Electrolyte materials and methods of formation

Abstract

To provide a solid electrolyte material which has low ionic conductivity and electrochemical stability.SOLUTION: In a solid electrolyte material which contains a composite metal halide containing ammonium, the composite metal halide containing ammonium is represented by (NH4)nM3-z(Mek+)fXn+3-z+k*f. In the formula, 0<n, 0≤z<3, 2≤k<6, and 0≤f≤1 hold. M comprises at least an alkali metal element. X comprises a halogen. Me comprises a divalent metal element, a trivalent metal element, a tetravalent metal element, a pentavalent metal element, a hexavalent metal element, or an arbitral combination of them.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The following relates to electrolyte materials and methods of forming the same, specifically ammonium-containing composites. The present invention relates to a solid electrolyte material containing a metal halide and a method for forming the same. [Background technology]

[0002] Solid-state lithium batteries offer a significant advantage over conventional lithium batteries by allowing for a lithium metal anode. Offers higher energy density and faster recharge times compared to lithium-ion batteries Current solid electrolyte materials are oxides, which are expected to pose fewer safety concerns. , halide, sulfide, fluoride, and solid polymer electrolytes.

[0003] Oxide-based materials are considered safe and have good chemical and electrochemical stability. The synthesis of these compounds typically involves high temperatures above 1000 to 1200°C. Oxide-based materials are typically dense, hard, and brittle, with a maximum melting point of 1.0 at room temperature. Ionic conductivity (IC) in mS / cm RT )

[0004] Halide compounds, such as chlorides and bromides, are generally safe and have good chemical - Electrochemical stability, deformability, and plasticity enable relatively high compatibility with electrode active materials. Some Li3YCl6 (LYC) and Li3YBr6 (LYB) electrolytes Room temperature ionic conductivity IC of over 1 mS / cm RT Halides are generally hygroscopic. It forms hydrates or undergoes hydrolysis when exposed to moisture. Halide solid electrolytes such as LYB and LYB have been synthesized in the solid state using high-energy ball milling. Furthermore, the synthesis requires expensive binary halide reactions. High volume applications present challenges due to the use of high temperature annealing and / or high temperature deposition. .

[0005] Fluorides are very similar to oxides in physical, chemical, and electrochemical properties. However, IC is generally less than 1 mS / cm. RT It has a value.

[0006] Sulfides have relatively high ionic conductivity. For example, IC RT is 25mS / cm can be high, while commercially available related sulfide or thiophosphate solid electrolytes Achieving 2-10 mS / cm is possible. Sulfide materials are mechanically flexible and deformable. However, sulfide materials have poor electrochemical stability and are susceptible to water and heat accidents. This raises safety concerns due to the risk of releasing toxic H2S gas when reacting with Furthermore, high surface area sulfide solid electrolyte powders tend to have high reactivity even at ambient humidity. Due to its reactive nature, it poses a particularly high H2S hazard.

[0007] Generally, solid polymer electrolytes containing lithium salts have a relatively low IC RT Value and It has electrochemical stability.

[0008] The industry continues to demand improved solid electrolyte materials. [Brief explanation of the drawings]

[0009] The present disclosure can be better understood and many of its aspects can be better understood by reference to the accompanying drawings, in which: Many features and advantages will be apparent to those skilled in the art.

[0010] [Figure 1] FIG. 1 is a cross-sectional view of a portion of a solid-state lithium battery, according to one embodiment. [Figure 2] 1 is a flow chart illustrating a process for forming a solid electrolyte material, according to one embodiment.

[0011] Skilled artisans will appreciate that elements in the figures are illustrated for simplicity and clarity and are not necessarily drawn to scale. It is understood that the dimensions of some of the elements in the figures are not necessarily those of the present invention. Some elements may be exaggerated relative to other elements to help improve understanding of the embodiments. The use of the same reference symbols in different drawings indicates similar or identical items. . DETAILED DESCRIPTION OF THE INVENTION

[0012] The following description in conjunction with the drawings will aid in understanding the teachings disclosed herein. The following discussion focuses on specific implementations and embodiments of the present teachings. This focus is provided to help explain the present teachings and This disclosure should not be construed as a limitation on the scope or applicability of the present disclosure.

[0013] As used herein, "comprise" and "comprise" "ising", "include", "including", "having The terms "has," "having," or any of these other The variants are intended to include non-exclusive inclusions, e.g., including a list of features. The process, method, article or apparatus is not necessarily limited to these characteristics. However, if not expressly listed or otherwise, any such process, method, article or apparatus Furthermore, unless expressly stated otherwise, Unless otherwise stated, "or" refers to an inclusive "or" and not an exclusive "or." For example, condition A or B is satisfied by one of the following: A is true (or A is false (or does not exist) and B is false (or does not exist), A is false (or does not exist) and B is is true (or exists), and both A and B are true (or exist).

[0014] The use of "a" or "an" refers to the elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This explanation is given to give one or more meanings unless it is clear that something else is meant. or at least one and the singular form should be read to include the plural, or vice versa. .

[0015] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by a person skilled in the art to which this invention pertains. The materials, methods, and examples are illustrative only and not intended to be limiting.

[0016] Embodiments herein provide a solid electrolyte material comprising an ammonium-containing complex metal halide. The metal may include at least one alkali metal element. The solid electrolyte material is In embodiments, the solid electrolyte material may have improved bulk ionic conductivity. It may be used to form the electrolyte, anode, and / or cathode. In some embodiments, the solid electrolyte material may be a suitable component of a solid-state battery. A more specific example is a solid-state lithium battery.

[0017] Embodiments relate to a method for forming a solid electrolyte material, which allows for cost-effective This may enable the mass production of solid electrolyte materials.

[0018] In one embodiment, the solid electrolyte material is (NH4) n M 3-z (Me k+ ) f X n+3- z+k*f The ammonium-containing complex metal halide may be represented by the formula: <n、 -3≦z≦3, 2≦k<6, 0≦f≦1, M may contain an alkali metal element, and X is , may include a halogen, and Me may include a metal element. In certain embodiments, f is not zero. In another particular embodiment, 0≦z<3. In yet another embodiment, 0≦z≦3. In another particular embodiment, z can be 3 and n is 0.5, or 1, or 2, or 3. , or 4.

[0019] In one embodiment, the solid electrolyte material is (NH4) n M 3-z Me k+ X n+3-z+k The ammonium-containing complex metal halide may be represented by the formula: <n、0≦z<3 , 2≦k<6, M may include an alkali metal element, X may include a halogen, Me may contain a metal element.

[0020] In one embodiment, ammonium is present in an amount of up to 40 mol % based on the total amount of ammonium and M. , up to 30 mol%, up to 20 mol%, etc., relative to the total amount of ammonium and M. In another embodiment, ammonium may comprise ammonium and M. at least 14 mol %, at least 20 mol %, or at least 25 mol %, based on the total amount of ammonium and M. In this embodiment, ammonium is present in the minimum and maximum percentages set forth herein. The range may include any of the above.

[0021] In one embodiment, M can be one or more metal elements, including alkali metal elements. In another example, M can be Li, Na, K, Cs, Rb, etc. In a further example, M may comprise one or more of: , Na, or a combination of Na with at least one of Cs and Rb In certain instances, M can be a combination of Li and Cs.

[0022] In another embodiment, M can consist of one or more alkali metal elements. For example, M can be Li In another example, M can be Li and In yet another example, M can consist of at least one of Li and N. It can consist of a.

[0023] In certain implementations, Na comprises up to 40 mol % of M, such as up to 34 mol % of M. For example, M may contain 0 mol % to 40 mol % Na. In a particular example, M contains up to 20 mol % Na, or even more specifically up to 10 mol % Na In at least one example, Na may comprise 40 mol % to 100 mol % of M. do.

[0024] In more specific implementations, Li is at least 50 mol % of M, or at least 6 It may constitute 0 mol %, or at least 66 mol %, or at least 75 mol %. In a specific example, M may contain 60 mol % to 100 mol % Li.

[0025] In another example, Cs is at least 30 mol %, at least 40 mol %, or at least 50 mol % of M. In another example, Cs may comprise at least 25 mol %, such as at least 50 mol %. , at most 50 mol %, or at most 40 mol %, or at most 30 mol %, or at most In certain instances, Cs may comprise as much as 20 mol %, or at most 10 mol % of M. It may constitute up to 1 mole %.

[0026] In one embodiment, X may include at least one of Cl, Br, I, and F. For example, X may include Cl or Br. In another example, X may include F. , X may include at least two of Cl, Br, and I. In yet another example, X may include any of Cl, Br, and I.

[0027] In one embodiment, X can include elements other than halogens. In some implementations, X may contain anionic groups in addition to halogens. Such anionic groups include amides (-NH 2), -(NH) 0.5 (imide), hydroxide (-OH), borohydride (-BH4), - The anionic groups may include impurities or dopants. In certain embodiments, X is at least one of Cl, Br, F, and I. and optionally amide (-NH2), hydroxide (-OH), BH4, and -B and at least one of Cl and Br. One or both of the amides (-NH2), -(NH) 0.5 (imide), hydroxide (-O and at least one of -H), -BH4, and -BF4. Further examples In the formula, X is F, amide (-NH2), hydroxide (-OH), -BH4, and -BF. 4. In at least one embodiment, X may consist of 1 There can be one or more halogens.

[0028] In one embodiment, Me is a divalent metal element, a trivalent metal element, a tetravalent metal element, a pentavalent metal element, a hexavalent metal element, a In an illustrative example, Me may comprise two or more valent metal elements, or any combination thereof. and k may be the average of the total valence of each Me metal element. If e contains equimolar amounts of trivalent and tetravalent metal elements, k = (3 + 4) / 2 = 3 In certain embodiments, k can be 3, or 4, or 5.

[0029] Exemplary divalent metal elements include Mg and / or Ca, Zn, or any of these. In a particular implementation, M e may include Zn, Ca, or any combination thereof. Ions with relatively small radii, such as Zn and Mg, are those in which the halogens include Cl or It may be particularly suitable if the ions consist of Cl, and ions with a relatively large radius such as Ca It may be particularly preferred if the halogen comprises or consists of Br. In its current form, including a replacement ion with a larger radius than the base ion is an important step in the electrolyte material. For example, Me can help widen the ion-conducting channels in the material. In another implementation, Mg Divalent elements with relatively light weights, such as Zn and Ca, may be preferred. For example, by substituting Sr or Ba for Y, the compounds SrX2 or BaX2 are obtained. This leads to the formation of complex metal halides, which affects the bulk ionic conductivity of the complex metal halides. It may be an impurity that can be detected.

[0030] Exemplary trivalent metal elements include Ce, Dy, Er, Eu, Gd, Ho, La, Lu, Rare earth elements, including Nd, Pr, Pm, Sm, Sc, Tb, Tm, Yb, Sc, and Y; Trivalent metals other than rare earth elements, such as In, Ga, Al, or Bi, or any of these In particular examples, Me can be selected from the group consisting of Sc, Y, La, Gd, or any combination thereof. In a more particular example, Me may include Y, Gd, or a combination thereof.

[0031] Exemplary tetravalent metal elements include Zr, Hf, Ti, Sn, Ge, Th, or any of the foregoing. In a particular example, Me may be any combination of Zr and Hf. In another particular example, Me can include Zr.

[0032] Exemplary pentavalent elements include Ta, Nb, W, Sb, or any combination thereof. Examples include:

[0033] In a further embodiment, Me is selected from the group consisting of rare earth elements, including Y, Gd, La, and / or Sc; Alkaline earth metal elements, 3d transition metals, Zn, Zr, Hf, Ti, Sn, Th, Ta, N b, Mo, W, Sb, In, Bi, Al, Ga, Ge, or any combination thereof In a particular example, Me can include Y, Gd, Zr, or any combination thereof. In certain instances, Me may include Y partially substituted by another Me element. For example, Y contributes to the improved crystal structure and and / or may be substituted by a specific content of another Me element that may promote improved properties. In a particular example, Me is present in a range of up to 70 mol % Y and 5 mol % to 30 mol % substituted Me In a further example, Y may be included to allow the formation of a stable phase of a complex metal halide. It can be partially substituted by Me elements having a suitable effective ionic radius. In this case, the effective ionic radius of the Me element is smaller than that of La, which is 103.2A, and is smaller than that of Li. The ionic radius may be at least as large as 0.76 A. In this case, the Me element may have an effective ionic radius of 0.76 A±5% to 93.5 A±5%.

[0034] In certain implementations, Me is Gd, Y, Ce, Er, Zr, Yb, or any of these. For example, Me may consist of Y. In another example, Me may consist of It may consist of Y and at least one of Ce, Er, Zr, and Gd. In one example, Me consists of Yb and Ce. In another example, Me consists of In, Y, Zr, H The alloy may consist of two or more of f, Sc, Zn, and Mg.

[0035] In a particular example, M can be Li and Me can be a combination of In, Mg, Zr, and Sc. X may be Cl or a combination of Cl and an anionic group.

[0036] In another particular example, M can be Li, Me can be Y, Zr, and Hf, and X can be Cl, or a combination of Cl and an anionic group.

[0037] In another particular example, M can be Na, Me can be Zr, and X can be Cl, or It may be a combination of Cl and an anionic group.

[0038] In certain embodiments, the complex ammonium-containing metal halide is (NH4) n (Li (1-d-e) Na (d) M' (e) )2Li (1-z) Me 3+ (1-u-p-q-r ) Me 4+ (u) Me 2+ (p) Me 5+ (q) Me 6+ (r) (Cl (1-y-w) B r (y) I (w) ) (6+u-p+2q+3r-z+n) where n>0, 0 ≦d<1, 0≦e<1, (d+e)≦1, and M' is Cs, Rb, K, or any of them. and Me 4+ is Zr 4+ , Hf 4+ , Ti 4+ , Sn 4+ , Th 4+ , Ge 4+ , or any combination thereof, and Me 3+ is a trivalent rare earth The element In 3+ , Y 3+ ,Sc. 3+ , Bi 3+ , Al 3+ , Ga 3+ , or it Any combination of these, Me 2+ is Mg 2+ , Zn 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Yb 2+ ,EU 2+ , or any combination thereof, and Me 5+ teeth, Ta 5+ , Nb 5+ , W 5+ , Sb 5+ , or any combination thereof, and Me 6+ is W 6+ or Mo 6+ where 0<=w<=1, 0<=y<=1, -1≦z≦1 , 0<=u<0.95, 0<=p<0.95, 0<=q<0.95, and 0<=r<0. 95. In certain embodiments, n=0.5, or 1, or 2, or 3, or 4. and z=1. In another particular embodiment, 0≦z<1. In a more particular embodiment, d = e = 0, p = 0, q = 0, and r = 0, and in an even more particular embodiment, w = 0. be.

[0039] In another particular embodiment, the ammonium-containing complex metal halide is (NH4) n L i3(Me k+ ) f X 3+k*f+n where Me is a rare earth element, Zr, or or a combination thereof, wherein n>0, 0≦f≦1, and X is a halogen and optionally Selectively amide (-NH2), -(NH) 0.5(imide), hydroxide (-OH), and and an anionic group, such as -BF4, where k can be 3, or 4, or 5. In one embodiment, f is not zero. In a particular embodiment, f=1. A particular example of Me is Examples include Y, Gd, Sc, Zr, or a combination thereof. Specific examples of nium-containing complex metal halides include (NH4)3Li3YCl9, ( NH4)3Li3Y 0.8 Gd 0.2 Br9, (NH4)3Li3Y 0.8 Gd 0.2 C l9, (NH4)3Li3InCl9, (NH4)3Li3Mg 0.2 Y 0.6 Zr 0. 2Cl9, (NH4)3Li3YBr9, etc., or any combination thereof It is possible.

[0040] In another particular embodiment, the ammonium-containing complex metal halide is (NH4) n ( Li 1-d Na 1-d )2LiMe k+ X 3+k+n where Me is a rare earth element. element, Zr, or a combination thereof, where n>0, 0≦d<1, and X is halide. and optionally (-NH), -(NH) 0.5 (imide), hydroxide (-OH ), and an anionic group, such as -BF4, and k is 3, or 4, or 5. In a more specific example, Me can be Y, Sc, Gd, Zr, or a combination thereof. Exemplary specific ammonium-containing complex metal halides include: , (NH4)3(Li 0.5 Na 0.5)3YCl9, (NH4)3(Li 0.5 Na0 .5 )3YBr9, (NH4)3Cs2LiYBr9, (NH4)LiCsCl3, or NH4Li2CsCl4, etc., or any combination thereof can be mentioned. can be mentioned.

[0041] In one embodiment, the ammonium-containing composite metal halide is composed of A t and B (1-t) and can be expressed by the formula, where 10 -6 <t ≦ 1, A contains ammonium, and B does not contain ammonium. does not contain ammonium.

[0042] In one example, A can be represented by (NH4) n Li 3-z (Me k+ ) f X 3-z+k*f+n and can be represented by and B can be represented by (Li 1-d-e Na d M e )2Li 1-z’ (Me’ k+ ) f’ X 3-z ’+k*f’ and can be represented by, where Me and Me’ are independently rare earth elements, Zr, divalent metal elements, trivalent metal elements other than rare earth elements, tetravalent metal elements other than Zr, pentavalent elements, hexavalent elements , or any combination thereof can be included, M can be K, Rb, Cs, or any combination thereof, 2 ≦ k ≦ 6, 0 ≦ d ≦ 1, 0 ≦ e < 1, -1 ≦ z’ ≦ 1, 0 ≦ f ≦ 1, 0 ≦ f’ ≦ 1, 0 < n, 0 ≦ z ≦ 3. In a specific example, d is less than 1. In a further specific example, z is not zero. In another specific example, f’ is greater than 0. In a specific example, when z = 3, n = 0.5, or 1, or 2, or 3, or 4. or 4. or 4.

[0043] In a particular example, A is (NH4) n Li3Me k+ X 3+k+n and B can be expressed as ( Li,Na)2LiMe' k+ X6, wherein Me and Me′ are independently Divalent metal elements, trivalent metal elements, tetravalent metal elements, pentavalent elements, or any combination thereof k may be 2≦k<6, n>0, and X may contain at least one halogen. In particular examples, k can be 3, or 4, or 5, and n can be 0.5, or 1, or can be 2 or 3, and Me includes rare earth elements, Zr, or a combination thereof. obtain.

[0044] In a particular example, A is (NH4) n Li3Me k+ X 3+k+n and B can be expressed as ( Li,Cs)2LiMe' k+ X6, wherein Me and Me′ are independently Divalent metal elements, trivalent metal elements, tetravalent metal elements, pentavalent elements, or any combination thereof k may be 2≦k<6, n>0, and X may contain at least one halogen. In particular examples, k can be 3, or 4, or 5, and n can be 0.5, or 1, or can be 2 or 3, and Me includes rare earth elements, Zr, or a combination thereof. obtain.

[0045] In one embodiment, the ammonium-containing complex metal halide is a single phase containing A and B. In a particular example, the single phase may consist of A t and B (1-t) It is a solid solution composed of It is possible.

[0046] In another embodiment, the ammonium-containing complex metal halide may include multiple phases. For example, A may be present in a first phase, and the first phase may not contain B. B may be present in a second phase. and the second phase may be free of A. In another example, the second phase may consist of B. In certain instances, multiple phases may exist in a eutectic-like intimate mixture.

[0047] A can improve the ionic conductivity of B, and A t and B (1-t) Ammonia with a composition of The ammonium-containing complex metal halide is an improvement over the complex metal halide having the composition of B. It is noteworthy that the ionic conductivity of the crystalline silicon can be improved.

[0048] In one embodiment, the ammonium-containing complex metal halide is an ion-conducting material of the electrolyte. For example, t may be at least 10 -5 , few At most 10 -4 , at least 10 -3 , at least 10 -2 , or at least 0.05 10 -6 In other instances, t may be at most 0.4, at most 0.3, or or may be at most 0.5, such as at most 0.2. Furthermore, t may be any of the values ​​mentioned herein. The range may be within a range including any of the minimum and maximum values ​​set forth above. t can be a bulk ionic conductivity enhancer parameter. For example, ammonium-containing In certain applications of ammonium-containing complex metal halides, when t is large, The higher bulk ionic conductivity of the halides may be exhibited.

[0049] In one embodiment, the ammonium-containing complex metal halide has ionic conductivity in bulk. In one embodiment, the ammonium-containing complex metal halide may have a cation concentration of at least 0.00 1 mS / cm, at least 0.01 mS / cm, at least 0.1 mS / cm, or less In another embodiment, the ammonium-containing The complex metal halides may have an ionic conductivity of greater than 0.5 mS / cm. The ionic conductivity is at least 0.6 mS / cm, at least 1.2 mS / cm, or In another example, the ion exchange rate may be at least 1.8 mS / cm, or at least 2.2 mS / cm. The bulk ionic conductivity is 15mS / cm, 13mS / cm, and 11mS / cm. cm, up to 8 mS / cm, up to 7.2 mS / cm, or up to 6.2 mS / cm In certain instances, the bulk ionic conductivity may be greater than or equal to the minimum and maximum values ​​mentioned herein. The value may be within a range including any of the greater values.

[0050] The bulk ionic conductivity was measured at 22°C with activation energies between 0.2 eV and 0.5 eV. In a further example, an activity of 0 to 1 eV can be determined for temperatures between 200°C and -80°C. For temperatures between 80°C and -30°C, the activation energy is , can be 0.1 to 0.6 eV. Above 0°C or below 10°C, the activation energy is , can be 0.1 to 0.5 eV.

[0051] In another embodiment, the ammonium-containing complex metal halide is heated to a temperature of from -80°C to 200°C. Temperature range, or -30℃ to 80℃, at least 0.01mS / cm to maximum It can exhibit a bulk ionic conductivity of 15 mS / cm at 1000 kJ / cm.

[0052] In a further embodiment, the ammonium-containing complex metal halide has a valence of 0.2 eV to 0. At an activation energy of 5 eV, at least The bulk ionic conductivity may range from 0.5 mS / cm up to 15 mS / cm.

[0053] In a further embodiment, A is (NH4) n Me k+ X k+n and B can be expressed as M2 Li(Me k+ ) f X 3+k*f wherein M is at least one alkali metal. Me may include rare earth elements, Zr, or a combination thereof; and and Zr, n=0.5, or 1, or 2, or 3, and 0 <f≦1であり、kは、 The valence of Me, and X is at least one halogen and optionally (-NH2), - (NH) 0.5 Anionic groups including (imide), hydroxide (-OH), -BH4, and -BF4 In a particular example, Me may include rare earth elements and Zr. In a particular example, Me is , Y, Zr, Gd, Sc, Er, or any combination thereof. In the example, Me is Y, or Gd, or two or more of Y, Zr, and Gd. In one embodiment, M is Li, Na, Rb, Cs, K, or any combination thereof. In a particular example, M includes Li. In another particular example, M includes Na. In another particular example, M includes Cs. In a more particular example, M includes L Li, or a combination of Li with at least one of Na and Cs. In this embodiment, Li is selected from the group consisting of Li and at least one of Na, Cs, Rb, and K. In a further embodiment, M may consist of Li and Na. In the above formula, M may consist of Na and at least one of Cs, Rb, and K. In the formula (I), X may consist of a halogen and, optionally, an anionic group. The halogen is at least one, at least two of Cl, Br, F, and I, or It may include at least three.

[0054] In one embodiment, A is (NH4)3Me k+ X 3+k and B is Li3Me k+ X 3+k wherein Me is a rare earth element, Zr, or a combination thereof. where X comprises one or more halogens and optionally an anionic group. In the formula, Me can be Y, Zr, Gd, Sc, Er, or any combination thereof. In a more particular example, Me is selected from the group consisting of Y, Gd, or Y, Zr, and Gd. In one example, X is a halogen and optionally an anion. In particular examples, the halogen can be selected from the group consisting of Cl, Br, F, and I. It may include at least one, at least two, or at least three.

[0055] In one embodiment, A is (NH4)3Li3Me k+ X 6+k B can be represented by Li 3MeX6, where Me represents a rare earth element, Zr, or a combination thereof. X may comprise one or more halogens and, optionally, an anionic group. Me can be Y, Zr, Gd, Sc, Er, or any combination thereof. In a more particular example, Me is Y or Gd, or Y, Zr, and Gd. It may be a combination of two or more. In one example, X is a halogen and optionally an anion. In particular examples, the halogen may be at least one of Cl, Br, F, and I. It may include at least one, at least two, or at least three.

[0056] In certain embodiments, A can be represented by (NH4)3Li3YX9 and B can be represented by (Li 1- d Na d )2LiMe k+ X 3+k where Me is a rare earth element, Zr, or may include any combination thereof, 0≦d≦1, and X is one or more halogens. , optionally (-NH2), -(NH) 0.5 (imide), hydroxide (-OH), and and an anionic group, such as -BF4. In a particular example, X may include a halogen and optionally In another example, X may comprise at least one halogen, and at least one anionic group. In a further example, the halogen can be Cl, At least one, at least two, or at least three of Br, F, and I In a particular example, the halogen can be Cl. In another particular example, the halogen can be , Br, or a combination of Br and Cl. The halogens may be a combination of Cl, Br, and I. In yet another particular example, the halogens The suffix can be F.

[0057] In one embodiment, A is (NH4)3Me k+ X 3+k and B can be expressed as (Li d Na d )2LiMe k+ X 3+k where Me is a rare earth element, Zr, or may include any combination thereof, 0≦d<1, and X is one or more halogens. , optionally anionic groups such as (-NH), hydroxide (-OH), and -BF In certain examples, d may be greater than 0, such as at least 0.2. In certain examples, d can be up to 0.5. In certain examples, Me can be Y, Gd, Zr In a further example, the halogen may include Cl, B, Sc, or a combination thereof. r, and I, In particular examples, the halogen can be Cl, Br, or a combination of Cl and Br. In another particular example, the halogens may be a combination of Cl, Br, and I. In yet another specific example, the halogen can be F.

[0058] In certain embodiments, A is (NH) n YX 3+n where n=0.5, 1, 2 , 3, and B can be represented by M2LiREX6, where M is Li, or Li and Na, or Li and Cs, and RE may include at least one rare earth element; X contains at least one halogen.

[0059] In certain embodiments, A may be represented by (NH4)3YX6 and B may be represented by (Li 1-d Na d )2LiMe k+ X 3+k where Me is a rare earth element, Zr, or and 0≦d<1, and X may comprise one or more halogens and optionally Optionally, anionic groups such as amide (-NH2), hydroxide (-OH), and -BF4 In certain examples, d may be greater than 0, such as at least 0.2. In certain examples, d can be up to 0.5. In certain examples, Me can be Y, Gd, Zr In a further example, the halogen may include Cl, B, Sc, or a combination thereof. r, and I, In particular examples, the halogen can be Cl, Br, or a combination of Cl and Br. In another particular example, the halogens may be a combination of Cl, Br, and I. In yet another specific example, the halogen can be F.

[0060] In another particular embodiment, A is (NH4) n Li3Me k+ F 3+k+n can be expressed as , B is (Li 1-d Na d )2LiMe k+ F 3+k where Me is a rare earth metal. The element may include a group element, Zr, or any combination thereof, where 0≦d<1. wherein A and / or B are optionally selected from the group consisting of (-NH), hydroxide (-OH), -B In a particular example, the anionic groups may be doped with d In another particular example, d can be greater than 0, such as at least 0.2. In another specific example, Me can be Y, or Y and Gd, Zr, and Sc. It may include a combination of one or more of these elements.

[0061] In another embodiment, A is (NH4) n (Li (1-d), Na (d) )2Li (1- z) Me 3+ (1-u--p-q-r) Me 4+ (u) Me 2+ (p) Me 5+ (q) M e 6+ (r) (Cl (1-y-w) Br (y) I (w) ) (6+u-p+2q+3r-z +n) and B can be expressed as (Li (1-d’), Na (d’) )2Li (1-z’) Me 3+ (1-u-v-w) Me 4+ (u) Me 2+ (p) Me 5+ (q) Me 6+ (r) ( Cl (1-y-w) Br (y) I (w) ) (6+u-p+2q+3r-z’+n) Represented by where 0≦d<1, 0≦d′<1, 0 <n、-1≦z<1、-1≦z’<1であり , when z=1, n=0.33, or 0.5, or 1, or 1.5, or 2, or or 3, or 4, and Me 3+ is a rare earth element, In, Bi, or any of them Includes combinations 4+ is Zr 4+ , Hf 4+ , Ti 4+ , Sn4+ 、Th 4+ 、 or any combination thereof, and Me 2+ is Mg 2+ 、Zn 2+ 、Ca 2+ 、 Sr 2+ 、Ba 2+ 、or any combination thereof, and Me 5+ is Ta 5+ 、 Nb 5+ 、W 5+ 、Sb 5+ 、or any combination thereof, and Me 6+ is W 6+ where 0 <= x <= 1, 0 <= y <= 1, -0.95 < z < 0.95, 0 <= u < 0.95, 0 <= p < 0.95, 0 <= q < 0.95, 0 <= r < 0.95, and w <= 1. When z = 0, A can be stoichiometric. When z is not zero, A can be non - stoichiometric. In certain examples, -0.95 < z < 0.95. In more specific embodiments, d = e = 0, p = 0, q = 0, and r = 0, and in even more specific embodiments w = 0.

[0062] In certain examples, A can be represented by NH4X and B can be a complex metal halide compound having the general formula MM’X. Examples of such compounds include LiCsCl2 and Li2CsCl3. Ammonium - containing complex metal halides can be eutectic - like compositions of NH4X + LiCsCl2 or NH4X + LiCsCl3 .

[0063] In one embodiment, A and B can contain the same halogen element. In certain examples, the halogen elements of A and B can be the same. In at least one embodiment, A is an alka In another embodiment, A and B may contain the same alkali metal. In particular examples, the alkali metals of A and B can be the same. and B are the same mole percentages of each alkali metal relative to the total amount of alkali metal in each compound. In further embodiments, A and B may be the same divalent, trivalent, or tetravalent element. element, and / or pentavalent element, etc. For example, A and B can be , may contain the same rare earth element. In certain instances, the rare earth elements of A and B may be the same. In another example, A and B may include Zr. In a more particular example, A and B may include Zr. Each compound may contain the same mole percent of each Me element relative to the total amount of Me in each compound.

[0064] In a particular implementation, A can be (NH4)3Li3YCl9 and B can be Li3YC In another specific implementation, A can be (NH4)3Li3YBr9. , B can be Li3YBr6. In yet another specific implementation, A is (NH4) 3(Na 0.5 ,Li 0.5 )2LiYCl9, B can be (Na 0.5 ,Li 0. 5)2LiYCl6. In yet another specific implementation, A can be (NH4)3( Na 0.5 ,Li 0.5 )2LiYBr9, where B is (Na 0.5 ,Li 0.5 ) 2LiYBr6. In yet another specific implementation, A can be (NH4)3Li3 Y 0.8 Gd 0.2 Br9, B can be Li3Y 0.8 Gd 0.2 Can be Br6 . In yet another specific embodiment, A can be (NH4)3Li3GdBr9 and B can be , Li3GdBr6. In yet another specific embodiment, A can be (NH4)3L i3Y 0.8 Zr 0.2 Br 9.2 [[ID=​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​In a more specific example, the RE comprises Y, Gd, Zr, or a combination thereof. In another embodiment, (NH4) n M3Me k+ X 3+k+n and (NH4) n M e k+ X 3+k+n may be present in different phases. In yet another embodiment, ammonium The containing complex metal halide may consist of a single phase containing A and B, where A is (NH4) n M 3Me k+ X 3+k+n and (NH4) n Me k+ X 3+k+n It can be composed of:

[0066] In further embodiments, simple metal halides such as rare earth halides (e.g., YCl3) can be used. Halides, and / or alkali metal halides (e.g., LiCl) are used in the due to incomplete reactions between the raw materials used to form the nium-containing complex metal halides. Simple metal halides can be generated due to the presence of ammonium-containing complex metal halides. In one embodiment, the ammonium-containing complex metal halide is at most 15% by weight based on the total weight of the ammonium-containing complex metal halide , for example, up to 14% by weight based on the total weight of the ammonium-containing complex metal halide , up to 13 wt%, up to 12 wt%, up to 11 wt%, up to 10 wt%, up to 9% by weight, up to 8% by weight, up to 7% by weight, up to 6% by weight, up to 5% by weight, up to 4% by weight, max. 3% by weight, max. 2% by weight, max. 1% by weight, max. 0.5% by weight, max. 0.4% by weight at most, 0.3% by weight at most, 0.2% by weight at most, 0.1% by weight at most, or In certain instances, the simple metal halides may contain up to 0.05% by weight. It may be present in even lower contents, such as 5 atomic % or up to 2.5 atomic %. In some embodiments, the simple metal halide may exist in a phase different from A and B. The ammonium-containing complex metal halide may essentially contain no simple metal halides. For example, metal halides may be less than 0.2 atomic percent. XRD analysis combined with the improvement of the solubility ... parasitic phases revealed the presence of characteristic diffraction peaks corresponding to the parasitic phases. It can be detected by quantitative analysis through the presence of XR using Rietveld refinement (RR). The shape and position of the peaks in the D diagram were analyzed at small increments of 2θ angle. Collecting 2θ data in XRD diffraction and converting the XRD data into ratios of different phases By this, the contribution of various phases can be quantitatively identified. When present in a powder sample at a molar or mass level of 0.3%, the impurity is XRD peaks strong enough to be used for the identification of impurity phases by XRD combined with Other analyses may be used to determine minor impurity phases. An example of this is LECO.

[0067] In one embodiment, the electrolyte material may comprise an ammonium-containing complex metal halide. In one embodiment, the electrolyte material is a single phase of an ammonium-containing complex metal halide and an impurity. If present, one or more impurity phases are included in the ammonium-containing complex metal halide. Specifically, the content of one or more impurity phases may be different from that of conventional complex metal halides. In a further aspect, the electrolyte material is an ammonia containing multiple phases. For example, the electrolyte material may consist of phases A and B. In one embodiment, the electrolyte material may comprise an ammonium-containing complex metal halide comprising: Used as raw materials to form electrolytes, electrodes, or other components of electrochemical devices It can be used.

[0068] In one embodiment, the solid-state electrolyte may comprise a solid electrolyte material. Compared with conventional solid-state electrolytes containing ammonium-free composite lithium-based halides, In certain instances, solid-state electrolytes may have improved ionic conductivity compared to solid-state electrolytes. In a more particular example, the solid-state electrolyte may be an ammonium-containing composite metal. The metal halide may be a metal halide.

[0069] In one embodiment, the composite ion-conducting layer may include an electrolyte material and an organic material. The material may include a binder material, a polymer electrolyte material, or a combination thereof. In another example, the composite ion-conducting layer may include a plasticizer, a solvent, or a combination thereof. Exemplary organic materials include polytetrafluoroethylene (PTFE), polyfluoride Polyvinylidene fluoride (PVdF), fluororubber, polypropylene, ethylene-propylene-diene Polypropylene monomer (EPDM), sulfonated EPDM, natural butyl rubber (NBR), paraffin Wax, polypropylene carbonate, polyisobutylene, polyvinylpyrrolidone, poly Dimethyl methacrylate, Poly(propylene oxide), Polyvinyl chloride, Poly(fluoride) vinylidene), poly(acrylonitrile), poly(dimethylsiloxane), poly[bis( methoxyethoxyethoxide)-phosphazene], polyethylene carbonate, polypropylene Pyrene glycol, polycaprolactone, poly(trimethylene carbonate), hydrogenated Tolylbutadiene rubber, Poly(ethylene vinyl acetate), High density polyethylene, Low density Polyethylene, polyurethane, or any combination thereof. In another example, the composite ion-conducting layer may include a lithium salt. Exemplary lithium salts include: For example, LiSbF6, LiN(SO2CF3)2, LiN(SO2C2F5)2, LiN (SO2CF3)(SO2C4F9), LiC(SO2CF3)3, LiAsF6, Li ClO4, LiPF6, LiBF4, LiCF3SO3, or any combination thereof Examples of such cases include:

[0070] In another embodiment, the mixed electronic and ionic conducting layer may comprise a solid electrolyte material. In embodiments, the mixed electronic and ionic conducting layer may further comprise a cathode active material. Examples of active materials include Li(Ni, Co, Al, Mn)O2 and LiCoO2. Lithium-containing transition metal oxides, transition metal fluorides, polyanions, and fluorinated polyanions materials, as well as transition metal sulfides, transition metal oxyfluorides, transition metal oxysulfides, transition metal oxynitrides, etc., or any combination thereof. Not limited to these.

[0071] In another embodiment, the mixed ionic and electronic conducting layer can include an anode active material. Suitable anode active materials include artificial graphite, graphite carbon fiber, resin-burned carbon, and pyrolysis steam-grown carbon. cellulose, coke, mesocarbon microbeads (MCMB), furfuryl alcohol resin Calcined carbon, polyacene, pitch-based carbon fiber, steam-grown carbon fiber, natural graphite, non-graphitized carbon Carbon materials such as lithium metal, lithium alloys, and other metallic materials, oxides, nitrides, and silicon dioxide. The compound may be a zinc compound, a silicon compound, or any combination thereof.

[0072] In one embodiment, the solid-state lithium battery comprises a cathode and an anode. With reference to FIG. 1, a portion of a cross section of an exemplary solid-state battery 100 is illustrated. The electrolyte layer 102 may be any of the electrolyte or composite layers referred to in the embodiments herein. The anode 104 overlies the electrolyte 102. In one embodiment, the anode 104 may include a solid electrolyte material and an anode active material. In another embodiment, the anode 104 is a metal anode. For example, the anode may be made of lithium. The cathode 106 may be made of lithium. The cathode 106 may be disposed on the other side of the electrolyte 106 opposite the node 102. In certain embodiments, the cathode 106 may include a solid electrolyte material and a cathode active material. , a three-dimensional structure cathode.

[0073] Some trivalent and tetravalent metal halides (i.e., rare earth halides) Metal halide hydrates tend to form stable hydrate phases, releasing water molecules from metal halide hydrates. Complex halogens based on ammonium halides, making them difficult to completely remove Conventional synthesis of ammonium-containing complex metal halides is not applicable to form ammonium-containing complex metal halides. It is noteworthy that increasing the temperature leads to the formation of desirable does not result in the formation of metal oxyhalide or metal oxyhydrate halide compounds. It can be done.

[0074] With reference to FIG. 2, a process for forming a solid electrolyte material 200 is illustrated.

[0075] The process 200 may begin at block 202. Metal compounds containing one or more oxides of Me, alkali metal carbonates (e.g., lithium carbonate) ), and hydrochloric acid. In another example, a reaction mixture containing sulfates, hydroxides, hydrates, The salts, oxalates, or other basic salts containing lithium or Me metals are and / or may be used as a raw material instead of the oxide of the metal Me. Divalent, trivalent, tetravalent, pentavalent, hexavalent elements, or their equivalents, as mentioned in the embodiments herein. In certain instances, the metal compound may be an alkali metal halide or the like. The alkali metal compound may be selected from the group consisting of:

[0076] The intermediate reaction product is a hydrate containing a metal halide (e.g., a rare earth halide). The water in the hydrated salt is replaced by NH4X, resulting in (NH4) n Me k+ X n+ k , where n>0. An exemplary reaction is illustrated below.

[0077] 3*Li2CO3+RE2O3+12*HX+6*NH4X--->2*(NH4)3 REX6+6*LiX+6*H2O+3*CO 2. In one example, the reaction product is filtered to remove larger particles and the subsequent solid Larger particles can be easily reacted with impurities in one of the raw materials. The material may include residual particles of the material, carbon, or any combination thereof.

[0078] The reaction product was dried and (NH4) n Me k+ X 3+k and MX (e.g., LiX ), wherein M is a 1 as mentioned in the embodiments herein. The drying may be carried out under vacuum or reduced pressure. The gas may be, but is not limited to, air, dry air, or nitrogen. Heat may be applied to accelerate the drying. The heating temperature may be 100°C to 140°C. This can be done until there is only a trace amount of water in the mixture, such as 1% to 3% by weight.

[0079] Process 200 may continue to block 204. In one example, (NH) n Me k + X 3+k The solid-state reaction of MX with N2 or MX can be carried out in a dry, neutral atmosphere. A stream of Ar can be used to facilitate the removal of trace amounts of water. In a specific example, (NH4)3Me k+ X 3+k can be carried out simultaneously with the solid-state reaction.

[0080] In certain instances, decomposition and solid state reactions are inert to the reactants and products. The melting can be carried out in a crucible made of any material. For example, the crucible can be made of quartz, alumina, silica, -can be made of alumina, BN, glassy carbon or graphite. Graphite is a particular implementation In certain instances, the heating temperature may be a halogenated aluminum coating. The temperature may be in the range of 400°C to 650°C, allowing for partial sublimation of the ammonium.

[0081] The process 200 may continue to block 206, where an ammonium-containing complex metal halide is produced. The product obtained after heating is an ammonium-containing complex metal halide. For example, ammonium-containing complex metal halides are (NH4) n M 3-z ( Me k+ ) f X 3+n-z+k*f where n>0, 0≦z<3, 2≦k<6 , 0≦f≦1. In a particular example, the ammonium-containing complex metal halide is (N H4) n M 3-z Me k+ X 3+n-z+k where n>0, 0≦z<3, 2 ≦k<6.

[0082] Using known techniques, the electrolyte, the composite ion-conducting layer, the anode, the cathode, or the solid Other components of solid-state lithium batteries may be formed using solid electrolyte materials. Techniques include casting, molding, vapor deposition, printing, pressing, heating, etc., or any combination thereof. In certain implementations, the invention may be applied to forming a multi-layer structure. To achieve this, layers such as the electrolyte and the anode and / or cathode are formed separately. and then laminated to form a multilayer structure. Alternatively, a green electrolyte layer, and Forming a laminate of anode and / or cathode layers, followed by pressing, extruding, and heating Further processing, such as drying, applying a voltage, or any combination thereof, may be carried out to obtain the final product. It is possible to form a multi-layer structure in which the layers are formed in a controlled manner.

[0083] In one example, the electrolyte material may be a coating for another component of an electrochemical device such as a solid-state battery. For example, the electrolyte material may be deposited on the separator as an electrolyte layer. It can be accumulated.

[0084] Many different aspects and embodiments are possible. After reading this specification, those skilled in the art will be able to understand those aspects and implementations. It will be understood that the embodiments are illustrative only and do not limit the scope of the present invention. It may be according to any one or more of the embodiments listed below.

[0085] Embodiment Embodiment 1. (NH4) n M 3-z (Me k+ ) f X n+3-z+k*f Material represented by A solid electrolyte material comprising a material, wherein: <n、0≦z<3、2≦k<6、0≦f≦1 wherein M contains at least one alkali metal element and X contains at least one halo Me includes divalent metal elements, trivalent metal elements, tetravalent metal elements, pentavalent metal elements, and hexavalent metal elements. a solid electrolyte material comprising a metal element, a fluorine atom ... Embodiment 2. A solid electrolyte material comprising an ammonium-containing complex metal halide, The metal contains at least one alkali metal element, and the complex metal halide is A solid electrolyte material that exhibits ionic conductivity. Embodiment 3.A t and B (1-t) Ammonium-containing complex metal halide A solid electrolyte material containing a fluoride, wherein the formula is: -6 <t≦1であり、Aは、アンモニウ B does not include ammonium, and the metal is at least one alkali metal element. Included are solid electrolyte materials. Embodiment 4. The ammonium-containing complex metal halide is (NH4) n M 3-z (Me k+ ) f X n+3-z+k*f where 0 <n、0≦z<3、2≦k<6、0≦ f≦1, M contains at least one alkali metal element, and X contains a halogen. , Me is a divalent metal element, a trivalent metal element, a tetravalent metal element, a pentavalent metal element, a hexavalent metal element, or any combination thereof. Embodiment 5. The ammonium-containing complex metal halide comprises a single phase or multiple phases. The solid electrolyte material according to any one of the first to fourth embodiments. Embodiment 6. The method of embodiments 1, 4, or 5, wherein M comprises at least one of Li and Na. 6. The solid electrolyte material according to any one of claims 1 to 5. Embodiment 7. The method of embodiment 1, wherein M comprises K, Rb, Cs, or a combination thereof. 7. The solid electrolyte material according to any one of 4 to 6. Embodiment 8. M is Li and at least one of Na, K, Cs, and Rb; The solid electrolyte material according to any one of embodiments 1 and 4 to 6, comprising: Embodiment 9.Me is a rare earth element, an alkaline earth metal element, a 3d transition metal, Zn, Ga , Al, Ge, Zr, Hf, Ti, Sn, Th, Ta, Nb, Mo, W, Sb, In, B i, or any combination thereof. 9. The solid electrolyte material according to any one of claims 8 to 8. Embodiment 10. X is selected from the group consisting of at least one of F, Cl, Br, and I, and optionally Typically, -NH2 (amide) group, -(NH) 0.5 (imide) group, -OH (hydroxide) group, -BH4 group and at least one of -BF4 groups, and the solid electrolyte material according to any one of Embodiment 1 and any one of 4 to 9. Embodiment 11. The ammonium-containing composite metal halide is (NH4) n Li 3-z ( Me k+ ) f X 3-z+k*f+n and is the solid electrolyte material according to any one of Embodiments 1 to 10 . Embodiment 12. The ammonium-containing composite metal halide is composed of A t and B (1-t) where 10 <t≦1, A contains ammonium, and B does not contain ammonium, and is the solid electrolyte material according to Embodiment 1 or 2. -6 Embodiment 13. A is (NH4) n Li 3-z Li k+ (Me k+ ) f 0X 3-z+k*f+n and is represented by B is (Li 1-d-e Na[[ID=]](M e )2Li 1-z’ (Me’ k+ ) f’ X 3- z’+k*f’ and is represented by where Me and Me’ are independently rare earth elements, Zr, divalent metal elements, trivalent metal elements other than rare earths, tetravalent metal elements other than Zr, pentavalent elements, hexavalent elements, or any combination thereof, M is K, Rb, Cs, or any combination thereof, 2≦k≦6, 0≦d≦l, 0≦e<1, [[ID=]]0≦f≦1, 0≦f≦1, 0<f’≦1,​​ 0 <nであり、 0≦z≦3, For z=3, n=0.33, 0.5, or 1, or 1.5, or 2, or 3 , or 4, Any one of embodiments 3-10, and 12, wherein X comprises at least one halogen. The solid electrolyte material according to any one of claims 1 to 4. Embodiment 14. A is represented by (NH4)3Li3YX9 and B is (Li 1-d Na d )2LiREX6, where RE contains at least one rare earth element, and 0≦d <1 and X comprises at least one halogen. The solid electrolyte material according to claim 1. Embodiment 15. X is a compound containing at least one halogen and, optionally, -NH2, or and at least one of —OH, —BH4, or —BF4. 15. The solid electrolyte material according to embodiment 14. Embodiment 16. RE is Y and at least one halogen is selected from the group consisting of Cl and Br. 16. The solid electrolyte material according to embodiment 14 or 15, comprising at least one of the following: Embodiment 17. An embodiment wherein RE is Y and at least one halogen is F. 15. The solid electrolyte material according to claim 14. Embodiment 18. RE is Y and at least one halogen is Cl, Br, I, or and F. . Embodiment 19. RE is Y and at least one halogen is Cl, Br, and 16. The solid electrolyte material of embodiment 14 or 15, consisting of I. Embodiment 20.A is (NH4) n (Me k+ ) f Xk*f+n and B is M2 Li(Me k+ ) f X 3+k*f wherein M is at least one alkali metal element, and Me is at least one element selected from the group consisting of rare earth elements and Zr. Contains elements, n=0.33, or 0.5, or 1, or 1.5, or 2, or 3, or 4, and X comprises at least one halogen. 13. The solid electrolyte material according to any one of 12. Embodiment 21.A is (NH4) n YX 3+n where n=0.5, 1, 2, 3. and B is represented by M2LiREX6, where M is Li, or Li and Na, or are Li and Cs, RE contains at least one rare earth element, and X is at least 21. The solid electrolyte material of embodiment 20, comprising one more halogen. Embodiment 22. M is Li and Na, or Li and K, or Li and Cs wherein the halogen comprises at least one of Cl, Br, F, and I. 22. The solid electrolyte material according to aspect 20 or 21. Embodiment 23. Any of embodiments 20 or 21, wherein at least one halogen comprises Br. The solid electrolyte material according to claim 1. Embodiment 24. Embodiment 20 or 21, wherein at least one halogen consists of Cl. The solid electrolyte material according to claim 1. Embodiment 25. At least one halogen is at least one of Cl, Br, F, and I. 22. The solid electrolyte material according to embodiment 20 or 21, comprising two of: Embodiment 26. An embodiment in which at least one halogen is selected from Cl, Br, and I. 22. The solid electrolyte material according to aspect 20 or 21. Embodiment 27. The compound of embodiment 20 or 21, wherein at least one halogen is F. The solid electrolyte material described herein. Embodiment 28. The RE is at least one of La, Ce, Gd, Er, Yb, Sc, and Y. 22. The solid electrolyte material according to embodiment 20 or 21, comprising at least one of: Embodiment 29. The solid state battery according to any one of embodiments 21 to 28, wherein RE is Y. solute material. Embodiment 30. The complex ammonium-containing metal halide is (NH4) n (Li (1- d-e) Na (d) M' (e) )2Li (1-z) Me 3+ (1-u-p-q-r) Me 4+ (u) Me 2+ (p) Me 5+ (q) Me 6+ (r) (Cl (1-y-w) Br (y ) I (w) ) (6+u-p+2q+3r-z+n) is expressed as 0 <nであり、 −1≦z≦1, 0≦d<1, 0≦e<1, M 3+ is a rare earth element, In, Bi, Ga, Al, Sb, Sn, or any of these Including combinations, M' is K, Rb, Cs, or any combination thereof; Me 4+ is Zr 4+ , Hf 4+ , Ti 4+ , Sn 4+ , Th 4+ , Ge 4+ ,or Any combination thereof, Me 2+ is Mg 2+ , Zn 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Yb 2+ ,EU 2 + or any combination thereof, Me 5+ Ta 5+ , Nb 5+ , W 5+ , Sb 5+ , or any combination thereof It is, Me 6+ is W 6+ , Mo 6+ or any combination thereof, 0<=w<=1, 0<=y<=1, 0<=u<0.95, 0<=p<0.95, 0<=q<0.95, 6. The solid electrolyte material according to any one of embodiments 1 to 5, wherein 0<=r<0.95. Embodiment 31.A is (NH4) n (Li (1-d-e), Na (d) M' (e) )2 Li (1-z) Me 3+ (1-u-p-q-r) Me 4+ (u) Me 2+ (p) Me 5+ (q) Me 6+ (r) (Cl (1-y-w) Br (y) I (w) ) (6+u-p+2q+ 3r-z+n) and B is expressed as (Li (1-d’-e’), Na (d’) M' (e’) )2Li (1-z’) Me 3+ (1-u-v-w) Me 4+ (u) Me 2+ (p) Me 5 + (q) Me 6+ (r) (Cl (1-y-w) Br (y) I (w) ) (6+u-p+2q +3r-z’) wherein: 0 <nであり、 For z=1, n=0.33, or 0.5, or 1, or 1.5, or 2, or or 3, or 4, 0≦d<1, 0≦e<1, 0≦d'<1, 0≦e′<1, −1≦z≦1, −1≦z′≦1, M is K, Rb, Cs, or any combination thereof; M 3+ is a rare earth element, In, Bi, Ga, Al, Sb, Sn, or any of these Including combinations, Me 4+ is Zr 4+ , Hf 4+ , Ti 4+ , Sn 4+ , Th 4+ , Ge 4+ ,or Any combination thereof, Me 2+ is Mg 2+ , Zn 2+ , Ca 2+ , Sr 2+ , Ba 2+ , or their respective It is a combination of intentions, Me 5+ Ta 5+ , Nb5+ , W 5+ , Sb 5+ , or any combination thereof It is, Me 6+ is W 6+ , Mo 6+ or any combination thereof, 0<=w<=1, 0<=y<=1, 0<=u<0.95, 0<=p<0.95, 0<=q<0.95, 12. The solid electrolyte material of embodiment 3 or 11, wherein 0<=r<0.95. Embodiment 32. A method for preparing a soluble ammonium hydroxide solution comprising a first phase containing ammonium and a second phase containing B, wherein the second phase The solid electrolyte material according to embodiment 3 or 6, wherein B is the component (B). Embodiment 33. A solid electrolyte according to embodiment 32, wherein the first phase comprises A and no B. quality material. Embodiment 34. A method for preparing a soluble solid solution comprising the steps of: 33. The solid electrolyte material of embodiment 32, comprising different compositions. Embodiment 35. The solid of embodiment 34, wherein the first phase and the third phase constitute A. Electrolyte materials. Embodiment 36. The second phase comprises or consists of Li3REX6, where R E comprises a rare earth element, Zr, or a combination thereof, and X comprises one or more halogens. and optionally an anionic group. Solid electrolyte material. Embodiment 37. The first phase is (NH4)3Li3Me k+ X 6+k or (NH4)3 Me k+ X 3+k wherein Me is a rare earth element, Zr, or a combination thereof. wherein X consists of one or more halogens and optionally an anionic group. 37. The solid electrolyte material according to any one of 32 to 36. Embodiment 38. The first phase is (NH4)3Li3RE k+ X 6+k and the third phase is , (NH4)3RE k+ X 3+k wherein RE is a rare earth element, Zr, or and X is selected from the group consisting of one or more halogens and, optionally, an anionic group. The solid electrolyte material according to any one of embodiments 34 to 37, Embodiment 39. The solid state battery according to any one of embodiments 3 to 38, wherein t≧0.01. solute material. Embodiment 40. The solid electrolytic solution according to any one of embodiments 3 to 39, wherein t≦0.2. quality material. Embodiment 41. At least 0.6 mS / cm, at least 1.2 mS / cm, at least Bulk ionic conductivity of at least 1.8 mS / cm, or at least 2.2 mS / cm 41. The solid electrolyte material according to any one of embodiments 1 to 40, comprising: Embodiment 42. Maximum 8 mS / cm, maximum 7.2 mS / cm, or maximum 6.2 m 42. The method of any one of claims 1 to 41, comprising a bulk ionic conductivity of 0.5 S / cm. Solid electrolyte material. Embodiment 43. At least 0.5 mS / cm, or at least 0.1 mS / cm, or or at least 0.01 mS / cm, or at least 0.001 mS / cm, 43. The solid electrolyte material according to any one of embodiments 1 to 40 and 42, which exhibits electrical conductivity. . Embodiment 44. A solid electrolyte material comprising the solid electrolyte material according to any one of embodiments 1 to 43. electrolyte layer. Embodiment 45: A solid electrolyte material according to any one of embodiments 1 to 43, and optionally and a cathode active material or an anode active material containing an additive for electronic conductivity. Mixed conductive layer with ZnO. Embodiment 46. A solid-state lithium battery comprising the solid electrolyte layer of embodiment 44. Embodiment 47. A solid-state conductive material comprising the mixed electronic and ionic conductive layer of embodiment 45. Lithium battery. Embodiment 48. (NH4) n Me k+ X n+k A process for forming a solid-state electrolyte material, comprising forming (NH4) n Me k+ X n+k Forming Me k+ X k Contains The method involves replacing water in the hydrated salt with NH4X, where Me is a rare earth element, Zr, or combinations thereof, wherein X is one or more halogens and Me is a divalent, trivalent, The process includes tetravalent, tetravalent, pentavalent, hexavalent, or a combination thereof. Embodiment 49. (NH4) n Me k+ X n+k and MX in the solid state. 49. The process of embodiment 48, further comprising: wherein M comprises an alkali metal element. Embodiment 50. (NH4) n Me k+ X n+k further comprising partially decomposing 50. The process of embodiment 48 or 49. Embodiment 51. (NH4) n Me k+ X n+k Partial decomposition of the solid-state reaction 51. The process of embodiment 50, wherein the reaction is carried out simultaneously. Embodiment 52. (NH4) n M 3-z Me k+ X n+k-z further comprising forming 52. The process of any one of embodiments 48 to 51, wherein −3≦z<3. [Example]

[0086] Example 1 Ammonium-containing complex metal halide samples were synthesized according to embodiments of the present invention. The composition and properties of the compounds are included in Table 1. The samples were prepared from pressed dense ceramic pellets. Some samples are polished. The bulk ionic conductivity is measured by a sine wave of 5 to 100 mV. by AC electrochemical impedance spectroscopy using a 3MHz to 10Hz wave voltage amplitude. , a blocking electrode configuration using an Au-plated electrode, and / or a porous graphite anode This is determined in a non-blocking electrode configuration using

[0087] Simple metal halide impurities (e.g., LiX and / or M) present in the sample eX k ) are included in Table 1, and the contents were analyzed using Rietveld refinement and composition for quantitative analysis. The results were determined by combined X-ray diffraction analysis. [Table 1]

[0088] Example 2 Additional samples were prepared. Sample 15 was prepared by dissolving LiBr in a welded quartz ampoule. A stoichiometric mixture of YBr3 and YBr4 was used and heated to a maximum of 650°C under vacuum. After the reaction mixture was melted, a soaking time of up to 1 hour was given at 650°C. The reaction product was then dissolved in the self-fluxing solution. The temperature is rapidly reduced (in 2-3 minutes) to 400°C to allow partial decomposition of the inharmonic Li3YBr6 phase. The temperature of the quartz ampoule was then increased at a rate of 50-100°C / hour. The temperature was gradually lowered to room temperature.

[0089] Samples 16 and 17 were subjected to the same procedures as described herein, optionally retaining residual ammonium. The residual ammonium amount was determined by completely removing the ammonium halide from the charge. The sample was estimated by heating the compound to its melting temperature at which it could be sublimated. The bulk ionic conductivity of the SiO2 was measured in a manner similar to that described in Example 1. Ta. [Table 2]

[0090] Benefits, other advantages, and solutions to problems have been described above with regard to specific embodiments. However, benefits, advantages, solutions to problems, and any benefits, advantages, or Any or all of the features that may cause the solution to occur or become more pronounced should not be construed as a key, essential, or essential feature of the claims As used herein, a material comprising one or more components refers to one or more components that are identified as such. "Consisting essentially of" may be interpreted to include at least one embodiment consisting essentially of. The term "includes identified materials and minor amounts that do not significantly change the properties of the material. "composition" shall be construed to include a composition that excludes all other materials except for the impurity content (e.g., impurity content). Additionally or alternatively, in certain non-limiting embodiments, Any of the compositions described may be essentially free of materials not expressly disclosed. The embodiments herein include ranges of content for certain components within the material, and may be used within a given range. It will be understood that the content of the components within the material totals 100%.

[0091] The specification and illustrations of the embodiments set forth herein are provided to provide a general understanding of the structure of the various embodiments. The specification and examples are intended to provide a thorough understanding of the structures or is a comprehensive and comprehensive description of all elements and features of apparatus and systems that use the method. Separate embodiments may also be combined into a single embodiment. Conversely, for the sake of brevity, the following may be provided in combination in the context of a single embodiment: The various features described herein may also be provided separately or in any subcombination. Further, references to values ​​stated in ranges are inclusive of the stated end-range values. Many other embodiments may be possible after reading this specification. Structural substitutions, logical substitutions, and other variations may be made without departing from the scope of the present disclosure. Other embodiments may be used from this disclosure, such that logical substitutions or other modifications may be made. Accordingly, the present disclosure should be considered illustrative rather than restrictive. is.

Claims

1. A ｔ and B （１－ｔ） wherein 0.01≦t≦0.2, A represents a first phase including the ammonium-containing metal halide, and B represents a second phase including the ammonium-free metal halide, and the ammonium-containing complex metal halide includes at least one alkali metal element and a metal element other than an alkali metal element.

2. 10. The solid electrolyte material of claim 1, wherein the at least one alkali metal element comprises Li, and Li is at least 50 mol% of the at least one alkali metal element.

3. 3. The solid electrolyte material according to claim 1, wherein ammonium is present in an amount of up to 50 mol% relative to the total amount of the at least one alkali metal element and ammonia.

4. A is (NH ４ ) ３ Me ｋ＋ X ｋ＋３ and B is Li ３ Me ｋ＋ X ３＋ｋ where k is the valence of Me, M is at least one alkali metal element, Me includes rare earth elements, Zr, Hf, Ti, Sn, Sb, In, Er, Sc, Bi, Al, Ga, Fe, alkaline earth metal elements, or any combination thereof, X is a halogen including at least one of Cl or Br, and (—NH ２ ), -(NH) ０．５ , -BH ４ , -BF ４ and optional anionic groups selected from:

5. A is (NH ４ ) ３ Li ３ Me ｋ＋ X ６＋ｋ and B is (Li １－ｄ Na ｄ ) ２ LiMe ｋ＋ X ３＋ｋ where 0≦d≦1, k is the valence of Me, M is at least one alkali metal element, Me includes rare earth elements, Zr, Hf, Ti, Sn, Sb, In, Er, Sc, Bi, Al, Ga, Fe, alkaline earth metal elements, or any combination thereof, X is a halogen including at least one of Cl or Br, and (—NH ２ ), -(NH) ０．５ , -BH ４ , -BF ４ and optional anionic groups selected from:

6. A is (NH ４ ) ３ Li ３ YX ９ and B is Li3MeX ６ The solid electrolyte material according to claim 5, represented by:

7. An electrolyte comprising the solid electrolyte material according to claim 1 .

8. A separator comprising a coating disposed on the separator, the coating comprising (NH ４ ) ｎ M ３－ｚ (Me ｋ＋ ) ｆ X ｎ＋３－ｚ＋ｋ＊ｆ wherein 0<n, 0≦z<3, 2≦k≦6, 0<f≦1, X includes a halogen including at least one of Cl or Br, M is at least one alkali metal element including Li, ammonium is up to 50 mol% based on the total amount of M and ammonium, and Me includes a rare earth element, Zr, Hf, Ti, Sn, Sb, In, Al, Ga, Bi, Fe, an alkaline earth metal element, or any combination thereof.

9. 9. The separator of claim 8, wherein Li is at least 50 mole percent of said at least one alkali metal element.

10. The ammonium-containing complex metal halide is (NH ４ ) ｎ Li ３－ｚ (Me ｋ＋ ) ｆ X ｎ＋３－ｚ＋ｋ＊ｆ The separator according to claim 8 or 9, wherein the separator is represented by the formula:

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