Electrolyte material and method for forming it

Abstract

To provide a solid electrolyte material including a halide material including at least two halide anions, and methods of forming the same.SOLUTION: A solid electrolyte material includes a halide material represented by Li3-x-fMfRE1-yMeky(Cl1-u-p-qBruFpIq)6-x+y*(k-3). The halide material includes at least two halide anions, and includes reduced content of one or more impurity phases, including a binary halide phase, oxyhalide phase, or ternary halide phase.SELECTED DRAWING: Figure 3

Description

[Technical Field]

[0001] The following describes a solid electrolyte material and a method for forming it, specifically, at least two H Solid electrolyte material containing a halogenated material containing a chlorogenide anion and a method for forming the same It applies to the law. [Background technology]

[0002] Solid-state lithium batteries, by enabling lithium metal anodes, are conventional Compared to lithium-ion batteries, it offers higher energy density and faster recharge time. This is expected to reduce safety concerns. As for current solid electrolyte materials... Examples include oxides, halides, sulfides, fluorides, and solid polymer electrolytes.

[0003] Oxide-based materials are considered safe and to have good chemical and electrochemical stability. These compounds have been synthesized using high temperatures of over 1000-1200°C. Oxide-based materials are typically high-density, rigid, and brittle, with a maximum density of 1.0 mS / cm². Ionic conductivity (IC) at room temperature RT ) has.

[0004] Halogenated compounds such as chlorides and bromides are generally safe and have good chemical properties. Furthermore, it possesses electrochemical stability, deformability at room temperature, and plasticity, and is relatively compatible with active electrode materials. This enables high compatibility. Halides are generally hygroscopic and form hydrates. or undergo hydrolysis when exposed to moisture. Li3YCl6(LYC) and Li3YB Halide solid electrolytes such as r6(LYB) are based on high-energy ball mill grinding. It is synthesized using a solid-phase synthesis method. Furthermore, it is a high-cost binary halide reactant and / or high Because hot annealing is used, the synthesis presents challenges for mass production applications.

[0005] Fluorides are very similar to oxides in their physical, chemical, and electrochemical properties. However, generally speaking, ICs with a wind speed of less than 1 mS / cm RT It has a value.

[0006] Sulfides have relatively high ionic conductivity. For example, ICs RT This is 25 mS / cm Although it can be at a certain height, commercially relevant sulfide or thiophosphate solid electrolytes are 2-1 It is possible to achieve 0 mS / cm. Sulfide materials are mechanically softer and more deformable. However However, sulfide materials tend to have low electrochemical stability and can accidentally react with water and heat. It raises safety concerns due to the risk of releasing toxic H2S gas when reacting with other substances. Furthermore, sulfide solid electrolyte powders with a high surface area are reactive even at ambient humidity. This increase leads to a particularly high risk of H2S.

[0007] Solid polymer electrolytes containing lithium salts generally have relatively low IC50. RT Value and electricity It has gaseous and chemical stability.

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

[0009] This disclosure will be better understood by referring to the attached drawings, and many of its features The advantages and benefits can be made apparent to those skilled in the art. [Figure 1A] Figure 1A includes a diagram showing XRD pattern readings of a halide material. [Figure 1B] Figure 1B includes a diagram showing XRD pattern readings of a halide material. [Figure 2] Figure 2 includes a diagram showing XRD pattern readings for additional halide materials. [Figure 3] Figure 3 includes a flowchart illustrating a process for forming a solid electrolyte material according to one embodiment. [Figure 4] Figure 4 includes a diagram of a portion of a cross-section of an exemplary electrochemical device. [Figure 5] Figure 5 includes the cyclic voltammetry VA diagram of the battery sample. [Figure 6] Figure 6 includes the cyclic voltammetry (VA) diagram of the battery sample. [Figure 7A] Figure 7A includes a diagram of an exemplary electrochemical device according to embodiments of this specification. [Figure 7B] Figure 7B includes a diagram of an exemplary electrochemical device according to embodiments of this specification. [Figure 8] Figure 8 includes a plot of Cl concentration versus ionic conductivity of a halide material according to one embodiment. [Figure 9A] Figure 9A includes a diagram showing XRD pattern readings for additional halide materials. [Figure 9B] Figure 9B includes a diagram showing XRD pattern readings for additional halide materials. [Figure 10] Figure 10 includes a diagram of the formation process according to one embodiment. [Figure 11A] Figure 11A includes a diagram showing the electrochemical stability of halide materials. [Figure 11B] Figure 11B includes a diagram showing the electrochemical stability of halide materials.

[0010] Those skilled in the art will see that the elements in the figures are shown for the purpose of simplification and clarity, and are not necessarily scaled. Please understand that it is not drawn exactly as shown. For example, the dimensions of some elements in the diagram are not as shown in the original. To help improve the understanding of the embodiment of the light, the field is exaggerated compared to other elements. There is a correspondence. The use of the same reference numeral in different drawings indicates the same or identical item. [Modes for carrying out the invention]

[0011] The following description, combined with the figures, is provided to aid in understanding the teachings disclosed herein. The following discussion focuses on specific embodiments and examples of the teaching. The points are provided to help explain the teaching and relate to the scope or applicability of the teaching. It should not be interpreted as a limitation.

[0012] As used herein, "comprises" and "comprising" )", includes", includes", has", has The term "having," or any other variation thereof, encompasses non-exclusive inclusion. It is intended to do so. For example, a process, method, article, or apparatus that includes a list of features is: It is not necessarily limited to those features, and may include those not explicitly listed or such This may include other characteristics inherent to the process, method, article, or apparatus. Furthermore, it may include contradictory descriptions. Unless otherwise specified, "or" refers to an inclusive "or" and not an exclusive "or". For example, condition A or B is satisfied by one of the following: A is true and (and (is true), B is false (or does not exist), A is false (or does not exist), B is true It is (or exists) that both A and B are true (or exist).

[0013] The use of "one (a)" or "one (an)" refers to the elements and components described herein. It is used for the description of the element. This is merely for convenience and to give a general meaning to the scope of the present invention. This description includes one or at least one, and unless otherwise clearly stated to mean something different, the singular form shall be read as including the plural form, or vice versa.

[0014] Unless otherwise defined, all technical and scientific terms used herein shall have the same meaning as commonly understood by those skilled in the art to which this invention pertains. The materials, methods, and examples are merely illustrative and not intended to be limiting.

[0015] Embodiments herein relate to solid electrolyte materials containing halide materials. In one embodiment, the halide material may include at least two halide anions, at least one alkali metal element, and at least one other metal element. In one embodiment, the solid electrolyte material may include a quaternary halide material. In another embodiment, the solid electrolyte material may include a halide material having one or more improved properties compared to conventional metal halide materials. For example, the halide material may have improved purity, crystal structure characteristics, or both. In another example, the halide material may have improved ionic conductivity, electronic conductivity, mechanical properties, electrochemical thermodynamic stability, or any combination thereof. In embodiments, the solid electrolyte material may be used to form an electrolyte, a coating, a cathode liquid and / or an anode liquid, or another component of an electrochemical device. In an exemplary application, the solid electrolyte material has its improved Due to its characteristics, it may be particularly suitable for forming the cathode liquid or the anode liquid. In certain embodiments the solid electrolyte material can be a suitable component of a solid-state lithium battery.

[0016] A further embodiment relates to a method of forming a solid electrolyte material comprising a halide material . This method enables improved formation of the solid electrolyte material and can facilitate the formation of a solid electrolyte material having improved properties. This method may be suitable for mass-producing the ion-conductive material in a cost-effective manner.

[0017] In one embodiment, the solid electrolyte material is Li 3-x-f M f RE 1-y Me k y (Cl 1-u-p-q Br u F p I q ) 6-x+y*(k-3) and may include a halide material represented by, where the halide material includes at least two halide anions, and - 1 <= x <= 1, 0 <= y <= 1, 0 <= u < 1, 0 <= p <= 1 / 3, 0 <= q <= 1 / 6, 0 < (u + p + q) < 1, and 0 <= f <= 0.3.

[0018] The halide anion can be an element selected from the group consisting of F, Cl, Br, and I. Examples of M can include at least one alkali metal other than Li . In certain examples, M can be one or more alkali metal elements selected from the group consisting of Na, K, Cs, Rb, and Fr . In another example, examples of M can include Na, K, Cs, or a combination thereof . In a more specific example, examples of M can include Na and K . At least one of these can be given. In a more specific example, M is Na It can consist of K, or a combination thereof.

[0019] REs include Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb , at least one rare selected from the group including Dy, Ho, Er, Tm, Yb, and Lu Earth elements can be cited. For example, REs include Sc, Y, La, Gd, or so Any combination of these can be listed. In another example, RE could be Y, Ce, Examples include Gd, Er, La, Yb, or combinations thereof. In specific examples... , RE, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, It may consist of one or more elements selected from the group consisting of Ho, Er, Tm, Yb, and Lu. More specifically, RE is Ce, Gd, Er, La, Yb, or a combination thereof. It can consist of a combination of two. In another, more specific example, RE can consist of Y, Gd, or a combination thereof. It can be made up of so. In a more specific example, RE can be made up of Y or Gd.

[0020] As for Me, at least one metallic element different from RE can be given. Example For example, Me is a group IIIB element, a group IVB element, V, Cr, Mn, Fe, Co, Ni, C Composed of u, Zn, Zr, Al, Sn, Pb, Bi, Sb, Mg, Ca, Ga, or Ge It can be one or more elements selected from the group. Another example is that Me could be Y, Ce, G d, Er, Sm, Eu, Pr, Tb, Al, Zr, La, Yb, Mg, Zn, Sn, Mg Examples include , and Ca, or any combination thereof. In a specific example, Me is at least one element selected from the group consisting of Gd, Yb, Zr, Zn, Mg, Al, and Ca and can be. In a more specific example, Me can be Gd, Zr, Hf, Zn, or any combination thereof. As used herein, the family of elements follows Han dbook of the Elements, 8th Edition, 1998.

[0021] Me can have a valence k. When Me contains two or more metal elements, k can be the average of the valences of each Me metal element. For example, when Me contains a trivalent element and a tetravalent element in equimolar amounts, k = (3 + 4) / 2 = 3.5. In another example, when Me contains a divalent element and a tetravalent element in equimolar amounts, k = (2 + 4) / 2 = 3. In certain embodiments, k can be 2 or 3 or 4 or 5.

[0022] In one embodiment, the halide material can have improved purity. For example, the halide material can have a reduced content of one or more impurity phases compared to the corresponding conventional halide material. As used herein, the corresponding conventional halide material refers to a halide material having the same formula as the halide material of the embodiments herein but formed by a process different from the processes described in the embodiments herein and is intended to. In one aspect, the impurity phase can include one or more phases such as unreacted starting materials, by-products, products resulting from the decomposition of the halide material or intermediate products, or any combination thereof and is intended to. In a further aspect, the impurity phase can include one or more phases of binary halides, ternary halides oxyhalides, oxynitrides, or any combination thereof and can include one or more phases of any combination thereof, or products resulting from the decomposition of the halide material or intermediate products, etc., or any combination thereof and can include one or more phases of any combination thereof. In a further aspect, the impurity phase can include one or more phases of binary halides, ternary halides oxyhalides, oxynitrides, or any combination thereof and can include one or more phases of any combination thereof.

[0023] ​ In one embodiment, the halide material is compared to a conventional corresponding halide material. It may contain a binary halide phase with a reduced total content. The binary halide is Li, M, It may contain cations of metal elements selected from the group consisting of Me and RE. In one embodiment, The halogenated material is a binary halogenated material with a total content of 9% by weight or less relative to the total weight of the halogenated material. Logenide phase, 8% by weight or less, 7% by weight or less, 6% by weight or less, 5% by weight or less, 4% by weight or more Below, the total content is 3% by weight or less, 2% by weight or less, 1% by weight or less, or 0.5% by weight or less. Total content of 10% by weight or less relative to the total weight of the halogenated material, such as the original halogenated phase. It may include a binary halide phase. In another embodiment, the halide material is a halide material At least 0.0005% by weight, at least 0.001% by weight, and less than the total weight of the ingredients. at least 0.005% by weight, at least 0.01% by weight, or at least 0.05% by weight At least 0% of the total weight of the halogenated material, such as the total content of the binary halide phase. It may contain a binary halide phase with a total content of 0.0001% by weight. In a further embodiment, The nitride material contains either of the minimum and maximum percentages shown herein. It may contain a binary halide phase with a total content in the range. In certain embodiments, the halide material is The binary halide phase does not necessarily have to be essentially present.

[0024] The content of one or more impurity phases that may be present in the halide material is Using known techniques such as powder X-ray diffraction analysis or innovative laser Raman mapping This can be determined by X-ray diffraction analysis, which determines the content of the impurity phase in the total halide material. This may be particularly suitable when the amount is at least 1% by weight relative to the total weight.

[0025] In one embodiment, the binary phase may include one or more alkali metal halide phases. In this embodiment, the halide material is 7% by weight or less of the total weight of the halide material. A large amount of alkali metal halogen phase, less than 6% by weight relative to the total weight of the halide material, 5 times Less than % by weight, less than 4% by weight, less than 3% by weight, less than 2% by weight, less than 1% by weight, or less than 0.5% by weight It may contain alkali metal halide phases with a total content of less than %. In some cases, halogen The halogenated material is at least 0.0005% by weight relative to the total weight of the halogenated material, and less 0.001% by weight, at least 0.005% by weight, at least 0.01% by weight, or A halogenated alkali metal halide phase with a total content of at least 0.05% by weight. Alkali metal halogens present in a total content of at least 0.0001% by weight relative to the total weight of the material. It may include a halogenated phase. In further examples, the halogenated material may be the minimum and as shown herein. Total content of alkali metal halides within the range of any of the maximum percentages It may contain a phase. In certain cases, halide materials essentially contain an alkali metal halide phase. It doesn't have to be included in the target.

[0026] In certain embodiments, the halide material is 7 times the total weight of the halide material. It may contain a total content of lithium halide phase of less than %. The lithium halide phase is Li It may contain one or more phases from among the Cl phase, LiBr phase, LiI phase, and LiF phase. One embodiment Therefore, the total content of the halide material is 6% by weight or less relative to the total weight of the halide material. The lithium halide phase, 5% by weight or less, and 4% by weight or less, relative to the total weight of the halide material. Below, the total content of 3% by weight or less, 2% by weight or less, 1% by weight or less, or 0.5% by weight or less. It may contain a lithium chloronide phase. In some cases, the halide material is a halide material At least 0.0005% by weight, at least 0.001% by weight, and less than the total weight of the ingredients. at least 0.005% by weight, at least 0.01% by weight, or at least 0.05% by weight At least It may contain a lithium halide phase in a total content of 0.0001% by weight. In a further embodiment, The chlorohydrate material is one of the minimum and maximum percentages shown herein. It may contain lithium halide phases in total content within a range. In certain embodiments, halides The material does not necessarily have to contain a lithium halide phase.

[0027] In one embodiment, the binary phase is a YX3 phase, where X represents a halide anion. It may contain one or more rare earth halide phases. In one embodiment, the halide material is halogen 9% or less by weight, 8% or less by weight, 7% or less by weight, 6% or less by weight, relative to the total weight of the chemical material. 5% by weight or less, 4% by weight or less, 3% by weight or less, 2% by weight or less, 1% by weight or less, or 0.5 Rare earth halide phases with a total content of 10% by weight or less, etc. It may include a halide phase. In another embodiment, the halide material is a halide material At least 0.0005% by weight, at least 0.001% by weight, and at least The total content is 0.005% by weight, at least 0.01% by weight, or at least 0.05% by weight. At least 0.5% of the total weight of the halide material, such as a large amount of rare earth halide phase. It may contain a rare earth halide phase with a total content of 0.001% by weight. In a further embodiment, halogen The nitride material contains either of the minimum and maximum percentages shown herein. It may contain a rare earth halide phase with a total content within a range. In certain embodiments, the halide material This does not necessarily have to contain a rare-earth halide phase.

[0028] In certain embodiments, the binary halide phase is YCl3, YBr3, YI3, or Y It may include one or more YX3 phases, such as one or more phases of F3. In one embodiment, halogen The halogen material is 9% by weight or less, 8% by weight or less, and 7% by weight relative to the total weight of the halogen material. % or less, 6% by weight or less, 5% by weight or less, 4% by weight or less, 3% by weight or less, 2% by weight or less, 1 YX3 phase and other components with a total content of 10% by weight or less, or 0.5% by weight or less. It may contain a large amount of YX3 phase. In another embodiment, the halide material is the total halide material At least 0.0005% by weight, at least 0.001% by weight, at least Total content of 0.005% by weight, at least 0.01% by weight, or at least 0.05% by weight. At least 0.0001% by weight of the total weight of the halide material, such as a certain amount of YX3 phase. It may contain a total content of YX3 phase. In a further embodiment, the halide material is as shown herein. The total content of the YX3 phase, which includes either the minimum or maximum percentage, It may include. In certain embodiments, the halide material does not have to essentially contain the YX3 phase. .

[0029] In one embodiment, the halide material is compared to a conventional corresponding halide material. It may contain one or more oxyhalide phases in reduced amounts. It may contain cations of metal elements selected from the group consisting of M, Me, and RE. In this case, the halide material contains 6% or less oxyhalogen by weight of the total weight of the halide material. 5% by weight or less, 4% by weight or less, and 3% by weight or less relative to the total weight of the halogenated phase and halogenated material. Below, oxyhalogenation with a total content of 2% by weight or less, 1% by weight or less, or 0.5% by weight or less. Oxyhalogens with a total content of 7% by weight or less relative to the total weight of the halogenated material, such as in the physical phase. It may include a halogenated phase. In another embodiment, the halogenated material is added to the total weight of the halogenated material. In contrast, at least 0.0005% by weight, at least 0.001% by weight, and at least 0.0 Total content of 0.5% by weight, at least 0.01% by weight, or at least 0.05% by weight At least 0.0001 of the total weight of the halide material, such as the xyhalide phase. It may contain an oxyhalide phase in a total content of weight percent. In a further embodiment, the halogenated material The amount is the total amount including either the minimum or maximum percentage shown herein. It may contain an oxyhalide phase. In certain embodiments, the halogen material is oxy The cyhalide phase does not necessarily have to be present.

[0030] The total content of impurity phases that may not be soluble in water is determined using the underwater method described below. This can be determined by dissolving 50g of halide material in distilled H2O. Obtain. The solution can be filtered through a 0.2 micron millipore filter. Insoluble The insoluble substances can be collected and weighed. The collected insoluble substances are present in the halide material. It may include the hydrated form of water-insoluble impurities present in halide materials. At least the majority of soluble impurities are oxyhalides of rare earth elements, rare earth oxides, M It may be an oxyhalide of e, MeO, or any combination thereof. The total content of water-insoluble impurities in the halide material is determined using the weight of the insoluble substance. This is possible. As an example, an insoluble impurity phase of MeOX, a metal oxyhalide, can be used. Then, the precipitated hydrated impurity form can be represented by MeX(OH)2, and MeOX The content is given by formula C MeOX =C MeOHX ×(MW MeOX / MW MeOHX ) use It can be determined by, in the formula, C MeOX However, the weight content of MeOX relative to the weight of the halide material It represents quantity, C MOHX However, the precipitated MeX(OH)2 relative to the weight of the halide material This represents the weight content, MW MeOX However, this represents the molar mass of MeOX, MW MeOHX but, This represents the molar mass of MeX(OH)2. The synthesis of halide materials may include melting and solidification. In such cases, trace amounts of organic residue may be present on the surface of the halogenated material synthesis block. Organic residue is carbon concentrated on the surface of the block and can be removed with a surgical scalpel. This can be done. Trace amounts of carbon are used as one or more elements to synthesize halide materials. It may be present in the material and may originate from the thermal decomposition of organic impurities.

[0031] In one embodiment, the halide material includes a reduced content of water-insoluble impurity phase. Obtained. In one embodiment, the halide material is obtained in an amount equal to 0.1 by weight relative to the total weight of the halide material. % or less, 0.09% by weight or less, 0.08% by weight or less, 0.07% by weight or less, 0.05% by weight % or less, 0.04% by weight or less, 0.03% by weight or less, 0.01% by weight or less, 0.008% by weight Less than % by weight, less than 0.006% by weight, less than 0.004% by weight, or less than 0.003% by weight Which water-insoluble impurities have a total content of less than 0.11% by weight relative to the total weight of the halide material? It may include a material phase. In another embodiment, the halide material is, relative to the total weight of the halide material and at least 0.0003% by weight, at least 0.0005% by weight, at least 0.00 1% by weight, at least 0.005% by weight, at least 0.01% by weight, at least 0.0 13% by weight, at least 0.015% by weight, at least 0.02% by weight, at least 0. Halo Water-insoluble impurities in total content of at least 0.0001% by weight relative to the total weight of the ionized material. It may include a physical phase. In a further embodiment, the halide material is the minimum and minimum shown herein. The total content of water-insoluble impurity phases may include any of the major percentages. In certain embodiments, the halide material may not inherently contain a water-insoluble impurity phase. In some cases, the majority of the water-insoluble impurity phase consists of rare earth oxyhalides, Me, and Xyhalides, rare earth oxides, Me oxides, or any combination thereof It may contain one or more phases. In another example, the water-insoluble impurity phase is rare earth oxyhalogenated. The substance, oxyhalides of Me, rare earth oxides, Me oxides, or any combination thereof. It can essentially consist of one or more of the combined phases.

[0032] In one embodiment, the oxyhalide phase is one or more rare earth oxyhalogens. A halogenated phase can be cited. In one embodiment, the halogenated material is 7% by weight or less, 6% by weight. % or less, 5% by weight or less, 4% by weight or less, 3% by weight or less, 2% by weight or less, 1% by weight or less, or It may contain a rare earth oxyhalide phase with a total content of 0.5% by weight or less. In certain embodiments, The total content of the rare earth oxyhalide phase is 0.0% of the total weight of the halide material. 2% less by weight, less than 0.12% by weight, less than 0.11% by weight, less than 0.10% by weight, 0.0 9% by weight or less, 0.07% by weight or less, 0.05% by weight or less, or 0.03% by weight or less, etc. It may be a rare earth oxyhalide phase of 0.3% by weight or less. In another embodiment, The chlorohydrate material is present in an amount of at least 0.0005% by weight relative to the total weight of the halide material. At least 0.001% by weight, at least 0.005% by weight, at least 0.01% by weight , with a total content of at least 0.02% by weight, or at least 0.05% by weight, of rare earth oxy At least 0.0001 by weight relative to the total weight of the halide material, such as the halide phase. It may contain a rare earth oxyhalide phase with a total content of %. In a further embodiment, halides The material is within a range including either the minimum or maximum percentage shown herein. It may contain a total amount of rare earth oxyhalide phase. In certain embodiments, the halide material It can be represented as REOX, where X is a halogen and RE is a rare earth element. It is not necessary to essentially contain a rare-earth oxyhalide phase.

[0033] In one embodiment, the halide material is compared to a conventional corresponding halide material. It may contain one or more ternary halide phases in a reduced total content. Exemplary ternary halide Halides are composed of two metal cations and one rare earth metal cation, such as alkali metal-rare earth metal halides. A logenide anion, or containing one metallic element and two halide anions, or both. It is possible. Exemplary metal cations include those of the metal elements Li, M, RE, and / or Me. Thione can be mentioned. In one embodiment, the halide material is the total halide material 6% or less by weight, 5% or less by weight, 4% or less by weight, 3% or less by weight, 2% or less by weight , ternary halide phases with a total content of 1% by weight or less, or 0.5% by weight or less, It may contain a ternary halide phase in a total content of 7% by weight or less relative to the total weight of the halide material. In another embodiment, the halide material is at least 0. 0.0005% by weight, at least 0.001% by weight, at least 0.005% by weight, at least A ternary halide phase with a total content of 0.01% by weight, or at least 0.05% by weight, etc. The total content of the ternary element is at least 0.0001% by weight relative to the total weight of the halogenated material. It may include a halide phase. In a further embodiment, the halide material is as shown herein. Ternary halides with total content ranging from the minimum to the maximum percentage. It may contain a phase. In certain embodiments, the halide material essentially contains a ternary halide phase. You don't have to.

[0034] In one embodiment, the ternary phase is one or more such as a lithium yttrium halide phase. It may contain a lithium-rare earth halide phase. In one embodiment, the halide material is a halogen Lithium-rare earth halide phase with a total content of 7% by weight or less relative to the total weight of the halide material. 5% by weight or less, 3% by weight or less, 2% by weight or less, 1% by weight or less, or 0.5% by weight or less It may contain a total lithium-rare earth halide phase. In another embodiment, a halide material The material is at least 0.0005% by weight of the total weight of the halide material, and at least 0 0.001% by weight, at least 0.005% by weight, at least 0.01% by weight, or less Halides such as lithium-rare earth halide phase with a total content of 0.05% by weight Lithium-rare earth halo content of at least 0.0001% by weight relative to the total weight of the material It may include a halogenated phase. In a further embodiment, the halogenated material is the minimum shown herein. and total content of lithium-rare earth halos including any of the maximum percentages It may contain a halogenated phase. In certain embodiments, the halogenated material is lithium-rare earth halogenated It does not necessarily have to contain an ionized phase.

[0035] In certain embodiments, the ternary halide phase is 6 times the total weight of the halide material. Weight % or less, 5 weight % or less, 4 weight % or less, 3 weight % or less, 2 weight % or less, 1 weight % or less or a ternary halide phase containing two anions in a total content of 0.5% by weight or less, YBr is a ternary phase containing two anions in a total content of 7% by weight or less. x Cl y or Li Br x Cl y One or more ternary halide phases containing two halide anions, such as It may include. In some cases, the halide material may be small relative to the total weight of the halide material. At least 0.0005% by weight, at least 0.001% by weight, at least 0.005% by weight %, at least 0.01% by weight, or at least 0.05% by weight of two anions in total content At least 0 of the total weight of the halide material, such as a ternary halide phase containing ON. It may contain a ternary halide phase with two anions in a total content of 0.0001% by weight. In one embodiment, the halogenated material is the minimum and maximum percentages shown herein. It contains a ternary halide phase containing two anions within the total content range that includes any of the following: In certain embodiments, the halide material is a ternary halide phase containing two anions. It does not necessarily have to include it in its essence.

[0036] In one embodiment, the halide material is compared to a conventional corresponding halide material. It may contain one or more nitride-based phases in reduced amounts. The nitride-based phases may include oxynitride phases, nitride phases, and nitrogen phases. It may contain one or more phases from the carbon phase or the nitride phase. The nitride phase may be Li, M, RE It may contain cations of metal elements selected from the group consisting of , and Me. In one embodiment, halo The halogenated material is 6% by weight or less, 5% by weight or less, and 4 times the total weight of the halogenated material. Total content of % by weight, 3% by weight or less, 2% by weight or less, 1% by weight or less, or 0.5% by weight or less. A total nitrogen content of 7% by weight or less relative to the total weight of the halogenated material, such as a nitride-based phase. It may include a halogenated phase. In another embodiment, the halogenated material is added to the total weight of the halogenated material. In contrast, at least 0.0005% by weight, at least 0.001% by weight, and at least 0.0 Nitrogen content of 0.5% by weight, at least 0.01% by weight, or at least 0.05% by weight At least 0.0001% by weight of the total weight of the halogenated material, such as the halogenated phase. It may contain a nitride-based phase of a certain content. In a further embodiment, the halide material is as shown herein. A nitride-based phase with a total content ranging from the minimum to the maximum percentage of the specified substance. It may include. In certain embodiments, the halide material does not necessarily have to contain a nitride-based phase. stomach.

[0037] In one embodiment, the halide material is compared to a conventional corresponding halide material. , reduced REO content x N y It may contain one or more oxynitride phases, such as a phase. This may include cations of metal elements selected from the group consisting of Me and RE. In one embodiment, The halide material shall be 6% by weight or less and 5% by weight or less of the total weight of the halide material. , 4% by weight or less, 3% by weight or less, 2% by weight or less, 1% by weight or less, or 0.5% by weight or less Total content of oxynitride phase and other halogenated materials is 7% by weight or less relative to the total weight of the halogenated materials. It may contain a certain amount of oxynitride phase. In another embodiment, the halide material is the total amount of halide material. At least 0.0005% by weight, at least 0.001% by weight, at least Total content of 0.005% by weight, at least 0.01% by weight, or at least 0.05% by weight. A quantity of oxynitride phase or other, at least 0.0001 by weight relative to the total weight of the halide material. It may contain an oxynitride phase with a total content of %. In a further embodiment, the halide material is as specified herein Total content of oxynitriding within a range including either the minimum or maximum percentage shown. It may contain an oxynitride phase. In certain embodiments, the halide material does not essentially contain an oxynitride phase. That's fine.

[0038] In one embodiment, the halide material is compared to a conventional corresponding halide material. , reduced content of REC x N y It may contain one or more carbon nitride phases, such as the carbon nitride phase. This may include cations of metal elements selected from the group consisting of Me and RE. In one embodiment, The halide material shall be 6% by weight or less and 5% by weight or less of the total weight of the halide material. , 4% by weight or less, 3% by weight or less, 2% by weight or less, 1% by weight or less, or 0.5% by weight or less Total content of carbon nitride phase and other halogenated materials is 7% by weight or less relative to the total weight of the halogenated materials. It may contain a certain amount of carbon nitride phase. In another embodiment, the halide material is the total amount of halide material At least 0.0005% by weight, at least 0.001% by weight, at least Total content of 0.005% by weight, at least 0.01% by weight, or at least 0.05% by weight. A quantity of carbon nitride phase or other such amount, at least 0.0001 by weight relative to the total weight of the halide material. It may contain a total content of carbon nitride phase of %. In further embodiments, the halide material is as specified herein Total carbon nitride content within a range including either the minimum or maximum percentage shown. It may contain an elementary phase. In certain embodiments, the halide material does not essentially contain a carbon nitride phase. That's fine.

[0039] In one embodiment, the halide material is compared to a conventional corresponding halide material. , such as a phase with reduced content of rare-earth nitrides (e.g., REN (rare-earth nitride)). It may contain one or more nitride phases. The nitride phases are selected from the group consisting of Li, M, Me, and RE. It may contain cations of selected metal elements. In one embodiment, the halide material is halogen 6% by weight or less, 5% by weight or less, 4% by weight or less, 3% by weight or less, relative to the total weight of the chemical material. Halo The nitride phase may be included in a total content of 7% by weight or less relative to the total weight of the nitride material. Another embodiment Therefore, the halide material is at least 0.0005 of the total weight of the halide material. weight%, at least 0.001 weight%, at least 0.005 weight%, at least 0.0 Halide material such as a nitride phase with a total content of 1% by weight, or at least 0.05% by weight. It may contain a nitride phase in a total content of at least 0.0001% by weight relative to the total weight of the material. In one embodiment, the halogenated material is the minimum and maximum percentages shown herein. It may contain a nitride phase with a total content ranging from any of the following. In certain embodiments, halogen The nitride material essentially does not contain at least one rare earth nitride phase and a Me metal nitride phase. It may also be the case that the nitride phase is present in the halide material. Alternatively, the phase may not essentially contain a cation of the metallic element Me. More specific embodiments Therefore, halide materials essentially do not contain rare earth nitride phases and Me metal nitride phases. That's good too.

[0040] In one embodiment, the halide material is 6% by weight of the total weight of the halide material. Below, 5% by weight or less, 4% by weight or less, 3% by weight or less, 2% by weight or less, 1% by weight or less, 0. Impurity phases, etc., with a total content of 5% by weight or less, 0.3% by weight or less, or 0.1% by weight or less, 15% by weight or less, 14% by weight or less, 13% by weight or less, relative to the total weight of the halide material. 12% or less by weight, 10% or less by weight, 9% or less by weight, 8% or less by weight, 7% or less by weight, etc. It may contain impurity phases with a total content of 6% by weight or less. In another embodiment, the halide material is At least 0.0005% by weight and at least 0.001% by weight relative to the total weight of the chlorohydrate material. Weight percent, at least 0.005% by weight, at least 0.01% by weight, or at least 0. At least 0.5% by weight of the halide material, such as impurity phases with a total content of 0.5% by weight. It may contain an impurity phase with a total content of 0.0001% by weight. In a further embodiment, a halogenated material The amount is the total amount including either the minimum or maximum percentage shown herein. It may contain impurity phases.

[0041] In certain embodiments, the halide material is a binary halide phase, a ternary halide The phase, oxynitride phase, and oxyhalide phase do not necessarily have to be included in their essence. In embodiments, the halide material may essentially consist of a single phase. For example, a halide The material is Li 3-x-f M f RE 1-y Me k y (Cl 1-u-p-q Br u F p I q ) 6-x+y*(k-3) It can consist of a phase represented by and an impurity phase, and the impurity phase The total content may be at most 0.5 mol% or at most 0.3 mol%.

[0042] In one embodiment, the halide material promotes the improved properties of the halide material. It may include specific crystal structure features. These crystal structure features include the crystal system and the lattice system. , space group, one or more unit cell parameters including unit cell volume, values ​​of a, b, c, or those Any combination of the following: the number of atoms in the unit cell, the stacking order, atomic vacancies, the occupancy rate of vacancies, or these. Any combination of these can be listed.

[0043] In one embodiment, the halide material is monoclinic, trigonal, hexagonal, or orthorhombic. The system may include a crystalline structure. In certain embodiments, the halide material is a monoclinic space group. It may include a crystal structure represented by [this]. In certain examples, the halide material is C2 / m air It may include a crystal structure represented by an intergroup.

[0044] In another specific embodiment, the halide material is R3,

[0045]

number

[0046]

number

[0047]

number

[0048] In another specific embodiment, the halide material is represented by a hexagonal space group. It may contain crystalline structures. Hexagonal crystal systems include P6, P61, P65, P62, P64, and P6. 3.

[0049]

number

[0050]

number

[0051] In certain embodiments, the halide material is at the atomic level, the nanometer level, Alternatively, it includes a mixed crystalline intermediate phase containing multiple crystalline intermediate phases integrated in both. The nearest interatomic distance is typically less than 0.5 nm, and the nanometer region is 1 nm. They can have sizes larger than the nearest interatomic distance, such as ultra-large. In one embodiment, halogenation The material consists of a first crystalline phase having a first crystalline structure represented by a first space group, and a second crystalline phase. It may include a second crystalline phase having a different second crystalline structure represented by the space group of .

[0052] In certain embodiments, the halide material is represented by a space group of rhombohedral lattice systems. A first crystalline intermediate phase having a first crystalline structure, and a monoclinic space group such as C2 / m It may include a second crystalline intermediate phase represented by . In certain examples, the halide material is

[0053]

number

[0054]

number

[0055] For example, the first crystalline intermediate phase is represented by the first crystalline structure, which is represented by a hexagonal space group. The second crystalline intermediate phase may be represented by a space group of trigonal or orthorhombic structures. It may have a crystalline structure. In certain examples, the second crystalline intermediate phase is

[0056]

number

[0057]

number

[0058] In one embodiment, the halide material is a unit cell smaller than the Li3YBr6 unit cell. It may include a crystalline structure containing the same as Li3YBr6. In certain embodiments, the halide material is the same as Li3YBr6. However, it may include a crystal structure having a smaller unit cell volume. In another specific embodiment, In the powder diffraction pattern of halide materials, the peaks of the halide material are the same as those of Li3YBr6. Compared to the corresponding peak, powder X-ray diffraction (powder X-ray diffraction) is shifted at a high angle. It may include fractional (XRD) patterns. See Figure 1A, Cu K-alpha emission. Li3YBr3Cl3 and Li3Y, which are representative halide materials measured using linear measurements. The powder XRD patterns of Br4Cl2 and Li3YBr6 are shown. The corresponding peaks for 3Cl3 and Li3YBr4Cl2 are different from those for Li3YBr6. It is shifting to a higher value 2-theta.

[0059] In another embodiment, the halide material is similar to Li3YCl6, but larger. It may include a crystalline structure having a unit cell volume. In certain examples, the halide material is a halogen The peak of the nitride material is compared to the corresponding peak in the powder diffraction pattern of Li3YCl6. This may include powder X-ray diffraction (XRD) patterns that are shifted at smaller angles. Figure 1B Referring to the data, representative halide materials measured with Cu K-alpha radiation are XRD of powders Li3YBr2Cl4, Li3YBr1Cl5, and Li3YCl6 The pattern is shown. The corresponding peak for Li3YBr1Cl5 is Li3YCl6 and In comparison, it is shifting to a smaller 2-theta value. XRD of Li3YBr4Cl2 The turn may suggest that the halide contains a mixed intermediate phase.

[0060] In a specific example, the halide material measured 13° with Cu K-alpha radiation. The XRD pattern may include at least two peaks in a 2-theta range of ~15°. Referring to Figure 2, Li 3-x Y(Cl 1-u Br u ) 6-x The Cu K- The alpha XRD pattern is shown. Sample 202, where u is 0.59±0.03, It shows one peak in the 2-theta range of 13° to 15°. u is 0.38 ± 0.0 for each. Samples 204 and 206, which are 3 and 0.31±0.03 respectively, are in the range of 13° to 15°. The graph shows two peaks.

[0061] In another embodiment, the halide material enhances the improved properties of the halide material. It may include a specific average diffraction crystallite size. The average diffraction crystallite size is a condensation. This can also be called the cohere X-ray scattering region size, and is relevant to halide-based materials. X-ray diffraction analysis and Scherrer's equation L = (Kλ) / (βcosθ) (where L is the mean diffraction) This represents the crystallite size, where K has a value close to 1 and is a dimensionless value with typical values ​​between 0.9 and 1. This is the dimensionless shape factor, where λ is the X-ray wavelength and β is the value of the instrument. Half a radian after subtracting the instrumental line broadening. The spread of the line in the full width of time (FWHM) is determined using θ, where θ is the Bragg angle. obtain.

[0062] In one embodiment, the halide material has a wavelength of at least 20 nm, at least 25 nm, and at least Average diffraction crystallite size of at least 30 nm, at least 35 nm, or at least 40 nm It may include. In another embodiment, the halide material is at most 500 nm, at most 400 Average diffraction pattern of nm, at most 300 nm, at most 200 nm, or at most 100 nm This may include the size of the crystal. In a further embodiment, the halide material is the minimum shown herein. The average diffraction crystallite size may include a range that includes either the value or the maximum value.

[0063] In one embodiment, the solid electrolyte material is a halogenated material and an improved solid electrolyte material. It may include a halide material containing a specific amount of Cl that can enhance the properties. In some embodiments, (1-upq) is at least 0.12, at least 0.15, and at least Also 0.17, at least 0.20, at least 0.23, at least 0.25, and at least 0.27, at least 0.29, at least 0.33, at least 0.36, and at least 0.43, at least 0.48, at least 0.50, at least 0.54, or less It could be at least 0.58. In another embodiment, (1-upq) is at most 0.92. At most 0.87, at most 0.83, at most 0.80, at most 0.77, at most 0.75, at most 0.70, or at most 0.66, etc., at most 0.99, and It can also be 0.97. In a further embodiment, (1-upq) is the most as shown herein. It may be within a range that includes either the minimum or maximum value.

[0064] In certain embodiments, the solid electrolyte material is Li 3-x-f M f RE 1-y Me k y ( Cl 1-u-p-q Br u F p I q ) 6-x+y*(k-3) halogens represented by It may include halogen materials, where u may be greater than 0. More specifically, halogen materials are It may contain Br in a certain amount that can promote improved properties of the halide material. In one embodiment, u is at least 0.12, at least 0.15, at least 0.17, At least 0.2, at least 0.23, at least 0.25, at least 0.27, small At least 0.29, at least 0.32, or at least 0.34, etc. It can be 0.1. In another embodiment, u is at most 0.85, at most 0.83, at most 0.8, at most 0.77, at most 0.75, at most 0.7, at most 0.67, many At most 0.65, at most 0.62, at most 0.6, at most 0.57, at most 0. 54, at most 0.52, at most 0.49, at most 0.45, or at most 0.42 It may be either of the minimum and maximum values ​​shown herein. It may be within the range that includes .

[0065] In another embodiment, the halide material enhances the improved properties of the halide material. It may include a specific ratio of Cl to Br (1-upq) / u. In one embodiment, the ratio of (1-upq) / u is at least 0.06, at least 0.1, At least 0.2, at least 0.3, at least 0.4, at least 0.5, and at least 0.6, at least 0.7, at least 0.8, at least 0.9, at least 1.0 , at least 1.2, at least 1.3, at least 1.4, at least 1.5, less 1.6, at least 1.7, at least 1.8, at least 1.9, or at least It could be at least 0.03, such as 2.0. In another embodiment, (1-upq) / u The ratios are 9 or less, 8.6 or less, 8.3 or less, 8 or less, 7.7 or less, 7.4 or less, 7 or less, 6.5 or less, 6.2 or less, 6 or less, 5.5 or less, 5 or less, 4 or less, 3 or less, 2 or less, or It may be 1.4 or less. In further embodiments, the ratio of (1-upq) / u is as shown herein. It may be within a range that includes either the minimum or maximum value.

[0066] In further embodiments, the halide material is an anhydrous halide composed of Cl and Br. It may contain on. In certain examples, the halide material is Li 3-x RE 1-y Me k y ( Cl 1-u Br u ) 6-x+y*(k-3) It can be expressed as follows, where u>0 For specific applications, 0.08 <= u <= 0.67. Another example is halogenated materials. The fee is Li 3-x Y(Cl 1-u Br u ) 6-x It can be represented by, and for specific purposes In a particular embodiment, u may be at least 0.55 or at most 0.45. 0.2 <= u <= 0.45.

[0067] After reading this disclosure, those skilled in the art will see that the properties of the halide materials in the embodiments herein are halo The amount of one or more of the genide anions, their ratio, the crystal structure of the halide material, This can be adjusted or regulated by carefully controlling any combination of them. You will understand that this is possible. In one embodiment, if both Br and Cl are present, B Carefully control the amounts of r and / or Cl, and / or the ratio of (1-upq) / u. As a result, the halide material has a layered crystal structure similar to Li3YBr6, Li3YC Improved ionic conductivity compared to l6, and improved electrical conductivity compared to Li3YBr6. This may include vapor-thermodynamic stability and similar mechanical deformability. In another embodiment, halogen The nitride material may include Br and Cl, and may include the mixed crystalline intermediate phase described in the embodiments herein. It may have a crystalline structure. The halide material is an improved ion compared to Li3YCl6. have a conductivity and an improved electrochemical and thermodynamic stability compared to Li3YBr6 can.

[0068] In another embodiment, when 0 < u < 0.33, the halide material has a crystal structure including a hexagonal / trigonal crystal structure similar to Li3YCl6, particularly improved ionic conductivity and mechanical deformability at low temperatures (i.e., below 200 °C), and an improved electrochemical and thermodynamic stability compared to Li3YBr6. Such halide materials may be particularly suitable for certain applications such as the manufacture of lightweight batteries due to their reduced density compared to Li3YBr6.

[0069] In certain embodiments, where p can be greater than 0, Li 3-x-f M f RE 1-y Me k y (Cl 1-u-p-q Br u F p I q ) 6-x+y*(k-3) represented by halide material. More specifically, the halide material may contain F in a specific amount that can promote the improved properties of the halide material. In one aspect, p can be at least 0.04, such as at least 0.06, at least 0.08, at least​​​​​​​​​​​​​​​​​​​​​​​is at most 0.33, such as at most 0.14, at most 0.12, or at most 0.10 obtained. In another aspect, p can be within a range including either the minimum value or the maximum value shown herein and can be within the range.

[0070] As an example of the halide material, Li3Me 3+ Cl 6(1-p) F 6p can be mentioned, where 0 < p < 0.58. In a specific example, Me can include In, and more specifically, it can consist of In. The solid solution of the chloride - fluoride halide phase can have a crystal structure represented by the space group C2 / m, and can have improved ionic conductivity compared to Li3InF6 and Li3 InCl6.

[0071] In another embodiment, the halide material can include a specific ratio (1 - u - p - q) / p of the amount of Cl to the amount of Br that promotes the improved properties of the halide material. In one aspect, the ratio (1 - u - p - q) / p is at least 0.7, at least 0.9, at least 1.0, at least 1.2, at least 1.4, at least 1.5, at least 1.6, at least 1.7, at least 1.8, at least 1.9, at least 2.0, at least 2.2, at least 2.4, at least 2.6, at least 2.8, at least 3.0, at least 3.2, at least 3.4, or at least 3.6, etc., and can be at least 0.5. In another aspect, the ratio (1 - u - p - q) / p is 21 or less, 19 or less, 17 or less, 15 or less, 13 or less, 12 or less, 11 or less, 9 or less, 8 or less, 6 or less, or 5 or less, etc., and can be 24 or less. In a further aspect, the ratio (1 - u - p - q) / p This may be within a range that includes either the minimum or maximum value shown herein.

[0072] In one embodiment, the halide material is of the formula Li a M a’ Me b Me' b’ X c X' c ’ It can be expressed by: M is, as described in the above embodiment, at least other than Li It could also be one alkali metal element. In certain cases, M is one of Na, K, and Cs. It can be at least one of the elements.

[0073] Me is a group IIIB element, a group IVB element, V, as described in the embodiments herein. Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Al, In, Sn, Pb, Bi, S It may be at least one element from the group consisting of b, Mg, Ca, Ga, and Ge. In a typical example, Me may be RE as considered in the embodiments herein.

[0074] Unlike Me, Me' is a group IIIB element, group IVB element, V, Cr, Mn, Fe , Co, Ni, Cu, Zn, Zr, Al, In, Sn, Pb, Bi, Sb, Mg, Ca, It may be at least one element from the group consisting of Ga and Ge. In certain examples, Me ' may be at least one element from the rare earth elements, Zr, and Fe.

[0075] X can be at least one halogen, and X' can be at least one other halogen. It can be a gen. In certain examples, X is at least one of the elements Cl, Br, and F. It could be a primary element. In another specific example, X' is at least one of the elements Br and F. could be.

[0076] In another embodiment, the solid electrolyte material may include a halide material represented by Li a M a’ Me b Me’ b’ X c X’ c’ where a ≥ a', b ≥ b', and c ≥ c' In particular, the halide material may contain low levels of one or more impurities, as described in the embodiments of this specification. In yet another embodiment, the solid electrolyte material is Li a M a’ M e b Me’ b’ X c X’ c’ and may include a halide material represented by, where the anions of the halide material may be within a single phase.

[0077] In one embodiment, the halide material may include at least four elements. In a further embodiment, the halide material may have a crystallographic phase transition that can be induced by adjusting the stoichiometric ratios of two or more elements. In certain embodiments, the stoichiometric ratios of the elements at the same site of the crystal structure may be adjusted such that the halide material may have improved properties including, for example, ionic conductivity, electrochemical stability, compatibility, etc., or any combination thereof. After reading this disclosure, those skilled in the art will understand that Li and M may be present at the same crystallographic site. Me and Me' may be present at the same crystallographic site, and X and X' may be present at the same crystallographic site. In one example, the stoichiometric ratio of Me and Me', or the stoichiometric ratio of Li and M, or the stoichiometric ratio of X and X', or any combination thereof, may be adjusted such that the halide material may have improved properties including, for example, ionic conductivity, electrochemical stability, compatibility, etc., or any combination thereof. After reading this disclosure, those skilled in the art will understand that Li and M may be present at the same crystallographic site. Me and Me' may be present at the same crystallographic site, and X and X' may be present at the same crystallographic site. In one example, the stoichiometric ratio of Me and Me', or the stoichiometric ratio of Li and M, or the stoichiometric ratio of X and X', or any Any combination of these is adjusted to improve one or more properties of the halide material. It is possible. In certain examples, X could be Cl, X' could be Br, and the chemistry between X and X' The stoichiometric proportion is Li of the halide material. + Ionic conductivity, electrochemical conductivity, etc. It can be adjusted to improve stability, or both. In another specific example, M is Na. Furthermore, the stoichiometric ratio of Li to M can be adjusted to improve ionic conductivity. In another example, Me can be Y, and Me' can be In, and the stoichiometry of Me and Me' The ratio can be adjusted to improve the ionic conductivity of the halide material.

[0078] Halide materials may have crystallographic phase transition boundaries on their compositional phase diagrams. Crystallographic phase transition boundaries are morphotropic phase boundaries. It can also be called MPB. In one embodiment, the crystallographic phase transition is due to the stoichiometric amounts of Me and Me'. This can be induced by changes in the theoretical proportion. In particular, for halide materials, b / (b+b') , (b / (b+b')) t * 0.84~(b / (b+b')) t * 1.16 Stoichiometric Class A phase transition may occur when the conditions are met, where (b / (b+b')) t However, at room temperature (i.e., 2 This corresponds to the crystallographic phase transition boundary on the compositional phase diagram at 2°C. In certain embodiments, b>b'>0 , c≧0, c'≧0, and (c+c')>0. In another embodiment, Me and Me' At least one example is the RE considered in the embodiments of this disclosure. In certain embodiments, Me can be RE, and Me' can be another tetravalent Alternatively, trivalent elements can be given. In a more specific embodiment, Y can be given as Me. It is possible, and as for Me', Zr can be cited. More specifically, Me is It can be Y, and Me' can be Zr.

[0079] In one embodiment, the halide material changes in the stoichiometric ratio of X and X' They may have induced crystallographic phase transitions. In particular, halide materials have c / (c+c') However, (c / (c+c')) t * 0.84~(c / (c+c')) t * 1.16 Compositional Phase Diagram A phase transition may occur when the stoichiometric range is as shown above, where (c / (c+c')) t However, room temperature This corresponds to the crystallographic phase transition boundary on the compositional phase diagram at (i.e., 22°C). In certain embodiments, , c≧c'>0, b≧0, b'≧0, and (b+b')>0. In another specific embodiment, For X, we can give Cl, and for X', we can give Br. More specifically In one particular mode, X can be Cl and X' can be Br. In another specific mode, M And at least one of M' may be an RE considered in embodiments of this disclosure. In more specific embodiments, one of M and M' may be Y.

[0080] In another embodiment, the halide material changes depending on the stoichiometric ratio of Li and M. It may have a crystallographic phase transition that can be induced. In particular, halide materials have a / (a+a' ) is (a / (a+a')) t * 0.84~(a / (a+a')) t * 1.16 stoichiometric quantity A phase transition may occur if it is within the scope of the theory, in the formula, (a / (a+a')) t However, room temperature (that is This corresponds to the crystallographic phase transition boundary on the crystallographic phase diagram at 22°C. In further embodiments, a>0 and a'>0. In a particular embodiment, a>a'. In another particular embodiment... Then, as M, we can give Na. In a more specific embodiment, M is Na It is possible.

[0081] In one embodiment, the halide material is a crystal containing a transition that crosses a crystallographic phase transition boundary. It may have a crystallographic phase transition. In another embodiment, the crystallographic phase transition is one or more characteristic of the crystal structure. This may include changes in characteristics. Examples of characteristics of the crystal structure include the volume of the unit cell, the space group, and the number of cells. You may specify one or more features of the crystal system, XRD pattern, or any combination thereof. can.

[0082] In one embodiment, the halide material is monoclinic, trigonal, hexagonal, or orthorhombic. A crystallographic phase transition can include a transition from one crystal system to another. In further embodiments, the halide material is a crystal that includes a transition from a layered structure to a non-layered structure. This may include a crystallographic phase transition. For example, a crystallographic phase transition could be a transition from monoclinic to trigonal crystal system. One example of a phase transition is C2 / m One example of a transition from a space group or R-3m space group to a P-3m1 or Pnma space group is: In yet another embodiment, the crystallographic phase transition is from a cubic close-packed structure to a hexagonal close-packed structure. One example is the transition to a packed structure.

[0083] In a further embodiment, the crystallographic phase transition is from one non-layered structure to another non-layered structure. A transition can be cited. In yet another embodiment, a crystallographic phase transition is a non-layered structure One example is the transition from a solid to a layered structure. In certain cases, a crystallographic phase transition is... One example is the transition from R3c to R3m. Another specific example is a crystallographic phase transition. For example, the transition from the P-3m1 or Pnma space group to the C2 / m space group or R-3m space group. One possible example is movement.

[0084] In further embodiments, if the halide material has a crystallographic phase transition, certain The crystal structure characteristics may not change. For example, the XRD pattern of a halide material. One example is a phase transition feature that represents an increase or decrease in unit cell volume, but a certain particular Other XRD characteristics may not change. In certain cases, halide materials may change by 5° Crystallographic phase transitions and XRD patterns, including the absence of peaks between 2 thetas and ~13°. It may include turns.

[0085] In one embodiment, the halide material is modified by changing the elements of the halide material. It may undergo a phase transition. As discussed above, the stoichiometric proportions of elements can be adjusted. The proportion of a prime element can be expressed in mol% or at%.

[0086] In one embodiment, the halide material may be stoichiometric. In another embodiment, Halide materials can be non-stoichiometric. For example, halide materials have a composition that It may include vacancies that replace some of the elements and maintain the electrical neutrality of the phase within a certain range.

[0087] In one embodiment, the halide material is Li a-f M a’ RE b Me' kb’ (Cl c Br c’ ) 6-f+(k-3)*b’ It can be expressed as follows, and in the formula, (a+a')= 3, -1 ≤ f ≤ 1, (c + c') = 1, and (b + b') = 1. In a particular embodiment, The halide material may include X and X', where c > c', and 0.63 ≤ c / ( c + c') ≤ 0.98.

[0088] In another embodiment, the halide material is Li 3-f RE b Me' k b’ (Cl c B r c’ ) 6-f+(k-3)*b’ It can be expressed by the formula, where 0≦f≦0.3, ( c+c')=1, (b+b')=1, b>0, and b'≧0. In certain embodiments, b ' can be 0. A specific example of a halide material is Li3Y1(Cl c Br c ’ )6 can be given, and in the formula, 0.63 ≤ c / (c+c') ≤ 0.87. Another In this embodiment, b > b' > 0. A specific example of a halide material is Li 3-f Y b Me' k b’ (Cl c Br c’ ) 6-f+(k-3)*b’ We can list them, and in the formula, k = 3 or 4, and 0.65 ≤ c / (c + c') ≤ 0.98. (Halogenated material) A more specific example is Li 3-b’ Y b Zr b’ (Cl c Br c’ ) List 6 This is possible, and in the formula, 0.72 ≤ c / (c+c') ≤ 0.98. Another halide material A more specific example is Li 3-f Y b Yb b’ (Cl c Br c’ ) 6-f List This can be done, and in the formula, 0.65 ≤ c / (c+c') ≤ 0.89. A more specific example is Li 3-f Y b In b’ (Cl c Br c’ ) 6-f List This is possible, and in the formula, 0.69 ≤ c / (c+c') ≤ 0.95.

[0089] A more specific example of a halide material is Li3Y1(Cl 0.8 Br 0.2 ) 6. Li3Y1(Cl 0.67 Br 0.33 )6, Li3Y1(Cl 0.79 Br 0.2 1) 6, Li3Y1(Cl 0.62 Br 0.38 )6, Li 2.95 (Y 0.95 Zr0 .05 )(Cl 0.9 Br 0.1 )6, Li3(Y 0.95 Yb 0.05 )1(Cl 0. 83 Br 0.17 )6, Li3(Y 0.95 In 0.05 )1(Cl 0.9 Br 0.1 ) I can give a number 6.

[0090] Figure 8 shows Li3YCl at room temperature. c Br c C in mol% units relative to the ionic conductivity Includes a plot of the concentration of l. As shown, Cl is at the crystallographic phase transition boundary (Figure 8). It is 75 mol% in the (indicated by a vertical dotted line and referred to as MPB). The nitride material is a layered crystal of LYB until the mol% of Cl increases to 75 mol%. It may have a crystal structure similar to the structure. Halide materials have a mol% of Cl of at least When present at 75 mol%, it may have a crystalline structure similar to the non-layered crystalline structure of LYC.

[0091] As shown in Figure 8, when the concentration of Cl increases to approximately 63 mol%, halogen The ionic conductivity of ionized materials can increase to approximately 2 ms / cm. As further shown... The concentration of Cl is approximately 65 mol% (referred to as "LYBC-65" in Figure 8) When adjusted to 80 mol% (referred to as "LYBC-80" in Figure 8), halogen The ionic conductivity of ionized materials can exceed 2 ms / cm. In particular, when the concentration of Cl is 63 m When adjusted to the range of ol% to 87 mol%, the ionic conductivity of the halide material is low. It could be at least 2.08 mS / cm or at least 2.20 mS / cm, which is LYB It is unexpectedly higher than the ionic conductivity of [another material].

[0092] LYB promotes higher ionic conductivity than LYC, which has a non-layered crystalline structure. It has a layered crystalline structure. The concentration of Cl is in the range of 63 mol% to less than 75 mol%. In this case, compared to the layered structure of LYB, the crystalline structure of the halide material is distorted, and typically... It is highly unlikely to be a layered structure. In addition, halide materials have a non-layered crystalline structure. Therefore, halide materials, It may be less desirable than the layered structure of LYB due to its higher ionic conductivity. When it has a crystalline structure, the halide material has a significantly higher ionic conductivity than LYB. It is unexpected that it may possess conductivity.

[0093] Figure 9A shows the Cu K-alpha emission overlaid on the XRD pattern of Li3YCl6. Li3Y(Cl) was measured using radiation, which is a typical halide material. 0.79 Br 0.2 1) Includes a diagram of the XRD patterns of 6 powders. The XRD peaks of typical halide materials are: Compared to the corresponding peak in the powder XRD pattern of Li3YCl6, the angle is smaller. It is showing. Referring to Figure 9B, a typical hyphen measured with Cu K-alpha radiation is shown. Li3Y(Cl) is a chlorohydrate material. 0.67 Br 0.33 )6 powder XRD patterns This is combined with the XRD pattern of Li3YBr6. Typical halide materials The corresponding peak is shifted to a larger value of 2θ compared to Li3YBr6. Li3Y(Cl 0.67 Br 0.33 )6 is observed to be a single-phase halide material. It is possible.

[0094] In one embodiment, the halide material is Li 3-f RE b Me' k b’ X 6-f+( k-3)*b’ It can be expressed as follows, where -1≦f≦1 and (b+b')=1 Yes, in certain cases, k=3. For example, In can be given as Me. In another specific embodiment, Y can be given as RE. Therefore, 0.67 ≤ b / (b+b') ≤ 0.93. As a specific example of a halide material... So, Li 3-f Y b In b X 6-f We can list some examples.

[0095] In another embodiment, the halide material is Li a M a It can be represented by REX6. In the equation, a > a' > 0, (a + a') = 3, and 0.942 ≤ a / (a + a') ≤ 0. The value is 958. In one embodiment, Na can be given as M. In another embodiment, R As E, Y can be given. In another embodiment, as X, Cl can be given. Yes, it is possible. In certain embodiments, the halide material is Li a Na a’ Represented by YCl6 Therefore, 0.942 ≤ a / (a+a') ≤ 0.958.

[0096] A more specific example of a halide material is Li3(Y 0.85 In 0.15 )C l6 and (Li 0.955 Na 0.045 )3YCl6 can be mentioned.

[0097] In one embodiment, the halide material is of the formula Li a M a’ RE b Me' b’ Cl c X' c’ It can be expressed as such, and Me may have a smaller ionic radius than RE. In one embodiment, RE can be Y. In one embodiment, Me having a smaller ionic radius is When b'=0, the crystallographic phase transition of a halide material from a non-layered structure to a layered crystalline structure occurs. This can accelerate the transition. For example, as a crystallographic phase transition, Pnma or P-3m1 to C2 / Another example of a crystallographic phase transition is: One example is the transition from orthorhombic to monoclinic crystallography. In a further aspect, crystallographic phase transitions are also mentioned. The transition can be controlled by adjusting the stoichiometric ratio of RE to Me. In particular, (b / (b+b')) t * 0.84 t * 1.16 In this case, the halide material is b / (b+b')>(b / (b+b')) t * 1.1 6 and b / (b+b')<(b / (b+b')) t * This is significantly different from the case where it is 0.84. It may have improved properties, including ionic conductivity. Examples of Me include divalent elements and trivalent elements. A specific example of Me could be a valence element, a tetravalent element, or any combination thereof. Examples include Yb, SC, In, Zr, Ga, or any combination thereof. It is possible.

[0098] In one embodiment, the halide material is of the formula Li a M a’ RE b Me' b’ Cl c X' c’ It can be expressed as follows, and X' may have a larger ionic radius than Cl. One embodiment For X', we can list Br, I, or a combination thereof. In some embodiments, RE may be Y. In further embodiments, X' may have a larger ionic radius. This is achieved by adjusting the stoichiometric ratio of Cl and X', so that when c'=0, the halo ​This can promote the crystallographic phase transition from a non-layered structure to a layered crystalline structure in ionized materials. In particular, Logenized materials are (c / (c+c')) t * 0.84 <c / (c+c’)<(b / (b +b')) t * If it is 1.16, then (c / (c+c')) t * 0.84 > c / (c + c) ') and c / (c+c')>(b / (b+b')) t * Compared to the case of 1.16, It may possess properties such as significantly improved ionic conductivity.

[0099] In another embodiment, the halide material is Li a M a’ RE b Me' b’ Cl c X ' c’ It can be expressed as such, and M may have a larger ionic radius than Li. One embodiment For M, we can list Na, K, Cs, Cu, or combinations thereof. In certain embodiments, RE may be Y. In further embodiments, a larger ionic radius may be The M possessed is such that when a'=0, the halide material changes from a non-layered structure to a layered crystalline structure or It may promote a crystallographic phase transition to another non-layered structure. For example, as a crystallographic phase transition, P Another example is the transition from nma or P-3m1 to C2 / m or C2 / c. As for the transition, we can mention the transition from orthorhombic to cubic elpasolite or monoclinic crystal structures. It is possible to do so. In certain embodiments, the transition adjusts the stoichiometric ratio of Li and M. It can be controlled by and. In particular, halide materials are (a / (a+a')) t * 0.8 4 t * If it is 1.16, then (a / (a+a ')) t * 0.84 > a / (a+a') and a / (a+a') > (a / (a+a')) t * Significantly improved ionic conductivity and electrochemical stability compared to the case of 1.16. It may possess properties such as compatibility, or any combination thereof.

[0100] In one embodiment, the halide material is of the formula Li a M a’ RE b Me' b’ Cl c X' c’ It can be expressed as such, and Me may have a larger ionic radius than RE. In one embodiment, RE can be Y. In one embodiment, Me having a larger ionic radius is When b'=0, the halide material changes from a non-layered structure to a layered or other non-layered crystalline structure. It can promote the crystallographic phase transition of Pnma or P-3. One example is the transition from m1 to C2 / m or C2 / c. One example of a transition is the transition from orthorhombic crystallography to monoclinic crystallography. In a further embodiment, The crystallographic phase transition can be controlled by adjusting the stoichiometric ratio of RE to Me. In particular, (b / (b+b')) t * 0.84 ) t * If 1.16, then for halide materials, b / (b+b')>(b / (b+b') )) t * 1.16 and b / (b+b')<(b / (b+b'))​​t * If it is 0.84 Compared to that, it may have significantly improved properties, including ionic conductivity. An example of Me is Examples include divalent elements, trivalent elements, tetravalent elements, or any combination thereof. Specific examples of Me include Bi, La, Ce, Gd, or any combination thereof. It can be listed.

[0101] In one embodiment, the halide material is of the formula Li a M a’ RE b Me' b’ Cl c X' c’ It can be expressed as follows, and X' may have a smaller ionic radius than Cl. One embodiment Therefore, as X', we can give F. In certain embodiments, RE can be Y. In a further embodiment, X' having a smaller ionic radius is used for stoichiometric division between Cl and X'. By adjusting the ratio, if c'=0, the non-layered structure of the halide material can be transformed into a layered structure. This can promote a crystallographic phase transition to a non-layered crystalline structure. In particular, halide materials , (c / (c+c')) t * 0.84 <c / (c+c’)<(b / (b+b’)) t * 1 If it is 0.16, then (c / (c+c')) t * 0.84>c / (c+c') and c / (c (b / (b+b')) > (c') t * Significantly improved compared to when it was 1.16. Properties such as ionic conductivity, electrochemical stability, compatibility, or any combination thereof. It may have.

[0102] In one embodiment, the crystallographic phase transition boundary is, for example, Li 3-x*k (Y 1-x M e k+ x )(Cl c Br c’ Using the halide material represented by 6, the following It can be determined as follows: The MBP of a halide material is given by the formula [c / (c+c')] t =0.7 5+12 * (Erotic manga) * It can be determined according to x), in the formula, Me k+ The ionic radius of is r, r=r_Y 3+* (1-δ) and r_Y 3+ However, Y 3+ This is the ionic radius of M. This is induced by adjusting Li substitutions, or by adjusting Me substitutions by Me'. MPBs of halide materials having a crystallographic phase transition induced by similar means It can be determined.

[0103] In one embodiment, the halide material includes a specific crystallographic phase transition boundary on the compositional phase diagram. It may include crystalline phases within the band range of Li and M. In one embodiment, the band range is among Li and M. Halogenated elements such as one of Me and Me', or one of X and X'. It can be expressed by the range of elemental concentrations in the material. For example, halide materials have a concentration range. Crystals with elemental concentrations within a range of 0.84 to 1.16 times the elemental concentration at the crystallographic phase transition boundary. It may have a stoichiometric phase. In particular, the stoichiometric ratio of elements is related to the crystallographic phase transition of halide materials. and can be adjusted to promote improvement of properties. In certain embodiments, the halide material is It can essentially consist of crystalline phases within a specific band range. For example, the a Nions can exist in the same phase. As considered in the embodiments herein, halides The material may contain small amounts of impurities, or may be essentially free of impurities. Example For example, the level of impurities may be below the level detectable using conventional detection methods. Therefore, "essentially consisting of a single phase" means that the halide material is a complex of halide materials. In addition to the main phase of the compound, it may contain low levels of impurity phases, or the halide material may This is intended to mean that the impurity phase may not be present. The impurity phase is included in this disclosure. In this context, it can also be referred to as a parasitic impurity phase.

[0104] In one embodiment, the halide material provides improved properties and / or properties of the solid electrolyte material. It may include a specific density that can enhance performance. In one embodiment, the density is at least 2.5 g / cm³. m 3 at least 2.7 g / cm³ 3 at least 2.9 g / cm³ 3 at least 3.1g / cm 3 at least 3.3 g / cm³ 3 , or at least 3.5 g / cm³ 3 2. 3g / cm 3 It can exceed 3.5 g / cm³. In another embodiment, the halide material is 3.5 g / cm³. 3 below 3.4 g / cm³ 3 Below, 3.3g / cm 3 The following, or 3.1 g / cm³ 3 The following, etc. 0.8g / cm³ 3 It may have a density of less than . In another embodiment, the halide material is as specified herein It may have a density within a range that includes either the minimum or maximum value shown. In this state, the density of the halide material is lower than that of Li3YBr6, and the density of Li3YCl6 is lower. It can have a density higher than a degree.

[0105] In one embodiment, the halide material is significantly improved compared to Li3YBr6. It may have thermodynamic and electrochemical stability. In another embodiment, the halide material is a solid Includes thermodynamic and electrochemical stability values ​​that can promote improved properties of electrolyte materials. The thermodynamic and electrochemical stability values ​​are obtained using the following cyclic voltammetry method. Alternatively, it may be determined based on the linear sweep voltammetry method. The electrochemical cell is 3 It can be made of two layers. The active layer (i.e., the working electrode) is made of carbon and a halide material. It may contain a mixture. The separator layer may be made of a halide material. The counter electrode layer is It can be made of indium metal or lithium-indium alloy. The voltage of the working electrode can gradually increase, and at the same time, the oxidation current indicates oxidation of the electrolyte. A peak or plateau may occur, and this can be measured. The starting value of the peak is the peak relative to the x-axis. It can be obtained by linear extrapolation of the rise, and is in volts. An offset of 0.62V In addition to the peak start value, thermodynamic and electrochemical stability values ​​were obtained, and the indium counter electrode potential was targeted. It can be converted to a quasi-Li / Li+ potential.

[0106] In one embodiment, the thermodynamic electrochemical stability value is at least 3.60V, and at least 3 It may be greater than 3.57V, such as 0.62V, 3.65V, or at least 3.71V. In this embodiment, the halogen material is 4.50V or less, 4.30V or less, 4.19V or less, 4.15V or less, 4.10V or less, 3.85V or less, 3.80V or less, 3.75V or less, Alternatively, it may include thermodynamic and electrochemical stability values ​​of 3.71V or less. In another embodiment, halogen The ionized material is subject to thermodynamics within a range that includes either of the minimum and maximum values ​​shown herein. It may include electrochemical stability values.

[0107] In another embodiment, the halide material is compared to the conventional corresponding halide material. For example, it may include improved bulk ionic conductivity, including lithium ion conductivity. The ionic conductivity in bulk can be measured at room temperature (i.e., 22°C). In one embodiment, The ionic conductivity is greater than 0.05 mS / cm, greater than 0.15 mS / cm, and at least 0.3 m S / cm, at least 0.5 mS / cm, at least 0.8 mS / cm, at least 0. 9 mS / cm, at least 1.1 mS / cm, at least 1.5 mS / cm, or less Both can be 1.7 mS / cm. In another embodiment, the halide material is at most 1.9 mS / cm, at most 1.8 mS / cm, or at most 1.7 mS / cm, etc., 4.5 Less than mS / cm, less than 3.4 mS / cm, less than 2.8 mS / cm, less than 2.0 mS / cm This may include the bulk ionic conductivity measured at 22°C. In another embodiment, the halogenated material The material is a bulk amount within the range of either the minimum or maximum value shown herein. It may have on-conductivity.

[0108] In further embodiments, the electrolyte material of the embodiments herein is, in particular, a halide material. However, certain phase transitions in crystallographic phase transition diagrams include morphotropic phase transition boundaries (MPBs). If the crystalline phase is within the range, it may have even improved ionic conductivity. In one embodiment, The halide material was measured at 22°C and had a minimum of 1.8 mS / cm, and at least 1 0.85 mS / cm, at least 1.87 mS / cm, at least 2.0 mS / cm, less Bulk ion conduction of at least 2.08 mS / cm, or at least 2.45 mS / cm. It may have a ratio. In another embodiment, the halide material has at most 6.5 mS / cm, and at most Also 6.1 mS / cm, at most 5.8 mS / cm, at most 5.3 mS / cm, at most 5.1 mS / cm, at most 4.7 mS / cm, at most 4.4 mS / cm, at most 4 0.1 mS / cm, at most 3.9 mS / cm, at most 3.6 mS / cm, at most 3. 2 mS / cm, at most 3.0 mS / cm, at most 2.8 mS / cm, or at most 2 This may include the bulk ionic conductivity measured at 22°C at 0.5 mS / cm. In another embodiment, The halide material is within a range that includes either the minimum or maximum value shown herein. It may have bulk ionic conductivity.

[0109] When used in this specification, the ionic conductivity in bulk is obtained by pressing the powder of the electrolyte material. Electrochemical impedance spectroscopy applied to high-density pellets formed by This can be measured by using [a specific method]. High-density pellets are placed between stainless steel electrodes. The measurement can be performed under a hydrostatic pressure of approximately 300 MPa, with the sinusoidal voltage signal being It can be applied to high-density pellets with an amplitude of 50 mV at frequencies ranging from 7 MHz to 1 Hz. The ionic conductivity in bulk can be measured at 22°C. In one embodiment, the bulk conductivity with respect to temperature To aid in understanding certain characteristics of electrolyte materials, such as ionic conductivity, activation Energy can be obtained in some cases. For example, lower activation energies can be obtained in response to temperature changes. This may suggest that the variation in ionic conductivity at lux is smaller. Determining the activation energy... To do this, the ionic conductivity of the bulk material was measured at temperatures from 22°C to 150°C, and the formula IC(T) was used. An Arrhenius plot can be created based on the formula =A × exp(-Ea / RT), In the middle, A is the previous exponential constant, Ea is the activation energy in eV units, and R is e This is a universal constant used to convert Kelvin degrees to V units, where T is the temperature in Kelvin degrees. The activation energy can be determined using the slope of the line of the lot. In certain embodiments, The activation energy can be in the range of 0.2 eV to 0.5 eV.

[0110] Referring to Figure 3, the process for forming a solid electrolyte material containing a halide material S300 is shown.

[0111] Process 300 differs from conventional solid-phase synthesis for forming complex halide materials. Conventional processes utilize high-energy ball mill grinding or metal halogenation. A mixture of solid reactants at a temperature near or below the melting point of a substance (for example, a simple metallic halogen). The solid-phase reaction is carried out by directly heating the compound. The individually separated particles in the mixture react. The probability of achieving 100.00% completion of the reaction decreases as the reaction progresses. This would theoretically require an infinite amount of time. Therefore, simple metal halogenation Due to incomplete reactions of materials, conventional solid-phase synthesis based on high-energy ball mill grinding has been discontinued. The reaction products produced are simple metal halides of higher concentration (e.g., halides). It is understood that it may contain impurities such as thium and / or yttrium halide.

[0112] Furthermore, conventional synthesis of complex halides based on the ammonium-halide pathway is It is worth noting that this may not be applicable in all cases for forming complex metal halides. Traditionally, metal halides have been used as starting materials. Some trivalent metal halides Metals and tetravalent metal halides, especially rare earth halides, are stable metal halide hydration The tendency to form substances allows for the complete removal of water molecules from these hydrates. This is difficult. By increasing the temperature, undesirable metal ions can be removed at higher concentrations. Formation of xyhalides or metal oxyhydrate halide compounds may occur. Furthermore, metal Halide hydrates and metal oxyhalides, especially those containing rare earth metals, are quite... It is a stable compound in which X is a halogen other than Cl, such as Li3RE(OX)Cl3. The likelihood of forming a complex compound phase containing high concentrations of Li is low. Furthermore, these complex formation The compound is likely to be unstable and decompose into simpler compounds.

[0113] The processes described in the embodiments of this disclosure overcome the problems described above.

[0114] Process 300 uses one of Li, M, RE, Me, or any combination thereof. A mixture of starting materials containing the above metal compound is formed in a stoichiometric or non-stoichiometric ratio. It can be started from there. The metal compound may be non-hygroscopic. In particular, the starting material is Ammonium halides may include NH4X, where X is Cl, Br, I, F, or the same. Any combination is included. The starting material is an aqueous solution, an alcohol solution, or another polar molecular solution. To promote acidic synthesis within the mixture, it may further contain an acid such as hydrochloric acid or hydrobromic acid.

[0115] In exemplary embodiments, the metal compound is an oxide, carbonate, sulfate, hydrate, or hydroxide. It may include oxalates, acetates, nitrates, or any combination thereof. For example, The generating material is, for example, Me2O containing one or more rare earth oxides. k Contains oxides Obtain. Another example is lithium carbonate, sodium carbonate, cesium carbonate, Fe(OH)2, Alternatively, hydroxides or carbonates such as Fe(CO3) or any combination thereof can be used. It is possible.

[0116] Referring to Figure 3, process 300 uses the starting material as shown in block 302. This may include forming ammonium-containing halides. Exemplary ammonium-containing As for halogenated compounds, (NH4) z RE 1-y Me k y (Cl 1-u-p-q Br u F p I q ) 3+z+y*(k-3) , (NH4) z RE 1-y Me k y (Cl 1-u Br u ) 3+z+y*(k-3) , (NH4) z RE 1-y Me k y (Cl 1-p F p ) 3+ z+y*(k-3) , (NH4) z RE 1-y Me k y (Cl) 3+z+y*(k-3) , (NH4) z RE 1-y Me k y (Br) 3+z+y*(k-3) , (NH4) z RE 1-y Me k y (I) 3+z+y*(k-3) , or combinations thereof Yes, it is possible. In certain embodiments, 0.33 <= z <= 5. In some cases, ammonia Forming um-containing metal halide materials can be carried out in a liquid medium such as an acidic solution. Examples of such acids include hydrochloric acid, hydrobromic acid, hydrofluoric acid, hydroiodic acid, or similar acids. Any combination of these can be listed. Further examples include ammonium-containing metal halogens. The formation of nucleotide materials can be carried out under specific drying conditions.

[0117] In one embodiment, forming an ammonium-containing metal halide material is possible up to 2 It can be carried out at a temperature of 50°C. For example, the temperature can be at least 20°C, at least 40°C, and less At least 50°C, at least 70°C, at least 90°C, at least 110°C, or less It could be as low as 140°C. In another example, the temperature could be below 200°C, below 180°C, or 160°C. It may be below ℃ or below 140℃. Further examples include ammonium-containing metal halogenation. The material is formed at a temperature range that includes either of the minimum and maximum values ​​shown herein. It is possible.

[0118] In an exemplary synthesis of halide materials, two ammonium-containing metal halides are used. It may comprise a metal cation and a halide anion, and the embodiments herein It can be used to form chlorohydrate materials. At least one exemplary synthesis The process involves treating ammonium-containing metal halides to form metal halides. This allows for the carrying out of reactions between metal halides having different halide anions. Thus, the halogenated materials of the embodiments specified herein can be formed. For example, Li3Y Br6 and Li3YCl6 are formed separately, and then mixed to form Li3YC, which is described in detail below. l 6(1-u) Br 6u The following reaction can be carried out with Li2CO3 and Y2O 3. The process is carried out in a mixture of starting materials containing HBr, NH4Br, and H2O, and Li3YBr It is possible to form 6. 3 * Li2CO3 + Y2O3 + 12 * HBr+10 * H2O → 2 * YBr3(H2O )8+6 * LiBr+3 * CO2 6 * NH4Br+2 * YBr3(H2O)8+6 * LiBr→2 * (NH4)3YB r6+6 * LiBr+16 * H2O

[0119] The reaction mixture above is heated under reduced pressure at 140°C to remove moisture, and the following reaction in solid form is obtained. This can facilitate a response. 2 * (NH4)3YBr6+6 * LiBr→2 * Li3YBr6+6 * NH4Br

[0120] The reaction mixture may be further heated to 550°C to sublimate the ammonium bromide.

[0121] Li3YCl6 contains Y2O3, Li2CO3, H2O, NH4Cl, and HCl. It can be formed from a mixture of starting materials as follows: Y2O3+3 * Li2CO3+10 * H2O+12* HCl → 2 * YCl3(H2O )8+6 * LiCl+3 * CO2 2 * YCl3(H2O)8+6 * LiCl+6 * NH4Cl→2 * (NH4)3YC l6+6 * LiCl+16 * H2O

[0122] The reaction mixture is heated under reduced pressure at 140°C to remove water, and the following reaction occurs in a solid state. It can be promoted. 2 * (NH4)3YC16+6 * LiCl → 2 * Li3YCl6+6 * NH4C1

[0123] The reaction mixture may be further heated to 550°C to sublimate the ammonium chloride.

[0124] After formation, the Li3YCl6 phase may be mixed with the Li3YBr6 phase in a stoichiometric ratio, and nitrogen The solid-phase reaction was carried out under dry conditions in an inert atmosphere such as an inert element, resulting in Li3YCl (1-u)*6 Br 6*u It is possible to form this.

[0125] In a particular example, Li3Y(Cl 1-u Br u ) Form a mass of 6 materials from a solid-phase reaction Alternatively, milling may be carried out in a neutral atmosphere of N2 or Ar to form a powder.

[0126] In further embodiments, ammonium-containing metal halides are formed to achieve the practical applications described herein. This can promote the formation of halogenated materials in various forms. For example, Li3YCl c X 'c’ Using a halide material represented by (NH₃) in aqueous solution, 33 Li3Y Br9 and (NH3)3Li3YCl9 are obtained using the raw materials described in the embodiments herein. They can be formed separately. In one embodiment, the solutions are mixed and dried at 100-170°C. This may allow for the evaporation of water and acid. In certain embodiments, halogenated compounds Solid-phase reactions of substances, and the sublimation of NH3Cl and NH3Br from charges, occur in parallel at relatively low temperatures. This can be carried out. For example, a flux containing LiCl and NH4Cl can be used to raise the level of NH4Cl. It can be formed at temperatures below the peak temperature. NH4Br can sublimate at temperatures above 350°C. While I do not wish to be bound by any theory, the presence of ammonium halides is comparative. Li3YCl c X c This may enable the formation of the final phase, and uniformity throughout the final phase. It helps to form a single C / C' ratio, and conventional solid-phase synthesis has a C / C' ratio in the final product. This results in a relatively high variance in the ratio, which usually means that the final product contains different c / c' ratios. Since it may have multiple phases, this is a conventional solid-phase reaction of LYC and LYB powders. It should be noted that this may be more advantageous than the synthesis of logenide powders.

[0127] In another embodiment, cooling may be carried out following the sublimation of ammonium. In particular, cooling may be performed Careful control is required to avoid segregation of the crystalline phase of the halide material. In this embodiment, the cooling rate is greater than 40°C / hour, at least 60°C / hour, and at least 7 0°C / hour, at least 90°C / hour, or at least 100°C / hour, at least 15 It can be 0°C / hour, or at least 180°C / hour, and up to 200°C / hour. (Figure) 10 is a halogen material, Li3Y(C), which includes a specific accelerated cooling step. 0.6 5Br 0.35 ) 6, Includes a diagram of an exemplary process that forms the process. Ammonium-containing LYB solution and ammonium-containing LYC solution are formed and then combined. The reaction mixture is dried at approximately 120°C. The reaction mixture is heated to approximately 550°C. Then, the solid-phase reaction is carried out, and the ammonium is sublimated in parallel. After sublimation, accelerated cooling is performed. It is made of a halide material, Li3YC 4.5 Br 1.5 It has a single phase.

[0128] Those skilled in the art can use additional alkali metal compounds such as Na2CO3 or NaCl as starting materials. It is understood that by adding it to a mixture, it can partially replace Li in the halide material. To understand. Similarly, by adding another RE or Me metal compound such as Fe2O3 to the mixture, It is also possible to substitute Y in halide materials.

[0129] In application, the reaction mixture is used to remove larger particles from the reactants in a solid state. It can be filtered. Larger particles are the starting material, the remaining particles of the starting material, carbon, or so It may contain impurities associated with any combination of these.

[0130] In another exemplary synthesis, an ammonium-containing ternary halide is used directly to form a halogen (NH4)3 can be used to form phosphate materials. Referring to the exemplary synthesis reaction above, (NH4)3 After forming YCl6 and (NH4)3YBr6 separately, (NH4)3YCl6 and Li The reaction mixture of Cl, (NH4)3YBr6, and LiBr in aqueous solution is combined. Alternatively, a mixture containing the four reactants can be dried together and used in a solid-phase reaction with Li3Y (Cl 1-u Br u )6 can be formed. Sublimation of ammonium halide is 5 This can be carried out at 50℃.

[0131] After the sublimation of ammonium halide, cooling is performed to form the halide material. For example, cooling can be carried out in air, dry air, or a nitrogen atmosphere. Examples include temperatures of 100°C at most, 70°C at most, 50°C at most, or 30°C at most. A cooling temperature of less than 200°C may be applied. In certain embodiments, cooling is performed at room temperature. This can be carried out in an atmospheric environment. Optionally, Ar or N2 may be used to facilitate cooling. .

[0132] In another embodiment, at least two halide anions are included in any predetermined ratio. Ammonium-containing metal halides can be formed in a single step. In certain embodiments, This involves mixing ternary halides in stoichiometric or non-stoichiometric ratios, and then adding ammonium halides. It can be dissolved in the presence of ammonium salts. Ammonium halides react with water. It can help in protection. For example, each ternary halide contains two metal cations and 1 It may contain two halide anions, and the halide anions differ between the ternary halides. It is possible. In certain cases, ternary halides contain two halide anions. The metal cation may be the same or different among the ternary halides. The ideal heating temperature is up to 600°C to help melt the material and promote the reaction in the solid state. It can be °C. The heating temperature further helps in the leaching of ammonium from the halide material. Heating may be carried out in a neutral atmosphere of nitrogen or argon. Cooling is then performed to remove halogens. The nitride material may be solidified.

[0133] An exemplary synthesis process is shown below. The reaction shown is Li3YCl6, Li3Y Ammonium-containing metal halo in one step from starting materials containing Br6 and NH4Br This can enable the formation of halogenated compounds. Those skilled in the art can use starting materials in various ratios to perform halogenation. It is possible to form a halide material having a predetermined ratio between anions. It will probably happen. Li3YCl6+Li3YBr6+6 * NH4Br→2 * (NH4)3Li3YCl 3Br6

[0134] Ammonium halide can sublimate at heating temperatures of 250°C to 650°C. This involves adding dopant materials such as Me compounds to the molten material to create one of the halogenated materials. The substitution of the above metal elements can be promoted. The reaction involves quartz, alumina, silica-alumina, and B This can be carried out in a crucible made of N, glassy carbon, or graphite. Cooling may be applied to the molten material to solidify the halogenated material.

[0135] In certain embodiments, the cooling rate is controlled to promote a specific crystal growth rate, This enables the growth of single crystals of a size visible to the naked eye, such as single crystal blocks measuring up to 10 centimeters. It is possible. For example, cooling can be performed in an external heat field at a cooling rate of 10°C / hour to 50°C / hour. It can be promoted by the following: The crystal growth rate is at least 0.2 mm / hour, at least 0. It may be 3 mm / hour, or at least 0.5 mm / hour. In addition or alternatively, Long speed is at most 8mm / hour, at most 6mm / hour, at most 5mm / hour, fast It could be 3 mm / hour, or at most 1 mm / hour, or at most 10 mm / hour. ru.

[0136] In another specific embodiment, the crystal growth rate is set to promote the growth of polycrystalline crystals. At least 8 mm / hour, at least 10 mm / hour, at least 15 mm / hour, or It can be relatively fast, such as at least 20 mm / hour. Additionally, or alternatively, growth rate At the fastest, it's 80mm / hour, at the fastest, it's 70mm / hour, at the fastest, it's 60mm / hour, and fast It can be 50 mm / hour, or at the fastest, 40 mm / hour.

[0137] In certain embodiments, solidification is used to promote the growth of crystals having a specific crystal orientation. This can be done by applying a thermal gradient to the molten zone. For example, a length-to-diameter aspergillus Using a crucible with a pectoral ratio greater than 5 can accelerate the solidification of blocks under a thermal gradient. This process may be particularly suitable for anisotropic crystals. In certain cases, the temperature may be less than 10°C / cm. A strong thermal gradient, such as the one shown above, can be applied.

[0138] In another embodiment, a crystal that is anisotropic with respect to permeability or dielectric constant, or orientational crystal growth, This can be carried out using a strong permanent magnetic field, solidification under a strong electric field, or any combination thereof. ru.

[0139] In another specific embodiment, elongated pellets in the crystalline direction have higher ionic conductivity. Alternatively, crystallization of the particles may occur. For example, single-crystal pellets have a specific crystallographic orientation. It can be adjusted to form a ceramic halide material. In a further example, cast Using shaping, compression, pressing, heating, molding, or any combination thereof, the orientation is multifaceted. The formation of crystalline halide materials can be promoted. In certain examples, a preferred crystallographic orientation can be achieved. Using single crystal pellets, oriented ceramic halide materials can be formed. Selectively, the orientation of the crystal may be identified using an X-ray goniometer. In further examples, By utilizing a support seed layer with lattice parameters similar to those of oriented ceramic materials, the flux Solidifying in a medium can help maintain the oriented polycrystalline structure.

[0140] Single-crystal halide materials are formed from much smaller chunks, typically several millimeters in size. Possible, or high-density blocks or large in size up to several tens of centimeters It can be a got. In an exemplary application, a single crystal is crushed to form a fine powder of single crystal particles. In a further example, a single-crystal ingot or block can be sliced ​​into thin sheets. For example, a thin sheet can have a thickness of 5 microns to 500 microns. In particular, To ensure that the crystallographic direction with high conductivity is the thickness direction of the thin sheet, Crystals can be sliced. For example, a halide material can be oriented. It has higher ionic conductivity than different crystallographic orientations. <hkl>(or <hklm>) It can be formed to have a crystallographic orientation represented by <HKL>(or <hklm>It can be sliced ​​so as to extend along the crystallographic orientation of ).

[0141] In certain cases where incompatible melting occurs, the resulting parasitic phase is the upper layer containing the parasitic phase. It can be removed from the solidified ingot by grinding, etc. The parasitic phase is present. In this case, the crystal content may be at most 10 vol%. Add an excess amount of dopant material to the molten material. Adding this helps reduce the formation of the parasitic phase, for example, by adding an excess of LiX or NaX. This may help promote the formation of stoichiometric single-phase crystals under self-flux conditions.

[0142] Forming halide materials using crystal growth is possible with Li, RE, Me, or M Helps further reduce one or more unreacted simple halide phases containing metal elements e. This process is simply a way of obtaining a form of halide material that does not essentially contain a metal halide phase. It can promote growth.

[0143] In another embodiment, ammonium-containing halides are mixed and co-melted to form crystalline halides. A chlorohydrate material can be formed. For example, ammonium-containing halides are as specified herein. A reaction mixture containing an ammonium-containing halide may be formed separately as described in the embodiment. The mixture may be combined, dried, and comelted. In certain examples, the exemplary synthesis reaction described above may be performed. For reference, (NH4)3YCl6 and (NH4)3YBr6 are formed separately, and then (N Reaction reaction of H4)3YCl6 and LiCl, (NH4)3YBr6 and L in aqueous solution The reaction mixture of iBr may be combined with the mixture containing the four reactants, and the mixture may be heated together and dried. It is then melted and subjected to a solid-phase reaction at a heating temperature of up to 600°C with a halogen material. Li3Y(Cl 1-u Br u )6 can be formed. Ammonium halide Sublimation can occur at heating temperatures. In some cases, the ammonium halide phase can sublimate up to 80°C. It can be removed by decomposition at higher temperatures such as 0°C. Solidification is described in the embodiments herein. It may be implemented as described.

[0144] The removal of ammonium halides involves removing ammonium halides that have leached from halide materials. Ammonium can be monitored by collecting and weighing it. Ammonium halides are They may be completely removed, and in certain cases, a certain amount of ammonium halide phase may be present. It may remain in the ammonium halide material. For example, heating may affect the portion of the ammonium halide. To enable partial or complete sublimation and / or decomposition, a temperature range of 350°C to 800°C is used. This can be carried out at a temperature of at least 15 minutes to at most 24 hours. Sublimation of ammonium halide or Decomposition occurs through evaporation, producing desirable substances such as water, CO2, ammonia, and halogens. It may be helpful in removing reaction products.

[0145] In one embodiment, the halide material does not essentially contain an ammonium halide phase. It can be formed as follows. In at least one embodiment, the halide material is a halide material At least 10 ppm, at least 100 ppm, and at least 300 ppm relative to the total weight of the ingredients. ppm, at least 2 ppm such as at least 500 ppm, at least 0.5% by weight, Or at least 0.2 wt% of the total weight of the halide material, such as at least 1 wt% It may contain a specific amount of residual ammonium halide in a certain percentage. Alternatively, or additionally, The halide material is present in an amount of at most 3% by weight relative to the weight of the halide material. It also contains 5% by weight of ammonium halide. Up to 5% by weight of halide in the halide material. The presence of an ammonium ionide phase helps improve the ionic conductivity of halide materials. Please note that it is possible to stand.

[0146] After cooling and / or solidification, the halide material takes shape as shown in block 304. It is possible.

[0147] The corresponding product is formed by conventional synthesis methods such as solid-phase reactions based on ball mill grinding. Halide materials typically contain higher levels of impurities, and Bridgman- Stockbarger, gradient freezing, Czochralski, or Bagdasarov (water When used to grow crystals according to the Bridgman process, it is incompatible. It is highly likely to melt, and the resulting crystals will have a higher content of impurities and parasitic phases. It is highly probable. Simple compounds can be used as starting materials for the molten material to directly grow crystals. This can also result in higher concentrations of impurities and parasitic phases. Typical impurity phases and The parasitic phase consists of LiX and Me k+ X k It may contain one or more simple metal halides, In the formula, X is a halogen. The process described in the embodiments herein is a corresponding conventional halogen Compared to chlorohydrate materials, it promotes the formation of halogenated materials with improved purity. It is noteworthy that this is possible. Even more noteworthy is that higher purity is achieved with halogens. This can promote the improvement of the ionic conductivity of the ionized material. In certain embodiments, halogen The ionized material consists of a single phase.

[0148] In a further embodiment, the halide material is Me such as YN. x N k , M such as LiN3 x It may contain impurities including metal nitrides containing N or any combination thereof. Metal nitride Me x N k The content is at most 0.1 times the weight of the halide material. Amount %, at most 500 ppm, at most 300 ppm, at most 100 ppm, at most 50 ppm, at most 40 ppm, at most 30 ppm, at most 20 ppm, or many It can be as low as 10 ppm, or at most 0.3% by weight relative to the weight of the halide material. In another example, metal nitride Me x N k The content is small relative to the weight of the halogenated material. Halogens, such as at least 0.5 ppm, at least 1 ppm, or at least 2 ppm. It may be at least 0.2 ppm relative to the weight of the nitride material. In another embodiment, metal nitride Me x N k The content of includes within the range of either the minimum or maximum value shown herein. It could be enclosed.

[0149] For example, metal nitride M x The N content is at most the weight of the halide material. 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, Or at most 0.3% by weight relative to the weight of the halide material, such as 10 ppm. It is possible. In another example, metal nitride M x The N content is relative to the weight of the halide material. and at least 0.5 ppm, at least 1 ppm, or at least 2 ppm, halo The concentration may be at least 0.2 ppm relative to the weight of the nitride material. In another embodiment, metallic nitrogen Monster M x The content of N is within the range of either the minimum or maximum value shown herein. It could be enclosed.

[0150] For example, the total content of metal nitrides is at most 0 relative to the weight of the halide material. 1% by weight, at most 500 ppm, at most 300 ppm, at most 100 ppm, many 50 ppm, at most 40 ppm, at most 30 ppm, at most 20 ppm, or At most 10 ppm, or at most 0.3% by weight relative to the weight of the halide material. It is possible. In another example, the total content of metal nitrides is small relative to the weight of the halide material. Halides such as 0.5 ppm, at least 1 ppm, or at least 2 ppm It may be at least 0.2 ppm relative to the weight of the material. In another embodiment, the total amount of metal nitride The content may be within a range that includes either the minimum or maximum value shown herein. .

[0151] This disclosure describes alkali nitrides and Me x N k The content of metal nitrides such as the following is as follows: It can be detected using the method. Complex metal halides can be hygroscopic, ON conductive materials can be dissolved in water. Metal nitrides are not hygroscopic and their aqueous solutions... It can be collected and analyzed after filtration. Metal nitrides with a content of more than 0.2% by weight are It can be detected using X-ray diffraction analysis. For content less than 0.2% by weight, LECO is used. It is possible.

[0152] In one embodiment, the halide material may include a crystalline structure containing stacking faults. Vacancies are caused by shifts in the position of occupied atoms or vacant atoms in the crystal structure. This represents a defect and causes disorder in the crystallographic planes of the crystal structure.

[0153] In certain embodiments, the halide material promotes the improved properties of the halide material. It may contain a crystal structure that includes a certain amount of stacking faults that can be advanced. Stacking faults are X-ray powder This can lead to changes in the final diffraction pattern, particularly the non-uniform spreading of only certain X-ray diffraction peaks. This can lead to stacking faults. In this disclosure, stacking faults are determined by X-ray powder diffraction analysis of halide materials. , and also Boulineau et, whose entirety is incorporated herein by reference. al.,Solid State Ionics 180(2010)1652-165 According to the stacking fault quantification method described in 9, Bruker Germany OPAS 4.2 or FullProf (version 7.30, released March 2020) Software such as TOPAS 4.2 or FullProf version 7.3 DIFFaX stains caused by using a different version or software equivalent to version 0. This can be determined by using simulation and Rietveld refinement. Briefly described The quantification method involves simulating the X-ray diffraction pattern of halide-based material powders. This may include fitting it to the system. The simulation defines the primary block of the crystal structure. These primary blocks can be composed of slabs and inter-slab spaces. Next, the primary block is stacked according to one of two or more possible stacking vectors. It is possible. The exclusive occurrence of only one of the stacking vectors results in a complete stacking, i.e., 0%. This results in stacking faults. Changes in the stacking vector in the stacking direction of the crystal structure cause stacking faults. To generate. To fit the simulation to the X-ray diffraction pattern of halide-based materials. This involves varying one or more parameters of the crystal structure (also known as "parameter refinement"). (It is known that) the least squares difference minimization algorithm is implemented, and stacking faults are identified and determined. This may include quantification.

[0154] In further embodiments, the halide material is at least 25%, at least 30%, At least 40%, at least 50%, at least 60%, at least 70%, and Having at least 20% stacking faults, such as 80% or at least 90% stacking faults. It may include a crystalline structure. In certain embodiments, the stacking of atomic layers may be completely disordered. For example, the crystal structure may contain 100% stacking faults. In another embodiment, the stacking faults are , at most 95%, at most 92%, at most 90%, at most 85%, at most 80% It could be at most 75%, or at most 70%, and possibly at most 99%. Furthermore, crystal The structure is any of the minimum and maximum percentages shown herein. It may include stacking faults in a range that includes . In a particular example, the solid electrolyte material has at least 50 This may include halide materials having a crystalline structure containing % stacking faults. In another specific example, Solid electrolyte materials are halide materials having more than 50% and at most 100% stacking faults. It may include.

[0155] In one embodiment, the halide material is a powder containing particles of complex metal halide, etc. It may be in the final form. In one embodiment, the powder is at least 0.3 microns, at least 0. 5 microns, or at least 1 micron, with an average particle size of at least 0.1 microns ( It may have D50). In another embodiment, the average particle size is at most 1 mm and at most 800 mm. Ron, at most 500 microns, at most 200 microns, at most 100 microns, many At least 50 microns, at most 10 microns, at most 5 microns, or at most 1 micron It may be ron. In certain examples, the powder is of the minimum or maximum value shown herein. It may contain particles having an average particle size within a range that includes any of the above. In another embodiment, the powder is strongly aggregated. It may contain particles or weakly aggregated particles.

[0156] In a further embodiment, the particles facilitate improved formation and performance of electrolytes and / or electrodes. They may have a specific shape. For example, particles can be spherical or elongated. In another example, the particles may have the shape of rods, flakes, or needles. The shape of the particles is The choice depends on the 2D or 1D anisotropy of the ionic conductivity of the chlorophosphate material. ru.

[0157] In another embodiment, the powder is in the form of an electrolyte and / or electrode having improved ionic conductivity. It may contain particles that promote growth and have a specific average aspect ratio of length:width. For example, The average aspect ratio is at least 1.2, at least 1.5, at least 2, at 2.3, at least 2.5, at least 2.8, or at least 3, such as at least 1 It is possible. In another example, the average aspect ratio is at most 30, at most 25, at most 22, at most 20, at most 15, at most 12, at most 10, at most 8, and It may also be 5, or at most 4. Furthermore, the particles have the minimum and maximum values ​​shown herein. It may have an average aspect ratio within a range that includes any of the following.

[0158] In another embodiment, the halide material may be a single crystal. In the form of a single crystal sheet, single crystal film, single crystal block, single crystal ingot, or other This can be a single crystal in the form of, or any combination thereof. In further embodiments, halo The ionized material can be a ceramic material. Ceramic materials consist of ceramic particles, single bonds. It may contain crystal particles, or any combination thereof.

[0159] In another embodiment, the halide material has a crystallographic configuration having higher ionic conductivity. They can be oriented to have a direction. For example, a halide material can be an oriented single crystal or an oriented ceramic. It could be Mick.

[0160] In one embodiment, the solid electrolyte is any form of halogen described in the embodiments herein. It may contain halogen materials. In certain applications, the solid electrolyte material may consist of a halogen material. In at least one application, the solid electrolyte material is another material in addition to the halide material. This may include, for example, solid-state electrolyte materials different from halide materials. Examples include materials, electronically conductive materials, additives, active electrode materials, or combinations thereof. Cut.

[0161] In one embodiment, the composite ion-conducting layer may include a solid electrolyte material and an organic material. As for organic materials, polymer electrolyte materials or combinations thereof are used as binder materials. One example is a composite ion conductive layer containing plasticizers, solvents, or similar materials. This may include combinations. An example of an organic material is polytetrafluoroethylene (poly tetrafluoroethylene (PTFE), polyvinylidene fluoride PVdF), fluorine rubber, polypropylene, ethylene-propylene-diene monomer (et (Hylene-propylene-diene monomer, EPDM), sulfonated EPDM, natural butyl rubber) Natural butyl rubber (NBR), paraffin wax, polypropylene carbonate, Polyisobutylene, polyvinylpyrrolidone, polymethyl methacrylate, poly(propylene) Poly(vinyl chloride), poly(vinylidene fluoride), poly(acrylonitrile) , poly(dimethylsiloxane), poly[bis(methoxyethoxyethoxide)-phospha Zen, polyethylene carbonate, polypropylene glycol, polycaprolactone, Poly(trimethylene carbonate), hydrogenated nitrile butadiene rubber, poly(ethylene vinegar) Vinyl acetate, high-density polyethylene, low-density polyethylene, polyurethane, or any of the above. One possible combination is to list the following. In another example, the composite ion conductive layer is lithium salt It may include. Examples of lithium salts include LiSbF6, LiN(SO2CF3)2, LiN(SO2C2F5)2, LiN(SO2CF3)(SO2C4F9), LiC(S O2CF3)3, LiAsF6, LiClO4, LiPF6, LiBF4, LiCF3S O3, or any combination thereof, can be cited.

[0162] In one embodiment, the cathode liquid material may include a solid electrolyte material containing a halide material. The cathode liquid material may also include a cathode active material. An example of a cathode active material is: Lithium-containing transition gold such as Li(NiCoAl)O2 and LiCoO2, but not limited to these. Group oxides, transition metal fluorides, polyanions, and fluorinated polyanion materials, and transitions Metal sulfides, transition metal oxyfluorides, transition metal oxysulfides, transition metal oxynitrides, etc. Or any combination thereof can be given. In a particular example, the cathode liquid material is The sword may contain particles of active material, and at least some of the particles may be coated with a solid electrolyte material. This can be done. In a more specific example, at least a portion of the surface of each particle of the cathode active material. These can be coated with solid electrolyte materials. Another more specific example is cathode activators. Most or all of the surface of the material particles can be coated with a solid electrolyte material.

[0163] In another embodiment, the anodic liquid material may include a solid electrolyte material containing a halide material. The anodic solution may also contain an active material. An example of an anode active material is artificial granulosic acid. Phyto, graphite carbon fiber, resin-fired carbon, pyrolysis vapor-grown carbon, coke, meso Carbon microbeads (mesocarbon microbeads, MCMBs), furfuryl alcohol resin Oil-calcined carbon, polyacene, pitch-based carbon fiber, vapor-grown carbon fiber, natural graphite, difficult Metallic materials including carbon materials such as graphitizable carbon, lithium metal, and lithium alloys. Examples include oxides, nitrides, tin compounds, silicon compounds, or combinations thereof. Yes, it is possible. In some cases, the anodic acid material may contain electron-conducting additives. Examples of materials include carbon fiber, carbon powder, stainless steel fiber, and nickel-coated glass. Examples include fights, or any combination thereof. In a particular example, The electrolyte material may contain particles of the active material, and at least some of the particles are coated with the solid electrolyte material. It can be done. In a more specific example, at least a portion of the surface of each particle of the active material , can be coated with a solid electrolyte material. In another, more specific example, particles of the active material Most or all of the surface can be coated with a solid electrolyte material.

[0164] In further embodiments, the solid electrolyte material is a cathode liquid layer, an anode liquid layer, or an electrolyte layer. Alternatively, they may be formed into layers such as a combination thereof. In a further embodiment, the layer is electrified It could be a component of a scientific device.

[0165] In another embodiment, the structure, such as a part of an electrochemical device, includes a solid electrolyte layer and an electrode layer. , and may include an intermediate layer disposed between the solid electrolyte layer and the electrode layer, the intermediate layer, electrolyte layer, and At least one of the electrode layers may contain a solid electrolyte material. In one embodiment, As an example of a chemical device, a solid-state lithium battery can be cited. See Figure 4. It includes an electrolyte layer 402 and an intermediate layer 406 disposed between the electrode layer 404 and the electrolyte layer 402. A portion of the cross-section of an exemplary solid-state battery 400 is shown. In one example, the intermediate layer 40 6 may include a solid electrolyte material. In a particular example, the electrode layer 404 may be an anode layer. One example is the liquid anodic layer adjacent to the anode layer, which can be considered as the intermediate layer 406. This is possible. In another specific example, the electrode layer 404 can be the cathode layer. An example of the intermediate layer 406 is the cathode liquid layer adjacent to the cathode layer.

[0166] The intermediate layer 406 is at most 400 microns, at most 300 microns, and at most 20 Up to 50, such as 0 microns, at most 100 microns, or at most 50 microns can include a thickness of 0 microns. Additionally or alternatively, the intermediate layer can be at least 5 microns , at least 8 microns, at least 10 microns, at least 12 microns, or at least 20 microns thick. Further, in certain examples, the thickness of the intermediate layer can be in a range including either of the minimum and maximum values shown herein .

[0167] FIG. 7A includes a diagram of a portion of an electrochemical device 700 according to an embodiment, including a solid electrolyte layer 704 including a solid electrolyte material of an embodiment herein covering an electrode layer . In particular, the solid electrolyte material can include a halide material including at least one of Cl and F, and optionally another halogen element such as Br, I, or both. Examples of the electrode layer can include a cathode layer including a cathode active material, and at least a portion of the cathode active material can be in contact with the solid electrolyte material. As shown, the electrode layer 702 and the electrolyte layer 7 04 are in contact with each other. In certain embodiments, when a voltage is applied to the electrochemical device 700 , the solid electrolyte layer 704 can be capable of forming a concentration gradient of one or more halogen anions . For example, the solid electrolyte layer 704 can include Li3Y(Br Cl u 1-u )6, where 0 < u < 1, and when a voltage is applied, a concentration gradient of Br−, Cl)6, where 0 < u < 1, and when a voltage is applied, a concentration gradient of Br−, Cl - or both can be formed. More specifically, under voltage, the solid electrolyte layer 704 can include a chlorine-deficient region proximal to the electrode layer 702, and the chlorine-deficient region can include a lower concentration of chlorine compared to a region of the solid electrolyte layer 704 remote from the electrode layer 7 02 .​ The concentration of the halogen anion is the concentration in at% or mol% relative to the total of the anions is obtained.

[0168] Referring to FIG. 7B, the electrochemical device 750 includes a solid electrolyte layer 704 and an electrode layer 7 02 may be included. In a particular example, the electrode layer 702 may be a cathode layer. As shown , the electrochemical device 750 includes an intermediate layer 70 3 between the solid electrolyte layer 704 and the electrode layer 702, and at least a portion of the intermediate layer 703 may be in contact with at least a portion of the cathode active material . As shown, the intermediate layer 703 may be in contact with the solid electrolyte layer 704 and the electrode layer 702 . In a particular example, the intermediate layer 703 may include a lithium-metal halide material different from the solid electrolyte material, and the lithium-metal halide material may include at least one halogen anion that is the same as the halogen anion of the solid electrolyte material . For example, the intermediate layer may be Li M 3-x-f M f RE 1-y Me k y (Cl 1-p F p ) 6-x+y*(k- 3) and may include a lithium-metal halide represented by, where -1 <= x <= 1, 0 <= y <= 1, 0 <= p <= 1 / 3, and 0 <= f <= 0.3. In a particular embodiment , the solid electrolyte layer may include an electrolyte material including a halide material represented by Li 3-x-f M f RE 1-y Me k y (Cl 1-p F p ) 6- x+y*(k-3) , where 0 < p <= 1 / 3, and the intermediate layer is Li ​ 1-x-f M f RE 1-y Me k y F 4-x +y*(k-3) It may contain lithium-metal halides represented by the formula, where -0. 3 <= x <= 0.3, 0 <= y <= 1, 0 <= f <= 0.3. A more specific example would be... The solid electrolyte material is Li3Y(Br u Cl 1-u ) may include 6, in the formula, 0 <u<1であ The intermediate layer is Li 3(1-z) Y (1+z) Lithium-metallic herb represented by Cl6 It may contain chlorohydrates, where 0 <= z < 0.3 in the formula. The solid electrolyte material is under oxidation conditions. This can help stabilize the intermediate layer over time. For example, solid electrolyte materials under oxidative conditions To reduce the decomposition of the intermediate layer, which may be caused by the depletion of halogen anions in the intermediate layer, It may help to sustain more than one halogen anion over time. The solid electrolyte layer 704 is Li in electrochemical devices + Further helps maintain ionic current, cation current, or both. It can stand. Li + Ions are generated under voltage conditions such as the charge state of a solid-state battery, as shown in Figure 7B. Thus, it can flow in direction 751.

[0169] In a further embodiment, if the intermediate layer 703 is positioned in contact with the cathode layer, improvement It may have improved oxidation stability. In particular, the intermediate layer has better oxidation stability compared to the intermediate layer containing Li3YBr6. , may show reduced degradation. In certain embodiments, the intermediate layer is Cl under oxidation conditions - concentration It may be possible to form a degree gradient, which means that the intermediate layer is self-passive under battery operation. It can be made possible to function as a layer. More specifically, under oxidative conditions, at a distance from each other Cl in place - Compared to the concentration of Cl, a higher concentration - However, it may be formed in the vicinity of the cathode layer. More specifically, Cl - The concentration is measured from the surface in contact with the cathode layer to the intermediate layer. It can be reduced in the direction toward the opposite surface.

[0170] In certain embodiments, the intermediate layer 703 improves the performance or formation of the electrochemical device. It may be a passivation layer having a specific thickness that can promote this process. For example, a medium The interlayer is at most 1 micron, at most 800 nm, at most 600 nm, at most 40 0nm, at most 300nm, at most 200nm, at most 100nm, at most 80 nm, at most 60 nm, at most 50 nm, at most 40 nm, at most 20 nm, many It may contain a thickness of at least 10 nm, or at most 8 nm. In another example, the intermediate layer is less All 1nm, at least 2nm, at least 3nm, at least 4nm, at least 5nm m may include a thickness of at least 10 nm, at least 20 nm, or at least 50 nm. Furthermore, the intermediate layer is a range that includes either the minimum or maximum value shown herein. This may include a thickness of at least 2 nm and at most 5 nm. In certain examples, the intermediate layer may include at least 2 nm and at most 5 nm. It may have a thickness within a certain range.

[0171] In one embodiment, the intermediate layer may be formed in situ from a solid electrolyte material. Therefore, the intermediate layer can be formed at the interface between the solid electrolyte material and the cathode active material. For example, If so, the intermediate layer may be formed at the interface between the cathode-active material particles and the solid electrolyte material particles. The cathode active material particles are coated with one or more solid electrolyte material particles. Obtain. In another example, referring to Figure 7A, at the interface between the solid electrolyte layer 704 and the electrode layer 702 An intermediate layer can be formed from a solid electrolyte material.

[0172] In further embodiments, the formation of an intermediate layer involves a solid electrolyte material and a cathode active material. This may include applying a voltage to an electrochemical device such as a 700, including the interface between it and the other. For example, the voltages are at least 3.0V, at least 3.6V, and at least 4.0V. A voltage of at least 4.5V, or at least 5.0V, can be given. Another example Therefore, the voltage can be at most 5.1V.

[0173] In one embodiment, forming an intermediate layer includes at least one of Cl and F. This may include partially decomposing the solid electrolyte material. In one exemplary embodiment, the solid The decomposed material is Li3Y(Br u Cl 1-u Includes a halide material represented by 6. Obtained. Under voltage, Li3Y(Br) is in contact with the cathode active material. u Cl 1-u )6 is, Li3Y(Br u Cl 1-u ) Subjected to an electrochemical reaction that can cause partial decomposition of 6, Li3YBr at the interface 6u and Li3YCl (1-u)6 This can lead to the formation of Li3YCl (1-u)6 This can be formed into a thin intermediate layer in contact with the cathode active material. Li3 Y Cr 6u This is a solid electrolyte material Li3Y(Br u Cl 1-u ) Reorganized by 6, absorb It can be collected.

[0174] Referring to Figures 7A and 7B, the partial decomposition of the solid electrolyte layer 704 under voltage is moderate. The formation of the interlayer 703 may occur. Furthermore, Cl- and / or F- A deficient region may be formed. As shown, the cathode active material contained in the electrode layer 702 The proximal region 756 has a lower concentration of C compared to region 758, which is further away from the cathode active material. It may contain l- and / or F-.

[0175] Electrolytes and composite ions in electrochemical devices using solid electrolyte materials according to embodiments of this specification. A conductive layer, anode, cathode, anodic solution, cathode solution, intermediate layer, or other component is formed. Known technologies may be used for this purpose. Such technologies include, but are not limited to, Sting, molding, deposition, printing, pressing, heating, etc., or any combination thereof. Examples include: Layers of electrolyte, electrode, anode, and cathode to form a multilayer structure. These can be formed separately and then stacked to form a multilayer structure. Alternatively, the untreated Forming layers, followed by pressing, heating, drying, or any combination thereof. Further processing may be performed to form the final multilayer structure.

[0176] In certain embodiments, a single crystal block or ingot is used to ensure close contact between the electrode and the electrolyte. To ensure contact, for example, the cathode or It can be processed together with an anode active material.

[0177] In another specific embodiment, single crystal blocks and ingots of halide material are used. The node and / or cathode active material is grown directly around the particles to form the anodic liquid layer or cathode liquid. A layer may be formed. In one embodiment, the anodic liquid layer or the cathode liquid layer is an anode or cathode activator. It may include a single-crystal halide material containing a substance containing a material. In another embodiment, the cathode liquid layer or The anodic liquid layer consists of anodes or cathodes densely packed within a single crystal ingot or block. It may contain active ingredients.

[0178] Many different embodiments and configurations are possible. Some of these embodiments and configurations This specification describes these aspects and embodiments. After reading this specification, those skilled in the art will see that these aspects and embodiments are simple. This is merely an example and should be understood as not limiting the scope of the present invention. The configuration may follow one or more of the embodiments listed below.

[0179] Embodiment Embodiment 1. At least two halos selected from the group consisting of F, Cl, Br, and I Contains genate anions, Li 3-x-f M f RE 1-y Me k y (Cl 1-u-p-q Br u F p I q ) 6-x+y*(k-3) Includes a halogenated material represented by Body electrolyte material, where in the formula -1 <= x <= 1, 0 <= y <= 1, 0 <= u < 1, 0 <= p <= 1 / 3, 0 <= q <= 1 / 6, 0 < (u + p + q) < 1, 0 <= f <= 0.3, and M is at least one alkali other than Li. It is a metallic element, RE is a rare earth element, k is the valence of Me, and Me is I Group IIB elements, Group IVB elements, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, At least one of the group consisting of Al, Sn, Pb, Bi, Sb, Mg, Ca, Ga, and Ge It is also an element, and unlike RE, halide materials are halide materials One or more binary halide phases in a total content of 10% by weight or less relative to the total weight, and seven heavy One or more oxyhalide phases with a total content of % or less by weight, and one with a total content of 7% or less by weight A solid electrolyte material comprising one or more ternary halide phases. Embodiment 2. The halide material does not have a peak in the 2-theta range of 5° to 13°. The implementation includes an X-ray diffraction pattern measured using a Cu K-alpha irradiation line, which includes the following: The solid electrolyte material described in Form 1. Embodiment 3. The halide material is 9% by weight or less of the total weight of the halide material. The binary halide phase, 8% by weight or less, 7% by weight or less, 6% by weight or less, 5% by weight or less, 4 Binary categories: less than or equal to % by weight, less than or equal to 3% by weight, less than or equal to 2% by weight, less than or equal to 1% by weight, or less than or equal to 0.5% by weight. A solid electrolyte material according to Embodiment 1 or 2, comprising a halide phase. Embodiment 4. The binary phase includes a lithium halide phase, and the halide material is a halogen Lithium halide phase at 7% by weight or less, 6% by weight or less, 5 times the total weight of the hydrate material. Less than % by weight, less than 4% by weight, less than 3% by weight, less than 2% by weight, less than 1% by weight, or less than 0.5% by weight Solid electrolytic body according to any one of Embodiments 1 to 3, comprising less than % lithium halide phase. quality material. Embodiment 5. The binary phase includes a rare earth halide phase, and the halide material is a halogen Rare earth halide phase of 10% by weight or less, 7% by weight or less, 5% of the total weight of the halide material Less than or equal to % by weight, less than or equal to 4% by weight, less than or equal to 3% by weight, less than or equal to 2% by weight, less than or equal to 1% by weight, or less than or equal to 0.5% by weight A solid-state electric current according to any one of Embodiments 1 to 4, comprising a rare-earth halide phase of less than % in quantity. solute material. Embodiment 6. The halide material is 6% by weight or less of the total weight of the halide material. The ternary halide phase, 5% by weight or less, 4% by weight or less, 3% by weight or less, 2% by weight or less, 1 Embodiments 1 to 5 include a ternary halide phase in an amount of 0% by weight or less, or 0.5% by weight or less. A solid electrolyte material as described in one of the following. Embodiment 7. The ternary halide phase includes a ternary phase containing two anions, and halogen The halogenated material contains three anions, each making up 7% by weight or less of the total weight of the halogenated material. Original halide phase, 4% by weight or less, 3% by weight or less, 2% by weight or less, 1% by weight or less, or 0 Embodiments 1 to 6 include a ternary halide phase containing 0.5% by weight or less of two anions. A solid electrolyte material as described in one of the following. Embodiment 8. The ternary phase includes a lithium-rare earth halide phase, and the halide material However, lithium-rare earth halides in an amount of 7% by weight or less relative to the total weight of the halide material. Phase 5% or less by weight, 3% or less by weight, 2% or less by weight, 1% or less by weight, or 0.5% or less by weight. A solid according to any one of Embodiments 1 to 6, comprising a lithium-rare earth halide phase. Electrolyte materials. Embodiment 9. The halide material is 6% by weight or less of the total weight of the halide material. The oxyhalide phase, 5% by weight or less, 4% by weight or less, 3% by weight or less, 2% by weight or less, Embodiments 1 to 8 include an oxyhalide phase of 1% by weight or less, or 0.5% by weight or less. A solid electrolyte material as described in any one of the following. Embodiment 10. The oxyhalide phase includes a rare earth oxyhalide phase, The halogen material contains 7% or less of rare earth oxyhalogens relative to the total weight of the halogen material. Calcium oxide phase, 5% by weight or less, 4% by weight or less, 3% by weight or less, 2% by weight or less, 1% by weight or less, Or any of Embodiments 1 to 9, which includes a rare earth oxyhalide phase of 0.5% by weight or less. One of the solid electrolyte materials. Embodiment 11. The halide material comprises a binary halide phase, a ternary halide phase, and It does not include at least one of the phases selected from the group consisting of oxyhalide phases. or a solid electrolyte material according to any one of Embodiments 1 to 10. Embodiment 12. The halide material comprises a binary halide phase, a ternary halide phase, and Solid electrolytics according to any one of Embodiments 1 to 11, which do not contain a bioxyhalide phase. quality material. Embodiment 13. In a single phase, at least one selected from the group consisting of F, Cl, Br, and I An electrolyte material comprising a halogen material containing two halide anions, Li 3-x-f M f RE 1-y Me k y (Cl 1-u-p-q Br u F p I q ) 6-x+y*(k-3) It is expressed as follows, where -1 <= x <= 1 and 0 <= y <= 1, 0 <= u < 1, 0 <= p <= 1 / 3, 0 <= q <= 1 / 6, 0<(u+p+q)<1, 0<=f<=0.3, and M is Li or It is at least one alkali metal element outside of the genotype, RE is a rare earth element, and k is Me The valency is that Me is a group IIIB element, a group IVB element, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Al, Sn, Pb, Bi, Sb, Mg, Ca, Ga, and Ge At least one element selected from the group consisting of, where Me is different from RE, quality material. Embodiment 14. The halide material is monoclinic, trigonal, hexagonal, or orthorhombic. A solid electrolyte material according to any one of embodiments 1 to 13, comprising the crystal structure of the crystalline material. Embodiment 15. The halide material includes a crystal structure represented by a rhombohedral space group. , the solid electrolyte material described in Embodiment 14. Embodiment 16. The crystal structure contains a unit cell smaller than the unit cell of Li3YBr6. A solid electrolyte material as described in application form 14 or 15. Embodiment 17. The peak of the powder diffraction pattern of the halide material is Li3YBr6 Compared to the corresponding peak in the powder diffraction pattern, Embodiment 1 shows a shift at a higher angle. A solid electrolyte material as described in any one of the following 16. Embodiment 18. The halogen material is Li 3-x-f M f RE 1-y Me k y (Cl 1-u-p Br u F p ) 6-x+y*(k-3) Embodiments 1 to 17, as represented by A solid electrolyte material as described in any one of the following. Embodiment 19. The halogen material is Li 3-x-f M f RE 1-y Me k y (Cl 1-u Br u ) 6-x+y*(k-3) Any of Embodiments 1 to 18, represented by One of the solid electrolyte materials. Embodiment 20. The halogen material is Li 3-x-f M f RE 1-y Me k y (Cl 1-p F p ) 6-x+y*(k-3) It is expressed by the equation where 0 <= p < 2, and the implementation A solid electrolyte material described in any one of Forms 1 to 18. Embodiment 21.Effect 1, wherein RE includes Y, Ce, Gd, Er, La, or Yb. A solid electrolyte material listed in any one of the following 20 items. Embodiment 22. Me is Y, Ce, Gd, Er, Sm, Eu, Pr, Tb, Al, Z Includes r, La, Yb, Mg, Zn, Sn, Mg, Ca, or any combination thereof , a solid electrolyte material according to any one of embodiments 1 to 21. Embodiment 23. RE is a solid according to any one of Embodiments 1 to 22, wherein RE consists of Y. Electrolyte materials. Embodiment 24. Me is a group consisting of Gd, Yb, Zr, Zn, Mg, Al, and Ca. At least one element selected from, according to any one of embodiments 1 to 23. Solid electrolyte material. Embodiment 25. Embodiment 1~, in which M contains Na or K, and M consists of Na or K. A solid electrolyte material as described in any one of the 24 items. Embodiment 26. In the formula, u>=0.1, u>=0.12, u>=0.15, u>=0. 17, u>=0.2, u>=0.23, u>=0.25, u>=0.27, u>=0.2 9, u>=0.32, or u>=0.34, in embodiments 1-19 and 21-25 A solid electrolyte material as described in one of the following. Embodiment 27. In the formula, u<=0.85, u<=0.83, u<=0.8, u<=0. 77), u<=0.75, u<=0.7, u<=0.67, u<=0.65, u<=0. 62, u<=0.6, u<=0.57, u<=0.54, u<=0.52, u<=0.4 9) In embodiments 1 to 19 and 21 to 25, where u <= 0.45 and u <= 0.42 A solid electrolyte material as described in one of the following. Embodiment 28. In the formula, p>=0.04, p>=0.06, p>=0.08, p>=0 .09, p>=0.10, p>=0.12, p>=0.14, p>=0.15, p>=0 Embodiments 1-20 and 22-25 have p>0.17, p>=0.2, or p>=0.22. A solid electrolyte material as described in any one of the following. Embodiment 29. In the formula, p<=0.33, p<=0.31, p<=0.29, p<=0 .27, p<=0.25, p<=0.22, p<=0.20, p<=0.18, p<=0 Embodiments 1-20, 22-25, where p<=0.16, p<=0.14, or p<=0.10. A solid electrolyte material as described in either of the two items of 28. Embodiment 30. In the formula, (1-upq)>=0.12, (1-upq)>=0 .15, (1-upq)>=0.17, (1-upq)>=0.20, (1-u -pq)>=0.23, (1-upq)>=0.25, (1-upq)>=0 .27, (1-upq)>=0.29, (1-upq)>=0.33, (1-u -pq)>=0.36, (1-upq)>=0.43, (1-upq)>=0 0.48, (1-upq)>=0.50, (1-upq)>=0.54, or (1 Solid electrolytic body according to any one of Embodiments 1 to 29, where -upq)>=0.58 quality material. Embodiment 31. In the formula, (1-upq)<=0.97, (1-upq)<=0 .92, (1-upq)<=0.87, (1-upq)<=0.83, (1-u -pq)<=0.80, (1-upq)<=0.77, (1-upq)<=0 The values ​​are 0.75, (1-upq)<=0.70, or (1-upq)<=0.66. , a solid electrolyte material according to any one of embodiments 1 to 30. Embodiment 32. The ratio of (1-upq) / u is at least 0.03, at least 0 0.06, at least 0.1, at least 0.2, at least 0.3, at least 0.4, At least 0.5, at least 0.6, at least 0.7, at least 0.8, and at least 0.9, at least 1.0, at least 1.2, at least 1.3, at least 1.4 , at least 1.5, at least 1.6, at least 1.7, at least 1.8, less Any of embodiments 1 to 19 and 21 to 31, both being 1.9 or at least 2.0. One of the solid electrolyte materials. Embodiment 33. The ratio of (1-upq) / u is 15 or less, 11 or less, 10 or less, 9 The following are 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, or 1.4 or less. The solid electrolyte material according to any one of embodiments 1 to 19 and 21 to 32. Embodiment 34. The halide material is Li 3-x RE 1-y Me k y (Cl 1-u B r u ) 6-x+y*(k-3) It is expressed as follows, where 0.08 <= u <= 0.67 The solid electrolyte material according to any one of embodiments 1 to 19 and 21 to 33. Embodiment 35. The halide material is Li 3-x Y(Cl 1-u Br u ) by 6 The solid electrolyte material according to embodiment 34, as shown. Embodiment 36. In the formula, u >= 0.55 or u <= 0.45, as in Embodiment 34 or Solid electrolyte material as described in 35. Embodiment 37. In the formula, 0.2 <= u <= 0.45, which is one of Embodiments 34 to 36. A solid electrolyte material as described in one of the following. Embodiment 38. In the formula, u < 0.33, as described in any one of Embodiments 34 to 37. Solid electrolyte material. Embodiment 39. A halogen material has at least two thetas in the range of 13° to 15°. The actual X-ray diffraction pattern, including two peaks, measured with Cu K-alpha radiation, is shown. A solid electrolyte material as described in any one of the application methods 1 to 38. Embodiment 40. The halide material has at least 20 nm, at least 25 nm, and At least 30 nm, at least 35 nm, or at least 40 nm average diffraction crystallite size A solid electrolyte material according to any one of embodiments 1 to 39, including a s. Embodiment 41. The halide material has a wavelength of at most 500 nm, at most 400 nm, and The average diffraction crystallite size is at least 300 nm, at most 200 nm, or at most 100 nm. A solid electrolyte material according to any one of embodiments 1 to 40, including a s. Embodiment 42. The halogen material is at least 2.3 g / cm³ 3 , at least 2. 5 g / cm 3 at least 2.7 g / cm³ 3 at least 2.9 g / cm³ 3 ,at least 3.1 g / cm³ 3 at least 3.3 g / cm³ 3 , or at least 3.5 g / cm³ 3 dense A solid electrolyte material according to any one of Embodiments 1 to 41, including a degree. Embodiment 43. The halide material is 3.8 g / cm³ 3 Below 3.5g / cm 3 below 3.4 g / cm³ 3 Below, 3.3g / cm 3 The following, or 3.1 g / cm³ 3 Contains the following densities The solid electrolyte material according to any one of Embodiments 1 to 42. Embodiment 44. The halide material has a voltage greater than 3.57V, at least 3.60V, and less than 3.57V. Thermodynamic and electrochemical stability values ​​of 3.62V, 3.65V, or at least 3.71V. A solid electrolyte material according to any one of embodiments 1 to 43, including the above. Embodiment 45. The halogen material is 4.30V or less, 4.19V or less, 4.15V Below the following: 4.10V or less, 3.85V or less, 3.80V or less, 3.75V or less, or 3.7 This includes any one of Embodiments 1 to 44, which includes thermodynamic and electrochemical stability values ​​of 1V or less. Solid electrolyte material. Embodiment 46. Halide material exhibits improved electrification compared to Li3YBr6. A solid electrolyte material according to any one of Embodiments 1 to 45, including scientific stability. Embodiment 47. The halide material has a filtration rate greater than 0.15 mS / cm and at least 0.3 mS / cm, at least 0.5 mS / cm, at least 0.8 mS / cm, at least 0.9 mS / cm, at least 1.1 mS / cm, at least 1.5 mS / cm, or at least This also includes the ionic conductivity measured at 22°C at 1.7 mS / cm, any of Embodiments 1 to 45. A solid electrolyte material as described in one of the following. Embodiment 48. The halide material has a radiation level of less than 2.0 mS / cm, and at most 1.9 mS / cm. Measurements taken at 22°C with a current of at most 1.8 mS / cm or at most 1.7 mS / cm. A solid electrolyte material according to any one of Embodiments 1 to 45, including on-conductivity. Embodiment 49. A negative Extreme liquid material. Embodiment 50. A material comprising cathode-active material particles, wherein at least a portion of the particles is a solid electrolytic material. A cathode liquid material according to Embodiment 49, which is coated with a high-quality material. Embodiment 51. A positive ion comprising a solid electrolyte material described in any one of Embodiments 1 to 48. Extreme liquid material. Embodiment 52. A material comprising particles of an anode active material, wherein at least a portion of the particles is a solid electrolytic material. The anodic solution material according to Embodiment 51, which is coated with a high-quality material. Embodiment 53. A layer comprising the solid electrolyte material described in any one of Embodiments 1 to 48. A layer comprising a cathode liquid layer, an anode liquid layer, an electrolyte layer, or a combination thereof. Embodiment 54. A cathode liquid layer comprising the cathode liquid material described in Embodiment 49 or 50. Embodiment 55. An anodic layer comprising the anodic material described in Embodiment 51 or 52. Embodiment 56. Solid-state electric material comprising any one of Embodiments 1 to 48 A dissolved layer in which the halide material contains at least one of Cl and F, solid It comprises an electrolyte layer and an electrode layer containing a cathode active material in contact with a solid electrolyte material, Under oxidative conditions, the solid electrolyte layer forms a chlorine-deficient region or a fluorine-deficient region near the electrode layer. It is possible to have a chlorine-deficient region or a fluorine-deficient region in a solid electrode distal to the electrode layer. Compared to the region of the disintegrated layer, the electrochemical devices contain lower concentrations of chlorine or fluorine, respectively. A chair. Embodiment 57. Solid electrolyte material comprising any one of Embodiments 1 to 48 The electrolyte layer, the electrode layer containing the cathode active material, and the space between the solid electrode layer and the cathode active material An electrochemical device comprising an intermediate layer. Embodiment 58. The electrochemical device according to Embodiment 57, wherein the intermediate layer includes a cathode liquid layer adjacent to the electrode layer. Electrochemical device. Embodiment 59. The intermediate layer contains a lithium-metal halide represented by Li 3-x-f M f RE 1-y Me k y (Cl 1-p F p ) 6-x+y*(k-3) where -1 <= x <= 1, 0 <= y <= 1, 0 <= p <= 1 / 3, and 0 <= f <= 0.3. The electrochemical device according to Embodiment 57. , -1 <= x <= 1, 0 <= y <= 1, 0 <= p <= 1 / 3, and 0 <= f <= 0.3, and An electrochemical device according to Embodiment 57. Embodiment 60. The solid electrolyte layer contains an electrolyte material containing a halide material represented by Li 3-x-f M f RE 1-y Me k y (Cl 1- p F p ) 6-x+y*(k-3) where 0 < p <= 1 / 3, and the intermediate layer contains a lithium-metal halide represented by Li where 0 < p <= 1 / 3, and the intermediate layer contains a lithium-metal halide represented by Li 1-x-f M f RE 1-y Me k y F 4-x+y*(k-3) where -0.3 <= x <= 0.3, 0 <= y <= 1, 0 <= f <= 0.3. The electrochemical device according to Embodiment 5 , -0.3 <= x <= 0.3, 0 <= y <= 1, 0 <= f <= 0.3, and 7. Embodiment 61. The solid electrolyte layer contains an electrolyte material containing a halide material represented by Li3Y(Br u Cl[[ID=​​​​​​​​​The electrochemical device according to embodiment 57, wherein 0 <= z < 0.3. Embodiment 62. The intermediate layer is at most 1 micron, at most 800 nm, and at most 60 0nm, at most 400nm, at most 300nm, at most 200nm, at most 10 0nm, at most 80nm, at most 60nm, at most 50nm, at most 40nm, Embodiment 57 includes a thickness of at most 20 nm, at most 10 nm, or at most 8 nm. and any one of the electrochemical devices described in 59-61. Embodiment 63. The intermediate layer is at least 1 nm, at least 2 nm, and at least 3 nm , at least 4nm, at least 5nm, at least 10nm, at least 20nm, and This includes a thickness of at least 50 nm, as described in any one of embodiments 57 and 59-62. Electrochemical devices. Embodiment 64. Embodiments 57 and 59-63, in which the intermediate layer is a passivation layer. An electrochemical device as described in any one of the following. Embodiment 65. A method for forming an intermediate layer for an electrochemical device, wherein electrochemical Applying voltage to the device, the electrochemical device is one of the embodiments 1 to 48 The application includes an interface between the solid electrolyte material and the cathode active material described in any one of the following. This involves forming an intermediate layer that is in contact with the cathode active material, and the intermediate layer is a solid-state electric It contains a lithium-metal halide material different from the decomposition material, and an intermediate layer is formed in situ. A method that includes forming, creating, and Embodiment 66. A lithium-metal halide material is used in the partial decomposition of a solid electrolyte material. Thus, the solid electrolyte material is formed, and the halogen contains at least one of Cl and F. The method according to embodiment 65, comprising a monoxide material. Embodiment 67. An electrochemical device comprises a solid electrolyte layer containing a solid electrolyte material, The method further comprises forming a Cl- or F- deficient region within the solid electrolyte layer, and Cl- or The F-deficient region is located proximal to the intermediate layer, compared to the region within the solid electrolyte layer that is far from the intermediate layer. The method according to Embodiment 65 or 66, comprising a lower concentration of Cl- or F-, respectively. . Embodiment 68. The voltage is at least 3.0V, at least 3.6V, and at least 4. Embodiments 65 to 67 include voltages of 0V, at least 4.5V, and at least 5.0V. Either one of the methods. Embodiment 69. The intermediate layer is Li 3-x-f M f RE 1-y Me k y (Cl 1-p F p ) 6-x+y*(k-3) It includes a lithium-metal halide represented by the formula, where, -1 <= x <= 1, 0 <= y <= 1, 0 <= p <= 1 / 3, and 0 <= f <= 0.3 The method according to any one of embodiments 65 to 68. Embodiment 70. The electrolyte material is Li 3-x-f M f RE 1-y Me k y (Cl 1-p F p ) 6-x+y*(k-3) It includes a halide material represented by the formula, where 0 <p <= 1 / 3, and the intermediate layer is Li 1-x-f M f RE 1-y Me k y F 4-x+y*( k-3) It contains lithium-metal halides represented by the formula, where -0.3 <= x < Any one of Embodiments 65 to 69, where = 0.3, 0 <= y <= 1, and 0 <= f <= 0.3 The method according to item 1 Embodiment 71. The electrolyte material contains a halide material represented by Li3Y(Br u Cl 1-u )6, where 0 < u < 1, and the intermediate layer contains Li Y 3(1-z) Y (1+ z) A lithium-metal halide represented by Cl6, where 0 <= z < 0. 3. The method according to any one of Embodiments 65 to 70 Embodiment 72. The intermediate layer has a thickness of at most 1 micron, at most 800 nm, at most 60 0 nm, at most 400 nm, at most 300 nm, at most 200 nm, at most 10 0 nm, at most 80 nm, at most 60 nm, at most 50 nm, at most 40 nm, At most 20 nm, at most 10 nm, or at most 8 nm. The method according to any one of Embodiments 65 ~71 Embodiment 73. The intermediate layer has a thickness of at least 1 nm, at least 2 nm, at least 3 nm 、at least 4 nm, at least 5 nm, at least 10 nm, at least 20 nm, or At least 50 nm. The method according to any one of Embodiments 65 to 72 Embodiment 74. A method for forming a solid electrolyte material, comprising forming a solid solution of a halide material containing at least two halide anions selected from the group consisting of F, Cl, Br, and I The halide material is Li M 3-x-f M f RE 1-y M​​​​​​​​​​​​​ 6-x+y*(k-3) Represented by, In the equation, -1 <= x <= 1, 0 <= y <= 1, 0 <= u < 1, and 0 <= p <= 1 / 3, 0 <= q <= 1 / 6, 0 <= (u + p + q) < 1, 0 < =f<=0.3, and M is at least one alkali metal element other than Li, R E is a rare earth element, k is the valence of Me, and Me is a group IIIB element, group IVB element. Elements, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Al, Sn, Pb, Bi , at least one element from the group consisting of Sb, Mg, Ca, Ga, and Ge, M e is a method different from RE. Embodiment 75. Further comprising forming an ammonium-containing metal halide material, The method according to Embodiment 74. Embodiment 76.(NH4) z RE 1-y Me k y (Cl 1-u-p-q Br u F p I q ) 3+z+y*(k-3) , (NH4) z RE 1-y Me k y (Cl 1-u Br u )3 +z+y*(k-3) , (NH4) z RE 1-y Me k y (Cl 1-p F p ) 3+z+y *(k-3) , (NH4) z RE 1-y Me k y (Cl) 3+z+y*(k-3) , (N H4) z RE 1-y Me k y (Br) 3+z+y*(k-3) , (NH4) z RE 1-y Me k y (I) 3+z+y*(k-3) or to further form a combination thereof The method according to embodiment 74 or 75, including, in the formula, 0.33 <= z <= 5. Embodiment 77. Formation of ammonium-containing metal halides, F, Cl, B Using a predetermined ratio between at least two halogen elements selected from the group consisting of r and I The method according to embodiment 75 or 76, which is carried out in a single step. Embodiment 78. Forming an ammonium-containing metal halide material in a liquid medium The method according to any one of embodiments 75 to 77, performed within. Embodiment 79. Forming an ammonium-containing metal halide material, up to 25 The method according to any one of embodiments 75 to 78, performed at a temperature of 0°C. Embodiment 80. The temperature is at least 20°C, at least 40°C, at least 50°C, At least 70°C, at least 90°C, at least 110°C, or at least 140°C A method according to one embodiment 79. Embodiment 81. Temperature is 200°C or lower, 180°C or lower, 160°C or lower, or 140°C The method according to Embodiment 79 or 80, which is as follows. Embodiment 82. The liquid medium contains an acidic solution, one of Embodiments 78 to 81. Method of description. Embodiment 83. The liquid medium is hydrochloric acid, hydrobromic acid, hydrofluoric acid, hydroiodic acid, or The acid described in any one of embodiments 78 to 82 includes any combination thereof. method. Embodiment 84. Ammonium-containing metal halide material Ammonium halide and Embodiment 7 further comprises partial or complete thermal decomposition of lithium-containing metal halides. The method described in any one of the following 5-83. Embodiment 85. Complete distribution of ammonium halide and lithium-containing metal halide Or the method according to embodiment 84, further comprising partial separation. Embodiment 86. The halide material has at least 20% stacking faults, at least 30 %, at least 40%, at least 50%, at least 60%, at least 70%, less Embodiments 1-4 include a crystal structure containing at least 80%, or at least 90%, stacking faults. A solid electrolyte material as described in any one of the eight items. Embodiment 87. The halogenated material is Me x N k M x N, or combinations thereof The formula includes a charged neutral metal nitride, where x is the valence of N and k is the valence of Me. Therefore, the total content of charged neutral metal nitrides is at most 0 relative to the weight of the halide material. A solid electrolyte material according to any one of embodiments 1 to 48 and 86, wherein the material is 0.3% by weight. Embodiment 88.Li a M a’ Me b Me' b’ X c X' c’ Haroge represented by A solid electrolyte material containing an oxide material, Halide materials, (b / (b+b')) t * 0.84 t * 1.16 (in the formula, (b / (b+b')) t However, the crystallographic phase diagram at a temperature of 22°C shows the crystallography. (corresponding to the anatomical phase transition boundary), (c / (c+c'))​ t * 0.84 <c / (c+c’)<(c / (c+c’)) t * 1.16 (in the formula, (c / (c+c')) t However, the crystallographic phase diagram at a temperature of 22°C shows the crystallography. (corresponding to a phasic phase transition), or (a / (a+a')) t * 0.84 t * 1.16 (In the formula, (a / (a+a')) t However, the crystallographic phase diagram at a temperature of 22°C shows the crystallography. It has a crystallographic phase transition within the stoichiometric range (corresponding to a stoichiometric phase transition), During the ceremony, Me is a group IIIB element, a group IVB element, V, Cr, Mn, Fe, Co, Ni, C u, Zn, Zr, Al, In, Sn, Pb, Bi, Sb, Mg, Ca, Ga, and Ge It is at least one element from the group, Me' is a group IIIB element, group IVB element, V, Cr, Mn, Fe, other than Me. Co, Ni, Cu, Zn, Zr, Al, In, Sn, Pb, Bi, Sb, Mg, Ca, G It is at least one element from the group consisting of a and Ge, b>=b', c>=c', a>=a', X is at least one halogen other than X', X' is at least one halogen, M is at least one alkali metal element other than Li. The halide material, relative to the total weight of the halide material, One or more binary halide phases with a total content of 10% by weight or less, One or more oxyhalide phases with a total content of 7% by weight or less, A solid electrolyte comprising one or more ternary halide phases in a total content of 7% by weight or less.​ material. Embodiment 89.Li a M a Me b Me' b’ X c X' c’ halogens represented by A solid electrolyte material containing a phosphated material, Halide materials, (b / (b+b')) t * 0.84 t * 1.16 (in the formula, (b / (b+b')) t However, the crystallographic phase diagram at temperatures of 20°C to 25°C (corresponding to the crystallographic phase transition above), (c / (c+c')) t * 0.84 <c / (c+c’)<(c / (c+c’)) t * 1.16 (in the formula, (c / (c+c')) t However, the crystallographic phase diagram at temperatures of 20°C to 25°C (corresponding to the above crystallographic phase transition), or (a / (a+a')) t * 0.84 t * 1.16 (In the formula, (a / (a+a')) t However, the crystallographic phase diagram at temperatures of 20°C to 25°C (corresponding to the above crystallographic phase transition), it has a crystallographic phase transition within the stoichiometric range, During the ceremony, Me is a group IIIB element, a group IVB element, V, Cr, Mn, Fe, Co, Ni, C u, Zn, Zr, Al, In, Sn, Pb, Bi, Sb, Mg, Ca, Ga, and Ge It is the smallest element from the group, Me' is a group IIIB element, group IVB element, V, Cr, Mn, Fe, other than Me. ​​Co, Ni, Cu, Zn, Zr, Al, In, Sn, Pb, Bi, Sb, Mg, Ca, G It is at least one element from the group consisting of a and Ge, b>=b', c>=c', a>=a', and X is a small number other than X'. At most, it is a single halogen, X' is a halogen, M is at least one alkali metal element other than Li. A solid electrolyte material in which anions of a halide material are present in a single phase. Embodiment 90. The halide material does not have a peak in the 2-theta range of 5° to 13°. This includes the implementation of X-ray diffraction patterns measured using Cu K-alpha irradiation. A solid electrolyte material as described in form 88 or 89. Embodiment 91. The halide material is monoclinic, trigonal, hexagonal, or orthorhombic. A solid electrolyte material according to any one of embodiments 88 to 90, comprising the crystal structure of the crystalline material. Embodiment 92. The crystallographic phase transition includes a transition from a layered crystal structure to a non-layered crystal structure. , a solid electrolyte material according to any one of embodiments 88 to 91. Embodiment 93. Crystallographic phase transition is a transition from a cubic close-packed structure to a hexagonal close-packed structure. A solid electrolyte material according to any one of embodiments 88 to 92, including the above. Embodiment 94. Crystallographic phase transition from C2 / m space group or R-3m space group to P-3m Solid according to any one of embodiments 88 to 93, including a transition to 1 or the Pnma space group. Electrolyte materials. Embodiment 95. Crystallographic phase transition from a non-layered crystal structure to another non-layered crystal structure or a layered structure. A solid electrolyte material according to any one of embodiments 88 to 93, including a transition to a crystalline structure. Embodiment 96. Embodiment 88, in which the crystallographic phase transition includes a transition from R3c to R3m. A solid electrolyte material as described in either of the following two items (91 and 95). Embodiment 97. Crystallographic phase transition from P-3m1 or Pnma space group to C2 / m space Any one of embodiments 88-91 and 95-96, including a transition to a group or R-3m space group. The solid electrolyte material described in [the text]. Embodiment 98.Me is at least one rare earth element, in Embodiments 88-97 A solid electrolyte material as described in any one of the following. Embodiment 99. Me' is at least one of the rare earth elements, In, Zr, and Fe. A solid electrolyte material according to any one of embodiments 88 to 98, comprising one element. Embodiment 100. M is at least one element among Na, K, and Cs. A solid electrolyte material according to any one of embodiments 88 to 99. Embodiment 101.X is an embodiment in which at least one element is Cl and Br. A solid electrolyte material as described in any one of the following categories 88 to 100. Embodiment 102.X' is an element of at least one of Br and F, A solid electrolyte material as described in any one of the following items 88 to 101. Embodiment 103. The halide material is Li a-f M a’ RE b Me' k b’ (Cl c Br c’ ) 6-f+(k-3)*b’ It is expressed by, in the formula, a + a' = 3, -1 ≤ f ≤ 1, c+c'=1, A solid electrolyte material according to any one of embodiments 88 to 102, wherein b+b'=1 . Embodiment 104. The halide material is Li 3-f RE b Me' k b’ (Cl c Br c’ ) 6-f+(k-3)*b’ It is expressed by, in the formula, -1 ≤ f ≤ 1, c+c'=1, A solid electrolyte material according to any one of embodiments 88 to 102, wherein b+b'=1 . Embodiment 105. In the formula, b>0, b'>0, and 0.65≦c / (c+c')≦0. The solid electrolyte material according to Embodiment 104, wherein the material is 95. Embodiment 106. RE includes Y, and Me' includes In, Yb, or Zr. A solid electrolyte material according to form 104 or 105. Embodiment 107. Me' is Yb, and 0.65 ≤ c / (c+c') ≤ 0.89 A solid electrolyte material according to any one of embodiments 104 to 106. Embodiment 108. Me' is In, and 0.69 ≤ c / (c+c') ≤ 0.95 A solid electrolyte material according to any one of embodiments 104 to 106. Embodiment 109. The halide material is Li3Y b Yb b’ (Cl c Br c’ ) 6 Thus, it is expressed as follows, where 0.65 ≤ c / (c+c') ≤ 0.89, Embodiment 104~ A solid electrolyte material as described in any one of 106. Embodiment 110. The halide material is Li3Y b In b’ (Cl c Br c’ ) 6 Thus, it is expressed as follows, where 0.69 ≤ c / (c+c') ≤ 0.95, Embodiment 104~ A solid electrolyte material as described in either 106 or 108. Embodiment 111. Me' is Zr, and 0.72 ≤ c / (c+c') ≤ 0.98 A solid electrolyte material according to any one of embodiments 104 to 106. Embodiment 112. The halide material is Li 3-b’ Y b Zr b’ (Cl c Br c’ Embodiment 1 is expressed by )6, where 0.72≦c / (c+c')≦0.98. A solid electrolyte material listed in any one of items 04 to 106. Embodiment 113. The halide material is Li 3-f RE(Cl c Br c’ ) 6-f to Thus it is expressed, and in the formula, 0 <= f <= 0.3, c+c'=1, Any one of embodiments 88 to 104 satisfies 0.63 ≤ c / (c+c') ≤ 0.87. The solid electrolyte material described in [the text]. Embodiment 114.RE includes Y, which is the solid electrolytic material described in Embodiment 113. quality material. Embodiment 115. RE consists of Y, and 0.65 ≤ c / (c+c') ≤ 0.87, and 0.66 ≤ c / (c+c') ≤ 0.85, or 0.67 ≤ c / (c+c') ≤ 0.83 The solid electrolyte material according to embodiment 113 or 114. Embodiment 116. The halide material is Li 3-f RE b Me' k b’ X 6-f+( k-3)*b’ It is expressed by, in the formula, 0 <= f <= 0.3, A solid electrolyte material according to any one of embodiments 88 to 104, wherein b+b'=1 . Embodiment 117. In the formula, 0.67 ≤ b / (b+b') ≤ 0.93, Embodiment 1 The solid electrolyte material described in 16. Embodiment 118. RE includes Y, Me' includes In, and X includes Cl. A solid electrolyte material as described in application form 116 or 117. Embodiment 119. The halide material is Li 3-f RE b In b’ X 6-f by Embodiments 116-118 express this, where 0.67 ≤ b / (b+b') ≤ 0.93 in the formula. A solid electrolyte material as described in any one of the following. Embodiment 120. The halide material is Li3Y b In b’ Represented by X6, Solid electrolyte material according to Embodiment 118, Embodiment 121. The halide material is Li 3-f RE b In b’ X 6-f by A solid electrolyte material according to any one of embodiments 116 to 117 shown. Embodiment 122. The halide material is Li a M a’ Represented by REX6, in the formula , a>a'>0, a + a' = 3, Any of embodiments 88 to 103, where 0.942 ≤ a / (a+a') ≤ 0.958. A solid electrolyte material as described in one of the following. Embodiment 123. A solid electrolyte material according to Embodiment 122, wherein M contains Na. Embodiment 124.RE is the solid electrolyte according to Embodiment 122 or 123, comprising Y. material. Embodiment 125.X is described in any one of Embodiments 122 to 124, which includes Cl. Solid electrolyte material. Embodiment 126. The halide material is Li a Na a’ Represented by YCl6, A solid electrolyte material according to any one of embodiments 122 to 124. Embodiment 127. The halide material has at least two thetas in the range of 13° to 15°. It also includes an X-ray diffraction pattern measured with Cu K-alpha radiation, which contains two peaks. For halide materials, (c / (c+c'))t * 0.84 <c / (c+c’)<(c / ( c+c'))t * If there is a crystallographic phase transition within the stoichiometric range of 1.16, then c / (c+ If c') < 0.75, then (c / (c+c'))t is the result at a temperature of 20°C to 25°C. This is described in any one of embodiments 88 to 126, corresponding to a crystallographic phase transition on the crystallographic phase diagram. Solid electrolyte material. [Examples]

[0180] Example 1 According to the embodiments herein, (NH4)3Li3YBr6 and (NH4)3Li3 Samples 1-8 were synthesized by forming a solid solution from YCl6. The composition and characteristics of the samples are as follows: Sex is shown in Table 1.

[0181] At room temperature (approximately 22°C), AC frequencies of 3MHz to 10Hz and 10 to 50mV are present. Under conditions of a two-peak sinusoidal AC voltage signal, electrochemical analysis using gold blocking electrodes The ionic conductivity of the sample was determined using impedance spectroscopy.

[0182] The ionic conductivity of bulk crystal grains is shown in Table 1. The conductivity characteristics of bulk crystal grains are as follows: It appears at high frequencies and is related to the lowest value of the double-layer capacitance, so is it a bulk crystal grain? We were able to separate the contribution of conductivity from grain boundaries and electrode contacts.

[0183] [Table 1]

[0184] Example 2 The following samples were formed. Sample 9 is an In / Li foil counter electrode, and is the same as described in Example 1. A separator made from a solid solution of Li3YBr2Cl4 formed in a similar manner, and Li The sample contains a working electrode made from a mixture of 3YBr2Cl4 and carbon powder. Sample 10 is the same as Sample 9. It is similar, except that the separator is made of Li3YBr6. First charge The cyclic voltammetry VA diagrams of samples 9 and 10 during the oxidation cycle are included in Figure 5. Rarely, the cyclic voltammetry VA diagram in the second charge / oxidation cycle is included in Figure 6. The scanning speed is 0.5 mV / s, and the cell area is 0.5 cm². 2 That was the case.

[0185] Sample 9, compared to Sample 10, showed that during the first and second battery charging processes... When Ias exceeded its electrochemical stability critical value, it exhibited remarkably slow oxidative degradation. In particular, In the first charging cycle, the oxidation peak observed in sample 10 exceeded 280 μA. When flow was present, sample 9 showed an oxidation current of less than 40 μA. Furthermore, as shown in Figure 6... In the second charging cycle / oxidation, sample 9 showed no decomposition with a moderate bias. However, sample 10 still showed signs of degradation.

[0186] Example 3 Typical halide material samples are subjected to accelerated cooling as described in the embodiments of this specification. Formed using ses. Briefly, ammonium-containing LYB and ammonium-containing LYC was formed in separate solutions, then combined and dried at 120°C. By heating the mixture to 550°C, the solid-phase reaction and ammonium sublimation are carried out in parallel. The procedure was carried out. The cooling rate was approximately 100°C. Single-phase LYBC sample, LYBC-1 9, LYBC-41, LYBC-62, LYBC-67, LYBC-79, and LYBC -91 was formed. Single-phase LYB and LYC were formed in the presence of ammonium. (Details of this specification) As described in the embodiments of this document, the ionic conductivity of the sample was measured. As shown in Table 2. Furthermore, samples LYBC-62, LYBC-67, and LYBC-79 were compared to LYB. It exhibited unexpectedly high ionic conductivity.

[0187] [Table 2]

[0188] Figure 9A shows the powder XRD pattern of sample LYBC-79 and the reference XRD pattern of LYC. It contains n. The two materials have the same structure as LYBC-79, and compared to LYC, peak This showed the expansion of the grid parameters suggested by the leftward shift.

[0189] Figure 9B shows the reference XRD patterns of powder XRD pattern samples LYBC-67 and LYB. It includes. The two materials have an isomorphic structure to LYBC-67, and compared to LYB, the peak is This shows the lattice parameter contraction suggested by shifting to the right.

[0190] Example 4 Representative halide materials were formed in the same manner as described in Example 10. The bands at the crystallographic phase transition boundary (MPB) and the halide material samples have been improved. Tables 3-5 show the phase transition range that can enable on-conductivity.

[0191] [Table 3]

[0192] [Table 4]

[0193] [Table 5]

[0194] Example 12 The following samples were prepared, and the electrochemical stability of the electrolytes in the samples was tested. Cell 60 This is an anode of In / Li foil, formed in the same manner as described in Example 10, and Li3Y (Cl 0.8 Br 0.2 Electrolytes prepared with a single-phase solid solution of 6, and Li3Y(Cl 0. 8Br 0.2 )6 and a cathode made of a mixture of carbon powder are included. Cell 74 contains Li3 Y(Cl 0.8 Br 0.2 )6 is a single phase formed in the same manner as described in Example 10 Li3Y(Cl 0.65 Br 0.35 Except for replacing it with 6, it is the same as cell 60. Therefore, cell 69 is formed by Li3Y(Cl) to form sample cell 69. 0.8 Br 0.2 It is the same as cell 60, except that 6 is replaced with Li3YBr6.

[0195] Figures 11A and 11B show cyclic voltammetry (C). V) Includes a figure showing the test results of the electrochemical stability of the electrolyte by method. Figure 11A shows the cell sample. This includes scanning the first charge and discharge cycles of the Li-In annoyance of the tested sample. Refer to D. As shown, when the voltage exceeds 2.9V, the electrolyte of cell 69 ( Li3YBr6) begins to decompose, which is characterized by a relatively high current in the measurement, and this This suggests that the Li3YBr6 electrolyte has limited electrochemical stability at the test voltage. It is. Cell 60 Li3Y(Cl 0.8 Br 0.2 )6 and Li3Y(Cl) of cell 74 0.65 Br 0.35 Cell 6 showed a significantly lower current compared to cell 69 at the same voltage. , surpassing Li3YBr6, Li3Y(Cl 0.8 Br 0.2 )6 and Li3Y(Cl0 .65 Br 0.35 This suggests a significantly improved electrochemical stability of 6. Li3Y (Cl 0.65 Br 0.35 The decomposition of 6 starts at a similar voltage compared to Li3YBr6. It seems that, as characterized by the current, Li3Y(Cl 0.65 B r 0.35 The decomposition dynamics of )6 are significantly lower than those of Li3YBr6. Li3Y(Cl 0. 8Br 0.2 The decomposition of )6 is Li3Y(Cl 0.65 Br 0.35 )6 and Li3YBr Compared to 6, the decomposition dynamics start at a higher voltage, and Li3Y(Cl) 0.65 Br 0. 35 It is significantly lower than 6 and Li3YBr6. It is not desired to be bound by any theory. However, Li3Y(Cl 0.8 Br 0.2 )6 and Li3Y(Cl 0.65 Br 0.35 )6 The improved stability is due to the formation of a thin passivation Cl-rich layer on the cathode. This may be due to the effect.

[0196] As shown in Figure 11B, Li3Y(Cl 0.8 Br 0.2 )6 has a voltage of 3.2 When the voltage exceeds V, it begins to decompose, Li3Y(Cl 0.65 Br 0.35 ) Better electrification than 6 It exhibits scientific stability. Li3Y(Cl 0.8 Br 0.2 )6 Improved electrochemical stability In particular, Li3Y(Cl) has a layered crystalline structure. 0.65 Br 0.35 ) 6, Compared Li3Y(Cl 0.8 Br 0.2 Considering the higher Cl / Br ratio and non-layered crystal structure of 6 Considering the circumstances, it's unexpected.

[0197] The NMC cathode, a state-of-the-art cathode for Li-In anodes, is 3.7V. The operating voltage is shown in Figure 11B, which is 4.3V relative to the Li / Li+ anode. Corresponds. Li3Y(Cl 0.8 Br 0.2 )6 is more at the operating voltage of the NMC cathode Excellent electrochemistry, as suggested by improved decomposition dynamics characterized by low current. It can be observed that it possesses stability.

[0198] Example 13 Sample CS13 was synthesized as follows. The target formula is Li3YCl3Br3. Yes, there was 28.23g of Y2O3, 176.52g of NH4Cl, and 65.13g of L iBr is defined as having a molar ratio between Y2O3, NH4Cl, and LiBr, where Y2O3:NH4Cl: LiBr was weighed to a ratio of 1:13.2:6 (i.e., a predetermined ratio based on stoichiometric ratios). The amount of NH4Cl is excessively high relative to the amount of Y2O3, so that it is 10 mol% more than the amount of Y2O3. (Weighed to the desired size). The raw materials were weighed, crushed, and subjected to a nitrogen atmosphere with a dew point of -80°C or lower. The fine powder was mixed in an air-filled quartz crucible. It was then mixed in a furnace ventilated with N2 24 hours prior to the mixing. The process was carried out. The crucible was heated to 200°C at a ramp rate of 50°C per hour and held for 15 hours. The temperature was then increased to 496°C at a rate of 50°C per hour in a nitrogen atmosphere and held for 1 hour. The crucible is cooled to room temperature, approximately 25°C, and then heated to approximately 100°C per hour. It was cooled at a rapid rate. The temperature was monitored using thermocouples placed inside the crucible. The crucible containing the synthesized material was protected and subjected to moisture-free conditions (dew point -80°C). The combined blocks were placed inside the robe box and then removed from the crucible. Organic residue was removed from the upper surface of the block. The resulting block was subjected to a grating process under an N2 atmosphere. It was ground into a powder inside a robe box.

[0199] Under dry conditions, XRD analysis was performed on the milled powder of sample CS13. The powder was: It showed a hexagonal crystal structure similar to Li3YCl6 prepared using conventional methods. XRD Spectrum Using the Lebail refinement method, the spread of lattice parameters in the material is improved. The Br / Cl ratio was determined. The sum of Cl or Br against anions (i.e., the sum of Cl and Br) The ratio of Br to Cl and the total Br is calculated to be 28% ± 2%, and Cl to Cl The ratio of the total of Br was 72% ± 2%.

[0200] By processing XRD diagrams using the FullProf software package Lebail refinement was implemented. First, the automatic routines of the winPLOTR software were improved. The background of the diffractogram is extracted via [method]. Then, the P-3m1 space group... Using the grid parameters (i.e., a, b, and c), the sample height correction parameter (" 0 points), as well as Lorentz components related to the size and strain of particles in the sample By refining the method of Lebail implemented in FullProf software The XRD plot is refined using [a specific method / tool]. Refinement is performed when the measured value of the chi-squared parameter is less than 6. If this occurs, it will be considered a complete conversion.

[0201] The total content of the water-insoluble impurity phase in sample CS13 is as described in the embodiments of this specification. The decision was made. In short, 50g of milled CS13 sample was dissolved in distilled water. The solution appeared visually pure, but contained 60 mg of hydrated insoluble impurities (e.g., YCl(OH)2) was collected from the filter. Sample CS13 is the total amount of water-insoluble impurities. It contained a total amount of water-insoluble impurities consisting of YOCl, amounting to 53.2 mg by weight. Sample CS13 contained a total content of 0.11% by weight of water-insoluble impurity phase.

[0202] A representative sample S14 was formed as follows. The target formula is Li3YCl3B It was r3.

[0203] 27.71g Li2CO3, 28.23g Y2O3, 192ml 47% concentrated H2O3 Br, 160g of NH4Br, and 50g of distilled H2O were measured and mixed at 95°C. A solution of the i2YBr6 precursor material was formed. Then, the solution was condensed into 0.2 micron millimeters. It was filtered through a pore filter.

[0204] Separately, 138.5g of Li2CO3, 141.1g of Y2O3, and 687ml of 37 %HCl, 435g of NH4Cl, and 150g of distilled H2O were measured and mixed at 95°C. Then, a solution of the Li3YCl6 precursor material was formed. Next, the solution was mixed with 0.2 micron Mi It was filtered through an Ilipore filter.

[0205] Both precursor materials were dried in a rotary evaporator to obtain the material in solid form. The material is crushed to form a fine powder, weighed, and then processed in a nitrogen atmosphere with a dew point of -80°C or lower. The mixture was prepared in a quartz crucible. Synthesis was carried out in a furnace ventilated with N2 24 hours prior. The mixture is heated to 540°C at a continuous ramp rate of 100°C per hour, and then held at 540°C for 1 hour. The crucible was cooled to room temperature, approximately 25°C, and then subjected to a run of up to 100°C per hour. It was cooled at a rapid rate. The temperature was monitored using thermocouples placed inside the crucible. The crucible containing the synthesized material was protected and subjected to a hydrostatic discharge under conditions free of moisture (dew point -80°C). The combined blocks were placed inside the block box and then removed from the crucible. Organic residue was removed from the upper surface of the rock. The resulting block was subjected to globulinization under an N2 atmosphere. It was ground into a powder inside a refrigerated box.

[0206] Under dry conditions, XRD analysis was performed on the milled powder of sample S14. It showed a hexagonal crystal structure similar to that of Li3YCl6 prepared in the conventional way. XRD spectrum Lebail refinement is performed using this method to determine the extent of B in the material through the spread of lattice parameters. The r / Cl ratio was determined. The ratio of Cl or Br to the total anion (total of Cl and Br) was calculated. The calculation shows that the ratio of Br to Cl and the total of Br is 20% ± 2%, and the ratio of Cl to Cl and Br is The total ratio was 80% ± 2%.

[0207] The total content of the water-insoluble impurity phase in sample S14 is determined as described in the embodiments of this specification. The result was determined. Simply put, 50g of milled sample S14 was dissolved in distilled water. 8. 9 mg of hydrated insoluble impurities, corresponding to 1 g of unhydrated, water-insoluble impurities, were collected from the filter. Sample S14 contained 0.016% by weight relative to the total weight of the halide material. It contained water-insoluble impurities.

[0208] Two pairs containing stainless steel electrodes and compressed electrolyte made from sample CS13 powder. A nominal battery cell was formed. The ionic conductivity and thickness of the electrolyte, as well as the ohmic resistance and quality of the cell, were determined. The quantities were measured and included in Table 6.

[0209] [Table 6]

[0210] Stainless steel electrode and compressed electrolyte (0.98 mm thick) made from the powder of sample S14. An additional symmetrical battery cell was formed, including the following: The ionic conductivity of the electrolyte was measured and included in Table 7. Ta.

[0211] [Table 7]

[0212] The advantages, other advantages, and solutions to the problems have been described above with respect to specific embodiments. While providing benefits, advantages, solutions to problems, and any benefits, advantages, or solutions. Any feature that may make any or all of the claims essential and necessary It should not be interpreted as a characteristic or essential feature. The references herein refer to materials that essentially consist of one or more identified components. It may be interpreted as including at least one embodiment. The term "essentially" is specified as Includes the material, and excludes all other materials except for those present in small amounts (e.g., impurities). This will be interpreted as including a composition that does not significantly alter the properties of the material. In particular, or instead, in certain non-limiting embodiments, the composition specified herein None of these materials necessarily have to contain any materials that are not explicitly disclosed. The embodiments of this book include a range of content of a particular component within a material, and the composition within a given material It will be understood that the total content of the ingredients is 100%.

[0213] The description and drawings of the embodiments described herein illustrate the general principles of the structure of various embodiments. The aim is to provide solutions. The specification and drawings will show the structures or methods described herein. This serves as a comprehensive and inclusive description of all elements and characteristics of the equipment and systems used. It is not intended that separate embodiments are provided in combination within a single embodiment. It may also be described in the context of a single embodiment for the sake of brevity, and conversely, various These features may be provided separately or in any partial combination. Furthermore, the scope is described below. References to the specified values ​​include all values ​​within that range. Many other embodiments are described herein. This may become apparent to those skilled in the art only after reading it. Without departing from the scope of this disclosure, Other embodiments can be used to enable structural substitution, logical substitution, or other modifications. This can be derived from the present disclosure. Therefore, the present disclosure is exemplary rather than restrictive. It should be considered an object.< / hklm> < / hklm> < / hkl>

Claims

1. Li ａ M ａ’ Me ｂ Me' ｂ’ Cl ｃ Br ｃ’ A solid electrolyte material comprising a halogenated material represented by, The aforementioned halogen material, (b / (b + b')) ｔ * 0.84 < b / (b + b') < (b / (b + b')) ｔ * 1.16 (where (b / (b + b')) ｔ corresponds to the crystallographic phase transition on the crystallographic phase diagram at a temperature of 20 to 25 °C), (c / (c + c')) ｔ *0.84<c / (c+c')<(c / (c+c')) ｔ *1.16 (in the formula, (c / (c+c')) ｔ (However, this corresponds to the crystallographic phase transition on the crystallographic phase diagram at a temperature of 20 to 25°C), or (a / (a ​​+ a')) ｔ *0.84<a / (a+a')<(a / (a+a')) ｔ *1.16 (wherein the formula is (a / (a+a')) ｔ However, it has the crystallographic phase transition within the stoichiometric range (corresponding to the crystallographic phase transition on the crystallographic phase diagram at a temperature of 20 to 25°C), During the ceremony, Me is at least one element from the group consisting of Group IIIB elements, Group IVB elements, Cu, Zn, Zr, In, Sn, Mg, and Ca. Me' is at least one element other than Me from the group consisting of Group IIIB elements, Group IVB elements, Cu, Zn, Zr, In, Sn, Mg, and Ca. b ≥ b', c >= c', a >= a', M is at least one alkali metal element other than Li, The halogenated material comprises a single phase of Li a M a' Me b Me' b' Cl c Br c' and a total content of one or more water-insoluble impurity phases of metal oxyhalides in an amount of 0.03% by weight or less relative to the total weight of the halogenated material, wherein the metal oxyhalides include Me oxyhalides, Me' oxyhalides, or both, in a solid electrolyte material.

2. The aforementioned crystallographic phase transition, Transition from layered crystal structure to non-layered crystal structure, Transition from cubic close-packed structure to hexagonal close-packed structure Transition from the C2 / m space group or R-3m space group to the P-3m1 or Pnma space group, Transition from one non-layered crystal structure to another non-layered crystal structure or a layered crystal structure. Transition from R3c to R3m, or Transition from P-3m1 or Pnma space group to C2 / m space group or R-3m space group The solid electrolyte material according to claim 1, comprising:

3. Me contains rare earth elements, and the halide material contains Li ａ－ｆ M ａ’ RE ｂ Me' ｋ ｂ’ (Cl ｃ Br ｃ’ ) ６－ｆ＋（ｋ－３）＊ｂ’ It is expressed by, in the formula, RE is one or more rare earth elements, k is the valence of Me', a + a' = 3, -1 ≤ f ≤ 1, c + c' = 1, c' > 0, The solid electrolyte material according to claim 1 or 2, wherein b + b' = 1.

4. Li ３－ｘ－ｆ M ｆ RE １－ｙ Me ｋ ｙ (Cl 1-u Br u) ６－ｘ＋ｙ＊（ｋ－３） A solid electrolyte material comprising a halogenated material represented by, During the ceremony, -1 ≤ x ≤ 1, 0 ≤ y ≤ 1, 0.08 <= u <= 0.67, 0 ≤ f ≤ 0.3, M is at least one alkali metal element other than Li, RE stands for rare earth element, k is the valence of Me, Me is at least one element from the group consisting of Group IIIB elements, Group IVB elements, Cu, Zn, Zr, Sn, Mg, and Ca, and Me is different from RE. The halogenated material comprises a single phase of Li 3-x-f M f RE 1-y Me k y (Cl 1-u Br u) 6-x + y*(k-3) and a total content of one or more water-insoluble impurity phases of metal oxyhalides of 0.03% by weight or less relative to the total weight of the halogenated material, wherein the metal oxyhalides include rare earth oxyhalides, Me oxyhalides, or both, in a solid electrolyte material.

5. The aforementioned halogen material is represented by Li 3-f RE(Cl c Br c') 6-f, RE includes Y, 0 ≤ f ≤ 0.3, c + c' = 1, The solid electrolyte material according to claim 1, wherein 0.63 ≤ c / (c + c') ≤ 0.

87.

6. The aforementioned halide material is represented by Li 3-f RE b Me' k b' (Cl c Br c') 6-f+(k-3)*b', -1 ≤ f ≤ 1, c + c' = 1, b > 0, b' > 0, 0.65 ≤ c / (c + c') ≤ 0.95, The solid electrolyte material according to claim 1, wherein b + b' = 1.

7. The halogen material is represented by Li a M a' REX 6, a > a' > 0, a + a' = 3, The solid electrolyte material according to claim 1, wherein 0.942 ≤ a / (a+a') ≤ 0.

958.

8. The crystal structure of the halide material is Li ３ YBr ６ The solid electrolyte material according to claim 4, comprising a unit cell smaller than the unit cell.

9. The solid electrolyte material according to claim 3 or 4, wherein RE comprises Y, Ce, Gd, Er, La, or Yb, Me comprises Y, Ce, Gd, Er, Sm, Eu, Pr, Tb, Zr, La, Yb, Mg, Zn, In, Sn, Ca, or any combination thereof, and RE is different from Me.

10. The solid electrolyte material according to claim 9, wherein RE is Y and Me is at least one element selected from the group consisting of Gd, Yb, Zr, Zn, Mg, In, and Ca.

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