Electrolyte materials and methods of formation

Abstract

To provide a solid electrolyte material including a disorder in the crystalline structure and methods of forming the same.SOLUTION: A solid electrolyte material includes a halide-based material having a crystalline structure including a disorder. In an embodiment, the solid electrolyte material includes a crystalline structure including stacking faults. In another embodiment, the solid electrolyte material includes a crystalline phase including a crystalline structure represented by a space group of the hexagonal system or a space group of a rhombohedral lattice system. In another embodiment, the solid electrolyte material includes a crystalline phase including a crystalline structure represented by a monoclinic system space group and a unit cell containing a reduced number of halogen atoms.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The following relates to electrolyte materials and methods of forming the same, particularly to solid state electrolytes containing irregularities in the crystal structure. The present invention relates to a porous material and a method for forming the same. [Background technology]

[0002] By enabling a lithium metal anode, solid-state lithium batteries offer a Compared to lithium-ion batteries, they offer higher energy density and faster recharge times, and are more reliable. The industry continues to seek improved solid electrolyte materials. do. Summary of the Invention

[0003] The present disclosure can be better understood by reference to the accompanying drawings, many of which are incorporated herein by reference. Many features and advantages will be apparent to those skilled in the art. [Brief explanation of the drawings]

[0004] [Figure 1A] FIG. 1 illustrates the crystal structure of an exemplary solid electrolyte material according to an embodiment. [Figure 1B] FIG. 1 shows another crystal structure. [Figure 1C] FIG. 2 illustrates the crystal structure of another exemplary solid electrolyte material, according to an embodiment. [Figure 2A] FIG. 1 shows further crystal structures. [Figure 2B] FIG. 1 shows another crystal structure. [Figure 2C] FIG. 2 illustrates the crystal structure of another exemplary solid electrolyte material, according to an embodiment. [Figure 2D] FIG. 2 illustrates the crystal structure of another exemplary solid electrolyte material, according to an embodiment. [Figure 3] FIG. 1 is a diagram showing a crystal structure. [Figure 4]FIG. 1 shows another crystal structure. [Figure 5] FIG. 1 illustrates different crystal structures. [Figure 6A] This is a simulated powder X-ray diffraction spectrum of a halide-based material. [Figure 6B] This is a simulated powder X-ray diffraction spectrum of a halide-based material. [Figure 6C] This is a simulated powder X-ray diffraction spectrum of a halide-based material. [Figure 7A] 1 shows a spectrum of an X-ray diffraction simulation of a halide-based electrolyte material. [Figure 7B] 1 is a simulated X-ray diffraction spectrum of another halide-based electrolyte material. [Figure 7C] 1 is a simulated X-ray diffraction spectrum of another halide-based electrolyte material. [Figure 7D] 1 is a simulated X-ray diffraction spectrum of another halide-based electrolyte material. [Figure 7E] 1 is a simulated X-ray diffraction spectrum of another halide-based electrolyte material. [Figure 8] 1 is a flowchart illustrating a process for forming a solid electrolyte material according to one embodiment. [Figure 9] FIG. 1 includes an X-ray diffraction pattern of a halide-based electrolyte material. [Figure 10] This is a crystal structure model of a solid electrolyte material. [Figure 11] This is a crystal structure model of a solid electrolyte material. [Figure 12] This is a crystal structure model of a solid electrolyte material. [Figure 13] This is a crystal structure model of a solid electrolyte material. [Figure 14A] FIG. 1 shows an X-ray diffraction pattern of a halide-based electrolyte material. [Figure 14B] FIG. 1 shows an X-ray diffraction pattern of a halide-based electrolyte material. [Figure 15]FIG. 1 shows an X-ray diffraction pattern of a sample of a halide-based electrolyte material. [Figure 16] FIG. 1 shows an X-ray diffraction pattern of a halide-based electrolyte material. DETAILED DESCRIPTION OF THE INVENTION

[0005] Those skilled in the art will appreciate that elements in the figures are illustrated for simplicity and clarity and are not necessarily drawn to scale. For example, the dimensions of some of the elements in the drawings may differ from those of the present invention. Some elements may be exaggerated relative to other elements to help better understand the embodiments. The use of the same reference symbols in different drawings indicates similar or identical Shows the item.

[0006] To facilitate an understanding of the teachings disclosed herein, the following description should be read in conjunction with the drawings, in which: The following description provides specific implementations and examples of the teachings. This focus is provided to facilitate explanation of the teachings and to clarify the scope of the teachings. or should not be construed as limiting the applicability thereof.

[0007] As used herein, "comprises" and "comprises" sing," "includes," "including," "has The terms "has," "having," or any other Variations are intended to cover non-exclusive inclusions. For example, a list of features The process, method, article, or apparatus comprising the features is not necessarily limited solely to those features. Any other features not expressly recited, or any such process, method, article, or apparatus. Additionally, unless expressly stated otherwise, "Or" refers to an inclusive "or" and not an exclusive "or." For example, "the condition "A or B" is satisfied by one of the following: A is true (or exists) and A is false (or does not exist) and B is true (or or exists), and both A and B are true (or exist).

[0008] The use of "a" or "an" refers to the elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention ( This description is made to give a general sense of the It is clear that the meaning should be read as including one more, and that it is not. Except where expressly stated, the singular includes the plural and vice versa.

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

[0010] Embodiments herein are directed to halide systems that contain certain irregularities in their crystal structure. The present invention relates to solid electrolyte materials including (electrolyte-based) electrolyte materials. exhibiting improved properties compared to other materials of the same composition without the Conductivity, mechanical properties such as deformability and plasticity, electrochemical stability, chemical stability, thermal stability electrical resistivity, particle morphology and / or size, electrode wettability, etc., and / or The solid electrolyte material can be used in electrochemical applications such as solid-state lithium-ion batteries. The present invention can be used in semiconductor devices. The present invention relates to a method for forming a solid electrolyte material having a controlled disorder in the crystal structure. This allows for controlled formation of the material while also allowing for control of the crystallinity of the material.

[0011] In one embodiment, the solid electrolyte material is M 3ーZ (Me k+ ) f X 3-Z+k*f Represented by wherein -3≦z<3 and k is Me valence of 2≦k<6, 0≦f≦1, M includes an alkali metal, Me In a further embodiment, X comprises a metal other than an alkali metal and X comprises a halogen. The halogenide-based electrolyte material is a complex metal halide. In certain embodiments, f is not 0. Me may contain two or more metal elements. k can be the average of the sum of the valences of each metal element, for example, when Me is equimolar. If the quantity of trivalent and tetravalent elements is included, k = (3 + 4) / 2 = 3.5. In embodiments, k can be 2 or 3 or 4 or 5.

[0012] Upon reading this application, one skilled in the art will recognize that atomic vacancies ( It helps to understand the crystal structure. To do this, atomic vacancies can be added to the formula of the halide-based material, and the formula including the atomic vacancies becomes , M 3-Z (Me k+ ) f · y X 3-Z+k*fwhere "·" represents the unit represents an atomic vacancy in the lattice, and Y is the atomic vacancy position. In certain embodiments, y is the number of * It can be (k-1).

[0013] In one embodiment, M can include at least one of Li and Na. For example, M can be: In another embodiment, M can be Li, Na, K, R In a further embodiment, M may comprise one or more of a, b, Cs, or any combination thereof. For example, M can be any of Li, Na, K, Rb, and Cs. The alkali metal element may consist essentially of one or more alkali metal elements selected from the group consisting of: In one example, M can consist of Li. In yet another example, M can consist of Li and Na, K, In yet another example, it may be a combination of at least one of Rb and Cs. In another example, M may consist of Na and at least one of Cs and Rb. , M can consist of at least one of Na and Cs.

[0014] In another embodiment, Me is selected from the group consisting of alkaline earth metal elements, 3d transition metals, rare earth elements, Zn, Z r, Hf, Ti, Sn, Th, Ge, V, Ta, Nb, Mo, W, Sb, Te, In, B For example, Me may include Mg, Al, Ga, Cu, or any combination thereof. Alkaline earth metals such as Ca, Sr, or Ba, Zn, Cu, or any combination thereof In another example, Me may include a rare earth element. In a particular implementation, Me may include a rare earth element. In another specific example, Me can be one or more of the following elements: Y, Ce , Gd, Er, Zr, La, Cu, Yb, In, Mg, Zn, Sn, or any of them It may include a combination.

[0015] In one embodiment, X can include a halogen, such as Cl, Br, I, or any combination thereof. In one example, X may include at least one of Cl and Br. In a particular implementation, X can consist of Cl, Br, or a combination thereof. In particular examples, X consists of one The halogens may be any of the above.

[0016] In another embodiment, the halide-based material is NH + In certain embodiments, the phase may include So, the halide material is (NH4) n M 3-Z (Me k+ ) f X n+3-Z+k* f (wherein n>0). In the formula of the embodiment of the present specification, M, Me, Symbolic letters such as n, f, Z, X, and k are used. As used in this disclosure, different implementations The same symbolic characters shown in the embodiments are intended to refer to the same or similar elements or values. In one embodiment, a particular element or value described with a symbolic character may be used with the same symbolic character. When letters are used, they may be applied to other embodiments. For example, The descriptions of M, Me, X, f, z, and k in this and other embodiments of the present disclosure are can be applied to.

[0017] In certain embodiments, the halide-based electrolyte material is Li 3-z Me k+ X 3-z+k When z is not 0, the metal halide complex is said to be non-stoichiometric. When z is 0, the metal halide complex is said to be stoichiometric. In another specific example, Me is selected from Y, Gd, Yb, Zr, In, Sc, Zn, Mg, Ca, Ba, Sn or a combination thereof, and X is Cl, B r or a combination thereof.

[0018] In a further embodiment, the halide-based electrolyte material may be represented by Li3MeBr6. In a further embodiment, the halide-based electrolyte material is represented by Li3MeCl6. In a particular example, Me can be selected from at least one metal element having a valence of 3. In another particular example, Me can include one or more metal elements, The average valence of the above metal elements is 3.

[0019] In another particular embodiment, the halide-based electrolyte material is a mixture of Li, Y, and Cl and B. For example, the halide-based electrolyte material can be , Li, Y, and Cl. In another example, the halide-based electrolyte material can be , Li, Y, and Br. The material can consist of Li, Y, Cl, and Br. In particular examples, the halides The electrolyte material is Li 3X Y 1-X Cl3 or Li 3X Y 1-X Br3 (0 in the formula <x<0 It can be expressed as (0.5).

[0020] In another particular embodiment, the halide-based electrolyte material contains Li, Gd, and Cl and For example, the halide-based electrolyte material can be composed of at least one of , Li, Gd, and Cl. In yet another example, the halide-based electrodes can be composed of Li, Gd, and Br. The electrolyte material can consist of Li, Gd, Cl, and Br. In a particular example, the halogen Lithium ion-based electrolyte materials 3x Gd 1-x Cl3 or Li 3x Gd 1-x Br3 (in the formula It can be expressed as: 0.01≦x<1.

[0021] Specific examples of halide-based materials include Li3YCl6, Li3YBr6, Li 2. 7Y 0.7 Zr 0.3 Cl6, Li 2.8 Y 0.8 Sn 0.2 Cl6, Li 3.2 Y 0. 8Zn 0.2 Cl6, Li 3.2 Y 0.8 Mg 0.2 Cl6, Li3Y 1 / 3 Zr 1 / 3 Mg 1 / 3 Cl6, Li3Y 1 / 3 Sn 1 / 3 Mg 1 / 3 Cl6, Li3Y 1 / 3 Zr1 / 3 Zn 1 / 3 Cl6, Li 2.95 Na 0.05 YBr6, Li 2.95 K 0.05 Y Br6, Li 2.95 Cs 0.05 YBr6, Li3Y 0.7 Gd 0.3 Br6, Li3 Y 0.8 Yb 0.2 Br6, Li3Y 0.9 La 0.1 Br6, Li 2.9Y 0.9 Ce 0.1 Br6, or Li3Y(Cl,Br)6.

[0022] In one embodiment, the halide-based electrolyte material has a crystal structure different from conventional crystal structures. For example, the crystal structure may have irregularities compared to conventional crystal structures. As used herein, "conventional structure" refers to a halide-based compound having the same composition. It is intended to refer to the regular crystalline structure of a material. Crystal structure is a system of crystals, lattices, and spaces. group, one or more unit cell parameters such as unit cell volume, valences a, b, c, or any of them combination, atomic number in the unit cell, stacking order, atomic vacancies, vacancy occupation, or any combination thereof Irregularity may include features including alignment. Irregularity may include a change in order related to any of these features. It could be.

[0023] In one embodiment, the halide-based electrolyte material comprises a layered atomic arrangement that may include disorder. In one embodiment, the crystal structure comprises atoms arranged in layers. The crystal structure may include stacking faults, and may include irregularities in the stacking of layers. Defects are occupied or vacant atomic positions (o) that cause disordering of the crystal planes in the crystal structure. vacant atomic position) It represents defects in the crystal structure caused by

[0024] Referring briefly to FIGS. 1A, 1B, and 1C, halide-based materials having the same composition Different crystal structures of the compound are shown. FIG. 1A is an illustration of a specific crystal structure of one example embodiment. 1B is a conventional crystal structure of a halide-based material. FIG. 1C is an alternative embodiment. 1 is an illustration of a specific crystal structure of an example of the crystal structure 100. Crystal structures 100, 101, and 102 are shown in FIG. In structure 101, the same atoms in different layers (i.e., That is, the position of atom 110, 120, or 130 remains the same in the stack, and the atom The locations of 110, 120, 130 and voids 140 follow the same pattern across the layers in structure 101. As shown, the structure 101 contains ordered layers of atoms and vacancies. In the structures 100 and 102, at least one of the atoms 110, 120, or 130 is stacked. At least some atomic positions are different from the positions of the same atoms in different layers or in the structure 100. Stacking faults are included because the positions of the atoms in the nuclei are shifted relative to the positions of the same atoms in the nuclei in the present disclosure. Upon reading this, one skilled in the art will understand that the shift in atomic position across the layers of a crystal structure can be stochastic. and that stacking faults in halide-based materials are present in the specific examples shown in FIGS. 1A and 1C. It can be understood that the present invention is not limited to the halide-based materials of the embodiments of the present specification. The material has more stacking faults (0% or close to 0%) than the structure shown in FIG. 1B, and 1C. Those skilled in the art will appreciate that the structure 100, 1 Please note that only a small portion representing 01 and 102 is shown in Figures 1A-1C, respectively. It can be further understood.

[0025] In certain embodiments, the halide-based material promotes improved properties of the halide-based material. The crystal structure may contain a certain amount of stacking faults that can cause the powder to break down. The final X-ray diffraction pattern may change, and in particular, only certain X-ray diffraction peaks may become unevenly broadened. Stacking faults are the cause of the solid state ionic breakdown. s 180(2010)1652-1659 (incorporated herein by reference in its entirety) According to the stacking fault quantification method described by TOPAS4.2 or FullProf (version 7.3 released in March 2020) 0), or another equivalent to TOPAS 4.2 or FullProf version 7.30 By using software such as the version of the software, Powder X-ray diffraction analysis of system materials, DIFFaX simulation and Rietveld Briefly, the quantitative method can be used to determine the The method may include fitting the simulation to an X-ray diffraction pattern of the powder. The primary blocks of the crystal structure can be defined by the These basic blocks can be made up of slabs and inter-slab spaces. Next, we divide the basic blocks into two or more possible stacking vectors (stackin g vector), the stacking vector can be If only one is generated exclusively, a complete stack (i.e., 0 % stacking faults). If the stacking vectors are staggered in the stacking direction of the crystal structure, Stacking faults occur. Simulation fitting to the X-ray diffraction patterns of halide-based materials The fitting involves changing one or more parameters of the crystal structure (called "parameter refinement"). ), and the least-squares difference minimization algorithm re difference minimization algorithm) This may include performing a test to identify and quantify stacking faults. After the torpedo analysis, instead of the stacking fault quantification method by Boulineau, the FAULTS software Software can be used.

[0026] In one embodiment, the crystalline structure has at least 20% stacking faults (e.g., at least 25%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, or at least 90% stacking faults). In some cases, the stacking of atomic layers is completely disordered. For example, the crystal structure is 100% In another embodiment, the stacking faults are at most 99%, for example at most 95%, Up to 92%, up to 90%, up to 85%, up to 80%, up to 75%, or up to 70%, etc. Furthermore, the crystalline structure may be within any of the minimum and maximum percentages set forth herein. In certain examples, the solid electrolyte material may include at least In another particular example, the solid may include a halide-based material having a crystalline structure comprising 50% or more of the halide-based material. The electrolyte material contains halide-based materials with more than 50% and up to 100% stacking faults. It can be seen.

[0027] A specific example of a halide-based material is yttrium bromide containing at least 50% stacking faults. May contain lithium yttrium bromide.

[0028] In certain embodiments, the halide-based material comprises a monoclinic crystal structure containing stacking faults. In certain embodiments, the crystal structure may be represented by the space group C2 / m. For example, Halide-based materials are yttrium bromide containing a crystal structure represented by C2 / m, which contains stacking faults. In another embodiment, the halide-based material may comprise rhombohedral silicon containing stacking faults. It may include a rhombohedral or hexagonal crystal structure.

[0029] Another specific example of a halide-based material is one in which the three stacking vectors are (0;0;1), (1 / 2;-1 / 6;1) and (1 / 6;-1 / 6;1) on the c-axis of the monoclinic lattice. Such halide-based materials may contain at least 50% stacking faults in the stacking direction along the A specific example of a material is yttrium lithium bromide. The halide-based materials having the specific stacking faults described above have improved properties such as ionic conductivity. For example, the vectors (0;0;1), (1 / 2;-1 / 6;1) and (1 / 6;-1 / 6;1) have at least 50% stacking faults along the c-axis of the monoclinic unit cell Yttrium lithium bromide has higher ionic conductivity than conventional yttrium lithium bromide. The exemplary yttrium lithium halide (li thium yttrium halide) has a pH of 1.7 to 3.1 mS / cm at room temperature. It can have ionic conductivity.

[0030] Compared to FIG. 1B, FIGS. 1A and 1C further show the positions of atoms 130 and vacancies 140. As shown, the position of atom 130 is 102 is highly intermixed with voids 140. Those skilled in the art will appreciate that the structure 100 and 102 is a highly mixed site of atoms 130 and vacancies. It is important to understand that this is a novel crystal structure that arises from the presence of the As shown in the specific example crystal structure 100, atom 130 interacts with vacancy 140. Similarly, in the crystal structure 102, the atoms 130 are highly intermixed with the vacancies 140. As shown in the crystal structure 101, the atoms 130 are separated from the vacancies 140. When the atoms 130 and vacancies 140 assume positions, there is an ordering of their positions. is further described later in this disclosure.

[0031] In another embodiment, the halide-based material comprises a crystal structure that differs from conventional crystal structures. In one aspect, the halide-based material may have a different crystalline structure than conventional materials. In certain embodiments, the solid state electrolyte may include a crystalline phase having a crystalline structure represented by a space group. The solution material is at the atomic level, the nanometer domain level (nanometric-do a halo comprising first and second crystalline phases integrated at the main-level, or both The nearest atomic distance is typically less than 0.5 nm, making it nanometer-sized. The domains of the molecule are larger than the nearest atomic distance, e.g., larger than 1 nm. In one embodiment, the halide-based material can have a first space group represented by and a first crystalline phase having a first crystalline structure represented by a second space group different from the first space group. and a second crystalline phase having a second crystalline structure represented by at least a first space group. The first crystal structure is different from conventional crystal structures. In particular, the first space group is different from conventional crystal structures. It is different from the space group of the structure.

[0032] In certain embodiments, the halide-based material promotes improved properties of the solid electrolyte material. For example, the solid electrolyte material may contain a halide or a first crystalline phase at a specific concentration. The concentration of the system material is at least 1% by weight, for example at least 4% by weight, at least 5% by weight, at least 8% by weight, at least 10% by weight, at least 15% by weight , at least 20% by weight, at least 25% by weight, at least 30% by weight, at least 3 5% by weight, at least 40% by weight, at least 45% by weight, at least 50% by weight, at least at least 60% by weight, at least 70% by weight, at least 80% by weight, or at least 90% by weight In yet another example, the halide-based material may include a first crystalline phase that is 0.01 wt. %. The halogenated materials may have a concentration of up to 95% by weight, for example up to 90% by weight, up to 85% by weight, % by weight, up to 80% by weight, up to 70% by weight, up to 65% by weight, up to 60% by weight, up to 55% by weight, up to 50% by weight, up to 45% by weight, up to 40% by weight, up to 30% by weight %, at most 25%, at most 15%, at most 8%, or at most 5% by weight Additionally, the halide-based material may contain a first phase having the minimum and maximum % of hydroxyl groups described herein. The first phase may be present in a range of concentrations, including any of the above percentages.

[0033] In another aspect, the halide-based material may facilitate improving the properties of the solid electrolyte material. In one example, the solid electrolyte material may contain a second phase at a specific concentration. The concentration of the compound-based material is at least 1% by weight, for example at least 4% by weight, at least 5% by weight, at least 8% by weight, at least 10% by weight, at least 15% by weight , at least 20% by weight, at least 25% by weight, at least 30% by weight, at least 3 5% by weight, at least 40% by weight, at least 45% by weight, at least 50% by weight, at least at least 60% by weight, at least 70% by weight, at least 80% by weight, or at least 90% by weight In yet another example, the material may include a halide-based material having a second crystalline phase that is 0.05 wt. The halogenated materials may have a concentration of up to 95% by weight, for example up to 90% by weight, up to 85% by weight, % by weight, up to 80% by weight, up to 70% by weight, up to 65% by weight, up to 60% by weight, up to 55% by weight, up to 50% by weight, up to 45% by weight, up to 40% by weight, up to 30% by weight %, at most 25%, at most 15%, at most 8%, or at most 5% by weight Additionally, the halide-based materials may contain certain second phases within the minimum and maximum percentages set forth herein. In an exemplary embodiment, the second phase may comprise a range of concentrations including any of the following: In a further exemplary embodiment, the second phase can have a conventional crystal structure. The crystal structure of the compound can have a second crystal structure that is different from the first crystal structure, and in certain embodiments, the second space group is , the space group of the conventional structure can be different.

[0034] In a further aspect, the halide-based material has a different crystal structure than the second and / or first. The third phase may include a third crystal structure having a third crystal structure that includes a crystal structure characteristic. The crystal structure may be represented by a third space group different from the first and second space groups. In a further aspect, the halide-based material can be described with respect to the concentration of the first or second phase. In still further embodiments, the halide-based material may include a third phase in any concentration as described above. The concentration of the amorphous phase may be up to 10% by weight or up to 5% by weight. The concentration of each phase in the halide-based material may be 1% by weight or up to 1% by weight. It is understood that the total may add up to 100% by weight.

[0035] In another embodiment, the halide-based material is a material having a space group different from the space group of conventional crystal structures. The crystal structure may consist essentially of a crystalline phase having a crystal structure represented by:

[0036] In certain embodiments, the solid electrolyte material has a first crystal structure represented by a first space group. The first space group may include a halide-based material including a first phase having a rhombohedral lattice system. The rhombohedral lattice system can be classified into the space groups R3, R-3, R32, R3m, and R3c. , R-3m, and R-3c space groups. In certain embodiments, the first crystalline phase is In another aspect, the compound can have a first crystal structure represented by the R-3m space group. , the second crystalline phase can be represented by a monoclinic space group. In certain embodiments, the second phase may include a crystal structure represented by C2 / m. Specific examples of halide-based materials include: Crystal phase with a crystal structure represented by R-3m, crystal with a crystal structure represented by C2 / m A further specific example of a halide-based material is the R-3m phase. The first crystalline phase has a crystal structure represented by C2 / m, and the second crystalline phase has a crystal structure represented by C2 / m. A further specific example of a halide-based material is a crystal represented by R-3m. a first crystalline phase having a structure represented by C2 / m; and a second crystalline phase having a crystal structure represented by Fd- The third crystalline phase may have a crystal structure represented by Fm-3m or Fm-3m. In this particular example, the halide-based material is a crystal having a crystal structure represented by R-3m. It can consist of a crystal phase.

[0037] Referring to Figures 1A, 1B, and 1C, Figure 1A shows an example of a R-3m FIG. 1B is a diagram of a specific example of a crystal structure represented by C2 / m. and FIG. 1C is a diagram of the crystal structure of one embodiment, represented in the C2 / m space group. In this case, the halide-based electrolyte material has a crystal structure represented by R-3m, as shown in Figure 1A. and a second phase having a crystal structure represented by C2 / m as shown in FIG. 1B. The first and second crystalline phases may include yttrium lithium bromide containing In another specific example, the nanometer domain level is integrated. As shown in Figure 1A, halide-based solid electrolyte materials have a crystal structure represented by R-3m. The composition may comprise yttrium lithium bromide, which may be comprised of a crystalline phase having a crystalline structure.

[0038] In another aspect, the solid electrolyte material has a crystal structure represented by a hexagonal space group. The hexagonal crystal system may include halide-based materials containing the

number

[0039] In another embodiment, the halide-based material is represented by a hexagonal crystal structure space group: A first crystal phase having a first crystal structure and a crystal structure represented by a space group of a crystal system other than a hexagonal crystal structure. and a second phase having a second crystal structure according to the present invention. In certain embodiments, the second phase may have a crystal structure represented by the space group P-3 In a further embodiment, the second phase may have a second crystalline structure represented by m1. can have a crystal structure that is represented by the orthorhombic crystal structure space group. In such a case, the second phase may have a second crystal structure described by the Pnma space group. do.

[0040] In certain embodiments, the halide-based electrolyte material is P63 / mcm or P63 / mm a first phase having a first crystal structure represented by P-3m1 or Pnma; and a second phase having a crystal structure of The inorganic electrolyte material has a first crystal structure represented by P63 / mcm or P63 / mmc. and a second phase having a second crystal structure represented by P-3m1 or Pnma. It can be.

[0041] Referring to Figures 2A-2D, Figure 2A is a diagram of a crystal structure 200 represented by Pnma. 2B is a diagram of a crystal structure 201 designated P-3m1, and FIG. 2C is a specific example of one embodiment. FIG. 2D is a diagram of an example crystal structure 202 represented by P63 / mcm. FIG. 2 is a diagram of the crystal structure 203 represented by a specific example of P63 / mmc.

[0042] In a particular example, the halide-based electrolyte material is P63 / mcm, as shown in FIG. 2C, or The first phase has a crystal structure represented by P63 / mmc as shown in Figure 2D, and the second phase has a crystal structure represented by P63 / mmc as shown in Figure 2A. The second one has a crystal structure represented by Pnma, as shown in FIG. 2B, or P-3m1, as shown in FIG. 2B. and yttrium lithium chloride including a first crystalline phase and a second crystalline phase. integrated at the child level, the nanometer domain level, or both. In the example, the halide-based solid electrolyte material is P63 / mcm as shown in FIG. 2C, or It can consist of a crystalline phase with a crystal structure represented by P63 / mmc as shown in Figure 2D. In another specific example, the halide-based solid electrolyte may include yttrium lithium chloride. The material is P63 / mcm as shown in Figure 2C or P63 / mmc as shown in Figure 2D. The first phase has a crystal structure shown in FIG. 2A, and the second phase has a crystal structure shown in FIG. 2B. A second phase having a crystal structure represented by P-3m1, which may consist of nitrite chloride. The compound may include lithium.

[0043] In one embodiment, the solid electrolyte material has a different structure within the unit cell compared to conventional crystal structures. In one aspect, the halide-based material may include a halide-based material having a crystalline structure containing a number of atoms. The bimetallic material may have a crystal structure that includes a unit cell that is disordered compared to conventional structures. In this embodiment, the irregular unit cell is a unit cell having a number of halogen atoms, a number of M atoms such as Li, a number of Me atoms, and a number of the number, the unit cell constant, the volume of a unit cell, such as a smaller unit cell, or any combination thereof In another aspect, the halide-based material may have a different crystal structure from conventional materials. It may include a crystalline structure that includes a unit cell that has a reduced content of halogen atoms compared to the crystalline structure.

[0044] In another particular embodiment, the halide-based material is a monohalide containing less than 12 halogen atoms. In one embodiment, the number of halogen atoms in a unit cell is at most In another embodiment, the units The number of halogen atoms in the lattice is at least 1, at least 2, at least 3, or less. Furthermore, the halide-based materials may be any of the minimum and maximum values ​​described herein. The crystal structure may include a unit cell containing halogen atoms in a range including any of the following: Halide-based materials may contain 2 to 6 halogen atoms within the unit cell.

[0045] In a further embodiment, the halide-based material is represented by a monoclinic space group and exhibits disorder. In one embodiment, the space group may be C2 / m. In other embodiments, the unit cell may contain fewer than 12 halogen atoms. Halide materials are represented by the monoclinic space group and are composed of units containing 3 to 5 halogen atoms. It may include a crystalline structure including a lattice.

[0046] In a further embodiment, the halide-based material is a crystal represented by a hexagonal space group. In one embodiment, the vacant The intervening group can be R-3m. In another embodiment, the unit cell contains up to eight halogen atoms. In at least one particular embodiment, the halide-based material has voids in a hexagonal crystal system. The term "halogen group" refers to a unit cell with up to six halogen atoms. In another aspect, the halide-based material is represented by a hexagonal space group and has at least It may also include a crystal structure containing a unit cell with 1.5 halogen atoms.

[0047] In a further embodiment, the halide-based material is represented by a rhombohedral lattice space group. In one embodiment, the unit cell may include less than 12 halogen atoms. , the unit cell can contain up to eight halogen atoms.

[0048] A conventional C2 / m unit cell contains 12 halogen atoms, e.g., Li3YBr6 Conventional Li3MeBr6 contains 12 bromine atoms in the unit cell. Representative examples of 3YBr6 include those containing less than 12 bromine atoms, e.g., up to 6 bromine atoms or up to A specific example of Li3YBr6 has four Br atoms. In one embodiment, Li3YBr6 may have a smaller monoclinic unit cell. A particular example may include an R-3m unit cell containing six Br atoms.

[0049] In one embodiment, the solid electrolyte material is a halogen-containing solid electrolyte material having a crystal structure with specific unit cell characteristics. In one embodiment, the halide-based material has unit lattice constants a, b, and A, B, and C can each independently comprise a unit cell having particular values ​​of A, B, and C. In another aspect, the unit cell may have a particular volume, a particular normalized volume, or any of these. It may include a combination.

[0050] In certain embodiments, the halide-based material is a crystalline material represented by the rhombohedral space group. The structure can include a structure in which the unit cell constants a and b are equal. Referring to FIG. 3, the parameters A rhombohedral unit cell 300 is shown, comprising a, b, and c. The lattice may be in the R-3m space group. In one embodiment, A or B or both contain specific values. For example, A or B may be at least 3.0 angstroms, at least 3.3 angstroms, Angstroms, at least 3.6 Angstroms, or at least 3.9 Angstroms In another example, A or B may be at most 4.8 Angstroms, at most 4. 6 angstroms, max 4.3 angstroms, max 4.2 angstroms, or up to 4.0 Angstroms. Furthermore, A or B may be any of the groups described herein. The range may include any of the minimum and maximum values. The fluoride-based material may include a crystalline structure containing specific C. In one example, C is at least one 5 Angstroms, at least 17 Angstroms, or at least 19 Angstroms In another example, C can be at most 21 Angstroms, at most 20.2 Angstroms. Angstroms, or up to 19.5 Angstroms. The range may be within a range including any of the minimum and maximum values ​​set forth in the specification.

[0051] In a further embodiment, the rhombohedral unit cell may include a unit cell volume V having a particular value. For example, V is at least 200 Å 3 , at least 210 Å 3 . Angstroms, at least 230 cubic angstroms, at least 250 cubic angstroms In another example, V can be: Up to 320 cubic angstroms, up to 310 cubic angstroms, up to 290 Angstroms cubic, up to 275 Angstroms cubic, or up to 270 Angstroms cubic In certain instances, V may be any of the minimum and maximum values ​​described herein. The range may include either one of the following:

[0052] In a further aspect, the rhombohedral unit cell has a unit volume V per formula unit. N / FU Contains The normalized volume can be included, V N / FU =V / N FU and N FU is the formula in the unit cell In certain embodiments, the unit cell is a specific V N / FU In one example, The halide-based material is at least 200 cubic angstroms, at least 210 cubic Angstroms, at least 230 cubic angstroms, at least 250 cubic on Angstroms, or at least 260 cubic Angstroms of V N / FU Crystal structure containing In another example, V N / FU is at most 290 cubic angstroms and at most 2 75 cubic angstroms, up to 270 cubic angstroms, or up to 268 cubic In a particular example, V N / FU is the minimum value and The range can be inclusive of either the maximum or minimum value.

[0053] In a further aspect, the rhombohedral unit cell has a unit volume per halogen atom, V N / AA The normalized volume can include V / NAA =V / N AA and N AA is in the unit cell In certain embodiments, the halide-based material may be a halogen-containing material having a specific V N / AA In one example, V N / AA is at least 30 cubic angstroms Angstroms, at least 34 cubic angstroms, at least 38 cubic angstroms, It may be at least 42 cubic angstroms, or at least 46 cubic angstroms. In another example, V N / AA is a maximum of 50 cubic angstroms and a maximum of 48 cubic ohms. Angstroms, or up to 47 cubic Angstroms. N / AA can be within a range that includes any of the minimum and maximum values ​​described herein. .

[0054] In certain embodiments, the halide-based materials have a unit cell volume that is smaller than that of conventional crystal structures. The crystal structure may be represented by a small monoclinic space group. See Figure 4. and a monoclinic unit cell 400 is shown, with parameters a, b, and c, and c are different from each other. In certain embodiments, the unit cell can be in the C2 / m space group. In the above example, A, B, and C may independently contain specific values. For example, A must be at least 5. 8 Å, at least 6.1 Å, at least 6.3 Å Angstroms, at least 6.5 Angstroms, at least 6.7 Angstroms, or In another example, A can be at least 6.9 Angstroms. stroms, up to 7.6 angstroms, up to 7.3 angstroms, up to 7 0.2 Angstroms, or up to 7.0 Angstroms. It may be within a range that includes any of the minimum and maximum values ​​set forth herein. In some examples, B is at least 3.0 Angstroms, at least 3.3 Angstroms. Angstroms, at least 3.6 Angstroms, or at least 3.9 Angstroms In another example, B is at most 4.8 angstroms, at most 4.6 angstroms. mm, up to 4.3 Angstroms, up to 4.2 Angstroms, or up to 4.1 Furthermore, B may be any of the minimum and maximum values ​​described herein. In one example, C is at least 6.1 Angstroms. Angstroms, at least 6.4 Angstroms, or at least 6.8 Angstroms. In another example, C may be at most 7.9 Angstroms, at most 7.6 Angstroms. The thickness may be up to 7.2 Angstroms, or up to 6.9 Angstroms. Additionally, C may be within a range that includes any of the minimum and maximum values ​​set forth herein. can.

[0055] In a further aspect, a monoclinic unit cell can include a unit cell volume V having a particular value For example, V is at least 110 Å 3 , at least 125 Å 3 . Angstroms, at least 140 cubic Angstroms, at least 160 cubic Angstroms In another example, V may be at least 170 cubic angstroms. Large: 500 cubic angstroms, Max: 400 cubic angstroms, Max: 310 cubic Angstroms, up to 250 cubic angstroms, up to 220 cubic angstroms Angstroms, up to 200 cubic Angstroms, or up to 180 cubic Angstroms In certain instances, V may be within a range that includes any of the minimum and maximum values ​​described herein. It can be within the range.

[0056] In certain embodiments, the monoclinic unit cell has a particular V N / FU In one example, a halo The nitride-based material has a thickness of at least 200 cubic angstroms, at least 210 cubic angstroms. Angstroms, at least 230 cubic angstroms, at least 250 cubic angstroms Angstroms, or at least 260 cubic Angstroms of V N / FU The crystal structure contains In another example, V N / FU is at most 320 cubic angstroms and at most 300 Angstroms cubic, up to 280 Angstroms cubic, or up to 270 Angstroms cubic In a particular example, V N / FU are the minimum and maximum values ​​described herein. The range may be inclusive of either the greater or lesser value.

[0057] In a further aspect, the monoclinic unit cell has a unit volume per halogen atom, V N / AA Including It can include a normalized volume, V N / AA =V / N AA and N AA is the unit cell represents the number of halogen atoms. In certain embodiments, the halide-based material may include a specific V N / AA of In one example, V N / AA At least 30 cubic angstroms mm, at least 34 cubic angstroms, at least 38 cubic angstroms, at least It may be at least 42 cubic angstroms, or at least 44 cubic angstroms. In another example, V N / AA is at most 54 cubic angstroms and at most 51 cubic angstroms. stroms, up to 49 cubic angstroms, or up to 47 cubic angstroms, Or it can be up to 45 cubic Angstroms. In a specific example, V N / AA This specification The range may include any of the minimum and maximum values ​​set forth in the document.

[0058] The conventional crystal structure of Li3YBr6 is represented by the C2 / m space group, with Two formula units, Li3YBr6, 12 Br atoms, and approximately 534 cubic angstroms of V An exemplary embodiment of Li3YBr6 has a crystal structure represented in the R-3m space group: and 1 formula unit, 6 Br atoms, and approximately 267 + / - 3% cubic angstroms per unit cell Another exemplary Li3YBr6 of an embodiment may contain 1000 mol of V per unit cell. The crystal structure is expressed in the C2 / m space group, contains 2 / 3 formula units, 4 Br atoms, and approximately 178+ / It may contain -3% cubic angstroms of V.

[0059] In another embodiment, the halide-based material has a crystalline structure represented by the hexagonal space group. The unit lattice constants a and b are equal. Referring to FIG. 5, the parameters a, A hexagonal unit cell 500 is shown, including a, b, and c. The molecule may be represented by the P63 / mcm space group. In another embodiment, the hexagonal unit cell is It can be represented by the P63 / mmc space group.

[0060] In one embodiment, the P63 / mcm unit cell can include a specific A, B, or C. , A or B, or both, are at least 5.0 angstroms, at least 5.5 angstroms angstroms, at least 6.1 angstroms, or at least 6.3 angstroms In another embodiment, A or B or both may be at most 8 Angstroms, or is at most 7.5 angstroms, or at most 7.0 angstroms, or at most 6. 5 Angstroms. Additionally, A, B, or both may be any of the most preferred In a further aspect, the halogen atom can be in a range including any of the lower and upper values. The nitride-based material may include a crystalline structure that includes a specific C. In one example, the C is at least 4. 8 Å, at least 5.3 Å, at least 5.7 Å In one example, C can be at most 6.0 Angstroms. 0.9 Angstroms, up to 6.4 Angstroms, or up to 6.1 Angstroms In a further example, C can be any of the minimum and maximum values ​​described herein. The range can be inclusive.

[0061] In a further aspect, the P63 / mcm unit cell comprises a unit cell volume V having a particular value. For example, V may be at least 150 cubic angstroms, at least 170 cubic angstroms, Angstroms, at least 190 cubic angstroms, at least 205 cubic on In a further example, V is at most 270 cubic angstroms, at most 250 cubic angstroms, at most 2 It may be 30 cubic angstroms, or up to 220 cubic angstroms. In examples, V can be within a range that includes any of the minimum and maximum values ​​described herein. can.

[0062] In certain embodiments, the P63 / mcm unit cell has a particular V N / FUIn one example, , halide-based materials are at least 150 cubic angstroms, at least 170 cubic angstroms Angstroms, at least 190 cubic angstroms, at least 200 cubic angstroms angstroms, or at least 210 cubic angstroms of V N / FU Crystal structure containing In another example, V N / FU is at most 270 cubic angstroms and at most 250 cubic angstroms, up to 230 cubic angstroms, or up to 220 cubic In a particular example, V N / FU is the minimum value described in this specification and maximum values.

[0063] In a further aspect, the P63 / mcm unit cell has a unit volume per halogen atom, V N / AA The normalized volume can include V N / AA =V / N AA and N AA is the unit represents the number of halogen atoms in the lattice. In certain embodiments, the halide-based material has a specific V N / AA In one example, V N / AA At least 25 cubic ounces Strome, at least 28 cubic Angstroms, at least 31 cubic Angstroms mm, at least 34 cubic angstroms, or at least 36 cubic angstroms Possibly. In another example, V N / AA is a maximum of 50 cubic angstroms and a maximum of 47 cubic Angstroms, up to 44 cubic angstroms, or up to 41 cubic angstroms Angstroms, or up to 38 cubic Angstroms. N / AA teeth , can be within a range including any of the minimum and maximum values ​​stated herein.

[0064] In one embodiment, the P63 / mmc unit cell can include a specific A, B, or C. , A or B, or both, are at least 2.5 angstroms, at least 2.8 angstroms angstroms, at least 3.2 angstroms, or at least 3.6 angstroms In another embodiment, A or B or both may be at most 5 Angstroms, at most 4.6 angstroms at maximum, 4.3 angstroms at maximum, 4.1 angstroms at maximum Angstroms, or up to 3.8 Angstroms. can be within a range that includes any of the minimum and maximum values ​​described herein. In further embodiments, the halide-based material may include a crystal structure containing specific C. , C is at least 4.8 angstroms, at least 5.3 angstroms, It may be at least 5.7 Angstroms, or at least 6.0 Angstroms. In the example, C may be at most 6.9 Angstroms, at most 6.4 Angstroms, or at most In a further example, C may be as small as 6.1 Angstroms. The range may be inclusive of either the maximum or minimum value.

[0065] In a further aspect, the P63 / mmc unit cell comprises a unit cell volume V having a particular value. For example, V may be at least 60 Å 3 , at least 65 Å 3 . Angstroms, at least 68 cubic angstroms, or at least 70 cubic angstroms In another example, V may be at most 85 cubic angstroms, at most 82 cubic angstroms, up to 78 cubic angstroms, up to 74 cubic angstroms In a further example, V may be any of the values ​​specified herein. The range may include any of the minimum and maximum values ​​set forth in the document.

[0066] In certain embodiments, the P63 / mmc unit cell has a particular V N / FU In one example, The halide-based material is at least 150 cubic angstroms, at least 170 cubic Angstroms, at least 190 cubic angstroms, at least 200 cubic on Angstroms, or at least 210 cubic Angstroms of V N / FU Crystal structure containing In another example, V N / FU is at most 270 cubic angstroms and at most 2 50 cubic angstroms, up to 230 cubic angstroms, or up to 220 cubic In a particular example, V N / FU is the minimum value and The range can be inclusive of either the maximum or minimum value.

[0067] In a further aspect, the P63 / mmc unit cell has a unit volume per halogen atom, V N / AA The normalized volume can include V N / AA =V / N AA and N AA is the unit represents the number of halogen atoms in the lattice. In certain embodiments, the halide-based material has a specific V N / AA In one example, V N / AA At least 25 cubic ounces Strome, at least 28 cubic Angstroms, at least 31 cubic Angstroms mm, at least 34 cubic angstroms, or at least 36 cubic angstroms Possibly. In another example, V N / AA is a maximum of 50 cubic angstroms and a maximum of 47 cubic Angstroms, up to 44 cubic angstroms, or up to 41 cubic angstroms Angstroms, or up to 38 cubic Angstroms. N / AA teeth , can be within a range including any of the minimum and maximum values ​​stated herein.

[0068] The conventional crystal structure of Li3YCl6 is in the Pnma space group, with a single unit cell of formula It contains 4 positions, 24 Cl atoms, and about 875 cubic Angstroms of V. Another conventional crystal structure of 6 is represented by the P-3m1 space group, with formula units per unit cell. 3 atoms, 18 Cl atoms, and approximately 655 cubic Angstroms of V. The typical Li3YCl6 can have a crystal structure represented by P63 / mcm, per molecule, 1 formula unit, 6 Cl atoms, and 218+ / -3% Å of V Another exemplary Li3YCl6 of an embodiment is represented by the P63 / mmc space group. The crystal structure may contain 1 / 3 formula units, 2 Cl atoms, and 7 It may contain 3+ / -3% cubic Angstroms of V.

[0069] In one embodiment, the solid electrolyte material has atomic disorder in the atomic positions of vacancies and Me. and irregular X1 and X2 atoms (X1 and X2 represent two different halogen atoms). , irregular vacancy sites and M atoms, irregular M and Me atoms, irregular M, Me, and vacancy sites Halide-based materials containing irregularities in the crystal structure, such as hole atoms, or any combination thereof. may include:

[0070] In another embodiment, the halide-based material has at least some of the positions of the vacancies and Me atoms. Crystal structures containing vacancies and Me atoms in which Me is disordered in atomic layers or linear atomic chains. In one embodiment, the halide-based material may have a structure in which the atomic positions of vacancies and Me atoms are atomically It may include a crystalline structure that is disordered, the disorder being at least 10%, at least At least 20%, at least 30%, at least 40%, at least 60%, at least 80% , or at least 90%.

[0071] Atomic disorder can be observed in the Rietveld refinement of X-ray powder diffraction patterns of halide-based materials. More specifically, the crystallographic structure including the positions of M atoms, Me atoms, and vacancies is refined by the After reading this application, those skilled in the art will be able to determine the crystal structure of the crystals based on the occupancy rate of the crystals. The atomic disorder can be understood based on the occupancy of the chemical sites, and can be analyzed in the following steps: Therefore, it can be determined on a case-by-case basis.

[0072] X-ray diffraction (XRD) analysis was performed on the powdered halide-based materials, and the XRD patterns were recorded. The simulated XRD patterns can be recorded to obtain the best fit. A set of methods to get the best fit and determine the occupancy of crystallographic sites. The crystal structure parameters (e.g., unit cell parameters, atomic vacancies, and By refining the XRD parameters (other parameters specified), the XRD of halide-based materials is fitted. Then, based on the occupancy of the crystallographic sites, The atomic disorder can be determined.

[0073] Here, Li3MeBr6 is used as an example of a halide material. Vacancies can be included in the formula, and halide-based materials are Li3Me· oct Expressed as 2Br6 The Li3MeBr6 according to the embodiment of the present invention is a crystal represented by the R-3m space group. When the occupancy of the Me site is 33.33%, the crystal structure is Octahedral vacancy oct and the position of Me atoms is complete It is completely atomically disordered, i.e., 100% Me-vacancy disorder (the atoms of vacancies and Me atoms) The molecular positions can be indistinguishable from the X-ray powder diffraction pattern. Li3MeBr6 can have a crystal structure represented by the C2 / m space group. To further aid in this, briefly referring to FIG. 1B, as shown, a Me atom 130 and a vacancy The co-occupancy of the crystallographic site 160 by 140 is low (i.e., less than 10%).

[0074] As another example, the vacancies in the crystal structure of Li3MeBr6 can be included in the formula, and the halogen Li3Me· oct 2Br6. Li3MeCl6 in the form of Li3MeCl6 can have a crystal structure described by the P63 / mcm space group. When the occupancy of the Me site is 33.33%, the crystal structure is composed of octahedral vacancies. oct and The Me sites are completely atomically disordered, i.e., 100 based on the powder XRD pattern. %Me-vacancy disorder (atomic positions of vacancies and Me atoms cannot be distinguished) do.

[0075] As described in the embodiments herein, halide-based materials can have multiple phases. The atomic disorder can be determined by considering the phase concentration. For example, The halide-based materials are represented by a first space group that differs from the corresponding conventional halide-based materials. A first crystalline phase having a crystal structure and a% atomic disorder (the concentration of the first crystalline phase is b% by weight) (can be expressed as follows) and a crystal structure represented by a second space group and irregular structures of c% of atoms. The second crystalline phase may have a regularity (the concentration of the second phase is d% by weight). The space group may be the same as or different from the corresponding conventional halide-based material. Niobium-based materials are linear total disordered. er) atomic disorder. D LT is the formula D LT =a% * b%+c% * To further aid understanding, in one example, the first phase has a concentration of 90%. and the atomic disorder can be 96%, and the second phase can have a concentration of 10 wt.% and The atomic disorder can be 6%. The atomic disorder of halide-based materials is D LT =90% * 96%+10% * 6%=87%.

[0076] In another embodiment, the halide-based material has a crystallographic structure in which both Me atoms and vacancies are occupied. In one embodiment, the multiplicity of the crystallographic site is 3. In another embodiment, the crystallographic site can be Wycoff position 3a or 3b.

[0077] In another embodiment, the halide-based material may be a crystallographic material dominated by both Me and M atoms. In one embodiment, the atomic disorder may include a crystalline structure containing Y and Li atoms. In certain embodiments, at least 5%, at least 10% of the Y atoms may be co-occupied. %, or at least 20% can co-occupy the Li sites. At most 50%, at most 70%, or at most 90% of the Y atoms may co-occupy the Li sites. In another particular embodiment, the Y atoms present at the Li sites are separated from one layer in the crystal structure to another. This can be caused by the migration of some Y atoms into the layer. This may result in a decrease (eg, a slight decrease) in the intensity of the first XRD peak of the nitride-based material.

[0078] In certain embodiments, the X-ray diffraction pattern of the halide-based material measured with CuK-α radiation is The peaks between 16° and 25° 2θ compared to the corresponding conventional halide-based materials. Specific examples of such halide-based materials are Li, Y, and B. In certain embodiments, X r (hereinafter referred to as "LYB") may have a chemical composition comprising: The X-ray diffraction pattern does not necessarily have to have multiple peaks between 2θ of 16° and 25°. In certain embodiments, the X-ray diffraction pattern essentially exhibits peaks between 16° and 25° 2θ. It does not have to be included.

[0079] Halide-based materials have XRD patterns that do not have peaks in a specific range of 2θ. It should be understood that the range may vary as the chemical composition changes. In this case, Me may be partially replaced by another Me metal, and the change in the 2θ range is This may be inversely correlated with the change in lattice constant caused by the substitution. The lattice constant of the LYB material described in the embodiment is determined by dividing Y by another Me ion of larger size. The 2θ range of 15.2°C to 23.75°C can be increased by 5% by selective substitution. In another example, the lattice constant of the LYB material is such that the Y is Partial substitution with other Me ions with smaller size can reduce the ion density by 7%, and There may be no XRD peaks at 2θ between 7.12° and 26.75°. Partial substitution of Me The lattice constants that can be affected by can include A, C, B, or any combination thereof. In some cases, A and C may be equally affected. In other cases, A and C may be slightly different. It can be affected.

[0080] Referring to FIGS. 1A to 1C, as shown in FIG. 1A, the crystal structure represented by R-3m is The positions of Me and vacancies are irregular. The octahedral site 160 is occupied by Me atoms 130 and vacancies 14. As shown, one-third of the octahedron 160 is occupied by Me. This structure indicates a relatively high degree of disorder in the Me vacancies. Compared to the conventional C2 / m shown in Figure 1B, atomic position 160 is nearly empty or nearly full. Therefore, one Me atom 130 and two vacancies 140 are arranged in the order of vacancy / vacancy (unfilled sphere). ) and filled / occupied (partially filled balls) This arrangement exhibits low disorder (i.e., less than 10%) of the Me vacancies. In Figure 1C, the illustrated C2 / m space group unit cell is much smaller than the conventional unit cell shown in Figure 1B. The volume is also small, and the Me atom and the vacancy are in the same position, i.e., 1 / 3 and 2 / 3 of the same position. This configuration also indicates a relatively high degree of disorder in the Me vacancies.

[0081] 6A and 6B show yttria bromide having the crystal structure shown in FIGS. 1A and 1B, respectively. The spectrum in Figure 6B includes a simulated powder X-ray diffraction spectrum of lithium. In comparison, the spectrum shown in Figure 6A has no peaks between 16° and 25° 2θ. This indicates that the Y and vacancy positions in the crystal structure of R-3m are completely random. Similarly, when compared with the spectrum in FIG. 6B, the spectrum shown in FIG. 6C shows This shows that the peaks from 6° to 25° 2θ are gone, which is the same as the conventional monoclinic crystal. Y in a crystal structure represented by the C2 / m space group with a unit cell approximately three times smaller than the unit cell The positions and void positions are completely random.

[0082] 7A to 7E show X-ray images of halide-based materials containing Li, Y, and Cl with different crystal structures. Figure 7A contains the spectrum of the diffraction simulation. Figure 7 shows the simulated spectra of halide-based materials with the crystal structure shown in Figure 7. B is a halide-based material having a crystal structure represented by P-3m1 as shown in Figure 2B. Figure 7C shows the simulated spectrum of the space group P63 / mc is a simulated spectrum of a halide-based material having a crystal structure represented by m. Referring to Figures 2A to 2C, the nuclei represented by Pnma (Figure 2A) or P-3m1 (Figure 2B) The crystal structure of P63 / mcm (Fig. 2C) has regular Y and vacancy positions. The structure is linearly irregular in the positions of Y210 and vacancies 220. The atomic order of O1 is such that Y210 and vacancies 220 alternate and regularly in a linear chain containing octahedra. The atomic disorder in Figure 2C is shown by the linear 2-chain structure containing the octahedron. 50% Y210 and 50% voids 220 are perfectly mixed within 30 In each XRD pattern, the linear irregularities are shown in Figure 7A. In comparison with Figure 7B, the peaks from 16.5 to 27.5° 2θ in Figure 7C are absent. This is demonstrated by:

[0083] Figure 7D shows a halo with irregularities in the crystal structure, including partial Y migration into the Li channel. 1 is a simulated spectrum of a fluoride-based material. In one example, at least 5 of the Y atoms %, at least 10%, or at least 20% can migrate into the Li channel. Figure 7E shows the simulation results of halide-based materials with the crystal structure of P63 / mmc. As shown in Figure 2D, and in comparison with Figures 2A and 2B, P63 / In the crystal structure of mmc, Y is completely mixed with Li atoms, as shown by 240. In a particular example, the halide-based material was yttrium lithium chloride. The disorder in the crystal structure may be a complete mixture of Y and Li sites. Compared with the spectra shown in FIGS. 7A and 7B, the spectra in FIGS. 7C to 7E At the torr, one or more peaks are missing from 16.5° to 27.5° 2θ. The XRD pattern shows the first XRD peak near 15.5° 2θ, even though it is reduced in intensity. The mark may be completely missing.

[0084] The halide-based materials of the embodiments herein may be any one or more of the halide-based materials referred to in the embodiments herein. The irregularities in the crystal structure, the average diffracting crystallite size, and the micro-strains ain), corrected mean FWHM, crystallographic density, or any combination thereof. It is worth noting that the crystallinity may be characterized by one or more irregularities, one or more Certain crystallinity characteristics, or any combination thereof, facilitate improved properties of solid electrolyte materials. Such properties may include, but are not limited to, ionic conductivity, mechanical properties, and the like. However, plasticity, conformability, compatibility, flexibility, electrochemical stability, chemical stability, and thermal stability are not properties, electronic resistivity, particle morphology and / or size, electrode wettability, etc., and / or their Any combination may be included.

[0085] In another embodiment, the solid electrolyte material is a halogen-containing solid electrolyte material having a particular average diffracting crystallite size. The average diffracting crystallite size may be greater than the coherent X-ray scattering domain size. Also known as X-ray diffraction analysis of halide materials and Scherrer's The formula L = (Kλ) / (β cos θ) (where L represents the average diffracting crystallite size and K is close to 1) is a dimensionless form factor with a typical value of 0.9 to 1; λ is the X-ray wavelength. β is the half maximum intensity (FWHM) after subtracting the instrumental line broadening. (where θ is the Bragg angle) It is possible.

[0086] In one embodiment, the average diffracting crystallite size is at least 20 nm, at least 25 nm, It may be at least 30 nm, at least 35 nm, or at least 40 nm. In the case of , the average diffracting crystallite size is 500nm max, 400nm max, 300nm max. m, at most 200 nm, or at most 100 nm. The crystallite size can be within a range including any of the minimum and maximum values ​​set forth herein. .

[0087] In further embodiments, the halide-based material may include microstrain. The microstrain ε is , a dimensionless parameter β=4ε tan θ as determined by X-ray diffraction analysis. , the minute distortion is 1% max, 0.6% max, 0.35% max, 0.2% max, or The strain may be at most 0.1%. In another embodiment, the strain may be zero. In some embodiments, the microstrain is at least 0.05%, at least 0.08%, at least It may be at least 0.005%, such as 0.1%, or at least 0.2%. The halogenide-based material may be a minor component of a range including any of the minimum and maximum percentages set forth herein. It may include distortion.

[0088] In a further embodiment, the halide-based material has a diffraction angle 2θ range of 10° to 80°. The correction may include a corrected FWHM averaged over the entire spectrum (referred to as the "corrected average FWHM"). Note that the positive mean FWHM refers to the mean FWHM corrected for instrument broadening. The broadening of the measurement instrument is performed under the same measurement conditions (diffraction) as the halide-based material being tested. under the conditions of the instrument geometry, slit, detector, or other hardware and optical parameters. , record the X-ray diffraction pattern of the highly crystalline standard commercial material LaB6 (supplier: NIST). The peak broadening of the standard material can be determined by the The peak broadening is subtracted to obtain the corrected FWHM as a function of the diffraction angle 2θ. The corrected average FWHM is less than 1.5%, up to 1.4%, up to 1.2%, and up to 1%. , at most 0.8%, or at most 0.5%. In another embodiment, the halide-based material is at least 0.5%, at least 0.8%, or at least 1% corrected mean FWHM Additionally, the corrected average FWHM may include any of the minimum and maximum % values ​​described herein. The range may be inclusive.

[0089] In one embodiment, the halide-based electrolyte material is a material having a specific conductivity determined by X-ray diffraction analysis. The crystallographic density can include the crystallographic density of the unit cell, which is given as the ratio of the mass to the volume of the unit cell: The mass of a unit cell is the number of atoms in the unit cell and the mass of each atom in the unit cell. In one aspect, the halide-based material has a low theoretical crystallographic density. In another embodiment, the halo may have a crystallographic density of at least 95% and up to 100%. The crystallographic density range for fluoride-based electrolyte materials is 2.0 g / cm 3 ~4.2g / cm 3 in It can be.

[0090] In certain embodiments, the crystallographic density range for the halide-based electrolyte material is If present, 3.0 g / cm 3 ~4.2g / cm 3 or 3.4 g / cm 3 ~3.9g / cm 3 In another particular embodiment, the crystallographic The density range is 2.0 g / cm when X is Cl. 3 ~3.2g / cm 3 or 2.2g / cm 3 ~2.8g / cm 3 It can be said that:

[0091] FIG. 8 illustrates a process for forming a solid electrolyte material including a halide-based material 800. The process 800 begins at block 802 with the addition of (NH4) n Me k+ X n+k Form In an exemplary embodiment, process 800 may include the step of: , NH4X, one or more Me metal compounds, one or more M metal compounds, or any of them In certain implementations, the method may include forming a reaction mixture containing the starting materials. Metal compounds can be non-hygroscopic. Metal compounds can be oxides, carbonates, sulfides, sulfates, hydrates, etc. The compound may be in the form of a salt, hydroxide, oxalate, acetate, nitrate, or any combination thereof. In a specific example, the starting material is Me2O k In certain instances, the starting material may include Earth oxides or hydroxides or carbonates, ZrO2 or Zr(OH)4 or Zr(CO3)2 or Zr(OH)2CO3·ZrO2 or any combination thereof. do.

[0092] In another example, the M metal compound may be a carbonate, such as lithium carbonate, sodium carbonate, or cerium carbonate. The metal may include, for example, sodium, or a combination thereof.

[0093] The starting materials are prepared in an acidic solution to facilitate synthesis in aqueous, alcoholic, or other polar liquid solutions. The acid may further comprise a carboxylic acid.

[0094] In one example, the metal compound can consist of M metal compounds. Exemplary M Metal Compounds may include halides (e.g., NaCl, CsCl, and LiCl).

[0095] The starting materials may be in a range of 0.1 to 1.5 wt % or ... They may be mixed together so that

[0096] In certain exemplary implementations, NH4X, one or more rare earth metal oxides (hereinafter "RE2O3 "), lithium carbonate, and hydrochloric or hydrobromic acid. can.

[0097] In an exemplary embodiment, process 800 can include steps of performing a reaction between starting materials. An exemplary reaction is shown below, focusing on the starting materials and reaction products in aqueous solution. 3 * Li2CO3+RE2O3+12 * HX+6 * NH4X--->2 * (NH4)3 REX6+3 * LiX+6 * H2O+3 * CO2

[0098] In view of the present application, one skilled in the art would be able to find a suitable compound in place of or in addition to Li2CO3. In addition to, or instead of, RE2O3, different alkali metals such as Na2CO3 or NaCl It is understood that compounds such as MgO or ZrO2 can also be used. Oxides of elements can be added to the reaction. It is understood that the reaction products may vary accordingly.

[0099] In an exemplary embodiment, the process 800 comprises the step of: k The moisture in (i.e. Using the reaction illustrated above as an example, The water in the hydrate can be converted to N It can be substituted with H4X to form (NH4)3REX6. The reaction product mixture includes an alkali metal halide such as Lix.

[0100] In one embodiment, process 800 comprises reacting (NH) n Me k+ X n+k and LiX In certain embodiments, process 800 may include forming a mixture of (NH) n M e k+ X n+k and forming a homogeneous mixture comprising LiX.

[0101] In one example, the reaction product mixture is filtered to remove larger particles and to separate the The larger particles can be used in either the starting material or the starting These include impurities associated with the remaining particles of the material, carbon, or any combination thereof.

[0102] Process 800 may proceed to block 804. In an exemplary embodiment, the reaction product The resulting mixture was dried and (NH4) n Me k+ X n+k and alkali metal halides This can promote the solid reaction with MX. Drying can be done in air or dry air, and / or can be used in vacuum or at 100mbar, 40mbar, 1mbar, or even 0.01mbar The reaction can be carried out under reduced pressure, such as under reduced pressure. In some cases, N2 or Ar may be used to facilitate the removal of water. In another example, heat may be applied to help evaporate the water. The heating temperature can be 100 to 160°C. The process can be continued until the amount of water remaining is a trace amount, such as 1% to 3% by weight.

[0103] In an exemplary embodiment, process 800 comprises reacting (NH) n Me k+ X n+k and MX In certain instances, the reaction may include carrying out a solid-state reaction using the reaction product described above. Continuing, the solid reaction of (NH4)3REX6 and LiX was carried out to obtain (NH4) n M 3-Z M e k+ X 3+n+k-z In a further example, the process 100 may include: (NH4) n M 3-Z (Me k+ ) f X 3+n-z+k*f The step of forming the

[0104] The process 800 proceeds to block 806, where M 3-Z (Me k+ ) f X 3-z+k*f of In an exemplary embodiment, the process 800 involves decomposing ammonium halide. In an exemplary embodiment, the solid solution may include a sublimation of ammonium halide. To achieve this, the material may be heated to a temperature of at least 150°C and up to 800°C. The heating temperature can be selected based on the composition of the halide-based material. For relatively volatile halide-based materials, the heating temperature can be relatively low. In the case of the melting point, the heating temperature may be at least 150°C lower than the melting point, and / or The heating temperature may be up to 50°C higher than the reactants and products. For example, the crucible may be made of quartz, alumina, silica-alumina, B It may be made of N, glassy carbon, or graphite. The sheet may have a pyrolytic carbon coating. Heating may be performed with air or dry air, etc. The process may be carried out in a dry, neutral atmosphere such as N2 or Ar to facilitate the process. Inert gas may be used. Heating should be carried out for at least 15 minutes and up to 12 hours. This may also be done.

[0105] In an exemplary implementation, the sublimation of NH4X is monitored by collecting and weighing the escaped NH4X. In certain instances, halide-based materials can essentially convert NH4X In another specific example, the amount of NH4X can be reduced to 0.5% by volume. may remain in the halide-based material.

[0106] In an exemplary implementation, after decomposition of NH4X, cooling can be performed. For example, in air, dry Cooling may be carried out in dry air or nitrogen atmosphere. In another example, the cooling temperature is less than 200°C ( For example, maximum 100°C, maximum 70°C, maximum 50°C, or maximum 30°C, etc.), or room temperature (e.g., 20 to 25°C). Optionally, Ar or N2 may be used to facilitate cooling. May be used.

[0107] In one embodiment, at certain cooling rates that can facilitate the formation of halide-based materials, Cooling can be performed. In one example, the cooling rate can be 10 to 100°C / min.

[0108] To form halide-based materials with higher stacking fault content, temperature cycling is used carefully. Note that the temperature should be carefully controlled, e.g., to prevent non-monotonous cooling or unintended activation. Annealing can reduce the stacking fault content. , annealing at a temperature less than 0.7Tm, where Tm is greater than 10 minutes. is the melting point (in Kelvin) of the halide-based material over time.

[0109] Oxygen-containing species (e.g., oxides, It is further noted that care should be taken to carefully control the number of Note that excess oxygen-containing species may be present in battery components formed using halide-based materials. This can lead to the formation of impurity phases that can reduce certain performance characteristics, such as the ionic conductivity of the For example, solid state or melt reactions may contain less than 10 ppm of water or limited oxygen levels. In a further example, the reaction can be carried out in a neutral atmosphere containing an acid or an ammonium halide. The initial amount of halide compounds such as fluorine is to obtain a complex halide material in a high yield, and an oxygen-containing phase derived from a metal oxide or metal carbonate raw material To reduce the level of β-glucan to below the level detectable by XRD, a theoretical chemical balance equation It may be higher than the stoichiometric amount based on (for example, at least 10% higher).

[0110] In another embodiment, the halide-based material has improved ionic conductivity. The on-conductivity can be measured at room temperature (i.e., 20°C to 25°C). , the ionic conductivity is at least 0.001 mS / cm, at least 0.01 mS / cm, At least 0.1mS / cm, at least 0.4mS / cm, at least 0.8mS / cm m, at least 1.2 mS / cm, at least 1.8 mS / cm, or at least 2.2 In another embodiment, the ionic conductivity can be at most 15 mS / cm, at most 13mS / cm, max. 11mS / cm, 8mS / cm, max. 7.2mS / cm, or Furthermore, the solid electrolyte may have a maximum resistance of 6.2 mS / cm. The material may include halide-based materials having ionic conductivities ranging from and including any of the maximum values. In one embodiment, the ionic conductivity may be primarily bulk.

[0111] In one embodiment, the halide-based materials have a higher thermal conductivity than corresponding conventional halide-based materials. The corresponding conventional halide-based materials are Although it can be represented by the same formula as the halide-based material described in the embodiment of this specification, Refers to halide-based materials formed by processes different from those described. In one embodiment, the halide-based material may contain a specific content of impurities. For example, impurities may be by-products formed by processes that form halide-based materials. Impurities may include complex compounds of halide-based materials, Those skilled in the art will appreciate that impurities may be present in relatively high amounts (i.e., At least 0.3% by weight of the halide-based material is subjected to X-ray diffraction analysis to identify impurity phases. For example, the spectrum of a halide-based material can be In a further example, the impurity may be a binary halo halides (e.g., LiCl, LiBr, YCl3, and / or YBr3), oxyhalides hydrides (e.g., YOCl and / or YOBr), nitrides, or any combination thereof may include:

[0112] In one embodiment, the halide-based material is characterized by the properties and / or crystal characteristics of the halide-based material. In one embodiment, all impurities that may promote improved performance may be included in a specific total content. The total content of pure materials is up to 15% by weight of the halide-based materials of the embodiments herein. For example, the total content of impurities may be calculated based on the weight of the complex metal halide. up to 14% by weight, for example up to 13% by weight based on the weight of the complex metal halide, Up to 12% by weight, up to 11% by weight, up to 10% by weight, up to 9% by weight, up to 8% by weight % by weight, up to 7% by weight, up to 6% by weight, up to 5% by weight, up to 4% by weight, up to 3 times %, max 2% by weight, max 1% by weight, max 0.5% by weight, max 0.3% by weight, max 0.1% by weight 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 at most, or In another embodiment, the total impurity content of the halide-based material may be: At least 0.2 ppm by weight of halide-based materials, e.g., halide-based materials at least 0.5 ppm, at least 1 ppm, or at least 2 ppm by weight In another aspect, the total content of impurities may be less than or equal to the minimum or maximum values ​​described herein. The range can be inclusive of any of the values.

[0113] The content of impurity phases is determined by the specific content corresponding to the by-product phases (parasitic phases). Quantitative analysis was performed based on the presence of characteristic diffraction peaks, and the XRD analysis was then converted into a Rietveld solution. It can be determined by combining refinement by Rietveld analysis. RR) is determined by analyzing the shape and position of the peaks in the XRD pattern and determining the degree of increment in the 2θ angle. Collect 2θ data in XRD diffraction and convert the XRD data into the ratio of different phases. allows the contributions of the various phases to be quantitatively identified.

[0114] In the case of nitride-based impurity phases, the nitride-based impurity phases are present in a molar amount or mass amount of less than 0.1%. If present, LECO analysis can also be used to determine and quantify the presence of the phase. O analysis is performed by combusting the sample and measuring the thermal conductivity of the boiled material gas or the nitrogen (or The method is based on the analysis of the presence of elements (which may be sulfur, carbon, hydrogen, or oxygen).

[0115] In certain embodiments, the halide-based materials may contain low levels of impurity phases, Phases may not be detected by powder XRD analysis. For example, halide-based materials In the spectrum, the characteristic peaks of the impurity phase may not be discernible. If available, a state-of-the-art diffractometer (e.g., Rigaku SmartLab or Bruker It will be appreciated that powder XRD can be performed using a 3D PHASER. Deaf.

[0116] In one embodiment, the impurity is a metal nitride, a metal oxynitride, a metal carbonitride, or any of the foregoing. In a further embodiment, the compound may comprise a nitride-based compound containing any combination of halides. The halide-based materials have specific total content that can help improve the properties and / or crystallographic characteristics of the halide-based materials. In one embodiment, the total content of nitride-based impurity phases is Maximum 0.5% by weight based on the weight of the halogenide-based material, e.g., Maximum 0.3% by weight, Maximum 0.2% by weight, Maximum 0.1% by weight, Maximum 50% by weight 0ppm, max 300ppm, max 100ppm, max 50ppm, max 40ppm pm, at most 30 ppm, at most 20 ppm, or at most 10 ppm. In an embodiment, the total content of the nitride-based impurity phase is less than the weight of the complex metal halide. 0.2 ppm or less, e.g., at least 0.5 ppm by weight of the complex metal halide , at least 1 ppm, or at least 2 ppm. The total content of the solid impurity phase is within a range including either the minimum or maximum value described herein. It may be.

[0117] In one embodiment, the halide-based material comprises an alkali metal halide (MX). Specific examples of MX include LiCl, LiBr, NaCl, CsCl, In another embodiment, the halogen may include NaBr, CsBr, or any combination thereof. Halide-based materials have specific properties that may facilitate improved properties and / or crystalline characteristics of halide-based materials. In one embodiment, the total content of MX phases is the weight of the halide-based material. Maximum 10% by weight of the amount of the halide-based material, e.g., maximum 9% by weight of the halide-based material % by weight, up to 8% by weight, up to 7% by weight, up to 6% by weight, up to 5% by weight, up to 4% by weight % by weight, up to 3% by weight, up to 2% by weight, up to 1% by weight, up to 0.5% by weight, up to 0.3% by weight, max 0.2% by weight, max 0.1% by weight, max 500 ppm, max 300ppm, max 100ppm, max 50ppm, max 40ppm, max 30 ppm, up to 20 ppm, or up to 10 ppm. The total content of halide-based materials is at least 0.2 ppm by weight, e.g., halo At least 0.5 ppm, at least 1 ppm, or less by weight of the fluorine-based material In another embodiment, the total content of MX phases may be at least 2 ppm. It may be within a range including either the lower or upper limit.

[0118] In one embodiment, the halide-based material comprises a metal oxyhalide (MeOX). It may contain impurities. Examples of MeOX include rare earth oxyhalides. In a further embodiment, the halide-based material is characterized by the properties of the halide-based material and / or In one embodiment, the total amount of MeOX may be present, which may promote the improvement of crystallinity. The content is up to 5% by weight based on the weight of the complex metal halide, e.g. Maximum 4% by weight, Maximum 3% by weight, Maximum 2% by weight, Maximum 1% by weight of the material , up to 0.5 wt%, up to 0.3 wt%, up to 0.2 wt%, up to 0.1 wt% , Maximum 500ppm, Maximum 300ppm, Maximum 100ppm, Maximum 50ppm, Maximum 40 ppm, maximum 30 ppm, maximum 20 ppm, maximum 10 ppm, etc. In another embodiment, the content of the MeOX phase is 0.01 to 0.01 wt. of the complex metal halide. at least 0.2 ppm by weight of halide-based materials, e.g., at least 0. It may be 5 ppm, at least 1 ppm, or at least 2 ppm. The total content of MeOX phases may be within a range including either the minimum or maximum value set forth herein. In certain embodiments, the halide-based material may be essentially free of MeOX. good.

[0119] In one embodiment, the halide-based material is a metal nitride, Me x Nk Contains impurities including Get. Me x N k Examples of the rare earth nitrides include rare earth nitrides. Halide-based materials may facilitate improved properties and / or crystalline characteristics of halide-based materials. , a certain total content of Me x N k In one embodiment, the Me x N k The total content of Maximum 0.3% by weight based on the weight of the halide-based material, e.g. Maximum 0.1% by weight, Maximum 500 ppm, Maximum 300 ppm, Maximum 10 0ppm, max 50ppm, max 40ppm, max 30ppm, max 20ppm , or up to 10 ppm, etc. In another embodiment, Me x N k The phase content is At least 0.2 ppm by weight of halogen-based materials, e.g., At least 0.5 ppm, at least 1 ppm, or at least 2 ppm, etc. In another embodiment, Me x N k The total content of the phases is the minimum or maximum value described herein. The range may be inclusive of either of the greater values.

[0120] In one embodiment, the halide-based material is a metal nitride M x It may contain N-containing impurities. M x Examples of N include alkali metal nitrides. In a further embodiment, halogen Halide-based materials can facilitate improved properties and / or crystalline characteristics of halide-based materials, particularly The total content of M x In one embodiment, the metal nitride M x The total N content is Maximum 0.3% by weight of the halide-based material, e.g. Maximum 0.1% by weight, Maximum 500 ppm, Maximum 300 ppm, Maximum 100 ppm, max 50ppm, max 40ppm, max 30ppm, max 20ppm, Or up to 10 ppm, etc. In another embodiment, M x The total N content is At least 0.2 ppm by weight of halogen-based materials, e.g., at least 0.2 ppm by weight of halogen-based materials at least 0.5 ppm, at least 1 ppm, or at least 2 ppm, etc. In another embodiment, M x The total N content is either the minimum or maximum value described herein. The range may be inclusive.

[0121] Many different aspects and embodiments are possible. Some of these aspects and embodiments are described herein. After reading this specification, those skilled in the art will be able to easily understand that these aspects and embodiments are It will be understood that these are merely examples and are not intended to limit the scope of the present invention. The embodiment may be according to any one or more of the following embodiments:

[0122] Embodiment Embodiment 1. A solid electrolyte material, M 3-z (Me k+ ) f X 3-z+k*f (wherein -3≦z<3; 2≦k<6, 0≦f≦1; M includes an alkali metal element; 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 X includes halogen; a crystalline structure containing at least 20% stacking faults; A solid electrolyte material comprising:

[0123] Embodiment 2. The solid electrolyte material according to embodiment 1, wherein the crystal structure is represented by the C2 / m space group. Fee.

[0124] Embodiment 3. A solid electrolyte material, M 3-z (Me k+ ) f X 3-z+k*f (In the formula, -3≦z<3;2≦k<6;0≦f ≦1; M includes an alkali metal element; Me includes a divalent metal element, a trivalent metal element, a tetravalent metal element, a metal element, a pentavalent metal element, a hexavalent metal element, or any combination thereof; X is halo; including rhogens) and A crystal structure expressed in the rhombohedral space group, A solid electrolyte material comprising:

[0125] Embodiment 4. The method according to embodiment 3, comprising: Solid electrolyte material.

[0126] Embodiment 5. A method for producing a crystal structure comprising: The solid electrolyte material according to any one of aspects 3 and 4.

[0127] Embodiment 6. A solid electrolyte material, X 3-z (Me k+ ) f X 3ーz+k*f (wherein -3≦z<3; 2≦k<6, 0≦f≦1; M includes an alkali metal element; 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 X includes halogen; A crystal structure expressed in the hexagonal space group, A solid electrolyte material comprising:

[0128] Embodiment 7. A crystal comprising a crystal structure represented by the P63 / mcm or P63 / mmc space group. 7. The solid electrolyte of embodiment 6, comprising a phase.

[0129] Embodiment 8. A crystal comprising a crystal structure represented by the P63 / mcm or P63 / mmc space group. 8. The solid electrolyte material of embodiment 6 or 7, consisting essentially of a phase.

[0130] Embodiment 9. The present invention relates to a crystalline phase having a crystalline structure represented by the P-3m1 or Pnma space group. 7. The solid electrolyte material according to embodiment 1, 3 or 6.

[0131] Embodiment 10. Concentration of a crystalline phase comprising a crystalline structure represented by the P-3m1 or Pnma space group However, up to 70% by weight, up to 50% by weight, up to 25% by weight, up to 15% by weight, up to 10. The solid electrolyte material of embodiment 9, wherein the SiO 2 content is 8 wt. %, or at most 5 wt. %.

[0132] Embodiment 11. Concentration of a crystalline phase comprising a crystalline structure represented by the P-3m1 or Pnma space group is at least 1 wt%, at least 4 wt%, at least 10 wt%, at least 25 %, at least 50% by weight, or at least 70% by weight. The solid electrolyte material according to claim 1.

[0133] Embodiment 12. A solid electrolyte material, M 3-z (Me k+ ) f X 3-z+k*f (wherein -3≦z<3; 2≦k<6, 0≦f≦1; M includes an alkali metal element; 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 includes halogen; Has a unit cell containing 3 to 5 halide atoms a crystal structure described by the monoclinic space group; A solid electrolyte material comprising:

[0134] Embodiment 13. The method of embodiment 1, comprising a crystalline phase comprising a crystalline structure represented by the C2 / m space group. 13. The solid electrolyte material according to any one of 3, 6, and 12.

[0135] Embodiment 14. The concentration of a crystalline phase comprising a crystalline structure represented by the C2 / m space group is at most 70 % by weight, up to 50% by weight, up to 25% by weight, up to 15% by weight, up to 8% by weight, or is at most 5 wt. %.

[0136] Embodiment 15. The concentration of a crystalline phase comprising a crystalline structure represented by the C2 / m space group is at least 1% by weight, at least 4% by weight, at least 10% by weight, at least 25% by weight, less 15. The solid of embodiment 13 or 14, wherein the total amount of the solid is 50% or at least 70% by weight. Electrolyte materials.

[0137] Embodiment 16. The solid state battery according to any one of embodiments 1 to 15, comprising a layered atomic arrangement. solute material.

[0138] Embodiment 17. A represents the value of the unit lattice constant a, B represents the value of the unit lattice constant b, and A= The solid electrolyte material according to any one of embodiments 3 to 8, wherein B is B.

[0139] Embodiment 18. A represents the value of the unit lattice constant a, B represents the value of the unit lattice constant b, and A or A or B is at least 3.0 angstroms, or at least 3.3 angstroms Angstroms, or at least 3.6 Angstroms, or at least 3.9 Angstroms The solid electrolyte material according to any one of embodiments 3 to 5 and 17, which is a polymer.

[0140] Embodiment 19. A or B or both are at most 4.8 Angstroms, or at most 4.6 Angstroms, or at most 4.3 Angstroms, or at most 4.2 Angstroms Angstroms, or up to 4.0 Angstroms, in embodiments 3-5, 17 and 18. The solid electrolyte material according to claim 1.

[0141] Embodiment 20. C represents the value of the unit cell constant c, and C is at least 17 Angstroms. , at least 18 angstroms, or at least 19 angstroms, 20. The solid electrolyte material according to any one of aspects 3 to 5 and 17 to 19.

[0142] Embodiment 21.C is at most 21 Angstroms, at most 20.2 Angstroms; or at most 19.5 angstroms. 1. The solid electrolyte material described in Item 1.

[0143] Embodiment 22. A represents the value of the unit lattice constant a, B represents the value of the unit lattice constant b, and A or A, B, or both are at least 5.0 angstroms, or at least 5.5 angstroms Angstroms, or at least 6.1 Angstroms, or at least 6.3 Angstroms The solid electrolyte material according to any one of embodiments 6 to 8, which is a polymer.

[0144] Embodiment 23. A or B or both are at most 8 Angstroms, or at most 7. 5 Angstroms, or up to 7.0 Angstroms, or up to 6.5 Angstroms The solid electrolyte material according to any one of embodiments 6 to 8 and 22, wherein the solid electrolyte material is ROHM.

[0145] Embodiment 24. C represents the value of the unit cell constant c, and C is at least 4.8 Å. Angstroms, at least 5.3 Angstroms, at least 5.7 Angstroms, or less In any one of embodiments 6 to 8, 22 and 23, the thickness is at most 6.0 angstroms. The solid electrolyte material described herein.

[0146] Embodiment 25. C is at most 6.9 angstroms, at most 6.4 angstroms; or at most 6.1 Angstroms. The solid electrolyte material according to any one of claims 1 to 4.

[0147] Embodiment 26: The solid electrolyte material according to any one of embodiments 3 to 8, It includes a lattice volume V, where V is at least 200 cubic angstroms, at least 210 cubic Angstroms, at least 230 cubic angstroms, at least 250 cubic on Angstroms, at least 260 cubic angstroms, of a solid electrolyte material.

[0148] Embodiment 27: The solid electrolyte material according to any one of embodiments 3 to 8, It contains a volume V, where V is at most 290 cubic angstroms and at most 275 cubic angstroms. Angstroms, up to 250 cubic angstroms, up to 230 cubic angstroms, or A solid electrolyte material that is up to 220 cubic angstroms.

[0149] Embodiment 28. Formula unit FU and normalized unit cell volume V per FU N / FU and , V N / FU = V / FU, and V N / FUis at least 200 cubic angstroms, at least 210 cubic angstroms, at least 230 cubic angstroms, or 28. Any one of embodiments 1 to 27, wherein the thickness is at least 250 cubic angstroms. Solid electrolyte material.

[0150] Embodiment 29. Formula unit FU and normalized unit cell volume V per FU N / FU and , V N / FU =V / N FU and N FU represents the number of formula units, and V N / FU The maximum is 290 Angstroms, up to 275 cubic angstroms, up to 270 cubic angstroms Any one of embodiments 1 to 28, wherein the thickness is 100 nm or at most 268 cubic angstroms. The solid electrolyte material according to claim 1.

[0151] Embodiment 30. Normalized unit cell volume V per halogen atom N / AA Including V N / AA =V / AA and AA is V N / AA At least 30 cubic angstroms, At least 34 cubic angstroms, at least 38 cubic angstroms, or at least 30. The solid electrolyte according to any one of embodiments 1 to 29, wherein the thickness of the solid electrolyte is 42 cubic angstroms or less. quality material.

[0152] Embodiment 31. Normalized unit cell volume V per atom of halogen N / AA Including V N / AA =V / AA and AA is V N / AA is at most 50 cubic angstroms, and at most 46 cubic angstroms, max 42 cubic angstroms, max 38 cubic angstroms 31. The solid electrolyte material according to any one of embodiments 1 to 30, which is a strom.

[0153] Embodiment 32. The average diffracting crystallite size is at least 20 nm, at least 25 nm, at least 30 nm, at least 35 nm, or at least 40 nm. 32. The solid electrolyte material according to any one of claims 1 to 31.

[0154] Embodiment 33. The average diffracting crystallite size is at most 500 nm, at most 400 nm, at most 300 nm at most, 200 nm at most, or 100 nm at most, according to any of embodiments 1 to 32. The solid electrolyte material according to any one of the above.

[0155] Embodiment 34. The minute distortion is 1% at most, 0.6% at most, 0.35% at most, 34. The solid according to any one of embodiments 1 to 33, wherein the amount of Electrolyte materials.

[0156] Embodiment 35. Corrected average FWHM is less than 1.5%, at most 1.4%, at most 1.2%; Any of embodiments 1-34, wherein the β-glucan content is at most 1%, at most 0.8%, or at most 0.5%. 1. The solid electrolyte material described in Item 1.

[0157] Embodiment 36. Corrected average FWHM is at least 0.5%, at least 0.8%, or less The solid electrolyte material according to any one of embodiments 1 to 35, wherein the number of the first and second electrodes is at least 1.

[0158] Embodiment 37. A crystallographic density of 2.0 g / cm 3 ~4.2g / cm 3 is within the range of The solid electrolyte material according to any one of embodiments 1 to 36.

[0159] Embodiment 38. The solid electrolyte material according to embodiment 37, When X is Br, the crystallographic density of the solid electrolyte material is 3.0 g / cm 3 ~4.2g / cm 3 or 3.4 g / cm 3 ~3.9g / cm 3 or When X is Cl, the crystallographic density of the solid electrolyte material is 2.0 g / cm 3 ~3.2g / cm 3 or 2.2 g / cm 3 ~2.8g / cm 3 is in the range of Solid electrolyte material.

[0160] Embodiment 39: The solid electrolyte material according to any one of Examples 1 to 38, wherein the crystal structure but, Atomically disordered vacancies and Me atoms; Irregular X1 and X2 atoms (X1 and X2 represent two different halogen atoms); Irregular vacancy positions and M atoms; Disordered M and Me atoms; Disordered M, Me and vacancy atoms; or any combination thereof, A solid electrolyte material comprising:

[0161] Embodiment 40: Atomically disordered vacancies and Me atoms are formed in atomic layers or linear atomic chains. 40. The solid electrolyte material of embodiment 39, wherein the solid electrolyte material is partially disordered.

[0162] Embodiment 41: The solid electrolyte material according to any one of embodiments 1 to 9 and 20. and atomic disorder is at least 10%, at least 20%, at least 30%, or less. at least 40%, at least 60%, at least 80%, or at least 90% Body electrolyte material.

[0163] Embodiment 42. The crystal structure has crystallographic sites occupied by both Me atoms and vacancies. 42. The solid electrolyte material according to any one of embodiments 1 to 41, comprising:

[0164] Embodiment 43. A solid electrolyte according to embodiment 42, wherein the multiplicity of the crystallographic site is 3. material.

[0165] Embodiment 44. Embodiment 42, wherein the crystallographic site is Wycoff position 3a or 3b 44. The solid electrolyte material according to claim 43.

[0166] Embodiment 45. In the X-ray diffraction pattern measured with CuKα radiation, 16° to 25° The solid electrolyte material according to any one of embodiments 1 to 44, wherein no peak exists between θ .

[0167] Embodiment 46. Any of embodiments 1 to 45, wherein M comprises at least one of Li or Na. 1. The solid electrolyte material according to any one of the preceding items.

[0168] Embodiment 47. The solid electrolyte of any one of embodiments 1 to 46, wherein M comprises Li. material.

[0169] Embodiment 48. Me is an alkaline earth metal element, a 3d transition metal, Mg, Ca, Ba, Z n, Zr, Hf, Ti, Sn, Th, Ge, V, Ta, Nb, Mo, W, Sb, In, B 48. Any one of embodiments 1 to 47, including i, Al, Ga, or any combination thereof. The solid electrolyte material described herein.

[0170] Embodiment 49. An embodiment in which Me comprises a rare earth element, Zr, Sn, or any combination thereof. The solid electrolyte material according to any one of the first to forty-eighth embodiments.

[0171] Embodiment 50. Me is Y, Ce, Gd, Er, Zr, La, Yb, In, Mg, Zn , Sn, or any combination thereof. Body electrolyte material.

[0172] Embodiment 51. The solid electrolyte of any one of embodiments 1 to 50, wherein Me comprises Y. material.

[0173] Embodiment 52. An embodiment in which X comprises F, Cl, Br, I, or any combination thereof. 52. The solid electrolyte material according to any one of aspects 1 to 51.

[0174] Embodiment 53. Any of embodiments 1-52, wherein X comprises Cl, Br, or a combination thereof. The solid electrolyte material according to any one of the above.

[0175] Embodiment 54. The solid electrolyte of any one of embodiments 1 to 53, wherein X comprises Br. material.

[0176] Embodiment 55. Any one of embodiments 1 to 54, consisting of Li, Y, Cl, and Br. The solid electrolyte material according to claim 1.

[0177] Embodiment 56. The crystalline structure has at least 20% stacking faults, at least 30%, or less At least 40%, at least 50%, at least 60%, at least 70%, at least 80 %, or at least 90% stacking faults. Solid electrolyte material.

[0178] Embodiment 57. Ionic conductivity is at least 0.001 mS / cm, at least 0.0 1mS / cm, at least 0.1mS / cm, at least 0.4mS / cm, at least 0.8mS / cm, at least 1.2mS / cm, at least 1.8mS / cm, or less 57. The solid electrolyte of any one of embodiments 1 to 56, wherein the electrical conductivity is at least 2.2 mS / cm. material.

[0179] Embodiment 58. The ionic conductivity is at most 15 mS / cm, at most 13 mS / cm, at most 11mS / cm, max 8mS / cm, max 7.2mS / cm, or max 6.2m 39. The solid, ionically conductive material of any one of embodiments 1-38, wherein the ionic conductivity is 0.05 S / cm.

[0180] example Example 1 A representative lithium yttrium bromide sample (Li3YBr6) is used in the embodiments herein. The decomposition of NH4Br was carried out at 400-600°C. The sample was further crushed in an automatic agate mortar to obtain finer powder particles. No milling was used. The crystal structure and crystalline properties of the final particles formed were as follows: This is shown in Table 1. [Table 1]

[0181] Example 2 Representative Li3YBr6 samples were formed using the processes described in the embodiments herein. FIG. 9 includes an X-ray diffraction spectrum recorded with CuKα radiation. Curve 910 represents the X-ray diffraction spectrum of the sample. The X-ray diffraction pattern is shown, with bars indicating the peaks expected for the conventional crystal structure. The sample does not show a peak between 16° and 25° 2θ.

[0182] Example 3 Representative Li3YBr6 samples were formed using the processes described in the embodiments herein. Figure 10 includes a structural model of the sample. The yttrium lithium bromide sample was R-3m. It has the crystal structure shown in

[0183] Example 4 Representative Li3YBr6 samples were formed using the processes described in the embodiments herein. Figure 11 contains a structural model of the sample. As shown in the figure, the sample contains a new small C2 / It has a crystal structure described by the m space group.

[0184] Example 5 Representative Li3YCl6 samples were formed using the processes described in embodiments herein. Figure 12 includes a structural model of the sample. As shown in the figure, the sample is composed of P63 / mcm voids. It has a crystal structure represented by the intermetallic group.

[0185] Example 6 Representative Li3YCl6 samples were formed using the processes described in embodiments herein. Figure 13 includes a structural model of the sample. As shown in the figure, the sample is composed of P63 / mmc voids. It has a crystal structure represented by the intermetallic group.

[0186] Example 7 Using the processes described in embodiments herein, lithium yttrium bromide, LiYB The decomposition of NH4Br was carried out at 450-650°C. The chemical properties are shown in Table 2 below. [Table 2]

[0187] When comparing Sample 7-1 with Samples 1-1 to 1-3, the average crystallite size of Example 7 is Increasing the decomposition temperature helps increase the crystallinity, as indicated by an increase in Note that this may be possible.

[0188] Example 8 After crushing in an automatic agate mortar, the mixture was subjected to additional energy boiling in a rolling mill at 400 rpm for 2 hours. A typical odor was obtained by the same method as described in Example 1, except that a fine powder was obtained by applying a fluorine-containing fluoride. The lithium yttrium nitride (Li3YBr6) sample was formed. The final formed particle crystals The structural and crystalline properties are presented in Table 3 below. [Table 3]

[0189] Example 9 The method according to the embodiment herein, which includes a liquid acidic reaction in addition to ammonium complexation, Thus, a representative lithium yttrium bromide Li3YBr6 (sample 10-1) was formed. Further investigation was carried out by direct solid-state reaction of LiBr and YBr3 at 450 °C for 24 h. Lithium yttrium bromide Li3YBr6 (sample 10-2) was formed.

[0190] FIG. 14A shows the powder X-ray diffraction pattern of sample 10-1 and the XRD pattern of conventional Li3YBr6. The scans are overlaid for comparison. Figure 14B shows the X-ray pattern of sample 10-2. The folded pattern and the XRD scan of conventional Li3YBr6 are overlaid for comparison. Sample 10-1 is the XRD scan of conventional Li3YBr6 and sample 10-2. Compared with the superposition, there are no peaks within 16 to 25 degrees (2θ Cu-K-α). Note that sample 10-1 contains approximately 83% + / - 5% stacking faults, and sample 10 -2 contains approximately 15% + / - 5% stacking faults. Quantification of stacking fault values ​​is described in the embodiments of this specification. As stated in the statement, the FAULTS software released in 2020 was used. is executed.

[0191] The crystal structure and crystallinity properties of Sample 10-2 are further presented in Table 4 below. [Table 4]

[0192] Example 10 Additional samples were prepared using the synthesis methods described in Table 5 below. The impurity contents of the materials are listed in Table 1, and the XRD analysis was analyzed by Rietveld refinement. In combination with the precipitation, characteristic phases corresponding to the parasitic phases The phases of each impurity were detected by quantitative analysis based on the presence of distinct diffraction peaks. At approximately 22°C, AC frequencies between 3MHz and 10Hz and peak-to-peak voltages between 10mV and 50mV Electrochemical impedance analysis using a gold blocking electrode under sinusoidal AC voltage signal conditions The ionic conductivity of the samples was determined using an optical method. The ionic conductivity referred to herein is the The bulk particle conductivity is characterized by the highest frequency, and the double layer capacitance is characterized by the ionic conductivity of the bulk particle. The barrier that can be separated from the grain boundaries and electrode contacts is related to the lowest value of the resistivity. The conductivity from the bulk particles contributes. [Table 5]

[0193] The synthesis by high-energy ball milling is a key step in the synthesis and characterization of the major metal halide complex phases. Note that the decomposition reaction may occur in parallel. Therefore, high-energy ball mill synthesis removes the impurities present near the main Li3YX6 phase. The content of simple compounds such as LiX and YX3 can be significantly increased. If the content is too high, the crystallinity of the halide-based material may decrease. Although annealing can be performed to partially restore the crystallinity, annealing Stacking faults in metallic materials may also be significantly reduced.

[0194] In a solid-state reaction at atmospheric pressure of 1 bar, ammonium halide was added to form oxide (Y Starting from either Li2O3 or carbonate materials (Li2CO3), a single phase of Li3YX6 is synthesized. Note also that rare earth metals (e.g., Y in the Li3YX6 example) are not At least two chemical reactions can occur to convert them to halogen compounds. In this reaction, YX3 is synthesized, which can further react to form the Li3YX6 phase. A second reaction can result in the formation of YOX, which is a stable compound and can be easily reacted with Li3 Impurities in the final product of YX6. High levels of rare earth oxynitrides in halide-based materials. The formation of a halide phase (i.e., at least 6 wt%) is characteristic of an impurity phase. Quantification of stacking faults based on XRD spectra, which may result in extraneous XRD peaks may not be reliable.

[0195] Example 11 Additional representative halide-based materials are the same as those described for Sample 10-1 in Example 9. The formula for each sample is shown in Table 6. The stacking fault content of each sample was determined using the method described in Example 9. Each sample is expected to have 30-85% stacking faults. can be. [Table 6]

[0196] Figure 15 shows the XRD spectrum of sample 11-6 and the XRD scan of conventional Li3YBr6. The XRD scans of Li3YBr3 and Li3YBr3 are overlaid for comparison. In comparison, the specific peak between 15° and 25° 2θ associated with Cu-Kα radiation is not observed in sample 11-6. Note that it is not present in the spectrum of

[0197] Example 12 Powder XRD measurements of sample 10-1 were performed using sealed Kapton capillaries in transmission geometry. Figure 16 shows the XRD spectra obtained in the test. Both spectra represent the conventional XRD peaks of Li3YBr3. Compared with the bar position, there is no specific peak between 15° and 25° 2θ for CuK-α radiation. Note that this indicates that

[0198] Example 13 Lithium yttrium bromide Li3YBr6 can be prepared by the process described in the embodiments herein. The reaction mixture is heated to 650°C for 30 minutes. Heat and hold for 15 minutes for decomposition of NH4Br, then cool to room temperature over 1 hour. Rapid cooling from high temperatures may promote the formation of stacking faults. The abundance is estimated to be about 50%.

[0199] Example 14 Lithium yttrium bromide Li3YBr6 can be prepared by the process described in the embodiments herein. The decomposition of NH4Br was allowed to proceed for at least 1.5 hours at 350°C before cooling. The temperature range is from 10 to 440°C. The stacking fault content of the samples is expected to be 10 to 20%.

[0200] Benefits, other advantages, and solutions to problems have been described above with regard to specific embodiments. while giving rise to benefits, advantages, solutions to problems, and any benefits, advantages, or solutions Any feature or features that may be made more pronounced may be added to any or all of the claims. These features should not be construed as critical, necessary, or essential features. When referring to a material containing more than one ingredient, it means that the material consists essentially of one or more of the ingredients identified. The term "consisting essentially of" may be interpreted to include at least one embodiment consisting of The term includes the specified material and may include minor inclusions that do not significantly change the properties of the material (e.g., "compositions" are understood to include compositions that exclude all other materials except for those containing impurities. Alternatively, in certain non-limiting embodiments, the compositions identified herein may be None may be essentially free of material not expressly disclosed. In some embodiments, the material contains various amounts of a particular component, and the components contained in a given material are It will be understood that the total content of is 100%.

[0201] The description and illustrations of the embodiments set forth herein provide a general understanding of the structure of the various embodiments. The present specification and drawings are intended to provide a method for manufacturing a semiconductor device using the structures or methods described herein. serve as a comprehensive and comprehensive description of all elements and features of the devices and systems Also, separate embodiments are not intended to be combined into a single embodiment. Conversely, various features that are described in the context of a single embodiment for the sake of brevity may be provided. The features may also be provided separately or in any subcombination. Reference to a range of values ​​includes any and all values ​​within that range. Many other embodiments will be apparent to those skilled in the art. Other embodiments may be incorporated into the present disclosure, such as by making component substitutions, logical substitutions, or other modifications. can be used and derived. Accordingly, this disclosure is illustrative rather than limiting. should be considered.

Claims

1. M ３－ｚ (Me ｋ＋ ) ｆ X ３－ｚ＋ｋ＊ｆ (wherein, −3≦z<3; 2≦k≦6; 0<f≦1; M contains an alkali metal element including Li; Me contains a metal element different from M; and X contains a halogen), A solid electrolyte material, wherein the halide-based material comprises a crystalline structure containing at least 70% stacking faults.

2. The solid electrolyte material according to claim 1 , wherein the crystal structure is represented by a monoclinic space group.

3. The solid electrolyte material according to claim 2 , wherein the crystal structure is represented by a C2 / m space group.

4. The solid electrolyte material according to claim 1 , wherein the crystal structure is represented by a rhombohedral lattice space group.

5. The solid electrolyte material according to claim 4, wherein the space group is an R-3m space group.

6. The solid electrolyte material according to claim 1, wherein the crystal structure is represented by one of the Fd-3m space group, the Fm-3m space group, the P-3m1 space group, and the Pnma space group.

7. M ３－ｚ (Me ｋ＋ ) ｆ X ３－ｚ＋ｋ＊ｆ (wherein, −3≦z<3; 2≦k<6; 0<f≦1; M includes an alkali metal element including Li; Me includes a metal element; and X includes a halogen including at least one of Br and Cl), and a crystalline structure described by the monoclinic space group having a unit cell containing from 3 to 5 halide atoms; A solid electrolyte material, wherein the crystalline structure contains at least 70% stacking faults.

8. The solid electrolyte material according to claim 7 , wherein the crystal structure is represented by a C2 / m space group.

9. 9. The solid electrolyte material of claim 1, wherein the halide-based material comprises 5 wt% or less of LiX, 5 wt% or less of MeXk, 5 wt% or less of oxyhalides of Me, or any combination thereof.

10. 10. The solid electrolyte material according to claim 1, wherein an X-ray diffraction pattern of the halide-based material measured with CuKα radiation does not include a peak between 16° and 25° 2θ or between 16.5° and 27.5° 2θ.

11. 11. The solid electrolyte material of claim 1, wherein Me comprises a rare earth element, In, Al, Ti, Zr, Sn, Bi, Hf, Fe, an alkaline earth metal element, or any combination thereof.

12. 12. The solid electrolyte material of claim 1, wherein the crystalline structure comprises a corrected average FWHM of less than 1.5%.

13. 13. The solid electrolyte material of claim 1, wherein the crystalline structure comprises an average diffracting crystallite size of at least 20 nm.

14. 14. The solid electrolyte material according to claim 1, wherein the crystalline structure comprises at least 90% stacking faults.

15. 15. The solid electrolyte material according to claim 1, wherein X comprises Cl and Br.

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