Solid electrolyte material and method for forming the same

Abstract

The solid electrolyte material may include a first solid electrolyte material covering at least a portion of the second solid electrolyte material. The first solid electrolyte material is M a Me f O b X c [In the formula, M may contain alkali metals, X may contain halogens, 0 ≤ f ≤ 1, (a / b) > 3, c = a + (k × f) - 2b, k is the valence of Me, and Me may contain metals other than M]. The second solid electrolyte material may contain halides.

Description

[Technical Field]

[0001] The present invention relates to a solid electrolyte material and a method for forming the same. [Background technology]

[0002] Solid-state lithium batteries, by using a lithium metal anode, are expected to have higher energy density, shorter recharge times, and fewer safety concerns compared to conventional lithium-ion batteries. The use of a solid electrolyte has been shown to help improve the performance of the lithium metal anode. Limited wettability of the solid electrolyte by lithium metal can increase interfacial resistance. Poor stability of the solid electrolyte in contact with the lithium metal anode can lead to uneven lithium plating and / or delamination during battery cycling, potentially resulting in lithium dendrites, dead lithium, and mechanical stress on both the solid electrolyte and the lithium metal anode. Industry demand for solid-state batteries with improved performance continues. [Brief explanation of the drawing]

[0003] This disclosure can be better understood by referring to the accompanying drawings, and many of its features and advantages can be made apparent to those skilled in the art.

[0004] [Figure 1] This figure shows a cross-section of a solid electrolyte material according to one embodiment of this specification. [Figure 2A] This figure shows a solid electrolyte material in particle form according to another embodiment. [Figure 2B] This figure shows a cross-section of the layer containing the solid electrolyte material shown in Figure 2A, according to one embodiment of this specification. [Figure 2C] This figure shows a cross-section of a portion of a structure including the layer shown in Figure 2B according to one embodiment of this specification. [Figure 3] This is a cross-sectional view showing a portion of a multilayer structure according to one embodiment of this specification. [Figure 4] This figure shows a process according to one embodiment of this specification. [Figure 5] This figure shows the X-ray diffraction analysis of a solid electrolyte material. [Figure 6] This figure shows the XPS analysis of typical solid electrolyte materials. [Figure 7] This is a plot of the voltage-to-relational capacitance of the solid electrolyte material according to the embodiments of this specification. [Figure 8] This graph shows the results of electrochemical impedance spectroscopy of solid electrolyte materials. [Figure 9] This is a plot of voltage-to-relational capacitance for solid electrolyte materials. [Figure 10] This graph shows the cyclic voltammogram analysis of a solid electrolyte material. [Figure 11] This is a plot of voltage-to-relational capacitance for solid electrolyte materials. [Figure 12] This is a plot of voltage versus relative capacitance for different solid electrolyte materials.

[0005] Those skilled in the art will understand that the elements in the drawings are illustrated for simplification and clarity and are not necessarily drawn to scale. For example, the dimensions of some elements in the drawings may be exaggerated compared to others to help improve the understanding of embodiments of the invention. The use of the same reference numerals in different drawings indicates similar or identical components. [Modes for carrying out the invention]

[0006] The following description, combined with the drawings, is provided to aid in understanding the teachings disclosed herein. The following discussion focuses on specific embodiments and examples of these teachings. This focus is provided to aid in illustrating the teachings and should not be construed as a limitation on the scope or applicability of the teachings.

[0007] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” or any other variations thereof are intended to encompass non-exclusive inclusion. For example, a process, method, article, or apparatus that includes an enumeration of features is not necessarily limited to those features alone, but may include other features not expressly enumerated or inherent to such process, method, article, or apparatus. Furthermore, unless otherwise stated, “or” refers to an inclusive “or” rather than an exclusive “or.” For example, condition A or B is satisfied by any one of the following: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), and both A and B are true (or exist).

[0008] The use of “one (a)” or “one (an)” is used to describe the elements and components described herein. This is done solely for convenience and to give a general sense of the scope of the invention. This specification should be read as one or at least one, and singular including plural, or vice versa, unless it becomes clear that otherwise.

[0009] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which the present invention pertains. The materials, methods, and examples are illustrative and not intended to be limiting.

[0010] Embodiments of this specification relate to a solid electrolyte material comprising a first solid electrolyte material comprising an oxyhalide material, the first solid electrolyte material covering at least a portion of a second solid electrolyte material comprising a halide different from the oxyhalide material. In one embodiment, the halide of the second solid electrolyte material may comprise at least two cations. The solid electrolyte material may have different forms. In certain embodiments, the solid electrolyte material may have a layered structure, and the first solid electrolyte material and the second electrolyte material may independently be in the form of a sheet, tape, block, film, etc. In another particular embodiment, the solid electrolyte material may be in the form of particles. For example, the solid electrolyte material may comprise coated particles comprising a coating comprising the first solid electrolyte material and a core comprising the second electrolyte material. The solid electrolyte material may have improved ionic conductivity, ionic diffusion rate, capacity retention rate, or any combination thereof. The solid electrolyte material may also facilitate improved stability of the solid electrolyte material and improved performance of the solid battery. Certain embodiments of this specification may relate to a first solid electrolyte material.

[0011] Further embodiments relate to methods for forming solid electrolyte materials. These methods can enable improved formation of solid electrolyte materials and facilitate the formation of solid electrolyte materials having improved properties. Certain embodiments may relate to the formation of a first solid electrolyte material.

[0012] In one embodiment, the solid electrolyte material may include a first solid electrolyte material comprising an oxyhalide material. In a further embodiment, the oxyhalide material is M a (Me) f O b X c[wherein M may include an alkali metal, Me may include a metal different from M, X may include a halogen, 0 ≤ f ≤ 1, (a / b) > 3, c = a + (k × f) - 2b, k is the valence of Me, and 2 ≤ k ≤ 6] may be expressed as follows. In at least one particular embodiment, M may include Li and optionally include another alkali metal including Na, K, Cs, Rb, or any combination thereof. For example, M may include Li and at least one of Na, K, and Cs. In another particular embodiment, M may include Li, Na, or both. For example, M may consist of Li, Na, or both. In a particular example, the oxyhalide is Li a (Me) f O b X c It may also be expressed as follows. In another example, M may contain Li, which may constitute at least 50 mol%, or at least 60 mol%, or at least 66 mol%, or at least 75 mol% of M. In a particular example, M may contain 60 mol% to 100 mol% Li. In a further example, M may contain at least 10 mol% Na, or at least 20 mol%, or at least 40 mol% Na. In another example, M may contain up to 40 mol% Na, or up to 34 mol%, or up to 30 mol%, or up to 20 mol%, or up to 10 mol% Na. In another example, M may contain essentially no Na. In a further example, M may contain 0 mol% to 100 mol% Na, or an amount of Na in the range of either the minimum percentage or maximum percentage described herein, for example, 40 mol% to 100 mol% of M.

[0013] In further embodiments, Me may include divalent, trivalent, tetravalent, pentavalent, hexavalent metal elements, or any combination thereof. Specific examples of Me include rare earth elements, transition metals, Y, Zr, or any combination thereof. Examples of rare earth elements include Sc, La, Ce, Pr, Nd, Sm, Gd, Dy, Tm, Yb, Eu, Tb, or any combination thereof. Exemplary transition metals include Sc, Ti, V, Cr, Mn, Fe, In, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Pd, Ag, Hf, Cd, W, Pt, Au, or any combination thereof. In specific examples, f=0.

[0014] In further embodiments, X may consist of Br, Cl, F, or any combination thereof. For example, X may consist of Br. In another example, X may consist of Cl. In yet another example, X may consist of Br and at least one of Cl, I, and F. In certain embodiments, X may consist of a halogen. For example, X may consist of Br, or X may consist of Br and one or more of Cl, F, and I. In another example, X may consist of Br, or X may consist of Br and one or more of Cl and F. In yet another example, X may consist of Br and Cl. In yet another example, X may consist of Br.

[0015] In one embodiment, a > 3. For example, a may be at least 4, at least 5, at least 6, or at least 7. In another example, a may be up to 9, up to 8, or up to 7. Furthermore, a may be a range that includes any of the minimum and maximum values ​​described herein.

[0016] In another embodiment, b > 1. For example, b may be at least 2, or at least 3. In another example, b may be at most 3, at most 2, or at most 1. Further, b may be in a range including any of the minimum and maximum values described herein.

[0017] In another embodiment, c may be greater than 1. For example, c may be at least 2 or at least 3. In another example, c may be at most 5, or at most 4, or at most 3. Further, c may be in a range including any of the minimum and maximum values described herein.

[0018] In a further embodiment, the ratio of a to b (a / b) may be at most 4. For example, a / b may be at most 3.8, or at most 3.7, or at most 3.6, or at most 3.5. In a further example, a / b may be greater than 3, for example, at least 3.1, at least 3.3, or at least 3.5. Further, a / b may be in a range including any of the minimum and maximum values described herein.

[0019] In a particular embodiment, the first solid electrolyte material may include Li7O2X3 [where X may include Br, Cl, F, or any combination thereof]. In another example, the first solid electrolyte may include Li7O2X3 doped with Y, Zr, Gd, Sc, Ce, Er, La, Yb, In, Mg, Zn, or any combination thereof.

[0020] In another embodiment, the metal oxyhalide may include Li7O2(Br d F e Cl (1-d-e) )3 [where 0 ≦ (d + e) ≦ 1]. In one example, (d + e) > 0. In a further example, d > 0 and e > 0. In a further example, d > e. In a further example, d > e > 0. In another example, 0 < (d + e) < 1. In a further example, (d + e) = 0.

[0021] In another embodiment, the metal oxyhalide is Li7O2(Br d F 1-d )3 [wherein 0 ≤ d ≤ 1] may be included. In certain examples, d may be greater than 0, for example, at least 0.1, at least 0.3, at least 0.5, or at least 0.7. Additionally or alternatively, d may be up to 1, for example, up to 0.9, up to 0.8, up to 0.6, or up to 0.4. Furthermore, d may be in a range that includes any of the minimum and maximum values ​​described herein, for example, a range greater than 0 and up to 1. In at least one particular example, d = 1. In another example, d = 0.

[0022] In certain embodiments, the metal oxyhalide is Li7O2(Br d Cl (1-d) )3 [wherein 0 ≤ d ≤ 1] may be included. In certain examples, d may be greater than 0, for example, at least 0.1, at least 0.3, at least 0.5, or at least 0.7. Additionally or alternatively, d may be up to 1, for example, up to 0.9, up to 0.8, up to 0.6, or up to 0.4. Furthermore, d may be in a range that includes any of the minimum and maximum values ​​described herein, for example, a range greater than 0 and up to 1. In at least one particular example, d = 1. In another example, d = 0.

[0023] In further embodiments, the first solid electrolyte material may contain a metal hydroxyl halide. The metal hydroxyl halide is M' m (Me') f’ (OH) n X' pIt may also be expressed as [wherein M' may include alkali metals, X' may include halogens, 1≦m≦5, 0≦f'≦1, 1≦n≦4, p=m+(k'×f')-n, k' is the valence of Me', and Me' may include metals different from M']. For example, Me' may include divalent metal elements, trivalent metal elements, tetravalent metal elements, pentavalent metal elements, hexavalent metal elements, or any combination thereof. Specific examples of Me' include rare earth elements, transition metals, Y, Zr, or any combination thereof. Examples of rare earth elements include Sc, La, Ce, Pr, Nd, Sm, Gd, Dy, Tm, Yb, Eu, Tb, or any combination thereof. Examples of transition metals include Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Pd, Ag, Hf, Cd, W, Pt, Au, or any combination thereof.

[0024] In one embodiment, M' may include alkali metals including Li, Na, K, Cs, Rb, or any combination thereof. In further embodiments, M' may include Li, Na, or both. In certain embodiments, M' may include Li and optionally one or more of Na, K, Cs, and Rb. For example, M' may include Li and Na. In another example, M' may be essentially Li.

[0025] In further embodiments, X' may consist of Br, Cl, F, or any combination thereof. For example, X' may consist of Br. In another example, X' may consist of Cl. In yet another example, X' may consist of Br and at least one of Cl, I, and F. In certain embodiments, X' may consist of a halogen. For example, X' may consist of Br and optionally one or more of Cl, F, and I. In another example, X' may consist of Br and optionally one or more of Cl and F. In yet another example, X' may consist of Br and Cl. In yet another example, X' may consist of Br and F.

[0026] In further embodiments, the metal hydroxide halide is Li m (OH) n X' m-n It may also be expressed as [wherein 2≦m≦5 and 1≦n≦4]. In at least one example, Li m (OH) n X' m-n It may be doped with Y, Zr, Gd, Sc, Ce, Er, La, Yb, In, Mg, Zn, or any combination thereof.

[0027] In another embodiment, the metal hydroxyl halide may include Li2(OH)X'.

[0028] In a further embodiment, the metal hydroxyl halide is Li2(OH)Br d’ F e’ Cl (1-d’-e’) The expression may include the condition "[0 ≤ (d' + e') ≤ 1]". In one example, 0 < (d' + e') ≤ 1. In a further example, d > 0 and e > 0. In yet another example, d > e' > 0. In yet another example, 0 < (d' + e') < 1.

[0029] In certain embodiments, the metal hydroxyl halide is Li2(OH)Br d’ F (1-d’) The expression may include [wherein 0 ≤ d' ≤ 1]. In more specific examples, d' may be greater than 0, for example at least 0.1, at least 0.3, at least 0.5, at least 0.7, or at least 0.9. Additionally or alternatively, d' may be up to 1, for example at most 0.9, at most 0.8, at most 0.7, or at most 0.5. Furthermore, d' may be a range that includes any of the minimum and maximum values ​​described herein, for example, a range greater than 0 and at most 1. In at least one specific example, d' = 1. In another example, d' = 0.

[0030] In certain embodiments, the metal hydroxyl halide is Li2(OH)Br d’ Cl(1-d’) The expression may include [wherein 0 ≤ d' ≤ 1]. In more specific examples, d' may be greater than 0, for example at least 0.1, at least 0.3, at least 0.5, or at least 0.7. Additionally or alternatively, d' may be up to 1, for example at most 0.9, at most 0.8, at most 0.6, or at most 0.4. Furthermore, d' may be in a range that includes any of the minimum and maximum values ​​described herein, for example, a range greater than 0 and at most 1. In at least one specific example, d' = 1. In another example, d' = 0.

[0031] In another embodiment, the metal hydroxyl halide may include Li4(OH)3X'.

[0032] In one embodiment, the first solid electrolyte material may have a specific weight ratio between metal oxy halides and metal hydroxy halides that can promote performance improvement of the solid electrolyte material. In one example, ratio C MOX / C M’OHX’ [In the formula, C MOX This can be the weight content of the metal oxyhalide relative to the total weight of the first solid electrolyte material, C M’OHX’ [wherein the weight content of metal hydroxide halide relative to the total weight of the first solid electrolyte material is at least 0.05, at least 0.07, at least 0.10, at least 0.13, at least 0.15, at least 0.18, at least 0.20, at least 0.23, at least 0.25, at least 0.28, at least 0.30, at least 0.32, at least 0.34, at least 0.36, at least 0.38, or at least 0.40. In further examples, the weight content ratio C MOX / C M’OHX’ This may be 100 or less, 50 or less, 20 or less, 10 or less, 6 or less, 3 or less, 2 or less, 1 or less, 0.90 or less, 0.80 or less, 0.70 or less, 0.60 or less, 0.50 or less, or 0.40 or less. Furthermore, the weight ratio C MOX / C M’OHX’ This may be a range that includes either the minimum or maximum value described herein.

[0033] In one embodiment, the first solid electrolyte material may include a specific content of a metal oxyhalide material that can promote performance improvement of the solid electrolyte material. For example, the content of the metal oxyhalide material may be at least 1% by weight relative to the total weight of the first electrolyte material, for example, at least 3% by weight, at least 5% by weight, at least 8% by weight, at least 10% by weight, at least 14% by weight, at least 18% by weight, at least 22% by weight, at least 26% by weight, at least 28% by weight, at least 30% by weight, at least 34% by weight, at least 38% by weight, at least 43% by weight, at least 48% by weight, at least 50% by weight, at least 54% by weight, or at least 56% by weight relative to the total weight of the first electrolyte material. In another example, the content of the metal oxyhalide material may be up to 56% by weight relative to the total weight of the first electrolyte material, for example, up to 53% by weight, up to 51% by weight, up to 49% by weight, up to 46% by weight, up to 43% by weight, up to 40% by weight, up to 37% by weight, up to 34% by weight, up to 31% by weight, up to 28% by weight, up to 24% by weight, up to 21% by weight, up to 18% by weight, up to 15% by weight, up to 12% by weight, up to 9% by weight, or up to 5% by weight relative to the total weight of the first electrolyte material. Furthermore, the content of the metal oxyhalide material may be within a range including any of the minimum and maximum percentages described herein.

[0034] In one embodiment, the first solid electrolyte material may contain a specific content of metal hydroxyl halide material that can enhance the performance of the solid electrolyte material. For example, the content of metal hydroxyl halide material may be more than 53% by weight of the total weight of the first electrolyte material, for example, at least 55% by weight, at least 58% by weight, at least 62% by weight, at least 65% by weight, at least 68% by weight, at least 70% by weight, or at least 72% by weight of the total weight of the first electrolyte material. In another example, the content of metal hydroxyl halide material may be up to 99% by weight of the total weight of the first electrolyte material, for example, up to 95% by weight, up to 91% by weight, up to 89% by weight, up to 86% by weight, up to 83% by weight, up to 80% by weight, up to 78% by weight, up to 75% by weight, up to 73% by weight, or up to 72% by weight of the total weight of the first electrolyte material. Furthermore, the content of metal hydroxyl halide material may be within a range including any of the minimum and maximum percentages described herein.

[0035] In one embodiment, the first solid electrolyte material may contain a specific content of a binary metal halide other than a binary metal fluoride such as LiBr, LiI, and / or LiCl, which may enhance the performance of the solid electrolyte material. In certain examples, the first electrolyte material may not contain a binary metal iodide in any way. In further embodiments, the first solid electrolyte material may contain a specific content of a binary alkali bromide, which may enhance the performance of the solid electrolyte material. In one example, the content of the binary alkali bromide may be less than 4% by weight of the total weight of the first electrolyte material, for example, up to 3% by weight, up to 2% by weight, up to 1% by weight, or up to 0.5% by weight. In certain examples, the first electrolyte material may not contain a binary metal bromide such as a binary alkali bromide in any way. In yet another example, the first electrolyte material may contain at least 0.001% by weight of a binary alkali bromide, for example, at least 0.01% by weight, at least 0.05% by weight, at least 0.1% by weight, or at least 0.2% by weight, relative to the total weight of the first electrolyte material. Furthermore, the content of the binary alkali bromide may be in a range including any of the minimum and maximum percentages described herein. In a further embodiment, the first electrolyte material may contain a binary alkali chloride in any of the contents described herein with respect to the binary alkali bromide.

[0036] In one embodiment, the first solid electrolyte material may have a specific weight ratio between metal oxyhalides and binary alkali bromides that can promote performance improvement of the solid electrolyte material. In one example, ratio C MOX / C ABr [In the formula, C MOX This can be the weight content of the metal oxyhalide relative to the total weight of the first solid electrolyte material, C ABr [wherein this can be the weight content of binary alkali bromide relative to the total weight of the first solid electrolyte material] may be 10.9 or more, for example, 13 or more. In further embodiments, the first solid electrolyte material may have a specific weight content ratio between metal hydroxyl halide and binary alkali bromide that can promote performance improvement of the solid electrolyte material. In one example, ratio CM’OHX’ / C ABr [In the formula, C M’OHX’ This can be the weight content of metal hydroxyl halide relative to the total weight of the first solid electrolyte material, C ABr [This can be the weight content of binary alkali bromide relative to the total weight of the first solid electrolyte material] may be at least 13.5, for example, at least 15 or more. The weight content ratio of metal hydroxyl halide to binary alkali chloride is C M’OHX’ / C ABr Please understand that any ratio described in relation to this may be included. The weight ratio of metal oxyhalides to binary alkali chlorides may include C MOX / C ABr It should be further understood that any ratio described in relation to this may be included.

[0037] In further embodiments, the first solid electrolyte material may include a plurality of crystalline phases, comprising a first phase which may contain a metal oxyhalide and a second phase which may contain a metal hydroxyl halide. In one embodiment, the first phase is M a Me f O b X c A crystalline phase containing M' m (Me') f’ (OH) n X' pThe first solid electrolyte material may include a first crystalline phase containing Li7O2X3 and a second crystalline phase containing lithium hydroxyl halide. In another example, the first solid electrolyte material may include a first crystalline phase in a certain amount, the amount of which may be any of the amounts described with respect to the content of metal oxyhalide. In yet another example, the first solid electrolyte material may include a second crystalline phase in a certain amount, the amount of which may be any of the amounts described with respect to the content of metal hydroxyl halide. In a particular example, the first solid electrolyte material may include a first crystalline phase containing Li7O2X3 and a second crystalline phase containing lithium hydroxyl halide. In yet another particular example, the first crystalline phase may contain Li7O2X3 and the second crystalline phase may contain Li2OHX'. In yet another example, the first crystalline phase may contain Li7O2X3 and the second crystalline phase may contain Li4(OH)3X'. In another embodiment, the first solid electrolyte material may include a third phase. In one example, the third phase may include a crystalline phase. In another example, the first solid electrolyte material may include a first crystalline phase containing Li7O2X3, a second crystalline phase containing Li2OHX', and a third crystalline phase containing Li4(OH)3X'. In at least one embodiment, the first solid electrolyte material may include a crystalline phase containing a binary alkali metal halide other than a fluoride, such as LiBr. In one embodiment, the first solid electrolyte material may contain a crystalline phase containing a binary alkali metal halide other than a fluoride in a certain content, such content may include any of the content described with respect to the content of binary alkali bromide. In another embodiment, the first solid electrolyte material may include a plurality of phases, including a crystalline phase, an amorphous phase, or any combination thereof.

[0038] In one embodiment, the first solid electrolyte material may contain a fluorine-containing dopant. For example, fluorine may be present in one or more interstitial positions, vacancies, and / or interlayers of the crystalline structure of a metal oxyhalide, a metal hydroxyl halide, or both. In another embodiment, the first solid electrolyte material may contain a fluorine-doped metal oxyhalide, a fluorine-doped metal hydroxyl halide, or both. For example, the first solid electrolyte may contain fluorine-doped Li7O2Br3, fluorine-doped Li2OHBr, fluorine-doped Li7O2Cl3, fluorine-doped Li2OHCl, or any combination thereof. In a particular example, the first solid electrolyte may contain fluorine-doped Li7O2Br3, fluorine-doped Li2OHBr, or both. In another particular example, the first solid electrolyte may contain fluorine-doped Li7O2Br3. In one embodiment, the first electrolyte material may not essentially contain a crystalline phase containing an alkali fluoride. For example, the first electrolyte material does not necessarily have to contain a crystalline phase containing LiF. In a further example, the first electrolyte material may contain fluorine species containing metallic fluorine bonds, oxyfluoride species, or any combination thereof.

[0039] In certain embodiments, the first solid electrolyte material may essentially consist of a metal oxy halide and a metal hydroxyl halide. For example, the first solid electrolyte material is M a Me f O b X c and M' m (Me') f’ (OH) n X' p It may essentially consist of Li7O2X3 and Li2OHX'. In further examples, the metal oxyhalides and metal hydroxyhalides may include the same alkali metal, such as Li, Na, or both. In more specific examples, the first solid electrolyte material may essentially consist of Li7O2Br3 and Li2OHBr, where Li7O2Br3 and / or Li2OHBr may be doped with fluorine.

[0040] In one embodiment, the first solid electrolyte material is A q and B (1-q) The polycrystal may include a first crystalline phase containing a metal oxy halide, and a second crystalline phase containing a metal hydroxy halide. In a particular embodiment, the polycrystal may contain a first crystalline phase containing a metal hydroxy halide. a Me f O b X c ) q It may be composed of (M' m (Me') f’ (OH) n X' p ) (1-q) The formula may consist of the following, where M and M' independently contain Li, Na, or a combination thereof. In one example, X and X' independently contain at least one of Cl and Br. In a particular example, A may contain Li7O2X3 and B may contain Li2OHX'. In a more particular example, X and X' independently or both may contain Br. In an even more particular example, A may contain or be represented as Li7O2Br3, B may contain or be represented as Li2OHBr, and Li7O2Br3 and / or Li2OHBr may be doped with fluorine.

[0041] In a further embodiment, the polycrystal may include a specific t that can promote the performance improvement of the solid electrolyte material. In one example, q may be at least 0.05, at least 0.07, at least 0.10, at least 0.13, at least 0.15, at least 0.18, at least 0.20, at least 0.23, at least 0.25, at least 0.28, at least 0.30, at least 0.32, at least 0.34, at least 0.36, at least 0.38, or at least 0.40. In a further example, q may be 0.95 or less, 0.90 or less, 0.85 or less, 0.80 or less, 0.75 or less, 0.70 or less, 0.65 or less, 0.60 or less, 0.55 or less, 0.50 or less, 0.45 or less, 0.40 or less, 0.35 or less, 0.30 or less, or 0.28 or less. Further, q may be in a range including any of the minimum and maximum values described herein.

[0042] In one embodiment, the first solid electrolyte material may have improved ionic conductivity compared to a corresponding solid electrolyte material having a single phase of the same metal oxyhalide or metal hydroxide halide. For example, the first solid electrolyte material is greater than 6.2×10 -4 mS / cm, for example, at least 6.5×10 -4 mS / cm, at least 6.8×10 -4 mS / cm, at least 7.0×10 -4 mS / cm, at least 7.2×10 -4 mS / cm, at least 7.5×10 -4 mS / cm, at least 7.8×10 -4 mS / cm, at least 8.0×10 -4 mS / cm, at least 8.2×10 -4 mS / cm, at least 8.4×10 -4 mS / cm, at least 8.7×10 -4 mS / cm, at least 9.0×10 -4 mS / cm, or at least 9.3×10 -4 mS / cm of bulk ionic conductivity. In another example, the bulk ionic conductivity is 11.2×10 -4 mS / cm or less, 10.8×10-4 less than mS / cm, 10.6×10 -4 less than mS / cm, 10.4×10 -4 less than mS / cm, 10.2×10 -4 less than mS / cm, 10.0×10 -4 less than mS / cm, 9.8×10 -4 less than mS / cm, 9.6×10 -4 less than mS / cm, or 9.4×10 -4 It may be less than mS / cm. Further, the first solid electrolyte material may have a bulk ionic conductivity within a range including either the minimum value or the maximum value described herein. As described herein, the bulk ionic conductivity is measured at room temperature (i.e., 20°C to 25°C).

[0043] In one embodiment, the solid electrolyte material may include a second solid electrolyte material including a halide material. In a further embodiment, the second solid electrolyte material is M’’ 3-z (Me’’) f X’’ 3-z+k’’*f’’ [where -3 ≤ z < 3, k’’ is the valence of Me’’, 2 ≤ k’’ < 6, 0 ≤ f’’ ≤ 1, M’’ may include an alkali metal element, Me’’ may include a metal element different from M’’, and X’’ may include a halogen] may be included. In a further embodiment, the second solid electrolyte material is (NH4) n’’ M’’ 3-z (Me’’) f’’ X’’ n’’+3-z’’+k’’*f’’It may include "[where 0 < n'' holds]". In a specific example, f'' > 0. Exemplary Me'' may include a divalent metal element, a trivalent metal element, a tetravalent metal element, a pentavalent metal element, a hexavalent metal element, or any combination thereof. Specific examples of Me'' include an alkaline earth metal element, a 3d transition metal, Zn, Zr, Hf, Ti, Sn, Th, Ge, Ta, Nb, Mo, W, Sb, In, Bi, Al, Ga, or any combination thereof. More specific examples of Me'' include a rare earth element, Y, Zr, or any combination thereof. Even more specifically, Me'' may include Y, Zr, Gd, Sc, Ce, Er, La, Yb, In, Mg, Zn, or any combination thereof.

[0044] An example of M'' can be Li. In a further example, M may also include Li and at least one of Na, K, and Cs. In another specific embodiment, M'' may include Li, Na, or both. For example, M'' may consist of Li, Na, or both. In another example, M'' may include Li, and Li may account for at least 50 mol%, or at least 60 mol%, or at least 66 mol%, at least 75 mol%, or up to 100 mol% of M''. In a specific example, M'' may include 60 mol% to 100 mol% of Li. In a further example, M'' may include at least 10 mol% of Na, or at least 20 mol%, or at least 40 mol% of Na. In another example, M'' may include up to 40 mol% of Na, or up to 34 mol%, or up to 30 mol%, or up to 20 mol%, or up to 10 mol% of Na. In another example, M'' may essentially not contain Na. In a further example, M'' may include 0 mol% to 100 mol% of Na, or a range including any of the minimum and maximum percentages described herein, for example, an amount of Na in the range of 40 mol% to 100 mol% of M''.

[0045] In one embodiment, X'' may comprise one or more of F, Cl, Br, and I. In a particular example, X'' may comprise at least two halogen elements. A more specific example of X'' may comprise at least two of F, Cl, and Br.

[0046] In certain embodiments, the halide material is Li 3-x-f M'' f’’ RE 1-y Me'' y (Cl 1-u-p-q Br u F p I q ) 6-x+y*(k’’-3) [The formula may be expressed as -1≦x≦1, 0≦y≦1, 0≦u<1, 0≦p≦1 / 3, 0≦q≦1 / 6, 0<(u+p+q)<1, 0≦f''≦0.3]. In a more specific embodiment, the halide material is Li 3-x RE 1-y Me'' y (Cl 1-u Br u ) 6-x+y*(k’’-3) It may also be expressed as [wherein 0.08 ≤ u ≤ 0.67]. M'' may be at least one alkali metal element other than Li. RE may be a rare earth element. Me'' is at least one element different from RE.

[0047] A specific example of a halide material is Li 3-a Na a Y( Gr x Cl y )6 [wherein 0≦a≦0.33 and x+y=1] may be included. In more specific examples, x≦y. Further specific examples of solid electrolyte materials are Li3YBr6, Li3YCl6, Li3Y(Cl 0.67 Br 0.33 )6, Li3Y(Cl 0.79 Br 0.21 )6, Li3Y(Br 0.35 Cl 0.65 )6, Li3Y(Cl 0.8 Br 0.2 )6, Li3Y(Cl 0.19 Br 0.81 )6, Li3(Y 0.95Yb 0.05 )1(Cl 0.83 Br 0.17 )6, Li3(Y 0.95 In 0.05 )(Cl 0.9 Br 0.1 )6, Li 2.95 (Y 0.95 Zr 0.05 )(Cl 0.9 Br 0.1 )6, Li3(Y 0.85 In 0.15 )Cl6, (Li 0.955 Na 0.045 )3Y1Cl6, Li3Y(Cl 0.41 Br 0.59 )6, Li3Y(Cl 0.62 Br 0.38 )6, Li3YCl6, LiGdBr6, LiGdCl6, Li3Y(Cl 0.67 Br 0.33 )6, Li3Y(Cl 0.79 Br 0.21 )6, or any combination thereof may be included.

[0048] In one embodiment, the solid electrolyte material may not essentially contain one or more MX [wherein X may include Br, Cl, I, or any combination thereof]. For example, the solid electrolyte material may not essentially contain LiX such as LiCl and LiBr.

[0049] Referring to Figure 1, a cross-section of the solid electrolyte material 100 is shown, which includes a first solid electrolyte material 102 covering a second solid electrolyte layer 104. As shown in the figure, the first solid electrolyte material 102 and the second solid electrolyte material 104 may be in the form of layers formed from the first solid electrolyte material and the second solid electrolyte material, respectively. The layers of the first solid electrolyte material 102 and the second solid electrolyte material 104 may be a film, tape, block, sheet, or the like.

[0050] The first solid electrolyte 102 may include a length L1 extending in the longitudinal direction or in the x-axis direction of the first solid electrolyte 102, and a thickness t1 extending in the stacking direction of the first solid electrolyte material 102 and the second solid electrolyte material 104, or in the y-axis direction which may be perpendicular to the length L1. The second solid electrolyte material 104 may include a length L2 extending in the longitudinal direction or in the x-axis direction of the second solid electrolyte material 104, and a thickness t2 extending in the stacking direction which may be perpendicular to the length L2, or in the y-axis direction.

[0051] In certain examples, L1 may be substantially the same as L2, for example, the difference between L1 and L2 may be within 8%, 5%, 3%, 2%, 1% of the larger of L1 and L2, or within 0.5% of the larger of L1 and L2. In another particular example, the first solid electrolyte material 102 may cover more than 50% of the surface area of ​​surface 124, for example, at least 60%, at least 70%, at least 85%, at least 90%, at least 95%, at least 97%, or at least 99% of the surface area of ​​surface 124.

[0052] As shown in Figure 1, the first solid electrolyte material 102 may be in direct contact with the second electrolyte material 104. In certain examples, the first solid electrolyte material 102 may be in direct contact with most or substantially the entire surface 124.

[0053] Referring to Figure 3, a cross-section of the structure 110, which includes the solid electrolyte material 100 and layer 106 illustrated in Figure 1, is shown. In one embodiment, layer 106 may contain an electrode active material. For example, layer 106 may contain a negative electrode active material such as Li, In, graphite, Si, or any combination thereof. In a further example, layer 106 may contain a negative electrode containing Li. In another example, layer 106 may contain a positive electrode active material.

[0054] As shown in Figure 3, the second solid electrolyte material 104 may include a main surface 114 opposite to the main surface 124. Layer 106 may include a main surface 116 opposite to the main surface 126. The first solid electrolyte material 102 may be located between layer 106 and the second solid electrolyte material 104. In certain embodiments, the first electrolyte material 102 may be configured to be interphase between layer 106 and the second solid electrolyte material 104. For example, the first electrolyte material 102 may separate at least a large portion or substantially the entire surface 124 from layer 106. In further examples, the first electrolyte material 102 may separate at least 60% of surface 124 from layer 106, for example, at least 70%, at least 85%, at least 90%, at least 94%, at least 98%, or even 100% of surface 124 from layer 106.

[0055] In further embodiments, the first solid electrolyte material 102 may be in direct contact with layer 106. In one example, the first solid electrolyte material 102 may be in contact with at least a portion of surface 116. In a particular example, the first solid electrolyte material 102 may be in contact with substantially the entire surface 116.

[0056] In further embodiments, the first solid electrolyte material 102 may have a specific thickness t1 that can facilitate improvements in the function and / or properties of the solid electrolyte material. For example, the first solid electrolyte material 102 may have a thickness of up to 1 μm, for example, up to 800 nm, up to 600 nm, up to 400 nm, up to 300 nm, up to 200 nm, up to 100 nm, up to 90 nm, up to 80 nm, up to 70 nm, up to 60 nm, up to 50 nm, up to 40 nm, up to 30 nm, up to 20 nm, up to 10 nm, up to 9 nm, up to 8 nm, up to 6 nm, or up to 4 nm. In another example, the first solid electrolyte material 102 may have a thickness t1 of at least 1 nm, at least 3 nm, at least 5 nm, at least 7 nm, at least 10 nm, at least 15 nm, at least 20 nm, at least 30 nm, at least 40 nm, at least 50 nm, at least 60 nm, at least 70 nm, at least 80 nm, at least 90 nm, at least 110 nm, at least 130 nm, at least 150 nm, at least 170 nm, or at least 200 nm. Furthermore, the first solid electrolyte material 102 may have a thickness in a range including any of the minimum and maximum values ​​described herein. For example, t1 may be in the range of at least 1 nm to a maximum of 1 μm, or in the range of at least 2 nm to a maximum of 400 nm.

[0057] In a further embodiment, the second solid electrolyte material 104 may have a specific thickness t2 that can facilitate improvements in the function and / or properties of the solid electrolyte material. For example, the second solid electrolyte material 104 may have a thickness of up to 1.3 mm, e.g., up to 1 mm, up to 900 μm, up to 800 μm, up to 700 μm, up to 600 μm, up to 500 μm, up to 400 μm, up to 300 μm, up to 200 μm, up to 100 μm, up to 80 μm, up to 70 μm, up to 50 μm, or up to 30 μm. In another example, the second solid electrolyte material 104 may have a thickness t2 of at least 10 μm, at least 15 μm, at least 20 μm, at least 30 μm, at least 40 μm, at least 50 μm, at least 60 μm, at least 70 μm, at least 80 μm, at least 90 μm, at least 100 μm, at least 200 μm, at least 300 μm, at least 400 μm, at least 500 μm, at least 600 μm, at least 700 μm, or at least 800 μm. Furthermore, the second solid electrolyte material 104 may have a thickness t2 within a range that includes any of the minimum and maximum values ​​described herein. For example, t2 may be in the range of at least 1 nm to a maximum of 800 nm, or in the range of at least 10 μm to a maximum of 1 mm.

[0058] In a further embodiment, the solid electrolyte material may have a specific ratio t1 to t2 (t1 / t2) that can facilitate improvements in the function and / or properties of the solid electrolyte material. In one example, the ratio t1 / t2 may be at least 0.00001, for example, at least 0.0001, at least 0.001, at least 0.005, at least 0.01, at least 0.05, at least 0.1, at least 0.2, at least 0.3, at least 0.4, at least 0.5, at least 0.6, at least 0.7, at least 0.8, or at least 1. In another example, the ratio t1 / t2 may be up to 10, for example, up to 8, up to 6, up to 3, up to 1, up to 0.1, up to 0.07, up to 0.05, up to 0.03, up to 0.01, up to 0.005, up to 0.001, up to 0.0005, or up to 0.0001. Furthermore, the ratio t1 / t2 may be within a range that includes either the minimum or maximum value described herein.

[0059] In further embodiments, the solid electrolyte material may include coating particles that cover the core. In another embodiment, the solid electrolyte material may be in the form of a powder, suspension, slurry, etc., including the coating particles. In a particular embodiment, the coating may include a first solid electrolyte material covering a core containing a second solid electrolyte material.

[0060] Referring to Figure 2A, a portion of an exemplary solid electrolyte material 150 is shown, including coating particles 152 with a coating 156 covering the core 158. The coating 156 may be in direct contact with the core 158. The coating 156 may essentially completely cover the core 108. The particles 156 may have a substantially uniform coating thickness.

[0061] In another embodiment, the solid electrolyte material 150 may include coating particles having varying coating thickness. For example, one portion of the coating may be thicker or thinner than another portion of the coating covering the core. As shown in the figure, the coating particles 153 may include a coating 154 covering the core 158, the coating 154 having varying thickness.

[0062] In another embodiment, the coated particles may include partially coated particles, fully coated particles, or any combination thereof. In a further embodiment, the solid electrolyte material may include partially and / or fully coated particles having a substantially uniform coating thickness.

[0063] In one embodiment, the solid electrolyte material 150 may include coating particles having a specific average coating thickness that can facilitate improvements in the performance and / or properties of the solid electrolyte material. In one embodiment, the average coating thickness may be less than 1 μm. For example, the coating may have an average thickness of up to 800 nm, e.g., up to 500 nm, up to 300 nm, up to 100 nm, up to 80 nm, up to 70 nm, up to 60 nm, up to 50 nm, up to 40 nm, up to 30 nm, or up to 20 nm. In another example, the coating may have an average thickness of at least 1 nm, e.g., at least 2 nm, at least 5 nm, at least 7 nm, at least 10 nm, at least 13 nm, at least 15 nm, at least 18 nm, or at least 20 nm. Furthermore, the coating may have an average thickness within a range that includes any of the minimum and maximum values ​​described herein.

[0064] The average coating thickness used herein can be determined by analyzing a sample of solid electrolyte material having a statistically significant sample size for representing the solid electrolyte material, using transmission electron microscopy.

[0065] In one embodiment, the solid electrolyte material 150 may include coating particles having a specific average coverage that can facilitate improvements in the performance and / or properties of the solid electrolyte material. For example, the average coverage may be at least 20% of the core surface area, for example, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 94% of the core surface area. In further examples, the coating may essentially cover the entire surface of the core. In other examples, the average coverage may be 99% or less, 96% or less, 90% or less, 88% or less, 85% or less, or 80% or less of the core surface area. Furthermore, the average coverage may be within a range that includes any of the minimum and maximum percentages described herein.

[0066] In one embodiment, the solid electrolyte material 150 may contain a certain amount of coating particles that can promote improvements in the performance and / or properties of the solid electrolyte material. For example, at least 20% by weight, at least 30% by weight, at least 40% by weight, at least 50% by weight, at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight, or at least 95% by weight of the weight of the solid electrolyte material may constitute the coating. In a particular example, essentially all particles may consist of coating particles, such as at least 97% by weight or at least 99% by weight of the weight of the solid electrolyte material. More specifically, 100% by weight of the weight of the solid electrolyte material may consist of coating particles. In a further example, the solid electrolyte material may contain uncoated particles. For example, 99% by weight or less of the weight of the solid electrolyte material may constitute the coating particles, for example, 98% by weight or less, 96% by weight or less, 94% by weight or less, 92% by weight or less, 90% by weight or less, or 88% by weight or less of the weight of the solid electrolyte material may constitute the coating particles. Furthermore, the amount of coated particles may be within the range of either the minimum or maximum percentage described herein. For example, a solid electrolyte material may contain at least 20% and up to 99% by weight of coated particles relative to the weight of the solid electrolyte material.

[0067] In further embodiments, the solid electrolyte material 150 may contain a certain number of coated particles that can facilitate improvements in the performance and / or properties of the solid electrolyte material. For example, at least 20% of the total number of particles in the solid electrolyte material may be coated particles, for example, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 95% of the total number of particles may be coated particles. In particular, in some examples, essentially all particles may be coated particles, such as at least 96% or at least 98% of the total number of particles. More specifically, all particles in the solid electrolyte material may be coated particles. In other examples, 99% or less of the total number of particles may be coated particles, for example, 98% or less, 96% or less, 94% or less, 92% or less, 90% or less, or 88% or less of the total number of particles may be coated particles. Furthermore, the solid electrolyte material may contain coated particles in a content range that includes either the minimum percentage or maximum percentage described herein.

[0068] In one embodiment, the content of coated particles can be determined by analyzing the cross-section using focused ion beam transmission electron microscopy (FIB-TEM) and energy-dispersive X-ray spectroscopy (EDX). A solid electrolyte material sample having a sample size that statistically represents the solid electrolyte material can be analyzed by FIB-TEM and EDX. The number or weight of coated particles can be determined based on the EDX results. The percentage of coated particles relative to the total number or weight of particles analyzed can be used as the content of coated particles in the solid electrolyte material.

[0069] In certain cases, the solid electrolyte material 150 may contain uncoated particles in addition to coated particles. In one example, a small portion of the particles may be uncoated particles, such as uncoated cores. In further examples, uncoated particles may constitute 30% by weight or less of the total particle weight, for example, 20% by weight or less, 10% by weight or less, 5% by weight or less, 3% by weight or less, or 1% by weight or less of the total weight of the solid electrolyte material. In yet another embodiment, the solid electrolyte material 150 may contain up to 30% of the total number of particles as uncoated particles, for example, 20% or less, 10% or less, 5% or less, 3% or less, or 1% or less of the total number of particles as uncoated particles. In certain embodiments, the solid electrolyte material 150 may not contain uncoated particles at all. The content of uncoated particles can be determined using FIB-TEM and EDX in a manner similar to that described in the embodiments relating to determining the content of coated particles.

[0070] In one embodiment, the solid electrolyte material 150 may have an average particle size. In one example, the average particle size may be less than 1 μm to several hundred μm, or even larger. In another example, the average particle size may be 1 μm to 500 μm, for example 10 μm to 300 μm, or 20 μm to 200 μm. In yet another example, the average particle size may be 1 μm to 10 μm, for example 2 microns to 5 microns. In yet another example, the solid electrolyte material 150 may contain free particles, aggregated particles, aggregates, or any combination thereof.

[0071] In one embodiment, the solid electrolyte material 150 may be formed into a specific shape such as a sheet, tape, block, film, or any combination thereof. Referring to Figure 2B, a cross-sectional view of a layer 160 according to one embodiment is shown, including a body 161 containing the solid electrolyte material 150. Referring to Figure 2C, a cross-sectional view of another exemplary structure 200 is shown, including a layer 160 covering a layer 210. In one embodiment, the layer 210 may include an electronically conductive material. For example, the electronically conductive material may include a negative electrode active material. In a particular example, the layer 210 may include a negative electrode containing a lithium-ion conductive material. In another example, the layer 210 may include a negative electrode containing lithium, Si, graphite, or any combination thereof.

[0072] Layer 160 may include the main surface 162. In one embodiment, at least 50% of the surface area of ​​the main surface 162 may be defined by the coatings 154 and / or 152 shown in Figure 2A. In certain examples, at least 60%, at least 70%, at least 80%, at least 90%, at least 93%, or at least 95% of the surface area of ​​the main surface 162 may be defined by the coatings 154 and / or 152 shown in Figure 2A. In further examples, up to 100% of the surface area of ​​the main surface 162 may be defined by the coatings 154 and / or 152 shown in Figure 2A.

[0073] In another embodiment, 40% or less of the surface area of ​​the main surface 162 may be defined by the core 158 shown in Figure 2A, for example, 30% or less, 20% or less, 10% or less, 5% or less, or 2% or less of the surface area of ​​the main surface 162 may be defined by the core 158 shown in Figure 2A.

[0074] The layer 210 may include a main surface 212, and at least a portion of the main surface 212 may be in contact with the main surface 162. In certain examples, substantially the entire main surface 212 may be in contact with the main surface 162. In further embodiments, at least a portion of the layer 210 may be in contact with the coatings 154 and / or 152 shown in Figure 2A. In one example, at least 55% of the surface area of ​​the main surface 212 may be in contact with the coatings 154 and / or 152 shown in Figure 2A, for example, at least 60%, at least 70%, at least 80%, at least 90%, at least 93%, or at least 95% of the surface area of ​​the main surface 212 may be in contact with the coatings 154 and / or 152 shown in Figure 2A. In further examples, up to 100% of the surface area of ​​the main surface 212 may be in contact with the coatings 154 and / or 152 shown in Figure 2A.

[0075] The structure 200 may include an interface 220 between layers 160 and 210, defined by at least a portion of the main surface 162 and at least a portion of the main surface 212. In certain embodiments, at least 55% of the interface 220 may be defined by the coatings 154 and / or 152 shown in Figure 2A and the main surface 212, for example, at least 60%, at least 70%, at least 80%, at least 90%, at least 93%, or at least 95% of the interface 220 may be defined by the main surface 212 and coatings 154 and / or 152 shown in Figure 2A. In further examples, up to 100% of the interface 220 may be defined by the main surface 212 and coatings 154 and / or 152 shown in Figure 2A.

[0076] In certain embodiments, layer 210 may include a negative electrode active material, and at least a portion of the main surface 212 may be defined by the negative electrode active material. In further embodiments, the negative electrode active material may be in contact with coatings 154 and / or 152 shown in Figure 2A. In certain examples, coatings 154 and / or 152 shown in Figure 2A may function as a phase interface between the negative electrode active material and the core 158 shown in Figure 2A. In more specific examples, the first solid electrolyte material may function as an interface between the second solid electrolyte material and the negative electrode active material. In another example, at least a large portion of the core 158 shown in Figure 2A may be separated from the negative electrode active material by coatings 154 and / or 152 shown in Figure 2A, for example, substantially or completely the entire core may be separated from the negative electrode active material.

[0077] As shown in Figure 2C, layer 160 may include a length L extending in the longitudinal direction or in the x-axis direction, and a thickness t extending in the stacking direction of layers 160 and 210 or in the y-axis direction. In a further embodiment, layer 160 may have a specific thickness that can facilitate improvements in the function and / or properties of the solid electrolyte material. For example, the thickness t may be up to 1.3 mm, e.g., up to 1 mm, up to 900 μm, up to 800 μm, up to 700 μm, up to 600 μm, up to 500 μm, up to 400 μm, up to 300 μm, up to 200 μm, up to 100 μm, up to 80 μm, up to 70 μm, up to 50 μm, or up to 30 μm. In another example, the thickness t may be at least 10 μm, at least 15 μm, at least 20 μm, at least 30 μm, at least 40 μm, at least 50 μm, at least 60 μm, at least 70 μm, at least 80 μm, at least 90 μm, at least 100 μm, at least 200 μm, at least 300 μm, at least 400 μm, at least 500 μm, at least 600 μm, at least 700 μm, or at least 800 μm. Furthermore, layer 160 may include a range thickness t that includes any of the minimum and maximum values ​​described herein.

[0078] In one embodiment, the structure 200 may be a component of an electrochemical device (not shown). For example, the electrochemical device may include one or more other components that may cover at least a portion of the structure 200. In a particular example, the positive electrode material may cover layer 160. In another example, the electrolyte layer may cover at least a portion of layer 160. In a particular case, the structure may be a component of a solid-ion battery, such as a solid lithium battery. In a further embodiment, the electrochemical device may have a cell structure comprising a solid electrolyte material 100 or 150, shown in Figure 1 or Figure 2A, between the positive and negative electrodes, wherein the first solid electrolyte material may be adjacent to the negative electrode and distal to the positive electrode. In the example of particles in the cell structure, the first solid electrolyte material may be in contact with the negative electrode, and the second solid electrolyte material may be adjacent to the positive electrode and distal to the negative electrode.

[0079] In one embodiment, the cell structure may include a solid electrolyte material 100 or 150 shown in Figure 1 or Figure 2A, respectively, and a negative electrode containing a negative electrode active material such as an alkali metal containing Li, graphite, Si, or any combination thereof, and the first solid electrolyte material may be in contact with the negative electrode. In a particular example, the negative electrode may contain, for example, an alkali metal containing Li, and more specifically, the first solid electrolyte material may be in contact with the alkali metal containing Li. The cell structure may have improved cell performance, such as discharge capacity, compared to a corresponding cell structure in which the first or second solid electrolyte material may be used instead of the solid electrolyte material. In a particular example, the cell structure containing the solid electrolyte material 100 or 150 shown in Figure 1 or Figure 2A, respectively, has a discharge capacity of 4 mAh g -1 For example, at least 10mAh g -1 , at least 20mAh g -1 , at least 40mAh g -1 , at least 50mAh g -1 , at least 60mAh g -1 , at least 80mAh g -1 , at least 90mAh g -1 , at least 100mAh g -1, at least 110mAh g -1 , at least 120mAh g -1 , at least 130mAh g -1 , or at least 140mAh g -1 It may have a discharge capacity of 220 mAh g. In another example, the discharge capacity is 220 mAh g -1 Below, 210mAh g -1 Below, 200mAh g -1 Below, 190mAh g -1 Below, 180mAh g -1 Below, 170mAh g -1 Below, 160mAh g -1 Below, 150mAh g -1 The following, or 140mAh g -1 The following may also apply. Furthermore, the discharge capacity may be within a range that includes either the minimum or maximum value specified herein.

[0080] When used herein, the discharge capacity can be determined by testing the constant current cycling performance of the cell structure. The cell structure may include, in the stacking direction, a current collector, a positive electrode layer, a solid electrolyte material, and a lithium metal negative electrode. The positive electrode layer is 60% (by weight / by weight) LiNi 0.6 Mn 0.2 Co 0.2 O (also known as NMC622) and 40% (weight / weight) Li3Y (Br 0.2 Cl 0.8 A mixture with 6 can be prepared and formed by adding 0.5% (weight / weight) of vapor-grown carbon fiber (VGCF) to the mixture. The mixture can be further mixed with toluene and roller-mixed for 4 days, after which the toluene can be evaporated from the cathode mixture by heating the mixture on a hot plate at 95°C. The cathode mixture can then be pressed onto a solid electrolyte material (second solid electrolyte material) at 40 bar. The Li anode can be placed on the other side of the solid electrolyte material. The cell structure can then be assembled using a torque force of 3.0 Nm and then tested with a constant current of 0.05 C over a potential range of 0 to 4.3 V against the Li metal anode.

[0081] In another embodiment, the solid electrolyte material 150 may be formed in a composite layer. For example, the composite layer may include the solid electrolyte material 150 and an electronically conductive material including, for example, a negative electrode active material, a positive electrode active material, an electronically conductive additive, or a combination thereof. In another example, the composite layer may have mixed ion conductivity and electronic conductivity. In yet another example, the composite layer may include a negative electrode liquid, a positive electrode liquid, etc.

[0082] In one embodiment, the solid electrolyte material may have improved ionic conductivity. In one example, the solid electrolyte material may have a bulk ionic conductivity of at least 0.001 mS / cm, at least 0.01 mS / cm, at least 0.1 mS / cm, at least 0.5 mS / cm, at least 1 mS / cm, or at least 2 mS / cm. In another example, the solid electrolyte material may have a bulk ionic conductivity of up to 3 mS / cm, up to 2.5 mS / cm, or up to 2.2 mS / cm. Furthermore, the solid electrolyte material may have a bulk ionic conductivity within a range that includes any of the minimum and maximum values ​​described herein.

[0083] Referring to Figure 4, process 400 is shown. Process 400 may begin in block 402 and form a first solid electrolyte material. In one embodiment, a mixture containing reactants may be formed. In one example, the reactants may include one or more of alkali fluorides (MF), alkali halides other than fluorides (MX, where X may be Br, Cl, or I), and alkali hydroxides (MOH). In further examples, the mixture may be in a dry or wet state. In another example, the reactants may be in the form of a powder, a sol-gel, a non-aqueous solution, a suspension, or any combination thereof. In yet another example, the reactants may be mixed in stoichiometric ratios, non-stoichiometric ratios, or a combination thereof.

[0084] In one embodiment, the mixture may contain MF such as LiF at a specific concentration to facilitate the formation of a solid electrolyte material and / or improve its properties and performance. For example, the concentration of MF is C MOX / CMOHX The ratio of the elements may be adjusted to have a specific ratio, which helps to minimize the formation of MX [wherein X may be Br, Cl, or I]. In another example, the concentration of MF can be controlled to facilitate the formation of a first solid electrolyte material with improved properties and / or performance, such as improved impedance, oxidation / reduction stability, bulk ion conductivity, or any combination thereof.

[0085] Increasing the concentration of MF in the mixture can promote increased formation of metal oxide halides and alkali metal halides other than fluorides. In one embodiment, the mixture may contain specific concentrations of MF that can promote improved metal oxide formation and control of alkali metal halides other than fluorides. For example, the mixture may contain at least 1 mol% of MF relative to MOH, for example, at least 6 mol%, at least 9 mol%, at least 11 mol%, at least 12 mol%, at least 14 mol%, at least 17 mol%, at least 20 mol%, at least 22 mol%, at least 25 mol%, at least 28 mol%, or at least 30 mol% of MF relative to MOH. Alternatively or additionally, the mixture may contain 35 mol% or less of MF relative to MOH, for example, 31 mol% or less, 29 mol% or less, 26 mol% or less, 23 mol% or less, 20 mol% or less, 17 mol% or less, 13 mol% or less, 11 mol% or less, or 9 mol% or less of MF relative to MOH. Furthermore, the mixture may contain MF concentrations within a range that includes either the minimum or maximum percentages described herein.

[0086] In one embodiment, the mixture can be heated to form a first electrolyte material. Heating may be facilitated by a heating device such as a furnace or a heating plate. In one embodiment, heating can be carried out in a specific environment to accelerate the reaction of the mixture. In one example, heating may be carried out in a dry atmosphere or an inert atmosphere. In a further example, heating may be carried out in an atmosphere having a specific pressure, such as higher or lower than atmospheric pressure. In another example, heating may be carried out in air.

[0087] In one embodiment, the mixture may be heated to a specific temperature that can promote improved formation of the first solid electrolyte material. In one embodiment, the temperature can be controlled to be below the melting temperature of the first solid electrolyte material. In another embodiment, the heating temperature can be controlled to promote the reaction between the reactants. For example, the heating temperature can be adjusted by taking into account the composition of the reactants, the kinetics of the reaction, the reaction rate, the reaction time, or any combination thereof.

[0088] In certain examples, heating may be carried out at temperatures of at least 250°C, for example, at least 260°C, at least 280°C, at least 300°C, at least 315°C, or at least 320°C. Additionally or alternatively, heating may be carried out at temperatures of 330°C or lower, for example, 320°C or lower, 270°C or lower, 260°C or lower, 250°C or lower, or 240°C or lower. Furthermore, heating may be carried out at temperatures within a range that includes any of the minimum and maximum temperatures described herein.

[0089] In another embodiment, the mixture may be heated for a specific period of time that can promote improved formation of the first solid electrolyte material. In one example, a relatively high temperature may be applied for a relatively short time. Alternatively, a lower temperature may be used for a relatively long heating time. In another example, the heating time may be adjusted taking into account the composition of the reactants, the concentrations of the reactants, and / or other reaction conditions.

[0090] In one example, heating may be carried out for at least 25 minutes, for example, at least 30 minutes, at least 40 minutes, at least 50 minutes, or at least 60 minutes. In another example, heating may be carried out for 90 minutes or less, for example, at least 80 minutes, at least 70 minutes, at least 60 minutes, at least 50 minutes, or at least 40 minutes. Furthermore, heating may be carried out over a time range including any of the minimum and maximum values ​​described herein.

[0091] In exemplary embodiments, the formation of the first solid electrolyte material may include monitoring the chemical reaction to facilitate improvement in the formation of the first solid electrolyte material. For example, the formation of the phase composition of the first solid electrolyte material may be confirmed by X-ray diffraction. In another example, the homogeneity and / or completeness of the reaction may be monitored and / or inspected by using an optical microscope, scanning electron microscope, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy (XPS), or a combination thereof.

[0092] In exemplary embodiments, a mixture may be formed by mixing powder materials of LiF, LiBr, and LiOH in stoichiometric ratios using a mixing device such as a mortar and pestle. Mixing may be carried out for 5 to 30 minutes, or otherwise until a homogeneous mixture is formed. After mixing, the mixture may be transferred to a muffle furnace and heat-treated at 320°C to 360°C for 40 to 60 minutes to obtain a first solid electrolyte containing Li2OHBr and Li7O2Br3.

[0093] Figure 5 shows the results of X-ray diffraction tests for representative first solid electrolyte materials formed by incorporating LiF at different concentrations. As shown, when the molar ratio of LiOH:LiF:LiBr is 0.7:0.3:1, the synthesized first solid electrolyte material may contain 53 wt% Li7O2Br3 crystalline phase, 34 wt% Li2OHBr crystalline phase, and 13% LiBr crystalline phase, relative to the total weight of the crystalline phase. When the molar ratio of LiOH:LiF:LiBr is 0.8:0.2:1, the synthesized first solid electrolyte material may contain 43 wt% Li7O2Br3 crystalline phase, 53 wt% Li2OHBr crystalline phase, and 4 wt% LiBr crystalline phase, relative to the total weight of the crystalline phase. When the molar ratio of LiOH:LiF:LiBr is 0.9:0.1:1, the synthesized first solid electrolyte material may contain 28 wt% of the Li7O2Br3 crystalline phase and 72 wt% of the Li2OHBr crystalline phase, relative to the total weight of the entire crystalline phase.

[0094] Figure 6 shows the results of XPS analysis of a representative first solid electrolyte material. As shown in the test results, the first solid electrolyte material may contain Li, O, Br, and F species. The separated high-resolution 1s spectrum of fluorine shows two peaks at approximately 685 eV and 689 eV, which may indicate the presence of two different fluorine species. The peak with a bond energy of approximately 685 eV may suggest a metallic fluorine bond, and the peak with a bond energy of 689 eV may represent an oxyfluoride species.

[0095] Process 400 may continue forming the solid electrolyte material in block 404. In one embodiment, the first solid electrolyte material may be placed on top of the second solid electrolyte material. In one embodiment, the first solid electrolyte material may be applied to the second electrolyte material by brushing, pressing, spraying, injecting, dipping, or any combination thereof. For example, the first solid electrolyte material may be aerosol-sprayed onto the second electrolyte material. In another example, the second electrolyte material may be dipped by immersing the second electrolyte material in the first solid electrolyte material. In one embodiment, the formation of the solid electrolyte material may include heating, pressing, polishing, grinding, molding, milling, cutting, or any combination thereof to form the solid electrolyte material in a desired shape.

[0096] In another example, the first solid electrolyte material may be placed on at least a portion of at least one of the main surfaces of the layer of the second electrolyte material. The layer of the second electrolyte material may be formed by casting, compression, cold pressing, warm pressing, or another technique known in the art. In one example, the first solid electrolyte material may be pre-formed, for example, into a film, sheet, block, etc., and then placed on the second solid electrolyte material. In another example, the first solid electrolyte material may be formed while applied to the second solid electrolyte material, or formed after applied to the second solid electrolyte material. In further examples, one or more organic materials such as binder materials, solvents, dispersants, and surfactants, or any combination thereof, can be used to facilitate the formation of the solid electrolyte material in a desired form. In at least one example, one or more organic materials may be partially or completely removed from the final formed solid electrolyte material.

[0097] Many different aspects and embodiments are possible. Some of these aspects and embodiments are described herein. After reading this specification, those skilled in the art will understand that these aspects and embodiments are illustrative only and do not limit the scope of the invention. Embodiments may follow one or more of the embodiments listed below. Embodiment

[0098] Embodiment 1. The first solid electrolyte material covers at least a portion of the second solid electrolyte material, The first solid electrolyte material contains MaMefObXc [wherein M contains an alkali metal, X contains a halogen, 0 ≤ f ≤ 1, a / b > 3, c = a + (k × f) - 2b, k is the valence of Me, and Me contains a metal different from M], The second solid electrolyte material is a solid electrolyte material containing halides.

[0099] Embodiment 2. The solid electrolyte material according to Embodiment 1, wherein M comprises Li, Na, or a combination thereof.

[0100] Embodiment 3.X is a solid electrolyte material according to Embodiment 1 or 2, comprising at least one of Cl or Br.

[0101] Embodiment 4. A solid electrolyte material according to any one of Embodiments 1 to 3, wherein X contains Br and M contains Li.

[0102] Embodiment 5. The first solid electrolyte material is M a Me f O b X c The first crystalline phase includes M' m (Me') f’ (OH) n X' p A solid electrolyte material according to any one of Embodiments 1 to 4, further comprising a second crystalline phase containing [wherein M' contains an alkali metal, X' contains a halogen, 1 ≤ m ≤ 5, 0 ≤ f' ≤ 1, 1 ≤ n ≤ 4, p = m + (k' × f') - n, k' is the valence of Me', and Me' contains a metal different from M'].

[0103] Embodiment 6. The solid electrolyte material according to Embodiment 5, wherein M' and M contain the same alkali metal element.

[0104] Embodiment 7. A solid electrolyte material according to Embodiment 5 or 6, wherein M' comprises Li, Na, or a combination thereof.

[0105] Embodiment 8.X' is a solid electrolyte material according to any one of Embodiments 5 to 7, wherein Embodiment 8.X' includes at least one of Cl and Br.

[0106] Embodiment 9. A solid electrolyte material according to any one of Embodiments 5 to 7, wherein X' contains Br and M' contains Li.

[0107] Embodiment 10. The first solid electrolyte material has a weight content C of the first crystalline phase to the second crystalline phase, such that C is at least 0.05, at least 0.07, at least 0.10, at least 0.13, at least 0.15, at least 0.18, at least 0.20, at least 0.23, at least 0.25, at least 0.28, at least 0.30, at least 0.32, at least 0.34, at least 0.36, at least 0.38, or at least 0.40. MOX / C MOHX [In the formula, C MOX M is the total weight of the first solid electrolyte material. a Me f O b X c This is the weight content, C M’OHX’ M' is the ratio of M' to the total weight of the first solid electrolyte material. m (Me' k+ ) f’ (OH) n X' p A solid electrolyte material according to any one of embodiments 5 to 9, having a weight content of [ ].

[0108] Embodiment 11. Weight content ratio C MOX / C MOHX The solid electrolyte material according to Embodiment 10, wherein the value is 100 or less, 50 or less, 20 or less, 10 or less, 6 or less, 3 or less, 2 or less, 1 or less, 0.90 or less, 0.80 or less, 0.70 or less, 0.60 or less, 0.50 or less, or 0.40 or less.

[0109] Embodiment 12. A solid electrolyte material according to any one of Embodiments 1 to 11, wherein the first solid electrolyte material comprises a first crystalline phase containing Li7O2X3.

[0110] Embodiment 13. A solid electrolyte material according to any one of Embodiments 1 to 12, wherein the second solid electrolyte material comprises a second crystalline phase containing Li2OHX.

[0111] Embodiment 14. A solid electrolyte material according to any one of Embodiments 1 to 12, wherein the first solid electrolyte material comprises a second crystalline phase containing Li4(OH)3X.

[0112] Embodiment 15. The solid electrolyte material according to any one of Embodiments 1 to 13, wherein the first solid electrolyte material includes a third crystal phase containing Li4(OH)3X.

[0113] Embodiment 16. The solid electrolyte material according to any one of Embodiments 1 to 15, wherein the first solid electrolyte material includes a dopant containing fluorine.

[0114] Embodiment 17. The solid electrolyte material according to Embodiment 16, wherein the dopant includes fluoride, oxyfluoride, or any combination thereof.

[0115] Embodiment 18. The halide is M’’ 3-z (Me’’) f’’ X’’ 3-z+k’’*f’’ [where -3 ≦ z < 3, 0 < f’’ ≦ 1, M’’ includes an alkali metal element, k’’ is the valence of Me’’, Me’’ includes a metal different from M’’, and X’’ includes a halogen] The solid electrolyte material according to any one of Embodiments 1 to 17 inclusive.

[0116] Embodiment 19. The solid electrolyte material according to any one of Embodiments 1 to 18, wherein the halide material includes at least two halogens selected from the group consisting of F, Cl, Br, and I, and M’’ includes Li.

[0117] Embodiment 20. The halide is Li 3-x RE 1-y Me’’ k’’ y (Cl 1-u Br u ) 6-x+y*(k’’-3) [where 0.08 ≦ u ≦ 0.67] represented by, the solid electrolyte material according to any one of Embodiments 1 to 19 inclusive.

[0118] <00006Embodiment 21. A solid electrolyte material according to any one of Embodiments 1 to 20, wherein the first solid electrolyte material or the second solid electrolyte material is in the form of a film, tape, block, sheet, or any combination thereof.

[0119] Embodiment 22. A solid electrolyte material according to any one of Embodiments 1 to 21, wherein the first solid electrolyte material is in direct contact with at least a portion of the second solid electrolyte material.

[0120] Embodiment 23. The solid electrolyte material according to any one of Embodiments 1 to 20, in the form of coated particles comprising a coating containing a first solid electrolyte material in direct contact with a core containing a second solid electrolyte material.

[0121] Embodiment 24. The solid electrolyte material according to any one of Embodiments 1 to 23, wherein the second solid electrolyte material has a thickness t2 of 10 μm to 1 mm or less.

[0122] Embodiment 25. The solid electrolyte material according to Embodiment 24, wherein the first solid electrolyte material has a thickness t1 of at least 1 nm and a maximum of 100 nm.

[0123] Embodiment 26. The solid electrolyte material according to Embodiment 25, wherein the ratio of t1 / t2 is at least 0.0001 and at most 10.

[0124] Embodiment 27. A solid electrolyte material according to any one of Embodiments 1 to 26, wherein the first solid electrolyte material essentially does not contain a crystalline phase containing LiF.

[0125] Embodiment 28. A solid electrolyte layer comprising the solid electrolyte material described in any one of Embodiments 1 to 27, It includes a negative electrode covering a solid electrolyte layer, A structure in which a first solid electrolyte material is located between the negative electrode and a second solid electrolyte material.

[0126] Embodiment 29. The structure according to Embodiment 28, wherein the first solid electrolyte material is configured to be an interface layer separating the second electrolyte material from the negative electrode, and the first solid electrolyte material is configured to completely separate the second solid electrolyte material from the negative electrode.

[0127] Embodiment 30. The structure according to Embodiment 28 or 29, wherein the first solid electrolyte material is in direct contact with the negative electrode.

[0128] Embodiment 31. The structure according to any one of Embodiments 28 to 30, further comprising a positive electrode covering a solid electrolyte layer.

[0129] Embodiment 32. A solid electrolyte material containing polycrystalline material, wherein the polycrystalline material is A q and B (1-q) [In the formula, A is M a Me f O b X c (In the formula, M contains alkali metals, X contains halogens, Me includes divalent metal elements, trivalent metal elements, tetravalent metal elements, pentavalent metal elements, hexavalent metal elements, or any combination thereof. 0≦f≦1, a / b > 3, c = a + (k × f) - 2b, k is present in the first crystalline phase (where k is the valence of Me), B is M' m (Me') f’ (OH) n X' p (In the formula, M' contains alkali metals, X' contains halogen, Me' includes divalent metal elements, trivalent metal elements, tetravalent metal elements, pentavalent metal elements, hexavalent metal elements, or any combination thereof. 1 ≤ m ≤ 5, 0≦f'≦1, 1≦n≦4, p = m + (k' × f') - n, k' is the valence of Me') and is present in the second crystalline phase, A polycrystalline solid electrolyte material containing a fluorine-containing dopant.

[0130] Embodiment 33. The solid electrolyte material according to Embodiment 32, wherein M' and M contain the same alkali metal element.

[0131] Embodiment 34. The solid electrolyte material according to Embodiment 32 or 33, wherein M and M' independently comprise Li, Na, or a combination thereof.

[0132] Embodiment 35. A solid electrolyte material according to any one of Embodiments 32 to 34, wherein X and X independently comprise at least one of Cl or Br.

[0133] Embodiment 36. A solid electrolyte material according to any one of Embodiments 32 to 35, wherein each of X and X' contains Br, and each of M and M' contains Li.

[0134] A solid electrolyte material according to any one of embodiments 32 to 36, wherein embodiment 37.q is at least 0.05, at least 0.07, at least 0.10, at least 0.13, at least 0.15, at least 0.18, at least 0.20, at least 0.23, at least 0.25, or at least 0.28.

[0135] The solid electrolyte material according to Embodiment 37, wherein Embodiment 38.q is 0.95 or less, 0.90 or less, 0.85 or less, 0.80 or less, 0.75 or less, 0.70 or less, 0.65 or less, 0.60 or less, 0.55 or less, 0.50 or less, 0.45 or less, 0.40 or less, 0.35 or less, 0.30 or less, 0.28 or less, or 0.25 or less.

[0136] Embodiment 39.A is a solid electrolyte material according to any one of Embodiments 32 to 38, comprising Li7O2X3.

[0137] Embodiment 40.B is a solid electrolyte material according to any one of Embodiments 32 to 39, comprising Li2OHX'.

[0138] Embodiment 41.B is a solid electrolyte material according to any one of Embodiments 32 to 39, comprising Li4(OH)3X'.

[0139] Embodiment 42. A solid electrolyte material according to any one of Embodiments 32 to 40, wherein the polycrystalline material comprises a third crystalline phase containing Li4(OH)3X'.

[0140] Embodiment 43. A solid electrolyte material according to any one of Embodiments 32 to 42, wherein the dopant comprises a fluoride, an oxyfluoride, or any combination thereof.

[0141] Embodiment 44. A solid electrolyte material according to any one of Embodiments 1 to 43, wherein the solid electrolyte material essentially does not contain LiCl and LiBr.

[0142] Embodiment 45. The structure according to any one of Embodiments 28 to 30, wherein the negative electrode comprises an alkali metal, graphite, In, Si, or any combination thereof. [Examples]

[0143] Example 1 Li2OHBr is synthesized as follows: LiBr powder and LiOH powder are mixed in stoichiometric ratios and ground using a mortar and pestle. After grinding for 15 minutes, the powder mixture is transferred to a muffle furnace and heat-treated at 350°C for 1 hour to obtain Li2OHBr powder.

[0144] Cell sample CS1 is formed. 6 mg of Li2OHBr powder is applied to completely cover the surface of the halide material Li-Y-Br-Cl pellet. The halide material pellet is then pressed with Li2OHBr at 30 bar to obtain a compressed pellet. A cathode composite is prepared by pre-mixing 60% (mW / mW) NMC622 with 40% (mW / mW) halide material and adding 0.5% (mW / mW) vapor-grown carbon fiber (VGCF) to the pre-mixture. The mixture is mixed with toluene and roller-mixed for 4 days. The toluene is then evaporated by heating the mixture at 95°C. The cathode composite is then pressed onto the halide material at 40 bar. The Li anode is placed on top of the Li2OHBr. The cell is then assembled using a torque force of 3.0 Nm.

[0145] The prepared cell is tested for constant current cycling performance by applying a constant current of 0.05C over a potential range of 0 to 4.3V relative to the Li metal anode.

[0146] Figure 9 is a plot of voltage-to-capacitance for the first five charge / discharge cycles tested in cell CS1. As shown, the discharge capacity drops significantly in the first five cycles. This decrease in discharge capacity may indicate some instability in the Li2OHBr and / or halide material on the negative electrode side.

[0147] Example 2 A typical first solid electrolyte material containing a mixed phase of Li2OHBr and Li7O2Br3 is synthesized according to the embodiments herein. Briefly, powders of LiF, LiBr, and LiOH are mixed in different ratios using the same mixing conditions as described in Example 1. The mixture is then heated at 350°C for 1 hour to form the first solid electrolyte material.

[0148] Sample S2 is prepared using a molar ratio of LiOH:LiF:LiBr of 0.9:0.1:1.

[0149] Sample S3 is prepared using a molar ratio of LiOH:LiF:LiBr of 0.8:0.2:1.

[0150] Sample S4 is formed using a molar ratio of LiOH:LiF:LiBr of 0.7:0.3:1.

[0151] Sample S5 is prepared using a molar ratio of LiOH:LiF:LiBr of 0.6:0.4:1.

[0152] The XRD patterns of the first solid electrolyte materials S2-S4 are shown in Figure 5, and the XPS analysis of sample S2 is included in Figure 6. Both of these are as previously described.

[0153] Figure 7 shows a plot of voltage-to-referential capacity for the first charge / discharge cycle tested with the first solid electrolyte materials S2-S4. Constant current cycles are performed under the same conditions as described in Example 1. Samples formed with a LiOH:LiF:LiBr ratio of 0.9:0.1:1 show improved discharge capacity compared to samples formed with a LiOH:LiF:LiBr ratio of 0.8:0.2:1 and a LiOH:LiF:LiBr ratio of 0.7:0.3:1. Samples formed with a LiOH:LiF:LiBr ratio of 0.8:0.2:1 show improved discharge capacity compared to samples formed with a LiOH:LiF:LiBr ratio of 0.7:0.3:1.

[0154] Figure 8 shows the electrochemical impedance spectroscopy (EIS) spectra of the first solid electrolyte materials S2-S5 and Li2OHBr. Sample S2 (formed using a LiOH:LiF:LiBr ratio of 0.9:0.1:1) showed improved bulk ion conductivity compared to Li2OHBr (a sample formed from LiOH and LiBr), reaching 6.2 × 10⁻⁶. -4 9.3 × 10⁻⁶ mS / cm -4 The values ​​were mS / cm. Samples S3-S5 showed a further decrease in bulk ion conductivity and an increase in impedance. This may be due to the presence of residual LiBr.

[0155] Figure 10 shows the cyclic voltammograms (CVs) of the first five charge / discharge cycles for Li2OHBr and sample S2. A scanning speed of 1 mV / sec was used. Cell CS6 with the configuration Li / Li2OHBr / Li2OHBr-VGCF / stainless steel and cell S7 with the configuration Li / sample S2 / sample S2-VGCF / stainless steel were used for the test. As shown, no redox reaction was observed in cell S7. On the other hand, the CV of Li2OHBr against the Li metal anode showed a potential difference of Li / Li + Hysteresis was observed when scanning from 0V to 4.3V, confirming the presence of the redox phenomenon. The data suggest that, compared to Li2OHBr, sample S2 exhibits higher conductivity and better stability when used in contact with a Li metal anode.

[0156] Example 3 Cell S8 is formed with a Li / sample S2 / LYBC / cathode composite cell configuration. Cell CS9 is formed with the same cell configuration, except that sample S2 is replaced with Li2OHBr. Cell CS10 is formed with a Li / LYBC / cathode composite configuration. The cell samples have the same cathode composite, containing 60% (wt / wt) NMC622 particles pre-treated with fluorine using plasma-enhanced chemical vapor deposition, LYBC (40% w / w), and 0.5% w / w vapor-grown carbon fibers relative to the total weight of NMC622 and LYBC. The discharge capacity of the cells in the first charge / discharge cycle is shown in Figure 11. It can be confirmed that the discharge capacity of cell S8 is significantly higher than that of cells CS9 and CS10. For example, cell S8 has a discharge capacity of 140 mAh g -1 While the discharge capacity was shown, cell CS10 was 4mAh g -1 The CS9 has a 107mAh battery. -1 That was the case.

[0157] Example 4 Solid electrolyte material sample S11 was formed as follows: Powders of LiF, LiCl, and LiOH were mixed and pulverized to form a soft mixture, which was then heated at 350°C for 1 hour to form sample S11. The molar ratio of LiOH:LiF:LiCl was 0.9:0.1:1.

[0158] Cell S12 is formed with the same configuration as cell S8, except that sample S2 is replaced with S11.

[0159] The constant current cycle was performed using the same conditions as described in Example 1. The test results for cells S8 and S12 are shown in Figure 12. Cell sample S12 had an initial specific capacity of 60 mAh g in the first charging step. -1 This indicates that in the subsequent discharge step, the specific capacity is 13 mAh g -1 It has decreased to this level. Cell sample S8 has an initial specific capacity of approximately 180mAh g in the first charging step. -1 This indicates that in the subsequent discharge step, approximately 140mAh g -1 It has decreased to this extent. Cell sample S8 appears to have improved charge / discharge capacity and capacity retention rate compared to cell sample S12.

[0160] Benefits, other advantages, and solutions to problems are described above in relation to specific embodiments. However, benefits, advantages, solutions to problems, and any features that may result in or enhance any benefit, advantage, or solution should not be construed as essential, necessary, or intrinsic features of any or all of the claims. References herein to materials comprising one or more components may be construed as including at least one embodiment in which the material essentially consists of one or more identified components. The term “essentially consists of” is to be construed as including a composition that includes the identified materials and excludes all other materials except in small amounts (e.g., impurity content) (i.e., in which the properties of the material do not substantially change). Additionally or alternatively, in certain non-limiting embodiments, none of the compositions identified herein may essentially contain materials not expressly disclosed. Embodiments herein include a range of content of a particular component in a material, and it is understood that the content of the components in a given material is 100% in total.

[0161] The description and illustrative drawings of the embodiments described herein are intended to provide a general understanding of the structures of various embodiments. The description and illustrative drawings are not intended to serve as a comprehensive and exhaustive description of all elements and features of apparatuses and systems using the structures or methods described herein. Different embodiments may be combined within a single embodiment, and conversely, various features described in the context of a single embodiment for brevity may also be provided separately or in any partial combination. Furthermore, references to values ​​within a range include all values ​​within that range. Many other embodiments may become apparent to those skilled in the art only after reading this specification. Other embodiments may be used and derived from this disclosure, in such a way that structural substitutions, logical substitutions, or other modifications may be made without departing from the scope of this disclosure. Therefore, this disclosure should be considered illustrative, not restrictive.

Claims

1. The first solid electrolyte material covers at least a portion of the second solid electrolyte material, The first solid electrolyte material is M ａ Me ｆ O ｂ X ｃ The oxyhalide material is represented by the formula [wherein M contains alkali metals, X contains halogens, 0 ≤ f ≤ 1, a / b > 3, c = a + (k × f) - 2b, k is the valence of Me, and Me contains metals other than M], A solid electrolyte material wherein the second solid electrolyte material includes a halide material different from the first solid electrolyte material.

2. The first solid electrolyte material is M' ｍ (Me') ｆ’ (OH) ｎ X' ｐ The solid electrolyte material according to claim 1, further comprising a hydroxyl halide material represented by the formula [wherein M' contains an alkali metal, X' contains a halogen, 1 ≤ m ≤ 5, 0 ≤ f' ≤ 1, 1 ≤ n ≤ 4, p = m + (k' × f') - n, k' is the valence of Me', and Me' contains a metal different from M'].

3. The solid electrolyte material according to claim 2, wherein M' and M contain the same alkali metal.

4. The solid electrolyte material according to claim 3, wherein the alkali metal includes Li.

5. The solid electrolyte material according to claim 2, wherein X' and X contain at least one of Cl and Br.

6. The weight content ratio C of the oxyhalide to the hydroxyl halide ＭＯＸ / C ＭＯＨＸ [wherein, C ＭＯＸ is the weight content of the oxyhalide with respect to the total weight of the first solid electrolyte material, and C Ｍ’ＯＨＸ’ is the weight content of the hydroxyl halide with respect to the total weight of the first solid electrolyte material] is at least 0.

05. The solid electrolyte material according to any one of claims 2 to 5.

7. The oxyhalogen material is Li ７ O ２ X ３ A solid electrolyte material according to any one of claims 1 to 5, including the above.

8. The hydroxyl halide material is Li ２ OHX, Li ４ (OH) ３ A solid electrolyte material according to any one of claims 2 to 5, comprising X, or a combination thereof.

9. The solid electrolyte material according to any one of claims 1 to 5, wherein the first solid electrolyte material comprises a fluorine-containing dopant.

10. The halide material of the second electrolyte material is M'' ３－ｚ (Me'') ｆ’’ X'' ３－ｚ＋ｋ’’＊ｆ’’ A solid electrolyte material according to any one of claims 1 to 5, comprising [wherein -3 ≤ z < 3, 0 < f'' ≤ 1, M'' contains an alkali metal element, k'' is the valence of Me'', Me'' contains a metal different from M'', and X'' contains a halogen].

11. The solid electrolyte material according to any one of claims 1 to 5, wherein the first solid electrolyte material is in direct contact with at least a portion of the second solid electrolyte material.

12. The solid electrolyte material according to any one of claims 1 to 5, comprising coated particles including a coating comprising the first solid electrolyte material covering at least a portion of the core comprising the second solid electrolyte material.

13. A solid electrolyte material according to any one of claims 1 to 5, comprising a layered structure, wherein the first solid electrolyte material is in the form of a film, tape, block, or sheet and has a thickness t1 of at least 1 nm and a maximum of 100 nm, and the second solid electrolyte material is in the form of a film, tape, block, or sheet and has a thickness t2 of 10 μm to 1 mm or less.

14. The first solid electrolyte material comprises a first crystalline phase containing the oxyhalide material and M' ｍ (Me') ｆ’ (OH) ｎ X' ｐ A solid electrolyte material according to any one of claims 1 to 5, comprising a second crystalline phase containing [wherein M' contains an alkali metal, X' contains a halogen, 1 ≤ m ≤ 5, 0 ≤ f' ≤ 1, 1 ≤ n ≤ 4, p = m + (k' × f') - n, k' is the valence of Me', and Me' contains a metal different from M'].

15. A structure comprising a solid electrolyte material and a negative electrode as described in claim 14, wherein the first solid electrolyte material is located between the negative electrode and the second solid electrolyte material.

Images