstituted. For example, the arylene group may be substituted with one or more substituents described herein in relation to aryl groups.

[0062] A "carbocyclic ring" refers to a cyclic compound in which all ring members are carbon atoms. Carbocyclic rings can be substituted or unsubstituted. Exemplary substitutions include cyano, hydroxyl, halo, nitro, carboxyaldehyde, carboxyl, alkoxy, oxo, or alkyl. Non-exclusive carbocyclic rings include cyclohexene, norbornene, naphthalene, tetrahydronaphthalene (e.g., 1,2,3,4-tetrahydronaphthalene), hydroanthraquinone (e.g., 1,4,4a,5,8,8a,9a,10a-octahydroanthracene-9,10-dione), and cross-linked polycyclic structures (e.g., tetracyclo[6.6.1.02,7.09,14]pentadeca-4,11-diene).

[0063] "Carboxaldehyde" refers to the -C(O)H group.

[0064] "Carboxyl" refers to the -CO2H group.

[0065] "Cyano" refers to the -CN group.

[0066] Unless otherwise specified, "cycloalkyl" refers to a group of 3 to 10 carbon atoms (for example, C 3~8 or C 3~10 ) refers to monovalent saturated or unsaturated non-aromatic cyclic hydrocarbon groups, exemplified by cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1.]heptyl, etc. The term cycloalkyl also includes "cycloalkenyl," which is defined as a non-aromatic carbon ring composed of 3 to 10 carbon atoms and containing at least one double bond, i.e., C=C. Examples of cycloalkenyl groups, but not limited to these, include cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, and cyclohexadienyl. Cycloalkyl groups can also be substituted or unsubstituted. For example, a cycloalkyl group may be substituted with one or more groups, including those described herein in relation to alkyl.

[0067] "Halo" means F, Cl, Br, or I.

[0068] "Heteroalkylene" means the divalent form of an alkylene group as defined herein, containing one, two, three, or four non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, selenium, or halo). Heteroalkylene groups may be substituted or unsubstituted. For example, a heteroalkylene group may be substituted with one or more substituents as described herein in relation to alkyl.

[0069] A "heterocyclic" compound is defined as a compound having one or more heterocyclyl moieties. Heterocyclic compounds can be substituted or unsubstituted. Examples of substitutions include cyano, hydroxyl, halo, nitro, carboxyaldehyde, carboxyl, alkoxy, oxo, or alkyl compounds. Non-restrictive heterocycles include tetrahydropyridine (e.g., 1,2,3,4-tetrahydropyridine, 1,2,3,6-tetrahydropyridine, or 2,3,4,5-tetrahydropyridine), tetrahydropyrazine (e.g., 1,2,3,4-tetrahydropyrazine), tetrahydropyrimidine (e.g., 1,4,5,6-tetrahydropyrimidine), dihydropyran (e.g., 3,4-dihydro-2H-pyran or 3,6-dihydro-2H-pyran), dihydrothiopyran (e.g., 3,4-dihydro-2H-thiopyran or 3,6-dihydro-2H-thiopyran), dihydrooxazine (e.g., 5,6-dihydro-4H-1,3-oxazine or 3,4-dihydro-2H-1,4-oxazine), and dihydrothiazine (e.g., 5,6-dihydro-4H-1,3-thiazine or 5,6 -Dihydro-4H-1,4-thiazine), heterobicycloheptene (e.g., 7-oxabicyclo[2.2.1]hepta-2-ene), crosslinked isoindole anhydride (e.g., 3a,4,7,7a-tetrahydro-4,7-epoxyisoisoindole-1,3-dione), crosslinked benzofuran anhydride (e.g., 3a,4,7,7a-tetrahydro-4,7-epoxyisobenzofuran-1,3-dione), tetrahydro Phthalic anhydride (e.g., 1,2,3,6-tetrahydrophthalic anhydride), heteronorbornene (e.g., 7-thianorbornene or 7-azanorbornene), cyclic anhydrides (e.g., unless otherwise specified, 3, 4, 5, 6, or 7-membered rings having a -C(O)-OC(O)- group in the ring (e.g., 5, 6, or 7-membered rings)), or cyclic imides (e.g., unless otherwise specified, rings having a -C(O)-NR group in the ring) N1 -C(O)- group (in the formula, R N1Examples of cyclic anhydride groups include radicals formed by removing one or more hydrogen atoms from succinic anhydride, glutaric anhydride, maleic anhydride, phthalic anhydride, isochroman-1,3-dione, oxepandione, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic dianhydride, naphthalic anhydride, 1,2-cyclohexanedicarboxylic acid anhydride, etc. Other examples of cyclic anhydride groups include dioxotetrahydrofuranil and dioxodihydroisobenzofuranil. Examples of cyclic imide groups include radicals formed by removing one or more hydrogen atoms from succinimide, glutarimide, maleimide, phthalimide, tetrahydrophthalimide, hexahydrophthalimide, pyromellitic diimide, naphthalimide, etc. Other exemplary cyclic imide groups include succinimido and phthalimido.

[0070] Unless otherwise specified, "heterocyclyl" means a 3, 4, 5, 6, or 7-membered ring (e.g., a 5, 6, or 7-membered ring) containing 1, 2, 3, or 4 non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, selenium, or halo). A 3-membered ring has 0 to 1 double bond, 4 and 5-membered rings have 0 to 2 double bonds, and 6 and 7-membered rings have 0 to 3 double bonds. The term "heterocyclyl" also includes bicyclic, tricyclic, and tetracyclic groups formed by the fusion of any of the above heterocyclic rings with 1, 2, or 3 rings.

[0071] "Hydroxyl" means -OH.

[0072] "Nitro" refers to the -NO2 group.

[0073] "Oxo" means an oxygen group.

[0074] "Thioc" means an -S- group. (organic phase)

[0075] An organic matrix may contain one or more types of polymers and may also be referred to as a polymer matrix or polymer binder. In some embodiments, the organic matrix may contain individual polymer chains that do not have meaningful crosslinks or any crosslinks between polymer chains. In some embodiments, the organic matrix may be or include a polymer network characterized by nodes that connect polymer chains. These nodes may be formed by crosslinking during polymerization. The organic matrix is ​​formed by in situ polymerization of precursors in a mixture having inorganic ion-conducting particles. The polymers of the organic matrix may be characterized by a backbone and one or more functional groups.

[0076] Organic matrix polymers have a non-volatile polymer backbone. The polymer binder is either a high molecular weight polymer or a mixture of different high molecular weight polymers. High molecular weight refers to a molecular weight of at least 30 kg / mol, and may be at least 50 kg / mol, or at least 100 kg / mol. The molecular weight distribution may be unimodal, bimodal, and / or multimodal.

[0077] Polymers or polymer binders have a functionalized backbone. In some embodiments, the polymer backbone is relatively nonpolar. Examples include copolymers (block, gradient, random, etc.) such as styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), styrene-ethylene / propylene-styrene (SEPS), styrene-ethylene-butylene-styrene (SEBS), styrene-butadiene rubber (SBR), and ethylene propylene diene monomer (EPDM) rubber, as well as homopolymers such as polybutadiene (PBD), polyethylene (PE), polypropylene (PP), and polystyrene (PS). In some embodiments, the polymer is relatively polar, examples of which include acrylonitrile-butadiene-styrene (ABS), nitrile rubber (NBR), ethylene vinyl acetate (EVA) copolymer, and oxidized polyethylene. Additional examples include fluorinated polymers such as PVDF, polytetrafluoroethylene, and perfluoropolyether (PFPE), as well as silicones such as polydimethylsiloxane (PDMS).

[0078] The polymer can be formed from any useful monomer or combination of monomers. In some embodiments, the monomer may be a substituted styrene monomer, a substituted ethylene monomer, a substituted propylene monomer, a substituted butylene monomer, a substituted butadiene monomer, a substituted perfluoroalkane monomer, a substituted perfluoroether monomer, a substituted isoprene monomer, a substituted ethylidene norbornene monomer, or a substituted diene monomer.

[0079] In embodiments where the binder is a copolymer, the constituent polymers can be distributed in any suitable manner such that the binder can be a block copolymer, random copolymer, statistical copolymer, graft copolymer, etc. The polymer backbone can be linear or nonlinear, with examples including branched, star-shaped, comb-shaped, and bottlebrush-shaped polymers. Furthermore, the transitions between the constituent polymers of the copolymer can be abrupt, tapered, or random.

[0080] The presence of a relatively large amount of organic matrix (e.g., 2.5–60 wt% of the solid composite) can result in composite materials with desirable mechanical properties. In various embodiments, the composite material is soft and can be processed into various shapes. In addition, the organic matrix can fill voids in the composite material, resulting in a high-density material.

[0081] The organic matrix may also contain functional groups that enable polymerization formation in the in situ polymerization reactions described below. Examples of terminal groups include cyano, thiol, amide, amino, sulfonic, epoxy, carboxyl, or hydroxyl groups. The terminal groups may also have surface interactions with the inorganic phase particles. Additional functional groups are discussed below. (polymerization without the generation of polymer precursors and in situ by-products)

[0082] In various embodiments, in situ polymerization is carried out by mixing ion-conductive particles, a polymer precursor, and any initiators, catalysts, crosslinkers, and other additives, if present, and then initiating polymerization. This can be done in solution or in a hot press. Polymerization may be initiated and carried out under pressure to establish close interparticle contact. However, some in situ polymerization processes may form byproducts that can lead to increased polarization, and therefore reduced cell performance and lifespan.

[0083] Polymer precursors can be low molecular weight monomers, oligomers, polymers, or binders. Polymerization reactions can form individual polymer chains from the precursors (or longer polymer chains from high molecular weight precursors) and / or introduce crosslinks between polymer chains to form a polymer network. Polymer precursors may contain functional groups whose properties depend on the polymerization method used.

[0084] The polymer precursor may be any of the polymer skeletons described above (e.g., polysiloxane, polyvinyl, polyolefin, polytetrahydrofuran, PFPE, cyclic olefin polymer (COP), or cyclic olefin copolymer (COC), or other non-polar or low-polarity polymers), or its constituent monomers or oligomers. Depending on the polymerization method, the polymer precursor may be a terminally and / or skeletal functionalized polymer.

[0085] The reactivity of ionically conductive inorganic particles (and particularly sulfide glasses) presents several challenges for in situ polymerization. The polymerization reaction should not decompose either the sulfide glasses or other types of particles, nor should it cause uncontrolled or premature polymerization of organic components. In particular, glass sulfides are susceptible to the influence of polar solvents and organic molecules, which can lead to decomposition or crystallization, the latter of which can result in a significant decrease in ionic conductivity. Methods using metal catalysts are also unsuitable for sulfide-based ionic conductors. High sulfur content can lead to catalyst poisoning and hinder polymerization. Therefore, methods such as platinum-mediated hydrosilylation, used for silicone rubber formation, cannot be employed.

[0086] By-product-free reactions are processes that form a main product without the formation of secondary by-products. These are desirable processes due to their economic and performance advantages. Processes that do not require by-product handling are more cost-effective because they do not require purification or additional processing steps associated with by-product removal. Furthermore, even after thorough purification, secondary products can persist, acting as impurities and potentially causing reduced or even destructive performance of the material.

[0087] Reactions that do not produce by-products are: A + B → C It is any process that can be described by the reaction scheme.

[0088] There are numerous byproduct-free chemical reactions, including various Michael addition or ring-opening methods. The synthesis of epoxy resins, radicals, and polyurethanes are just a few of the many byproduct-free polymerization techniques. Exemplary Michael addition reactions include the reaction of nucleophiles (e.g., carbanions or other nucleophiles) with α,β-unsaturated carbonyl compounds, while exemplary ring-opening reactions include the ring-opening reactions of nucleophiles with strained heterocyclyl electrophiles (e.g., cyclic ethers, cyclic carbonates, cyclic cycloalkenes, cyclic trisiloxanes, lactones, lactides, etc.).

[0089] Some polymerization techniques, including the Diels-Alder and "click" chemistry methods, do not produce byproducts. These types of reactions yield desirable mechanical properties in organic or hybrid matrices, which still allow for the use of low-pressure processing methods, and can result in a rich variety of monomers and compositions. In addition, some polymer materials produced by these methods exhibit self-healing properties, automatically recovering physical damage under heat treatment, and thus can increase the safety index and effective life of the batteries into which they are incorporated.

[0090] In some embodiments, the polymer precursor is functionalized with functional groups to enable a byproduct-free reaction. Functional groups can be incorporated during the polymerization step and / or in the post-polymerization functionalization step. The polymer may also be prepared using one or more types of functional groups, depending on the characteristics of the target binder. Properties include, but are not limited to, solubility in organic solvents, adhesion to inorganic particles, adhesion to current collectors, dispersibility of inorganic materials, mechanical properties, ionic conductivity, electrochemical and chemical stability, and electronic conductivity.

[0091] Furthermore, other click chemistry reactions can be described by reactions between a pair of reactants (e.g., two click chemistry groups). Exemplary pairs include the hysgene 1,3-dipolar cycloaddition reaction between an alkynyl group and an azide group that forms a triazole-containing linker; the Diels-Alder reaction between a diene having a 4π-electron system (e.g., an optionally substituted 1,3-unsaturated compound, e.g., optionally substituted 1,3-butadiene, 1-methoxy-3-trimethylsilyloxy-1,3-butadiene, cyclopentadiene, cyclohexadiene, or furan) and a dienophile or heterodienophile having a 2π-electron system (e.g., an optionally substituted alkenyl group or an optionally substituted alkynyl group); ring-opening reactions between a nucleophile and a strained heterocyclyl electrophile; thiols and optionally substituted alkynes; as well as sprint ligation reactions between a phosphorothioate group and an iodo group; nucleophiles and optionally substituted α,β-unsaturated carbonyl compounds; nucleophiles and optionally substituted strained cyclic compounds; and reductive amination reactions between an aldehyde group and an amino group.

[0092] Examples of reactants include optionally substituted 1,3-butadienes, optionally substituted alkenes, optionally substituted alkynes, optionally substituted α,β-unsaturated aldehydes, optionally substituted unsaturated α,β-thioaldehydes, optionally substituted α,β-unsaturated ketones, optionally substituted azides, optionally substituted thiols, optionally substituted unsaturated cycloalkyls, optionally substituted unsaturated heterocycles, optionally substituted α,β-unsaturated imines, optionally substituted aldehydes, optionally substituted imines, optionally substituted nitroso compounds, optionally substituted diazenes, optionally substituted thioketones, optionally substituted α,β-unsaturated ketones, optionally substituted α,β-unsaturated aldehydes, optionally substituted anionic nucleophiles, and optionally substituted strained epoxys. Optional substituents may be any of those described herein (e.g., in relation to alkyl or aryl groups). (By-product non-generation method) (Diels-Alder reaction)

[0093] In some embodiments, the polymer matrix is ​​formed by a Diels-Alder reaction. The Diels-Alder reaction is a method for preparing a six-membered ring. This may also be known as a [4+2] cycloaddition reaction. This process occurs between a conjugated diene and an alkene or alkyne known as a dienophile. Diels-Alder cycloadditions can be classified into two subgroups. One subgroup is normal electron-demanding Diels-Alder (DA) (Scheme 1A), where the diene is electron-rich and the dienophile is electron-deficient. In the second subgroup, namely reverse electron-demanding Diels-Alder (rDA) (Scheme 1B), the roles are reversed, and the diene is electron-deficient compared to the dienophile. In some embodiments, the polymer precursor comprises at least one functional group that is a diene and at least one functional group that is a dienophile. Scheme 1: Schematic diagram of the Diels-Alder [4+2] cycloaddition reaction using (A) normal electron-demanding Diels-Alder and (B) reverse electron-demanding Diels-Alder. (A) Normal electron-demand type (DA) (B) Reverse electron-demand type (rDA) [ka]

[0094] The chemical structures of the diene and dienophile determine how easily the reaction occurs. For example, the reaction of butadiene, an unsubstituted reagent (G1=H, G2=H, where G1=diene, G2=dienophile), with ethylene requires a high temperature of 700°C to form cyclohexene. However, the Diels-Alder reaction can be controlled by modifying the properties / structure of the diene and / or dienophile. In some embodiments involving normal electron-demanding DA reactions, electron-withdrawing (EWD) substituents can be introduced to the dienophile (G2=EWD), which may accelerate the reaction, and the more electron-deficient the dienophile, the easier the reaction occurs. As an example, introducing one nitrile group to ethylene can reduce the reaction temperature from 700°C to 140°C (Scheme 2A), and adding three more nitrile functionalities can further reduce it to 20°C (Scheme 2B). Scheme 2: DA cyclization reaction of butadiene with (A) acrylonitrile or (B) tetracyanoethylene [ka]

[0095] In some embodiments, the diene functional group has at least one EWD substituent, e.g., -SO2CF3 (triflate), -CF3, -CCl3 (trihalide), -CN (nitrile), -SO3R (e.g., a sulfonic acid where R is H, an optionally substituted alkyl, or an optionally substituted aryl, as defined herein), -NO2 (nitro), -NR3 +This may include (for example, an ammonium salt where R is H, an optionally substituted alkyl, or an optionally substituted aryl as defined herein), -CHO (aldehyde), -COR (for example, a ketone where R is an optionally substituted alkyl or an optionally substituted aryl as defined herein), -COOH (acid), -COCl (acyl chloride), -COOR (for example, an ester where R is an optionally substituted alkyl or an optionally substituted aryl as defined herein), -CONR2 (for example, an amide where R is H, an optionally substituted alkyl, or an optionally substituted aryl as defined herein), or -X (halides such as -Cl, -F, -Br, -I).

[0096] By using electron-donating (EDG) substituents located in the diene reactant, similar activation effects can be achieved for normal electron-demanding DA reactions. In some embodiments involving normal electron-demanding DA reactions, electron-donating (EDG) substituents can be introduced into the diene (G1=EDG), which may accelerate the reaction, and the more electron-rich the diene, the more readily the reaction occurs. In the following example, the more reactive 1-methoxy-1,3-butadiene reacted with acrolein at 100°C (Scheme 3B) compared to a reaction using butadiene that required 160°C (Scheme 3A). In some embodiments, the diene functional group may include at least one EDG substituent, for example, in descending order of electron-donating strength, -OAr (e.g., an aromatic oxide where Ar is an optionally substituted aryl as defined herein), -NR2 (e.g., primary, secondary, and tertiary amines where each R is independently H or an optionally substituted alkyl as defined herein), -OR (e.g., an ether where R is an optionally substituted alkyl or an optionally substituted aryl as defined herein), -ArOH (e.g., an aromatic alcohol where Ar is an optionally substituted aryl or an optionally substituted arylene as defined herein), -NHCOR (e.g., an amide where R is an optionally substituted alkyl or an optionally substituted aryl as defined herein), -OCOR (e.g., an ester where R is an optionally substituted alkyl or an optionally substituted aryl as defined herein), -R (e.g., an alkyl where R is an optionally substituted alkyl as defined herein), -Ar (e.g., an aromatic where Ar is an optionally substituted aryl as defined herein), or -CH=CH2 (vinyl). Scheme 3: DA cyclization addition reaction of acrolein with (A) butadiene or (B) 1-methoxy-1,3-butadiene [ka]

[0097] In some embodiments, the reverse electron-demanded rDA reaction occurs during polymerization. In the reverse electron-demanded rDA reaction, one process involves cycloaddition between an electron-rich dienophile (containing EDG functionality) and an electron-deficient diene (containing an EWD group). In general, the EWD and EDG substituents described above can be used for the rDA reaction (G1=EWD, G2=EDG). In such embodiments, the diene functional group may contain at least one EDG substituent, and / or the dienophile functional group may contain at least one EWD substituent. This technique may be useful for synthesizing heterocyclic compounds, such as pyran, piperidine, and their derivatives. Scheme 4: rDA cyclization reaction between acrolein and methyl vinyl ether [ka]

[0098] In some embodiments, the normal electron-demanding Diels-Alder reaction can be catalyzed by a Lewis acid, such as a metal chloride, such as tin chloride, zinc chloride, or boron trifluoride. The bonding of the catalyst to the dienophile enhances its electrophilicity, and therefore its reactivity, thus easing the thermal reaction requirements.

[0099] One of the advantages of DA reactions is that they can be thermally reversible. A retro-DA reaction is a process in which a six-membered ring reacts to form a diene and a dienophile, typically achieved by thermal treatment. Some retro-DA reactions can also be facilitated by chemical activation, such as Lewis acid or base mediated. The thermal reversibility of some DA reactions allows for self-healing properties, as heating of the polymer dissociates the DA crosslinks, which can then be reformed upon subsequent cooling. In some embodiments, the polymer precursor is functionalized with groups that can accept retro-DA and either normal DA or reversed rDA. (1+3-dipole cycloaddition "click" reaction)

[0100] In some embodiments, the polymer matrix can be formed by a [1+3] dipole cycloaddition reaction. [1+3] dipole cycloaddition is a method for preparing a five-membered ring via the reaction of a 1,3-dipole with a parent dipole. One example is a [3+2] cycloaddition between an azide and an alkyne that produces a 1,2,3-triazole, also known as hysgen cycloaddition (Scheme 5). Scheme 5: Hysgene cycloaddition between azides and alkynes [ka]

[0101] In some embodiments, the 1,3-dipole is an allyl or propargyl / alenyl type zwitterion, such as azomethine ylides and imines, nitrones, nitro compounds, carbonyl oxides and imides, carbonyl ylides and imines, azides, diazoalkanes, thiosulfines, etc. In some embodiments, the parent dipole can be a variety of alkenes and alkynes, as well as carbonyls and imines. In some embodiments, a metal catalyst, such as a copper-based catalyst, may be used to increase the reaction rate. In some embodiments, the reaction rate can also be improved in the presence of a strained parent dipole, such as cyclooctyn and its analogs and substituted derivatives. In some embodiments, strain-enhanced cycloaddition reactions can occur spontaneously without a catalyst. (Thiol-ene "click" reaction)

[0102] In some embodiments, the polymer matrix can be formed by a thiol-ene "click" reaction between a thiol that forms a sulfide and an alkene or alkyne (Scheme 6). This process can occur via a free radical mechanism catalyzed by a radical initiator, UV light or temperature, or Michael addition, and accelerated by a base and a nucleophile. The thiol-ene "click" method is a highly efficient reaction that proceeds in high yield and can be an attractive synthetic means for a variety of applications. Scheme 6: Thiol-ene addition between thiols and (A) alkenes and (B) alkynes [Chemistry]

[0103] Scheme 7 shows examples of various thiol-ene reactions that can occur in various embodiments. Thiols are reactive with many alkenes and alkynes. For example, polybutadiene can be "in situ" crosslinked with various dithiols using temperature, UV light, or a radical initiator as a co-catalyst to form a crosslinked network (Scheme 7A). This process is similar to the vulcanization of rubber but is more efficient and requires milder conditions than conventional methods using sulfur. In addition, the wide availability of reactive groups facilitates the post-modification of polymer precursors in the preparation of thiol-ene click reactions. For example, the hydroxyl end groups in hydrogenated polybutadiene can be converted to thiol-reactive acrylate groups, which can be further reacted with a thiol crosslinking agent to form a crosslinked network (Scheme 7B). Furthermore, the thiol-ene reaction may be used to control the functionalization of unsaturated polymers. Due to the wide availability of various thiol reagents and the highly efficient reaction, the "thiol-ene" process is an excellent choice for controlling the functionalization of polymers such as polybutadiene (Scheme 7C) or poly(styrene-b-butadiene) rubber. Scheme 7: Examples of the use of thiol-ene reactions including (A) polybutadiene crosslinking, (B) acrylate modification of the end groups of hydrogenated polybutadiene using thiol reactive groups, and (C) control of the chemical modification of polybutadiene [Chemistry]

[0104] Figure 1 shows representative examples of commercially available thiol and alkene / alkyne crosslinking agents that may be useful for thiol-ene-based polymerization / crosslinking. In some embodiments, at least some polymer precursors may contain at least one thiol group and / or at least one alkene / alkyne, or may be functionalized using such groups. Non-limiting compounds include compounds (I-1) to (I-8) in Figure 1, where the ethylene oxide group in compound (I-4) can be any useful number n (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or greater) and the methylene group in compound (I-8) can be any useful number n (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or greater). (Diels-Alder method in hybrid electrolytes)

[0105] Diels-Alder functionalities can be located either as a binder or a low-molecular-weight additive in the polymer precursor. Functionality (f) of 2 results in linear polymers, and f≧3 enables crosslinked polymers. In some embodiments, at least one polymer precursor possesses a diene group, and at least one polymer precursor possesses a dienophile group. In general, polymer precursors can carry at least one type of dienophile or diene group, or both, functionalities per molecule.

[0106] In some embodiments, the diene group may include any conjugated diene in a cis configuration. Dienes can be divided into two main groups: all-carbon (Figure 2A) and heteroatom systems (Figure 2B). All-carbon dienes include linear and cyclic dienes, as well as unsaturated conjugated chains composed only of carbon atoms, such as butadiene, cyclopentadiene, anthracene, α-terpinene, furan, and thiofuran. Further examples include compounds (II-1) to (II-10) in Figure 2A, where R may be H, an optionally substituted alkyl, or an optionally substituted aryl, as described herein.

[0107] Heteroatomic dienes may contain at least one heteroatom, such as O, N, or S, in their conjugated diene structure. Examples of heteroatomic dienes include α,β-unsaturated aldehydes, ketones, and imines, such as acrolein and thioacrolein. Further examples include compounds (II-11) to (II-14) in Figure 2B, where R may be H, an optionally substituted alkyl, or an optionally substituted aryl, as described herein.

[0108] Similar to dienes, dienophile groups can also be classified into all-carbon (Figure 3A) and heteroatom (Figure 3B) dienophiles. Examples of all-carbon dienophiles include various alkene and alkyne compounds, such as acrolein, acrylonitrile, fumarate esters, maleate esters, maleic anhydride, and imides. Further examples include compounds (III-1) to (III-11) in Figure 3A, where R may be H, an optionally substituted alkyl, or an optionally substituted aryl, as described herein.

[0109] Examples of dienophiles having heteroatoms in the reactive group include aldehydes, imines, nitroso compounds, diazenes, and thioketones. Further examples include compounds (III-12) to (III-19) in Figure 3B, where R may be H, an optionally substituted alkyl, or an optionally substituted aryl, as described herein.

[0110] In some embodiments, DA-reactive polymers are modified using functional groups of varying concentrations, such as dienes or dienophiles, either directly or indirectly. Figures 4A to 4D provide examples of various functionalized polymers. Copolymerization of DA-inactive monomers with DA-reactive monomers or macromonomers can yield functionalized copolymers (Figure 4B) and graft copolymers (Figure 4C), respectively. In embodiments using indirect methods, polymers can be functionalized with DA groups in a post-functionalization treatment that may involve modification of specific groups, such as terminal groups (Figure 4A) or functional monomers (Figure 4D).

[0111] Scheme 8 shows some examples of reactions that can be used for post-functionalization of various polymers using furfuryl groups in some embodiments. For example, the hydroxyl terminal group of polybutadiene can be modified via isocyanate reactions to form urethane bonds (Scheme 8A), maleic anhydride copolymerized with ethylene can react with amines to form cyclic amides (Scheme 8B), and unsaturated bonds in polybutadiene can react with mercaptans in thiol-ene reactions (Scheme 8C). Scheme 8: Post-functionalization of (A) hydrogenated polybutadiene terminal groups, (B) maleic anhydride-ethylene copolymer, and (C) polybutadiene using furfuryl groups [ka]

[0112] In some embodiments, in addition to the functional polymer, the organic matrix may contain low molecular weight monomers and crosslinking agents. Figure 5 shows some examples of low molecular weight dienes and dienophile monomers and crosslinking agents. In some embodiments, the organic matrix may also contain high molecular weight crosslinking agents and monomers shown in Figure 5, such as compounds (V-1) to (V-7), where the ethylene oxide group or propylene oxide group in compound (V-6) can be any useful number n (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or greater). (Examples) (Example 1: Diels-Alder cross-linked SEBS film)

[0113] Thermoplastic elastomers such as SEBS, SBS, or SIS can be used as binders for the production of all-solid thin-film electrolytes. The low polarity and hydrophobic properties of such binders allow for a high degree of retention of the initial conductivity of pure inorganic conductors such as lithium phosphate sulfide (LPS) glass, and their block-system structure results in good mechanical properties for the hybrid electrolytes produced in the process. However, such binders are thermoplastic systems, which means they form a physical cross-linking network that is bound together by non-covalent interactions.

[0114] The solid binder was modified using furfuryl groups to enable DA crosslinking in the presence of low molecular weight bismaleimide. DA crosslinking of SEBS allowed for the incorporation of covalent crosslinks into the physical crosslinking network formed by the binder, thereby improving its mechanical strength and making it resistant to dissolution in good solvents.

[0115] SEBS was doped with 2 wt% maleic anhydride in a soft block (SEBS-gMA) and reacted with furfurylamine. SEBS-gFA was synthesized by reacting SEBS-gMA with excess furfurylamine, as shown in Scheme 9.1. Scheme 9.1: Modification of SEBS-gMA using a furan group that forms SEBS-gFA [ka]

[0116] In a glove box operated under nitrogen, 30.0 g (6.1 mmol of maleic anhydride) of polystyrene-β-poly(ethylene-ran-butylene)-β-polystyrene-g-maleic anhydride (SEBS-gMA, Sigma-Aldrich) and 250 g of anhydrous toluene were placed in a 500 ml pressure vessel pre-dried at 145°C. The vessel was sealed, and the mixture was stirred on a hot plate at 60°C until the polymer was completely dissolved. The vessel was then returned to the glove box, cooled to room temperature, and 2.4 g (24.7 mmol) of furfurylamine was added to the mixture. The reaction was then stirred further at 60°C for 18 hours (hr). The reaction mixture was then precipitated in methanol, the solid was redissolved in dichloromethane, and then precipitated again in methanol. This process was repeated two more times to obtain furfuryl-modified SEBS (SEBS-gFA) as a white solid. Next, SEBS-gFA was dried under vacuum at 100°C for 16 hours.

[0117] The thermal stability and purity of SEBS-gMA were tested using thermogravimetric analysis. When SEBS-gMA was heated to 500°C under nitrogen, it showed virtually no weight loss down to approximately 370°C, demonstrating the high thermal stability of the polymer and the absence of significant volatile impurities or water content (see Figure 6).

[0118] Figure 7 shows the FTIR spectra of SEBS-gMA and SEBS-gFA. The spectra are similar due to high concentrations of overlapping signals related to the SEBS skeleton. The large difference between the spectra is related to the maleic anhydride ring in SEBS-gMA, at approximately 1790 cm⁻¹. -1 This is the disappearance of the carbonyl (-C=O) stretch. The absence of a visible -C=O stretch in SEBS-gFA is thought to be related to the weaker intensity of the carbonyl signal in the maleimide ring compared to the anhydride, which is difficult to detect at such low concentrations.

[0119] As shown in Fig. 8, proton nuclear magnetic resonance ( 1 H NMR) analysis of the starting material SEBS-gMA and the product SEBS-gFA was performed using a 700 MHz instrument. Due to the low concentration of functional groups in SEBS-gMA (2 wt%) and SEBS-gFA (3.5 wt%), quantitative analysis of the spectra was impossible. However, qualitative analysis of the signals corresponding to the functional groups in the product and the starting material showed shifts in the peaks and changes in their intensities. Fig. 8 shows an overlay of the SEBS-gMA (black) and SEBS-gFA (gray) spectra in the region having characteristic peaks corresponding to the cyclic rings of maleic anhydride and maleimide.

[0120] Next, SEBS-gFA was tested in a Diels-Alder crosslinking process using 1,1'-(methylenedi-4,1-phenylene)bismaleimide (BMI). A solution of SEBS-gFA in toluene was mixed with BMI at a ratio of 2:1 for the furfuryl group to the maleimide group. 1.50 g (0.037 mmol of furfuryl groups), 27.0 mg (0.075 mmol) of BMI, and 3.0 g of 1,2,4-trimethylbenzene were placed in a 20 mL vial equipped with a stir bar. The mixture was stirred at 40 °C until all components were dissolved and then cooled to room temperature. Next, the solution was cast onto Mylar using a doctor blade, and the thin film was air-dried and then transferred to a vacuum oven and heated at 100 °C for 12 hours. The film was cut into three pieces, and one of them was further heated at 120 °C for 5 hours. After the film was cooled to room temperature, it was peeled off from the substrate (Scheme 9.2). Scheme 9.2: Crosslinking of SEBS-gFA with BMI in the Diels-Alder process

Chemical Structure

[0121] Tensile tests were performed on the crosslinked membranes to determine their modulus of elasticity, tensile strength, and elongation at break. The properties of the SEBS-gFA+0.5BMI membrane were compared with those of pure SEBS (unfunctionalized), SEBS-gMA, and SEBS-gFA membranes treated under the same conditions. All membranes were cut into 8mm × 50mm strips, and at least three measurements were performed per membrane using a small tensile testing machine. Due to the short grip distance of the machine, the tensile strength and elongation at break could not be measured because the machine reached its limits before material fracture occurred. Each polymer membrane was highly elastic, reaching elongation of over 800%. Figure 9 shows representative curves obtained from stress-strain tests of SEBS (thick black line), SEBS-gMA (thin black line), SEBS-gFA (dashed line), and SEBS-gFA+0.5BMI (gray line) membranes tested at a speed of 0.05 in / min (1.27 mm / min). Table 1 summarizes the modulus of elasticity from the stress-strain curves of SEBS, SEBS-gMA, SEBS-gFA, and Diels-Alder cross-linked SEBS-gFA+0.5BMI films. Table 1: Elastic modulus of various polymer films [Table 1]

[0122] The elastic moduli measured for SEBS, SEBS-gMA, SEBS-gFA, and crosslinked SEBS-gFA + 0.5BMI differed significantly from each other, providing evidence that the overall composition and type of functional groups are important. Adding 2 wt% polar maleic anhydride grafts to the SEBS composition dramatically improved the binder's elastic moduli, reaching over 70% higher (20.82 MPa) than the SEBS hybrid. Further modification of SEBS-gMA with furfuryl groups resulted in an even more polar SEBS-gFA binder and an even higher elastic moduli of 26.82 MPa. Finally, when SEBS-gFA was crosslinked with BMI, the film exhibited an elastic moduli of 28.54 MPa, demonstrating that a Diels-Alder reaction occurred and that the additional covalent crosslinks formed during this process enhanced the overall toughness of the polymer film. (Example 2: Hybrid electrolyte using Diels-Alder crosslinking)

[0123] After testing the mechanical properties of pure SEBS, SEBS-gMA, SEBS-gFA, and BMI-crosslinked SEBS-gFA films, the polymers were incorporated into composite electrolytes. Each polymer was tested as a binder in hybrids prepared using 80 wt% 75:25=Li2S:P2S5 sulfide glass. The composites were prepared as thin films by slurry casting, dried, and hot-pressed at 160°C. The binder structures for (A) SEBS, (B) SEBS-gMA, (C) SEBS-gFA, and (D) BMI-crosslinked SEBS-gFA are provided below. [ka]

[0124] The conductivity of composite materials was measured to evaluate the effect of binders on maintaining the conductivity of pure 75:25=Li2S:P2S5 sulfide glass. The incorporation of polar groups into non-polar binders such as SEBS had a dramatic effect on the conductivity of the measured films. When SEBS was used as the binder, the conductivity was approximately 0.18 mS / cm, representing a 33% retention of the conductivity of the original inorganic material (approximately 0.55 mS / cm) (Table 2). When SEBS was modified with a small amount of polar functionality that could strongly bond to the surface of the glass particles, the conductivity decreased to almost one-tenth. In the case of SEBS-gMA hybrids, the conductivity decreased to approximately one-eighth, and in the case of BMI-crosslinked SEBS-gFA, it decreased to approximately one-sixth (Table 2).

[0125] When pure SEBS-gFA was used as the organic matrix, the conductivity decreased to only 1 / 2.3. This suggests that the addition of BMI to the system had a significant impact on the conductivity of the organic matrix, and therefore the resulting hybrid. This difference between hybrids containing SEBS-gFA and hybrids containing SEBS-gFA with BMI crosslinking agent may be related to the difference in viscosity of the organic matrix in both composites. The higher viscosity of the organic matrix can lead to suppression of particle flow during hot pressing and thus hinder good inter-particle contact, which can result in good conductive performance of the electrolyte composite. During casting of hybrids containing SEBS-gFA and BMI, it was observed that the viscosity of the slurry became abnormally high, requiring a much higher dilution ratio to cast the hybrid film. The increase in viscosity was due to the Diels-Alder process between the furfuryl groups and maleimide groups occurring in the slurry. This resulted in the formation of polymers with much higher molecular weight than the starting SEBS-gFA, and therefore higher viscosity and interference with particle motion during hot pressing. Table 2: Conductivity and mechanical properties measured in hybrids containing 80wt%75:25=Li2S:P2S5 glass and various polymer binders [Table 2]

[0126] Next, mechanical tests were performed on all hybrids to obtain their modulus of elasticity, tensile strength, and elongation at break. The mechanical tests were conducted under the same conditions as for the pure polymer films. Representative stress-strain curves for each hybrid are shown in Figure 10, and the derived values ​​for modulus of elasticity, tensile strength, and elongation at break are summarized in Table 2.

[0127] Visual comparison of stress-strain curves obtained in hybrids containing various binders reveals clear differences in all their mechanical properties. Tensile strength and elongation at break tend to increase in hybrids prepared with higher polarity binders. In the case of SEBS hybrids, the sample breaks at only 2.2% elongation (Table 2). When only 2 wt% maleic acid grafts are incorporated into SEBS (SEBS-gMA), the value doubles to 4.7%. Further modification with furfuryl groups (SEBS-gFA) increased the wt% of polar groups to 3.5 wt%. This modification dramatically increased the elongation at break to 17.0%, which is 8.5 times and 4 times that of SEBS and SEBS-gMA, respectively. The same trend was observed in the tensile strength of the membrane, with values ​​of 4.2, 5.6, and 8.3 MPa for SEBS, SEBS-gMA, and SEBS-gFA binders, respectively, demonstrating improved resistance to membrane fracture when incorporating more polar binders into the organic matrix (Table 2).

[0128] The properties of the BMI-crosslinked SEBS-gFA hybrid lie between those of the SEBS-gMA hybrid and the SEBS-gFA hybrid (Table 2), and compared to pure SEBS-gFA, crosslinking caused a decrease in the hybrid's performance. It is hypothesized that high-packing-density inorganic particles reduce the efficiency of crosslinking between the furfuryl and maleimide groups, potentially affecting the mechanical properties. In addition, the inefficiency of the Diels-Alder reaction may result in more partially reactive BMI groups. Thus, instead of forming crosslinking bonds, such groups may act as bulky, rigid functionalities that can be less efficient at harmonizing with the surface of the inorganic particles. This can affect not only the mechanical properties of the organic matrix but also alter the adhesion of the binder to the inorganic particles, and therefore, the mechanical performance of the hybrid film. (Example 3: Synthesis of hybrid electrolytes based on POSS nanocomposites)

[0129] The inorganic-organic hybrid matrix is ​​empirically formulated R n (SiO 1.5 )n The organic-inorganic hybrid (n=8, 10, or 12) may be based on a polyhedral oligomeric silsesquioxane (POSS) compound having dimensions equivalent to a polymer segment or coil. A rigid cubic cage can be considered the smallest possible silica particle. Each cage silicon atom is bonded to a single R substituent, which may be a reactive or non-reactive organic group (e.g., glycidyl, phenyl, cyclohexyl), or to an organic-inorganic hybrid (e.g., -OSiMe2OPh). The reactive organic group allows for the preparation of composite materials in which the inorganic POSS core is molecularly dispersed in the matrix. Compared to polymer materials, POSS nanocomposites may have superior properties, including higher operating temperatures, oxidation resistance, and improved mechanical properties, as well as lower dielectric constant, flammability, and exothermic properties.

[0130] FG-POSS was synthesized by reacting glycidyl (G)POSS with furfurylamine (F). 12.1 g of G-POSS (9.0 mmol, 72.0 mmol epoxy group) was dissolved in 60 ml of dimethylformamide under argon. 8.7 g of furfurylamine (89.7 mmol amide group) was added dropwise to the solution. After reacting at 60°C for 1 day, unreacted furfurylamine and excess solvent were removed using a centrifuge (4500 rpm, -4°C) to obtain a viscous, clear liquid. The hybrid POSS matrix was obtained by dissolving 5 g of FG-POSS in 40 ml of anhydrous tetrahydrofuran (THF), followed by the addition of stoichiometric amounts of 1,1'-(methylenedi-4,1-phenylene)bismaleimide (BMI). After stirring at room temperature for 3 hours, the THF was gradually removed by centrifugation. The resulting viscous liquids (15, 25, 30, and 35 wt%) were mixed with an inorganic conductor (e.g., lithium-ion conductive argyrodite) in dichlorobenzene. Eight 10 mm diameter zirconia balls were placed in a cup as the mixing medium. The cup was closed and tightly sealed with insulating tape. The slurry was mixed in a tube roller at a speed of 80 rpm for 16 hours. The thin film was cast onto nickel foil using the doctor blade technique. Casting was performed in a coater equipped with a vacuum chuck. The film was dried under ambient pressure at room temperature and 45°C for 5 hours, then transferred to an ante chamber and dried further overnight under vacuum. The dried thin film was cut into 50 mm × 70 mm rectangular test pieces. A single film piece was sandwiched between FEP sheets and pressed in a vertical press at 15 MPa for 18 hours while the sample was heated to 100°C. After the sample cooled to 40°C, the pressure was released and the sample was extracted. (inorganic phase)

[0131] The inorganic phase of the composite materials described herein conducts alkali ions. In some embodiments, this is responsible for all of the ionic conductivity of the composite material and provides an ionic conductivity pathway through the composite material.

[0132] The inorganic phase is a fine-particle solid material that conducts alkali ions. The examples below primarily describe lithium-ion conductive materials, but sodium-ion conductive or other alkali-ion conductive materials may also be used. In various embodiments, the material may be glass particles, ceramic particles, or glass-ceramic particles. This method is particularly useful for composites having glass or glass-ceramic particles. In particular, as described above, this method can be used to provide composites having glass or glass-ceramic particles and a polar polymer without inducing particle crystallization (or further crystallization).

[0133] The solid compositions described herein are not limited to any particular type of compound, and any solid inorganic ion-conducting fine particle material, as exemplified below, may be used.

[0134] In some embodiments, the inorganic material is a single-ionic conductor with a transportity close to 1. The transportity of an ion in an electrolyte is the proportion of that ion in the total current flowing through the electrolyte. A single-ionic conductor has a transportity close to 1. In various embodiments, the transportity of the inorganic phase of the solid electrolyte is at least 0.9 (e.g., 0.99).

[0135] The inorganic phase may be an oxide-based composition, a sulfide-based composition, or a phosphate-based composition, and may be crystalline, partially crystalline, or amorphous. As described above, certain embodiments of the method are particularly useful for sulfide-based compositions that can be decomposed in the presence of a polar polymer.

[0136] In certain embodiments, the inorganic phase may be doped to enhance conductivity. Examples of solid lithium-ion conductive materials include perovskites (e.g., Li 3x La (2 / 3)-x TiO3 (0 ≤ x ≤ 0.67), lithium superionic conductor (LISICON) compounds (e.g., Li 2+2x Zn 1-x GeO4, 0≦x≦1;Li 14 ZnGe4O 16), thioLISICON compounds (e.g., Li 4-x A 1-y B y S4, where A is Si, Ge, or Sn, and B is P, Al, Zn, or Ga; Li 10 SnP2S 12 ), garnet (for example, Li7La3Zr2O 12 Li5La3M2O 12 , M is Ta or Nb); NASICON type Li ion conductor (e.g., Li 1.3 Al 0.3 Ti 1.7 (PO4)3), oxide glass or glass ceramic (e.g., Li3BO3-Li2SO4, Li2O-P2O5, Li2O-SiO2), argyrodite (e.g., Li6PS5X (where X=Cl, Br, I)), sulfide glass or glass ceramic (e.g., 75Li2S-25P2S5, Li2S-SiS2, LiI-Li2S-B2S3), and phosphate (e.g., Li 1-x Al x Ge 2-x (PO4)3(LAGP), Li 1+x Ti 2-x Al x (PO4)) is one example. Further examples include lithium-rich anti-perovskite (LiRAP) particles. As described in Zhao and Daemen, J.Am.Chem.Soc., 2012, Vol.134(36), pp.15042-15047, which is incorporated herein by reference, these LiRAP particles are 10 at room temperature. -3 It has ionic conductivity exceeding S / cm.

[0137] Examples of solid lithium-ion conductive materials include sodium superionic conductor (NASICON) compounds (e.g., Na 1+x Zr2Si x P 3-x O 12, including 0 < x < 3). Further examples of solid lithium ion conductive materials can be found in Cao et al., Front. Energy Res., 2014, Vol. 2, Article 25 (10 pp.), and Knauth, Solid State Ionics, 2009, Vol. 180 (14 - 16), pp. 911 - 916, both of which are incorporated herein by reference.

[0138] Further examples of ion conductive glasses are disclosed in Ribes et al., J. Non - Cryst. Solids, 1980, Vol. 38 - 39 (Pt. 1), pp. 271 - 276, and Minami, J. Non - Cryst. Solids, 1987, Vol. 95 - 96, pp. 107 - 118, both of which are incorporated herein by reference.

[0139] In various embodiments, the inorganic phase may include one or more types of inorganic ion - conductive particles. The particle size of the inorganic phase can be varied according to a particular application, and the average diameter of the particles of the composition is, in most applications, from 0.1 μm to 500 μm. In some embodiments, the average diameter is from 0.1 μm to 100 μm. In some embodiments, a multimodal size distribution can be used to optimize particle packing. For example, a bimodal distribution can be used. In some embodiments, particles having a size of 1 μm or less are used such that the average distance between the closest particles in the composite is 1 μm or less. This can help prevent the growth of dendrites. In some embodiments, the average particle size is less than 10 μm or less than 7 μm. In some embodiments, a multimodal size distribution having a first size distribution with an average size of less than 7 μm and a second size greater than 10 μm can be used. Larger particles result in a membrane with more robust mechanical properties and better conductivity, while smaller particles result in a denser, more uniform membrane with less porosity and better density.

[0140] Inorganic phases can be prepared by any suitable method. For example, crystalline materials can be obtained using various synthesis methods such as solution methods, sol-gel methods, and solid-phase reaction methods. Glass electrolytes can be obtained by quenching and melting, solution synthesis, or mechanical grinding methods, as described in Tatsumisago et al., J. Power Sources, 2014, Vol. 270, pp. 603-607, which is incorporated herein by reference.

[0141] As used herein, the term amorphous glass material refers to a material that is amorphous, but may have narrow crystalline regions. For example, amorphous glass particles may be completely amorphous (100% amorphous), at least 95% amorphous, at least 80% amorphous, or at least 75% amorphous. These amorphous particles may have one or more narrow crystalline regions, but ion conduction through the particles occurs through mostly or completely isotropic conductive paths.

[0142] Ion-conductive glass-ceramic particles have amorphous regions, but at least half are crystalline, for example, having at least 75% (vol.) crystalline. Glass-ceramic particles can be used in the composites described herein, and in certain embodiments, the glass-ceramic particles have a relatively large amount of amorphous characteristics (e.g., at least 40% (vol.) amorphous) that are useful for their isotropic conductive paths. In some embodiments, ion-conductive ceramic particles may be used. Ion-conductive ceramic particles refer to materials that are mostly crystalline, but may have a narrow amorphous region. For example, ceramic particles may be completely crystalline (100% vol. crystalline) or at least 95% (vol.) crystalline.

[0143] In some embodiments, the inorganic phase includes an argyrodite. The general formula for an argyrodite is: A 7-x PS 6-x Hal x (wherein A is an alkali metal, and Hal is selected from chlorine (Cl), bromine (Br), and iodine (I)) may have. In certain embodiments, x is greater than 0. In other embodiments, x is 3 or less. In yet another embodiment, 0 <x≦2である。 In some embodiments, argyrodites have the general formula shown above and can be further doped. One example is argyrodite doped with a thiophilic metal: A 7-x-(z*m) M z m PS 6-x Hal x (wherein A is an alkali metal, M is a metal selected from manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), and mercury (Hg), Hal is selected from chlorine (Cl), bromine (Br), and iodine (I), z is the oxidation state of the metal, 0 ≤ x ≤ 2, and 0 ≤ m < (7-x) / z). In some embodiments, A is lithium (Li), sodium (Na), or potassium (K). In some embodiments, A is Li. Metal-doped argyrodites are further described in U.S. Patent Application No. 16 / 829,962, published as U.S. Patent Publication No. 2021-0047195, which is incorporated herein by reference. In some embodiments, the composite material may include, for example, an oxide argyrodite described in U.S. Patent Application No. 16 / 576,570, published as U.S. Patent Publication No. 2020-0087155, which is incorporated herein by reference. Examples of alkali metal argyrodites include the argyrodites of the formulas shown above, as well as Li 7-x+y PS 6-x Cl x+y Argyrodite as described in U.S. Patent Publication No. 2017-0352916, which includes the formulas 0.05 ≤ y ≤ 0.9 and -3.0x + 1.8 ≤ y ≤ -3.0x + 5, or A 7-x+y PS 6-x Hal x+yOther argyrodites having the formula A can also be doped with the metals listed above, such as A 7-x+y-(z*m) M z m PS 6-x Hal x+y These are some examples.

[0144] Argyrodite, a mineral of Ag8GeS6, can be considered a cocrystal of Ag4GeS4 and two equivalents of Ag2S. Both cationic and anionic substitutions can occur in this crystal while maintaining the same overall spatial arrangement of various ions as before. In Li7PS6, PS4 3- The ion is GeS4 in its original mineral form. 4- While S is present in the crystallographic position that was previously occupied, 2- The ions retain their original positions, Li + The ion is the original Ag + It occupies the ionic position. Because the number of cations in Li7PS6 is less than in the original Ag8GeS6, some of the cation sites are vacancies. These structural analogs of the original argyrodite mineral are also called argyrodites.

[0145] Both Ag8GeS6 and Li7PS6 are orthorhombic at room temperature, but undergo a phase transition to a cubic space group upon heating. Further substitution of one equivalent of Li2S with LiCl yields the material Li6PS5Cl, which still retains the argyrodite structure but undergoes a phase transition from orthorhombic to cubic below room temperature, resulting in significantly higher lithium ion conductivity. In this material as well, the overall arrangement of cations and anions remains the same, and therefore it is also generally referred to as an argyrodite. Thus, further substitutions that similarly retain this overall structure can also be referred to as argyrodites. Alkali metal argyrodites are more generally those in which the alkali metal Ag is present in the original argyrodite structure. + It is one of a class of conductive crystals that occupies a site and retains the spatial arrangement of anions found in the original mineral.

[0146] One example of lithium content in this mineral species, namely Li7PS6, is PS4 3- The ion is GeS4 in its original mineral form. 4- While S is present in the crystallographic position that was previously occupied, 2- The ions retain their original positions, Li + The ion is the original Ag + It occupies the position of the ions. Since there are fewer cations in Li7PS6 compared to the original Ag8GeS6, some cation sites are vacancies. As shown above, further substitution of one Li2S with one equivalent of LiCl yields the material Li6PS5Cl, which still retains the argyrodite structure. In an example of cubic argyrodite Li6PS5Cl, Li + Ag in argyrodite minerals + They occupied the site, PS4 3- This is the original mineral GeS4 4- Occupy the site, in a 1:1 ratio S 2- and Cl - and the two original S 2- To occupy the site.

[0147] There are various methods that can perform substitutions while preserving the overall argyrodite structure. For example, the original mineral is O 2- , Se 2- , and Te 2- Two equivalents of S can be substituted with chalcogen ions such as the following. 2- It has a significant proportion of S 2- It can be replaced with a halogen, for example, although the exact amount depends on other ions in the system, 2 equivalents of S 2- Of these, up to approximately 1.6 is Cl - , Br - , and I - It can be replaced with Cl. - The size is S 2- Similar to the above, but with a charge of 1 instead of 2, and substantially different bonding and reaction properties. Other substitutions may be made, for example, some S 2- use halogens (for example, Cl- Replace with ) and the rest with Se 2- It can be replaced with. Similarly, various substitutions can be made with GeS4 3- This can be done on the site. PS4 3- Furthermore, PO4 3- , PSe4 3- SiS4 3- GeS4 3- These can be replaced. These are all tetrahedral ions with four chalcogen atoms, and overall S 2- It is larger than and has 3 or 4 valent values.

[0148] In other examples comparable to the Li6PS5Cl argyrodite structure described above, Li6PS5Br and Li6PS5I substitute a larger halide (e.g., Li6PO5Cl and Li6PO5Br, see Kong et al., Z. Inorg. Allg. Chem. [J. Inorg. Gen. Chem.], 2010, Vol. 636, pp. 1920-1924) for the chloride. These compounds incorporated herein by reference for the purpose of describing a particular argyrodite contain the halide-substituted derivatives described, S 2- Aeon and PS4 3- In both the ionic and ionic forms, all sulfur atoms in the structure are exchanged for oxygen. PS4 is found in most examples of lithium-containing argyrodites. 3- The phosphorus atoms in the ion can also be partially or completely substituted, for example, a series of Li 7+x M x P 1-x S6(M=Si,Ge) forms aldyrodite structures over a wide range of x. See Zhang et al., J.Mater.Chem.A, 2019, Vol.7, pp.2717-2722, incorporated herein by reference for the purpose of describing a particular aldyrodite. Substitution of P can also be carried out simultaneously with the incorporation of halogens. For example, Li 6+x Si x P 1-xS5Br is stable at x=0 to approximately 0.5. See Minafra et al., J.Mater.Chem.A, 2018, Vol.6, pp.645-651, incorporated herein by reference for the purpose of describing a particular argyrodite. SbS4 3- and MS4 4- A mixture with PS4 3- It is replaced by I - Cl - A series of 6 used instead 7+x M x S 1-x Compounds in S6(M=Si, Ge, Sn) have been prepared and found to form argyrodite structures. See Zhou et al., J.Am.Chem.Soc., 2019, Vol.141, pp.19002-19013, incorporated herein by reference for the purpose of describing certain argyrodites. In addition to lithium (or silver), other cations can also be substituted at the cationic site. Cu6PS5Cl, Cu6PS5Br, Cu6PS5I, Cu6AsS5Br, Cu6AsS5I, Cu 7.82 SiS 5.82 Br 0.18 Cu7SiS5I, Cu 7.49 SiS 5.49 I 0.51 Cu 7.44 SiSe 5.44 I 0.56 Cu 7.75 GeS 5.75 Br 0.25 , Cu7GeS5I, and Cu 7.52 GeSe 5.52 I 0.48These are all synthesized and have an argyrodite crystal structure. See Nilges and Pfitzner, Z. Kristallogr., 2005, Vol. 220, pp. 281-294, incorporated herein by reference for the purpose of describing a particular argyrodite. From the list of several examples, it can be seen that not only can a single element be substituted in any of the various parts of the argyrodite structure, but combinations of substitutions also often result in an argyrodite structure. These include Li 7-x+y PS 6-x Cl x+y The argyrodite described in U.S. Patent Publication No. 2017 / 0352916 includes the formulas 0.05 ≤ y ≤ 0.9 and -3.0x + 1.8 ≤ y ≤ -3.0x + 5.7 (wherein x and y satisfy the formulas 0.05 ≤ y ≤ 0.9 and -3.0x + 1.8 ≤ y ≤ -3.0x + 5.7).

[0149] The argyrodites used in the compositions described herein contain a substantial amount (at least 20%, often at least 50%) of sulfur-containing anions (e.g., S 2- and PS4 3- It contains sulfide-based ion conductors. Sulfide-based lithium argyrodite materials have high Li + It exhibits mobility and is of interest from the perspective of lithium batteries. As shown above, an example of a material in this group is Li6PS5Cl, which is a ternary eutectic of Li3PS4, Li2S, and LiCl. Various embodiments of argyrodites described herein have thiophilic metals that can occupy lithium cation sites in the argyrodite crystal structure. For example, each cation is PS4 3- The elements of anion are two sulfur atoms and one S atom. 2- It can coordinate to a sulfur anion and two chloride anions. In some embodiments, the thiophilic metal occupies a certain proportion of these lithium cation sites, thereby suppressing hydrogen sulfide production. The thiophilic metal may also be used to similarly dope other alkali metal argyrodites. (composite material)

[0150] Composite materials comprising an organic phase and nonionic conductive particles are provided herein. In some embodiments, the organic phase is substantially nonionic and is referred to as "nonionic conductive." The nonionic conductive polymers described herein have an ionic conductivity of less than 0.0001 S / cm. In some embodiments, the organic phase may include an ionic conductive polymer in the presence of a salt such as LiI. Ionic conductive polymers such as polyethylene oxide (PEO), polypropylene oxide (PPO), polyacrylonitrile (PAN), and poly(methyl methacrylate) (PMMA), which are ionic conductive in the presence of a salt, dissolve or dissociate salts such as LiI. Nonionic conductive polymers do not dissolve or dissociate salts and are not ionic conductive even in the presence of salts. This is because, if the salt is not dissolved, there are no mobile ions to conduct.

[0151] The polymer filling rate in the solid-phase composite may be relatively high in some embodiments, for example, at least 2.5% to 30% by weight. In various embodiments, it may be 0.5 wt% to 60 wt% of polymer, 1 wt% to 40 wt% of polymer, or 5 wt% to 30 wt%. The solid-phase composite forms a continuous film.

[0152] As shown above, the composite material contains a functionalized polymer backbone binder. The binder may be a mixture of a functionalized polymer binder and a non-functionalized polymer binder. For example, in some embodiments, the binder may be a mixture of a non-polar polymer (e.g., SEBS) and a functionalized polymer, the functionalized polymer may be crosslinked as described herein (e.g., SEBS-gFA, SEBS-gFA-0.5BMI). In various embodiments, the mixture may be 1:9 to 9:1 wt% polymer:functionalized polymer, for example, 1:5 to 5:1 or 1:4 to 4:1 wt% polymer:functionalized polymer.

[0153] In various embodiments, the polymer binder may be essentially the entirety of the organic phase of the composite, or it may be at least 95 wt%, 90 wt%, at least 80 wt%, at least 70 wt%, at least 60 wt%, or at least 50 wt% of the composite.

[0154] In some embodiments, the composite material essentially consists of ion-conducting inorganic particles and an organic phase. However, in alternative embodiments, one or more additional components may be added to the solid composite material.

[0155] In various embodiments, the solid composition may or may not contain added salts. Lithium salts (e.g., LiPF6, LiTFSI), potassium salts, sodium salts, etc., can be added to improve ionic conductivity in embodiments containing an ion-conducting polymer such as PEO. In some embodiments, the solid composition is substantially free of added salts. "Substantially free of added salts" means that it contains only trace amounts of salt. In some embodiments, the ionic conductivity of the composite is substantially provided by inorganic particles. Even when an ion-conducting polymer is used, it may not contribute more than 0.01 mS / cm, 0.05 mS / cm, or 0.1 mS / cm to the ionic conductivity of the composite. In other embodiments, it may contribute more.

[0156] In some embodiments, the solid composition may comprise one or more conductive additives. In some embodiments, the electrolyte may comprise one or more filler materials, including ceramic fillers such as Al2O3. When used, the fillers may be ion conductors or not, depending on the particular embodiment. In some embodiments, the composite may comprise one or more dispersants. Furthermore, in some embodiments, the organic phase of the solid composition may comprise one or more additional organic components that facilitate the production of an electrolyte having desired mechanical properties for a particular application.

[0157] In some embodiments discussed further below, the composite material may be incorporated into or immediately incorporated into the electrode and comprises an electrochemical active material and, optionally, an electron-conducting additive. Examples of electrode components and compositions are provided below.

[0158] In some embodiments, the electrolyte may include an electrode stabilizer that can be used to form a passivation layer on the electrode surface. An example of an electrode stabilizer is described in U.S. Patent No. 9,093,722. In some embodiments, the electrolyte may include conductive additives, fillers, or organic components, as described above.

[0159] The composite material may be provided as a self-supporting film, a self-supporting film provided on a release film, a film laminated on components of other devices such as batteries or electrodes or separators, or a film cast on electrodes, separators, or other components.

[0160] The composite film can be of any suitable thickness depending on the specific battery or other device design. In many applications, the thickness can be 1 to 250 microns, for example, 30 microns. In some embodiments, the electrolyte may be significantly thicker, for example, about several millimeters.

[0161] In some embodiments, the composite material is provided as a slurry or paste. In such cases, the composition includes a solvent that is later evaporated. In addition, the composition may include one or more components for storage stability. Examples of such compounds include acrylic resins. Once ready for processing, the slurry or paste can be appropriately cast or coated onto a substrate and dried.

[0162] In some embodiments, the composite material is provided as an extrudeable solid mixture. (device)

[0163] The composite materials described herein may be incorporated into any device using ionic conductors, including but not limited to batteries and fuel cells. For example, in a battery, the composite material may be used as an electrolyte separator.

[0164] The electrode composition further comprises an electrode active material and, optionally, a conductive additive. Examples of cathode and anode compositions are shown below.

[0165] Table 3 below shows examples of cathode compositions. Table 3 [Table 3]

[0166] In various embodiments, the cathode active material is a transition metal oxide, one example being lithium nickel manganese cobalt oxide (LiNiMnCoO2, or NMC). Various forms of NMC, for example LiNi 0.6 Mn 0.2 Co 0.2 O2 (NMC-622), LiNi 0.4 Mn 0.3 Co 0.3 O2 (NMC-4330) and other materials may be used. The lower limit of the wt% range is determined by the energy density, and compositions with less than 65 wt% of active material have a low energy density and may not be useful.

[0167] Any suitable inorganic conductor described above in the explanation of inorganic conductors can be used. 5.6 PS 4.6 Cl 1.4 Li is an example of an argyrodite with high conductivity. 5.4 Cu 0.1 PS 4.6 Cl 1.4 This is an example of an argyrodite that maintains high ionic conductivity and suppresses hydrogen sulfide. Compositions containing less than 10 wt% argyrodite have low Li + It is conductive. Sulfide glass and glass ceramics can also be used.

[0168] Electronically conductive additives are useful for active materials with low electronic conductivity, such as NMCs. Carbon black is one example of such an additive, but other carbon-based additives, including other carbon blacks, activated carbon, carbon fibers, graphite, graphene, and carbon nanotubes (CNTs), may also be used. Less than 1 wt% may not be sufficient to improve electronic conductivity, while more than 5% can lead to a decrease in energy density and interference with active material-argyrodite contact.

[0169] Any suitable organic phase can be used as described above. Less than 1 wt% may not be sufficient to achieve the desired mechanical properties, while more than 5% may cause a decrease in energy density and interference with the active material-inorganic conductor-carbon contact. In some embodiments, polyvinylidene fluoride (PVDF) is used with or without a nonpolar polymer (e.g., polystyrene or PS).

[0170] Table 4 below shows examples of anode compositions. Table 4 [Table 4]

[0171] Graphite can be used as a secondary active material to improve the initial Coulomb efficiency (ICE) of Si anodes. Si has the disadvantage of low ICE (e.g., sometimes less than 80%) compared to NMC and other cathodes, causing irreversible capacity degradation in the first cycle. Graphite has high ICE (e.g., over 90%), enabling full capacity utilization. Hybrid anodes utilizing both Si and graphite as active materials result in an ICE that increases with increasing graphite content, meaning that by adjusting the Si / graphite ratio, the anode's ICE can be made comparable to the cathode's ICE, thus preventing irreversible capacity degradation in the first cycle. ICE can be varied by processing, allowing for a relatively wide range of graphite content depending on the specific anode and its processing. In addition, graphite can improve electronic conductivity and contribute to higher anode density.

[0172] Any suitable inorganic conductor listed above can be used in relation to the cathode.

[0173] High-surface-area electronically conductive additives (e.g., carbon black) may be used in some embodiments. Si has low electronic conductivity, and such additives may be beneficial in addition to graphite (which is an excellent electronically conductive material but has a low surface area). However, silicon-carbon composites and silicon-containing alloys have moderately high electronic conductivity, and in some embodiments, the use of additives may not be necessary. Other high-surface-area carbons (carbon black, activated carbon, graphene, carbon nanotubes) can also be used instead of Super C.

[0174] Any suitable organic phase can be used. In some embodiments, PVDF is used.

[0175] Alkali metal batteries and alkali metal ion batteries are provided herein, comprising an anode, a cathode, and a flexible solid electrolyte composition operably coupled to the anode and cathode. The batteries may also include a separator that physically isolates the anode and cathode, which may be a solid electrolyte composition.

[0176] Examples of suitable anodes, but not limited to those listed here, include anodes formed from carbonaceous materials such as lithium metal, lithium alloys, sodium metal, sodium alloys, and graphite, and combinations thereof. Examples of suitable cathodes, but not limited to those listed here, include cathodes formed from transition metal oxides, doped transition metal oxides, metal phosphates, metal sulfides, lithium iron phosphate, sulfur, and combinations thereof. In some embodiments, the cathode may be a sulfur cathode.

[0177] In alkali metal-air batteries such as lithium-air batteries, sodium-air batteries, or potassium-air batteries, the cathode may be oxygen-permeable (e.g., mesoporous carbon, porous aluminum, etc.), and optionally, the cathode may contain a metal catalyst (e.g., manganese, cobalt, ruthenium, platinum, or silver catalyst, or a combination thereof) incorporated to facilitate the reduction reaction that occurs between lithium ions and oxygen in the cathode.

[0178] In some embodiments, a lithium-sulfur cell is provided comprising a lithium metal anode and a sulfur-containing cathode. In some embodiments, the solid composite electrolyte described herein is unique in that it enables the use of the lithium metal anode by preventing dendrite formation and enables the use of the sulfur cathode by not dissolving the polysulfide intermediate formed at the cathode during discharge.

[0179] Furthermore, a separator formed from any suitable ion-permeable material may be provided to prevent the anode and cathode from making direct electrical contact with each other. However, if the electrolyte composition described herein is a solid composition, particularly in the form of a membrane, they can function as separators.

[0180] In some embodiments, the solid electrolyte composition functions as an electrolyte between the anode and cathode in an alkaline-ion battery that relies on the intercalation of alkaline ions during cycling.

[0181] As described above, in some embodiments, the solid composite composition may be incorporated into one or both of the anode and cathode of the battery. The electrolyte may be a flexible solid electrolyte as described above, or any other suitable electrolyte including a liquid electrolyte.

[0182] In some embodiments, the battery comprises an electrode / electrolyte bilayer, each layer incorporating an ion-conductive solid composite material as described herein.

[0183] Figure 11A shows an example of a schematic diagram of a cell described in a particular embodiment of the present invention. The cell comprises a negative electrode current collector 102, an anode 104, an electrolyte / separator 106, a cathode 108, and a positive electrode current collector 110. The negative electrode current collector 102 and the positive electrode current collector 110 may be any suitable electronically conductive material such as copper, steel, gold, platinum, aluminum, and nickel. In some embodiments, the negative electrode current collector 102 is copper and the positive electrode current collector 110 is aluminum. The current collectors may be in any suitable form such as sheets, foils, meshes, or foams. In various embodiments, one or more of the anode 104, cathode 108, and electrolyte / separator 106 are solid composite materials having the organic and inorganic phases described above. In some embodiments, two or more of the anode 104, cathode 108, and electrolyte 106 are solid composite materials having the organic and inorganic phases described above.

[0184] In some embodiments, the current collector is a porous material that can be embedded in the corresponding electrode. For example, it may be a mesh. Electrodes having a hydrophobic polymer may not adhere well to the current collector when in foil form, but a mesh provides good mechanical contact. In some embodiments, two composite film materials described herein can be pressed onto a mesh current collector to form a current collector embedded in the electrode. In some embodiments, a hydrophilic polymer is used to achieve good adhesion.

[0185] Figure 11B shows an example schematic diagram of an assembled lithium metal cell according to a particular embodiment of the present invention. The assembled cell comprises a negative electrode current collector 102, an electrolyte / separator 106, a cathode 108, and a positive electrode current collector 110. The lithium metal is generated during the initial charge and forms a film on the negative electrode current collector 102 to form the anode. One or both of the electrolyte 106 and the cathode 108 may be the composite materials described above. In some embodiments, the cathode 108 and the electrolyte 106 together form an electrode / electrolyte bilayer. Figure 11C shows an example schematic diagram of a cell according to a particular embodiment of the present invention. The cell comprises a negative electrode current collector 102, an anode 104, a cathode / electrolyte bilayer 112, and a positive electrode current collector 110. Each layer in the bilayer may have a sulfide conductor. Such a bilayer can be prepared, for example, by preparing an electrolyte slurry and depositing it onto the electrode layer.

[0186] All components of the battery can be enclosed in or placed in a suitable rigid or flexible container having external leads or contacts for establishing electrical connections with the anode and cathode, in accordance with known techniques.

[0187] In some embodiments, the composite separator has an organic phase that undergoes in situ polymerization without the formation of by-products as described herein. In some embodiments, one or both electrodes of the battery may have an organic phase that can undergo in situ polymerization without the formation of by-products. In some embodiments, the composite separator and the two electrodes are each formed and assembled separately.

[0188] In some implementations, the composite separator and one or both electrodes are crosslinked via a by-product-free reaction described herein. In such embodiments, the composite separator and one or both electrodes have an organic phase comprising a polymer and low molecules functionalized by by-product-free reactive groups, such as Diels-Alder reactive groups. In some embodiments, the molecules functionalized by Diels-Alder reactive groups may be part of the separator and / or one or both electrodes. In such embodiments, during the polymerization step, the reactive groups can crosslink the composite separator and one or both electrodes. Thus, the composite separator and one or both electrodes have a crosslinked polymer matrix that is substantially free of by-products. This technique can produce a full cell with an intralayer separator having higher mechanical properties without forming by-products. (process)

[0189] The solid composition can be prepared by any suitable method. In various embodiments, in situ polymerization is carried out by mixing ion-conducting particles with a polymer precursor and, if present, any binders, initiators, catalysts, crosslinkers, and other additives, and then initiating polymerization. This can be done in solution or in a dry press, as described below. Polymerization may be initiated and carried out under pressure to establish close interparticle contact.

[0190] Homogeneous films can be prepared by solution processing methods. In one example, all components are mixed together using laboratory and / or industrial equipment such as ultrasonic crushers, homogenizers, high-speed mixers, rotary mills, vertical mills, and planetary ball mills. Mixing media can be added to improve mixing and aid in homogenization by crushing aggregates and lumps, thereby eliminating film defects such as pinholes and high surface roughness. The resulting mixture is in the form of a homogeneously mixed slurry with viscosity varying depending on the hybrid composition and solvent content. Substrates for casting can have various thicknesses and compositions. Examples include aluminum, copper, and mylar. Inorganic particles can be added to the slurry before or at the same time as the addition of crosslinking agents, but generally not after crosslinking.

[0191] The casting of the slurry onto the selected substrate can be achieved by various industrial methods. In some embodiments, porosity can be reduced by mechanically densifying the film (resulting in a thickness change of, for example, up to approximately 50%) by methods such as calendering between rollers, vertical flattening press, or hydrostatic pressing. The pressure associated with the densification process ensures that the particles maintain close contact with each other. For example, an external pressure of approximately 1 MPa to 600 MPa or 1 MPa to 100 MPa is applied. In some embodiments, pressure applied by calendering rolls is used. The pressure is kept low enough to prevent the uncured polymer from being pushed out of the press, but sufficient to achieve interparticle contact. Polymerization, which may include crosslinking, can occur under pressure to form a matrix. In some configurations, thermally initiated or photo-initiated polymerization techniques are used, which begin polymerization using the application of thermal energy or irradiation with ultraviolet light. Ion-conductive inorganic particles are trapped in the matrix and remain in close contact even after being released from external pressure. The composite material prepared by the above method may be, for example, a pellet or a thin film, and can be incorporated into an actual solid-state lithium battery by a well-established method.

[0192] In some embodiments, solid composite separators are fabricated by intralayer thermosetting polymers without forming byproducts during the full cell manufacturing process. For example, a polymer and a low molecular weight functionalized by a Diels-Alder reactive group may react during the full cell calendering stage at a given temperature and pressure (e.g., a temperature of 60°C to 140°C and a pressure of 0.2 ton / cm (200 kg / cm) to 3 ton / cm (3000 kg / cm)). The polymer may be part of the separator and / or electrode, and the molecule functionalized by the Diels-Alder reactive group may be part of the separator and / or electrode. Polymerization in the full cell calendering stage (under controlled temperature and pressure) can produce a full cell with an intralayer separator having higher mechanical properties without forming byproducts.

[0193] In some embodiments, the film is not treated in solution but is treated dry. For example, the film may be extruded. Extrusion or other dry treatments can be alternatives to solution treatment, particularly in organic phases with higher packing density (e.g., in embodiments where the organic phase is at least 30 wt%).

[0194] Figure 12 provides an example of a schematic diagram of multiple cast films containing ion-conducting inorganic particles in a polymer matrix undergoing in situ polymerization for crosslinking polymer chains, for example, in a fuel cell calendar. In the example of Figure 12, three films, namely a first electrode 1201, a separator 1203, and a second electrode 1204, each contain various particles in their polymer matrix. Each polymer matrix may be functionalized with reactive groups that do not form byproducts, such as Diels-Alder reactive groups. The particles and other components of the first electrode, separator, and second electrode are discussed elsewhere in this specification. In some embodiments, the films may be subjected to pressure to increase the density of the films and cause the ion-conducting particles to adhere. Polymerization is initiated by applying an external stimulus, which, in the example of Figure 12, crosslinks the polymer chains of the polymer matrix 1206 of each film. Specifically, the polymer matrices of the first electrode 1201, separator 1203, and / or the second electrode 1204 may crosslink with the polymer matrices of separate films after polymerization. In embodiments where pressure is applied to the membrane, the pressure is released when the crosslinked membrane remains high-density and the ion-conducting particles are in close contact. In some embodiments, only one electrode membrane and separator are present, where the same process can be used to produce a crosslinked polymer matrix of the electrode and separator. (Conclusion)

[0195] While the embodiments described above are described in some detail for the purpose of clarifying understanding, it will be apparent that certain changes and modifications may be made within the scope of the appended claims. Embodiments disclosed herein may be made without some or all of these specific details. In other cases, well-known process steps are not described in detail so as not to unnecessarily obscure the embodiments of this disclosure. Furthermore, while embodiments of this disclosure are described with specific embodiments, it will be understood that these specific embodiments are not intended to limit the embodiments of this disclosure. It should be noted that many alternative means exist for implementing the processes, systems, and apparatus of these embodiments. Therefore, these embodiments should be considered illustrative and non-restrictive, and embodiments should not be limited to the details shown herein.

Claims

1. 60 wt% to 95 wt% ion-conducting inorganic material, An in situ crosslinking matrix comprising 5 wt% to 40 wt% of a binder and a plurality of crosslinking agents, wherein the plurality of crosslinking agents form thermoreversible bonds within the in situ crosslinking matrix. The aforementioned binder -[RM-(L*-R1*)] n- or -[RM1] n1-[RM2] n2-[RM3-(L*-R1*)] n3-[RM4] n4- It includes the structure, R M is a monomer, RM1 is the first monomer, RM2 is the second monomer, RM3 is the third monomer, RM4 is the fourth monomer, L* is a divalent linker, R 1* is a conjugated diene, n is between 1 and 10, Each of n1, n2, n3, and n4 is independently between 0 and 10, and at least one of n1, n2, n3, and n4 is not 0. The aforementioned thermoreversible bond does not generate byproducts, and the in situ crosslinking matrix A hybrid electrolyte composition comprising the following features.

2. The hybrid electrolyte composition according to claim 1, wherein the thermoreversible bond is formed by a Diels-Alder cycloaddition reaction, a Huisgen cycloaddition reaction, a thiol-ene reaction, a Michael addition reaction, a ring-opening reaction, or a click chemistry reaction.

3. The hybrid electrolyte composition according to claim 1 or 2, wherein the ion-conducting inorganic material has lithium.

4. The hybrid electrolyte composition according to claim 3, wherein the ion-conducting inorganic material is a sulfide-based material.

5. The hybrid electrolyte composition according to any one of claims 1 to 4, wherein the binder comprises a polymer skeleton, a copolymer skeleton, or a graft copolymer skeleton.

6. The hybrid electrolyte composition according to claim 5, wherein the binder comprises perfluoroether, epoxy, polybutadiene, poly(styrene-b-butadiene), polyolefin, polysiloxane, polytetrahydrofuran, polystyrene, polyethylene, polybutylene, poly(styrene-butadiene-styrene) (SBS), poly(styrene-ethylene-butylene-styrene) (SEBS), poly(styrene-isoprene-styrene) (SIS), acrylonitrile butadiene rubber, ethylene propylene diene monomer polymer, or copolymers thereof.

7. The hybrid electrolyte composition according to any one of claims 1 to 4, wherein the binder comprises a plurality of inorganic cages.

8. The hybrid electrolyte composition according to claim 7, wherein each of the plurality of inorganic cages comprises silica, silsesquioxane, hydridesilsesquioxane, or partially condensed silsesquioxane.

9. Each of the inorganic cages mentioned above is (SiO １．５ ) ｎ The hybrid electrolyte composition according to claim 7 or 8, comprising n being an integer of 8, 10, or 12.

10. Each of the aforementioned crosslinking agents is (SiO １．５ ) ｎ Bonded to a silicon atom in the first inorganic cage containing (SiO １．５ ) ｎ The hybrid electrolyte composition according to claim 9, wherein the silicon atom is bonded to another silicon atom in a second inorganic cage containing the silicon atom.

11. Each of the plurality of crosslinking agents is -L １ -X １ -L ２ -, -L １ -X １ -L ２ -X ２ -L ３ -, or (-L １ )(-L １ａ )X １ -L ２ -X ２ (L ３ -)(L ３ａ -) has a structure of L １ , L １ａ , L ２ , L ３ , and L ３ａ Each of these comprises an alkylene, a heteroalkylene, or an arylene, each of which may be independently substituted. X １ or X ２ Each of these independently includes a Diels-Alder cycloaddition product, a Husgen cycloaddition product, a thiol-ene reaction product, a Michael addition product, or a ring-opening reaction product. The hybrid electrolyte composition according to any one of claims 1 to 10.

12. L １ , L １ａ , L ２ , L ３ , and L ３ａ Each of these is independently an optionally substituted alkylene, an optionally substituted heteroalkylene, or an optionally substituted arylene. The hybrid electrolyte composition according to claim 11.

13. L １ , L １ａ , L ２ , L ３ , and L ３ａ Each of these is independent: -Cy-, -Ak-Cy-, -Het-Cy-, -Cy-Ak-, -Cy-Het-, -Ak-Cy-Ak, -Het-Cy-Het-, -(Ar) ａ -, - (Ak) ｂ - (O-Ak) ａ - or - (Ak-O) ｂ - (Ak) ａ - and Cy is a divalent linker containing a heterocycle or carbocyclic ring, Ak is an optionally substituted alkylene, Het is an optionally substituted heteroalkylene, and Ar is an optionally substituted arylene. a is an integer between 1 and 10, b is 0 or 1, The hybrid electrolyte composition according to claim 12.

14. X １ or X ２ Each of these independently contains a divalent linker that includes a thio, heterocycle, or carbocycle. The hybrid electrolyte composition according to any one of claims 11 to 13.

15. X １ or X ２ Each of them operates independently, 【Chemistry 1】 It is a part selected from the group consisting of, X ａ ga-C(R １ ) ２ -, -NR １ -, -O-, or -S- X ｂ ga = CR １ - or -N-, X ｃ ga-[C(R １ ) ２ ] ｃ１ -, -NR １ -, -O-, -S-, or -C(O)-O-, R １ is H or an optionally substituted alkyl, c1 is an integer between 1 and 3, The aforementioned portion may be substituted with cyano, hydroxyl, halo, nitro, carboxyaldehyde, carboxyl, alkoxy, oxo, or alkyl. The hybrid electrolyte composition according to claim 14.

16. A membrane comprising the hybrid electrolyte composition according to any one of claims 1 to 15.

17. The film according to claim 16, wherein the elastic modulus of the film is in the range of 0.2 GPa to 3 GPa.

18. A method for forming a hybrid electrolyte composition, The step involves preparing a mixture having a binder component bonded to a first linker containing a first reactive group and an ion-conducting inorganic material, The binder component comprises a monomer bonded to the first linker containing the first reactive group, The aforementioned binder -[RM-(L*-R1*)] n- or -[RM1] n1-[RM2] n2-[RM3-(L*-R1*)] n3-[RM4] n4- It includes the structure, R M is a monomer, RM1 is the first monomer, RM2 is the second monomer, RM3 is the third monomer, RM4 is the fourth monomer, L* is a divalent linker, R 1* is a conjugated diene, n is between 1 and 10, The stage in which each of n1, n2, n3, and n4 is independently between 0 and 10, and at least one of n1, n2, n3, and n4 is not 0, A step of reacting the binder component with a binder to form an in situ crosslinked matrix, wherein the binder includes a second reactant configured to react together with the first reactant to form a thermoreversible bond within the in situ crosslinked matrix, and the thermoreversible bond does not generate byproducts. A method that includes [a certain feature].

19. The method according to claim 18, wherein the first reactant and the second reactant react together to form a Diels-Alder cycloaddition product, a Huisgen cycloaddition product, a thiol-ene reaction product, a Michael addition product, or a ring-opening reaction product.

20. The method according to claim 18 or 19, wherein the first reactive group and the second reactive group are selected from one of the following: a diene-dienophile pair, a 1,3-dipole-parent dipole pair, a thiol-and-optionally-substituted alkene pair, a thiol-and-optionally-substituted alkyne pair, a nucleophile-and-strained heterocyclyl electrophile pair, a nucleophile-and-optionally-substituted α,β-unsaturated carbonyl compound pair, or a nucleophile-and-optionally-substituted strained cyclic compound pair.

21. The method according to claim 20, wherein the first reactant and the second reactant are selected from the group consisting of optionally substituted 1,3-butadiene, optionally substituted alkene, optionally substituted alkyne, optionally substituted α,β-unsaturated aldehyde, optionally substituted unsaturated α,β-thioaldehyde, optionally substituted α,β-unsaturated ketone, optionally substituted azide, optionally substituted thiol, optionally substituted unsaturated cycloalkyl, optionally substituted unsaturated heterocyclyl, optionally substituted α,β-unsaturated imine, optionally substituted aldehyde, optionally substituted imine, optionally substituted nitroso compound, optionally substituted diazene, optionally substituted thioketone, optionally substituted α,β-unsaturated ketone, optionally substituted α,β-unsaturated aldehyde, optionally substituted anionic nucleophile, and optionally substituted strained epoxy.

22. The method according to claim 18, wherein the monomer comprises an optionally substituted styrene monomer, an optionally substituted ethylene monomer, an optionally substituted propylene monomer, an optionally substituted butylene monomer, an optionally substituted butadiene monomer, an optionally substituted perfluoroalkane monomer, an optionally substituted perfluoroether monomer, an optionally substituted isoprene monomer, an optionally substituted ethylidene norbornene monomer, or an optionally substituted diene monomer.

23. The method according to claim 18, wherein each of the first monomer, the second monomer, the third monomer, and the fourth monomer independently comprises an optionally substituted styrene monomer, an optionally substituted ethylene monomer, an optionally substituted propylene monomer, an optionally substituted butylene monomer, an optionally substituted butadiene monomer, an optionally substituted perfluoroalkane monomer, an optionally substituted perfluoroether monomer, an optionally substituted isoprene monomer, an optionally substituted ethylidene norbornene monomer, or an optionally substituted diene monomer.

24. The method according to claim 18, wherein the binder component comprises an inorganic cage bonded to the first linker containing the first reactive group.

25. The method according to any one of claims 18 to 24, wherein the binder further comprises a third reactive group, and at least one of the first reactive group and the second reactive group reacts together to form the thermoreversible bond in the in situ crosslinking matrix, and another first reactive group and the third reactive group react together to form another thermoreversible bond.

26. The method according to claim 25, wherein the second reactant and the third reactant are the same.

27. The aforementioned binder R ２＊ -L ＊ -R ３＊ It has a structure, R ２＊ The second reactive group is, L ＊ It is a divalent linker, R ３＊ The third reactive group is The method according to claim 25 or 26.

28. L ＊ are independently -Cy-, -Ak-Cy-, -Het-Cy-, -Cy-Ak-, -Cy-Het-, -Ak-Cy-Ak, -Het-Cy-Het-, -(Ar) ａ -, - (Ak) ｂ - (O-Ak) ａ - or - (Ak-O) ｂ - (Ak) ａ - and Cy is a divalent linker containing a heterocycle or carbocyclic ring, Ak is an optionally substituted alkylene, Het is an optionally substituted heteroalkylene, and Ar is an optionally substituted arylene. a is an integer between 1 and 10, b is 0 or 1, The method according to claim 27.

29. R ２＊ and R ３＊ The method according to claim 27 or 28, wherein each of is independently selected from the group consisting of optionally substituted alkenes, optionally substituted alkynes, optionally substituted unsaturated cycloalkyls, optionally substituted heterocyclyls, optionally substituted imines, optionally substituted nitroso compounds, optionally substituted azo compounds, optionally substituted thioketones, optionally substituted thiophosphates, and optionally substituted thion oxide compounds.

30. The method according to any one of claims 18 to 29, wherein the thermoreversible bond is formed by a Diels-Alder cycloaddition reaction, a Huisgen cycloaddition reaction, a thiol-ene reaction, a Michael addition reaction, a ring-opening reaction, or a click chemistry reaction.

31. The method according to any one of claims 18 to 29, wherein the thermally reversible bond comprises a Diels-Alder cycloaddition product, a Huisgen cycloaddition product, a thiol-ene reaction product, a Michael addition product, or a ring-opening reaction product.

32. The method according to any one of claims 18 to 31, wherein the thermally reversible bond comprises a thio, an optionally substituted heterocyclyl, or an optionally substituted cycloalkyl.

33. The aforementioned thermoreversible bond, 【Chemistry 2】 Includes a portion selected from the group consisting of, X ａ ga-C(R １ ) ２ -, -NR １ -, -O-, or -S- X ｂ ga = CR １ - or -N-, X ｃ ga-[C(R １ ) ２ ] ｃ１ -, -NR １ -, -O-, -S-, or -C(O)-O-, R １ is H or an optionally substituted alkyl, c1 is an integer between 1 and 3, The aforementioned portion may be substituted with cyano, hydroxyl, halo, nitro, carboxyaldehyde, carboxyl, alkoxy, oxo, or alkyl. The method according to any one of claims 18 to 32.

34. The method according to any one of claims 18 to 33, wherein the hybrid electrolyte composition is the hybrid electrolyte composition according to any one of claims 1 to 15.

35. The steps include casting the hybrid electrolyte composition as a film, The process optionally involves repairing the film by heating it to a temperature range of 100°C to 190°C. The method according to any one of claims 18 to 34, further comprising:

36. A battery comprising the hybrid electrolyte composition according to any one of claims 1 to 15 or the membrane according to claim 16 or 17.

37. An electrode comprising a hybrid electrolyte composition according to any one of claims 1 to 15 or a membrane according to claim 16 or 17.

38. An in situ crosslinking matrix having a binder and a plurality of crosslinking agents, wherein the plurality of crosslinking agents form thermoreversible bonds within the in situ crosslinking matrix, and the thermoreversible bonds do not generate byproducts. The aforementioned binder -[RM-(L*-R1*)] n- or -[RM1] n1-[RM2] n2-[RM3-(L*-R1*)] n3-[RM4] n4- It includes the structure, R M is a monomer, RM1 is the first monomer, RM2 is the second monomer, RM3 is the third monomer, RM4 is the fourth monomer, L* is a divalent linker, R 1* is a conjugated diene, n is between 1 and 10, An in situ crosslinking matrix in which each of n1, n2, n3, and n4 is independently between 0 and 10, and at least one of n1, n2, n3, and n4 is not 0, Electrochemical active materials and Ion-conducting particles and, Optionally, carbon additives and An electrode equipped with the following features.

39. A separator having an ion-conducting inorganic material and a first in-situ crosslinking matrix, An electrode having a second in situ crosslinking matrix, wherein the first in situ crosslinking matrix and the second in situ crosslinking matrix comprise a binder and a plurality of crosslinking agents, The aforementioned binder -[RM-(L*-R1*)] n- or -[RM1] n1-[RM2] n2-[RM3-(L*-R1*)] n3-[RM4] n4- It includes the structure, R M is a monomer, RM1 is the first monomer, RM2 is the second monomer, RM3 is the third monomer, RM4 is the fourth monomer, L* is a divalent linker, R 1* is a conjugated diene, n is between 1 and 10, Each of n1, n2, n3, and n4 is independently between 0 and 10, and at least one of n1, n2, n3, and n4 is not 0. The plurality of crosslinking agents form thermoreversible bonds between the in situ crosslinking matrices, and the thermoreversible bonds do not generate byproducts, and the electrode and A composition comprising the following:

40. In the step of preparing the electrode and the separator composition, the electrode and the separator composition each have a binder component bonded to a first linker containing a first reactive group, The aforementioned binder -[RM-(L*-R1*)] n- or -[RM1] n1-[RM2] n2-[RM3-(L*-R1*)] n3-[RM4] n4- It includes the structure, R M is a monomer, RM1 is the first monomer, RM2 is the second monomer, RM3 is the third monomer, RM4 is the fourth monomer, L* is a divalent linker, R 1* is a conjugated diene, n is between 1 and 10, The stage in which each of n1, n2, n3, and n4 is independently between 0 and 10, and at least one of n1, n2, n3, and n4 is not 0, A step of reacting the electrode and the binder component of the separator composition with a binder to form an in situ crosslinked matrix between the electrode and the separator composition, wherein the binder includes a second reactant configured to react together with the first reactant to form a thermoreversible bond within the in situ crosslinked matrix, and the thermoreversible bond does not produce byproducts. A method for providing this.

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