Ion conductive material, electrolyte including ion conductive material, and methods of forming the same

Abstract

To provide a solid electrolyte material that provides higher energy density and shorter recharging time and causes less safety concerns.SOLUTION: A solid ion conductive material can include a complex metal halide. The complex metal halide can include at least one alkali metal element. In an embodiment, the solid ion conductive material including the complex metal halide can be a single crystal. In another embodiment, the ion conductive material including the complex metal halide is a crystalline material having a particular crystallographic orientation. A solid electrolyte includes the ion conductive material including the complex metal halide.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] Technical Field The following relates to a solid ion conductive material, an electrolyte containing the ion conductive material, and a method for forming the same and, in particular, to a solid ion conductive material containing a composite metal halide, an electrolyte containing the same and a method for forming the same.

Background Art

[0002] Background Art Solid lithium batteries are expected to have a higher energy density, a shorter charging time, and less concern about safety than conventional lithium ion batteries by using lithium metal as the negative electrode Currently, existing solid electrolyte materials include oxides, halides, sulfides, fluorides, solid polymer electrolytes, and the like.

[0003] Oxide-based materials are considered to be highly safe and have good chemical and electrochemical stability In general, high temperatures exceeding 1000 - 1200 °C are used for the synthesis of these compounds Oxide-based materials are generally dense, hard, and brittle, and the ionic conductivity at room temperature is at most 1.0 mS / cm (IC RT ).

[0004] Halide compounds such as chlorides and bromides are generally safe and have good chemical and electrochemical stability, deformability, plasticity, and relatively high compatibility with electrode active materials Among the Li3YCl6 (LYC) and Li3YBr6 (LYB) electrolytes, there are those showing an ionic conductivity IC of 1 mS / cm or more at room temperature RT Halides are generally hygroscopic and form hydrates or undergo hydrolysis when exposed to moisture. LYC and LYB Halide-based solid electrolytes such as are synthesized by a solid-state synthesis method using high-energy ball milling. However, since expensive binary halide reactants and high-temperature annealing are used, there are problems in mass production.

[0005] Fluorides are very similar to oxides in terms of physical, chemical, and electrochemical properties, but generally, the value of IC RT is less than 1 mS / cm.

[0006] Sulfides have relatively high ionic conductivity. For example, IC RT is as high as 25 mS / cm, and commercially relevant sulfide or thiophosphate solid electrolytes can achieve 2 - 10 mS / cm. Sulfide-based materials are mechanically soft and prone to deformation. However, sulfide materials tend to have low electrochemical stability and have a risk of reacting accidentally with water and heat to release toxic H2S gas, so there are safety concerns. Also, high-surface-area sulfide solid electrolyte powders are highly reactive even under humidity, so the risk of H2S is particularly high.

[0007] Generally, solid polymer electrolytes containing lithium salts have relatively low ICRT values and electrochemical stability.

[0008] In the industry, improvements in solid electrolyte materials are continuously demanded.

Brief Description of the Drawings

[0009] Brief Description of the Drawings This disclosure can be better understood and its numerous features and advantages can be made apparent to those skilled in the art by referring to the accompanying drawings.

Figure 1

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[0010] Skilled artisans will appreciate that elements in the figures are illustrated for simplicity and clarity and are not necessarily drawn to scale. It will be understood that the drawings are not drawn to scale. For example, the dimensions of some elements in the drawings are not necessarily accurate to the scope of the present invention. To facilitate understanding of the embodiments, the dimensions of certain elements may be exaggerated relative to other elements. The use of the same reference numbers indicates similar or identical items. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Detailed Description of the Preferred Embodiment The following description in conjunction with the figures is intended to aid in understanding the teachings disclosed herein. The following discussion focuses on specific implementations and embodiments of the present teachings. The focus is provided to help explain the teachings and not to limit the scope or applicability of the teachings. should not be construed as a

[0012] As used herein, the terms "comprise," "include," "includes," "having," " "having," "including," or other variations thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that contains a list of features does not necessarily include those features. This includes, but is not limited to, any other features or such features not expressly listed. It may include features specific to a process, method, article, or apparatus. Unless expressly stated to the contrary, "or" shall mean an inclusive "or" and not an exclusive "or." For example, condition A or B can be satisfied by one of the following: For example, condition A or B can be expressed as: A is true (or exists), B is false (or does not exist), A is false (or does not exist), B is true (or exists), A and B are both true (or exist) It is fulfilled by one of two things.

[0013] The use of "a" or "one" describes elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This specification, unless otherwise clear, refers to one or more shall be read to include at least one, and the singular shall include the plural and vice versa. The same is true.

[0014] Unless otherwise defined, all technical and scientific terms used herein are within the meaning of the present invention. has the same meaning as commonly understood by a person of ordinary skill in the art to which it pertains. The materials, methods, and examples are illustrative only and are not intended to be limiting.

[0015] Embodiments herein relate to solid, ionically conductive materials including complex metal halides, The group can include at least one alkali metal element. In one embodiment, the solid ion The ion conducting material may include a dopant that includes ammonium. , Solid ionic conductive materials can include crystalline materials, and in certain embodiments, oriented crystalline materials such as single crystals or oriented ceramics having a specific crystallographic orientation. The solid ionic conductive material can include an oriented crystalline material such as a single crystal or an oriented ceramic having a specific crystallographic orientation. The solid ionic conductive material can have improved properties such as purity, bulk ionic conductivity, electrochemical stability, or any combination thereof compared to conventional metal halide materials. In embodiments, the solid ionic conductive material can be used to form an electrolyte, an anode, and / or a cathode, or another component of an electrochemical device. In certain embodiments, the solid ionic conductive material can be a suitable component of a solid lithium battery.

[0016] Embodiments relate to a method of forming an ionic conductive material. The method can enable the formation of an ionic conductive material having improved properties such as purity, ionic conductivity, electrochemical stability, or a combination thereof. The method can also enable the improvement of the formation of the ionic conductive material. The method can be suitable for mass-producing ionic conductive materials in a cost-effective manner. Referring to FIG. 1, a process for forming a solid ionic conductive material 100 is shown.

[0017] Process 100 is different from conventional solid syntheses for forming complex metal halides. Conventional processes utilize high-energy ball milling or directly heat a reactant mixture (e.g., a simple metal halide) at a temperature near or below the melting point of the metal halide to perform a solid-state reaction. The individually separated particles in the mixture react

[0018] differently from those in Process 100. Conventional processes utilize high-energy ball milling or directly heat a reactant mixture (e.g., a simple metal halide) at a temperature near or below the melting point of the metal halide to perform a solid-state reaction. The individually separated particles in the mixture react differently from those in Process 100. As the reaction progresses, the probability of reaction decreases, so theoretically, it would take infinite time to complete 100.00% of the reaction. For this reason, the reaction products obtained by conventional high-energy ball milling solid synthesis have high impurity concentrations because the reactions of simple metal halides (e.g., lithium halide and / or yttrium halide) are incomplete.

[0019] Furthermore, it should be noted that the conventional synthesis of composite halides based on the ammonium-halide route may not be applicable to the formation of composite metal halides. Metal halides have been conventionally used as starting materials. Trivalent and tetravalent metal halides, especially rare-earth metal halides, tend to form stable metal halide hydrates, and it may be difficult to completely remove water molecules from the hydrates. Therefore, trivalent metal halides are used as starting materials. When the temperature is increased, unwanted metal oxyhalides and metal oxy halide compounds of hydrates may be produced at high concentrations. Furthermore, metal halide hydrates and metal oxyhalides, especially those containing rare-earth metals, are rather stable compounds and are less likely to form high-concentration complex compound phases containing Li such as Li3RE(OX)Cl3, where X is a halogen other than Cl. Also, such

[0020] complex compounds are not stable and are likely to decompose into simple compounds.

[0021] Process 100 may start at block 102. A reaction mixture containing starting materials is formed It may be formed. In an embodiment, the starting material is ammonium halide, NH4X and can include X which includes Cl, Br, I, F, or any combination thereof. The starting material can further include one or more metal compounds, and the metal can include an alkali element, an alka line earth element, a transition metal element, a lanthanide, a rare earth element, or any combination thereof.

[0022] In certain embodiments, the metal compound may be non-hygroscopic. In one aspect, the metal compound can include the metal in the form of an oxide, carbonate, sulfate, hydrate, hydroxide, oxalate, acetate, nitrate, or any combination thereof. In a particular aspect, the starting material can include one or more metal oxides. For example, the starting material can include Me 2O where Me can be a divalent metal, trivalent metal, tetravalent metal, pentavalent k metal, or hexavalent metal; k is the valence of the metal; and 2 ≦ k ≦ 6 can be the case. In a particular example, Me can include rare earth elements such as Ce, Dy, Er, Eu, Gd, Ho, La, L u, Nd, Pr, Pm, Sm, Sc, Tb, Tm, Yb, Sc, and Y, In, Zn, alkali metal elements, Hf, Zr, or any combination thereof. In a more specific example, the starting material can include one or more of rare earth oxides or hydroxides or carbonates, ZrO2 or Zr(OH)4 or Zr(CO3)2 or Zr(OH)2 CO3·ZrO2 or any combination thereof. In another aspect, the starting material is lithium carbonate, sodium carbonate, cesium carbonate, or the

[0023] like. ​​It can contain an alkali metal compound such as these combinations. The starting material is an aqueous solution, an alcohol, or an acid can be further included to promote acid synthesis in other polar molecular liquid solutions. It can contain.

[0024] In another specific example, the metal compound can contain an alkali metal compound. For example, the starting material can contain an alkali metal halide (e.g., NaCl, CsCl, and LiCl) and can not contain a compound containing Me.

[0025] In an embodiment, the starting materials can be mixed in a stoichiometric ratio. In other embodiments, the ratio between the starting materials can enable the formation of a non-stoichiometric complex metal halide. It can.

[0026] In an exemplary embodiment, a reaction mixture containing NH4X, one or more rare earth metal oxides (hereinafter referred to as "RE2 O3"), lithium carbonate, and hydrochloric acid or hydrobromic acid can be formed. The starting substances and reaction products in an aqueous solution are described below, and an example of the reaction is shown. 3 * Li2CO3 + RE2O3 + 12 * HX + 6 * NH4X ---> 2 * (NH4)3REX6 + 6 * LiX + 6 * H2O + 3 * CO2

[0027] The above reaction is an example intended to assist in the understanding of Process 100. From the perspective of the present application, those skilled in the art will understand that another alkali metal compound such as Na2CO3 or NaCl can be used as a starting substance. Similarly, oxides of non-rare earth elements, such as Fe2 O3, O3 may be added to the reaction. One skilled in the art will further understand that if the starting materials change, the reaction products may change accordingly.

[0028] In certain embodiments, Process 100 can include chemically substituting the water (i.e., water) in the hydrated salt containing MeX with NH4X. In one aspect, the process can include forming (NH4) k Me X (where n > 0; and 2 ≦ k < 6). In certain embodiments, 0 < n ≦ 3. In certain examples, n can be 0.33, 0.5, 1, 1.5, 2, 3, or 4, depending on what Me is. In the above-exemplified reaction, hydrated rare earth halides may be formed as intermediate products, and the water in the hydrate may be replaced with NH4X to form the advantageous non-hydrate compound ( n k+ n+k NH4)3REX6, allowing the operation and maintenance of a hydroxide-free halide phase. As further exemplified, alkali metal halides such as LiX may also be formed.

[0029] In one example, the mixture of reaction products may be filtered to remove larger particles to facilitate subsequent reactions in the solid state. Larger particles may include impurities associated with any of the starting materials, residual particles of the starting materials, carbon, or any combination thereof.

[0030] Process 100 can continue to block 104. In embodiments, the mixture of reaction products is (NH4) Me n k+ X n+k and an alkali metal halide, MX ( Here, M can be dried to promote the solid reaction of the alkali metal element). Drying can be carried out in air or dry air and / or under vacuum or reduced pressure, for example, 100 mba r, 40 mbar, 1 mbar, or 0.01 mbar. In some examples, an N2 or Ar flow may be used to facilitate the removal of moisture. In other examples, heat may be applied to assist in the evaporation of water. The heating temperature can be 100 °C to 160 °C. Drying may be carried out until a trace amount of water, for example, 1 wt% to 3 wt%, remains in the mixture.

[0031] In an embodiment, process 100 may include performing a solid reaction of (NH4) n Me k+ X n+k and MX. In a specific example, a solid reaction of (NH4)3R EX6 and LiX can be performed from the above reaction product. In another embodiment, process 100 may include forming (NH4) 100 may include forming (NH4) n M 3-z Me k+ X 3+n+k-z where -3 ≦ z < 3. When z = 0, (NH4) 100 may include forming (NH4) n M 3-z Me k+ X 3+n+k -z is stoichiometric. When z is not 0, (NH4) n M 3-z Me k+ X 3+n +k-z is non - stoichiometric. In a specific example, 0 ≦ z < 1. In a further example, process 100 is M 3-z (Me k+ ) f X 3-z+k*fmay include forming, where -3 ≤ z < 3; 2 ≤ k < 6; 0 ≤ f ≤ 1.

[0032] Process 100 can continue to block 106. In an embodiment, forming an ion-conductive material can include decomposing an ammonium halide. In one aspect, the decomposition can include separating a composite metal halide phase from an ammonium halide phase. In another aspect, forming an ion-conductive material can further include desorbing the ammonium halide.

[0033] In one aspect, the decomposition can be performed in a crucible made of a material inert to the reactants and products. For example, the crucible can be made of quartz, alumina, silica-alumina, BN, glassy carbon, or graphite. In certain embodiments, the graphite can have a coating of pyrolytic carbon.

[0034] In another aspect, the decomposition can be performed in a dry, neutral atmosphere such as air or dry air. An inert gas such as N2 or Ar can be used to facilitate the process.

[0035] In a further aspect, the decomposition can be performed for at least 15 minutes to a maximum of 24 hours. In one aspect, the solid solution can be heated to a temperature in the range of 350°C to 800°C to allow partial or complete sublimation of the ammonium halide. In some aspects, the sublimation of NH4X can be monitored by collecting and weighing the escaped NH4X that condenses on the opposite side.

[0036] ​​​In a further aspect, at least 60 wt%, at least 80 wt%, or at least 90 wt% of the ammonium halide may be removed by sublimation, compared to the weight of the initially added ammonium halide. In a further aspect, aluminum halide may be essentially removed by sublimation. In another aspect, sublimation may be performed such that the remaining ammonium halide is contained by an ion conductive material.

[0037] In another aspect, the decomposition of the ammonium-containing complex metal halide serves to remove reaction products other than the complex metal halide from the solid solution. For example, water, CO2, ammonia, and halogens can be evaporated.

[0038] Alternatively, the starting materials may be heated at a higher temperature so that the ammonium-containing complex metal halide is formed in one step. An exemplary one-step reaction is shown below. 3 * Li2CO3 + RE2O3 + 18 * NH4Br ----> 2 * (NH4)3Li3REBr9 + 6 * H2O + 3 * CO2 + 12 * NH3.

[0039] In particular, heating can be performed such that the decomposition of ammonium and the solid-phase reaction can be carried out simultaneously. For example, the heating temperature can be in the range of 250 °C to 650 °C or up to 800 °C to enable the formation of a solid solution and the sublimation of ammonium halide. It has been pointed out that when using one-step synthesis to form complex metal halides, a relatively high content of oxyhalides may be produced. ​​​​​​​​​​​​

[0040] In another embodiment, process 100 can include forming an ion conductive material comprising a composite metal halide. In one aspect, the composite metal halide can be represented by M 3- z Me k+ X 3-z+k In another aspect, the composite metal halide can be represented by M 3-z (Me k+ ) f X 3-z+k*f where 0 ≦ f ≦ 1.

[0041] In some embodiments, cooling may be performed after decomposition. For example, the cooling may be performed in air, dry air, or a nitrogen atmosphere. In another example, the cooling temperature may be 200 °C or less, such as at most 100 °C, at most 70 °C, at most 50 °C, or at most 30 °C. In certain embodiments, the cooling can be performed in a dry atmosphere at room temperature (e.g., 20 - 25 °C). Optionally, Ar or N2 can be used to facilitate the cooling.

[0042] In another aspect, the ion conductive material comprising the composite metal halide may be formed after cooling.

[0043] In embodiments, the composite metal halide can be formed to include a specific amount of residual ammonium halide. In at least one example, the ion conductive material is at least 2 ppm ammonium halide, such as at least 10 ppm, at least 100 ppm, at least 300 ppm, at least 500 ppm, at least 0.2 wt%, at least 0.5 wt%, or at least with respect to the total weight of the composite metal halide. at least 0.2 wt%, at least 0.5 wt%, or at least ​It can contain at least 1 wt% of ammonium halide. In another example, the ionic conductivity material can contain up to 5 wt%, for example up to 3 wt% of ammonium halide, based on the weight of the composite metal halide. The composite metal halide can contain a residual ammonium halide content within a range including either the minimum or maximum value described herein. It will be understood that in at least one example, the composite metal halide may be essentially free of ammonium halide.

[0044] In an embodiment, the ionic conductive material may be in the form of a powder containing particles of the composite metal halide. In one aspect, the powder can have an average particle size (D50) of at least 0.1 micron, such as at least 0.3 micron, at least 0.5 micron, or at least 1 micron. In another aspect, the average particle diameter can be up to 1 mm, up to 800 microns, up to 500 microns, up to 200 microns, up to 100 mic rons, up to 50 microns, up to 10 microns, up to 5 microns, or up to 1 micron In a particular aspect, the powder may contain particles having an average particle diameter within a range including either the minimum or maximum value described herein. In another aspect, the powder may contain agglomerated particles.

[0045] In a further aspect, the particles can have a specific shape that can promote improved formation and performance of the electrolyte and / or the electrode. For example, the particles can be spherical or elongated. In another example, the particles can have the shape of rods, flakes, or needles. It can be done. The shape of the particles can be selected according to the two-dimensional or one-dimensional anisotropy of the ionic conductivity of the composite metal halide.

[0046] In another aspect, the powder can include particles having a specific average aspect ratio of length:width to facilitate the formation of electrolytes and / or electrodes having improved ionic conductivity . In one example, the average aspect ratio can be at least 1, such as at least 1.2, at least 1.5, at least 2, at least 2.3, at least 2.5, at least 2.8, and can be at least 3. In another example, the average aspect ratio can be at most 30, at most 25, at most 22, at most 20, at most 15, at most 12, at most 10, at most 8, at most 5, or at most 4. Furthermore, the particles can have an average aspect ratio within the range including any of the minimum and maximum values described herein.

[0047] In embodiments, the ionic conductive material can contain certain impurities at relatively low contents. The impurities can include simple metal halides containing Me k+ X k , such as rare earth halides, alkali halides such as LiCl and / or NaCl, M3N, and Me metal nitrides such as N x N y , or any combination thereof. The coefficients x and y are the respective valences of N and Me for the neutrally charged Me x N y . In a further example, the impurities can include amide (NH2), imide (NH), hydroxide (OH), ammonia (NH3), or any combination thereof.

[0048] In an embodiment, the complex metal halide is M 3-z (Me k+ ) f X 3-z+k* f where -3≦z≦3; 2≦k<6; and 0≦f≦1. In certain embodiments, f is not zero. In certain embodiments, z<3. In this embodiment, when f=0, z may not be 3. M includes an alkali metal element. Me is a divalent metal element, a trivalent metal element, a tetravalent metal element, a pentavalent metal element, , hexavalent metallic elements, or any combination thereof; and X is halovalent metallic element. It may contain aldehydes.

[0049] In another embodiment, the complex metal halide is M 3-z Me k+ X 3-z+k Expressed as where -3≦z≦3; M can include an alkali metal element; M can be a divalent metal elements, trivalent metal elements, tetravalent metal elements, pentavalent metal elements, hexavalent metal elements or any of these and X can include a halogen. In this case, z<3.

[0050] In one aspect, M is one or more alkali metals including Li, Na, Cs, and Rb. In a further embodiment, M can include Li. For example, M can include Li. In another embodiment, M can include Li and another arsenic. For example, M can be Li and any one of Na, Cs, and Rb. In another example, M can include at least one of Li and Na, Cs, and It can include at least one of Rb. In a more specific example, M can include a combination of Li and Na. In another aspect, M can include Na, or a combination of Na and at least one of Cs and Rb. In another example, M can include at least one of Na and Cs.

[0051] In a specific embodiment, Na can constitute up to 40 mol% of M, for example up to 34 mol% of M, for example, M can contain 0 mol% to 40 mol% of Na. In a specific example, M can contain up to 20 mol% of Na, more specifically up to 10 mol% of Na. In at least one example, Na can constitute from 40 mol% to 100 mol% of M.

[0052] In a further specific embodiment, Li can constitute at least 50 mol% or at least 60 mol% or at least 66 mol% or at least 75 mol% of M, and in a specific example, M can contain 60 mol% to 100 mol% of Li.

[0053] In another example, Cs can occupy at least 25 mol% of M, for example at least 30 mol% of M, at least 40 mol%, or at least 50 mol%, and in another example, Cs can occupy up to 50 mol% or up to 40 mol% or up to 30 mol% or up to 20 mol% or up to 10 mol% of M, and in a specific example, Cs can occupy up to 1 mol% of M.

[0054] In an embodiment, the composite metal halide is (Li 1-d ,Nad )2Li 1-z M e k+ X 3+k-z , where 0 <d<1;-0.95≦z≦0.95;Meは、2価金 metal elements, trivalent metal elements, tetravalent metal elements, pentavalent metal elements, hexavalent metal elements, or any of these elements and X may include a halogen.

[0055] In an embodiment, (Li 1-d-e ,Na d ,M' e )2Li 1-z’ (Me k+ ) f X 3+k*f-z The complex metal halides represented by the formula: 0≦d≦1; 0≦e<1; -3≦z '≦3; 2≦k<6; 0≦f≦1; M' contains at least one of K, Rb, and Cs and Me are divalent, trivalent, tetravalent, and pentavalent metal elements. cations, ... X comprises at least a halogen. In certain aspects, z'<3. In this case, d+e>0. In a specific aspect, f is not 0. In a more specific aspect, e= 0 and d is not zero.

[0056] In some aspects, d is at least 0.01, or at least 0.05, or at least In another embodiment, d is at most 0.8 or at most 0.2. In certain embodiments, d includes any of the minimum and maximum values. Can be in range.

[0057] In some aspects, e is at least 0.01, or at least 0.05, or at least It may be 0.1 or at least 0.2. In another embodiment, e may be at most 0.8 or at most 0.5. In certain embodiments, e can be in a range that includes either the minimum or maximum value.

[0058] In an embodiment, the composite metal halide represented by Li 3-z Me k+ X 3-z+k has -0.95 ≦ z < 0.95, Me can 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; and X can include a halogen.

[0059] In one embodiment, z can be at most 0.5, such as at most 0.3 or at most 0.2. In another embodiment, z can be at least -0.5 or at least -0.2. In certain examples, z can be in a range that includes either the minimum or maximum value indicated herein. When z is not 0, the composite metal halide can be non-stoichiometric. When z is 0, the composite metal halide can be stoichiometric.

[0060] Exemplary divalent metal elements can include alkaline earth elements such as Mg and / or Ca, Zn, or any combination thereof. In certain embodiments, Me can include Zn, Ca, or any combination thereof. In certain embodiments, ions with relatively small radii such as Zn and Mg may be particularly suitable when the halogen includes or consists of Cl, and ions with relatively large radii such as Ca ​​​​​​​​​​​​​On may be particularly suitable when the halogen contains Br or contains Br. Another special In certain embodiments, including substitution ions having a radius larger than the base ion may help to expand the ion conduction channels in the electrolyte material. For example, Me can include Ca and Y, and Ca can be suitable for partially substituting Y In another embodiment, divalent elements having a relatively light weight such as Mg, Zn, and Ca may be preferred. In certain embodiments, substituting Y with Sr or Ba may result in the formation of compounds of SrX2 or BaX2, which can be impurities that affect the bulk ion conductivity of the complex metal halide.

[0061] Exemplary trivalent metal elements can include rare earth elements, trivalent metals other than rare earth elements, such as In, Ga, Al, or Bi, or any combination thereof. In a specific example Me can include Sc, Y, La, Gd, or any combination thereof. In a more specific example, Me can include Y, Gd, or a combination thereof.

[0062] Exemplary tetravalent metal elements can include Zr, Hf, Ti, Sn, Ge, Th, or any combination thereof. In a specific example, Me can include Zr and Hf In another specific example, Me can include Zr.

[0063] Exemplary pentavalent elements can include Ta, Nb, W, Sb, or any combination thereof and the like can be included.

[0064] In one aspect, Me is a rare earth element, an alkaline earth metal element, a 3d transition metal, Zn , Zr, Hf, Ti, Sn, Th, Ge, Ta, Nb, Mo, W, Sb, In, Bi, S c, Yb, Al, Ga, Fe or any combination thereof can be included.

[0065] In a further aspect, Me can include rare earth elements, Zr, or any combination thereof.

[0066] In another aspect, Me can include Y, Ce, Gd, Er, Zr, La, Yb, In, Mg, Zn , or any combination thereof.

[0067] When Me contains a plurality of metal elements, k can be the average value of the sum of the valences of each Me metal element. For example, when Me contains equimolar amounts of a trivalent element and a tetravalent element, k = (3 +4) / 2 = 3.5 can be taken. In certain embodiments, k can be 3 or 4 or 5.

[0068] In a further aspect, Me includes rare earth elements containing Y, Gd, La, and / or Sc, alkaline earth metal elements, 3d transition metals, Zn, Zr, Hf, Ti, Sn, Th, Ta , Nb, Mo, W, Sb, In, Bi, Al, Ga, Ge or any combination thereof. In a specific example, Me can include Y, Gd, Zr, or any combination thereof. In a specific example, Me can include Y partially substituted by another Me element. For example, Y can be substituted by a specific content of another Me element that can promote the improved crystal structure and properties of the complex metal halide. In a specific example, Me can include up to 70 mol% of Y and 5 mol% - 30 mol ​​​​It can contain a replacement Me element of %. In a further example, Y is a composite metal halide It may be partially replaced by a Me element having an appropriate effective ionic radius that can enable the formation of a stable phase of In a specific example, the Me element is smaller than the effective ionic radius of La of 103.2 Å and has an ionic radius at least similar to the effective ionic radius of Li of 0.76 Å and may also have an effective ionic radius of 0.76 Å ± 5% to 93.5 Å ± 5% in a more specific example. In a specific embodiment, Me can be composed of Gd, Y, Ce, Er, Zr, Yb, or any combination thereof. For example, Me can consist of Y In another example, Me can consist of Y and at least one of Ce, Er, Zr, and Gd

[0069] In a further example, Me contains Yb and Ce. In another example, Me can consist of two or more of In Y, Zr, Hf, Sc, Zn, and Mg. In one aspect, X can contain at least one of Cl, Br, I, and F For example, X can contain Cl or Br, and in another example, X can contain F In another example, X can contain at least two of Cl, Br, and I, and in yet another example, X can contain all of Cl, Br, and I

[0070] In one aspect, X can contain elements other than halogens. In some embodiments X can contain an anion group in addition to halogens. Such an anion group can be an amide (-NH2), -(NH) (imide), hydroxide (-OH), -BF

[0071] 0.5 0.5 (imide), hydroxide (-OH), -BF 0.5 (imide), hydroxide (-OH), -BF 4. It can contain -BH4 (borohydride), or combinations thereof. Anionic groups may be included as impurities or dopants.

[0072] In certain aspects, X can be at least one of F, Cl, Br, and I, and optionally -NH2 (amide), -(NH) 0.5 (imide), -OH (hydroxide), -BH 4 (borohydride), -BF4 group, or anionic groups containing any combination thereof. For example, X can contain one or both of Cl and Br, and at least one anionic group. In a further example, X can contain F and at least one anionic group. In at least one embodiment, X can be one or more halogens.

[0073] In a particular example, M is Li, Me is a combination of In, Mg, Zr, and Sc, and X can be Cl or a combination of Cl and anionic groups.

[0074] In another particular example, M is Li, Me is Y, Zr, and Hf, and X can be Cl or a combination of Cl and anionic groups.

[0075] In another particular example, M is Na, Me is Zr, and X can be Cl or a combination of Cl and anionic groups.

[0076] In certain embodiments, the complex metal halide is (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) is represented by 0≦d≦1, 0≦e<1; -3≦z≦3; M’ contains at least one of K, Rb, Cs, and M 3+ is a rare earth element, In, Bi, Sc, Y, Al, Ga, or any combination thereof; Me 4+ is Zr 4+ , Hf 4+ , Ti 4+ , Sn 4+ , Th 4+ , Ge 4+ or any combination thereof. Me is Mg 2+ is Mg 2+ , Zn 2+ , Ca 2+ , Yb 2+ , Eu 2+ or any combination thereof; Me is Ta 5+ is Ta 5+ , Nb 5+ , W 5+ , Sb 5+ or any combination thereof; Me is W 6+ is W 6+ , Mo 6+ or any combination thereof; 0<=w<=1; 0<=y<=1; -0.95<z<0.9 5; 0<=u<0.95; 0<=p<0.95; 0<=q<0.95; and 0<=r< 5; 0<=u<0.95; 0<=p<0.95; 0<=q<0.95; and 0<=r< 0.95.

[0077] In a particular aspect, M 3+ is Y 3+ , Gd 3+, In 3+ , Er 3+ , Sc 3+ , or any combination thereof. In a more specific aspect, M 3+ is Y 3 + , Gd 3+ , In 3+ , Er 3+ , Sc 3+ , or can be composed of any combination thereof.

[0078] In a particular aspect, M 4+ is Zr 4+ , Hf 4+ , Ce 4+ , or a combination thereof. In a more specific aspect, M is Zr 4+ , Hf 4+ , Ce 4+ , 4+ , or a combination thereof.

[0079] In another particular aspect, any one or more of p, q, r, and u can be 0 , and in a more specific aspect, all of p, q, r, and u can be 0.

[0080] In a particular embodiment, k can be 2 or 3 or 4 or 5.

[0081] In another particular embodiment, the complex metal halide is (Li (1-d), Na (d) ) 2Li (1-z) RE (1-u) Zr 4+ (u) (Cl (1-y) Br (y))(6+u -z ), where 0 < d < 1; 0 < z < 0.95; and 0 <= u < 0.95. ​It is. In one example, d is at least 0.0001, at least 0.001, at least 0. 005, at least 0.008, at least 0.01, at least 0.02, at least 0.03, at least 0.05, or at least 0.06. In a further example d can be at most 0.5, at most 0.3, at most 0.2, at most 0.1, at most 0.08, at most 0. 06, at most 0.05, at most 0.04, or at most 0.03. In a further example , d may be within a range including any of the minimum and maximum values pointed out in this specification. For example, 0 < d < 0.05. In a further example, z is at least 0.02, at least 0.03, at least 0.05, at least 0.07, at least 0.09, at least 0.1, at least 0.15, at least 0.18, or at least 0.2 can be. In another example, z can be at most 0.5, at most 0.4, at most 0.38, at most 0.3 5, at most 0.33, at most 0.3, at most 0.28, at most 0.25, at most 0.23, or at most 0.2. Further, z can be within a range including any of the minimum and maximum values pointed out in this specification. For example, 0 < z < 0.2. In another example, u is at least 0.01, at least 0.03, at least 0.05, at least 0.07, at least 0.09, at least 0.1, at least 0.13, at least 0.15, at least 0.18, at least 0.2, at least 0.22, at least 0.25 or at least 0.3 may be. In another example, u is at most 0.8, at most 0.78, at most 0 .75, at most 0.73, at most 0.7, at most 0.68, at most 0.65, at most 0.63, or at most 0.6 may be. Further, u is the minimum and maximum values pointed out in this specification It can be in a range including any of them. For example, 0.2 < u < 0.6.

[0082] In certain embodiments, the composite metal halide may be doped with a dopant. In particular In certain examples, Li may be partially substituted by a dopant. In more specific examples the dopant can include ammonium, such as ammonium halide NH4X, where X can be Cl, Br, I, F, or any combination thereof.

[0083] In one aspect, the composite metal halide can include up to 20 wt%, such as up to 15 wt%, up to 10 wt%, up to 8 wt%, up to 5 wt%, or up to 3 wt% of ammonium halide, based on the total weight of the composite metal halide. In another aspect, the ammonium halide can be present in the ionic conductive material in an amount of at least 10 ppm, such as at least 100 ppm, at least 500 ppm, at least 0.1 wt%, at least 0.3 wt%, at least 0.5 wt%, at least 0.8 wt%, or at least 1 wt%, based on the mass of ammonium halide relative to the total weight of the composite metal halide. Furthermore, the composite metal halide can include ammonium halide in a content within a range including any of the minimum and maximum values described herein.

[0084] Referring to FIG. 2, an exemplary process 200 for forming a solid ionic conductive material is illustrated. Process 200 is exemplified by blocks 102, 104, and 106 of FIG. 1 and can include steps similar to those described in the embodiments with respect to process 100. ​​​​​​​

[0085] After obtaining the composite metal halide in block 106, process 200 can continue to block 208. In an embodiment, process 200 can include forming a solid ion conductive material including a single crystal material including the composite metal halide. In one aspect, crystal growth can be performed in a crucible made of a material inert to the composite metal halide. For example, the crucible can be made of quartz, alumina, silica-alumina, BN, vitreous carbon, or graphite. In certain embodiments, the graphite can have a coating of pyrolytic carbon.

[0086] The composite metal halide obtained by process 100 can be used directly as a charge for forming a single crystal. In one aspect, process 200 can include partially or completely melting the complex metal ha logenide. In some aspects, a dopant material such as a metal compound can be added to the melt to facilitate substitution of one or more metal elements of the composite metal halide.

[0087] In a further aspect, process 200 can include a specific crystal growth rate that can facilitate the growth of a single crystal having a macroscopic size such as a single crystal block up to 10 centimeters. For example, the growth rate can be at least 0.2 mm / hour, at least 0. 3 mm / hour, or at least 0.5 mm / hour. In another example, the growth rate can be at most 10 mm / hour, such as at most 8 mm / hour, at most 6 mm / hour, at most 5 mm / hour, at most 3 mm / hour, or at most 1 mm / hour. In a specific example, ​ and the growth rate is in a range including either the minimum value or the maximum value described in this specification is possible.

[0088] In another aspect, process 200 can include cooling the melt. In certain aspects, the cooling can be carried out in a controlled manner to assist in the formation of single crystals having complex metal halides. In certain aspects, the cooling can be facilitated by an external heat field having a cooling rate of 10 °C / hour to 5 0 °C / hour. In another specific example, the starting material of the complex metal halide may form a melting phase inconsistent due to the presence of impurities such as simple metal halides. In those examples, the melt can contain a non-stoichiometric mixture containing an excess amount of complex metal halide and dopant material to promote the formation of stoichiometric single-phase crystals under self-flux conditions.

[0089] The single crystal can be formed by process 100 and can have the same composition as the complex metal halide described in the embodiments of this specification.

[0090] The single crystal can be a small lump on the order of several millimeters, or a dense block or large ingot with a size of several tens of centimeters.

[0091] In embodiments, the ingot or block may be polished to remove any visible impurities and / or parasitic phases if present.

[0092] In a further embodiment, the single crystal may be crushed to form a fine powder having single crystal particles. In an exemplary application, the single crystal particles are ions in an electrochemical device ​​​​​​​​​It may be used to form the ion-conductive component. In another embodiment, a single crystal ingot or block may be sliced into thin sheets. For example, the thin sheet may have a thickness of 5 microns rons to 500 microns.

[0093] In certain embodiments, process 200 may include forming a single crystal having a specific crystallographic orientation. In one aspect, the oriented growth of a single crystal can be carried out. In a particular aspect, the oriented crystal growth can be carried out for anisotropic crystals. In an exemplary embodiment, the crystallization of pellets or particles elongated in a crystallographic direction having higher conductivity can be carried out. In another example, a high temperature gradient such as 10 °C / cm or more can be applied to promote the oriented growth of a single crystal. In a further example, an X-ray goniometer can be used to specify the orientation of the crystal. In another aspect, for crystals having anisotropy in permeability or permittivity, the oriented crystal growth can be carried out using a strong permanent magnetic field, solidification under a strong electric field, or any combination thereof. In yet another aspect a support seed layer having a lattice constant close to that of the oriented ceramic material can be utilized, and an oriented polycrystalline structure may be maintained by solidifying in a flux medium. In another aspect, the single crystal can be sliced such that the crystallographic direction having higher conductivity is in the thickness direction of the thin sheet. In certain embodiments, the ion-conductive material is In another aspect, the oriented crystal growth can be carried out using a strong permanent magnetic field, solidification under a strong electric field, or any combination thereof. In yet another aspect a support seed layer having a lattice constant close to that of the oriented ceramic material can be utilized, and an oriented polycrystalline structure may be maintained by solidifying in a flux medium. In another aspect, the single crystal can be sliced such that the crystallographic direction having higher conductivity is in the thickness direction of the thin sheet.

[0094] In another aspect, the single crystal can be sliced such that the crystallographic direction having higher conductivity is in the thickness direction of the thin sheet. In another aspect, the single crystal can be sliced such that the crystallographic direction having higher conductivity is in the thickness direction of the thin sheet.

[0095] In certain embodiments, the ion-conductive material is <hkl>or <hklm>represented by and may include an oriented crystal material such as a single crystal material having a crystallographic orientation, <hkl>Or <HK The ionic conductivity in the crystallographic orientation of LM> is higher than the ionic conductivity in different crystallographic orientations in which the single crystal can be oriented.

[0096] For example, Li3YBr6 has a higher ionic conductivity in the crystallographic orientation <100> compared to <001>. A Li3YBr6 single crystal having the crystallographic orientation <100> may be formed to have a higher bulk ionic conductivity. Alternatively, a slice of Li3YBr6 having a cut surface extending in the crystal orientation <0 01> may be formed from the single crystal, and its thickness may be extended in the crystal orientation <100>.

[0097] Referring to FIG. 3A, a sheet 300 is illustrated. In an embodiment, the sheet 300 can include the single crystal described in the embodiments of the present specification. The sheet 300 can have a thickness t extending between major surfaces 3 02 and 304. FIG. 3B includes an exemplary illustration of the crystallographic orientation of the single crystal. The single crystal can have a mica-like layered structure in which the length of the layer extends in the crystallographic direction <100> and the stack of layers extends in the crystallographic direction <001>. A particular single crystal can have a greater ionic conductivity in the crystallographic direction <100> compared to <001>. In a particular example, the thickness t of the sheet 300 can extend in the crystallographic direction <10 0>. In a further example, one or both of the major surfaces of 302 and 304 can be sliced surfaces. Alternatively, the sheet 300 can be formed by epitaxial crystal growth to have a crystallographic orientation, and the thickness t extends in the crystallographic direction <100>.

[0098] The formation process of the embodiments described herein can enable the formation of an ion-conductive material having a higher purity, which is noted. It is further noted that an ion-conductive material having a higher purity may have further improved ion conductivity. When forming a complex metal halide using a conventional method such as a solid reaction using ball milling, the content of impurities such as simple metal halides may increase. Using a complex metal halide with a high content of simple metal halides or directly using a simple compound as a starting material to grow crystals according to the Bridgman-Stockbarger, Gradient-Freeze, Chokralski, or Budanurov (horizontal Bridgman) processes, the melt shows incongruent melting, and a high content of impurity phases and parasitic phases are formed in the resulting crystals.

[0099] The impurity phases and parasitic phases include one or more simple metal halides such as LiX and MeX, where X is a halogen such as Cl and / or Br. The process of the embodiments described herein may enable the formation of a complex metal halide with a low impurity content. In an embodiment, the complex metal halide has a total content of simple metal halides of at most 15 wt%, for example at most 12 wt%, at most 11 wt%, at most 10 wt%, at most 9 wt%, at most 8 wt%, at most 7 wt%, at most 6 wt%, at most 5 wt%, at most 4 wt%, at most 3 wt%, at most 2 wt%, at most 1 wt% or at most 0. When forming a complex metal halide using a conventional method such as a solid reaction using ball milling, the content of impurities such as simple metal halides may increase. Using a complex metal halide with a high content of simple metal halides or directly using a simple compound as a starting material to grow crystals according to the Bridgman-Stockbarger, Gradient-Freeze, Chokralski, or Budanurov (horizontal Bridgman) processes, the melt shows incongruent melting, and a high content of impurity phases and parasitic phases are formed in the resulting crystals. The impurity phases and parasitic phases include one or more simple metal halides such as LiX and MeX, where X is a halogen such as Cl and / or Br. k+ X k such as one or more simple metal halides, and X is a halogen such as Cl and / or Br.

[0100] The process of the embodiments described herein may enable the formation of a complex metal halide with a low impurity content. In an embodiment, the complex metal halide has a total content of simple metal halides of at most 15 wt%, for example at most 12 wt%, at most 11 wt%, at most 10 wt%, at most 9 wt%, at most 8 wt%, at most 7 wt%, at most 6 wt%, at most 5 wt%, at most 4 wt%, at most 3 wt%, at most 2 wt%, at most 1 wt% or at most 0. wt%, for example, at most 12 wt%, at most 11 wt%, at most 10 wt%, at most 9 wt%, at most 8 wt%, at most 7 wt%, at most 6 wt%, at most 5 wt%, at most 4 wt%, at most 3 wt%, at most 2 wt%, at most 1 wt% or at most 0. It can have. It is 5 wt%. In certain embodiments, the composite metal halide single crystal can be essentially free of simple metal halides. For example, all the total content of simple metal halides can be less than 0.2 wt% based on the weight of the single crystal and may be. Further, the composite metal halide of the embodiments herein is noted to have a higher bulk ion conductivity compared to those produced using conventional methods.

[0101] In embodiments, further purification of the composite metal halide can be facilitated by performing crystal growth. In further embodiments, crystal growth can promote the formation of an ion conductive material having improved bulk ion conductivity. The single crystal of the composite metal halide of the embodiments herein has a further improved bulk ion conductivity compared to the non-single crystal form (e.g., powder) of the same composite metal halide of the embodiments herein. It is worth noting that it tends to have.

[0102] In at least one embodiment, the single crystal of the embodiments herein can contain a low content of nitride-based phase impurities. The nitride-based phase can include one or more phases of metal nitrides, metal oxynitrides, metal carbonitrides, or any combination thereof. The formation of the nitride-based phase can result from Process 100, Process 200, or a combination thereof. In some embodiments, the presence of certain species of metal nitrides, such as Li3N, can help improve the bulk ion conductivity of the metal halide material.

[0103] Referring to FIG. 4, a process 400 for forming an ion conductive material is illustrated. It is. Process 400 is illustrated in FIG. 1 and described in an embodiment with respect to Process 100 and can include all steps.

[0104] In an embodiment, Process 400 can include forming a solid conductive material including an oriented ceramic material. In one aspect, particles of the complex metal halide formed by Process 100 can be used. In one example, the particles can have a specific shape such as an elongated shape, and the longitudinal axis of the particles can be arranged to extend parallel to the direction of the crystallographic orientation having higher ionic conductivity. In another example, casting, compression, pressing, heating, shaping, or any combination thereof can be used to facilitate the orientation of the particles. In another example, a magnetic field, a discharge, a thermal gradient, or a combination thereof can be used to promote the crystal orientation of the ceramic particles.

[0105] In another embodiment, Process 400 can include performing crystal growth to form an oriented ceramic. In one aspect, Process 400 can include forming a melt similar to Process 200. In a further aspect, the crystal growth can be performed at a specific growth rate. For example, the growth rate can be at least 8 mm / hour, at least 10 mm / hour, at least 15 mm / hour, or at least 20 mm / hour. In another example, the growth rate can be at most 80 mm / hour, at most 70 mm / hour, at most 60 mm / hour, at most 50 mm / hour, or at most 40 mm / hour. In another example, the growth rate can be in a range including any of the minimum and maximum values described herein. is possible. In another aspect, to promote the growth of oriented polycrystalline crystals, a thermal gradient can be applied.

[0106] In an embodiment, process 400 can include forming a single crystal as described in the embodiments related to process 200. In one aspect, the single crystal pellet may be arranged to form a ceramic ion conductive material having a specific crystallographic orientation as described. In one example, casting, compression, pressing, heating, shaping, or any combination thereof can be used to promote the formation of a ceramic ion conductive material having a crystal orientation. In a specific example, the single crystal pellet can be oriented and preferably have a crystallographic orientation as described. In one example, the composite metal halide can be anisotropic and have a higher ionic conductivity at the crystallographic orientation <100> and a lower ionic conductivity at the crystallographic orientation <001>. Referring to FIG. 3b, single crystals or ceramic pellets of the complex metal halide 322 can be arranged as shown to form a crystal orientation ceramic material. The solid ion conductive materials of the embodiments herein can be in different forms. In one embodiment, the ion conductive material can include a powder containing a composite metal halide as described. In another embodiment, the ion conductive material can include a single crystal of the composite metal halide

[0107] as described. For example, the ion conductive material can include a powder containing single crystal particles. In another example, the ion conductive material can be a single crystal sheet, single crystal film, single crystal block, single crystal as described. as described. as described.

[0108] In an embodiment, the ion conductive material can include a powder containing a composite metal halide. In another embodiment, the ion conductive material can include a single crystal of the composite metal halide. For example, the ion conductive material can include a powder containing single crystal particles. In another example, the ion conductive material can be a single crystal sheet, single crystal film, single crystal block, single crystal as described. as described. as described. For example, the ion conductive material can include a powder containing single crystal particles. In another example, the ion conductive material can be a single crystal sheet, single crystal film, single crystal block, single crystal as described. It can include a crystal ingot, or another form of single crystal, or any combination thereof. In a further embodiment, the ion conductive material can include a ceramic material including a composite metal halide. For example, the ceramic material can include ceramic particles, single crystal particles, or any combination thereof.

[0109] In another embodiment, the solid ion conductive material can be a polycrystalline, single crystal, or crystallographically oriented crystalline material. For example, the solid conductive material can be a single crystal of a composite metal halide. In another example, the solid conductive material can be a ceramic including a single crystal of a composite metal halide. In another example, the solid conductive material can be a crystallographically oriented crystalline material of a composite metal halide.

[0110] In an embodiment, the solid ion conductive material may include an impurity content. The impurity may exist as a phase different from the composite metal halide, or may be complexed with the metal halide in the same phase. For example, a simple metal halide may exist as a phase different from the composite metal halide. In an example, ammonium halide may be completely or partially complexed with the composite metal halide. In particular, the solid ion conductive material can have an improved purity compared to a conventional solid ion conductive material that can be represented by the same general formula but is formed using a process different from the processes pointed out in the embodiments herein. For example, the total content of all impurities (also referred to as the "total impurity content") can be at most 15 wt% based on the weight of the composite metal halide in the solid ion conductive material of the embodiments herein. ​​​​​It may be configured. For example, the total impurity content may be at most 14 wt% based on the weight of the composite metal halide, for example, at most 13 wt%, at most 12 wt%, at most 11 wt%, at most 10 wt%, at most 9 wt%, at most 8 wt%, at most 7 wt%, at most 6 wt%, at most 5 wt%, at most 4 wt%, at most 3 wt% , at most 2 wt%, at most 1 wt%, at most 0.5 wt%, at most 0.3 wt% , at most 0.1 wt%, at most 500 ppm, at most 300 ppm, at most 10 0 ppm, at most 50 ppm, at most 40 ppm, at most 30 ppm, at most 2 0 ppm, or at most 10 ppm by weight of the composite metal halide can be obtained. In another example, the composite metal halide may contain at least 0 .2 ppm, for example, at least 0.5 ppm, at least 1 ppm, or at least 2 ppm of the total impurity content. In another aspect, the total impurity content may be within a range including any of the minimum or maximum values described herein. The content of the impurity phase can be determined as follows. Each impurity phase can be detected by XRD analysis combined with Rietveld refinement for quantitative analysis through the presence of characteristic diffraction peaks corresponding to the parasitic phase. The Rietveld method (RR) analyzes the shape and position of the peaks in the XRD diagram, collects the 2 - theta data during XRD diffraction while gradually increasing the 2 - theta angle, and converts it into the ratio of different phases to quantitatively identify the contribution degree of each phase.

[0111]

[0112] ​​​​​​​ Regarding the nitride-based impurity phase, especially when the nitride-based impurity phase is present in an amount of less than 0.1% in molar amount or mass amount, its presence can also be determined and quantified using LECO analysis. LECO analysis is based on the combustion of the sample and the analysis of the presence of nitrogen (or sulfur, carbon, hydrogen, oxygen) by the thermal conductivity or infrared absorption pattern of the boiled source gas.

[0113] In a further aspect, the content of all nitride-based impurity phases such as metal nitrides, metal oxynitrides, and / or metal-carbon nitrides present in the ion-conductive material can be at most 0.3 wt%, at most 0.2 wt%, at most 0 .1 wt%, at most 500 ppm, at most 300 ppm, at most 100 ppm, at most 50 ppm, at most 40 ppm, at most 30 ppm, at most 20 ppm, or at most 10 ppm based on the weight of the complex metal halide. In another example, the content of all metal nitrides can be at least 0.2 ppm based on the weight of the complex metal halide, for example, at least 0.5 ppm, at least 1 ppm, or at least 2 ppm based on the weight of the complex metal halide. In another aspect, the content of all nitride-based phases can be in a range including either the minimum value or the maximum value described herein.

[0114] In a further aspect, the content of alkali halide (MX) can be at most 10 wt%, for example at most 9 wt%, at most 8 wt%, at most 7 wt%, at most 6 wt%, at most 5 wt%, at most 4 wt%, at most 3 wt% based on the weight of the complex metal halide. wt%, at most 2 wt%, at most 1 wt%, at most 0.5 wt%, at most 0.3 wt%, at most 0.2 wt%, at most 0.1 wt%, at most 500 ppm, at most also 300 ppm, at most 100 ppm, at most 50 ppm, at most 40 ppm, at most 30 ppm, at most 20 ppm, or at most 10 ppm of the composite metal halide with respect to the weight, it is. In another example, the content of MX is with respect to the weight of the composite metal halide at least 0.2 ppm, for example, at least 0.5 ppm, at least 1 ppm, or at least 2 ppm with respect to the weight of the composite metal halide can be. In another aspect, the content of MX may be within a range including either the minimum value or the maximum value described herein In another aspect, the content of MX may be within a range including either the minimum value or the maximum value described herein may be.

[0115] In a further aspect, the content of metal oxyhalide (MeOX) such as rare earth oxyhalide is at most 5 wt%, for example at most 4 wt%, at most 3 wt%, at most 2 wt%, at most 1 wt%, at most 0.5 wt %, at most 0.3 wt%, at most 0.2 wt%, at most 0.1 wt%, at most 5 00 ppm, at most 300 ppm, at most 100 ppm, at most 50 ppm, at most 40 ppm, at most 30 ppm, at most 20 ppm, or at most 10 ppm with respect to the weight of the composite metal halide, it can be done like that. In another example, the content of the MeO X phase is at least 0.2 ppm with respect to the weight of the composite metal halide, for example , at least 0.5 ppm, at least 1 ppm, or at least 2 ppm with respect to the weight of the composite metal halide. In another aspect, the content of the MeOX phase is It may also be within a range including either the minimum value or the maximum value described in this specification. In certain embodiments, the complex metal halide can be essentially free of MeOX.

[0116] In a further embodiment, the content of the metal nitride Me x N k is at most 0.3 wt%, for example at most 0.1 wt%, at most 500 ppm, at most 300 ppm, at most 100 ppm, at most 50 ppm, at most 40 p pm, at most 30 ppm, at most 20 ppm, or at most 10 ppm, based on the weight of the complex metal halide. In another example, the content of the metal nitride is at least 0.2 ppm, for example at least 0.5 ppm, at least 1 ppm, or at least 2 ppm, based on the weight of the complex metal halide. In another embodiment the total content of the metal nitride Me N may be in a range including either the minimum value or the maximum value pointed out in this specification. In a further embodiment, the content of the metal nitride M x N is at most 0.3 wt%, for example at most 0.1 wt%, at most 500 ppm, at most 300 pp k m, at most 100 ppm, at most 50 ppm, at most 40 ppm, at most 30 ppm, at most 20 p pm, or at most 10 ppm, based on the weight of the complex metal halide. In another example, the content of the metal nitride is at least 0.2 ppm, for example at least 0.5

[0117] ppm, at least 1 ppm, or at least 2 ppm, based on the weight of the complex metal halide. x m, at most 100 ppm, at most 50 ppm, at most 40 ppm, at most 30 ppm, at most 20 p pm, or at most 10 ppm, based on the weight of the complex metal halide. In another example, the content of the metal nitride is at least 0.2 ppm, for example at least 0.5 ppm, at least 1 ppm, or at least 2 ppm, based on the weight of the complex metal halide. It can be 2 ppm. In another aspect, the total content of the metal nitride MeN may be in a range including either the minimum value or the maximum value described herein. It may be in a range including either the minimum value or the maximum value described herein.

[0118] In the present disclosure, the total content of the nitride-based phase and the content of metal nitrides such as alkali nitrides and Me x N k can be detected by the following method. Since the complex metal halide of the ion-conductive material is hygroscopic, it can be dissolved in water and used. Since the metal nitride has no hygroscopicity, it can be recovered and analyzed after filtering the aqueous solution. If it is 0.2 wt% or more, it can be detected by X-ray diffraction analysis. When it is 0.2 wt% or less, LECO can be used. Regarding the content of the metal halide alone, it can be analyzed by X-ray diffraction without dissolving the ion-conductive material. Regarding the content of the metal halide alone, it can be analyzed by X-ray diffraction without dissolving the ion-conductive material. Regarding the content of the metal halide alone, it can be analyzed by X-ray diffraction without dissolving the ion-conductive material. Regarding the content of the metal halide alone, it can be analyzed by X-ray diffraction without dissolving the ion-conductive material. Regarding the content of the metal halide alone, it can be analyzed by X-ray diffraction without dissolving the ion-conductive material.

[0119] Regarding the content of the metal halide alone, it can be analyzed by X-ray diffraction without dissolving the ion-conductive material. Regarding the content of the metal halide alone, it can be analyzed by X-ray diffraction without dissolving the ion-conductive material.

[0120] In a specific example, the solid ion-conductive material can include NH3, NH4X, or a combination thereof, where X includes a halogen. In the example, NH3 and / or NH4 X may exist as a separate phase in addition to the complex metal halide. In another example, NH3 and / or NH4 X may be a dopant or impurity of the complex metal halide. In a specific example, the solid ion-conductive material can include NH3, NH4X, or a combination thereof, where X includes a halogen. In the example, NH3 and / or NH4 X may be a dopant or impurity of the complex metal halide.

[0121] In yet another example, the solid ion-conductive material can include Li4(NH2)3Cl, Li7(NH 2)6Cl, Li2Br(NH2), Li 13 [NH]6Cl, LiCl-NH3, Li Br-4NH3, or a combination thereof. In one example, the complex metal halide In addition to the nitride, one or more compounds may be present in a separate phase. In another example, one or more of the compounds may be by-products resulting from processes 100, 200, and / or 300. In another example, the compound may be a dopant or impurity in the presence of a complex metal halide.

[0122] In an embodiment, the ion-conductive material has a bulk ion conductivity of at least 0.01 mS / cm, such as at least 0.05 mS / cm, at least 0.08 mS / cm, measured by electrochemical impedance spectroscopy performed on a pelletized sample sandwiched between ion-blocking electrodes. For example, at least 0.1 mS / cm, or at least 0.3 mS / cm, or at least 0.5 mS / cm. In certain examples, the bulk ion conductivity can be at least 0.6 mS / cm, at least 1.2 mS / cm, at least 1.8 mS / cm, or at least 2.2 mS / cm. In another example, the bulk ion conductivity can be up to 15 mS / cm, up to 13 mS / cm, up to 11 mS / cm, up to 8 mS / cm, up to 7.2 mS / cm, or up to 6.2 mS / cm. In certain examples, the bulk ion conductivity can be in a range including any of the minimum and maximum values described herein. The bulk ion conductivity can be measured at room temperature, such as 22 °C, with an activation energy in the range of 0.2 eV and 0.5 eV. In a further embodiment, an activation energy of 0 to 1 eV may be used for temperatures from 200 °C to -80 °C. For temperatures from 80 °C to -30 °C, the activation energy may be 0.1 to 0.6 eV. When the temperature is 0 °C or higher or 10 °C or lower, the activation energy is 0.1 to 0 ​​​​​​​​​​It can be 0.5 eV.

[0123] In an embodiment, the solid electrolyte can include an ion-conductive material. The ion-conductive material can be a single crystal, a polycrystal, or a combination thereof. The solid electrolyte has improved ion conductivity compared to a solid electrolyte containing a conventionally formed complex lithium-based metal halide. In a specific example, the solid electrolyte can be composed of an ion-conductive material. In a more specific example, the solid electrolyte can be composed of a single-crystal composite metal halide, a polycrystalline composite metal halide, or an oriented-crystal composite metal halide including a single crystal or an oriented ceramic having a specific crystal orientation. In a specific application, the electrolyte may include a crystallographically oriented solid ion-conductive material, and the

[0124] electrolyte may have a thickness extending in a direction parallel to the orientation of the solid ion-conductive material. In an embodiment, the composite ion-conductive layer can include an ion-conductive material and an organic material. The organic material can be included as a binder material, a polymer electrolyte material, or a combination thereof. In another example, the composite ion-conductive layer can include a plasticizer, a solvent, or a combination thereof. Exemplary organic materials can include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), fluororubber, polypropylene, ethylene-propylene-dieneIt includes poly(vinylidene fluoride), poly(acrylonitrile), poly(dimethylsiloxane ), poly[bis(methoxyethoxy)-phosphazene], polyethylene carbonate, p olypropylene glycol, polycaprolactone, poly(trimethylene carbonate), hydr ogenated nitrile butadiene rubber, poly(ethylene vinyl acetate), high density polyethylene, low density polyethylene, polyurethane, or any combination thereof. In another example, the composite ion conductive layer can include a lithium salt. Exemplary lithium salts are LiSbF6, LiN(SO2CF3)2, LiN(SO2C2F5)2, LiN(SO2CF3)(SO2C4F9), LiC(SO2CF3)3, LiAsF6, LiC lO4, LiPF6, LiBF4, LiCF3SO3, or any combination thereof can be included.

[0125] In another embodiment, the mixed electron and ion conductive layer can include an ion conductive material In one aspect, the mixed electron and ion conductive layer can further include a positive electrode active material Examples of positive electrode active materials include lithium containing transition metal oxides such as Li(NiCoAl)O2 and LiCoO2, transition metal fluorides, polyanions, and fluorinated polyanions materials, and transition metal sulfides, transition metal oxyfluorides, transition metal oxysulfides, transition metal oxynitrides, or any combination thereof, but are not limited thereto

[0126] In another aspect, the mixed ion and electron conductive layer can include a negative electrode active material. Exemplary negative electrode active materials are carbon materials, such as artificial graphite, graphite carbon fibers, resin-fired carbon, pyrolytic gas ​Coke, mesocarbon microbeads (MCMB), furfuryl alcohol resin calcined carbon, polyacene. Pitch-based carbon fiber, vapor-grown carbon fiber, natural graphite, non-graphite carbon, etc., metal materials such as lithium metal and lithium alloy, oxides, nitrides, tin compounds, sili con compounds, or combinations thereof.

[0127] In some embodiments, the mixed ion and electron conduction layer can include an electron conductive additive. Examples of electron conductive additives can include carbon fibers, carbon powders, stainless steel fibers, nickel coated graphite, etc., or any combination thereof.

[0128] In an embodiment, the solid lithium battery can include an electrolyte disposed between the anode and the cathode. Referring to FIG. 5, a partial cross-section of an exemplary solid battery 500 is illustrated. The electrolyte layer 502 can be any of the electrolyte layers or composite layers pointed out in the embodiments of this specification. The anode 504 covers the electrolyte 502. In an embodiment, the negative electrode 504 can include a solid ion conductive material and a negative electrode active material. In a particular embodiment, the negative electrode 504 can be a three-dimensionally structured negative electrode. In another embodiment, the negative electrode 504 can be a metal negative electrode. For example, the negative electrode may be composed of lithium. The cathode 506 may be disposed on the opposite side of the electrolyte 506 from the anode 502. The positive electrode 506 can include a solid electrolyte material and a positive electrode active material. In a particular embodiment, the positive electrode 506 can be a three-dimensionally structured positive electrode.

[0129] In a particular example, the electrolyte 502 can be the single crystal sheet 302 illustrated in FIG. 3. It can be cut. The anode 504 can be on the major surface 304 shown in FIG. 3. As shown in FIG. 3 The major surface 306 shown can be on the cathode 506.

[0130] Known techniques can be used to form electrolytes, composite ion-conducting layers, negative electrodes, positive electrodes, or other components of solid lithium batteries using solid electrolyte materials. Such techniques include, but are not limited to, casting, molding, deposition, printing, pressing, heating, etc., or any combination thereof. In certain embodiments, to form a multilayer structure layers such as the electrolyte and the negative and / or positive electrodes can be formed separately and then laminated to form a multilayer structure. Alternatively, stacks of green electrolyte and anode and / or cathode layers can be formed and then subjected to further processing such as pressing, heating, drying, or any combination thereof to form the ultimately formed multilayer structure. In certain embodiments, single crystal blocks or ingots can be processed, together with the positive or negative electrode active materials, for example, by mechanical pressing or thermally activated co-extrusion, to ensure intimate contact between the electrodes and the electrolyte. In another particular embodiment, single crystal blocks and ingots can be grown directly around the particles of the negative and / or positive electrode active materials to form a mixed layer with electron and ion conductivity. In one aspect, the mixed ion and electron conducting layer can include a single crystal ion conducting material containing inclusions including the negative or positive electrode active material. In another aspect, the mixed ion and electron conducting layer is filled with the negative or positive electrode active material at high density within the single crystal ingot or block.

[0131] In certain embodiments, single crystal blocks or ingots, together with the positive or negative electrode active materials, can be processed, for example, by mechanical pressing or thermally activated co-extrusion to ensure intimate contact between the electrodes and the electrolyte. In another particular embodiment, single crystal blocks and ingots can be grown directly around the particles of the negative and / or positive electrode active materials to form a mixed layer with electron and ion conductivity. In one aspect, the mixed ion and electron conducting layer can include a single crystal ion conducting material containing inclusions including the negative or positive electrode active material. In another aspect, the mixed ion and electron conducting layer

[0132] is filled with the negative or positive electrode active material at high density within the single crystal ingot or block. In another particular embodiment, single crystal blocks and ingots can be grown directly around the particles of the negative and / or positive electrode active materials to form a mixed layer with electron and ion conductivity. In one aspect, the mixed ion and electron conducting layer can include a single crystal ion conducting material containing inclusions including the negative or positive electrode active material. In another aspect, the mixed ion and electron conducting layer In another aspect, the mixed ion and electron conducting layer can include a single crystal ion conducting material containing inclusions including the negative or positive electrode active material. In another aspect, the mixed ion and electron conducting layer is filled with the negative or positive electrode active material at high density within the single crystal ingot or block. can include.

[0133] Many different aspects and embodiments are possible. Some of those aspects and embodiments are described herein. After reading this specification, those skilled in the art will understand that those aspects and embodiments are merely illustrative and do not limit the scope of the present invention. Embodiments may conform to any one or more of the embodiments listed below.

[0134] Embodiment Embodiment 1. A solid ion conductive material comprising a composite metal halide: The composite metal halide is doped with a dopant containing ammonium; and the composite metal halide is M 3-z (Me k+ ) f X 3-z+k*f represented by, where , -3 ≤ z < 3; 2 ≤ k < 6; 0 ≤ f ≤ 1; M contains an alkali metal element, Me contains a divalent metal element, a trivalent metal element, a tetravalent metal element, a pentavalent metal element, a hexavalent metal element, or any combination thereof; and X contains a halogen. Embodiment 2. A solid ion conductive material comprising the following: M 3-z (Me k+ ) f X 3-z+k*f a composite metal halide represented by, -3 ≤ z < 3; 2 ≤ k < 6; 0 ≤ f ≤ 1; M contains an alkali metal element, Me contains a divalent metal element, a trivalent metal element, a tetravalent metal element, a pentavalent metal element, a hexavalent comprising a metal element, or a combination thereof; and X comprises a halogen; electrically neutral Me x N k or M x at least one of N, where x is the valence of N and k is the valence of M e. Embodiment 3. A solid ion conductive material according to Embodiment 1 or 2, wherein the complex metal halide is (Li , Na 1-d-e , M' d )2Li e (Me 1-z’ ) k+ ) f X 3+k*f-z , characterized by a solid ion conductive material represented by: 0 ≦ d ≦ 1; 0 ≦ e < 1; M consists of at least one of Li, Na, and M'; and M' consists of at least one of K, Rb, Cs. Embodiment 4. A solid ion conductive material comprising a complex metal halide represented by Li 1-d-e , Na d , M' e )2Li 1-z (Me k+ ) f X 3+k *f-z . -3 ≦ z < 3; 2 ≦ k < 6; 0 ≦ f ≦ 1; 0 < d ≦ 1; 0 ≦ e < 1; M contains an alkali metal element, Me contains a divalent metal element, a trivalent metal element, a tetravalent metal element, a pentavalent metal element, a hexavalent metal element, or a combination thereof; and X contains a halogen; electrically neutral Me x N k or M x at least one of N, where x is the valence of N and k is the valence of M It is the valence of e. M consists of at least one of Li, Na, and M', and M' consists of at least one of K, Rb, and Cs. In Embodiment 5, z is from -0.95 to 0.95, and M consists of Na and Li. The solid ion conductive material according to any one of Embodiments 1 to 4. In Embodiment 6, Me includes one or more selected from rare earth elements, alkaline earth metal elements, 3d transition metals, Zn, Zr, Hf, Ti, Sn, Th, Ge, Ta, Nb, Mo, W, Sb, In, Bi, Al, Ga, Fe, or combinations thereof. The solid ion conductive material according to any one of Embodiments 1 to 5. In Embodiment 7, Me includes rare earth elements, Zr, or any combination thereof. The solid ion conductive material according to any one of Embodiments 1 to 6. In Embodiment 8, Me includes Y, Ce, Gd, Er, Zr, La, Yb, In, Mg, Zn, or any combination thereof. The solid ion conductive material according to any one of Embodiments 1 to 7. In Embodiment 9, X includes at least one of F, Cl, Br, and I, and optionally, -NH 2 (amide), -(NH) 0.5 (imide), -OH (hydroxide), -BH4 (borohydride), -BF4 group, or an anion group including any combination thereof. The solid ion conductive material according to any one of Embodiments 1 to 8. In Embodiment 10, Me consists of Gd, Y, or a combination thereof. The solid ion conductive material according to any one of Embodiments 1 to 9.

[0135] In Embodiment 11, Me consists of Ce, Y, or a combination thereof. The solid ion conductive material according to any one of Embodiments 1 to 9. Embodiment 12. The solid ion conductive material according to any one of Embodiments 1 to 9, wherein Me consists of Er, Y, or a combination thereof. Embodiment 13. The solid ion conductive material according to any one of Embodiments 1 to 9, wherein Me consists of Yb, Ce, or a combination thereof. Embodiment 14. The solid ion conductive material according to any one of Embodiments 1 to 9, wherein Me consists of Y, Zr, or a combination thereof. Embodiment 15. The solid ion conductive material according to any one of Embodiments 1 to 9, wherein Me consists of two or more of In, Y, Zr, Hf, Sc, Zn, and Mg. Embodiment 16. The solid ion conductive material according to any one of Embodiments 1 to 15, wherein the halogen consists of any one of Cl, Br, I, and F. Embodiment 17. The solid ion conductive material according to any one of Embodiments 1 to 16, wherein the halogen consists of at least two or more of Cl, Br, I, and F. Embodiment 18. The solid ion conductive material according to any one of Embodiments 1 to 17, wherein the halogen consists of Cl, Br, and I. Embodiment 19. The composite metal halide is represented by Li3-zMek+X3-z+k, wherein Me consists of a rare earth element, Zr, or any combination thereof. The solid ion conductive material according to any one of Embodiments 1 and 4 to 18. Embodiment 20. The solid ion conductive material according to any one of Embodiments 1 to 18, which is a composite metal halide represented by (Li 1-d Na d )2Li 1-z Me k+ X 3+k-z and Me contains a rare earth element, Zr, or a combination thereof, and 0 ≦ d < 1, -0.95 ≤ z < 0.95.

[0136] Embodiment 21. The solid ion conductive material according to any one of Embodiments 1 to 20 is such that z ≤ 0.5 or z ≤ 0.3 or z ≤ 0.2. Embodiment 22. The solid ion conductive material according to any one of Embodiments 2 to 21 is such that d ≥ 0.01 or d ≥ 0.05 or d ≥ 0.1, the solid ion conductive material . Embodiment 23. The solid ion conductive material according to any one of Embodiments 2 to 22 is such that d ≤ 0. Embodiment 24. The solid ion conductive material according to any one of Embodiments 1 to 9 wherein the composite metal halide is (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’) and is characterized by being represented by, the solid ion conductive material. 0 ≤ d ≤ 1; 0 ≤ e < 1; -3 ≤ z’ < 3; M’ includes at least one of K, Rb, and Cs. M 3+ is a rare earth element, In, Bi, Sc, Y, Al, Ga, or any combination thereof. combination. Me 4+ is Zr 4+ , Hf 4+ , Ti 4+ ,Sn 4+ ,Th 4+ ,Ge 4+ Or It is a combination of: 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 a combination thereof. Me 6+ is W 6+ , Mo 6+ , or any combination thereof. 0<=w<=1; 0<=y<=1; -0.95 <z<0.95; 0<=u<0.95; 0<=p<0.95; 0<=q<0.95; and 0<=r<0.95. Embodiment 25.M 3+ But, Y 3+ , Gd 3+ , In 3+ , Er 3+ , La 3+ , Sc 3 + or any combination thereof, 3+ But, Y 3+ , Gd 3+ , In 3+ , Er 3+ , La 3+ , Sc 3+ or any combination thereof. 24 solid ionically conductive materials. Embodiment 26.M 4+ Zr 4+ , Hf 4+ , Ce 4+ , or a combination thereof, containing M 4+ being Zr 4+ , Hf 4+ , Ce 4+ , or a combination thereof, a solid ionic conductive material of Embodiment 24 or 25. Embodiment 27. The solid ionic conductive material according to any one of Embodiments 24 to 26 wherein p = 0; q = 0; r = 0; u = 0; or a combination thereof. Embodiment 28. k = 2 or 3 or 4 or 5, the solid ionic conductive material according to any one of Embodiments 1 to 9 and 24 to 27. Embodiment 29. The solid ionic conductive material according to any one of Embodiments 1 to 28 wherein, based on the total weight of the composite metal halide, at least 10 ppm by weight of ammonium halide, at least 100 ppm, at least 500 ppm, at least 0.1 w t%, at least 0.3 wt%, at least 0.5 wt%, at least 0.8 wt% or at least 1 wt% is contained. Embodiment 30. At most 20 wt%, at most 15 wt%, at most 10 wt%, at most 8 wt%, at most 5 wt %, or at most 3 wt% of ammonium is contained, based on the total weight of the composite metal halide, the solid ionic conductor material according to any one of Embodiments 1 to 29.

[0137] Embodiment 31. At most 0.5 wt%, at most 0.3 wt%, at most 0.1 wt%, at most 500 ppm, at most 300 ppm, based on the weight of the composite metal halide, , a total content of simple metal halides of at most 100 ppm, at most 50 ppm, at most 40 ppm, at most 30 ppm, at most 20 ppm or at most 10 ppm further contained, the solid ion conductor material according to any one of Embodiments 1 to 30. Embodiment 32. The solid ion conductive material according to Embodiment 31, containing at least 0.2 ppm, at least 0.5 ppm, or at least 1 ppm of simple metal halides with respect to the total weight of the composite metal halides. Embodiment 33. The simple metal halide is an alkali metal halide, a rare earth metal halide, or any combination thereof, and the solid ion conductive material according to Embodiment 31 or 32. Embodiment 34. The ion conductive material according to any one of Embodiments 1 to 33, containing at least 0 x N k .1 mass ppm and at most 10 mass ppm of charge-neutral Me with respect to the weight of the composite metal compound. Embodiment 35. With respect to the weight of the composite metal compound, x , the ion conductive material according to any one of Embodiments 1 to 34, containing at least 0.1 x mass ppm and at most 10 mass ppm of charge-neutral M N. Embodiment 36. The solid ion conductor material according to any one of Embodiments 1 to 35, including an ionic conductivity in bulk of at least 0.001 mS / cm, at least 0.01 mS / cm, at least 0.1 mS / cm, at least 0.4 mS / cm, at least 0.8 mS / cm, at least 1.2 mS / cm, at least 1.8 mS / cm or at least 2.2 mS / cm. Embodiment 37. A maximum of 15 mS / cm, a maximum of 13 mS / cm, a maximum of 11 mS / cm, a maximum of Ions in the bulk with a conductivity of 8 mS / cm, a maximum of 7.2 mS / cm, or a maximum of 6.2 mS / cm The solid ion conductor material of Embodiment 36, including conductivity. Embodiment 38. The composite metal halide is in the form of a powder with an average particle size of at least 0.1 micron to 1 mm The solid ion conductive material according to any one of Embodiments 1 to 37. material. Embodiment 39. The solid conductive material is a single crystal or a polycrystal, The solid ion conductive material according to any one of Embodiments 1 to 38. Embodiment 40. The solid ion conductive material is a single crystal or <hkl>Or <hklm>It is an oriented polycrystal having a crystal orientation represented by <hkl>Or <hklm>of The solid ion conductive material according to Embodiment 39, wherein the ionic conductivity in the crystal orientation is higher than the ionic conductivity in different crystal orientations. The solid ion conductive material according to Embodiment 39.

[0138] Embodiment 41. The solid ion conductive material has a crystallographic orientation selected from the group including <100> and <001>, and is the solid ion conductive material according to Embodiment 39 or 40. The solid ion conductive material according to Embodiment 39 or 40, having a crystallographic orientation selected from the group including <100> and <001>. Embodiment 42. The solid ion conductive material according to any one of Embodiments 1 to 41, further including Li4(NH2)3Cl, Li7(NH2)6Cl, Li2Br(NH 2), Li 13 [NH]6Cl, LiCl·NH3, LiBr·4NH3, or a combination thereof. The solid ion conductive material according to any one of Embodiments 1 to 41, further including Li4(NH2)3Cl, Li7(NH2)6Cl, Li2Br(NH2), Li[NH]6Cl, LiCl·NH3, LiBr·4NH3, or a combination thereof. The solid ion conductive material according to any one of Embodiments 1 to 41, further including Li4(NH2)3Cl, Li7(NH2)6Cl, Li2Br(NH2), Li[NH]6Cl, LiCl·NH3, LiBr·4NH3, or a combination thereof. Embodiment 43. The solid ion conductive material according to any one of Embodiments 1 to 42, further including NH3, NH4X, or a combination thereof. The solid ion conductive material according to any one of Embodiments 1 to 42, further including NH3, NH4X, or a combination thereof. Embodiment 44. A solid electrolyte layer including the solid ion conductive material according to any one of Embodiments 1 to 43. The solid electrolyte layer including the solid ion conductive material according to any one of Embodiments 1 to 43. Embodiment 45. An electron- and ion-conductive mixed layer including the solid ion conductive material according to any one of Embodiments 1 to 43, a positive electrode or a negative electrode active material, and optionally an electron-conductive additive. The electron- and ion-conductive mixed layer including the solid ion conductive material according to any one of Embodiments 1 to 43, a positive electrode or a negative electrode active material, and optionally an electron-conductive additive. The electron- and ion-conductive mixed layer including the solid ion conductive material according to any one of Embodiments 1 to 43, a positive electrode or a negative electrode active material, and optionally an electron-conductive additive. Embodiment 46. A solid lithium battery including the solid electrolyte layer according to Embodiment 44. Embodiment 47. A solid lithium battery including the electron-ion mixed conduction layer according to Embodiment 45. The solid lithium battery including the electron-ion mixed conduction layer according to Embodiment 45. Embodiment 48. A solid electrolyte layer including a single crystal material containing a composite metal halide represented by M 3-z (Me k+ ) f X 3-z+k*f where -3 ≦ z < 3; 2 ≦ k < 6; 0 ≦ f ≦ 1; 2 ≦ k < 6; 0 ≦ f ≦ 1; M contains an alkali metal element. Me contains a divalent metal element, a trivalent metal element, a tetravalent metal element, a pentavalent metal element, a hexavalent metal element, or any combination thereof; and X is composed of a halogen; and wherein the single crystal material is charge-neutral Me x N k , and M x further contains either of N , x is the valence of N, and k is the valence of Me. Embodiment 49. M 3-z (Me k+ ) f X 3-z+k*f having a composition represented by a solid electrolyte layer including an oriented -3 ≦ z < 3; 2 ≦ k < 6; 0 ≦ f ≦ 1; M contains an alkali metal element. Me contains a divalent metal element, a trivalent metal element, a tetravalent metal element, a pentavalent metal element, a hexavalent metal element, or any combination thereof; and X contains a halogen. Embodiment 50. The solid electrolyte layer according to Embodiment 49, wherein the oriented crystalline material is an oriented ceramic or an oriented single crystal.

[0139] Embodiment 51. The solid electrolyte layer according to any one of Embodiments 48 to 50, wherein M contains at least one of Li and Na. Embodiment 52. The solid electrolyte layer according to any one of Embodiments 48 to 51, wherein M contains Li, or a combination of Li and at least one of Na, Cs, Rb, and K. Embodiment 53. The composition is (Li 1-d , Na d )2Li 1-z Me k+ X 3+k-z The solid electrolyte layer according to any one of Embodiments 47 to 51, represented by 0≦d<1; -0.95≦z<=0.95; 2≦k<6; Me includes a divalent metal element, a trivalent metal element, a tetravalent metal element, a pentavalent metal element, a hexavalent metal element, or any combination thereof; and X contains a halogen. Embodiment 54. The solid electrolyte layer according to any one of Embodiments 47 to 53, wherein Me includes a rare earth element and optionally one or more of an alkaline earth metal element, Zn, Zr, H f, Ti, Sn, Th, Ta, Nb, Mo, W, Sb, In, and Bi. Embodiment 55. The solid electrolyte layer according to any one of Embodiments 47 to 54, wherein Me includes Y, Ce, Gd, Er, Zr, La, Yb, In, Mg, or any combination thereof. Embodiment 56. The solid electrolyte layer according to any one of Embodiments 47 to 55, wherein X contains at least one of F, Cl, Br, and I, and optionally , -NH2 (amide), -(NH) 0.5 (imide), -OH (hydroxide), -BF4 group , or an anion group containing a combination thereof. Embodiment 57. The solid electrolyte layer according to any one of Embodiments 47 to 55, wherein Me includes Gd, Ce, Er, Yb, Zr, Y, or any combination thereof. Embodiment 58. The solid electrolyte layer according to any one of Embodiments 47 to 55, wherein Me includes Gd and optionally at least one of Ce, Er, Y, and Zr. Embodiment 59. The solid electrolyte layer according to any one of Embodiments 47 to 55, wherein Me consists of Yb and Ce. Embodiment 60. Me is a solid electrolyte layer according to any one of Embodiments 47 to 55, which consists of Y and optionally at least one of Zr, Ce, Er, and Gd.

[0140] Embodiment 61. The halogen is one of Cl, Br, I, and F, and the solid electrolyte layer is according to any one of Embodiments 47 to 60. Embodiment 62. The halogen consists of at least two or more of Cl, Br, I, and F, and the solid electrolyte layer is according to any one of Embodiments 47 to 61. Embodiment 63. The halogen consists of Cl, Br, and I, and the solid electrolyte layer is according to any one of Embodiments 47 to 62. Embodiment 64. The composition is represented by Li 3-z RE k+ X 3-z+k , where RE is a rare earth element , Zr, or any combination thereof, and the solid electrolyte layer is according to any one of Embodiments 47 to 63. Embodiment 65. k = 3 or 4 or 5, and the solid electrolyte layer is according to any one of Embodiments 47 to 64. Embodiment 66. The composition is (Li (1-d) ,Na (d) )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)で represented by , and it is a solid electrolyte layer according to any one of Embodiments 47 to 65, where: 0 < d <= 1; -0.95 <= z <= 0.95;​​​​​​ 0 <= u < 0.95; 0 <= p < 0.95; 0 <= q < 0.95; 0 <= r < 0.95; M 3+ Contains rare earth elements. Me 4+ is Zr 4+ , Hf 4+ , Ti 4+ , Sn 4+ , Th 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+ is Ta 5+ , Nb 5+ , W 5+ , Sb 5+ , or a combination thereof. Me 6+ is W 6+ ; 0 <= y <= 1; and w <= 1. Embodiment 67. M 3+ is Y 3+ , Gd 3+ , In 3+ , Er 3+ , La 3+ , or any combination thereof, and M 3+ is Y 3+ , Gd 3+ , In 3+ , Er 3+ , La 3+ , or any combination thereof, and the solid electrolyte layer of Embodiment 66 . Embodiment 68. M 4+ is Zr 4+ , Ce 4+ or combinations thereof, wherein M 4 + is Zr 4+ , Ce 4+ or combinations thereof, as described in Embodiment 66 or 67 solid electrolyte layer. Embodiment 69. The solid electrolyte layer according to any one of Embodiments 63 to 68. p = 0; q = 0; u = 0; or combinations thereof. Embodiment 70. The solid electrolyte layer according to any one of Embodiments 47 to 69, wherein z ≤ 0.5 or z ≤ 0.3 or z ≤ 0.2, solid electrolyte layer.

[0141] Embodiment 71. The solid electrolyte layer according to any one of Embodiments 47 to 70, wherein d ≥ 0.01 or d ≥ 0.05 or d ≥ 0.1, the solid electrolyte layer according to any one of Embodiments 47 to 70 solid electrolyte layer. Embodiment 72. The solid electrolyte layer according to any one of Embodiments 47 to 71, wherein d ≤ 0.8 or d ≤ 0.5. Embodiment 73. The solid electrolyte layer according to any one of Embodiments 47 to 72, The crystalline material contains a total impurity content of at most 0.5 wt%, at most 0.2 wt% %, at most 0.1 wt%, at most 500 ppm, at most 200 ppm, at most 100 ppm, or at most 50 ppm, based on the total weight of the crystalline material. Embodiment 74. The impurity is a rare earth halide, an alkali halide, a charge-neutral Me x N k , a charge-neutral M x N, or any combination thereof, the solid electrolyte layer according to Embodiment 73 solid electrolyte layer. Embodiment 75. A solid electrolyte layer according to any one of Embodiments 47 to 74, comprising a crystalline substance in which the total impurity content is at least 2 ppm, at least 5 ppm, or at least 10 ppm with respect to the weight of the composite metal halide. Embodiment 76. A solid electrolyte layer according to any one of Embodiments 47 to 75, wherein the crystalline material contains at least 0. 1 mass ppm and at most 10 mass ppm of charge-neutral Me x N k Embodiment 77. A solid electrolyte layer according to any one of Embodiments 47 to 76, wherein the crystalline material contains at least 0.1 mass ppm and at most 10 mass ppm of charge-neutral M x N. Embodiment 78. A solid electrolyte layer according to any one of Embodiments 47 to 77, wherein the crystalline material contains Li4(NH2)3Cl, Li7(NH2)6Cl, Li 2Br(NH2), Li 13 [NH]6Cl, LiCl-NH3, LiBr-4NH3, or a combination thereof. Embodiment 79. A solid electrolyte layer according to any one of Embodiments 47 to 78, wherein the crystalline material contains NH3, NH4X, or a combination thereof. Embodiment 80. A solid electrolyte layer according to any one of Embodiments 47 to 79, wherein the crystalline material has a bulk ionic conductivity of at least 0.01 mS / cm, at least 0. 1 mS / cm, at least 0.2 mS / cm, at least 0.4 mS / cm, at least 0.5 mS / cm, at least 0.8 mS / cm, at least 1.2 mS / cm, at least 1.8 mS / cm at 22°C, and the crystal has a band gap within the range of at least 0.01 eV to 0.5 eV. ​​​​​​​Composed of crystals having active energy, the crystals are crystals with an ionic conductivity of at least 0.01 eV as described in Embodiment 79. 8 mS / cm, or at least 2.2 mS / cm at 22 °C, and an activation energy in the range of 0.01 eV and 0.5 eV, or the crystalline material has an ionic conductivity of up to 15 mS / cm, up to 11 mS / cm, up to 9 mS / cm, up to 8 mS / cm, up to 7.2 mS / cm or up to 6.2 mS / cm. Examples of crystalline materials constituting the same.

[0142] Embodiment 81. Having a thickness, the thickness being <hkl>Or <hklm>extends in the crystallographic orientation , <hkl>or <hklm>The ionic conductivity in the crystallographic orientation is higher than the ionic conductivity in the crystallographic orientation where the crystallographic orientations are different. The solid electrolyte layer according to any one of Embodiments 1 to 80. Embodiment 82. The crystallographic direction is selected from the group including <100>, <001>, and <010>. The solid electrolyte layer according to Embodiment 81. Embodiment 83. The single crystal material is sheet-shaped. The solid electrolyte layer according to any one of Embodiments 47 to 82. Embodiment 84. The solid electrolyte layer according to any one of Embodiments 1 to 83, having a thickness of 5 μm to 500 μm. Embodiment 85. A process for forming a solid ion conductive material, including the following. (NH4) n Me k+ 3+k Forming (NH4) n Me k+ 3+k Forming Includes chemically substituting the moisture of the hydrated salt-containing REX3 with NH4X, where n > 0; Me includes a rare earth element, Zr, or a combination thereof, and X is one or more halogens. . Embodiment 86. Further includes performing a solid reaction of (NH4) n Me k+ 3+k and MX, where M includes an alkali metal. The process according to Embodiment 85. Embodiment 87. Further includes decomposing (NH4) n Me k+ X 3+k . The process according to Embodiment 85 or 86. Embodiment 88. M 3-z Me k+ X 3-z+k , where -3 ≦ z < 3; 2 ≦ k < 6; M ​​​​​contains at least one of Li and Na, and the solid ion conductive material forms a complex metal halide containing a total impurity content of up to 0.5 wt% based on the weight of the solid ion conductive material, further comprising the process according to any one of embodiments 85 to 87. Embodiment 89. The process according to embodiment 88, wherein the impurities comprise Me k+ X k , MX, or a combination thereof. Embodiment 90. The process according to any one of embodiments 86 to 89, further comprising growing crystals comprising the composite metal halide.

[0143] Embodiment 91. The process according to any one of embodiments 85 to 90, further comprising forming an oriented crystalline material comprising a crystalline orientation selected from the group comprising <010>, <100>, and <001>. Embodiment 92. The process according to embodiment 90 or 91, further comprising growing crystals from a melt, the melt comprising the composite metal halide and optionally a dopant material. Embodiment 93. The process according to any one of embodiments 85 to 92, wherein the ion conductive material is polycrystalline. Embodiment 94. The process according to any one of embodiments 85 to 93, wherein the ion conductive material comprises a charge-neutral Me content of up to 0.5 wt% based on the weight of the ion conductive material. x N k Embodiment 95. The process according to any one of embodiments 85 to 94, wherein the ion conductive material comprises a Me N x content of at least 0.1 ppm and at most 10 ppm by mass ratio based on the weight of the ion conductive material. k ​​​​​​​​​Embodiment 96. The ionic conductive material has a maximum of 0.5 wt % of charge-neutral M x N content, and the process according to any one of Embodiments 85 to 95 . Embodiment 97. The ionic conductive material has a mass ratio of at least 0.1 ppm and at most 10 ppm of charge-neutral M x N content, and the process according to any one of Embodiments 85 to 96. Embodiment 98. The ionic conductive material further forms Li4(NH2)3Cl, Li7(NH2)6C l, Li2Br(NH2), Li 13 [NH]6Cl, LiCl-NH3, LiBr-4 NH3, or a combination thereof, and the process according to any one of Embodiments 85 to 97 . Embodiment 99. The ionic conductive material further contains NH3, NH4X, or a combination thereof , and the process according to any one of Embodiments 85 to 97.

[0144] Example Example 1 Samples 1 to 30 with the compositions shown in Table 1 were prepared. Table 1 lists the contents of impurities in simple metal halides, and the phases of the individual impurities were detected by XRD analysis combined with Rietveld refinement for quantitative analysis by the presence of characteristic diffraction peaks corresponding to parasitic phases . All samples had a metal nitride content of at most 10 ppm. .

[0145] Samples 1, 2, 4 to 6, 15, 17, 30 were prepared by pressing ceramic pellets and heating them under dry inert conditions. The pellets, except for Sample 6, were prepared according to the embodiments of this specification . It was formed according to the wet ammonium route described above. Sample 6 was formed using the one-step forming process described in the embodiments of this specification. It was formed using the one-step forming process described in the embodiments of this specification. The pellets are 5 - 13 mm (diameter ) × 0.5 - 4 mm (thickness). Samples 8 - 14 and samples 18 - 29 are sliced from single crystals formed according to the embodiments of this specification. Also, for the formation of samples 20, 21 , 23, LiCl salt, LiBr salt, and LiI salt were used respectively as additives to the starting materials for the crystal growth of the anion substitution compound. , 23, LiCl salt, LiBr salt, and LiI salt were used respectively as additives to the starting materials for the crystal growth of the anion substitution compound. l salt, LiBr salt, LiI salt were used respectively as additives to the starting materials for the crystal growth of the anion substitution compound.

[0146] The ionic conductivity of the samples was measured by electrochemical impedance spectroscopy using gold block electrodes, under the conditions of an alternating current frequency of 3 MHz - 10 Hz, a peak-to-peak sinusoidal alternating voltage signal of 10 - 5 0 mV, and room temperature (about 22 °C).

[0147] The ionic conductivities of the bulk crystals of samples 1, 2, 4 - 6, 15, 17, 30 are included in Table 1. The characteristics of the conductivity of the bulk grains appear at the highest frequency and are related to the lowest value of the double-layer capacitance. Therefore, the contribution of the conductivity from the bulk grains can be separated from the grain boundaries and electrode contacts. The characteristics of the conductivity of the bulk grains appear at the highest frequency and are related to the lowest value of the double-layer capacitance. Therefore, the contribution of the conductivity from the bulk grains can be separated from the grain boundaries and electrode contacts. be distinguished.

[0148] In sample 3, neither direction A nor direction B corresponds to the azimuth showing the maximum thermal conductivity and / or ionic conductivity of Li3YCl6. When sliced in the A direction, a ceramic sample with randomly oriented crystallite grains was obtained. The A direction can be determined by the vector a, where a = α * <100> + β * <010>, where -1.0 < α < 1.0 and -1.0 < β < 1.0. When sliced in the B direction, an arrangement close to the crystal orientation <001> An oriented ceramic sample having a direction was obtained.

[0149]

Table 1

Table 1

[0150] Example 2 A polycrystalline block of Li3YB6 was formed in a cylindrical shape of 7 cm x 10 cm. This block is composed of single crystals sized from mm to cm densely arranged in a mica-like layered structure. For a small piece cut out from the center of this block, the bulk ionic conductivity was measured. This small piece was polished into a parallel plate sample with a thickness of about 0.7 mm, and the impedance was measured in the same manner as in Example 1. As a result, it was about 0.5 or 2.5 mS / cm depending on the direction of the selected sample. By X RD analysis, it was confirmed that the two samples had different crystallographic orientations. The first sample mainly (more than 80%) having crystal grains oriented substantially along the crystallographic direction <100> had the highest thermal conductivity and showed a higher ionic conductivity. The second sample demonstrated randomly oriented crystal grains having a crystallographic orientation belonging to a plane orthogonal to the <0

[0151] 01> direction. The first sample mainly (more than 80%) having crystal grains oriented substantially along the crystallographic direction <100> had the highest thermal conductivity and showed a higher ionic conductivity. The second sample demonstrated randomly oriented crystal grains having a crystallographic orientation belonging to a plane orthogonal to the <0 01> direction. The first sample mainly (more than 80%) having crystal grains oriented substantially along the crystallographic direction <100> had the highest thermal conductivity and showed a higher ionic conductivity. The second sample demonstrated randomly oriented crystal grains having a crystallographic orientation belonging to a plane orthogonal to the <0

[0152] Example 3 The crystalline pure raw material was ground using a grinder of an automatic mortar and pestle. This low-energy grinding maintains the purity of the material. When the same material was ground with a high-energy ball mill, partial decomposition of the pure substance was observed as indicated by the appearance of a small signal of a simple halide in the XRD analysis. The conductivity of the decomposed powder was that of the pure powder and the oriented crystal ... It was lower than that of the ceramic.

[0153] Example 4 [Table 4]

[0154] It should be noted that high-energy ball milling synthesis can cause not only the synthesis reaction of the main complex metal halide phase, but also the decomposition reaction to occur in parallel. High-energy ball milling synthesis, compared with the process of the embodiments of this specification, has a significantly higher content of simple compounds such as LiX and YX3 that exist as impurities in the vicinity of the main Li3YX6 phase. There is a possibility of becoming high.

[0155] Also, when starting from an oxide (Y2O3) or a carbonate material (Li2CO3) and adding ammonium halide in a solid-phase reaction at 1 bar atmospheric pressure, it should be noted that a single phase of Li3YX6 may not be synthesized. For the conversion of rare-earth metals (i.e., Y in the example of Li3YX6) to halide compounds, at least two chemical reactions can occur. One main reaction can result in the synthesis of YX3 that can further react to form the Li3YX6 phase. The second reaction can result in the formation of YOX. YOX is a stable compound and may exist as an impurity in the final product of Li3YX6.

[0156] Example 5 Additional samples were formed. Sample 35 was synthesized by placing a stoichiometric mixture 3 of LiBr and YBr in a welded quartz ampoule and heating it to 650 °C under vacuum. After the reaction mixture melted, it was given a soak time of up to 1 hour at 650 °C until the reaction product dissolved in its own flux. ​It was made to be so. After that, the temperature of the quartz ampoule was quickly lowered (within 2 - 3 minutes) to 400 °C , which helped to minimize the partial decomposition of the inconsistent Li3YBr6 phase. After that, the temperature of the quartz ampoule was gradually lowered to room temperature at a rate of 50 - 100 °C / hour.

[0157] Samples 36 and 37 were synthesized according to the embodiments of this specification and optionally maintained ammonium. The amount of residual ammonium was estimated by post - heating the compound to a melting temperature that allows complete sublimation of ammonium halide from the charge. The ionic conductivity in the bulk of the samples was measured in the same manner as described in Example 1.

Table 5

[0158] Advantages, other advantages, and solutions to problems have been described above with respect to specific embodiments. However, advantages, advantages, solutions to problems, and any features (s) that may give rise to or make more prominent any advantage, advantage, or solution should not be construed as important, essential, or essential features of any or all of the claims. In this specification, references to a material containing one or more components can be construed to include at least one embodiment in which the material consists essentially of the one or more specified components. The term "consisting essentially of" is construed to include a composition that contains these specified materials and excludes all other materials except minor contents (e.g., impurity contents) that do not significantly change the properties of the materials. Additionally, or alternatively, in certain non - limiting embodiments, any of the compositions specified herein may essentially exclude materials not explicitly disclosed. ​​​​​​​​​​ It is included. Embodiments of this specification include ranges of the contents of specific components within a material, and it will be understood that the contents of the components within a given material total 100%.

[0159] The specification and illustrations of the embodiments described herein are intended to provide a general understanding of the structures of the various embodiments. The specification and illustrations are not intended to be an exhaustive and comprehensive description of all elements and features of the devices and systems using the structures or methods described herein. Separate embodiments may also be provided in combination in a single embodiment, and conversely, for the sake of brevity, the various features described in the context of a single embodiment may also be provided separately or in any sub-combination. Further, references to values within a range include each and every value within that range. Many other embodiments may become apparent to those skilled in the art after reading this specification. Other embodiments may be used and derived from this disclosure such that structural substitutions, logical substitutions, or other changes can be made without departing from the scope of this disclosure. Accordingly, this disclosure is regarded as illustrative rather than restrictive. ​​​​​​​​​​​< / hklm> < / hkl> < / hklm> < / hkl> < / hklm> < / hkl> < / hklm> < / hkl> < / hkl> < / hklm> < / hkl>

Claims

1. 1. A solid, ionically conductive material comprising a complex metal halide material, Here, the composite metal halide material is M ３－ｚ (Me ｋ＋ ) ｆ X ３－ｚ＋ｋ＊ｆ ,in Represented, −3≦z<3; 2≦k<6; 0≦f≦1; M comprises an alkali metal element; Me is a divalent metal element, a trivalent metal element, a tetravalent metal element, a pentavalent metal element, a hexavalent metal element, a metal element, or a combination thereof; and X comprises a halogen; Here, the complex metal halide material is a charge-neutral Me ｘ N ｋ Or M ｘ At least N The solid ion conductive material further includes one of the above, wherein x is the valence of nitrogen N and k is the valence of Me. material.

2. M ３－ｚ (Me ｋ＋ ) ｆ X ３－ｚ＋ｋ＊ｆ The present invention includes a complex metal halide material represented by 1. A solid, ionically conductive material comprising an oriented ceramic material comprising: −3≦z<3; 2≦k<6; 0≦f≦1; M includes an alkali metal element including Li; Me is a divalent metal element, a trivalent metal element, a tetravalent metal element, a pentavalent metal element, a hexavalent metal element, The solid ion includes a metal element, or a combination thereof, and X includes a halogen. Conductive material.

3. M' The complex metal halide material is １－ｄ－ｅ , Na ｄ , M ｅ ) ２ Li １－ｚ’ (Me ｋ＋ ) ｆ X ３＋ｋ＊ｆ－ｚ’ is represented by: 0≦d≦1; 0≦e<1; 0<=(d+e)<1; −1≦z′<1; M comprises at least one of Li, Na, and M′; and The solid according to claim 1 or 2, wherein M' comprises at least one of K, Rb, and Cs. Ion conductive material.

4. z is -0.95 to 0.95, and M is at least one of Na and Li. The solid ionically conductive material according to claim 1 or 2.

5. Me is a rare earth element, an alkaline earth metal element, Sn, In, Zn, Zr, or any of these. The solid, ionically conductive material of any one of claims 1 to 4, comprising a combination of:

6. Me is Y, Ce, Gd, Er, Zr, La, Yb, In, Mg, Sn, Zn or the like. The solid, ionically conductive material according to any one of claims 1 to 5, comprising any combination thereof. 。

7. X is F, Cl, Br, and I, and optionally -NH ２ (amide), -(NH) ０ ．５ (imide), -OH (hydroxide), -BH ４ (borohydride), -BF ４ Also comprises at least one anionic group including any combination thereof.

7. The solid, ionically conductive material according to any one of claims 6 to 6.

8. The complex metal halide is (Li １－ｄ Na ｄ ) ２ Li １－ｚ Me ｋ＋ X ３＋ｋ－ｚ in Represented, Me comprises a rare earth element, In, Sn, Zr, or a combination thereof; According to any one of claims 1 to 6, 0≦d<1 and -0.95≦z=<0.

95. of solid ionically conductive materials.

9. 9. The composition according to claim 1, wherein z≦0.5, z≦0.3, or z≦0.

2.

2. The solid, ionically conductive material as described above.

10. d≧0.01 or d≧0.05 or d≧0.1, and d≦0.8 or d The solid, ionically conductive material of any one of claims 1 to 9, wherein the n-th order is ≦0.

5.

11. The composite metal halide material may be a single crystal, a ceramic, or any combination thereof.

13. The solid, ionically conductive material of claim 1 comprising a combination of

12. The weight of the complex metal halide material is calculated based on the weight of the simple metal halide material.

12. The method according to claim 1, wherein the total content of halogenated compounds is up to 10 wt. %. of solid ionically conductive materials.

13. The composite metal halide material has a crystal orientation represented by <HKL> or <HKLM>. The ionic conductivity in the crystal orientation of <HKL> or <HKLM> is different from that in the crystal orientation of <HKL> or <HKLM>. The method according to any one of claims 1 to 12, characterized in that the ionic conductivity is higher than that of The solid ionically conductive material described above.

14. A layer comprising the solid, ionically conductive material according to any one of claims 1 to 13, , an electrolyte layer, a mixed ionic and electronic conducting layer, or any combination thereof. Lithium secondary battery.

15. (NH ４ ) ｎ Me ｋ＋ X ３＋ｋ forming a solid ionically conductive material, The method comprises: (NH ４ ) ｎ Me ｋ＋ X ３＋ｋ The formation of REX ３ The water content of the hydrated salt containing N.H. ４ X, where n>0; Me is a rare earth element, Zr or and combinations thereof, wherein X is one or more halogens.

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