Composite electrolyte with binder

Abstract

Functionalized polymeric binders for electrolyte and electrode compositions include polymers having a polymer backbone and functional groups. In some embodiments, the polymer includes a non-polar polymer backbone and functional groups that are 0.1 to 5 weight percent of the polymer. In some embodiments, the polymer includes a polar backbone and functional groups that are 0.1 to 50 weight percent of the polymer. Also described are composites for electrolyte separators and electrodes that include an argyrodite ionic conductor and a polar polymer.

Description

[Background technology]

[0001] A PCT application is filed concurrently with this specification as part of this application. As confirmed in the concurrently filed PCT application, each application on which this application claims benefit or priority is incorporated herein by reference in its entirety for any purpose.

[0002] 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. Furthermore, because solid electrolytes are not affected by dendrite formation, the use of lithium metal electrodes may be easier. Solid electrolytes can also offer advantages such as high energy density, good cycle stability, and electrochemical stability under a wide range of conditions. However, there are various challenges to the large-scale practical application 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. -4Although they possess a conductivity (higher than S / cm), they 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 into dense thin films on a large scale. As a result, the bulk electrolyte resistance may be high due to excessive film thickness, or dendrites may form due to the presence of voids that allow dendrite intrusion. Even the relatively ductile mechanical properties of sulfide glasses do not make them suitable for fabricating into dense thin films. Techniques to improve adhesion, such as the addition of solid polymer binders, tend to reduce ionic conductivity, so improving these mechanical properties without sacrificing ionic conductivity is a particular challenge. It is not uncommon to see a decrease in conductivity of more than an order of magnitude with the introduction of just 1 wt% of binder. Solid polymer electrolyte systems can improve mechanical properties that facilitate adhesion and thin film formation, but they may have low ionic conductivity at room temperature or low mechanical strength.

[0003] For the mass production and practical application of solid-state batteries, a material is needed that possesses high ionic conductivity at room temperature without sacrificing ionic conductivity, and is sufficiently suitable to be processed into a dense thin film. [Overview of the project]

[0004] One aspect of the present disclosure relates to a composite comprising inorganic ion-conducting particles and an organic phase containing a polymer binder, wherein the polymer binder comprises a first polymer modified with functional groups, the functional groups comprising 0.1 to 5% by weight of the first polymer. In some embodiments, the first polymer is a nonpolar polymer, and the functional groups are polar groups. In some embodiments, the functional groups are selected from the following: [ka] In the formula, R, R1, R2, and R3 are independent of each other: -CN, -H, -OH, and Me. + ,-OMe +, selected from arbitrarily substituted aryls, arbitrarily substituted alkoxys, arbitrarily substituted alkyls, arbitrarily substituted alkenyls, and arbitrarily substituted alkynyls, where X is independently selected from -F, -Cl, -Br, and -I for each occurrence, and n is an integer from 1 to 10.

[0005] In some embodiments, the first polymer is one of styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), styrene-ethylene / propylene-styrene (SEPS), styrene-ethylene / butylene-styrene (SEBS), styrene-butadiene rubber (SBR), ethylene propylene diene monomer (EPDM) rubber, polybutadiene (PBD), polyethylene (PE), polypropylene (PP), and polystyrene (PS).

[0006] In some embodiments, the polymer binder comprises SEBS (SEBS-gMA) modified with maleic anhydride. In some embodiments, the polymer binder comprises SEBS (SEBS-gFA) modified with furfurylamine.

[0007] In some embodiments, the polymer binder comprises a mixture of a first polymer modified with functional groups and an unmodified first polymer.

[0008] Another aspect of the present disclosure relates to a slurry comprising: a solvent; a polymer binder dissolved in the solvent, wherein the polymer binder comprises a first polymer modified with functional groups, the functional groups comprising 0.1 to 5% by weight of the first polymer; and ion-conducting sulfide particles suspended in the solvent.

[0009] In some embodiments, the solvent has a polarity index of less than 3.5. In some embodiments, the solvent is halogenated and has a polarity index greater than 3.5. In some embodiments, the first polymer is a nonpolar polymer and the functional groups are polar groups. In some embodiments, the functional group is selected from the following: [ka] In the formula, R, R1, R2, and R3 are independent of each other: -CN, -H, -OH, and Me. + ,-OMe + , selected from arbitrarily substituted aryls, arbitrarily substituted alkoxys, arbitrarily substituted alkyls, arbitrarily substituted alkenyls, and arbitrarily substituted alkynyls, where X is independently selected from -F, -Cl, -Br, and -I for each occurrence, and n is an integer from 1 to 10.

[0010] In some embodiments, the first polymer is one of styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), styrene-ethylene / propylene-styrene (SEPS), styrene-ethylene / butylene-styrene (SEBS), styrene-butadiene rubber (SBR), ethylene propylene diene monomer (EPDM) rubber, polybutadiene (PBD), polyethylene (PE), polypropylene (PP), and polystyrene (PS). In some embodiments, the polymer binder comprises SEBS modified with maleic anhydride (SEBS-gMA). In some embodiments, the polymer binder comprises SEBS modified with furfurylamine (SEBS-gFA).

[0011] In some embodiments, the polymer binder comprises a mixture of a first polymer modified with functional groups and an unmodified first polymer.

[0012] Another aspect of the present disclosure relates to a composite comprising inorganic ion-conducting particles and an organic phase comprising a polymer binder, wherein the polymer binder comprises a first polymer modified with functional groups, the functional groups comprising 0.1 to 50% by weight of the first polymer. In some embodiments, the functional groups comprising 5 to 50% by weight of the first polymer.

[0013] In some embodiments, the unmodified first polymer is insoluble in solvents having a polarity index of less than 4.5. In some such embodiments, the modified first polymer is soluble in solvents having a polarity index of less than 4.5. In some embodiments, the unmodified first polymer is insoluble in solvents having a polarity index of less than 3.5. In some such embodiments, the modified first polymer is soluble in solvents having a polarity index of less than 3.5. In some embodiments, the first polymer is polyvinylidene fluoride (PVDF). In some embodiments, the polymer binder comprises styrene-modified PVDF.

[0014] Another aspect of the present disclosure relates to a slurry composition comprising: a solvent; a polymer binder dissolved in the solvent, wherein the polymer binder comprises a first polymer modified with functional groups, the functional groups comprising 0.1 to 50% by weight or 1 to 5% by weight of the first polymer; and ion-conducting sulfide particles suspended in the solvent. In some embodiments, the unmodified first polymer is insoluble in the solvent. In some such embodiments, the solvent has a polarity index of less than 4.5. In some such embodiments, the solvent has a polarity index of less than 3.5. In some embodiments, the first polymer is polyvinylidene fluoride (PVDF). In some embodiments, the polymer binder comprises styrene-modified PVDF.

[0015] Another aspect of the present disclosure relates to a composite comprising inorganic ion-conducting argyrodite-containing particles and an organic phase comprising a polar polymer binder.

[0016] In some embodiments, the composite maintains a temperature of at least 0.2 mS·cm at 25°C. -1 At 25℃, at least 0.25 mS·cm -1 , or 0.3 mS·cm at 25℃ -1has an ionic conductivity. In some such embodiments, the inorganic ion-conductive allidolite-containing particles are 90 wt% or less, 85 wt% or less, or 80 wt% or less of the composite. In some embodiments, the composite has an ionic conductivity of at least 0.6 mS·cm at 25 °C -1 and has an ionic conductivity of at least 0.6 mS·cm at 25 °C -1 or has an ionic conductivity of 0.6 mS·cm at 25 °C -1 . In some such embodiments, the composite has an elongation at break of at least 10%, 15%, or 20%.

[0017] In some embodiments, the polymer binder is poly(vinyl acetate) or nitrile butadiene rubber having a maximum of 30% nitrile groups.

[0018] In some embodiments, the polymer binder is poly(acrylonitrile-co-styrene-co-butadiene) (ABS), poly(ethylene-co-vinyl acetate), poly(styrene-co-acrylonitrile) (SAN), poly(styrene-co-maleic anhydride), poly(meth)acrylate, poly(alkylene glycol), poly(butadiene-co-acrylate), poly(butadiene-co-acrylic acid-co-acrylonitrile), poly(ethylene-co-acrylate), polyether, a polyester of dialkyl phthalate or poly(vinyl chloride) (PVC).

[0019] In some embodiments, the polymer binder comprises a first polymer modified with a functional group, and the functional group is 0.1 to 5 wt% of the first polymer.

[0020] In some embodiments, the polymer binder comprises a first polymer modified with a functional group, and the functional group is 0.1 to 50 wt% of the first polymer. In some such embodiments, the unmodified first polymer is insoluble in a solvent having a polarity index of less than 3.5. In some embodiments, the modified first polymer is soluble in a solvent having a polarity index of less than 3.5.

[0021] In some embodiments, the argyrodite has the formula Li 7-x PS 6-x X x (where X = Cl, Br, I, and 0 < x < 2). In some such embodiments, X is greater than 1.

[0022] Another aspect of the present disclosure relates to a composite comprising inorganic ion-conductive argyrodite-containing particles and an organic phase comprising a polar polymer binder. In some embodiments, the polar polymer binder is poly(vinyl acetate) or nitrile butadiene rubber having up to 30% nitrile groups.

[0023] In some embodiments, the polymer binder is poly(acrylonitrile-co-styrene-co-butadiene) (ABS), poly(ethylene-co-vinyl acetate), poly(styrene-co-acrylonitrile) (SAN), poly(styrene-co-maleic anhydride), poly(meth)acrylate, poly(alkylene glycol), poly(butadiene-co-acrylate), poly(butadiene-co-acrylic acid-co-acrylonitrile), poly(ethylene-co-acrylate), polyether, a polyester of dialkyl phthalate or poly(vinyl chloride) (PVC).

[0024] In some embodiments, the polymer binder comprises a first polymer modified with a functional group, and the functional group is 0.1 to 5 wt% of the first polymer.

[0025] In some embodiments, the polymer binder comprises a first polymer modified with functional groups, the functional groups comprising 0.1 to 50% by weight of the first polymer.

[0026] In some such embodiments, the unmodified first polymer is insoluble in solvents having a polarity index of less than 3.5. In some such embodiments, the modified first polymer is soluble in solvents having a polarity index of less than 3.5.

[0027] These and other aspects will be explained in detail below. [Brief explanation of the drawing]

[0028] [Figure 1A] This section provides schematic examples of cells in various embodiments. [Figure 1B] This section provides schematic examples of cells in various embodiments. [Figure 1C] This section provides schematic examples of cells in various embodiments.

[0029] [Figure 2] This shows the crystal structure of cubic argyrodite Li6PS5Cl. [Modes for carrying out the invention]

[0030] An ion-conductive composite electrolyte having an ion-conductive inorganic phase and an organic phase is provided herein. The composite is a single-ion conductor having good electrochemical stability and room-temperature conductivity. The organic phase comprises a polymer binder that provides sufficient mechanical properties to enable processing and incorporation into all-solid-state batteries. Furthermore, the composite electrolyte can provide the high elasticity, bendability, and mechanical strength required for devices such as flexible electronics that are subjected to significant stress during operation.

[0031] The term "number-average molecular weight" or "Mn" in reference to a specific component of a solid composition (e.g., a high molecular weight polymer binder) refers to the statistical average molecular weight of all molecules of the component, expressed in units of g / mol. The number-average molecular weight can be determined by techniques known in the art, such as gel permeation chromatography (Mn may be calculated based on known criteria based on online detection systems such as refractive index, ultraviolet light, or other detectors), viscometery, mass spectrometry, or colligative methods (e.g., vapor pressure osmosis, end-group determination, or proton NMR). The number-average molecular weight is defined by the following formula:

number

[0032] In the formula, Mi is the molecular weight of the molecule, and Ni is the number of molecules of that molecular weight. In the explanation below, references to the molecular weight of a particular polymer refer to the number-average molecular weight.

[0033] As used herein, the term “alkyl” refers to a linear or branched hydrocarbon containing any number of carbon atoms and not having double or triple bonds in its main chain. As used herein, “lower alkyl” refers to a subset of alkyl groups containing 1 to 6 carbon atoms and being linear or branched hydrocarbon groups. Unless otherwise indicated, the terms “alkyl” and “lower alkyl” both include substituted and unsubstituted alkyl or lower alkyl groups. Examples of lower alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.

[0034] Furthermore, alkyl groups may be substituted or unsubstituted. For example, an alkyl group may be substituted with one, two, three, or, in the case of an alkyl group with two or more carbon atoms, four substituents independently selected from the group consisting of: (1)C 1-6 Alkoxy (e.g., -O-Ak, where Ak is optionally substituted C) 1-6(1) Alkyl, (2)C 1-6 Alkyl sulfinyl (e.g., -S(O)-Ak, where Ak is optionally substituted C) 1-6 (3)C 1-6 Alkylsulfonyl (e.g., -SO2-Ak, where Ak is optionally substituted C) 1-6 (4) Alkyl, (4) Amino (for example, NR N1 R N2 , where R N1 and R N2 Each of them is independently either H or an optionally substituted alkyl, or R N1 and R N2 (1) (1) (2) (3) (3) (4) (3) (4) (3) (4) (4) (3) (4) (4) (3) (4) (4) (4) (3) (4) (4) (4) (4) (4) (4) (4) (4) (4) (4) (5 3-8 Cycloalkyl (e.g., monovalent saturated or unsaturated non-aromatic cyclic C 3-8 Hydrocarbon groups; (12) Halo (e.g., F, Cl, Br, or I), (13) Heterocyclyl (e.g., a 5-membered, 6-membered, or 7-membered ring containing one, two, three, or four noncarbon heteroatoms such as nitrogen, oxygen, phosphorus, sulfur, or halo, unless otherwise specified), (14) Heterocyclyloxy (e.g., -O-Het, where Het is a heterocyclyl as described herein), (15) Heterocycliroyl (e.g., -C(O)-Het, where 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 (for example, alkylene or heteroalkylenedi radicals in which both ends are bonded to the same carbon atom of the parent group), (21)C1-6 Thioalkoxy (e.g., -S-Ak, where Ak is optionally substituted C) 1-6 (Alkyl), (22)thiol (e.g., -SH), (23)-CO2R A , where R A (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl, and (d)(C 4-18 Ariel)C 1-6 Selected from the group consisting of alkyl groups (for example, -L-Ar, where L is the divalent form of an optionally substituted alkyl group and Ar is an optionally substituted aryl group), (24)-C(O)NR B R C , where R B and R C Each of them independently consists of (a) hydrogen and (b) C 1-6 Alkyl, (c)C 4-18 Ariel, (d)(C 4-18 Ariel)C 1-6 Selected from the group consisting of alkyls (for example, -L-Ar, where L is the divalent form of an optionally substituted alkyl group and Ar is an optionally substituted aryl), (25)SO2R D , where R D (a)C 1-6 Alkyl, (b)C 4-18 Aryl, and (c)(C 4-18 Ariel)C 1-6 Selected from the group consisting of alkyl groups (for example, -L-Ar, where L is the divalent form of an optionally substituted alkyl group and Ar is an optionally substituted aryl group), (26)-SO2NR E R F , where R E and R F Each of them independently consists of (a) hydrogen and (b) C 1-6 Alkyl, (c)C 4-18 Ariel, (d)(C 4-18 Ariel)C 1-6Selected from the group consisting of alkyl groups (e.g., -L-Ar, where L is the divalent form of an optionally substituted alkyl group and Ar is the optionally substituted aryl group) and (27)-NR G R H , where R G and R H Each of these independently consists of (a) hydrogen, (b) an N-protecting group, and (c) C 1-6 Alkyl, (d)C 2-6 Alkenyls (e.g., optionally substituted alkyls having one or more double bonds), (e)C 2-6 Alkynnyl (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, where 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 A alkyl group is selected from the group consisting of alkyl groups (e.g., -L-Cy, where L is a divalent form of an optionally substituted alkyl group, and Cy is an optionally substituted cycloalkyl group as described herein), where 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.

[0035] "Alkenyl {XE "Alkenyl"}" refers to an optionally substituted carbon having one or more double bonds. 2-24means an alkyl group. An alkenyl group may be cyclic (e.g., C 3-24 cycloalkenyl), or acyclic. Also, the alkenyl group may be substituted or unsubstituted. For example, the alkenyl group may be substituted with one or more substituents as described herein for alkyl. In some embodiments, an unsubstituted alkenyl group is a C 2-6 C 2-12 C 2-16 C 2-18 C 2-20 or C 2-24 alkenyl group.

[0036] "Alkynyl {XE "Alkynyl"}" means an optionally substituted C 2-24 alkyl group having one or more triple bonds. The alkynyl group may be cyclic or acyclic, and examples thereof include ethynyl and 1-propynyl. Also, the alkynyl group may be substituted or unsubstituted. For example, the alkynyl group may be substituted with one or more substituents as described herein for alkyl. In some embodiments, an unsubstituted alkynyl group is a C 2-6 C 2-12 C 2-16 C 2-18 C 2-20 or C 2-24 alkynyl group.

[0037] "Alkoxy" means -OR, where R is an optionally substituted alkyl group as described herein. Exemplary alkoxy groups include methoxy, ethoxy, butoxy, trihaloalkoxy such as trifluoromethoxy, etc. The alkoxy group may be substituted or unsubstituted. For example, the alkoxy group may be substituted with one or more substituents as described herein for alkyl. Exemplary unsubstituted alkoxy groups include C 1-3 C 1-6 C 1-12 C 1-16 C 1-18 C1-20 , or C 1-24 An example is an alkoxy group.

[0038] As used herein, the term "aryl" refers to groups containing monocyclic and bicyclic aromatic groups. Examples include phenyl, benzyl, anthracenyl, anthryl, benzocyclobutenyl, benzocyclooctenyl, biphenylyl, crisenyl, dihydroindenyl, fluoranthenyl, indacenyl, indenyl, naphthyl, phenanthryl, phenoxybenzyl, picenyl, pyrenyl, terphenyl, and condensed benzo-C groups. 4-8 Cycloalkyl groups (as defined herein, for example), such as indanyl, tetrahydronaphthyl, and fluorenyl. The term aryl also includes heteroaryl groups, which are defined as groups containing an aromatic group in which at least one heteroatom is incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Similarly, the term nonheteroaryl is also included in the term aryl and defines groups containing an aromatic group that does not contain a heteroatom. The aryl group may be substituted or unsubstituted. The aryl group may be substituted with one, two, three, four, or five substituents, as described herein for alkyl groups. 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.

[0039] Unless otherwise specified, "heterocyclyl" refers to 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 in which any of the above heterocycles are fused to 1, 2, or 3 rings independently selected from the group consisting of aryl rings, cyclohexane rings, cyclohexene rings, cyclopentane rings, cyclopentene rings, and other monocyclic heterocycles, such as indolyl, quinolyl, isoquinolyl, tetrahydroquinolyl, benzofuryl, benzothienyl, etc. As heterocycles, acridinyl, adenyl, alloxadinyl, azaadamantanyl, azabenzimidazolyl, azabicyclononyl, azacycloheptyl, azacyclooctyl, azacyclononyl, azahypoxanthinyl, azaidazolyl, azaindyl, azesinyl, azepanyl, azepinyl, azetidinyl, azetyl, aziridinyl, azilinyl, azokanyl, azosinyl, azonanyl, benzimidazolyl, benzisothiazolyl, benzisoxazolyl, benzodiazepinyl, benzodiazosinyl, benzodihydrofuryl, benzodioxepinyl, benzodioxenyl, benzodioxonyl, benzodioxosinyl, benzodioxolyl, benzodithiepinyl, benzodithyinyl Benzodioxosinil, benzofuranil, benzophenazinil, benzopyranonil, benzopyranil, benzopyrenil, benzopyronil, benzoquinolinil, benzoquinolidinil, benzothiadiazepinil, benzothiadiazolyl, benzothiazepinil, benzothiazosinil, benzothiazolyl, benzothienyl, benzothiophenyl, benzothiadinil, benzothiadinil, benzothiopyranil, benzothiopyronil, benzotriazepinil, benzotriazinil, benzotriazinil, benzotriazolyl, benzooxathinil, benzotrioxepinil, benzooxadiazepinil, benzooxathiazepinil, benzooxathiepinil, benzooxathiosinil, benzooxazepinil,Benzoxazinyl, benzoxazosinyl, benzoxazolinonyl, benzoxazolinyl, benzoxazolyl, benzylsultamyl, benzylsultimyl, bipyradinyl, bipyridinyl, carbazolyl (e.g., 4H-carbazolyl), carborinyl (e.g., β-carborinyl), chromanonyl, chromanil, clomenyl, cinolinil, coumarinil, cytidinyl, cytosinyl, decahydroisoquinolinyl, decahydroquinolinyl, diazabicyclooctyl, diazetyl, diaziridinionyl, diaziridinonyl, diazirinyl, diazirinyl Dibenzisoquinolinyl, dibenzoacridinyl, dibenzocarbazolyl, dibenzofuranyl, dibenzophenadinyl, dibenzopyranonyl, dibenzopyronyl (xanthonyl), dibenzoquinoxalinyl, dibenzothiazepinyl, dibenzothiepinyl, dibenzothiophenyl, dibenzooxepinyl, dihydroazepinyl, dihydroazetyl, dihydrofuranyl, dihydrofuryl, dihydroisoquinolinyl, dihydropyranyl, dihydropyridinyl, dihydropyridyl, dihydroquinolinyl, dihydrothienyl, dihydroindolyl, dioxane Dioxazinyl, dioxyindolyl, dioxyranyl, dioxenyl, dioxynyl, dioxobenzofuranyl, dioxolyl, dioxotetrahydrofuranyl, dioxothiomorpholinyl, dithianyl, dithiazolyl, dithienyl, dithinyl, furanyl, furazanyl, froyl, furyl, guaninyl, homopiperazinyl, homopiperidinyl, hypoxanthinyl, hydantoinyl, imidazolidinyl, imidazolinyl, imidazolyl, indazolyl (e.g., 1H-indazolyl), indrenyl, indolinyl, indolidinyl, indolyl (For example, 1H-indolyl or 3H-indolyl), isatinyl, isatyl, isobenzofuranil, isochromanil, isoclomenil, isoindazoyl, isoindolinil, isoindolyl, isopyrazolonil, isopyrazolyl, isoxazolidinil, isoxazolyl, isoquinolinil, isoquinolinil, isothiazolidinil, isothiazolyl, morpholinil, naphthindazolyl, naphthoindolyl, naphthilidinil, naphthopyranil, naphthothiazolyl, naphthothioxolyl, naphthitriazolyl, naphthitoxindolyl, naphthilidinil,Octahydroisoquinolinyl, oxabicycloheptyl, oxauracil, oxadiazolyl, oxazinyl, oxaziridinyl, oxazolidonyl, oxazolinyl, oxazolonyl, oxazolyl, oxepanil, oxetanonyl, oxetanyl, oxetyl, oxetanyl, oxyindolyl, oxyranil, oxobenzoisothiazolyl, oxoclomenyl, oxoisoquinolinyl, oxoquinolinyl, oxothiolanil, phenanthidinyl, phenanthrolinyl, phenadinyl, phenothiazinyl, phenothienyl (ben Zothiofuranil), phenoxathinyl, phenoxadinyl, phthalazinyl, phthalazonyl, phthalidyl, phthalimidinyl, piperadinyl, piperidinyl, piperidonyl (e.g., 4-piperidonyl), pteridinyl, prinyl, pyranyl, pyrazinyl, pyrazolidinyl, pyrazolinyl, pyrazolopyrimidinyl, pyrazolyl, pyridadinyl, pyridinyl, pyridopyramidinyl, pyridopyrimidinyl, pyridyl, pyrimidinyl, pyrimidyl, pyronyl, pyrrolidinyl, pyrrolidonyl (e.g., 2-pyrrolidonyl), pyrrolidinyl, pyrrolidinyl, pyrrolyl ( For example, 2H-pyrrolyl), pyrylium, quinazolinyl, quinolinyl, quinolidinyl (for example, 4H-quinolidinyl), quinoxalinyl, quinuclidinyl, serenadinyl, serenazolyl, selenofenyl, succinimidyl, sulforanyl, tetrahydrofuranyl, tetrahydrofuryl, tetrahydroisoquinolinyl, tetrahydroisoquinolyl, tetrahydropyridinyl, tetrahydropyridyl (piperidyl), tetrahydropyranyl, tetrahydropyronyl, tetrahydroquinolinyl, tetrahydroquinolyl, tetrahydrothienyl, tetrahydrothio Phenyl, tetradinyl, tetrazolyl, thiadiazinyl (e.g., 6H-1,2,5-thiadiazinyl or 2H,6H-1,5,2-dithiadinyl), thiadiazolyl, thiantrenil, thianyl, thianaphthenyl, thiazepinyl, thiadinyl, thiazolidinyl, thiazolidinyl, thiazolyl, thienyl, thiepanyl, thiepinyl, thietanyl, thiichil, thiiranil, thiokanyl, thiochromanonyl, thiochromanyl, thioclomenyl, thiodiadinyl, thiodiazolyl, thioindoxyl, thiomorpholinyl, thiophenyl, thiopyranil,Examples include thiopyronyl, thiotriazolyl, thiourazolyl, thioxanil, thioxolyl, thymidinyl, thyminyl, triazinyl, trizolyl, trithianil, urazolyl, uretidinyl, uretinyl, uricin, uridinyl, xanthenyl, xanthinyl, xanthionyl, and their modified forms (e.g., including one or more oxo and / or amino) and their salts. The heterocyclyl group may be substituted or unsubstituted. For example, the heterocyclyl group may be substituted with one or more substituents, as described herein for alkyl groups. Introduction

[0040] Ion-conductive composite electrolytes, having an ion-conductive inorganic phase and a non-ion-conductive organic phase, can address various challenges in the manufacture and use of solid electrolytes. Certain embodiments of the composite electrolyte have a relatively high polymer load (e.g., about 50% by volume). This enables use in flexible electronics and provides good mechanical properties.

[0041] Most modern composite electrolytes containing a high proportion of organic matter rely on an ion-conducting polymer matrix rather than an inorganic conductor. Typical polymer electrolytes are prepared by dissolving inorganic salts in a polymer matrix, resulting in a non-uniform ion conductor with relatively low ion conductivity and transportability, requiring high temperatures for proper operation. Furthermore, these electrolytes have low oxidative stability and tend to decompose during cell operation, leading to inefficient cycle performance and reduced cell life. However, the mechanical properties of the polymer allow for easy processing, good interfacial contact with electrodes, and flexibility for proper handling and operation of solid-state batteries. Polymer electrolytes can be prepared as composites with either ion-conducting or non-conducting inorganic fillers, improving both mechanical and electrochemical properties. However, even with the addition of inorganic particles, polymer electrolytes still suffer from stability issues and the drawbacks of non-uniform ion transportability.

[0042] Ion-conductive composite electrolytes having an ion-conductive inorganic phase and an organic phase are provided herein. In some embodiments, the composite is a single-ion conductor having good electrochemical stability and room-temperature conductivity. The organic phase comprises a polymer binder that provides sufficient mechanical properties to enable processing and incorporation into all-solid-state batteries. Furthermore, the composite electrolyte can provide the high elasticity, bendability, and mechanical strength required for devices such as flexible electronics that are subjected to significant stress during operation. organic phase

[0043] The organic polymer phase may contain one or more polymers and is chemically compatible with inorganic ion-conducting particles. In some embodiments, the organic phase has substantially no ionic conductivity and is referred to as "non-ionic conductor." Non-ionic conductor polymers are described herein as having an ionic conductivity of less than 0.0001 S / cm.

[0044] According to various embodiments, the organic phase may contain a polymeric binder that is polar or nonpolar. There are various types of physical forces that occur within molecules. The strength of such forces varies and largely depends on the structure of the interacting molecules. The weakest force is known as dispersion force (also called London dispersion force or van der Waals force) and is present in all atoms and molecules. Such forces are brought about by transient dipoles, which arise from the uneven distribution of electrons within an atom / molecule, inducing dipoles in the opposite direction in adjacent molecules / atoms. The formation of transient dipoles induces positive and negative partial charges, which are the source of positive attraction. Such attraction increases with the size of the electron cloud, the molar mass of the particle, and the surface area. These are the only types of interactions found in nonpolar molecules and noble gases. Dipole-dipole forces arise from permanent dipoles in polar molecules, in which case the molecules are positioned such that the positive partial charge of one particle is next to the negative charge of an adjacent molecule. This force is stronger than the London dispersion force and increases as the electronegativity difference between the dipole-forming atoms increases. Furthermore, this attraction increases as the distance between the attracting molecules decreases, and as the size of the attracted molecule decreases. Hydrogen bonding is a special, strong type of dipole-dipole interaction that occurs between molecules containing hydrogen atoms directly bonded to small, highly electronegative atoms such as nitrogen (N), oxygen (O), or fluorine (F). In such cases, positive and negative permanent partial charges are formed on both the hydrogen atom and the electronegative atom. These permanent partial charges result in an even stronger attraction than in the case of dipole-dipole forces. Ionic-dipole forces are forces that arise when either an ion or charge is attracted to an opposing permanent dipole generated within a polar molecule, causing the ion to be surrounded by molecules with dipoles of the opposite charge. These forces are involved in the dissolution of salts, such as electrolytes in lithium-ion batteries or metal-ion complexes with organic ligands.

[0045] In this specification, a nonpolar binder refers to a material that, in its pure form, undergoes intramolecular interactions through weak dispersion forces. In such materials, other stronger interactions, such as dipole-dipole or hydrogen bonding, which can affect the complex electrolyte, contribute little. Examples include styrene-ethylene-butylene-styrene (SEBS), styrene-butadiene-styrene (SBS), polystyrene (PSt), styrene-isoprene-styrene (SIS), and polyethylene. Such materials exhibit low affinity and weak interactions with inorganic materials such as solid lithium-ion conductors or lithium salts. In some cases, the presence of polar groups at low concentrations may be acceptable as long as the contribution of stronger forces is negligible. For example, a binder having less than 2% by weight or less than 0.5% by weight of polar groups may still be nonpolar if the contribution of stronger forces is negligible. Other polymeric binders are polar. In yet another embodiment, the nonpolar binder is a hydrocarbon (e.g., containing only carbon and hydrogen atoms) or contains hydrocarbons. Polar binders have a significant effect in providing a stronger attraction to the properties of the composite electrolyte. These properties include, but are not limited to, tensile strength, modulus of elasticity, elongation at break, ionic conductivity, and particle dispersibility. The level of polarity can range from very low to very high. Examples of low-polarity binders include SEBS modified with grafted maleic anhydride or SBS modified with carboxylic acid. Polarity depends not only on the properties of the polar groups but also on their weight fraction. In some embodiments, this may be as low as 0.1% by weight. In some embodiments, it is greater than 0.5% by weight, e.g., 1-5% by weight. Examples of more polar binders include polymers having more than 5% grafted polar groups. Examples of very polar polymers include poly(vinyl acetate) and poly(methyl methacrylate) PMMA. In yet another embodiment, the polarity binder is or contains a hydrocarbon having one or more non-carbon heteroatoms (e.g., nitrogen, oxygen, sulfur, silicon, etc.).Such heteroatoms can be provided by grafted functional groups, as described herein.

[0046] In some embodiments, the organic phase comprises a polymer binder, a relatively high molecular weight polymer, or a mixture of polymers with different molecular weights. The polymer binder has a molecular weight of at least 30 kg / mol, and may be at least 50 kg / mol, or even 100 kg / mol. The molecular weight distribution can be monomodal, bimodal, or multimodal.

[0047] In some embodiments, the polymer binder has a nonpolar backbone. Examples of nonpolar polymer binders include polymers or copolymers containing styrene, butadiene, isoprene, ethylene, and butylene. Styrene-based block copolymers, including polystyrene blocks and rubber blocks, may be used; examples of rubber blocks include polybutadiene (PBD) and polyisoprene (PI). The rubber blocks may be hydrogenated or not. Specific examples of polymer binders include styreneethylenebutylenestyrene (SEBS), styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), styrene-butadiene rubber (SBR), polystyrene (PSt), PBD, polyethylene (PE), and PI. Because nonpolar polymers do not coat inorganic particles, they may reduce conductivity.

[0048] The main chain or backbone of the polymer components in the organic phase does not strongly interact with the inorganic phase. Examples of backbones include saturated or unsaturated polyalkyls, polycyclic aromatics, and polysiloxanes. Examples of backbones that may interact too strongly with the inorganic phase include those with strong electron-donating groups, such as polyalcohols, polyacids, polyesters, polyethers, polyamines, and polyamides. It should be understood that molecules with other parts that reduce the bond strength of oxygen or other nucleophiles may be used. For example, the perfluoro properties of the perfluoropolyether (PFPE) backbone delocalize the electron density of the ether oxygen, enabling its use in certain embodiments.

[0049] In some embodiments, hydrophobic block copolymers having both a plastic copolymer segment and an elastic copolymer segment are used. Examples include styrene-based block copolymers, such as SEBS, SBS, SIS, styrene-isoprene / butadiene-styrene (SIBS), styrene-ethylene / propylene (SEP), styrene-ethylene / propylene-styrene (SEPS), and isoprene rubber (IR).

[0050] In embodiments where the binder is a copolymer, the constituent polymers can be distributed in any suitable manner, such as the binder being a block copolymer, random copolymer, statistical copolymer, graft copolymer, etc. The polymer backbone may be linear or nonlinear, in examples including branched, star-shaped, comb-shaped, and bottlebrush-shaped polymers. Furthermore, the transitions between the constituent polymers of the copolymer may be sharp, tapered, or random.

[0051] In some embodiments, the organic phase is substantially nonionic conductive, and examples of nonionic conductive polymers include PDMS, PBD, and other polymers mentioned above. Unlike ionic conductive polymers such as polyethylene oxide (PEO), polypropylene oxide (PPO), polyacrylonitrile (PAN), and poly(methyl methacrylate) (PMMA), which are ionic conductive by dissolving or dissociating salts such as LiI, nonionic conductive polymers are not ionic conductive even in the presence of salts. This is because, unless the salt is dissolved, there are no mobile ions to conduct. In some embodiments, one or another ionic conductive polymer may be used. PFPE, described above and incorporated herein by reference in Compliant glass-polymer hybrid single ion-conducting electrolytes for lithium ion batteries, PNAS, 52-57, vol.113, no.1 (2016), is ionic conductive and a single ion conductor of lithium, and may be used in some embodiments.

[0052] In some embodiments, the organic phase may include crosslinking. In some embodiments, the organic phase is a crosslinked polymer network. The crosslinked polymer network can be crosslinked in situ, that is, after inorganic particles have been mixed with a polymer or polymer precursor to form a composite. In-situ polymerization of polymers (including in-situ crosslinking) is described in U.S. Patent No. 10,079,404, which is incorporated herein by reference. Polar polymer binder

[0053] Polar polymer binders used in other battery applications, such as carboxymethylcellulose (CMC), polyethylene oxide (PEO), and polyvinylidene fluoride (PVDF), result in composites with low ionic conductivity when mixed with inorganic conductors. This is because the polymers can strongly bond to the surface of inorganic particles, forming a dense insulating film that prevents direct contact between adjacent particles. Such polymers can insulate particles even at low concentrations of 1-5% by weight, blocking the lithium ion pathway throughout the composite, thus resulting in highly resistant materials.

[0054] In some embodiments, the polymer binder is a thermoplastic elastomer such as SEBS, SBS, or SIS. The nonpolarity and hydrophobicity of such binders make it possible to maintain high initial conductivity of the pure inorganic conductor. In composite materials including electrolyte separators and electrodes, solvents and / or polymers may cause chemical or morphological changes and / or a decrease in conductivity of the inorganic conductor. For example, sulfide-based inorganic conductors containing argyrodite-like inorganics may decompose due to polar polymers and / or polar solvents.

[0055] Another issue addressed in this disclosure is the instability of sulfide-based materials in composite electrolytes in solvents with moderate or very high polarity. Table 1 below shows the effect of solvent polarity on the stability of sulfide-based materials. Table 1: Effect of solvent polarity on the stability of sulfide-based materials [Table 1] * Sulfide-based materials are stable in halogenated solvents in this range, including chloroform.

[0056] Glass materials (such as LPS glass) are susceptible to crystallization by polar solvents or polymers, which can lead to severe loss of conductivity, whereas crystalline argyrodites retain conductivity better. Therefore, in some embodiments, argyrodite-containing composites can be prepared using a variety of polymeric binders, including highly polar ones, as long as the process is carried out without using polar solvents that degrade inorganic materials. Examples of such binders include poly(vinyl acetate), nitrile butadiene rubber having up to 30% nitrile groups, poly(acrylonitrile-co-styrene-co-butadiene) (ABS), poly(ethylene-co-vinyl acetate), poly(styrene-co-acrylonitrile) (SAN), poly(styrene-co-maleic anhydride), poly(meth)acrylate, poly(alkylene glycol), poly(butadiene-co-acrylate), poly(butadiene-co-acrylic acid-co-acrylonitrile), poly(ethylene-co-acrylate), polyether, dialkyl phthalate polyester, or poly(vinyl chloride) (PVC).

[0057] The embodiments described herein comprise a polymer binder containing one or more functional groups. The functional groups can improve one or more of the following properties: solubility in organic solvents, adhesion to inorganic particles, adhesion to current collectors, dispersibility of inorganic particles, mechanical properties, ionic conductivity, and electronic conductivity.

[0058] In certain embodiments, nonpolar binders such as SEBS are modified with small amounts of polar functional groups. The binders thus obtained have mechanical properties suitable for use in complexes. In certain embodiments, polar binders such as PVDF are modified with functional groups. The binders thus obtained are soluble in less polar solvents. Functionalized polymer binders

[0059] The polymer of the polymer binder has a functionalized or otherwise functionalized backbone. As described above, in some embodiments, the polymer backbone is nonpolar. Examples include copolymers (block, gradient, random, etc.), e.g., styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), styrene-ethylene / propylene-styrene (SEPS), styrene-ethylene-butylene-styrene (SEBS), styrene-butadiene rubber (SBR), ethylene propylene diene monomer (EPDM) rubber, and homopolymers, e.g., polybutadiene (PBD), polyethylene (PE), polypropylene (PP), and polystyrene (PS). In some embodiments, the polymer is polar, examples of which include acrylonitrile-butadiene-styrene (ABS), nitrile rubber (NBR), ethylene vinyl acetate (EVA) copolymer, and oxidized polyethylene. Further examples include fluoropolymers, e.g., PVDF, polytetrafluoroethylene, and perfluoropolyether (PFPE), and silicones, e.g., polydimethylsiloxane (PDMS). functional group

[0060] Functional groups include aromatics, alkyls (saturated and unsaturated, e.g., alkenyls or alkynyls), alcohols (-OH), amines (-N-R1R2, where R1 and R2 are independently H, optionally substituted alkyls, or optionally substituted aryls, or R1 and R2 together with the nitrogen atom to which they are each bonded to form a heterocyclyl group), heterocyclyls (e.g., substituted furanyls, thiophenyls, or pyrrolyls), carboxylic acids (-C(=O)OH), and carboxylates (-C(=O)O - M + ), carboxylic acid esters (C(=O)OR), amides (-C(=O)NR1R2), ethers (-OR), thiols (-SH), thioethers (-SR), disulfides (-SS-R), nitros (-NO2), sulfonic acids (-S(=O)2OH), sulfonates (-S(=O)2O - M +), sulfonic acid ester (-S(=O)2OR), sulfoxide (-S(=O)2R), sulfinic acid (-S(=O)OH), sulfinate (-S(=O)O - M + ), sulfinic acid esters (-S(=O)OR), sulfinamides (-S(=O)NR1R2), sulfonamides (-S(=O)2NR1R2), nitriles (-CN), azides (-N3), anhydrides (-C(=O)OC(=O)R), ketones (-C(=O)R), aldehydes (-C(O)H), acids, salts and esters of phosphates (-OP(=O)(OR)2), acids, salts and esters of phosphonates (-P(=O)(OR) 2) Examples include, but are not limited to, acids, salts and esters of phosphinates (-P(-R)(=O)OR), phosphines (-P(=O)(-R)3), phosphates, phosphonates, amides and amide esters of phosphinates and phosphines, carbonates, cyclic esters, cyclic anhydrides, β-keto acids, esters and salts, maleic acid, esters, salt anhydrides, maleimides, malamides, and succinic acid derivatives. Examples are given below. [ka] In the formula, R, R1, R2, and R3 are independently -CN, -H, -OH, metal cation, and Me for each occurrence. + ,-OMe + , selected from optionally substituted aryl, optionally substituted alkoxy, optionally substituted alkyl, optionally substituted alkenyl, and optionally substituted alkynyl, where X is independently selected from -F, -Cl, -Br, and -I for each occurrence, and n is an integer from 1 to 10. Metal cation Me + For example, Li + Na + , K + Examples include: In some cases, metal cations Me + It interacts with non-carbon heteroatoms (e.g., O, N, S, etc.).

[0061] Functional groups can be incorporated during the polymerization and / or post-polymerization functionalization stages. Polymers can be prepared with one or more functional groups, depending on the target function of the 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.

[0062] In certain cases, nonpolar skeletons may be functionalized with polar groups to improve mechanical performance. Functionalization of nonpolar skeletons such as SEBS with groups such as maleic anhydride and furfurylamine is described in detail below.

[0063] In some embodiments, the polymer binder has a nonpolar backbone. Polar backbones, such as PVDF and NBR, may be functionalized with functional groups to improve solubility in solvents with lower P-indexes. Examples of functional groups include, but are not limited to, fully and partially saturated and unsaturated linear, branched, or cyclic hydrocarbons, i.e., n-butyl, n-hexyl, n-dodecyl, 2-ethylhexyl, cyclohexyl, palmitoyl, linoleoyl, or butenyl groups. Other nonpolar groups include aromatic groups such as phenyl, benzyl, and naphthalene functional groups. Furthermore, more polar functional groups may be used, as long as they are soluble in solvents of a particular P-index (Table 1). Examples include, but are not limited to, various mono-, di-, oligo-, and polyesters such as esters of fatty acids or higher C alcohols, i.e., palmitate, myristate, or dodecanol esters, polyesters, i.e., poly(lauryllactone)-block-polytetrahydrofuran, or other polymers such as poly(methyl methacrylate) and poly(2-ethylhexyl acrylate). Functionalization of PVDF with nonpolar groups such as styrene will be discussed in detail below.

[0064] In some embodiments, the binder is functionalized to improve adhesion to the current collector. In some embodiments, the binder may be functionalized with a silane to improve adhesion to metal current collectors, particularly aluminum and copper. In some embodiments, the binder may be functionalized with an acidic functional group such as a phosphate or carboxylate that bonds to the metal surface by a chemical reaction. Furthermore, adhesion can be enhanced by physical interactions, such as hydrogen bonding or ionic coordination, that occur between species present on the surface of the current collector and the binder functional groups, such as alcohols, amides, and esters.

[0065] In some embodiments, the binder is functionalized to improve the mechanical properties and processability of the composites. The presence of polar groups can induce ionic conductivity in the polymer phase when mixed with lithium salts, i.e., LiPF6, LiTFSI, LiClO4, etc. However, in many embodiments, ionic conductivity through the polymer phase is expected to be several orders of magnitude lower than that of inorganic conductors, and therefore its contribution to total ionic conductivity is expected to be negligibly small. This is generally true unless the polymer is specifically designed to be ionically conductive. Hydrophobic binders modified with polar groups

[0066] In some embodiments, the polymer binder is a thermoplastic elastomer such as SEBS, SBS, or SIS. The low polarity and hydrophobicity of such binders make it possible to maintain high initial conductivity of pure inorganic conductors such as LPS glass or argyrodite.

[0067] In some embodiments, the polymer binder backbone is SEBS. SEBS is saturated SBS. Saturation reduces unwanted chemical reactions with inorganic materials or gelation on electrodes, improving thermal stability. This is especially true for SBS with a high 1,2-vinyl content. Pure PBD (0% styrene) is a rubber-like material, and pure PS is a brittle resin. These copolymers, such as SBS or SEBS, exhibit mixed properties, with their plastic and elastic behavior controlled by the volume ratio of their components. According to various embodiments, SBS or SEBS with a styrene volume fraction of 10% to 90%, and more specifically 15% to 65%, can be used. The triblock polymer backbone provides high elasticity and mechanical strength while maintaining a highly hydrophobic composition. Polyolefin and polystyrene blocks rely on London forces and π-π forces, and their interaction with inorganic conductive particles is very weak. Therefore, relatively low pressure and temperature (above the Tg of polystyrene) are sufficient to break the physical bond between the binder and the inorganic surface, enabling interparticle contact and, consequently, high conductivity of the composite electrolyte. However, weak particle-polymer interactions can significantly affect interphase contact, degrading the mechanical properties of the composite and potentially leading to problems with wetting, adhesion, and delamination.

[0068] Provided herein are hydrophobic binders modified with a low proportion of polar groups (at a few percent level, e.g., 0.5–5%) that are well used as binders for hybrid electrolytes and exhibit improved mechanical properties while maintaining acceptable ionic conductivity at room temperature.

[0069] Thermoplastic elastomers such as SEBS, SBS, or SIS may be modified with polar groups such as maleic anhydride or furfurylamine. Examples 1 and 2 below describe the increased modulus, tensile strength, and elongation at break of a modified SEBS binder. Polar binders modified with nonpolar groups

[0070] In some embodiments, the polymer binder backbone is a polar polymer such as PVDF or NBR. In some embodiments, the polar polymer is functionalized to improve its solubility in solvents compatible with inorganic conductors. In some embodiments, the polar polymer is functionalized to improve its compatibility with inorganic conductors.

[0071] In composite materials containing electrolyte separators and electrodes, solvents and / or polymers can cause chemical or morphological changes and / or a decrease in conductivity of inorganic conductors. For example, sulfide-based inorganic conductors such as Li2S-P2S5, Li2S-P2S5-LiX, Li2S-P2S5-Li2O, LiX-P2S5-Li3PO4 glass, glass ceramics, and ceramics, as well as argyrodite-like inorganic materials, can be decomposed by polar solvents and / or polar polymers.

[0072] Very polar to moderately polar solvents such as NMP, DMF, DMSO, ethanol, THF, acetone, and ethyl acetate should be avoided as they interfere with conductivity loss or other undesirable changes. Low-polarity solvents, including hydrocarbons (pentane, hexane, heptane, cyclohexane), aromatics (toluene, xylene, trimethylbenzene), chlorinated aromatics and hydrocarbons (chlorobenzene, dichlorobenzene, dichloromethane, dichloroethane, chloroform), higher C esters, ethers, and ketones (2-ethylhexyl acetate, butyl butyrate, dibutyl ether, cyclohexanone) are usable as they have no effect on inorganic conductors. Table 1 above provides guidelines regarding the polarity index of solvents usable in some embodiments.

[0073] Binders with moderate polarity, such as NBR, are insoluble or have low solubility in solvents with P < 3.5, typically requiring solvents with P around 4, such as THF or acetone. For highly polar binders, such as PVDF, only solvents like NMP (P = 6.7) can dissolve the binder. In some embodiments, polar binders are provided that are functionalized with functional groups to reduce polarity and provide improved solubility in sulfide-compatible solvents. That is, binders such as NBR or PVDF are functionalized with non-polar groups to improve solubility in solvents with low P index. In some embodiments, up to 50% by weight of the binder consists of functional groups.

[0074] In some embodiments, modified PVDF binders are provided. PVDF is either directly copolymerized with styrene during synthesis (Scheme 1A) or modified with a radical-active monomer such as chlorotrifluoroethylene (Scheme 1B). Furthermore, PVdF can be modified by post-functionalization processes such as oxide formation by ozone pretreatment or double bond incorporation by base treatment. [ka] Scheme 1 (A) Direct copolymerization with styrene, (B) Graft polymerization from PVdF copolymerized with chlorotrifluoroethylene, and (C) Incorporation of polystyrene into PVdF by radical styrene graft polymerization from base-treated PVdF.

[0075] Table 2 below shows examples of polymers that have low solubility in nonpolar solvents and can be functionalized to improve their solubility for use as polymeric binders in complexes. Table 2: Polymers and Solubility [Table 2] Examples Example 1: Elastic modulus of SEBS, SEBS-gMA, and SEBS-gFA

[0076] SEBS modified with 2% maleic anhydride (SEBS-gMA) and SEBS-gMA functionalized with furfurylamine (SEBS-gFA). SEBS-gFA was synthesized by reacting SEBS-gMA with excess furfurylamine, as shown in Scheme 1. [ka] Scheme I: In a glove box operated under nitrogen, 30.0 g (6.1 mmol) of maleic anhydride from polystyrene-β-poly(ethylene-ran-butylene)-β-polystyrene-g-maleic anhydride (SEBS-gMA, Sigma-Aldrich) and 250 g of dry toluene were placed in a 500 ml pressure vessel dried to 145°C before use. The flask was sealed and the mixture was stirred on a hot plate at 60°C until the polymer was completely dissolved. Next, the flask was returned to the box and cooled to room temperature, after which 2.4 g (24.7 mmol) of furfurylamine was slowly added to the mixture. This reaction was further stirred at 60°C for 18 hours. The reaction mixture was then precipitated in methanol, the solid was redissolved in dichloromethane, and precipitated again in methanol. This process was repeated two more times to obtain furfuryl-modified SEBS (SEBS-gFA) as a white solid. This product was dried under vacuum at 100°C for 16 hours. The weight percentage of functional groups in SEBS-gFA was 3.5%.

[0077] Tensile tests were performed on the crosslinked membranes to measure their modulus of elasticity, tensile strength, and elongation at break. The properties of SEBS-gMA and SEBS-gFA membranes were measured against SEBS membranes processed under the same conditions. All membranes were cut into 8mm x 50mm strips, and each membrane was measured at least three times using a small tensile testing machine. Due to the short grip separation of the measuring instrument, the instrument's limits were reached before material fracture occurred, making it impossible to measure tensile strength and elongation at break. Each polymer membrane was highly elastic, reaching elongation rates of >800%. Table 3 summarizes the moduli of elasticity extracted from the stress-strain curves of SEBS, SEBS-gMA, and SEBS-gFA membranes. Table 3 Elastic modulus of different polymer films [Table 3] The elastic moduli measured for SEBS, SEBS-gMA, and SEBS-gFA differed significantly from each other, providing evidence of the importance of the overall composition and the types of functional groups. Adding 2% by weight of a polar maleic anhydride graft to the SEBS composition dramatically increased the binder's elastic moduli, reaching a value higher than 70% compared to unmodified SEBS. Furthermore, modification of SEBS-gMA with a furfuryl group yielded a SEBS-gFA binder with an even higher elastic moduli of 26.82 MPa. Example 2: Composite electrolyte containing SEBS, SEBS-gMA, and SEBS-gFA as binders

[0078] After testing the mechanical properties of pure SEBS, SEBS-gMA, and SEBS-gFA, the polymers were incorporated into a composite electrolyte. Each polymer was tested as a binder in a hybrid prepared with 80 wt% of 75:25=Li2S:P2S5 sulfide glass. SEBS and SEBS-gMA were also combined with 80 wt% Li 5.6 PS 4.6 Cl 1.4 The composite electrolyte was also incorporated using argyrodite. The composite was prepared as a thin film by slurry casting, dried, and then hot-pressed at 160°C. The binder structures are shown below: (A) SEBS, (B) SEBS-gMA, and (C) SEBS-gFA. [ka]

[0079] To evaluate the effect of binders on the conductivity retention of 75:25=Li2S:P2S5 sulfide glass, the conductivity of the composite was measured. Incorporating polar groups into nonpolar binders such as SEBS dramatically affected the conductivity of the measured film. When SEBS was used as the binder, the conductivity was approximately 0.18 mS / cm, showing a high conductivity retention rate (33%) compared to the original inorganic material (approximately 0.55 mS / cm) (Table 3).

[0080] When SEBS was modified with a small amount of polar functional group that can strongly bond to the glass particle surface, its conductivity decreased by almost an order of magnitude (Table 5). A composite using a mixed binder of SEBS and SEBS-gMA (1:4, w / w) showed a good conductivity of 0.102 mS / cm (Table 5), providing evidence that the ionic conductivity of the composite electrolyte decreased exponentially with increasing proportion of SEBS-gMA in the total 20 wt% of the polymer phase. This trend indicates a linear decrease in conductivity on a semi-logarithmic scale. When pure SEBS-gFA was used as the organic matrix, the conductivity decreased by only about 2.3 times. In the case of argyrodite composites, the conductivity was about 90% lower with the glass composite compared to about 30% lower with SEBS-gMA. These results indicate that glassy materials are susceptible to crystallization by polar solvents or polymers, which severely impairs their conductivity. On the other hand, crystalline argyrodites do not suffer from the disadvantage of reduced conductivity during the crystallization process, thus demonstrating superior conductivity retention (compared to composites using nonpolar SEBS binders rather than actual inorganic powders).

[0081] In some embodiments, argyrodite (or other crystalline sulfide-based conductor) composites can be prepared using a variety of polymeric binders, including highly polar ones, as long as the process is carried out without using polar solvents that degrade the inorganic material. Table 4 below lists 5 wt% binders (95 wt% argyrodite), SEBS-gMA, and NBR that increase polarity. 20This report summarizes composites prepared with 20% nitrile groups and polyvinyl acetate (PVAc), exhibiting conductivity of approximately 0.5 mS / cm to 0.7 mS / cm. While composites using more polar binders show a decrease in conductivity, the decrease is not as abrupt as in the case of glass. The manufactured composites maintain good conductivity while possessing superior mechanical properties. Table 4: Conductivity of argyrodite-containing composites [Table 4]

[0082] Mechanical tests were performed on all composites to determine their modulus of elasticity, tensile strength, and elongation at break. The mechanical tests were conducted under the same conditions as those for pure polymer films. The values ​​for modulus of elasticity, tensile strength, and elongation at break were extracted from the stress-strain curves and summarized in Table 5. Table 5: 80 wt% 75:25 = Li2S:P2S5 glass or Li 5.6 PS 4.6 Cl 1.4 Measurements of conductivity and mechanical properties of argyrodite and hybrids using different polymer binders (20% by weight). [Table 5]

[0083] Visual comparison of stress-strain curves obtained for composites with different binders revealed clear differences in mechanical properties. Increased tensile strength and elongation at break were observed in composites prepared with high-polarity binders. For composites with SEBS alone, samples fractured with an elongation of approximately 2%. When SEBS-gMA, containing only 2 wt% maleic acid grafts, was incorporated into the composite, the value for the 75:25=Li2S:P2S5 glass composite doubled to 4.5%. In the case of argyrodite-containing composites, the modulus of elasticity of the composite increased further by approximately 10 times, providing an elongation of 20.24%. 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 of the 75:25=Li2S:P2S5 glass composite to 17.0%, which was 8.5 times and 4 times higher than that of SEBS and SEBS-gMA, respectively. The same trend was observed in the tensile strength of the membranes, with values ​​of 4.2, 5.6, and 8.3 MPa for SEBS, SEBS-gMA, and SEBS-gFA binders, respectively, providing evidence that incorporating highly polar binders through an organic matrix improves the membrane's resistance to fracture.

[0084] Furthermore, in the argyrodite film, when the binder was changed from SEBS to SEBS-gMA, the ultimate strength changed from 5.74 MPa to 11.6 MPa, and a similar observation was made. The elastic modulus was almost independent of the type of binder, changing from 0.57 to 0.65 GPa for glass and from 0.76 to 0.82 GPa for argyrodite composites.

[0085] The composites in Table 5 exhibit lower conductivity than those in Table 4, due to higher polymer loading. However, the conductivity retention of the argyrodite-containing composites is evident. In some embodiments, argyrodite in polar polymers, with maximum ion-conducting particle content of 90% by weight, 85% by weight, or 80% by weight, exhibits conductivity of at least 0.2 mS·cm at 25°C. -1 At 25℃, at least 0.25 mS·cm -1 , or at least 0.35 mS·cm at 25℃ -1It may have a conductivity of . At the same time, due to the presence of polar groups, it may have good mechanical properties, for example, the elongation at break is at least 5%, 10%, 15%, or 20%.

[0086] This data demonstrates that the properties of the composite electrolyte can be finely tuned by controlling the composition of both the organic and inorganic phases. Subtle changes in the binder's chemical composition can significantly influence the properties of the resulting composite. Adding just 2% polar functional groups can increase mechanical strength and elasticity several times over, while conductivity remains within an acceptable room temperature range. inorganic phase

[0087] The inorganic phase of the composite materials described herein conducts alkali ions. In some embodiments, the inorganic phase is involved in all aspects of the ionic conductivity of the composite material and provides ionic conduction pathways through the composite material.

[0088] The inorganic phase is a particulate solid material that conducts alkali ions. Sodium ion conductive materials or other alkali ion conductive materials may be used, but lithium ion conductive materials are primarily described in the examples shown below. According to 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 crystallization (or further crystallization) of the particles.

[0089] The solid compositions described herein are not limited to any particular type of compound, and any solid inorganic ion-conducting particulate material may be used, examples of which are shown below.

[0090] In some embodiments, the inorganic material is a single-ionic conductor with a transport number close to 1. The transport number 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 transport number close to 1. According to various embodiments, the transport number of the inorganic phase of the solid electrolyte is at least 0.9 (e.g., 0.99).

[0091] 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, the method of the particular embodiment is particularly useful for sulfide-based compositions that may degrade in the presence of a polar polymer.

[0092] In certain embodiments, the inorganic phase may be doped to increase 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+2 xZn 1-x GeO4, 0≦x≦1;Li 14 ZnGe4O 16 ), thio-LISICON compounds (e.g., Li 4-x A 1-y B y S4, A is Si, Ge or Sn, B is P, Al, Zn, 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 Ti1.7(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., Li1-x Al x Ge 2-x (PO4)3(LAGP), Li 1+x Ti 2-x Al x (PO4)) can be mentioned. As a further example, lithium-rich antiperovskite (LiRAP) particles can be mentioned. As described in Zhao and Daement, Jour J.Am.Chem.Soc., 2012, 134(36), pp 15042-15047, which is incorporated herein by reference, these LiRAP particles have an ionic conductivity higher than 10 -3 S / cm at room temperature.

[0093] 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 , 0 < x < 3). Further examples of solid lithium ion conductive materials can be found in Cao et al., Front.Energy Res. (2014) 2:25 and Knauth, Solid State Ionics 180(2009) 911-916, both of which are incorporated herein by reference.

[0094] Further examples of ion conductive glasses are disclosed in Ribes et al., J.Non-Cryst.Solids, Vol.38-39(1980) 271-276 and Minami, J.Non-Cryst.Solids, Vol.95-96(1987) 107-118, which are incorporated herein by reference.

[0095] According to various embodiments, the inorganic phase may contain one or more types of inorganic ion-conducting particles. The particle size of the inorganic phase may vary according to the specific application, and the average diameter of the particles in the composition is 0.1 μm to 500 μm in most applications. In some embodiments, the average diameter is 0.1 μm to 100 μm. In some embodiments, a multimodal size distribution may be used to optimize particle packing. For example, a bimodal distribution may be used. In some embodiments, particles having a size of 1 μm or less may be used such that the average distance between the nearest particles in the composite is 1 μm or less. This may help to inhibit dendrite growth. In some embodiments, the average particle diameter is less than 10 μm or less than 7 μm. In some embodiments, a multimodal size distribution may be used having a first size distribution with an average size of less than 7 μm and a second size distribution with an average size greater than 10 μm. Larger particles result in a film with stronger mechanical properties and better conductivity, while smaller particles result in a denser and more uniform film with lower porosity and better density.

[0096] The inorganic phase can be produced 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 dissolution, solution synthesis, or mechanical grinding, as described in Tatsumisago, M.; Takano, R.; Tadanaga K.; Hayashi, AJ Power Sources 2014, 270, 603-607, which are incorporated herein by reference.

[0097] As used herein, the term amorphous glass material refers to a material that may have a narrow region of crystallinity, but is at least half amorphous. For example, amorphous glass particles may be perfectly amorphous (100% amorphous), at least 95% (volume) amorphous, at least 80% (volume) amorphous, or at least 75% (volume) amorphous. These amorphous particles may have one or more narrow regions of crystallinity, but ion conduction through the particles is mostly or completely isotropic conductive paths.

[0098] Ion-conductive glass-ceramic particles have amorphous regions but are at least half crystalline, for example, having at least 75% (volume) crystallinity. Glass-ceramic particles can be used in the composites described herein, and glass-ceramic particles having a relatively high amount of amorphous properties (e.g., at least 40% (volume) amorphous) are useful in certain embodiments due to their isotropic conductive paths. In some embodiments, ion-conducting ceramic particles may be used. Ion-conducting ceramic particles refer to materials that are mostly crystalline, although they may have a narrow amorphous region. For example, ceramic particles may be completely crystalline (100% by volume) or at least 95% (by volume) crystalline.

[0099] In some embodiments, the inorganic phase includes an argyrodite. The argyrodite may have a general formula: A 7-x PS 6-x Hal x A is an alkali metal, and Hal is selected from chlorine (Cl), bromine (Br), and iodine (I). In some embodiments, the argyrodite has the general formula shown above and may be further doped. One example is an argyrodite doped with a thiophilic metal. A 7-x-(z*m) M z m PS 6-x Hal x In the formula, 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), and z is the oxidation state of the metal, where 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 described in detail in U.S. Patent Application No. 16 / 829,962, which is incorporated herein by reference. In some embodiments, the composite may include oxide argyrodites such as those described in U.S. Patent Application No. 16 / 576,570, which is incorporated herein by reference. Alkali metal argyrodites include not only the argyrodites shown in the above formula, but also Li(x) as described in U.S. Patent Publication No. 20170352916, where x and y satisfy the formulas 0.05 ≤ y ≤ 0.9 and -3.0x + 1.8 ≤ y ≤ -3.0x + 5. 7-x+y PS 6-x Cl x+y Argyrodite containing, or A 7-x+y PS 6-x Hal x+y An example of an argyrodite having the formula is shown. Furthermore, such an argyrodite may be doped with metal as described above, and this includes A 7-x+y-(z*m) M z m PS 6-x Hal x+y These are some examples.

[0100] The mineral argyrodite (Ag8GeS6) can be considered a cocrystal of Ag4GeS4 and two equivalents of Ag2S. Even if both the cation and anion in this crystal are substituted, the same overall spatial arrangement of various ions can still be maintained. In Li7PS6, PS4 3- The ion is GeS4 in the original mineral. 4- It exists in the crystallographic position that was occupied by S 2- The ions retain their original positions, Li+ The ion is originally Ag + It takes the position of an ion. Li7PS6 has fewer cations than the original Ag8GeS6, so some of the cation sites are vacant. Minerals that are structurally similar to argyrodites are also sometimes called argyrodites.

[0101] Both Ag8GeS6 and Li7PS6 are orthorhombic at room temperature, but undergo a phase transition to a cubic space group at high temperatures. Furthermore, substituting one equivalent of LiCl for one Li2S atom yields the material Li6PS5Cl, which, while retaining its argyrodite structure, undergoes a phase transition from orthorhombic to cubic below room temperature and exhibits significantly higher lithium ion conductivity. This material is also generally called an argyrodite because its cation and anion arrangement is generally the same. Materials with further substitutions while retaining this overall structure are also sometimes called argyrodites. More generally, alkali metal argyrodites are those in which the alkali metal Ag is 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.

[0102] In one example, Li7PS6, which is an example of lithium content in this mineral species, contains PS4 3- Ions in the original mineral GeS4 4- It exists in the crystallographic position that was occupied by S 2- The ions retain their original positions, Li + The ion is the original Ag + The ions take their positions. Since Li7PS6 has fewer cations than the original Ag8GeS6, some cation sites are vacant. As mentioned above, if one equivalent of LiCl is further substituted for one Li2S, the material Li6PS5Cl is obtained while retaining the argyrodite structure. Figure 2 shows the cubic argyrodite Li6PS5Cl. In the example in Figure 2, Ag is the argyrodite mineral. + Site Li + It is occupied by the original GeS4 4- Site PS4 3- occupied by the original S2- Site 2 S 2- and Cl - They occupy it in a 1:1 ratio.

[0103] There are various methods for replacing argyrodites while preserving their overall structure. For example, the original mineral may contain 2 equivalents of sulfur. 2- It has this O 2- , Se 2- and Te 2- It can be substituted with chalcogen ions such as S. 2- A significant portion of it can be replaced with halogens. For example, 2 equivalents of S 2- Of which, up to approximately 1.6, Cl - , Br - and I -1 It can be substituted with Cl, and the exact amount depends on other ions in the system. - is S 2- Although similar in size, it has one charge instead of two, and its bonding and reactivity are substantially different. Other substitutions may be made, for example, S 2- A portion of the halogen (for example, Cl - Replace with ) and the rest with Se 2- It can be replaced with GeS4. 3- The site can also be replaced in various ways. GeS4 3- Instead, PS4 3- , also PO4 3- , PSe4 3- SiS4 3- These may also be used. These are all tetrahedral ions having four chalcogen atoms, and as a whole they are S 2- It is larger and triple or quadruple charged.

[0104] In other examples comparable to the Li6PS5Cl argyrodite structure described above, Li6PS5Br and Li6PS5I substitute larger halides, e.g., Li6PO5Cl and Li6PO5Br, for the chloride. Z. anorg. Allg. Chem., 2010, 636, 1920-1924 is incorporated herein by reference for the purpose of describing specific argyrodites, but includes not only the halide substitutions described, but also S 2- and PS4 3- Both ions replace all sulfur atoms in the structure with oxygen. PS4 is found in most examples of lithium-containing argyrodites. 3- The phosphorus atom in the ion can also be partially or completely substituted, for example, Li 7+x MxP 1-x The S6(M=Si,Ge) series forms argyrodite structures over a wide range of x. For the purpose of describing specific argyrodites, please refer to J.Mater.Chem.A,2019,no.7,2717-2722, which is incorporated herein by reference. Furthermore, P substitution can also be carried out while incorporating halogens. For example, Li 6+x Si x P 1-x S5Br is stable at x=0 to approximately 0.5. See J.Mater.Chem.A,2017,no.6,645-651, incorporated herein by reference for the purpose of describing specific argyrodites. PS4 3- SbS4 instead 3- and MS4 4- Substitute the mixture with Cl - Instead of I - Li using 7+x M x S 1-xCompounds in the S6 (M=Si, Ge, Sn) series were prepared and found to form argyrodite structures. For the purpose of describing specific argyrodites, please refer to J.Am.Chem.Soc., 2019, no.141, 19002-19013, which is incorporated herein by reference. It is also possible to substitute other cations besides lithium (or silver) at the cation sites. Examples include 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 0.48 All of these have been synthesized and possess an argyrodite crystal structure. See Z. Kristallogr, 2005, no. 220, 281-294, incorporated herein by reference for the purpose of describing specific argyrodites. From this list of examples, it can be seen that not only is it possible to substitute a single element in any of the various parts of the argyrodite structure, but often the argyrodite structure is also obtained by combinations of substitutions. These include Li, described in U.S. Patent Publication No. 20170352916, where x and y satisfy the equations 0.05 ≤ y ≤ 0.9 and -3.0x + 1.8 ≤ y ≤ -3.0x + 5.7. 7-x+y PS 6-x Cl x+y Argyrodites containing these are examples.

[0105] The argyrodites used in the compositions described herein contain substantial (at least 20%, often at least 50%) sulfur-containing anions (e.g., S 2- and PS4 3- Examples include sulfide-based ionic conductors. Sulfide-based lithium argyrodite materials have high Li+ They exhibit mobility and are attracting attention as materials for lithium batteries. As mentioned above, Li6PS5Cl, a ternary cocrystal of Li3PS4, Li2S, and LiCl, is an exemplary material of this family. Various embodiments of argyrodites described herein have thioaffinity metals that can occupy lithium cation sites in the argyrodite crystal structure. In an argyrodite as shown in Figure 2, each cation is PS4 3- The anion consists of two sulfurous atoms and one S atom. 2- It is coordinated to a sulfur anion and two chloride anions. In some embodiments, a thiophilic metal occupies a portion of these lithium cation sites to suppress the generation of hydrogen sulfide. The thiophilic metal can similarly be used to dope other alkali metal argyrodites. complex

[0106] A composite comprising an organic phase and nonionic conductive particles is provided. In some embodiments, the organic phase has substantially no ionic conductivity 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 contain a polymer that is ionic conductive in the presence of a salt such as LiI. Ionic conductive polymers include, for example, polyethylene oxide (PEO), polypropylene oxide (PPO), polyacrylonitrile (PAN), and poly(methyl methacrylate) (PMMA), which are ionic conductive polymers that dissolve or dissociate salts such as LiI in the presence of a salt. Nonionic conductive polymers do not dissolve or dissociate salts and are not ionic conductive in the presence of salts. This is because, if the salt is not dissolved, there are no mobile ions to conduct.

[0107] The polymer load in the solid-phase composite may be relatively high in some embodiments, for example, at least 2.5% to 30% by weight. According to various embodiments, it may be 0.5% to 60% by weight of polymer, 1% to 40% by weight of polymer, or 5% to 30% by weight of polymer. The solid-phase composite forms a continuous film.

[0108] In some embodiments, the inorganic conductor constitutes at least 75% by weight, at least 80% by weight, at least 85% by weight, at least 90% by weight, or at least 95% by weight of the composite. Conductivity increases with increasing content, but mechanical strength may decrease. In some embodiments, the inorganic conductor constitutes 75% to 98% by weight, for example, 80% to 95% by weight. The remainder of the composite may be a polymer.

[0109] As described above, the complex includes a functionalized polymer backbone binder. The binder may be a mixture of a functionalized polymer binder and an unfunctionalized polymer binder. For example, in some embodiments, the binder may be a mixture of a nonpolar polymer (e.g., SEBS) and a functionalized polymer (e.g., SEBS-gFA). The mixture may be a polymer:functionalized polymer ratio of 1:9 to 9:1 wt%, for example, 1:5 to 5:1 or 1:4 to 4:1 wt%, depending on the various embodiments. Examples of unmodified polymers (SEBS) include unfunctionalized polymers and polymers containing a group of non-essential functional groups that do not alter the properties of the polymer. Similarly, in some embodiments, the binder may be a mixture of two or more polymers having different degrees of functionalization (e.g., 1 wt% and 4 wt%).

[0110] According to various embodiments, the polymer binder may be essentially all of the organic phase of the composite, or at least 95% by weight, 90% by weight, at least 80% by weight, at least 70% by weight, at least 60% by weight, or at least 50% by weight of the composite.

[0111] In some embodiments, the composite 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.

[0112] In various embodiments, the solid composition may or may not contain added salts. In embodiments containing an ion-conducting polymer such as PEO, lithium salts (e.g., LiPF6, LiTFSI), potassium salts, sodium salts, etc., can be added to improve ionic conductivity. 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 provided substantially by inorganic particles. Even when an ion-conducting polymer is used, its contribution to the ionic conductivity of the composite may not exceed 0.01 mS / cm, 0.05 mS / cm, or 0.1 mS / cm. In other embodiments, it may contribute more.

[0113] In some embodiments, the solid composition may comprise one or more conductivity enhancers. In some embodiments, the electrolyte may comprise one or more filler materials, including ceramic fillers such as Al2O3. When used, the fillers may be ionic 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 electrolytes having mechanical properties desirable for a particular application.

[0114] In some embodiments discussed further below, the composite is incorporated into or ready to be incorporated into an electrode and comprises an electrochemical active material and optionally an electronically conductive additive. Examples of electrode components and compositions are shown below.

[0115] In some embodiments, the electrolyte may include an electrode stabilizer that can be used to form a passivation layer on the electrode surface. Examples of electrode stabilizers are described in U.S. Patent No. 9,093,722. In some embodiments, the electrolyte may include conductivity enhancers, fillers, or organic components as described above.

[0116] The composite can be provided as a self-supporting film, a self-supporting film provided on a release film, a film laminated on components of a battery or other device such as an electrode or separator, or a film cast on an electrode, separator, or other component.

[0117] The composite film can have any suitable thickness depending on the design of the particular battery or other device. In many applications, the thickness can be between 1 and 250 microns, for example, 15 microns. In some embodiments, the electrolyte may be considerably thicker, for example, on the order of millimeters.

[0118] In some embodiments, the composite is provided as a slurry or paste. In such cases, the composition includes a solvent that is later evaporated. Furthermore, the composition may include one or more components for storage stability. Examples of such compounds include acrylic resins. Once the slurry or paste is ready to process, it may be cast or coated onto a substrate and dried as appropriate. According to various embodiments, the slurry may have a solid content of about 40% to 50% by weight, for example, 42% to 45% by weight. The solid content is inorganic particles (e.g., 80% to 95% by weight of inorganic conductors and 5% to 20% by weight of polymers).

[0119] In some embodiments, the composite is provided as an extruded solid mixture. device

[0120] The composites described herein can be incorporated into any device using ion conductors, including but not limited to batteries and fuel cells. For example, in a battery, the composite can be used as an electrolyte separator.

[0121] The electrode composition further comprises an electrode active material and, optionally, a conductive additive. Examples of cathode and anode compositions are shown below.

[0122] Examples of cathode compositions are shown in the table below. [Table 6]

[0123] According to various embodiments, the cathode active material is a transition metal oxide, with lithium nickel cobalt manganese oxide (LiMnCoMnO2, or NMC) being an example. NMC is LiNi 0.6 Mn 0.2 Co 0.2 O2 (NMC-622), LiNi 0.4 Mn 0.3 Co 0.3 Various forms of active material, including O2 (NMC-4330), can be used. The lower limit of the weight percent range is set by the energy density. Compositions containing less than 65% by weight of active material may have low energy density and be unsuitable.

[0124] As described above in the explanation of inorganic conductors, any suitable inorganic conductor can be used. Li 5.6 PS 4.6 Cl 1.4 This is an example of an algyrodite 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 with less than 10% by weight of argyrodite are Li + It has low conductivity. Sulfide glass and glass ceramics can also be used.

[0125] 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. Below 1% by weight, it may not be sufficient to improve electronic conductivity, while above 5%, it reduces energy density and inhibits contact between the active material and argyrodite.

[0126] As described above, any suitable organic phase can be used. Below 1% by weight, it may not be sufficient to obtain the desired mechanical properties, and above 5%, the energy density may decrease and the junction between the active material, inorganic conductor, and carbon may be inhibited. In some embodiments, PVDF is used with or without a nonpolar polymer.

[0127] Examples of anode compositions are shown in the table below. [Table 7]

[0128] Hybrid anodes using Si and graphite as active materials provide higher ICE (electronic inductance) with higher graphite content. This means that the anode's ICE can be matched to the cathode's ICE by adjusting the Si / graphite ratio, thus preventing irreversible capacity loss during the first cycle. Since ICE can be altered by processing, a relatively wide range of graphite content is possible depending on the specific anode and its processing. Furthermore, graphite is thought to improve electronic conductivity and contribute to anode densification.

[0129] As for the cathode, any suitable inorganic conductor can be used, as described above.

[0130] High-surface-area electronically conductive additives (e.g., carbon black) may be used in some embodiments. Since Si has low electronic conductivity, such additives can be useful in addition to graphite (which is a better electronically conductive but has a smaller surface area). However, the electronic conductivity of Si alloys is moderately high, and in some embodiments, additives may not be necessary. It is also possible to use other high-surface-area carbons (carbon black, activated carbon, graphene, carbon nanotubes) instead of Super C.

[0131] Any suitable organic phase can be used. In some embodiments, PVDF is used.

[0132] This specification provides alkali metal batteries and alkali metal ion batteries comprising an anode, a cathode, and a compatible solid electrolyte composition as described above that is operably coupled to the anode and cathode. The battery may include a separator for physically separating the anode and cathode, which may be a solid electrolyte composition.

[0133] Examples of suitable anodes include, but are not limited to, those formed from carbonaceous materials such as lithium metal, lithium alloys, sodium metal, sodium alloys, and graphite, and combinations thereof. Examples of suitable cathodes include, but are not limited to, those 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.

[0134] 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 incorporated therein to facilitate the reduction reaction between lithium ions and oxygen that occurs in the cathode (e.g., manganese, cobalt, ruthenium, platinum, or silver catalysts, or combinations thereof).

[0135] In some embodiments, lithium-sulfur cells comprising a lithium metal anode and a sulfur-containing cathode are provided. In some embodiments, the solid composite electrolyte described herein uniquely enables both a lithium metal anode by preventing dendrite formation and a sulfur cathode by not dissolving the polysulfide intermediate formed at the cathode during discharge.

[0136] Furthermore, a separator formed from any suitable ion-permeable material may be included to prevent the anode and cathode from directly contacting each other electrically. However, since the electrolyte compositions described herein are solid compositions, they can function as separators, especially when they are in the form of a film.

[0137] 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.

[0138] As described above, in some embodiments, the solid composite composition can be incorporated into the electrodes of the battery. The electrolyte can be a suitable solid electrolyte as described above, or any other suitable electrolyte including a liquid electrolyte.

[0139] In some embodiments, the battery comprises an electrode / electrolyte bilayer, each layer incorporating an ion-conductive solid composite material as described herein.

[0140] Figure 1A shows an example of a schematic diagram of a cell according to a particular embodiment. The cell comprises a negative current collector 102, an anode 104, an electrolyte / separator 106, a cathode 108, and a positive current collector 110. The negative current collector 102 and the positive current collector 110 may be any suitable electronically conductive material, such as copper, steel, gold, platinum, aluminum, and nickel. In some embodiments, the negative current collector 102 is copper and the positive current collector 110 is aluminum. The current collector may be in any suitable form, such as a sheet, foil, mesh, or foam. According to various embodiments, one or more of the anode 104, cathode 108, and electrolyte / separator 106 are solid composites containing the organic phase and sulfide conductor as described above. In some embodiments, two or more of the anode 104, cathode 108, and electrolyte 106 are solid composites containing the organic phase and sulfide conductor as described above.

[0141] In some embodiments, the current collector is a porous material that can be embedded in the corresponding electrode. For example, the current collector may be a mesh. Electrodes containing hydrophobic polymers may not adhere well to foil-like current collectors, but a mesh structure provides good mechanical contact. In some embodiments, two composite membranes described herein can be pressed against a mesh current collector to form an embedded current collector in the electrode. In some embodiments, a hydrophilic polymer is used to provide good adhesion.

[0142] Figure 1B shows an example of a schematic diagram of an assembled lithium metal cell according to a particular embodiment of the invention. The assembled cell comprises a negative current collector 102, an electrolyte / separator 106, a cathode 108, and a positive current collector 110. During the initial charge, lithium metal is generated, a plate is formed on the negative current collector 102, and an anode is formed. One or both of the electrolyte 106 and the cathode 108 may be a composite material as described above. In some embodiments, the cathode 108 and the electrolyte 306 together form an electrode / electrolyte bilayer. Figure 1C shows a schematic example of a cell according to a particular embodiment of the invention. The cell comprises a negative current collector 102, an anode 104, a cathode / electrolyte bilayer 112, and a positive current collector 110. Each layer of the bilayer may contain a sulfide-based conductor. Such a bilayer can be prepared, for example, by preparing an electrolyte slurry and depositing it on the electrode layer.

[0143] All battery components may be contained in or packaged in a suitable rigid or flexible container with external leads or contacts to establish electrical connections to the anode and cathode according to known techniques.

[0144] In the above explanation, in the claims, a numerical range includes the endpoint of the range. For example, "y is a number between 0 and 0.8" includes 0 and 0.8. Similarly, a range represented by ~ also includes the endpoint of the range.

Claims

1. Inorganic ion-conducting argyrodite-containing particles, Organic phase containing a polar polymer binder and Equipped with, The polar polymer binder comprises a first polymer modified with functional groups, wherein the functional groups constitute 0.1 to 50% by weight of the first polymer. The polymer binder comprises SEBS modified with maleic anhydride (SEBS-gMA), a mixture of unmodified SEBS and SEBS-gMA, or SEBS modified with furfurylamine (SEBS-gFA), in a composite.

2. The composite material reacts at 25°C to at least 0.2 mS·cm －１ The composite according to claim 1, having the ionic conductivity of the specified value.

3. The composite reacts at 25°C to at least 0.25 mS·cm －１ The composite according to claim 1, having the ionic conductivity of the specified value.

4. The composite material has a temperature of at least 0.3 mS·cm at 25°C. －１ The composite according to claim 1, having the ionic conductivity of the specified value.

5. The composite according to any one of claims 1 to 4, wherein the inorganic ion-conducting argyrodite-containing particles constitute 90% by weight or less of the composite.

6. The composite according to any one of claims 1 to 4, wherein the inorganic ion-conducting argyrodite-containing particles constitute 85% by weight or less of the composite.

7. The composite according to any one of claims 1 to 4, wherein the inorganic ion-conducting argyrodite-containing particles constitute 80% by weight or less of the composite.

8. The composite material reacts at 25°C to at least 0.5 mS·cm －１ The composite according to claim 1, having the ionic conductivity of the specified value.

9. The composite according to any one of claims 1 to 8, wherein the composite has an elongation at break of at least 10%.

10. The composite according to any one of claims 1 to 8, wherein the composite has an elongation at break of at least 15%.

11. The composite according to any one of claims 1 to 8, wherein the composite has an elongation at break of at least 20%.

12. The aforementioned argyrodite, formula Li ７－ｘ PS ６－ｘ Hal ｘ The composite according to any one of claims 1 to 11, having (Ha = Cl, Br, I, and 0 < x < 2).

13. The composite according to claim 12, wherein X is greater than 1.

14. The composite according to any one of claims 1 to 13, wherein the composite has an elongation at break of at least 10%.

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