Solid-state electrochemical cell, method for preparing the same, and use thereof

Abstract

All-solid-state electrochemical cells are described that include inorganic particle-polymer composites, where the polymer is a crosslinked polymer and the inorganic particle content in the composite is at least 50% by weight. Methods for preparing such all-solid-state electrochemical cells, all-solid-state batteries comprising them, and their use in portable devices, electric or hybrid vehicles, or in renewable energy storage are also described. The technology generally relates to the field of electrochemical cells that include composites of ion-conducting inorganic particles and crosslinked aprotic polymers, and methods for their manufacture.

Description

[Technical Field]

[0001] Related applications This application claims priority to U.S. Provisional Patent Application No. 63 / 015,952, filed April 27, 2020, which, under applicable law, is incorporated herein by reference in its entirety for all purposes.

[0002] Technical field This technology generally relates to the field of electrochemical cells, which include composite materials consisting of ion-conducting inorganic particles and crosslinked aprotic polymers, and to methods for manufacturing the same. [Background technology]

[0003] background Lithium-ion conductive polymer electrolytes allow for the development of safer and more affordable manufacturing methods and can be easily scaled up to large-scale all-solid-state batteries (see, for example, U.S. Patent No. 6,903,174). However, their low ionic conductivity limits their applications at room temperature, and their charge / discharge rates are relatively slower compared to conventional lithium-ion batteries.

[0004] On the other hand, solid inorganic electrolytes offer even higher lithium-ion conductivity, comparable to liquid electrolytes, making them promising candidates for solid-state batteries. Furthermore, the unique ionic conductivity of inorganic electrolytes reduces concentration unevenness at the lithium-metal interface, enabling faster battery charging and discharging. In high-density bulk phases, despite their high ionic conductivity, complete cells using ceramic solid electrolytes suffer from poor electrochemical performance due to high interfacial resistance at the grain boundaries of ceramic particles and between particles in composite electrodes consisting of active material particles, carbon additives, and solid electrolyte mixtures. + Since ion conduction must occur between particles, the electrochemical performance is limited by poor distribution of solid electrolyte particles and the presence of voids between particles (see Figure 1).

[0005] The group of K. Yoshima et al. described a hybrid electrolyte containing LLZO particles and a gel polymer electrolyte in a composite cathode, which exhibited even lower interfacial resistance and improved electrochemical performance. However, the presence of a liquid electrolyte carries the risk of electrolyte leakage, which could pose a safety problem due to its flammability (see K. Yoshima et al., Journal of Power Sources, (2016), vol. 302, 283-290).

[0006] L. Cong et al. developed a low molecular weight PVdF-HFP polymer using LGPS (Li 10 GeP2S 12 ) Incorporated into the particles, thereby improving the mechanical properties and processability of the film, however, the insulating polymer, Li + This hinders ion conduction and reduces the ionic conductivity of hybrid solid electrolytes (see L. Cong et al., Journal of Power Sources, (2020), vol. 446, 227365).

[0007] D. Sugiura et al. used butadiene rubber as an additive to control the particle size of solid sulfide ceramics and form self-supporting electrolyte films, but again, the presence of an insulating polymer increased interfacial resistance and decreased ionic conductivity (see U.S. Patent Application Publication No. 20140093785A1). The group of J. Zhang et al. reported that adding 5-20% by weight of poly(ethylene oxide) (POE) to argyrodite particles (Li6PS5X) improved mechanical properties and stabilized the electrolyte interface, leading to a reduction in lithium dendrite formation (see J. Zhang et al., Journal of Power Sources, (2019), vol. 412, 78). However, the high molecular weight POE homopolymer used must be dissolved in a large amount of polar solvent. These conditions are not advantageous for large-scale production methods and may cause technical problems such as particle precipitation and increased porosity due to solvent evaporation. Therefore, the development of novel electrolytes and solid-state batteries, as well as methods for their production, is necessary. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] U.S. Patent No. 6,903,174 [Patent Document 2] U.S. Patent Application Publication No. 20140093785A1 [Non-patent literature]

[0009] [Non-Patent Document 1] K. Yoshima et al., Journal of Power Sources, (2016), vol. 302, 283-290 [Non-Patent Document 2] L. Cong et al., Journal of Power Sources, (2020), vol. 446, 227365 [Non-Patent Document 3] J. Zhang et al., Journal of Power Sources, (2019), vol. 412, 78 [Overview of the project] [Means for solving the problem]

[0010] summary According to a first aspect, this specification provides an all-solid-state electrochemical cell comprising a positive electrode containing an electrochemical active material, a negative electrode containing an electrochemical active material, and an electrolyte between the positive and negative electrodes, The positive electrode, negative electrode, and electrolyte each form a solid layer. At least one of the positive electrode, negative electrode, and electrolyte comprises a composite material containing alkali metal or alkaline earth metal ion conductive inorganic particles and a crosslinked aprotic polymer. The inorganic particle content in the composite material is in the range of 50% to 99.9% by weight. The crosslinked aprotic polymer is in a solid state at 25°C, while its polymer precursor before crosslinking is in a liquid state at 25°C. Regarding all-solid-state electrochemical cells.

[0011] In one embodiment, the inorganic particles include amorphous, ceramic, or glass-ceramic type ion-conducting inorganic compounds selected from, for example, the oxide, sulfide, or oxysulfide families. In another embodiment, the inorganic particles include compounds having a structure selected from garnet, NASICON, LISICON, thio-LISICON, LIPON, perovskite, inverse perovskite, or argyrodite, or compounds containing the elemental combination MPS, MPSO, MPSX, MPSOX, where M is an alkali metal or alkaline earth metal, and X is F, Cl, Br, I, or a mixture thereof, and the elemental combination optionally includes one or more additional elements (metals, metalloids, or nonmetals), and the compound is in crystalline form, amorphous form, glass-ceramic form, or a mixture of at least two thereof.

[0012] In another embodiment, the inorganic particles are in crystalline form, amorphous form, glass-ceramic form, or a mixture of at least two of these, compound MLZO(M7La3Zr2O12 and M (7-a) La3Zr2Al b O 12 and M (7-a) La3Zr2Ga b O 12 and M (7-a) La3Zr (2-b) Ta b O 12 and M (7-a) La3Zr (2-b) Nb b O 12 etc.); MLTaO (M7La3Ta2O 12 M5La3Ta2O 12、 M6La3Ta 1.5 Y 0.5 O 12 etc.); MLSnO (M7La3Sn2O<000002​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​d O e etc.); MSnPS (M a Sn b P c S d etc., for example, M 10 SnP2S 12 ); MSnPSO (M[[ID=???]] a Sn b P c S d O e etc.); MPS (M a P b S c etc., for example, M7P3S 11 ); MPSO (M a P b S c O d etc.); MZPS (M a Zn b P c S d etc.); MZPSO (M a Zn b P c S d O e [[ID=???]] a P b S c X d etc., for example, M7P3S 11 X, M7P2S8X, M6PS5X); MPSOX (M a P b S c O d X<000********>etc.); MGPSX (M a Ge b P c S d X e ); MGPSOX (M a Ge b P c S d O[[ID=********]] e XIt should be noted that there are some "???" in the translated content because the original text seems to have some unclear or incorrect tags in the middle part. You may need to check and correct the original text for a more accurate translation.f );MSiPSX(M a Si b P c S d X e );MSiPSOX(M a Si b P c S d O e X f );MSnPSX(M a Sn b P c S d X e );MSnPSOX(M a Sn b P c S d O e X f );MZPSX(M a Zn b P c S d X e );MZPSOX(M a Zn b P c S d O e X f );M3OX;M2HOX;M3PO4;M3PS4;or M a PO b N c (a = 2b + 3c - 5) includes at least one of these, During the ceremony, M is an alkali metal ion, an alkaline earth metal ion, or a combination thereof, and the number of M is adjusted to achieve electrical neutrality when M includes alkaline earth metal ions. X is F, Cl, Br, I, or a combination thereof. a, b, c, d, e, and f are non-zero numbers, and in each equation, they are independently chosen to achieve electrical neutrality. v, w, x, y, and z are non-zero numbers, and in each formula, they are independently selected to obtain a stable compound.

[0013] In one embodiment, M is selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba or a combination thereof, for example, M is lithium. Alternatively, M includes Li, as well as at least one of Na, K, Rb, Cs, Be, Mg, Ca, Sr, and Ba. According to another embodiment, M is Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba or a combination thereof, or M is Na, K, Mg or a combination thereof.

[0014] In another embodiment, the crosslinked aprotic polymer is >4V (relative to Li + It is stable in (Li). In another embodiment, the crosslinked aprotic polymer comprises a polyether, polythioether, polyester, polythioester, polycarbonate, polythiocarbonate, polysiloxane, polyimide, polysulfonimide, polyamide, polysulfonamide, polyphosphazene, polyurethane segment, or at least one aprotic polymer segment selected from at least two copolymers or combinations thereof.

[0015] In one embodiment, the crosslinked aprotic polymer comprises at least one aprotic polymer segment, which includes a block copolymer having at least two different repeating units to reduce the crystallinity of the crosslinked polymer. In another embodiment, the aprotic polymer segment comprises a block copolymer, which includes a crosslinkable segment containing at least one alkali metal ion or alkaline earth metal ion solvation segment and a crosslinkable unit prior to crosslinking. In one embodiment, the alkali metal or alkaline earth metal ion solvation segment is of formula (I): [ka] (In the formula, R is H, C1~C 10 Alkyl and -(CH2-OR a R b ) are selected from, R a (CH2-CH2-O)y And, R b C1~C 10 (It is an alkyl group.) Selected from homopolymers and copolymers containing repeating units.

[0016] In another embodiment, the crosslinkable unit comprises a functional group selected from acrylates, methacrylates, allyls, vinyls, and combinations thereof.

[0017] In one embodiment, the composite material forms an electrolyte layer, and for example, a crosslinked aprotic polymer is present between inorganic particles.

[0018] In another embodiment, the electrolyte layer comprises, for example, alkali metal or alkaline earth metal cations and hexafluorophosphate ions (PF6). - ), bis(trifluoromethanesulfonyl)imide (TFSI - ), bis(fluorosulfonyl)imide (FSI - ), (flurosulfonyl)(trifluoromethanesulfonyl)imide ((FSI)(TFSI) - ), 2-trifluoromethyl-4,5-dicyanoimidazolate (TDI - ), 4,5-dicyano-1,2,3-triazolate (DCTA - ), bis(pentafluoroethylsulfonyl)imide (BETI - ), difluorophosphate ion (DFP - ), tetrafluoroborate ion (BF4 - ), bis(oxalato)borate ion (BOB - ), nitrate ion (NO3 - ), chloride ions (Cl - ), bromide ions (Br - ), fluoride ions (F - ), perchlorate ion (ClO4 - ), hexafluoroarsenate ion (AsF6 - ), trifluoromethanesulfonate ion (SO3CF3 - )(Tf -), fluoroalkyl phosphate ion [PF3(CF2CF3)3 - ](FAP - ), tetrakis(trifluoroacetoxy)borate ion [B(OCOCF3)4] - (TFAB - ), bis(1,2-benzenediolato(2-)-O,O')borate ion [B(C6O2)2] - (BBB - ), difluoro(oxalato)borate ion (BF2(C2O4) - )(FOB - ), formula BF2O4R x - anion (R x =C 2~4 The present invention further comprises at least one salt containing an anion selected from alkyl groups and combinations thereof. In one embodiment, the alkali metal or alkaline earth metal cation of the salt is identical to the alkali metal or alkaline earth metal present in the inorganic particles.

[0019] In another embodiment, the electrolyte layer is made from, for example, imidazolium, pyridinium, pyrrolidinium, piperidinium, phosphonium, sulfonium, and morpholinium cations, or 1-ethyl-3-methylimidazolium (EMI), 1-methyl-1-propylpyrrolidinium (PY 13 + ), 1-butyl-1-methylpyrrolidinium (PY 14 + ), n-propyl-n-methylpiperidinium (PP 13 + ) and n-butyl-n-methylpiperidinium (PP 14 + ) Cations selected from cations, and PF6 - BF4 - AsF6 - ClO4 - CF3SO3 - , (CF3SO2)2N-(TFSI), (FSO2)2N - (FSI), (FSO2)(CF3SO2)N - (C2F5SO2)2N -(BETI), PO2F2 - (DFP), 2-trifluoromethyl-4,5-dicyanoimidazole (TDI), 4,5-dicyano-1,2,3-triazolate (DCTA), bis-oxalatobolate (BOB), and (BF2O4R x ) - (R x The ionic gel or ionic liquid further comprises an anion selected from C2-C4 alkyl groups, wherein the ionic liquid is present in such an amount that the electrolyte layer remains in a solid state.

[0020] In another embodiment, the electrolyte layer further comprises an aprotic solvent having a boiling point higher than 150°C, selected from, for example, ethylene carbonate (EC), propylene carbonate (PC), gamma-butyrolactone (γ-BL), poly(ethylene glycol) dimethyl ether (PEGDME), dimethyl sulfoxide (DMSO), vinylene carbonate (VC), vinylethylene carbonate (VEC), 1,3-propylene sulfite, 1,3-propanesultone (PS), triethyl phosphate (TEPa), triethyl phosphate (TEPi), trimethyl phosphate (TMPa), trimethyl phosphate (TMPi), dimethylmethyl phosphonate (DMMP), diethyl ethyl phosphonate (DEEP), tris(trifluoroethyl) phosphate (TFFP), fluoroethylene carbonate (FEC), and mixtures thereof, wherein the aprotic solvent is present in such an amount that the electrolyte layer remains in a solid state.

[0021] According to another embodiment, the positive electrode electrochemical active material present in the positive electrode layer includes metal oxides, metal sulfides, metal oxysulfides, metal phosphates, metal fluorophosphates, metal oxyfluorophosphates, metal sulfates, metal halides, sulfur, selenium, or a mixture of at least two thereof. In one embodiment, the metal of the metal oxide, metal sulfide, metal oxysulfide, metal phosphate, metal fluorophosphate, metal oxyfluorophosphate, metal sulfate, or metal halide includes metals selected from iron (Fe), titanium (Ti), manganese (Mn), vanadium (V), nickel (Ni), cobalt (Co), aluminum (Al), chromium (Cr), zirconium (Zr), niobium (Nb), and at least two combinations thereof, and optionally further includes alkali metals or alkaline earth metals. In one embodiment, the positive electrode electrochemical active material includes a lithium metal oxide, such as lithium nickel cobalt manganese oxide (NCM). In another embodiment, the positive electrode electrochemical active material includes a lithium metal phosphate, such as lithium iron phosphate (LiFePO4).

[0022] In another embodiment, the positive electrode layer further comprises a conductive material comprising at least one of the following: carbon black (e.g., Ketjenblack® or Super P®), acetylene black (e.g., Shawinigan black or Denka® black), graphite, graphene, carbon fibers or nanofibers (e.g., vapor-grown carbon fibers (VGCF)), carbon nanotubes (e.g., single-walled carbon nanotubes (SWNTs), multi-walled carbon nanotubes (MWNTs)), or metal powder.

[0023] In another embodiment, the positive electrode layer comprises a composite material, for example, a crosslinked aprotic polymer present between inorganic particles, between particles of the positive electrode electrochemical active material, and, if present, between particles of conductive material as needed.

[0024] In another embodiment, the cathode layer further comprises a polymer binder selected from crosslinked aprotic polymers, fluorinated polymers (e.g., PVDF, HFP, PTFE, and copolymers or mixtures of two or three thereof), polyvinylpyrrolidone (PVP), poly(styrene-ethylene-butylene) copolymer (SEB), and synthetic rubbers (e.g., SBR (styrene-butadiene rubber), NBR (acrylonitrile-butadiene rubber), HNBR (hydrogenated NBR), CHR (epichlorohydrin rubber), ACM (acrylate rubber), EPDM (ethylene propylene diene monomer rubber), and combinations thereof, and optionally further comprising carboxyalkylcellulose, hydroxyalkylcellulose, or combinations thereof).

[0025] In another embodiment, the positive electrode layer further comprises a salt as defined herein, which comprises at least one salt, for example, an alkali metal or alkaline earth metal cation, preferably the alkali metal or alkaline earth metal cation of the salt is the same as the alkali metal or alkaline earth metal present in the inorganic particles. In another embodiment, the positive electrode layer further comprises an ionic gel or ionic liquid, such as those described with respect to the electrolyte layer. In another embodiment, the positive electrode layer further comprises an aprotic solvent, selected from, for example, those described herein, having a boiling point higher than 150°C. The amount of ionic liquid and / or aprotic solvent is understood to be such that the positive electrode layer remains in a solid state.

[0026] According to one embodiment, the anode electrochemical active material comprises a metal film of an alkali metal or alkaline earth metal, or an alloy containing at least one of them, for example, the alkali metal or alkaline earth metal is lithium or an alloy containing lithium. In an alternative embodiment, the anode electrochemical active material comprises a metal film of a non-alkali metal and non-alkaline earth metal (such as In, Ge, Bi), or an alloy or intermetallic compound thereof (e.g., SnSb, TiSnSb, Cu2Sb, AlSb, FeSb2, FeSn2, CoSn2). In one embodiment, the metal film has a thickness in the range of 5 μm to 500 μm, preferably in the range of 10 μm to 100 μm.

[0027] In yet another embodiment, the negative electrode electrochemical active material is in the form of particles and has a lower redox potential than the positive electrode electrochemical active material. In one embodiment, the negative electrode electrochemical active material is a non-alkali metal or non-alkaline earth metal (such as In, Ge, Bi), an intermetallic compound (e.g., SnSb, TiSnSb, Cu2Sb, AlSb, FeSb2, FeSn2, CoSn2), a metal oxide, a metal nitride, a metal phosphide, a metal phosphate (such as LiTi2(PO4)3), a metal halide, a metal sulfide, a metal oxysulfide or a combination thereof, or carbon (such as graphite, graphene, reduced graphene oxide, hard carbon, soft carbon, exfoliated graphite and amorphous carbon), silicon (Si), silicon-carbon composite material (Si-C), silicon dioxide (SiO₂) x ), silicon dioxide-carbon composite material (SiO x -C), tin (Sn), tin-carbon composite material (Sn-C), tin oxide (SnO x ), tin oxide-carbon composite material (SnO x -C), and mixtures thereof. In one embodiment, the metal oxide is of formula M' b O cCompounds of (M' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb or a combination thereof, and b and c are numbers such that the ratio c:b is in the range of 2-3 (e.g., MoO3, MoO2, MoS2, V2O5, and TiNb2O7)), spinel oxides M'M”2O4 (e.g., NiCo2O4, ZnCo2O4, MnCo2O4, CuCo2O4, and CoFe2O4), and Li a M' b O c (M' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb or a combination thereof (Lithium titanate (Li4Ti5O 12 (etc.), or lithium molybdate (Li2Mo4O 13 Selected from (etc.).

[0028] According to one embodiment, the negative electrode layer further includes a conductive material, such as one defined with respect to the positive electrode layer.

[0029] In another embodiment, the negative electrode layer comprises a composite material, for example, a crosslinked aprotic polymer present between inorganic particles, between particles of the negative electrode electrochemical active material, and between particles of the conductive material, if present.

[0030] In other embodiments, the negative electrode layer further comprises a polymer binder selected from crosslinked aprotic polymers, fluorinated polymers (such as PVDF, HFP, PTFE, and copolymers or mixtures of two or three thereof), polyvinylpyrrolidone (PVP), poly(styrene-ethylene-butylene) copolymer (SEB), and synthetic rubbers (such as SBR (styrene-butadiene rubber), NBR (acrylonitrile-butadiene rubber), HNBR (hydrogenated NBR), CHR (epichlorohydrin rubber), ACM (acrylate rubber), EPDM (ethylene propylene diene monomer rubber), and combinations thereof, and optionally further comprising carboxyalkylcellulose, hydroxyalkylcellulose, or combinations thereof).

[0031] According to another embodiment, the negative electrode layer further includes at least one salt as defined herein, for example, including cations of an alkali metal or an alkaline earth metal. For example, the cations of the alkali metal or alkaline earth metal of the salt may be the same as the alkali metal or alkaline earth metal present in the inorganic particles. In another embodiment, the negative electrode layer further includes an ionic liquid such as those defined herein. In another embodiment, the negative electrode layer further includes an aprotic solvent having a boiling point higher than 150 °C. It is understood that the amount of the ionic liquid and / or aprotic solvent is such that the negative electrode layer remains in a solid state.

[0032] In some embodiments, the all-solid-state electrochemical cell further includes an intermediate layer between the positive electrode layer and the electrolyte layer and / or between the negative electrode layer and the electrolyte layer. In one embodiment, the intermediate layer is an alkali metal or alkaline earth metal-ion conductive polymer layer, and the layer includes alkali metal or alkaline earth metal ion conductive inorganic particles or a combination thereof. Preferably, the intermediate layer is an alkali metal or alkaline earth metal-ion conductive polymer layer (for example, a lithium ion conductive polymer).

[0033] According to a second aspect, the present specification is a method for preparing an all-solid-state electrochemical cell as defined herein, the method comprising (i) preparing a positive electrode layer containing a positive electrode electrochemically active material on a current collector; (ii) preparing an electrolyte layer; (iii) optionally preparing or providing a negative electrode layer containing a negative electrode electrochemically active material on a current collector, and (iv) assembling an all-solid-state electrochemical cell by combining the positive electrode layer, the electrolyte layer, and the negative electrode layer and including Steps (i) to (iii) are performed in any order, and step (iv) is performed after steps (i) to (iii), or simultaneously with one or two of steps (i) to (iii), or after two of steps (i) to (iii) are performed, and then a part is performed. At least one of steps (i), (ii) and (iii) is a step of mixing alkali metal or alkaline earth metal ion conductive inorganic particles and a polymer precursor, and optionally a solvent, wherein the polymer precursor is a non-protic polymer segment containing crosslinkable units and is in a liquid form at 25°C, and a step of crosslinking the crosslinkable units of the polymer precursor, wherein the crosslinked polymer is in a solid form at 25°C. The content of the inorganic particles in the mixture of the particles and the polymer precursor is in the range of 50% to 99.9% by weight. Relates to a method.

[0034] In a first embodiment of the method, step (i) includes preparing a positive electrode material mixture containing a positive electrode electrochemically active material and applying it onto a current collector, step (ii) includes preparing an electrolyte composition and applying the composition onto a support, and the method includes assembling a positive electrode layer and an electrolyte layer, and removing the support from the electrolyte layer before or after assembly with the positive electrode layer, and optionally, then applying pressure and / or heat. In one embodiment, step (i) further includes applying an intermediate layer onto the positive electrode layer.

[0035] In a second embodiment of the method, step (i) includes preparing a positive electrode material mixture containing a positive electrode electrochemically active material and applying it onto a current collector, and optionally, then applying an intermediate layer onto the positive electrode layer, and step (ii) includes preparing an electrolyte composition and applying the composition onto the positive electrode layer or, if present, onto the intermediate layer.

[0036] In a third embodiment of the present method, step (ii) includes the steps of preparing an electrolyte composition and coating the composition onto a support, and step (i) includes the steps of preparing a cathode material mixture containing a cathode electrochemical active material and coating it onto an electrolyte layer, optionally including the step of coating it after coating an intermediate layer onto the electrolyte layer, wherein the support is removed from the electrolyte layer before or after the formation of the cathode.

[0037] In some embodiments of the first, second, or third embodiment of this method, the negative electrode electrochemical active material is - A metal film is included, and step (iii) includes the steps of preparing the metal film and applying it to the surface of the electrolyte layer opposite the positive electrode layer, and optionally further including the step of forming an intermediate layer on the negative electrode layer or on the electrolyte layer before application, or - In the form of particles, step (iii) includes the steps of preparing a negative electrode material mixture containing a negative electrode electrochemical active material and coating it onto the surface of the electrolyte layer opposite the positive electrode layer, and optionally further including the steps of forming an intermediate layer on the electrolyte layer and coating the negative electrode material mixture onto the intermediate layer, or - In the form of particles, step (iii) includes the steps of preparing a negative electrode material mixture containing a negative electrode electrochemical active material, coating it onto a current collector to form a negative electrode layer, and coating the negative electrode layer onto the surface of the electrolyte layer opposite the positive electrode layer, and optionally further including the step of forming an intermediate layer on the negative electrode layer or on the electrolyte layer before coating.

[0038] In a fourth embodiment of the Method, step (iii) includes preparing a negative electrode material comprising a negative electrode electrochemical active material and optionally coating it onto a current collector; step (ii) includes preparing an electrolyte composition and coating the composition onto a support; the Method further includes assembling the negative electrode layer and the electrolyte layer, and removing the support from the electrolyte layer before or after assembly with the negative electrode layer, and optionally then applying pressure and / or heat. In the embodiment, step (iii) further includes coating an intermediate layer onto the negative electrode layer.

[0039] In a fifth embodiment of the present method, step (iii) includes preparing a negative electrode material comprising a negative electrode electrochemical active material, and optionally coating it onto a current collector, and optionally subsequently forming an intermediate layer on the negative electrode layer; and step (ii) includes preparing an electrolyte composition, and coating it onto the negative electrode layer, or onto the intermediate layer, if present.

[0040] In a sixth embodiment of the present method, step (ii) includes the steps of preparing an electrolyte composition and coating the composition onto a support, and step (iii) includes the steps of preparing a negative electrode material comprising a negative electrode electrochemical active material and coating it onto an electrolyte layer, which optionally includes coating it after coating an intermediate layer onto the electrolyte layer or the negative electrode layer, wherein the support is removed from the electrolyte layer before or after the formation of the negative electrode.

[0041] In some embodiments of the fourth, fifth, or sixth embodiment of this method, step (i) is: - The steps include preparing a positive electrode material mixture containing a positive electrode electrochemical active material, and coating it onto the surface of the electrolyte layer opposite the negative electrode layer, and optionally further including forming an intermediate layer on the electrolyte layer, and coating the positive electrode material mixture onto the intermediate layer, or - The process includes the steps of preparing a positive electrode material mixture containing a positive electrode electrochemical active material, applying it onto a current collector to form a positive electrode layer, and applying the positive electrode layer to the surface of the electrolyte layer opposite the negative electrode layer, and optionally further including the step of forming an intermediate layer on the positive electrode layer or on the electrolyte layer before application.

[0042] In some embodiments of the fourth, fifth, or sixth embodiment of this method, the anode electrochemical active material comprises a metal film, and step (iii) comprises a step of preparing the metal film. In other embodiments of the fourth, fifth, or sixth embodiment of this method, the anode electrochemical active material comprises a material in the form of particles, and step (iii) comprises a step of preparing a anode material mixture comprising the anode electrochemical active material before coating.

[0043] In one of the above-described embodiments of the method, if the negative electrode electrochemical active material is in the form of particles, the negative electrode material mixture may further comprise a conductive material, and optionally a salt, an ionic liquid, and / or an aprotic solvent. In one embodiment, the negative electrode material mixture further comprises a polymer binder. In another embodiment, the negative electrode material mixture further comprises alkali metal or alkaline earth metal ion conductive inorganic particles, a polymer precursor, and optionally a solvent, and step (iii) further comprises crosslinking the polymer precursor after coating the mixture. Alternatively, the negative electrode material mixture is a solid mixture further comprising alkali metal or alkaline earth metal ion conductive inorganic particles, and step (iii) comprises coating the solid mixture, adding the polymer precursor and optionally a solvent to the coated solid mixture to disperse the polymer precursor between the particles, and crosslinking.

[0044] In one of the above-described embodiments of the method, the electrolyte composition comprises a polymer or polymer precursor, and optionally a salt, an ionic liquid, and / or an aprotic solvent.

[0045] In any one embodiment of the above-described embodiments of the present method, the electrolyte composition comprises alkali metal or alkaline earth metal ion conductive inorganic particles, a polymer precursor, and optionally a solvent, and step (ii) further comprises crosslinking the polymer precursor after coating the composition. Alternatively, the electrolyte composition is a solid composition comprising alkali metal or alkaline earth metal ion conductive inorganic particles, and step (ii) comprises coating the solid composition, adding a polymer precursor and optionally a solvent to the coated solid composition to allow the polymer precursor to penetrate between the particles, and crosslinking the polymer precursor.

[0046] In another embodiment of any of the above-described embodiments of the method, the cathode material mixture further comprises a conductive material, and optionally a salt, an ionic liquid, and / or an aprotic solvent. In one embodiment, the cathode material mixture further comprises a polymer binder. In another embodiment, the cathode material mixture further comprises alkali metal or alkaline earth metal ion conductive inorganic particles, a polymer precursor, and optionally a solvent, and step (iii) further comprises crosslinking the polymer precursor after coating the mixture. Alternatively, the cathode material mixture is a solid mixture further comprising alkali metal or alkaline earth metal ion conductive inorganic particles, and step (iii) comprises coating the solid mixture, adding the polymer precursor and optionally a solvent to the coated solid mixture to disperse the polymer precursor between the particles, and crosslinking.

[0047] In another embodiment, the method further includes a photoinitiator in which the crosslinking step is carried out by UV irradiation, or a thermal initiator in which the crosslinking step is carried out by heat treatment, or a combination thereof. In another embodiment, the crosslinking step is carried out by an electron beam or another energy source, with or without the use of an initiator.

[0048] According to a third aspect, the present specification relates to a all-solid-state battery including at least one all-solid-state electrochemical cell of the present invention. In one embodiment, the all-solid-state battery is a rechargeable battery. In another embodiment, the all-solid-state battery is a lithium battery or a lithium ion battery. In yet another embodiment, the all-solid-state battery is for use in portable devices such as mobile phones, cameras, tablets or laptops, in electric vehicles or hybrid vehicles, or in renewable energy storage.

Brief Description of the Drawings

[0049] [Figure 1] FIG. 1 (Comparative Example) illustrates a solid-state battery including inorganic electrolyte particles that do not contain a polymer electrolyte and do not contain a polymer binder.

[0050] [Figure 2] FIG. 2 illustrates an embodiment of the present electrochemical cell including a positive electrode layer including an electrolyte composed of inorganic particles interconnected by a crosslinked polymer, inorganic particles, and a crosslinked polymer, in which a metal film is used as the negative electrode material.

[0051] [Figure 3] FIG. 3 illustrates an embodiment of the present electrochemical cell including a polymer electrolyte layer between the positive electrode and the metal negative electrode, in which case the positive electrode layer includes inorganic particles and a crosslinked polymer.

[0052] [Figure 4] FIG. 4 illustrates another embodiment of the present electrochemical cell including an intermediate polymer between a positive electrode and an electrolyte layer each including inorganic particles and a crosslinked polymer, and a metal film as the negative electrode material.

[0053] [Figure 5] FIG. 5 illustrates an embodiment of the present electrochemical cell including an intermediate polymer layer between a positive electrode and an electrolyte layer each including inorganic particles and a crosslinked polymer, a second intermediate polymer layer between the negative electrode and the electrolyte layer, and a negative electrode layer including a metal film.

[0054] [Figure 6] Figure 6 illustrates another embodiment of the electrochemical cell, in which the positive electrode layer and the electrolyte layer each contain inorganic particles and a crosslinked polymer, and the cell includes an intermediate polymer layer and a negative electrode layer containing a metal film between the negative electrode layer and the electrolyte layer.

[0055] [Figure 7] Figure 7 illustrates another embodiment of the electrochemical cell, in which the negative electrode active material is in the form of particles, and the positive electrode layer, electrolyte layer, and negative electrode layer each contain inorganic particles and a crosslinked polymer, respectively.

[0056] [Figure 8] Figure 8 shows the capacity retention result (cycle life) as a function of the number of cycles for the solid battery of Example 1, when cyclically tested between 4.0V and 2.0V at a rate of C / 12 at 30°C.

[0057] [Figure 9] Figure 9 shows the capacity retention result (cycle life) as a function of the number of cycles for the solid battery of Example 2, when cycled between 4.0V and 2.0V at a rate of C / 6 or C / 12 at 30°C.

[0058] [Figure 10] Figure 10 shows scanning electron microscope images of the half-cell prepared in Example 3(b), showing (a) a cross-sectional view in the secondary electron mode and (b) a cross-sectional view in the backscattered electron mode.

[0059] [Figure 11] Figure 11 shows the capacitance results for the cells prepared in Example 3, as a function of applied current, for charge and discharge cycles between 2.5V and 4.3V.

[0060] [Figure 12]Figure 12 shows the capacitance results for the cells prepared in Example 4, as a function of applied current, for charge and discharge cycles between 2.5V and 4.3V.

[0061] [Figure 13] Figure 13 shows scanning electron microscope images of (a) the surface (top) and (b) a cross-sectional view of the electrolyte layer prepared in Example 5.

[0062] [Figure 14] Figure 14 shows the ionic conductivity results as a function of temperature for the electrolyte layer prepared in Example 5. [Modes for carrying out the invention]

[0063] Detailed explanation All technical and scientific terms and expressions used herein have the same definitions as those commonly understood by those skilled in the art. Nevertheless, for clarity, the definitions of some terms and expressions used herein are provided below.

[0064] When the term "approximately" is used herein, it means roughly within and around a given area. When the term "approximately" is used in reference to a numerical value, it can modify that value, for example, by a 10% variation from its apparent value. The term may also take into account, for example, experimental errors inherent in the measuring instrument or rounding of the value.

[0065] If a range of values ​​is specified in this application, unless otherwise specified, the lower and upper limits of that range are always included in this definition. If a range of values ​​is specified in this application, all intermediate and partial ranges, as well as the individual values ​​within those ranges of the value, are included in this definition.

[0066] When the article "a" is used to introduce an element in this application, it does not mean "one" but rather "one or more." Naturally, where this specification states that a step, component, element, or particular feature "may be included" or "may be included," that step, component, element, or particular feature is not required to be included in each embodiment.

[0067] This specification describes a solid electrochemical cell comprising a positive electrode containing a positive electrochemical active material, a negative electrode containing a negative electrochemical active material, and an electrolyte between the positive and negative electrodes, wherein the positive electrode, negative electrode, and electrolyte are each in the form of solid layers. The electrochemical cell is characterized in that at least one of the positive electrode, negative electrode, and electrolyte layer contains a composite material as defined herein.

[0068] The composite material present in one or more of the above layers comprises alkali metal or alkaline earth metal ion-conducting inorganic particles and a crosslinked aprotic polymer, wherein the concentration of inorganic particles in the composite material is at least 50% by weight, for example, in the range of 50% to 99.9% by weight, the crosslinked aprotic polymer is in solid form at 25°C, while the polymer precursor before crosslinking is in liquid form at 25°C.

[0069] The concentration of inorganic particles in the composite material is at least 50% by weight (e.g., between 50% and 99.9% by weight), but other values ​​within this range may be preferred depending on the inorganic particles used (e.g., particle size, surface area, etc.) and whether the composite material exists in the electrolyte layer or as part of the electrode material. Non-limiting examples of inorganic particle concentration ranges include 50%–80% by weight, 60%–80% by weight, 55%–75% by weight, 70%–99.9% by weight, 80%–99.9% by weight, 75%–90% by weight, 65%–85% by weight, and other similar ranges.

[0070] For example, inorganic particles may include oxide, sulfide, or oxysulfide type inorganic compounds, or compounds having a structure selected from garnet, NASICON, LISICON, thio-LISICON, LIPON, perovskite, inverse perovskite, or argyrodite types, and / or compounds containing the element MPS, MPSO, MPSX, or MPSOX (where M is an alkali metal or alkaline earth metal, and X is F, Cl, Br, I, or a mixture thereof), and the above-mentioned compounds may further contain one or more additional elements (metals, metalloids, or nonmetals), and may be in crystalline form, amorphous form, glass-ceramic form, or a mixture of at least two thereof.

[0071] Non-limiting examples of inorganic compounds that form particles include compounds MLZO(M7La3Zr2O) in crystalline, amorphous, glass-ceramic, or mixtures of at least two thereof. 12 M (7-a) La3Zr2Al b O 12 M (7-a) La3Zr2Ga b O 12 M (7-a) La3Zr (2-b) Ta b O 12 M (7-a) La3Zr (2-b) Nb b O 12 etc);MLTaO(M7La3Ta2O 12 M5La3Ta2O 12、 M6La3TA 1.5 Y 0.5 O 12 etc); MLSnO(M7La3Sn2O 12 etc); MAGP(M 1+a Al a Ge 2-a (PO4)3 etc);MATP(M 1+a Al a Ti 2-a (PO4)3 etc); MLTiO(M 3a La (2 / 3-a)TiO3 etc.); MZP(M a Zr b (PO4) c etc); MCZP(M a Ca b Zr c (PO4) d etc);MGPS(M a Ge b P c S d For example, M 10 GeP2S 12 );MGPSO(M a Ge b P c S d O e etc); MSiPS(M a Si b P c S d For example, M 10 SiP2S 12 );MSiPSO(M a Si b P c S d O e etc); MSnPS(M a Sn b P c S d For example, M 10 SnP2S 12 );MSnPSO(M a Sn b P c S d O e etc); MPS(M a P b S c For example, M7P3S 11 );MPSO(M a P b S c O d etc); MZPS(M a Zn b P c S d etc); MZPSO(M a Zn b P c S d O e);xM2S-yP2S5;xM2S-yP2S5-zMX;xM2S-yP2S5-zP2O5;xM2S-yP2S5-zP2O5-wMX;xM2S-yM2O-zP2S5; xM2S-yM2O-zP2S5-wMX;xM2S-yM2O-zP2S5-wP2O5;xM2S-yM2O-zP2S5-wP2O5-vMX;xM2S-ySiS2;MPSX(M a P b S c X d For example, M7P3S 11 X, M7P2S8X, M6PS5X); MPSOX(M a P b S c O d X e etc); MGPSX(M a Ge b P c S d X e etc);MGPSOX(M a Ge b P c S d O e X f etc); MSiPSX(M a Si b P c S d X e etc); MSiPSOX(M a Si b P c S d O e X f etc); MSnPSX(M a Sn b P c S d X e etc); MSnPSOX(M a Sn b P c S d O e X f etc); MZPSX(M a Zn b P c S d X e etc); MZPSOX(M a Zn b Pc S d O e X f etc); M3OX; M2HOX; M3PO4; M3PS4; M a PO b N c The formula includes (a=2b+3c-5), where M is an alkali metal ion, an alkaline earth metal ion, or a combination thereof, and if M includes an alkali metal ion, the number of M is adjusted to achieve electrical neutrality, where X is F, Cl, Br, I, or a combination thereof, where a, b, c, d, e, and f are non-zero numbers, independently selected in each formula to achieve electrical neutrality, and where v, w, x, y, and z are non-zero numbers, independently selected in each formula to obtain a stable compound.

[0072] For example, alkali metals or alkaline earth metals (M) are selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, or combinations thereof. For example, M is lithium, or a combination of Li and at least one of Na, K, Rb, Cs, Be, Mg, Ca, Sr, and Ba. Alternatively, M is Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, or a combination of at least two of them, for example, M is Na, K, Mg, or a combination of at least two of them.

[0073] In composite materials, crosslinked aprotic polymers are generally prepared from polymer precursors and crosslinkable units in the form of aprotic polymer segments containing heteroatoms (e.g., O, N, P, S, Si, etc.). Crosslinked polymers are solid at room temperature and have a glass transition temperature of -40°C or below T. g The polymer preferably exhibits high chain flexibility to facilitate lithium ion transfer.

[0074] Crosslinked aprotic polymers have a V of 4V and higher (relative to Li +The aprotic polymer is preferably electrochemically stable and / or compatible with high-capacity cathode materials (>150 mAh / g) in Li(I) ions. The crosslinked aprotic polymer preferably comprises an aprotic polymer segment such as polyethers, polythioethers, polyesters, polythioesters, polycarbonates, polythiocarbonates, polysiloxanes, polyimides, polysulfonimides, polyamides, polysulfonamides, polyphosphazenes, polyurethanes, or copolymers or mixtures thereof. For example, the aprotic polymer segment comprises a block copolymer having different repeating units to reduce the crystallinity of the polymer after crosslinking. In some examples, the aprotic polymer segment comprises a block copolymer consisting of at least one alkali metal ion or alkaline earth metal ion solvation segment and at least one crosslinkable segment containing crosslinkable units before crosslinking. For example, the alkali metal ion or alkaline earth metal ion solvation segment is of formula (I): [ka] (In the formula, R is H, C1~C 10 Alkyl or -(CH 2- Ure a R b ) are selected from, R a (CH2-CH2-O) y And, R b C1~C 10 (It is an alkyl group.) Selected from homopolymers and copolymers containing repeating units.

[0075] Crosslinkable units generally contain unsaturated bonds, which may be crosslinked after film casting. The polymer may contain more than one crosslinkable functional group to form a multidimensional network, including a highly branched or highly branched network, after crosslinking. Examples of functional groups present in a crosslinkable unit include at least one group selected from acrylates, methacrylates, allyls, and vinyls.

[0076] The branched portion of the polymer may also contain a graft copolymer containing block copolymer segments. The copolymer may further contain non-solvated segments that can improve the mechanical strength of the film.

[0077] As described above, the aprotic polymer is in the liquid phase at room temperature before crosslinking, which facilitates the penetration of the aprotic polymer into the electrolyte particle network at the electrode / electrolyte interface and / or within the electrode material without the use of a considerable amount of additional solvent. The pores between inorganic particles (and, in the case of electrodes, inorganic particles of the electrode material) are filled with the polymer precursor in the liquid phase before crosslinking. The average molecular weight of the polymer precursor before crosslinking is preferably in the range of 250 to 50,000 g / mol.

[0078] The electrolyte may consist of a layer of composite material, or it may include a composite material and additional components. Alternatively, if the composite material is present on one of the electrodes, the electrolyte layer may be a solid polymer electrolyte layer, for example, a crosslinked aprotic polymer as defined herein, and optionally additional components.

[0079] The electrolyte layer may further contain at least one alkali metal salt or alkaline earth metal salt. Non-limiting examples of salts include alkali metal or alkaline earth metal cations, as well as hexafluorophosphate ions (PF6). - ), bis(trifluoromethanesulfonyl)imide (TFSI - ), bis(fluorosulfonyl)imide (FSI - ), (flurosulfonyl)(trifluoromethanesulfonyl)imide ((FSI)(TFSI) - ), 2-trifluoromethyl-4,5-dicyanoimidazolate (TDI - ), 4,5-dicyano-1,2,3-triazolate (DCTA - ), bis(pentafluoroethylsulfonyl)imide (BETI -), difluorophosphate ion (DFP - ), tetrafluoroborate ion (BF4 - ), bis(oxalato)borate ion (BOB - ), nitrate ion (NO3 - ), chloride ions (Cl - ), bromide ions (Br - ), fluoride ions (F - ), perchlorate ion (ClO4 - ), hexafluoroarsenate ion (AsF6 - ), trifluoromethanesulfonate ion (SO3CF3 - )(Tf - ), fluoroalkyl phosphate ion [PF3(CF2CF3)3 - ](FAP - ), tetrakis(trifluoroacetoxy)borate ion [B(OCOCF3)4] - (TFAB - ), bis(1,2-benzenediolato(2-)-O,O')borate ion [B(C6O2)2] - (BBB - ), difluoro(oxalato)borate ion (BF2(C2O4) - )(FOB - ), formula BF2O4R x - Compound (R x =C 2~4 The salt contains anions selected from alkyl groups and at least two combinations thereof. For example, the molar ratio of heteroatoms of the aprotic polymer to alkali metal or alkaline earth metal ions of the salt can be in the range of 4:1 to 50:1, preferably 10:1 to 30:1. In some preferred examples, the alkali metal or alkaline earth metal forming the cation of the salt is identical to the alkali metal or alkaline earth metal present in the inorganic particles.

[0080] This electrolyte may further include at least one ionic liquid. Non-limiting examples of ionic liquids include cations selected from imidazolium, pyridinium, pyrrolidinium, piperidinium, phosphonium, sulfonium, and morpholinium, or 1-ethyl-3-methylimidazolium (EMI), 1-methyl-1-propylpyrrolidinium (PY 13 + ), 1-butyl-1-methylpyrrolidinium (PY 14 + ), n-propyl-n-methylpiperidinium (PP 13 + ) and n-butyl-n-methylpiperidinium (PP 14 + A cation selected from ) and PF6 - BF4 - AsF6 - ClO4 - CF3SO3 - (CF3SO2)2N - (TFSI), (FSO2)2N - (FSI), (FSO2)(CF3SO2)N - (C2F5SO2)2N - (BETI), PO2F2 - (DFP), 2-trifluoromethyl-4,5-dicyanoimidazole (TDI), 4,5-dicyano-1,2,3-triazolate (DCTA), bis-oxalatobolate (BOB), and (BF2O4R x ) - (R x The ionic liquid contains anions selected from C2-C4 alkyl groups, and is present in such an amount that the electrolyte layer remains solid (e.g., less than 30% by weight, or less than 20% by weight, or less than 10% by weight of the electrolyte solid layer).

[0081] Aprotic solvents having a boiling point higher than 150°C may also be included in the electrolyte. Examples of such aprotic solvents include ethylene carbonate (EC), propylene carbonate (PC), gamma-butyrolactone (γ-BL), poly(ethylene glycol) dimethyl ether (PEGDME), dimethyl sulfoxide (DMSO), vinylene carbonate (VC), vinylethylene carbonate (VEC), 1,3-propylene sulfite, 1,3-propanesultone (PS), triethyl phosphate (TEPa), triethyl phosphate (TEPi), trimethyl phosphate (TMPa), trimethyl phosphate (TMPi), dimethylmethyl phosphonate (DMMP), diethyl ethyl phosphonate (DEEP), tris(trifluoroethyl) phosphate (TFFP), fluoroethylene carbonate (FEC), or mixtures thereof, wherein the aprotic solvent is present in an amount such that the electrolyte layer remains solid (e.g., less than 30% by weight, or less than 20% by weight, or less than 10% by weight of the electrolyte solid layer).

[0082] The positive electrode layer preferably includes an electrode material on a current collector, in which case the material includes at least one electrochemical active material. Non-limiting examples of the positive electrode electrochemical active material include metal oxides, metal sulfides, metal oxysulfides, metal phosphates, metal fluorophosphates, metal oxyfluorophosphates, metal sulfates, metal halides, sulfur, selenium, or mixtures of at least two thereof. For example, the metal oxides, metal sulfides, metal oxysulfides, metal phosphates, metal fluorophosphates, metal oxyfluorophosphates, metal sulfates, or metal halides include metals selected from the elements iron (Fe), titanium (Ti), manganese (Mn), vanadium (V), nickel (Ni), cobalt (Co), aluminum (Al), chromium (Cr), zirconium (Zr), niobium (Nb), and combinations of at least two thereof. In some examples, the metal further includes alkali metals or alkaline earth metals (e.g., lithium). In one preferred example, the positive electrode electrochemical active material includes a lithium metal oxide, such as lithium nickel cobalt manganese oxide (NCM). In another preferred example, the positive electrode electrochemical active material includes a lithium metal phosphate, such as lithium iron phosphate (LiFePO4).

[0083] The positive electrode may contain one or more conductive materials, binders, and / or additional elements such as inorganic ion conductive materials (e.g., alkali metal or alkaline earth metal ion conductors). Examples of conductive materials include, but are not limited to, carbon black (e.g., Ketjenblack® and Super P®), acetylene black (e.g., Shawinigan black and Denka® black), graphite, graphene, carbon fibers or nanofibers (e.g., vapor-grown carbon fibers (VGCF)), carbon nanotubes (e.g., single-walled carbon nanotubes (SWNTs), multi-walled carbon nanotubes (MWNTs)), or metal powders.

[0084] In some cases, the cathode material includes composite materials described herein, in which crosslinked aprotic polymers act as binders and are present between inorganic particles and between particles of the cathode electrochemical active material.

[0085] Alternatively, the cathode layer further comprises a polymer binder selected from the following as defined herein: crosslinked aprotic polymers, fluorinated polymers (PVDF, HFP, PTFE, or copolymers or mixtures of at least two thereof), polyvinylpyrrolidone (PVP), poly(styrene-ethylene-butylene) copolymer (SEB), and synthetic rubbers (e.g., SBR (styrene-butadiene rubber), NBR (acrylonitrile-butadiene rubber), HNBR (hydrogenated NBR), CHR (epichlorohydrin rubber), ACM (acrylate rubber), EPDM (ethylene propylene diene monomer rubber), and optionally further comprising carboxyalkylcellulose or hydroxyalkylcellulose).

[0086] If necessary, the cathode layer may also further contain salts, ionic liquids, and / or high-boiling aprotic solvents as defined herein.

[0087] In some embodiments, the anode electrochemical active material includes a metal film. For example, the metal film is a film of an alkali metal, an alkaline earth metal, or an alloy containing them, such as a film of lithium or an alloy thereof. Alternatively, the metal film may be made from a non-alkali metal and non-alkaline earth metal (e.g., In, Ge, Bi), or an alloy or intermetallic compound (e.g., SnSb, TiSnSb, Cu2Sb, AlSb, FeSb2, FeSn2, CoSn2). Preferably, the metal film has a thickness of 5 μm to 500 μm, preferably 10 μm to 100 μm.

[0088] In other embodiments, the negative electrode electrochemical active material includes a particulate material having a redox potential lower than that of the positive electrode electrochemical active material. Non-limiting examples of the negative electrode electrochemical active material include non-alkali metals and non-alkaline earth metals (e.g., In, Ge, Bi), intermetallic compounds (SnSb, TiSnSb, Cu2Sb, AlSb, FeSb2, FeSn2, CoSn2, etc.), metal oxides, metal nitrides, metal phosphides, metal phosphates (e.g., LiTi2(PO4)3), metal halides, metal sulfides, metal oxysulfides or combinations thereof, or carbon (graphite, graphene, reduced graphene oxide, hard carbon, soft carbon, exfoliated graphite and amorphous carbon, etc.), silicon (Si), silicon-carbon composites (Si-C), silicon oxide (SiO2). x ), silicon dioxide-carbon composite material (SiO x -C), tin (Sn), tin-carbon composite material (Sn-C), tin oxide (SnO x ), tin oxide-carbon composite material (SnO x -C), or mixtures thereof. Examples of metal oxides include, non-limitingly, formula M' b O c Compounds of the formula M'M''2O4 (where M' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb or a combination thereof, and b and c are numbers such that the ratio of c to b is in the range of 2-3 (e.g., MoO3, MoO2, MoS2, V2O5, and TiNb2O7)), spinel oxides of the formula M'M''2O4 (e.g., NiCo2O4, ZnCo2O4, MnCo2O4, CuCo2O4, and CoFe2O4), and Li a M' b O c The oxide (M' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb or a combination thereof) (Lithium titanate (e.g., Li4Ti5O) 12 ) etc.), or lithium molybdate (e.g., Li2Mo4O 13 )) includes.

[0089] If the negative electrode electrochemical active material is in the form of particles, the negative electrode may also contain additional elements such as conductive materials, binders, and / or inorganic lithium-ion conductive materials. Examples of possible conductive materials and binders are as defined above with respect to the positive electrode material. If necessary, the negative electrode layer may also contain salts, ionic liquids, and / or high-boiling aprotic solvents as defined herein.

[0090] In some examples, the negative electrode material includes this composite material, and the crosslinked aprotic polymer acts as a binder, present between inorganic particles and between particles of the negative electrode electrochemical active material.

[0091] The electrochemical cell may also further include intermediate layers between the electrolyte layer and the positive electrode layer, between the electrolyte layer and the negative electrode layer, or between the electrolyte layer and each of the positive and negative electrode layers. Such intermediate layers are preferably solid films having a thickness thinner than the electrolyte layer, and include films containing an alkali metal or alkaline earth metal ion conductive polymer layer, or an alkali metal or alkaline earth metal ion conductive inorganic layer, or a combination thereof. In one preferred embodiment, the intermediate layer is an alkali metal or alkaline earth metal ion conductive polymer layer (e.g., a lithium ion conductive polymer). The role of the intermediate layer may include protecting the electrode material from the electrolyte, or the electrolyte layer from the electrode material, or promoting adhesion between the electrode layer and the electrolyte layer. This intermediate layer should have alkali metal or alkaline earth metal ion conductivity and electron tunneling resistance properties.

[0092] This all-solid-state electrochemical cell is (i) A step of preparing a solid positive electrode layer containing a positive electrode electrochemical active material on a current collector, (ii) Step of preparing a solid electrolyte layer, (iii) the step of preparing or providing a solid negative electrode layer containing a negative electrode electrochemical active material on the current collector as necessary, (iv) Step of assembling a solid electrochemical cell by combining a solid cathode layer, a solid electrolyte layer, and a solid anode layer. It is preferably prepared by a method including [a certain component].

[0093] Steps (i) to (iii) may be performed in any order, and step (iv) may be performed after steps (i) to (iii), simultaneously with one or two of steps (i) to (iii), or partially after two of steps (i) to (iii) have been completed.

[0094] In this method, at least one of steps (i), (ii), and (iii) further comprises mixing alkali metal or alkaline earth metal ion-conducting inorganic particles and a polymer precursor, and optionally a solvent, in which case the polymer precursor is an aprotic polymer segment containing crosslinkable units and is in a liquid state at 25°C. The method further comprises crosslinking the crosslinkable units of the polymer precursor to obtain a crosslinked polymer that is in a solid state at 25°C. The concentration of inorganic particles in the mixture of particles and polymer precursor is in the range of 50% to 99.9% by weight.

[0095] According to one alternative, the solid positive electrode layer, the solid electrolyte layer, and the solid negative electrode layer are each formed individually, and these three layers are assembled together at one time, or one of the electrode layer and the electrolyte layer is assembled together, and then the other electrode layer is assembled onto the free surface of the electrolyte layer. The formation of the electrolyte layer may involve the use of a support, which may be removed thereafter, or can act as an intermediate layer between the electrolyte and one of the electrodes. Such a method involving the formation of these layers may further include the step of independently compressing two or three layers together with or without heating.

[0096] Alternatively, the multilayer material may be prepared by forming a first layer (electrode or electrolyte) and then directly coating a second layer (electrolyte or electrode) onto the first layer.

[0097] These layers are formed by following steps (i), (ii), and (iii) above, and / or as illustrated below.

[0098] For example, step (ii) includes the steps of preparing an electrolyte composition and coating the resulting mixture. The electrolyte composition comprises a polymer or polymer precursor, and optionally a salt, an ionic liquid and / or an aprotic solvent, followed by drying and / or crosslinking of the coated mixture. The electrolyte composition may also comprise alkali metal or alkaline earth metal ion-conducting inorganic particles as defined herein, a polymer precursor and optionally a solvent, and step (ii) further comprises the step of crosslinking the polymer precursor after coating the composition, or the electrolyte composition is a solid composition comprising alkali metal or alkaline earth metal ion-conducting inorganic particles, and step (ii) includes the steps of adding a polymer precursor and optionally a solvent onto the coated solid composition to permeate the precursor between the particles, and crosslinking the polymer precursor. The electrolyte composition may be coated onto a substrate before assembly with a positive or negative electrode on a pre-formed electrolyte layer, or before coating a positive or negative electrode on a pre-formed electrolyte layer. Alternatively, the electrolyte composition may be coated onto a positive or negative electrode layer, or onto an intermediate layer (displaced between the electrolyte layer and the electrode layer). Next, other electrode layers (positive or negative electrodes) are formed on the electrolyte layer or pre-formed on the current collector and assembled together with the electrolyte. The intermediate layer may also be coated onto the electrolyte layer or electrodes before assembly.

[0099] Step (i) generally includes the steps of preparing a cathode material mixture comprising a cathode electrochemical active material and coating it onto a current collector, an intermediate layer, or a solid electrolyte layer (as described above). The cathode material mixture may further comprise a conductive material as defined herein, and optionally a binder, a salt, an ionic liquid, and / or an aprotic solvent. For example, the cathode material mixture may further comprise alkali metal or alkaline earth metal ion conductive inorganic particles, a polymer precursor, and optionally a solvent, and the method further comprises the step of crosslinking the polymer precursor after coating the mixture, or the cathode material mixture may be a solid mixture further comprising alkali metal or alkaline earth metal ion conductive inorganic particles, and the method may comprise the steps of coating the solid mixture, adding a polymer precursor and optionally a solvent on the coated solid mixture for dispersion between the particles, and crosslinking.

[0100] In one example, the negative electrode electrochemical active material includes a metal film, and step (iii) includes the step of preparing a metal film as defined herein.

[0101] In another example, the anode electrochemical active material comprises particulate material, and step (iii) comprises preparing a anode material mixture comprising the anode electrochemical active material before coating. The anode material mixture may also further comprise a conductive material, and optionally a binder, salt, ionic liquid and / or aprotic solvent. The anode material mixture may further comprise alkali metal or alkaline earth metal ion conductive inorganic particles, a polymer precursor, and optionally a solvent, and step (iii) comprises crosslinking the polymer precursor after coating the mixture. Alternatively, the anode material mixture is a solid mixture further comprising alkali metal or alkaline earth metal ion conductive inorganic particles, and step (iii) comprises coating the solid mixture, adding the polymer precursor and optionally a solvent to the coated solid mixture for dispersion between particles, and crosslinking.

[0102] In the above method, the polymer to be crosslinked may further contain a photoinitiator, and the crosslinking may be carried out by UV irradiation, or it may contain a thermal initiator, and the crosslinking may be carried out by heat treatment, or a combination thereof. Alternatively, the crosslinking may be carried out by electron beam or another energy source, with or without the use of an initiator.

[0103] Figure 1 illustrates a possible three-dimensional configuration for an all-solid-powder cell for comparative purposes. This example includes a positive electrode layer (1) containing positive electrode electrochemical active material particles (5), a conductive material (6), and inorganic particles (7) on a current collector (4). The electrolyte layer (2) contains inorganic particles (7), and the negative electrode layer (3) contains a metal film (8). Contact between particles can only be ensured under compressed conditions.

[0104] Figure 2 illustrates a possible three-dimensional configuration for this cell, in which case the composite material is present in the positive electrode layer and the electrolyte. This example includes a positive electrode layer (1) on a current collector (4) containing positive electrode electrochemical active material particles (5), a conductive material (6), inorganic particles (7), and a crosslinked aprotic polymer (9). The electrolyte layer (2) includes a composite material consisting of inorganic particles (7) and a crosslinked aprotic polymer (9). In this example, the negative electrode layer (3) includes a metal film (8). Since the polymer precursor is liquid before crosslinking, the crosslinked aprotic polymer is found in the pores, thus forming a network of particles interconnected by the polymer in the positive electrode and electrolyte layers. The polymer precursor may be added to a slurry before coating (e.g., positive electrode slurry), or it may be allowed to penetrate the pores after the formation of a dry solid film. The positive electrode and electrolyte films may be cast separately and then laminated by pressurization and heat. Preferably, the electrolyte slurry may be cast directly onto the dry cathode to form an electrolyte layer.

[0105] Figure 3 shows another three-dimensional configuration of the cell, in which case the composite material is located in the positive electrode layer, and the electrolyte consists of a crosslinked aprotic polymer layer (9) preferably containing at least one salt. In this case, the polymer electrolyte layer (2) may be coated on the positive electrode layer (1), which contains a positive electrode electrochemical active material (5) as defined herein, a conductive material such as carbon (6), and inorganic particles (7). Next, the polymer forms a thin polymer electrolyte layer between the positive electrode and the metal film (8) of the negative electrode material. The solid layer of the crosslinked polymer electrolyte generally has a thickness in the range of about 3 μm to about 100 μm, preferably in the range of about 5 μm to about 30 μm. The polymer found on the inside of the positive electrode layer acts as a binder and may be added in the slurry preparation step (mixing), or may be allowed to penetrate into the pores on the inside of the porous film of the positive electrode layer when an excess coating of the electrolyte layer is performed.

[0106] Figure 4 shows a three-dimensional configuration in which an intermediate layer (10) (such as a protective layer) is inserted between the electrolyte layer (2) and the cathode layer (1). In this example, the intermediate layer is a film of a crosslinked aprotic polymer (9) and may further contain at least one salt as defined herein. This intermediate layer may be formed on the cathode layer or the electrolyte layer before the formation of the other layer, improving adhesion and reducing the interfacial resistance between the cathode layer and the hybrid electrolyte layer.

[0107] Figure 5 illustrates a stereochemical configuration in which an intermediate layer (10) is inserted between the electrolyte layer (2) and the positive electrode layer, and an intermediate layer (11) is inserted between the electrolyte layer (2) and the negative electrode layer. In this example, the intermediate layers are films of a crosslinked aprotic polymer (9) and may further contain at least one salt as defined herein. However, intermediate layers (10) and (11) may also be different. Preferably, intermediate layer (10) has high oxidation stability at >4V, and intermediate layer (11), which is in contact with the negative electrode, has demonstrated high reduction stability with respect to the negative electrode metal material (8) used. These intermediate layers may be formed by coating them onto the electrode layer or electrolyte layer before the formation of the other layer.

[0108] Figure 6 shows a three-dimensional configuration in which an intermediate layer (11) is inserted between the electrolyte layer and the negative electrode layer. In this example, the intermediate layer may be a film of a crosslinked aprotic polymer, further comprising at least one salt as defined herein, or composed of a denser inorganic material different from the inorganic particles of the electrolyte. The intermediate layer generally has high resistance to electron tunneling and simultaneously has ionic conductivity to alkali metals or alkaline earth metals. The intermediate layer may be formed on the negative electrode layer or the electrolyte layer before formation or assembly with the other layer.

[0109] Figure 7 illustrates the three-dimensional structure of an example of this cell, in which the composite material is present in the positive electrode layer, electrolyte layer, and negative electrode layer. This example includes a positive electrode layer (1) on a current collector (4) comprising positive electrode electrochemical active material particles (5), a conductive material (6), inorganic particles (7), and a crosslinked aprotic polymer (9). The electrolyte layer (2) comprises a composite material consisting of inorganic particles (7) and a crosslinked aprotic polymer (9). The negative electrode layer (3) on a current collector (4), which may be made from a material different from the positive electrode material, comprises negative electrode electrochemical active material particles (12), a conductive material (6), inorganic particles (7), and a crosslinked aprotic polymer (9) as defined herein. The crosslinked aprotic polymer is then present inside the pores of the entire cell, thus forming a network of particles interconnected by the polymer in all elements. The polymer precursor may be added to the slurry (e.g., the cathode or anode slurry) before coating, or it may be impregnated into the pores of an already prepared dry solid film. The electrode film and electrolyte film can be cast separately and then laminated by pressurization and heat. Preferably, the electrolyte slurry may be cast directly onto the dry cathode or anode solid film to form a coating of the electrolyte layer.

[0110] Solid-state batteries comprising at least one electrochemical cell as defined herein are also contemplated herein. For example, a solid-state battery is a rechargeable battery. In some examples, a solid-state battery is a lithium battery or lithium-ion battery. Similarly, the use of these solid-state batteries is contemplated in portable devices such as mobile phones, cameras, tablets or laptops, in electric or hybrid vehicles, or in renewable energy storage. [Examples]

[0111] The following non-limiting examples are illustrative embodiments and should not be construed as further limiting the scope of the invention. These examples are better understood by referring to the accompanying drawings.

[0112] Unless otherwise specified, all numbers used herein to express quantities such as components, preparation conditions, concentrations, and properties should be understood in all cases to be modified by the term “approximately.” At a minimum, each numerical parameter should be interpreted in light of the reported significant figures and by applying standard rounding techniques. Thus, unless otherwise specified, the numerical parameters described herein are approximate and may vary depending on the properties to be obtained. Regardless of whether the numerical ranges and parameters illustrating the broad range of embodiments are approximate, the numerical values ​​described in the following examples are reported as accurately as possible. However, all numerical values ​​inherently contain some degree of error due to variability in experiments, test measurements, statistical analyses, etc.

[0113] The crosslinkable polymer (polymer precursor) used in the following examples is an aprotic poly(ethylene oxide) copolymer containing acrylate functional groups. The polymer used has a molecular weight of approximately 8,000 g / mol and is in the liquid phase at 25°C before crosslinking. (Example 1) (a) Preparation of positive electrode film (C-LFP containing LLZO)

[0114] Powder of C-LFP particles (carbon-coated LiFePO4, 6.50g) with an average diameter of 200nm is mixed with c-LLZO (cubic phase Li7La3Zr2O) with an average diameter of 5μm. 12 A dry powder mixture was formed by mixing 1.90 g of LiTFSI with carbon black (0.20 g). A polymer solution was prepared by individually dissolving LiTFSI (0.16 g), 2,2-dimethoxy-1,2-diphenylethane-1-one (4 mg) as an initiator, and a crosslinkable polymer (0.67 g) in a mixture of toluene (0.31 g) and acetonitrile (1.24 g). The polymer solution was added to the dry powder mixture and mixed using a planetary centrifugal mixer (Thinky® ARE-250 mixer). Further solvent (acetonitrile and toluene in an 8:2 volume ratio) was added to this slurry to reach a viscosity suitable for coating (approximately 10,000 cP). The resulting thick slurry was applied to carbon-coated aluminum foil using the doctor blade method. After drying the solvent at 60°C for 10 minutes, the film was irradiated with UV light for 5 minutes in a nitrogen-purged atmosphere. (b) Preparation and deposition of c-LLZO-polymer electrolyte (half cell)

[0115] c-LLZO (20 g) and crosslinkable polymer (7.2 g) were mixed in a 100 mL polypropylene vial filled with 30% by volume stainless steel balls (a 1:1 mixture of 1 mm and 3 mm balls) in a glove box. Next, the mixture was mixed for 2 hours in a high-energy ball mill (8000M Mixer / Mill®, SPEX SamplePrep® LLC), with intermittent stops to avoid overheating (>60°C). Further solvents (acetonitrile and toluene in an 8:2 volume ratio) were added to this slurry to reach a viscosity suitable for coating (approximately 10,000 cP). Initiator 2,2-dimethoxy-1,2-diphenylethane-1-one (36 mg) was added to this slurry, and the mixing was resumed for a further 1 minute. Next, this slurry was coated onto the free surface of the electrode film obtained in (a), and left under vacuum for 30 minutes to allow the composite electrolyte to penetrate into the pores. Next, the coated film was irradiated with UV light for 2 minutes in a nitrogen-purged atmosphere. The ceramic-polymer electrolyte layer on the cathode had a thickness of 28 μm. (c) Cell assembly

[0116] The half-cell prepared in step (b) was placed on a thin film of metallic lithium (approximately 40 μm) and compressed at 100 psi for 10 minutes between two plates heated to 80°C. Next, the cell was sealed under vacuum in a metallized plastic bag. The active area of ​​the assembled cell was 4 cm². 2 That was the case. (d) Electrochemical test

[0117] At 30°C, the cell was cycled at a rate of C / 12 between 4.0V and 2.0V. The same current was applied for charging and discharging. The discharge capacity results for this cell are shown in Figure 8. (Example 2) (a) Preparation of the positive electrode film (C-LFP)

[0118] Powdered C-LFP particles (6.80 g) with an average diameter of 200 nm were mixed with carbon black (0.20 g). A polymer solution was prepared by individually dissolving LiTFSI (0.32 g), 2,2-dimethoxy-1,2-diphenylethane-1-one (8 mg), and a crosslinkable polymer (1.59 g) in a mixture of toluene (0.74 g) and acetonitrile (2.97 g). The polymer solution was added to the above dried powder, and this combination was mixed using a planetary centrifugal mixer (Thinky® ARE-250 mixer). Further solvent (acetonitrile and toluene in an 8:2 v / v ratio) was added to this slurry to reach a viscosity suitable for coating (approximately 10,000 cP). Using a doctor blade, the slurry was coated onto carbon-coated aluminum foil. After drying the solvent at 60°C for 10 minutes, the film was irradiated with UV light for 5 minutes in a nitrogen-purged atmosphere. (b) Preparation and deposition of c-LLZO-polymer electrolyte (half cell)

[0119] c-LLZO (16.67 g) and a crosslinkable polymer in the liquid phase (9.72 g) were mixed in a 100 mL polypropylene vial filled with 30% volume of stainless steel balls (a 1:1 mixture of 1 mm and 3 mm balls) in a glove box. The mixture was then mixed for 2 hours in a high-energy ball mill (8000M Mixer / Mill®, SPEX SamplePrep® LLC), with intermittent stops to avoid overheating (>60°C). Further solvents (acetonitrile and toluene in an 8:2 v / v ratio) were added to this slurry to reach a viscosity suitable for coating (approximately 10,000 cP). LiTFSI (1.94 g) and 2,2-dimethoxy-1,2-diphenylethane-1-one (49 mg) were added to this slurry, and the mixing was resumed for 5 minutes. Next, this slurry was coated onto the free surface of the electrode film obtained in (a), and left under vacuum for 30 minutes to allow the composite electrolyte to penetrate into the pores. Then, the coated film was irradiated with UV light for 2 minutes in a nitrogen-purged atmosphere. The electrolyte layer on the positive electrode had a thickness of 20 μm. The electrolyte film was laminated onto the positive electrode by placing the combination of the two layers between two hot plates at 80°C and 100 psi, completing the formation of a half cell. (c) Cell assembly

[0120] A thin film of metallic lithium (approximately 40 μm) was placed on the half-cell prepared in step (b), and the cell was stacked at 100 psi at a temperature of 80°C. Next, this cell was sealed under vacuum in a metallized plastic bag. The active area of ​​the assembled cell was 4 cm². 2 That was the case. (d) Electrochemical test

[0121] At 30°C, the cells were cycled at C / 6 and C / 12 speeds, ranging from 4.0V to 2.0V. The same current was applied for charging and discharging. The results for the discharge capacity of these cells are shown in Figure 9. (Example 3) (a) Preparation of the positive electrode film (NMC)

[0122] Carbon black (0.8g) was dispersed in anhydrous xylene (22.8g) in the presence of NBR (nitrile-butadiene rubber 1.2g) by high-energy milling for 15 minutes, with intermittent stops to prevent the mixture temperature from rising above 60°C. NCM (Li[Ni 0.6 Co 0.2 Mn 0.2 2.0 g of O2 powder and 0.71 g of argyrodite (Li6PS5Cl, 0.71 g) particles with an average diameter of 3 μm were added to 1.77 g of the above mixture. The combination was then mixed to form a homogeneous slurry. This slurry was cast onto carbon-coated aluminum foil using a doctor blade and dried under vacuum at 120°C to evaporate the solvent. This procedure was carried out under argon with a moisture level of less than 10 ppm. (b) Preparation and deposition of electrolytes (half-cell)

[0123] In a 300 mL glass bottle, LiTFSI (6 g) was dissolved in a crosslinkable polymer (30 g) containing 2,2-dimethoxy-1,2-diphenylethane-1-one (15 mg) by rotating the bottle at room temperature for 24 hours. This solution was cast onto the cathode film obtained in (a), placed under vacuum for 1 hour to fill the pores of the electrode material with the liquid-phase polymer precursor, and then crosslinked by UV irradiation under nitrogen for 5 minutes.

[0124] Figure 10 shows scanning electron microscope images of cross-sections of a half-cell in (a) secondary electron mode and (b) backscattered electron mode, where the current collector, the cathode layer containing the cross-linked polymer that has penetrated the pores (prepared in (a)), and the cross-linked polymer electrolyte layer can be observed from bottom to top. (c) Cell assembly

[0125] Using the half-cells and thin-layer lithium metallic foil (approximately 40 μm) obtained in (b), the cells were assembled into coin cells and compressed at 100 psi and 70°C. (d) Electrochemical test

[0126] At 30°C, the cell was cycled at a rate of C / 10 between 2.5V and 4.3V. The same current was applied for charging and discharging. Figure 11 shows the capacitance results for the charge and discharge cycles as a function of the applied current for this cell. (Example 4)

[0127] Half cells were prepared in the same manner as in Examples 3(a) and (b). Argyrodite particles (100 mg) having an average diameter of 100 μm were compressed at 300 MPa between two stainless steel plates. The formed argyrodite pellets were placed between the half cells and a thin film of metallic lithium (approximately 40 μm) and compressed at 70°C under a pressure of 100 psi.

[0128] The cell was cycled in the same manner as in Example 3(d). The capacitance results for the charge and discharge cycles as a function of the applied current to this cell are shown in Figure 12. (Example 5)

[0129] In a glove box, argyrodite particles were mixed with a crosslinkable polymer in a liquid phase in a 100 mL polypropylene vial. To avoid overheating, the slurry was mixed in a mixer for 15 minutes with intermittent stops. Further solvents (acetonitrile and toluene in an 8:2 v / v ratio) were added to the slurry as needed to reach a viscosity suitable for coating (approximately 10,000 cP). LiTFSI (20% by weight of polymer) and AIBN (0.5% by weight of polymer) were added to the slurry, and the whole mixture was mixed again for 5 minutes. The slurry was cast onto aluminum foil and the solvent was evaporated under vacuum.

[0130] Figure 13 shows scanning electron microscope images of (a) the surface (top) and (b) a cross-section of an electrolyte layer containing a composite material.

[0131] Next, the ionic conductivity of the prepared film was measured as a function of temperature between 0°C and 80°C. The results are shown in Figure 14.

[0132] Numerous modifications can be made to any of the above embodiments without departing from the intended scope of the invention. References, patents, or scientific documents mentioned herein are incorporated in their entirety by reference for all purposes. The present invention provides, for example, the following items: (Item 1) An all-solid-state electrochemical cell comprising a positive electrode containing an electrochemically active material, a negative electrode containing an electrochemically active material, and an electrolyte between the positive electrode and the negative electrode, The positive electrode, the negative electrode, and the electrolyte each form a solid layer. At least one of the positive electrode, the negative electrode, and the electrolyte comprises a composite material containing alkali metal or alkaline earth metal ion conductive inorganic particles and a crosslinked aprotic polymer. The inorganic particle content in the composite material is in the range of 50% by weight to 99.9% by weight. The crosslinked aprotic polymer is in a solid state at 25°C, while its polymer precursor before crosslinking is in a liquid state at 25°C. All-solid-state electrochemical cell. (Item 2) The all-solid-state electrochemical cell according to item 1, wherein the inorganic particles include amorphous, ceramic, or glass-ceramic type ion-conducting inorganic compounds such as oxides, sulfides, or oxysulfides. (Item 3) The all-solid-state electrochemical cell according to item 2, wherein the inorganic particles include oxide, sulfide, or oxysulfide compounds having a structure selected from garnet, NASICON, LISICON, thio-LISICON, LIPON, perovskite, inverse perovskite, or argyrodite, or compounds containing the elemental combination MPS, MPSO, MPSX, where M is an alkali metal or alkaline earth metal, X is F, Cl, Br, I or a mixture thereof, the elemental combination optionally includes one or more additional elements (metals, metalloids, or nonmetals), and the compound is in crystalline form, amorphous form, glass-ceramic form, or a mixture of at least two thereof. (Item 4) The inorganic particles are in crystalline form, amorphous form, glass-ceramic form, or a mixture of at least two of these, as follows: - MLZO(M 7 La 3 Zr 2 O 12 、M (7-a) La 3 Zr 2 Al b O 12 、M (7-a) La 3 Zr 2 Ga b O 12 、M (7-a) La 3 Zr (2-b) Ta b O 12 、M (7-a) La 3 Zr (2-b) Nbb O 12 etc.); - MLTaO(M 7 La 3 Ta 2 O 12 、M 5 La 3 Ta 2 O 12、 M 6 La 3 Ta 1.5 Y 0.5 O 12 etc.); - MLSnO(M 7 La 3 Sn 2 O 12 etc.); - MAGP(M 1+a Al a Ge 2-a (PO 4 ) 3 etc.); - MATP(M 1+a Al a Ti 2-a (PO 4 ) 3 etc.); - MLTiO(M 3a La (2 / 3-a) TiO 3 etc.); - MZP(M a Zr b (PO 4 ) c etc.); - MCZP(M a Ca b Zr c (PO 4) d etc.); - MGPS(M a Ge b P c S d For example, M 10 GeP 2 S 12 ); - MGPSO(M a Ge b P c S d O e etc.); - MSiPS(M a Si b P c S d For example, M 10 SiP 2 S 12 ); - MSiPSO(M a Si b P c S d O e etc.); - MSnPS(M a Sn b P c S d For example, M 10 SnP 2 S 12 ); - MSnPSO(M a Sn bP c S d O e etc.); - MPS(M a P b S c For example, M 7 P 3 S 11 ); - MPSO(M a P b S c O d etc.); - MZPS(M a Zn b P c S d etc.); - MZPSO(M a Zn b P c S d O e etc.); - xM 2 S-yP 2 S 5 ; - xM 2 S-yP 2 S 5 -zMX; - xM 2 S-yP 2 S 5 -zP 2 O 5 ; - xM 2 S-yP 2 S 5 -zP 2 O 5 -wMX; - xM 2 S-yM 2 O-zP 2 S 5 ; - xM 2 S-yM 2 O-zP 2 S 5 -wMX; - xM 2 S-yM 2 O-zP 2 S 5 -wP 2 O 5 ; - xM 2 S-yM 2 O-zP 2 S 5 -wP 2 O 5 -vMX; - xM 2 S-ySiS 2 ; - MPSX(M a P b S c X d For example, M 7 P 3 S 11 X, M 7 P 2 S 8 X, M 6 PS 5 X); - MPSOX(M a P b S c O d X e etc.); - MGPSX(M a Ge b P c S d X e ); - MGPSOX(M a Ge b P c S d O e X f ); - MSiPSX(M a Si b P c S d X e ); - MSiPSOX(M a Si b P c S d O e X f ); - MSnPSX(M a Sn b P c S d X e ); - MSnPSOX(M a Sn b P c S d O e X f ); - MZPSX(M a Zn b P c S d X e); - MZPSOX(M a Zn b P c S d O e X f ); - M 3 OX; - M 2 HOX; - M 3 PO 4 ; - M 3 PS 4 ;or - M a PO b N c (a = 2b + 3c - 5); (In the formula, M is an alkali metal ion, an alkaline earth metal ion, or a combination thereof. If M includes an alkaline earth metal ion, the number of M is adjusted to achieve electrical neutrality, and X is F, Cl, Br, I, or a combination thereof. a, b, c, d, e, and f are non-zero numbers, and in each equation, they are independently chosen to achieve electrical neutrality. v, w, x, y, and z are non-zero numbers, and in each formula, they are independently selected to obtain a stable compound. An all-solid-state electrochemical cell as described in item 2, comprising at least one compound selected from the above. (Item 5) An all-solid-state electrochemical cell as described in item 3 or 4, wherein M is selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba or a combination thereof. (Item 6) A solid-state electrochemical cell as described in item 3 or 4, where M is lithium. (Item 7) An all-solid-state electrochemical cell according to item 3 or 4, wherein M comprises Li and at least one of Na, K, Rb, Cs, Be, Mg, Ca, Sr, and Ba. (Item 8) An all-solid-state electrochemical cell as described in item 3 or 4, where M is Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, or a combination thereof. (Item 9) An all-solid-state electrochemical cell as described in item 3 or 4, where M is Na, K, Mg, or a combination thereof. (Item 10) The aforementioned crosslinked aprotic polymer has >4V (relative to Li + A solid-state electrochemical cell that is stable in Li, as described in any one of items 1 to 9. (Item 11) An all-solid-state electrochemical cell according to any one of items 1 to 10, wherein the crosslinked aprotic polymer comprises polyethers, polythioethers, polyesters, polythioesters, polycarbonates, polythiocarbonates, polysiloxanes, polyimides, polysulfonimides, polyamides, polysulfonamides, polyphosphazenes, and polyurethane segments, or at least one aprotic polymer segment selected from at least two copolymers or combinations thereof. (Item 12) An all-solid-state electrochemical cell according to any one of items 1 to 10, comprising at least one aprotic polymer segment, wherein the crosslinked aprotic polymer comprises a block copolymer having at least two different repeating units for reducing the crystallinity of the crosslinked polymer. (Item 13) The all-solid-state electrochemical cell according to item 12, wherein the aprotic polymer segment comprises a block copolymer including, prior to crosslinking, a crosslinkable segment containing at least one alkali metal ion or alkaline earth metal ion solvation segment and a crosslinkable unit. (Item 14) The alkali metal or alkaline earth metal ion solvation segment is defined by formula (I):

change

Claims

1. A method for preparing an all-solid-state electrochemical cell, The all-solid-state electrochemical cell comprises a positive electrode containing an electrochemical active material, a negative electrode containing an electrochemical active material, and an electrolyte between the positive electrode and the negative electrode. The positive electrode, the negative electrode, and the electrolyte each form a solid layer. At least one of the positive electrode, the negative electrode, and the electrolyte comprises a composite material containing alkali metal or alkaline earth metal ion conductive inorganic particles and a crosslinked aprotic polymer. The inorganic particle content in the composite material is in the range of 50% by weight to 99.9% by weight. The aforementioned crosslinked aprotic polymer is in a solid state at 25°C, while its polymer precursor before crosslinking is in a liquid state at 25°C. The inorganic particles include amorphous, ceramic, or glass-ceramic type ion-conducting inorganic compounds. The electrolyte layer includes the composite material, The method described above is (i) A step of preparing the positive electrode layer containing the positive electrode electrochemical active material on a current collector, (ii) Step of preparing the electrolyte layer, (iii) the step of preparing or providing the negative electrode layer containing the negative electrode electrochemical active material, and (iv) The step of assembling the all-solid-state electrochemical cell by combining the positive electrode layer, the electrolyte layer, and the negative electrode layer. Includes, Here, step (i) includes the step of preparing a positive electrode material mixture containing the positive electrode electrochemical active material and applying it onto a current collector, and step (ii) includes the step of preparing an electrolyte composition, applying the composition onto the positive electrode layer and crosslinking the electrolyte composition, or Step (iii) includes the step of preparing a negative electrode material comprising the negative electrode electrochemical active material, and step (ii) includes the step of preparing an electrolyte composition, and applying it onto the negative electrode layer, and crosslinking the electrolyte composition. Step (iv) is performed in part after two of steps (i) to (iii) have been performed. Step (ii) further comprises a step of mixing alkali metal or alkaline earth metal ion conductive inorganic particles and a polymer precursor, wherein the polymer precursor is an aprotic polymer segment containing crosslinkable units and is in liquid form at 25°C, and a step of crosslinking the crosslinkable units of the polymer precursor, wherein the crosslinked polymer is in solid form at 25°C. The crosslinked aprotic polymer is present between the inorganic particles in the composite material, The crosslinked aprotic polymer in the electrolyte layer fills the pores of the positive or negative electrode interface, forming a network of inorganic particles interconnected by the crosslinked aprotic polymer. method.

2. The inorganic particles include oxide, sulfide, or oxysulfide compounds having a structure selected from garnet, NASICON, LISICON, thio-LISICON, LIPON, perovskite, inverse perovskite, or argyrodite, or compounds containing the elemental combination M-P-S, M-P-S-O, M-P-S-X, where M is an alkali metal or alkaline earth metal, and X is F, Cl, Br, I or a mixture thereof, and the compound is in crystalline form, amorphous form, glass-ceramic form or a mixture of at least two thereof, or The inorganic particles are in crystalline form, amorphous form, glass-ceramic form, or a mixture of at least two of these, as follows: - MLZO; - MLTaO; - MLSnO; - MAGP; - MATLAB; - MLTiO; - M a Zr b (PO 4 ) c; - M a Ca b Zr c (PO 4 ) d; - M a Ge b P c S d ; - M a Ge b P c S d O e; - M a Si b P c S d ; - M a Si b P c S d O e; - M a Sn b P c S d; - M a Sn b P c S d O e; - M a P b S c ; - M a P b S c O d ; - M a Zn b P c S d ; - M a Zn b P c S d O e ; -xM2S-yP2S5; -xM2S-yP2S5-zMX; -xM2S-yP2S5-zP2O5; -xM2S-yP2S5-zP2O5-wMX; - xM 2 S-yM 2 O-zP 2 S 5 ; -xM2S-yM2O-zP2S5-wMX; -xM2S-yM2O-zP2S5-wP2O5; -xM2S-yM2O-zP2S5-wP2O5-vMX; - xM 2 S-ySiS 2 ; - M a P b S c X d; - M a P b S c O d X e ; - M a Ge b P c S d X e ; - M a Ge b P c S d O e X f ; - M a Si b P c S d X e; - M a Si b P c S d O e X f; - M a Sn b P c S d X e ; - M a Sn b P c S d O e X f; - M a Zn b P c S d X e; - M a Zn b P c S d O e X f ; - M3OX; - M2 HOX; - M 3 PO 4; - M3 PS4; or - M a PO b N c, where a = 2b + 3c - 5; (In the formula, M is an alkali metal ion, an alkaline earth metal ion, or a combination thereof. If M includes an alkaline earth metal ion, the number of M is adjusted to achieve electrical neutrality. X is F, Cl, Br, I, or a combination thereof. a, b, c, d, e, and f are non-zero numbers, and in each equation, they are independently chosen to achieve electrical neutrality. v, w, x, y, and z are non-zero numbers, and in each formula, they are independently selected to obtain a stable compound. The method according to claim 1, comprising at least one compound selected from.

3. M is selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba or a combination thereof, M is lithium, or M contains Li, and at least one of Na, K, Rb, Cs, Be, Mg, Ca, Sr, and Ba, or M is Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba or a combination thereof, The method according to claim 2, wherein M is Na, K, Mg or a combination thereof.

4. The method according to any one of claims 1 to 3, wherein the crosslinked aprotic polymer is stable at >4V (vs. Li+ / Li), and / or the crosslinked aprotic polymer comprises at least one aprotic polymer segment selected from polyethers, polythioethers, polyesters, polythioesters, polycarbonates, polythiocarbonates, polysiloxanes, polyimides, polysulfonimides, polyamides, polysulfonamides, polyphosphazenes, and polyurethane segments, or at least two copolymers or combinations thereof, or the crosslinked aprotic polymer comprises at least one aprotic polymer segment comprising a block copolymer having at least two different repeating units to reduce the crystallinity of the crosslinked polymer.

5. The method according to claim 4, wherein the crosslinked aprotic polymer comprises at least one aprotic polymer segment comprising a block copolymer having at least two different repeating units for reducing the crystallinity of the crosslinked polymer, the aprotic polymer segment comprising a block copolymer comprising, prior to crosslinking, at least one alkali metal or alkaline earth metal ion solvation segment and a crosslinkable unit, and the crosslinkable unit comprises a functional group selected from one of acrylate, methacrylate, allyl, vinyl and combinations thereof.

6. The alkali metal or alkaline earth metal ion solvation segment is of formula (I): 【Transformation 3】 (In the formula, R is selected from H, C1-C10 alkyl and -(CH2-O-R a R b), Ra is (CH2-CH2-O)y, Rb is a C1-C10 alkyl group. The method according to claim 5, selected from homopolymers and copolymers containing repeating units.

7. The method according to any one of claims 1 to 6, wherein the positive electrode electrochemical active material comprises a metal oxide, a metal sulfide, a metal oxysulfide, a metal phosphate, a metal fluorophosphate, a metal oxyfluorophosphate, a metal sulfate, a metal halide, sulfur, selenium, or a mixture of at least two thereof, wherein the metal in the metal oxide, metal sulfide, metal oxysulfide, metal phosphate, metal fluorophosphate, metal oxyfluorophosphate, metal sulfate, or metal halide comprises a metal selected from iron (Fe), titanium (Ti), manganese (Mn), vanadium (V), nickel (Ni), cobalt (Co), aluminum (Al), chromium (Cr), zirconium (Zr), niobium (Nb), and at least two combinations thereof, and further comprises an alkali metal or an alkaline earth metal.

8. The method according to claim 7, wherein the positive electrode electrochemical active material comprises a lithium metal oxide or a lithium metal phosphate.

9. The method according to any one of claims 1 to 8, wherein the positive electrode layer further comprises a conductive material comprising at least one of carbon black, acetylene black, graphite, graphene, carbon fibers or nanofibers, carbon nanotubes or metal powder.

10. The method according to any one of claims 1 to 9, wherein the positive electrode layer comprises the composite material, and the crosslinked aprotic polymer is present between the inorganic particles and between the particles of the positive electrode electrochemical active material.

11. The method according to any one of claims 1 to 9, wherein the positive electrode layer further comprises a polymer binder selected from the crosslinked aprotic polymer, fluorinated polymer, polyvinylpyrrolidone (PVP), poly(styrene-ethylene-butylene) copolymer (SEB), synthetic rubber, and combinations thereof, as described in any one of claims 4 to 6.

12. The negative electrode electrochemical active material includes a metal film of an alkali metal or an alkaline earth metal, or an alloy containing at least one of these, or The method according to any one of claims 1 to 11, wherein the anode electrochemical active material comprises a metal film of a non-alkali metal, a non-alkaline earth metal, or an alloy or intermetallic compound thereof.

13. The method according to claim 12, wherein the anode electrochemical active material comprises a metal film of lithium or a lithium-containing alloy.

14. The method according to claim 12 or 13, wherein the metal film has a thickness in the range of 5 μm to 500 μm.

15. The method according to any one of claims 1 to 11, wherein the negative electrode electrochemical active material is in the form of particles and has a redox potential lower than the redox potential of the positive electrode electrochemical active material.

16. The method according to claim 15, wherein the anode electrochemical active material comprises a non-alkali metal or non-alkaline earth metal, an intermetallic compound, a metal oxide, a metal nitride, a metal phosphide, a metal phosphate, a metal halide, a metal sulfide, a metal oxysulfide or a combination thereof, or carbon, silicon, silicon-carbon composite material, silicon oxide, silicon oxide-carbon composite material, tin, tin-carbon composite material, tin oxide, tin oxide-carbon composite material, and mixtures thereof.

17. The method according to claim 16, wherein the metal oxide is selected from the compounds of formula M' b O c (where M' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb or a combination thereof, and b and c are numbers in which the ratio c:b is in the range of 2 to 3), spinel oxide M'M” 2 O 4 and Li a M' b O c (where M' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb or a combination thereof).

18. The method according to any one of claims 15 to 17, wherein the negative electrode layer further comprises a conductive material comprising at least one of carbon black, acetylene black, graphite, graphene, carbon fibers or nanofibers, carbon nanotubes or metal powder.

19. The method according to any one of claims 15 to 18, wherein the negative electrode layer comprises the composite material, and the crosslinked aprotic polymer is present between the inorganic particles and between the particles of the negative electrode electrochemical active material.

20. The method according to any one of claims 15 to 19, wherein the negative electrode layer further comprises a polymer binder selected from the crosslinked aprotic polymer, fluorinated polymer, polyvinylpyrrolidone (PVP), poly(styrene-ethylene-butylene) copolymer (SEB), synthetic rubber, and combinations thereof, as described in any one of claims 4 to 6.

21. The electrolyte layer, the positive electrode layer, and / or the negative electrode layer further comprises at least one salt, and / or The electrolyte layer, the positive electrode layer, and / or the negative electrode layer further contain an ionic liquid, the ionic liquid present in such an amount that the electrolyte, positive electrode, and / or negative electrode layer remain in a solid state, and / or The method according to any one of claims 1 to 20, wherein the electrolyte layer, the positive electrode layer, and / or the negative electrode layer further comprises an aprotic solvent having a boiling point higher than 150°C, and the aprotic solvent is present in such an amount that the electrolyte, the positive electrode, and / or the negative electrode layer remain in a solid state.

22. An intermediate layer between the positive electrode layer and the electrolyte layer, and / or Intermediate layer between the negative electrode layer and the electrolyte layer It further includes, The method according to any one of claims 1 to 21, wherein the intermediate layer is an alkali metal or alkaline earth metal ion conductive polymer layer, a layer containing alkali metal or alkaline earth metal ion conductive inorganic particles, or a combination thereof.

23. Step (i) is a step of preparing the positive electrode material mixture containing the positive electrode electrochemical active material and a step of applying it onto the current collector, followed by a step of applying an intermediate layer onto the positive electrode layer, and step (ii) further includes a step of applying the electrolyte composition onto the intermediate layer, or In step (iii), after the step of preparing the negative electrode material containing the negative electrode electrochemical active material, the step of forming an intermediate layer on the negative electrode layer is followed. Step (ii) further includes the step of coating the electrolyte composition onto the intermediate layer, The method according to any one of claims 1 to 22, wherein the intermediate layer is an alkali metal or alkaline earth metal ion conductive polymer layer, a layer containing alkali metal or alkaline earth metal ion conductive inorganic particles, or a combination thereof.

24. The method according to any one of claims 1 to 23, wherein step (ii) further comprises mixing the alkali metal or alkaline earth metal ion conductive inorganic particles and the polymer precursor with a solvent.

25. Step (i) includes the step of preparing a positive electrode material mixture containing the positive electrode electrochemical active material and applying it onto a current collector, and step (ii) includes the step of preparing an electrolyte composition and applying the composition onto the positive electrode layer. (a) The negative electrode electrochemical active material comprises a metal film, and step (iii) comprises the steps of preparing the metal film and applying it to the surface of the electrolyte layer opposite the positive electrode layer, or (b) The negative electrode electrochemical active material comprises a material in the form of particles, and step (iii) comprises the steps of preparing a negative electrode material mixture comprising the negative electrode electrochemical active material and applying it to the surface of the electrolyte layer opposite the positive electrode layer, or (c) The method according to any one of claims 1 to 24, wherein the negative electrode electrochemical active material comprises a material in the form of particles, and step (iii) comprises the steps of preparing a negative electrode material mixture comprising the negative electrode electrochemical active material, applying the mixture onto a current collector to form the negative electrode layer, and applying the negative electrode layer to the surface of the electrolyte layer opposite the positive electrode layer.

26. Step (i) is a step of preparing the positive electrode material mixture containing the positive electrode electrochemical active material and a step of applying it onto the current collector, followed by a step of applying an intermediate layer onto the positive electrode layer, and step (ii) further includes a step of applying the electrolyte composition onto the intermediate layer. Step (iii) further includes the step of forming an intermediate layer on the negative electrode layer or the electrolyte layer before coating, or Step (iii) further includes the step of forming an intermediate layer on the electrolyte layer and the step of coating the negative electrode material mixture on the intermediate layer, The method according to claim 25, wherein the intermediate layer is an alkali metal or alkaline earth metal ion conductive polymer layer, a layer containing alkali metal or alkaline earth metal ion conductive inorganic particles, or a combination thereof.

27. Step (iii) includes the step of preparing a negative electrode material comprising the negative electrode electrochemical active material, and step (ii) includes the step of preparing an electrolyte composition and the step of coating it onto the negative electrode layer. The method according to any one of claims 1 to 22, wherein step (i) includes the steps of preparing a positive electrode material mixture containing the positive electrode electrochemical active material and applying it to the surface of the electrolyte layer opposite to the negative electrode layer, or the method according to any one of claims 1 to 22, wherein step (i) includes the steps of preparing a positive electrode material mixture containing the positive electrode electrochemical active material, applying it onto a current collector to form the positive electrode layer, and applying the positive electrode layer to the surface of the electrolyte layer opposite to the negative electrode layer.

28. In step (iii), the step of preparing the negative electrode material comprising the negative electrode electrochemical active material is followed by the step of forming an intermediate layer on the negative electrode layer, and step (ii) further includes the step of coating the electrolyte composition onto the intermediate layer. Step (i) further includes the steps of forming an intermediate layer on the electrolyte layer and coating the cathode material mixture on the intermediate layer, or Step (i) further includes the step of forming an intermediate layer on the positive electrode layer or the electrolyte layer before coating, The method according to claim 27, wherein the intermediate layer is an alkali metal or alkaline earth metal ion conductive polymer layer, a layer containing alkali metal or alkaline earth metal ion conductive inorganic particles, or a combination thereof.

29. (a) The negative electrode electrochemical active material includes a metal film, and step (iii) includes a step of preparing the metal film, or (b) The method according to claim 27 or 28, wherein the anode electrochemical active material comprises a material in the form of particles, and step (iii) comprises preparing a anode material mixture comprising the anode electrochemical active material before coating.

30. The method according to any one of claims 25(b), 25(c), 26, and 29(b), wherein the negative electrode material mixture further comprises a conductive material and / or the negative electrode material mixture further comprises a polymer binder.

31. The negative electrode material mixture further comprises alkali metal or alkaline earth metal ion conductive inorganic particles and the polymer precursor, and step (iii) further comprises a step of crosslinking the polymer precursor after the mixture has been applied, or The method according to any one of claims 25(b), 25(c), 26, 29(b), and 30, wherein the negative electrode material mixture is a solid mixture further comprising alkali metal or alkaline earth metal ion conductive inorganic particles, and step (iii) comprises the steps of coating the solid mixture, adding the polymer precursor to the coated solid mixture in order to disperse the polymer precursor between the particles, and crosslinking.

32. The negative electrode material mixture further contains a solvent, or The method according to claim 31, further comprising step (iii) of adding a solvent to the coated solid mixture in order to disperse the polymer precursor between the particles.

33. The method according to any one of claims 25 to 31, wherein the cathode material mixture further comprises a conductive material and / or the cathode material mixture further comprises a polymer binder.

34. The cathode material mixture further comprises alkali metal or alkaline earth metal ion conductive inorganic particles and the polymer precursor, and step (iii) further comprises a step of crosslinking the polymer precursor after coating the mixture, or The method according to any one of claims 25 to 33, wherein the positive electrode material mixture is a solid mixture further comprising alkali metal or alkaline earth metal ion conductive inorganic particles, and step (iii) comprises the steps of coating the solid mixture, adding the polymer precursor to the coated solid mixture in order to disperse the polymer precursor between the particles, and crosslinking.

35. The positive electrode material mixture further contains a solvent, or The method according to claim 34, further comprising step (iii) of adding a solvent to the coated solid mixture in order to disperse the polymer precursor between the particles.

36. The method further includes a photoinitiator in which the crosslinking step is carried out by UV irradiation, or a thermal initiator in which the crosslinking step is carried out by heat treatment, or a combination thereof. The method according to any one of claims 1 to 35, wherein the crosslinking step is carried out by an electron beam or another energy source, with or without the use of an initiator.

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