Novel lithium rare earth halides

Abstract

The present invention relates to novel lithium rare earth halides that can be used as solid electrolytes or in electrochemical devices. The present invention also relates to wet and dry processes for synthesizing such lithium rare earth halides, as well as lithium rare earth halides that are accessible by these processes.

Description

[Technical Field]

[0001] This application claims priority under European applications Nr20169464.3 and Nr20169467.6 filed on April 14, 2020, the entire contents of each of these applications being incorporated herein by reference for any purpose.

[0002] The present invention relates to novel lithium rare earth halides that can be used as solid electrolytes or in electrochemical devices. The present invention also relates to wet and dry processes for synthesizing such lithium rare earth halides, as well as lithium rare earth halides readily obtainable by these processes. [Background technology]

[0003] Lithium batteries are used to power portable electronics and electric vehicles due to their high energy and power density. Conventional lithium batteries utilize a liquid electrolyte composed of lithium salts dissolved in an organic solvent. The aforementioned system raises safety concerns because the organic solvent is flammable. When lithium dendrites form and pass through the liquid electrolyte medium, they can cause short circuits and generate heat, which can lead to accidents resulting in serious injury. Because the electrolyte solution is a flammable liquid, there are concerns about leakage, ignition, etc., when used in batteries. Considering such concerns, the development of solid electrolytes with a higher level of safety is expected to be the electrolyte for next-generation lithium batteries.

[0004] Non-flammable inorganic solid electrolytes offer a solution to safety concerns. Furthermore, their mechanical stability helps suppress lithium dendrite formation, prevent self-discharge and overheating problems, and extend battery life.

[0005] Glass and glass-ceramic electrolytes are advantageous for lithium battery applications due to their high ionic conductivity and mechanical properties. These electrolytes can be pelletized and attached to electrode materials by cold pressing, eliminating the need for high-temperature assembly processes. Eliminating the high-temperature sintering process removes one of the problems associated with using lithium metal anodes in lithium batteries. Due to the widespread use of all-solid-state lithium batteries, there is a growing demand for solid-state electrolytes with high conductivity to lithium ions.

[0006] In recent years, it has been reported that the rare earth halide Li3YCl6, produced by dry mechanosynthesis, exhibits enhanced oxidative stability at high potentials, particularly compared to thiophosphate-based electrolytes. However, further improvement in ionic conductivity is required.

[0007] Therefore, there is a need for novel solid electrolytes that possess optimized performance, such as higher ionic conductivity and lower activation energy, without compromising other important properties, such as chemical and mechanical stability. [Overview of the Initiative] [Means for solving the problem]

[0008] Surprisingly, it has been found that by using at least two types of rare earth metals, a novel solid lithium rare earth halide with higher ionic conductivity and lower activation energy compared to conventional Li3YCl6 materials can be obtained. The novel LiREX solid material of the present invention also exhibits chemical and mechanical stability and processability at least similar to conventional lithium halides. The solid material of the present invention can also be manufactured with improved productivity and allows for control over the morphology of the resulting product. Furthermore, the rare earth metal materials used as raw materials, particularly for producing lithium rare earth halides, appear to be less expensive and have better scalability than conventional rare earth halide materials.

[0009] The present invention thus relates to a solid material according to the following general formula (I): Li , y , , RE x T y X6(I) (wherein, - X is a halogen selected from the group consisting of F, Cl, I, and Br; - 0 < x + (4 / 3)y < 2; preferably 0.8 ≦ x + (4 / 3)y ≦ 1.5; more preferably 0.95 ≦ x + (4 / 3)y ≦ 1.25; - 0 ≦ y ≦ 0.8; preferably 0.1 ≦ y ≦ 0.7; more preferably 0.2 ≦ y ≦ 0.6; - RE represents two or more different rare earth metals; - T is Zr or Hf, provided that when y = 0 and RE represents two rare earth metals, one rare earth metal is Y and the other is selected from the group consisting of Gd, Yb, Ho, Er, Dy, Ce, Tb, and Nd).

[0010] The present invention relates to a solid material according to the following general formula (I): Li 6-3x-4y RE x T y X6(I) (wherein X, x, y, RE, and T are as defined above) and a method for producing the same, comprising reacting, optionally in one or more solvents, at least one lithium halide with at least two different rare earth metal halides and an optional zirconium or hafnium halide, wherein the rare earth metals in such halides are different from each other).

[0011] The present invention relates to a method for preparing a solid material according to the following general formula (I): Li 6-3x-4y RE x T y X6(I) (wherein X, x, y, RE, and T are as defined above) and comprising a) A step of obtaining a composition by mixing a stoichiometric amount of lithium halide with at least two different rare earth metal halides and an optional zirconium or hafnium halide in an inert atmosphere and optionally one or more solvents, wherein the rare earth metals in such halides are different from each other; b) A step of mechanically treating the composition obtained in step a) in order to obtain a solid material; and c) A step of optionally removing at least a portion of one or more solvents from the composition obtained in step b) in order to obtain a solid material; This also relates to preparation methods that include this.

[0012] The present invention also relates to solid materials that are easily obtained by the above method.

[0013] The present invention also relates to the use of a solid material of the following formula (I) as a solid electrolyte: Li 6-3x-4y RE x T y X6(I) (In the formula, X, x, y, RE, and T are as defined above). Use of solid materials as solid electrolytes.

[0014] The present invention also relates to a solid electrolyte comprising at least one solid material of the following formula (I): Li 6-3x-4y RE x T y X6(I) (In the formula, X, x, y, RE, and T are as defined above).

[0015] The present invention also relates to an electrochemical device comprising at least one solid electrolyte comprising at least one solid material of the following formula (I): Li 6-3x-4y RE x T y X6(I) (In the formula, X, x, y, RE, and T are as defined above).

[0016] The present invention also relates to a solid-state battery comprising at least one solid electrolyte comprising at least one solid material of the following formula (I): Li 6-3x-4y RE x T y X6(I) (wherein X, x, y, RE, and T are as defined above).

[0017] The present invention also relates to a vehicle comprising at least one solid-state battery comprising at least one solid electrolyte comprising at least one solid material of the following formula (I): Li 6-3x-4y RE x T y X6(I) (wherein X, x, y, RE, and T are as defined above).

[0018] Surprisingly, it has also been found that a novel method for producing solid lithium rare earth halides results in an improved ionic conductivity and a reduced activation energy as compared to conventional methods. The new LiREX solid materials of the present invention also exhibit at least similar chemical and mechanical stability and processability to their conventional lithium halides. The solid materials of the present invention can also be produced with improved productivity and enable control of the morphology of the resulting products.

[0019] Thus, the present invention relates to a solid material according to the following general formula (I): Li 6-3x-4y RE x T y X6(I) (wherein - X is a halogen; - 0 < x + (4 / 3)y < 2; preferably 0.8 ≦ x + (4 / 3)y ≦ 1.5; more preferably 0.95 ≦ x + (4 / 3)y ≦ 1.25; - 0 ≦ y ≦ 0.8; preferably 0.1 ≦ y ≦ 0.7; more preferably 0.2 ≦ y ≦ 0.6; - RE represents one or more rare earth metals different from each other; - T is Zr or Hf) A method for preparing, a) A step of obtaining a composition by mixing a stoichiometric amount of lithium halide, at least one rare earth metal halide, and an optional zirconium or hafnium halide in one or more solvents under an inert atmosphere; b) A step of mechanically treating the composition obtained in step a) in order to obtain a solid material; and c) A step of removing at least a portion of one or more solvents from the composition obtained in step b) in order to obtain a solid material; This also relates to preparation methods that include this.

[0020] The present invention further relates to solid materials that are easily obtained by the above method.

[0021] Finally, the present invention also relates to the use of the above-mentioned solid materials as solid electrolytes: the present invention also relates to solid electrolytes comprising at least one of the above-mentioned solid materials. The present invention also relates to electrochemical devices comprising at least one solid electrolyte comprising at least one of the above-mentioned solid materials. The present invention also relates to solid batteries comprising at least one solid battery comprising at least one solid electrolyte comprising at least one of the above-mentioned solid materials. The present invention also relates to vehicles comprising at least one solid battery comprising at least one solid electrolyte comprising at least one of the above-mentioned solid materials.

[0022] definition Throughout this specification, unless the context requires otherwise, the words “comprise,” “include,” or variations such as “comprises,” “comprising,” “includes,” and “inclusive” are understood to mean the inclusion of the element or process or group of elements or processes described, but not the exclusion of any other element or process or group of elements or processes. In a preferred embodiment, the words “comprise” and “include,” and variations thereof, mean “consisting of only.”

[0023] As used herein, the singular forms "a," "an," and "the" encompass the plural unless the context explicitly indicates otherwise. The term "and / or" encompasses the meanings "and," "or," and all other possible combinations of elements related to this term.

[0024] The term "~" should be understood to include the limit point.

[0025] Ratios, concentrations, quantities, and other numerical data may be expressed in range form as herein. It should be understood that such range forms are used merely for convenience and brevity, and should be interpreted flexibly to include not only the numerical values ​​explicitly listed as limits of the range, but also all individual numerical values ​​or subranges contained within that range, as if each numerical value and subrange were explicitly listed. For example, a temperature range of approximately 120°C to approximately 150°C should be interpreted to include not only the explicitly listed limit of approximately 120°C to approximately 150°C, but also subranges such as 125°C to 145°C, 130°C to 150°C, etc., as well as individual quantities such as small quantities within the specified range, for example, 122.2°C, 140.6°C, and 141.3°C.

[0026] The term "electrolyte" specifically refers to ions through which, for example, Li + This refers to a material that allows electrons to move but does not conduct electrons through it. An electrolyte is a material that allows ions to move through it, for example, Li + It is useful for conducting electricity while electrically insulating the cathode and anode of the battery. The "solid electrolyte" according to the present invention is particularly useful for ions, such as Li, while the material is in a solid state. + It means any type of material that can move around within it.

[0027] As used herein, the term "crystalline phase" refers to a fraction of a material that exhibits crystalline properties, such as clearly defined X-ray diffraction peaks as measured by X-ray diffraction (XRD).

[0028] As used herein, the term “peak” refers to a peak at position (2Θ) on the x-axis of an XRD powder pattern with intensity v and degree (2Θ) that has a peak intensity substantially greater than the background. In a series of XRD powder pattern peaks, the primary peak is the highest intensity peak associated with the compound or phase being analyzed. The second primary peak is the second highest intensity peak. The third primary peak is the third highest intensity peak.

[0029] The term "electrochemical device" specifically refers to a device that generates and / or stores electrical energy, for example, by electrochemical and / or electrostatic processes. Electrochemical devices may include batteries, particularly electrochemical cells such as solid-state batteries. Batteries can be primary (i.e., single or "disposable") batteries or secondary (i.e., rechargeable) batteries.

[0030] As used herein, the terms "cathode" and "anode" refer to the electrodes of a battery. During a charging cycle in a lithium-ion battery, lithium ions move away from the cathode through the electrolyte to the anode. During a charging cycle, electrons move away from the cathode through the external circuit to the anode. During a discharging cycle in a lithium-ion battery, lithium ions move through the electrolyte and from the anode towards the cathode. During a discharging cycle, electrons move away from the anode through the external circuit to the cathode.

[0031] The terms “vehicle” or “of a vehicle” or other similar terms, as used herein, are understood to generally include motor vehicles such as passenger cars, including sport utility vehicles (SUVs), buses, trucks, various commercial vehicles, watercraft, including various boats and ships, and aircraft, and to include hybrid vehicles, electric vehicles, plug-in hybrid electric vehicles, hydrogen vehicles, and other alternative fuel vehicles (e.g., vehicles using fuels derived from resources other than petroleum). As referred to herein, a hybrid vehicle is a vehicle having two or more different power sources, such as a gasoline-powered and an electric-powered vehicle.

[0032] The present invention relates to a solid material of the following formula (I): Li 6-3x-4y RE x T y X6(I) (wherein, - X is a halogen; - 0 < x + (4 / 3)y < 2; preferably 0.8 ≦ x + (4 / 3)y ≦ 1.5; more preferably 0.95 ≦ x + (4 / 3)y ≦ 1.25; - 0 ≦ y ≦ 0.8; preferably 0.1 ≦ y ≦ 0.7; more preferably 0.2 ≦ y ≦ 0.6; - RE represents two or more different rare earth metals; - T is Zr or Hf, provided that when y = 0 and RE represents two rare earth metals, if one rare earth metal is Y, the other is selected from the group consisting of Gd, Yb, Ho, Er, Dy, Ce, Tb, and Nd). )

[0033] In a first embodiment of the present invention, y = 0, and the solid material is of the formula (Ia): Li 6-3x RE x X6(Ia) (wherein, - X is a halogen; - 0 < x < 2; preferably 0.8 ≦ x ≦ 1.5; more preferably 0.95 ≦ x ≦ 1.25; - RE represents two or more different rare earth metals, provided that when RE represents two rare earth metals, if one is Y, the other is selected from the group consisting of Gd, Yb, Ho, Er, Dy, Ce, Tb, and Nd).

[0034] The solid material of the present invention has a neutral charge. It is understood that the formula (I) / (Ia) is an empirical formula (gross formula) determined by elemental analysis. Thus, the formula (I) defines the composition averaged over all phases present in the solid material.

[0035] The 17 rare earth elements are cerium (Ce), dysprosium (Dy), erbium (Er), europium (Eu), gadolinium (Gd), holmium (Ho), lanthanum (La), lutetium (Lu), neodymium (Nd), praseodymium (Pr), promethium (Pm), samarium (Sm), scandium (Sc), terbium (Tb), thulium (Tm), ytterbium (Yb), and yttrium (Y).

[0036] X is a halogen selected from the group consisting of F, Cl, I, and Br, and X is preferably Cl or Br.

[0037] In equation (Ia): 0 ≤ x ≤ 2; preferably 0.8 ≤ x ≤ 1.5; more preferably 0.95 ≤ x ≤ 1.25. In particular, x is 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.1, 1.3, 1.4, and 1.5, or any range made from these values.

[0038] The solid material of the present invention may be amorphous (glass) and / or crystalline (glass-ceramic). Only a portion of the solid material may be crystalline. The crystalline portion of the solid material may contain only one crystalline structure or may contain multiple crystalline structures. The content of amorphous and crystalline components in the solid material can be evaluated using the whole powder pattern fitting (WPPF) method with Al2O3 crystals, a typical reference material, as described in "RSC Adv., 2019, 9, 14465". The solid material of the present invention preferably contains a fraction consisting of a glass phase.

[0039] The composition of the compound of formula (I) / (Ia) can be determined, in particular, by chemical analysis using techniques well known to those skilled in the art, such as X-ray diffraction (XRD) and inductively coupled plasma-mass spectrometry (IPC-MS).

[0040] Preferably, the average ionic radius of RE, that is, the value of the average ionic radius of the rare earth metal, exhibits an ionic radius value (Å) of less than 0.938 Å. Each of the rare earth metals (e.g., RE1 and RE2) constituting RE does not necessarily need to satisfy this condition. The average radius can be defined as the arithmetic mean of the radii of the rare earths (RE with 6 coordination numbers 3+ +) in the compound. For example, according to the present invention, the average radius is - 0.904 Å (RE1 is Y (90 mol%) and RE2 is Gd (10 mol%)); - 0.895 Å (RE1 is Y (50 mol%) and RE2 is Er (50 mol%)); and can be set as such.

[0041] The solid material of the present invention may have the following formula (II): Li 6-3x-4y RE1 a RE2 b T y X6 (II) (In the formula, - X is a halogen; - 0 < x + (4 / 3)y < 2; preferably 0.8 ≤ x + (4 / 3)y ≤ 1.5; more preferably 0.95 ≤ x + (4 / 3)y ≤ 1.25; - 0 ≤ y ≤ 0.8; preferably 0.1 ≤ y ≤ 0.7; more preferably 0.2 ≤ y ≤ 0.6; - a + b = x, 0.05 ≤ a ≤ 0.95 and 0.0 < b ≤ 0.95; preferably 0.5 ≤ a ≤ 0.9 and 0.05 < b ≤ 0.5; - RE1 is selected from the group consisting of Y, Yb, Ho, and Er; - RE2 is selected from the group consisting of Yb, Ho, Gd, Er, Sm, Dy, La, Nd, Ce, and Tb, and RE1 and RE2 are different; - T is Zr or Hf, provided that when y = 0 and RE1 is Y, RE2 is selected from the group consisting of Gd, Yb, Ho, Er, Dy, Ce, Tb, and Nd).

[0042] When Y = 0, the solid material has the following formula (IIa): Li 6-3x RE1 a RE2 b X6(IIa) (wherein, - X is a halogen; - 0 < x < 2; preferably 0.8 ≦ x ≦ 1.5; more preferably 0.95 ≦ x ≦ 1.25; - a + b = x, 0.05 ≦ a ≦ 0.95 and 0.0 < b ≦ 0.95; preferably 0.5 ≦ a ≦ 0.9 and 0.​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​- 0 < x + (4 / 3)y < 2; preferably 0.8 ≤ x + (4 / 3)y ≤ 1.5; more preferably 0.95 ≤ x + (4 / 3)y ≤ 1.25; - 0 ≤ y ≤ 0.8; preferably 0.1 ≤ y ≤ 0.7; more preferably 0.2 ≤ y ≤ 0.6; - a + b + c = x, where 0.05 ≤ a ≤ 0.95, 0.0 < b ≤ 0.95, 0.0 < c ≤ 0.95, and 0.05 ≤ b + c; - RE1 is selected from the group consisting of Y, Yb, Ho, Er; - RE2 is selected from the group consisting of Yb, Ho, Gd, Er, Sm, Dy, La, Nd, Ce, Tb, - RE3 is selected from the group consisting of Ho, Gd, Er, Sm, Dy, La, Nd, Ce, Tb; RE1, RE2, and RE3 are different; - T is Zr or Hf).

[0047] When y = 0, the solid material is a compound of the following formula (IIIa): Li 6-3x RE1 a RE2 b RE3 c X6(IIIa) (where - X is a halogen; - 0 ≤ x ≤ 2; preferably 0.8 ≤ x ≤ 1.5; more preferably 0.95 ≤ x ≤ 1.25; - a + b + c = x, where 0.05 ≤ a ≤ 0.95, 0.0 < b ≤ 0.95, 0.0 < c ≤ 0.95, and 0.05 ≤ b + c; - RE1 is selected from the group consisting of Y, Yb, Ho, Er; - RE2 is selected from the group consisting of Yb, Ho, Gd, Er, Sm, Dy, La, Nd, Ce, Tb, - RE3 is selected from the group consisting of Ho, Gd, Er, Sm, Dy, La, Nd, Ce, Tb; RE1, RE2, and RE3 are different).

[0048] Preferably, the average ionic radius of RE, that is, the values of the average ionic radii of rare earth metals RE1, RE2, and RE3, exhibit an ionic radius value (Å) smaller than 0.938 Å.

[0049] Preferably, the solid material of formula (III) / (IIIa) according to the present invention can be as follows:

[0050] [Table 2]

[0051] The solid material of the present invention may be a compound of the following formula (IV): Li 6-3x-4y RE1 a RE2 b RE3 c RE4 d T y X6(IV) (wherein, - X is a halogen; - 0 < x + (4 / 3)y < 2; preferably 0.8 ≤ x + (4 / 3)y ≤ 1.5; more preferably 0.95 ≤ x + (4 / 3)y ≤ 1.25; - 0 ≤ y ≤ 0.8; preferably 0.1 ≤ y ≤ 0.7; more preferably 0.2 ≤ y ≤ 0.6; - a + b + c + d = x, 0.05 ≤ a ≤ 0.95, 0.0 < b ≤ 0.95, 0.0 < c ≤ 0.95, 0.0 < d ≤ 0.95, and 0.05 ≤ b + c + d; - RE1 is selected from the group consisting of Y, Yb, Ho, and Er; - RE2 is selected from the group consisting of Yb, Ho, Gd, Er, Sm, Dy, La, Nd, Ce, and Tb, - RE3 is selected from the group consisting of Ho, Gd, Er, Sm, Dy, La, Nd, Ce, and Tb; - RE4 is selected from the group consisting of Er, Gd, Sm, Dy, La, Nd, Ce, and Tb; RE1, RE2, RE3, and RE4 are different; - T is Zr or Hf).

[0052] When y = 0, the solid material is a compound of the following formula (IVa): Li 6-3x RE1 a RE2 b RE3 c RE4 d X6(IVa) (Wherein, - X is a halogen; - 0 < x < 2; preferably 0.8 ≦ x ≦ 1.5; more preferably 0.95 ≦ x ≦ 1.25; - a + b + c + d = x, 0.05 ≦ a ≦ 0.95, 0.0 < b ≦ 0.95, 0.0 < c ≦ 0.95, 0.0 < d ≦ 0.95, and 0.05 ≦ b + c + d; - RE1 is selected from the group consisting of Y, Yb, Ho, Er; - RE2 is selected from the group consisting of Yb, Ho, Gd, Er, Sm, Dy, La, Nd, Ce, Tb, - RE3 is selected from the group consisting of Ho, Gd, Er, Sm, Dy, La, Nd, Ce, Tb;[[ID=2】 - RE4 is selected from the group consisting of Gd, Er, Sm, Dy, La, Nd, Ce, Tb; RE1, RE2, RE3, and RE4 are different).

[0053] Preferably, the average ionic radius of RE, that is, the value of the average ionic radius of the rare earth metals RE1, RE2, RE3, and RE4, shows an ionic radius value (Å) smaller than 0.938 Å.

[0054] Preferably, the solid material of formula (IV) / (IVa) according to the present invention can be as follows:

[0055]

Table 3

[0056] The solid material of the present invention may also be a compound of the following formula (V): Li 6-3x-4y RE1 a RE2 b RE3c RE4 d RE5 e T y X6(V) (wherein - X is halogen; - 0 < x+(4 / 3)y < 2; preferably 0.8 ≦ x+(4 / 3)y ≦ 1.5; more preferably 0.95 ≦ x+(4 / 3)y ≦ 1.25; - 0 ≦ y ≦ 0.8; preferably 0.1 ≦ y ≦ 0.7; more preferably 0.2 ≦ y ≦ 0.6; - a + b + c + d + e = x, 0.05 ≦ a ≦ 0.95, 0.0 < b ≦ 0.95, 0.0 < c ≦ 0.95, 0.0 < d ≦ 0.95, 0.0 < e ≦ 0.95, and 0.05 ≦ b + c + d + e; - RE1 is selected from the group consisting of Y, Yb, Ho, Er; - RE2 is selected from the group consisting of Yb, Ho, Gd, Er, Sm, Dy, La, Nd, Ce, Tb; - RE3 is selected from the group consisting of Ho, Gd, Er, Sm, Dy, La, Nd, Ce, Tb; - RE4 is selected from the group consisting of Er, Gd, Sm, Dy, La, Nd, Ce, Tb; - RE5 is selected from the group consisting of Gd, Sm, Dy, La, Nd, Ce, Tb; RE1, RE2, RE3, RE4, and RE5 are different; - T is Zr or Hf).

[0057] When y = 0, the solid material is a compound of the following formula (Va): Li 6-3x RE1 a RE2 b RE3 c RE4 d RE5 e X6(Va) (wherein - X is halogen; - 0 < x < 2; preferably 0.8 ≦ x ≦ 1.5; more preferably 0.95 ≦ x ≦ 1.25; - a + b + c + d + e = x, where 0.05 ≤ a ≤ 0.95, 0.0 < b ≤ 0.95, 0.0 < c ≤ 0.95, 0.0 < d ≤ 0.95, 0.0 < e ≤ 0.95, and 0.05 ≤ b + c + d + e; - RE1 is selected from the group consisting of Y, Yb, Ho, Er; - RE2 is selected from the group consisting of Yb, Ho, Gd, Er, Sm, Dy, La, Nd, Ce, Tb,[[ID=​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​0.1 Selected from the group consisting of Cl6.

[0062] The solid material of the present invention may preferably be in powder form having a particle size distribution containing D50 within 0.05 μm to 10 μm. The particle size can be evaluated by SEM image analysis or laser diffraction analysis.

[0063] D50 has the usual meaning used in the field of particle size distribution. Dn corresponds to the diameter of particles whose diameter is less than Dn for n% of the particles. D50 (median) is defined as the size value corresponding to the cumulative distribution at 50%. These parameters are usually determined from the volume distribution of diameters of a dispersion system of solid material particles in a liquid, obtained by a laser diffractometer using standard procedures predetermined by the instrument software. A laser diffractometer measures particle size by measuring the intensity of light scattered as a laser beam passes through a dispersed particulate sample, using the technique of laser diffraction. A laser diffractometer could be, for example, the Mastersizer 3000 manufactured by Malvern.

[0064] D50 can be measured, in particular, after ultrasonic treatment. Ultrasonic treatment may include inserting an ultrasonic probe into a dispersion of a solid material in a liquid and subjecting the dispersion to ultrasonic treatment.

[0065] The present invention also relates to a method for producing a solid material, particularly the solid material of formulas (I), (Ia), (II), (IIa), (III), (IIIa), (IV), (IVa), (V), and (Va) described above, which optionally involves reacting at least one lithium halide with at least two different rare earth metal halides and an optionally selected zirconium or hafnium halide in one or more solvents, wherein the rare earth metals in such halides are different from each other.

[0066] One or more types of lithium halides can be used in particular.

[0067] The solid material of the present invention can be produced by any method used in the prior art known for producing glass solid electrolytes, such as melt extraction, mechanical milling, or slurry methods in which the raw materials react in optionally one or more solvents.

[0068] Preferably, the solid materials of formulas (I), (Ia), (II), (IIa), (III), (IIIa), (IV), (IVa), (V), and (Va) can be manufactured by dry or wet mechanosynthesis.

[0069] Therefore, the present invention relates to a method for preparing the aforementioned solid materials, particularly solid materials of general formulas (I), (Ia), (II), (IIa), (III), (IIIa), (IV), (IVa), (V), and (Va), a) A step of obtaining a composition by mixing a stoichiometric amount of lithium halide with at least two different rare earth metal halides and an optional zirconium or hafnium halide in an inert atmosphere and optionally one or more solvents, wherein the rare earth metals in such halides are different from each other; b) A step of mechanically treating the composition obtained in step a) in order to obtain a solid material; and c) A step of optionally removing at least a portion of one or more solvents from the composition obtained in step b) in order to obtain a solid material; This relates to a preparation method that includes the following.

[0070] The inert atmosphere used in step a) refers to the use of an inert gas; that is, a gas that does not undergo harmful chemical reactions under the conditions of the reaction. Inert gases are generally used to avoid undesirable chemical reactions, such as oxidation and hydrolysis reactions with oxygen and moisture in the air. Therefore, an inert gas means a gas that does not chemically react with other reagents present in a particular chemical reaction. In relation to this disclosure, the term “inert gas” means a gas that does not react with solid material precursors. Examples of “inert gases” include, but are not limited to, nitrogen, helium, argon, carbon dioxide, neon, xenon, and O2, including water in liquid and suspended forms at less than 1000 ppm, including condensed gases. The gas may also be pressurized.

[0071] It is preferable that the raw materials are stirred when they come into contact with each other under an atmosphere of an inert gas such as nitrogen or argon. The dew point of the inert gas is preferably -20°C or lower, and particularly preferably -40°C or lower. The pressure may be 0.0001 Pa to 100 MPa, preferably 0.001 Pa to 20 MPa, and preferably 0.01 Pa to 0.5 MPa.

[0072] Preferably, in step a), the inert atmosphere includes an inert gas such as dry N2, dry argon, or dry air (drying may refer to a gas having less than 800 ppm of liquid and suspended water, including condensation).

[0073] The composition ratio of each element can be controlled by adjusting the amount of raw material compounds when the solid material is manufactured. Precursors and their molar ratios are selected according to a target stoichiometry. The target stoichiometry determines the ratios between the elements Li, RE, T, and X obtained from the applied amount of precursors under conditions of complete conversion without side reactions and other losses.

[0074] Lithium halides refer to compounds comprising one or more sulfur atoms and one or more lithium atoms, or alternatively, one or more halogen-containing ionic groups and one or more lithium-containing ionic groups. In certain preferred embodiments, lithium halides may consist of halogen atoms and lithium atoms. Preferably, lithium halides are LiCl, LiBr, LiF, and LiI.

[0075] Rare earth metal halides refer to compounds containing one or more halogen atoms, such as F, Cl, Br, or I, via chemical bonds (e.g., ionic or covalent bonds) to other atoms constituting the compound. In certain preferred embodiments, halogen compounds may contain one or more of F, Cl, Br, or I, or a combination thereof, and one or more rare earth metal atoms. Non-limiting examples include, appropriately, YCl3, ErCl3, YbCl3, GdCl3, LaCl3, YBr3, ErBr3, YbBr3, GdBr3, and LaBr3. Mixed rare earth halides REX3 can also be used as precursors, non-limiting examples of which are (Y,Yb,Er)Cl3 and (La,Y)Cl3. The rare earth metal halide is preferably selected from the group consisting of YCl3, ErCl3, YbCl3, GdCl3, LaCl3, YBr3, ErBr3, YbBr3, GdBr3, LaBr3, (Y,Yb,Er)Cl3, and (La,Y)Cl3.

[0076] In particular, it is entirely possible to use one or more rare earth metal halides in which the rare earth metals are different from each other.

[0077] Preferably, the lithium halide and rare earth halide have an average particle size ranging from 0.5 μm to 400 μm. The particle size can be evaluated by SEM image analysis or laser diffraction analysis.

[0078] It is also possible to add a dopant, preferably a heterovalent dopant such as zirconium or hafnium, to the composition in step a) to form lithium vacancies. Any zirconium halide or hafnium halide containing one or more halogen atoms such as F, Cl, Br, or I, which is added to the composition in step a), is suitable for this purpose. Preferably, ZrCl4 is added to the composition in step a).

[0079] The composition of step a) may also include one or more solvents. The solvent can be appropriately selected from one or more polar or nonpolar solvents that do not dissolve lithium halide and rare earth metal halide.

[0080] The solvent of the present invention thus constitutes a continuous phase in a dispersion system of one or more of the above components in step a).

[0081] Depending on the components and solvent, some of the components are therefore either dissolved, partially dissolved, or in the form of a slurry (i.e., some components are not dissolved and, as a result, form a slurry with the solvent).

[0082] In certain preferred embodiments, the solvent may preferably be a nonpolar solvent. The solvent is preferably selected from the group consisting of aliphatic hydrocarbons such as hexane, pentane, 2-ethylhexane, heptane, decane, and cyclohexane, and aromatic hydrocarbons such as xylene and toluene.

[0083] In this specification, references to "solvent" are understood to include one or more mixed solvents.

[0084] A mixture can be prepared by mixing approximately 1% to 80% by weight of the powder mixture with approximately 20% to 99% by weight of the solvent, based on the total weight of the powder mixture and the solvent. Preferably, a mixture can be prepared by mixing approximately 25% to 75% by weight of the powder mixture with approximately 25% to 75% by weight of the solvent, based on the total weight of the powder mixture and the solvent. In particular, a mixture can be prepared by mixing approximately 40% to 60% by weight of the powder mixture with approximately 40% to 60% by weight of the solvent, based on the total weight of the powder mixture and the solvent.

[0085] The temperature in step a) in the presence of a solvent is preferably between the melting temperature of the selected solvent and the boiling temperature of the selected solvent, at a temperature in which no undesirable reactivity between the solvent and the mixed compound is observed. Preferably, step a) is carried out at -20°C to 40°C, more preferably 15°C to 40°C. In the absence of a solvent, step a) is carried out at a temperature of -20°C to 200°C, preferably 15°C to 40°C.

[0086] The duration of step a) is preferably 1 minute to 1 hour.

[0087] The mechanical treatment of the composition in step b) may be carried out by wet or dry milling; in particular, the powder mixture may be added to a solvent and then milled at about 100 rpm to 1000 rpm for a duration of 10 minutes to 80 hours, more preferably about 4 hours to 40 hours.

[0088] The aforementioned milling is also known as reactive milling in the conventional synthesis of lithium rare earth halides.

[0089] Mechanical milling also has the advantage that grinding occurs simultaneously with the formation of the glass mixture. Various methods can be used in mechanical milling, such as rotary ball mills, tumbling ball mills, vibrating ball mills, and planetary ball mills. Mechanical milling can be carried out with or without balls such as ZrO2.

[0090] Under such conditions, lithium halides and rare earth halides react for a predetermined amount of time.

[0091] The temperature in step b) in the presence of a solvent is between the melting temperature of the selected solvent and the boiling temperature of the selected solvent, at a temperature in which no undesirable reactivity between the solvent and the compound is observed. Preferably, step b) is carried out at a temperature of -20°C to 80°C, more preferably 15°C to 40°C. In the absence of a solvent, step a) is carried out at a temperature of -20°C to 200°C, preferably 15°C to 40°C.

[0092] Typically, a paste or a blend of the paste and a liquid solvent may be obtained at the end of step b).

[0093] Optionally, in step c), it is entirely possible to remove at least a portion of the solvent to remove, for example, at least about 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, or 100% of the total weight of the solvent used, or any range falling between these values, such as 30% to 100% or 50% to 90%. Solvent removal can be carried out by known methods used in the art, such as decantation, filtration, centrifugation, drying, or a combination thereof.

[0094] Preferably, when drying is selected as a method for solvent removal, the temperature is selected as a function of the vapor partial pressure of the selected solvent and is below the boiling point of the selected solvent.

[0095] The duration is 1 second to 100 hours, preferably 1 hour to 20 hours. Such low durations can be achieved by using flash evaporation, for example, by spray drying.

[0096] The solvent can be removed under an atmosphere of an inert gas such as nitrogen or argon. The dew point of the inert gas is preferably -20°C or lower, and particularly preferably -40°C or lower. The pressure may be 0.0001 Pa to 100 MPa, preferably 0.001 Pa to 20 MPa, and more preferably 0.01 Pa to 20 MPa. In particular, the pressure may be in the range of 0.0001 Pa to 0.001 Pa by using ultra-vacuum techniques. In particular, the pressure may be in the range of 0.01 Pa to 0.1 MPa by using primary vacuum techniques.

[0097] It is also entirely possible to heat the solid material after step b) or step c). Heating or heat treatment can, in particular, convert the amorphous powder mixture (glass) obtained above into a crystalline solid material or a mixture of glass and crystalline material (glass ceramic).

[0098] The heat treatment is carried out at a temperature in the range of 50°C to 700°C for a duration of 1 minute to 100 hours, preferably 30 minutes to 20 hours. In some embodiments, the heat treatment is carried out at a temperature in the range of 100°C to 400°C. In some other embodiments, the heat treatment is carried out at a temperature in the range of 150°C to 300°C. The heat treatment may be started directly at a high temperature, or it may be started by raising the temperature at a rate including 1°C / min to 20°C / min. The heat treatment may be finished by quenching with air, or by natural cooling from the heating temperature, or by a temperature-controlled ramp at a rate including 1°C / min to 20°C / min.

[0099] Such processing can be carried out in an atmosphere containing an inert gas such as dry N2 or dry argon (drying may refer to gas containing less than 800 ppm of liquid and suspended water, including condensation). Preferably, the inert atmosphere is a protective gas atmosphere used to minimize the approach of oxygen and moisture, and is therefore preferably excluded.

[0100] The pressure during heating may be standard pressure or reduced pressure. The atmosphere may be an inert gas such as nitrogen and argon. The dew point of the inert gas is preferably -20°C or lower, and particularly preferably -40°C or lower. The pressure may be 0.0001 Pa to 100 MPa, preferably 0.001 Pa to 20 MPa, and preferably 0.01 Pa to 20 MPa. In particular, the pressure may be in the range of 0.0001 Pa to 0.001 Pa by using ultra-vacuum technology. In particular, the pressure may be in the range of 0.01 Pa to 0.1 MPa by using primary vacuum technology.

[0101] In particular, after steps b) and c) or after heat treatment, the solid material can be processed to a desired particle size distribution. If necessary, the solid material obtained by the process according to the present invention as described above is ground into a powder (e.g., milled). Preferably, the powder has a D50 value of a particle size distribution of less than 100 μm, more preferably less than 10 μm, and most preferably less than 5 μm, as measured by dynamic light scattering or image analysis.

[0102] Preferably, the powder has a D90 value for a particle size distribution of less than 100 μm, more preferably less than 10 μm, and most preferably less than 5 μm, as measured by dynamic light scattering or image analysis. In particular, the powder has a D90 value for a particle size distribution that falls between 1 μm and 100 μm.

[0103] In some embodiments of the method, which is carried out in the presence of one or more solvents, the solid materials of formulas (I), (Ia), (II), (IIa), (III), (IIIa), (IV), (IVa), (V), and (Va) are produced by wet mechanosynthesis.

[0104] Therefore, the present invention relates in particular to a method for preparing solid materials represented by general formulas (I), (Ia), (II), (IIa), (III), (IIIa), (IV), (IVa), (V), and (Va), a) A step of obtaining a composition by mixing stoichiometric amounts of lithium halide, at least one rare earth metal halide, and an optional zirconium or hafnium halide in one or more solvents under an inert atmosphere; b) A step of performing mechanical treatment on the composition obtained in step a) to obtain a solid material; and c) A step of removing at least a part of one or more solvents from the composition obtained in step b) to obtain a solid material; relates to a preparation method comprising the above steps.

[0105] The present invention relates to a solid material of the following general formula (I): Li 6-3x-4y RE x T y X6(I) (wherein, - X is a halogen; - 0 < x+(4 / 3)y < 2; preferably 0.8 ≤ x+(4 / 3)y ≤ 1.5; more preferably 0.95 ≤ x+(4 / 3)y ≤ 1.25; - 0 ≤ y ≤ 0.8; preferably 0.1 ≤ y ≤ 0.7; more preferably 0.2 ≤ y ≤ 0.6; - RE represents one or more different rare earth metals; - T is Zr or Hf) and a preparation method of the solid material, comprising: a) A step of obtaining a composition by mixing stoichiometric amounts of lithium halide, at least one rare earth metal halide, and an optional zirconium or hafnium halide in one or more solvents under an inert atmosphere; b) A step of performing mechanical treatment on the composition obtained in step a) to obtain a solid material; and c) A step of removing at least a part of one or more solvents from the composition obtained in step b) to obtain a solid material; also relates to a preparation method comprising the above steps.

[0106] Therefore, the present invention relates to any one of the following general formulas (II) to (V): Li 6-3x-4y RE1a RE2 b T y X6(II) (where a + b = x, 0.05 ≤ a ≤ 0.95 and 0.0 < b ≤ 0.95; preferably 0.5 ≤ a ≤ 0.9 and 0.05 < b ≤ 0.5); Li 6-3x-4y RE1 a RE2 b RE3 c T y X6(III) (where a + b + c = x, 0.05 ≤ a ≤ 0.95, 0.0 < b ≤ 0.95, 0.0 < c ≤ 0.95, and 0.05 ≤ b + c); Li 6-3x-4y RE1 a RE2 b RE3 c RE4 d T y X6(IV) (where a + b + c + d = x, 0.05 ≤ a ≤ 0.95, 0.0 < b ≤ 0.95, 0.0 < c ≤ 0.95, 0.0 < d ≤ 0.95, and 0.05 ≤ b + c + d); Li 6-3x-4y RE1​​​​​​​​​​​​​​​​​​​​​​​​​​​- RE2 is selected from the group consisting of Yb, Ho, Gd, Er, Sm, Dy, La, Nd, Ce, and Tb. - RE3 is selected from the group consisting of Ho, Gd, Er, Sm, Dy, La, Nd, Ce, and Tb; - RE4 is selected from the group consisting of Er, Gd, Sm, Dy, La, Nd, Ce, and Tb; - RE5 is selected from the group consisting of Gd, Sm, Dy, La, Nd, Ce, and Tb; RE1, RE2, RE3, RE4, and RE5 are different; - T is either Zr or Hf) A method for preparing, a) A step of obtaining a composition by mixing a stoichiometric amount of lithium halide with at least two different rare earth metal halides and an optional zirconium or hafnium halide in an inert atmosphere and optionally one or more solvents, wherein the rare earth metals in such halides are different from each other; b) A step of mechanically treating the composition obtained in step a) in order to obtain a solid material; and c) A step of removing at least a portion of one or more solvents from the composition obtained in step b) in order to obtain a solid material; This also relates to preparation methods that include this.

[0107] The present invention further relates to solid materials that are easily obtained by the above method.

[0108] The present invention also relates to the aforementioned solid materials obtained according to the methods of the present invention, such as solid materials of formulas (I), (Ia), (II), (IIa), (III), (IIIa), (IV), (IVa), (V), and (Va), as well as solid electrolytes comprising at least one of the aforementioned solid materials obtained according to the methods of the present invention, such as solid materials of formulas (I), (Ia), (II), (IIa), (III), (IIIa), (IV), (IVa), (V), and (Va).

[0109] The solid electrolyte, therefore, comprises at least one solid material of formula (I), (Ia), (II), (IIa), (III), (IIIa), (IV), (IVa), (V), and (Va), and an optional other solid electrolyte, such as lithium argyrodite, lithium thiophosphate, glass or glass ceramic sulfide Li3PS4, Li7PS 11 , and lithium conductive oxides, such as lithium-filled garnet Li7La3Zr2O 12 Includes (LLZO).

[0110] The solid electrolyte may optionally include a polymer such as styrene-butadiene rubber, an organic or inorganic stabilizer such as SiO2, or a dispersant.

[0111] The present invention also relates to an electrochemical device comprising a solid electrolyte comprising at least one of the aforementioned solid materials obtained according to the method of the present invention, such as solid materials of formula (I), (Ia), (II), (IIa), (III), (IIIa), (IV), (IVa), (V), and (Va).

[0112] Preferably, in an electrochemical device, particularly a rechargeable electrochemical device, the solid electrolyte is a component of the solid structure for the electrochemical device, selected from the group consisting of a cathode, an anode, and a separator.

[0113] In this specification, preferably, the solid electrolyte is a component of a solid structure for an electrochemical device, where the solid structure is selected from the group consisting of a cathode, an anode, and a separator. Accordingly, the solid material according to the present invention can be used alone or in combination with additional components for manufacturing a solid structure for an electrochemical device, such as a cathode, an anode, or a separator.

[0114] The electrode that generates a net negative charge during discharge is called the anode, and the electrode that generates a net positive charge during discharge is called the cathode. A separator electrically isolates the cathode and anode in an electrochemical device.

[0115] Suitable electrochemically active cathode materials and suitable electrochemically active anode materials are well known in the art. In the electrochemical device according to the present invention, the anode preferably comprises graphite carbon, metallic lithium, Si, silicon compounds such as SiO x and lithium-containing metal alloys containing an anode active material such as lithium titanate such as Li4Ti5O 12 or Sn.

[0116] In the electrochemical device according to the present invention, the cathode preferably comprises a metal chalcogenide of the formula LiMQ2, where M is at least one metal selected from transition metals such as Co, Ni, Fe, Mn, Cr and V, and Q is a chalcogen such as O or S. Among these, it is preferable to use a lithium-based composite metal oxide of the formula LiMO2, where M is the same as defined above. Preferred examples thereof include LiCoO2, LiNiO2, LiNi x Co 1-x O2 (0 < x < 1) and spinel structured LiMn2O4. Another preferred example thereof includes a lithium-nickel-manganese-cobalt-based metal oxide of the formula LiNi x Mn y Co z O2 (x + y + z = 1, referred to as NMC), for example LiNi 1 / 3 Mn 1 / 3 Co 1 / 3 O2, LiNi 0.6 Mn 0.2 Co 0.2 O2 and a lithium-nickel-cobalt-aluminum-based metal oxide of the formula LiNi x Co y Al z O2 (x + y + z = 1, referred to as NCA), for example LiNi 0.8 Co 0.15 Al 0.05 O2 may be mentioned. The cathode may include a lithiated or partially lithiated transition metal oxyanion-based material such as LiFePO4.

[0117] For example, the electrochemical device may have a cylindrical or prism shape. The electrochemical device may include a housing that may be made of steel, aluminum, or multilayer film polymer / metal foil.

[0118] Further aspects of the present invention refer to batteries, more preferably alkaline metal batteries, and in particular lithium batteries comprising at least one, for example, two or more inventive electrochemical devices. The electrochemical devices in the inventive alkaline metal battery can be combined with each other, for example, in series or parallel connections.

[0119] The present invention also relates to a solid-state battery comprising a solid electrolyte containing at least one of the aforementioned solid materials obtained according to the method of the present invention, such as the solid materials of formulas (I), (Ia), (II), (IIa), (III), (IIIa), (IV), (IVa), (V), and (Va).

[0120] Typically, a lithium solid-state battery includes a positive electrode active material layer containing a positive electrode active material, a negative electrode active material layer containing a negative electrode active material, and a solid electrolyte layer formed between the positive electrode active material layer and the negative electrode active material layer. At least one of the positive electrode active material layer, the negative electrode active material layer, and the solid electrolyte layer contains a solid electrolyte as defined above.

[0121] The cathode of an all-solid-state electrochemical device typically includes a solid electrolyte as an additional component in addition to the cathode active material. The anode of an all-solid-state electrochemical device typically includes a solid electrolyte as an additional component in addition to the anode active material.

[0122] The form of the solid structure for electrochemical devices, particularly all-solid-state lithium batteries, depends in particular on the form of the electrochemical device itself being manufactured. The present invention further provides a solid structure for an electrochemical device, selected from the group consisting of cathodes, anodes, and separators, wherein the solid structure for an electrochemical device comprises a solid material according to the present invention.

[0123] Multiple electrochemical cells can be combined to form an all-solid-state battery that has both solid electrodes and a solid electrolyte.

[0124] The solid materials disclosed above can be used to prepare electrodes. The electrodes may be positive or negative electrodes.

[0125] The electrodes are typically at least - Metal substrate and, - At least one layer directly bonded to the metal substrate, (i) Solid materials obtained according to the method of the present invention, such as solid materials of formulas (I), (Ia), (II), (IIa), (III), (IIIa), (IV), (IVa), (V), and (Va); (ii) at least one electroactive compound (EAC); (iii) Optionally, at least one lithium-ion conductive material (LiCM) other than the solid material of the present invention; (iv) Optionally, at least one conductive material (ECM); (v) optional lithium salts (LIS); and (vi) At least one optional polymer binder (P); A composition comprising at least one layer and Includes.

[0126] An electroactive compound (EAC) refers to a compound that can incorporate or insert lithium ions into its structure and release them during the charging and discharging phases of an electrochemical device. An EAC may be a compound that can insert and deinsert lithium ions into its structure. For the positive electrode, the EAC is given by formula LiMeQ2 (wherein, - Me is at least one metal selected from the group consisting of Co, Ni, Fe, Mn, Cr, Al, and V; - Q is a chalcogen such as O or S. It may be a composite metal chalcogenide.

[0127] The EAC can more specifically be of the formula LiMeO2. Preferred examples of the EAC include LiCoO2, LiNiO2, LiMnO2, LiNi x Co 1-x O2 (0 < x < 1), LiNi x Co y Mn z O2 (0 < x, y, z < 1 and x + y + z = 1), for example LiNi 1 / 3 Mn 1 / 3 Co 1 / 3 O2, LiNi 0.6 Mn 0.2 Co 0.2 O2, LiNi 0.8 Mn 0.1 Co 0.1 O2, Li(Ni x Co y Al z )O2 (x + y + z = 1), as well as spinel-structured LiMn2O4 and Li(Ni 0.5 Mn 1.5 )O4.

[0128] The EAC can also be a lithiated or partially lithiated transition metal oxyanion-based electroactive material of the formula M1M2(JO4) f E 1-f (wherein - M1 is lithium which can be partially substituted by another alkali metal that occupies less than 20% of M1; - M2 is a transition metal at a +2 oxidation level selected from Fe, Co, Mn, Ni or mixtures thereof, which can be partially substituted by one or more additional metals representing less than 35% of the M2 metal at an oxidation level of +1 to +5 and including 0; - JO4 is any oxyanion where J is any of P, S, V, Si, Nb, Mo or combinations thereof; - E is a fluoride, hydroxide or chloride anion; - f is generally the mole fraction of the JO4 oxyanion included in 0.75 to 1) ).

[0129] M1M2(JO4) as defined abovef E 1-f The electroactive material is preferably a phosphate system. It may exhibit an ordered or modified olivine structure.

[0130] For the positive electrode, the EAC may be sulfur or Li2S.

[0131] For the positive electrode, the EAC may be a conversion material such as FeS2, FeF2, or FeF3.

[0132] For the negative electrode, the EAC can be selected from the group consisting of graphite carbon into which lithium can be inserted. Further details on this type of EAC can be found in Carbon 2000, 38, 1031-1041. This type of EAC typically exists in the form of powder, flakes, fibers, or spheres (e.g., mesocarbon microbeads).

[0133] EAC refers to lithium metal; lithium alloy compositions (e.g., those described in U.S. Patent No. 6,203,944 and International Publication No. 00 / 03444); generally, the formula Li4Ti5O 12 Lithium titanate, represented by (these compounds are generally mobile ions, i.e., Li + When incorporated, it is considered a "zero-strain" insertion material that expands physically at a low level; lithium-silicon alloys, particularly those with the formula Li, are commonly known as lithium silide with a high Li / Si ratio. 4.4 Lithium silide of Si; and Li 4.4 It may also be a lithium-germanium alloy containing a crystalline phase of Ge. EAC may also be a silicon and / or silicon oxide-containing carbonaceous material, particularly a composite material based on graphite-carbon / silicon and graphite / silicon oxide, where graphite-carbon consists of one or more carbon atoms into which lithium can be inserted.

[0134] ECM is typically selected from the group consisting of conductive carbonaceous materials and metal powders or fibers. Conductive carbonaceous materials may be selected from the group consisting of, for example, carbon black, carbon nanotubes, graphite, graphene, and graphite fibers, and combinations thereof. Examples of carbon black include Ketjenblack and acetylene black. Metal powders or fibers include nickel and aluminum powders or fibers.

[0135] Lithium salts (LIS) can be selected from the group consisting of LiPF6, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, LiB(C2O4)2, LiAsF6, LiClO4, LiBF4, LiAlO4, LiNO3, LiCF3SO3, LiN(SO2CF3)2, LiN(SO2C2F5)2, LiC(SO2CF3)3, LiN(SO3CF3)2, LiC4F9SO3, LiCF3SO3, LiAlCl4, LiSbF6, LiF, LiBr, LiCl, LiOH, and lithium 2-trifluoromethyl-4,5-dicyanoimidazole.

[0136] The function of a polymer binder (P) is to bind the components of a composition. Polymer binders are typically inert. They should also preferably be chemically stable and facilitate electronic and ionic transport. Polymer binders are well known in the art. Non-limiting examples of polymer binders include, among others, vinylidene fluoride (VDF)-based (co)polymers, styrene-butadiene rubber (SBR), styrene-ethylene-butylene-styrene (SEBS), carboxymethylcellulose (CMC), polyamide-imide (PAI), poly(tetrafluoroethylene) (PTFE), and poly(acrylonitrile) (PAN) (co)polymers.

[0137] The proportion of the solid material of the present invention in the composition may be 0.1% to 80% by weight, based on the total weight of the composition. In particular, this proportion may be 1.0% to 60% by weight, and more specifically, 5% to 30% by weight. The electrode thickness is not particularly limited and should be adjusted with respect to the energy and output required in the application. For example, the electrode thickness may be 0.01 mm to 1,000 mm.

[0138] Inorganic materials M can also be used in the preparation of separators. A separator is an ion-permeable film placed between the anode and cathode of a battery. Its function is to allow lithium ions to pass through while blocking electrons and ensuring physical separation between the electrodes.

[0139] The separator of the present invention typically comprises at least, - Solid materials obtained according to the method of the present invention, such as solid materials of formulas (I), (Ia), (II), (IIa), (III), (IIIa), (IV), (IVa), (V), and (Va); - At least one optional polymer binding material (P); - At least one optional metal salt, in particular a lithium salt; and - At least one optional plasticizer Includes.

[0140] Electrodes and separators can be prepared using methods well known to those skilled in the art. This typically involves mixing the components in a suitable solvent and then removing the solvent. The suitable solvent is inert to the solid material of the present invention and therefore does not dissolve it. For example, solvents used in the preparation of the solid material of the present invention, such as xylene, can be used to prepare the electrode or separator layer.

[0141] For example, the electrodes are made through the following process: - A step of applying a slurry containing the components of the composition and at least one solvent onto a metal substrate; - Step to remove the solvent It can be prepared by a process that includes [a certain component].

[0142] Common techniques known to those skilled in the art include: coating and calendering, dry and wet extrusion, 3D printing, sintering of porous foams, and subsequent impregnation. Common techniques for preparing electrodes and separators are provided in the Journal of Power Sources, 2018, 382, ​​160-175.

[0143] Electrochemical devices, particularly batteries such as the solid-state batteries described herein, can be used to manufacture or operate stationary applications such as automobiles, computers, mobile devices, mobile phones, watches, camcorders, digital cameras, thermometers, calculators, laptop BIOS, communication equipment, or energy storage devices for remote car locks and power plants.

[0144] Electrochemical devices, and in particular batteries such as the solid-state batteries described herein, can be used in, among other things, in powered vehicles, electric motor-driven bicycles, robots, aircraft (e.g., unmanned aerial vehicles such as drones), ships, or stationary energy storage facilities. Mobile devices such as vehicles, e.g., automobiles, bicycles, aircraft, or water vehicles such as boats or ships are preferred. Other examples of mobile devices are portable ones, e.g., computers, especially laptops, telephones, or power tools from the construction sector, e.g., especially drills, battery-powered screwdrivers, or battery-powered nail guns.

[0145] If any disclosure of a patent, patent application, or publication incorporated herein by reference conflicts with the description of this application to such an extent that it could obscure the terminology, the description herein shall prevail. [Brief explanation of the drawing]

[0146] [Figure 1] This is the powder XRD pattern of Li3YCl6 obtained by dry mechanochemistry in Example 1. [Figure 2] This is the powder XRD pattern of Li3GdCl6 obtained by dry mechanochemistry in Example 2. [Figure 3] Powder XRD pattern of Li3Y0.9Gd0.1Cl6 obtained by dry mechanochemistry in Example 3. [Figure 4] Powder XRD pattern of Li3Y0.3Er0.3Yb0.3Gd0.1Cl6 obtained by dry mechanochemistry in Example 4. [Figure 5] Powder XRD pattern of Li2.7YGd0.1Cl6 obtained by dry mechanochemistry in Example 5. [Figure 6] Powder XRD pattern of Li3(Y0.45Er0.45Gd0.1)Cl6 obtained by dry mechanochemistry in Example 6. [Figure 7] Powder XRD pattern of Li3YCl6 obtained by dry mechanochemistry in Example 8. [[ID=十六]]

Mode for Carrying Out the Invention

[0147] [[ID=二十]] [[ID=二十一]]Example [[ID=二十二]] [[ID=二十三]]The following examples are helpful for explaining the present invention but have no limiting characteristics. [[ID=二十四]] [[ID=二十五]]

[0148] [[ID=二十六]] [[ID=二十七]]X-ray diffraction [[ID=二十八]] Powder XRD diffractograms were acquired using an XRD goniometer with a Bragg Brentano geometry and a Cu X-ray tube (Cu Kalpha wavelength of 1.5406 Å). The setup could be used in different optical configurations, i.e., with variable or fixed divergent slits or Soller slits. A Panalytical monochromator or primary-side filtering device such as a Bragg Brentano HD optical system could also be used. When a variable divergent slit was used, the typical illumination area was 10 mm × 10 mm. The sample holder was loaded into the spinner; the rotation speed was typically 60 rpm during acquisition. The tube settings were 40 kV / 30 mA for variable slit acquisition and 45 kV / 40 mA for fixed slit acquisition with the incident Bragg Brentano HD optical system. The acquisition stroke was 0.017° per stroke. The angular range was typically 5° to 90° with 2 theta or more. The total acquisition time was typically 30 minutes or more. The powder is covered with a Kapton film to prevent it from reacting with moisture in the air.

[0149] Conductivity measurement Conductivity was obtained for pellets produced using a uniaxial press operating at 500 MPa. Pelleting was performed using a laboratory-scale uniaxial press in a glove box filled with a moisture-free argon atmosphere. Two sheets of carbon paper foil (Mersen Papyex soft graphite N998 Ref: 496300120050000, 0.2 mm thick) were used as current collectors. Measurements were performed in a Swagelok cell closed using a manual spring. Impedance spectra were acquired with a Biologic VMP3 device, and temperature control was ensured by a Binder climate chamber. A duration of 2 hours was set to allow temperature equilibrium between two measurements. Impedance spectroscopy was acquired in PEIS mode with an amplitude of 10 mV and a frequency range of 1 MHz to 1 kHz (25 points every 10 times, an average of 50 measurements per frequency point). Electronic conductivity was obtained by applying a potential difference of 1 V for 2 minutes and measuring the resulting current to extract the electronic resistance of the pellet.

[0150] Example 1: Comparison - Li3YCl6 by Dry Mechanochemistry The weighing of the precursors and the preparation of the samples were carried out in an Ar-filled glove box where the levels of oxygen and moisture were both less than 1 ppm. In a typical experiment, a 30 mL glass vial was used to weigh LiCl (≥99.9%, Sigma Aldrich, 1.98 g) and dry YCl3 (≥99%, Sigma Aldrich, 3.004 g) according to the target stoichiometry of Li3YCl6. The precursors used here were powders with an average particle size included in 10 μm to 400 μm.

[0151] The sample was poured into a 20 mL ZrO2 milling jar containing 30 g of ZrO2 balls with a diameter of 5 mm. The jar was fitted with a Viton seal and the inside of the jar was sealed with an Ar atmosphere. The jar was taken out of the glove box and set in a planetary ball mill (Pluverisette 7 premium line, Fritsch). The mechanosynthesis was carried out at 600 rpm for 10 minutes with a 10-minute rest time between each cycle for 207 cycles.

[0152] After the mechanosynthesis was completed, the jar was put into the glove box. The obtained gray powder was recovered. This XRD was in agreement with the reported pattern of Li3YCl6 (orthorhombic phase). When the white part of the powder was separately recovered, a large amount of precursors was shown.

[0153] The transport properties of the gray powder were measured after pelletization: - Ionic conductivity measured at 20 °C: 0.16 mS / cm - Activation energy for lithium transport: 0.42 eV - Electronic conductivity at 20 °C: 3.17E-09 S / cm

[0154] Example 2: Comparison - Li3GdCl6 by Dry Mechanochemistry Precursor weighing and sample preparation were performed in an Ar-filled glove box with oxygen and moisture levels below 1 ppm. In a typical experiment, LiCl (≧99.9%, Sigma Aldrich, 1.24 g) and dried GdCl3 (≧99%, Sigma Aldrich, 2.58 g) were weighed using a 30 mL glass vial according to the target stoichiometry Li3YCl6. The sample was poured into a 20 mL ZrO2 milling jar containing 30 g of 5 mm diameter ZrO2 balls. The jar was fitted with a Viton seal and sealed (in an Ar atmosphere). The jar was removed from the glove box and placed in a planetary ball milling machine (Pluverisette 7 premium line, Fritsch). Mechanosynthesis was performed for 155 cycles at 600 rpm for 10 minutes each, with a 10-minute rest period between each cycle.

[0155] After the mechanosynthesis was complete, the jar was placed in a glove box. The resulting gray powder was collected. The XRD analysis of this powder matched the reported patterns of LiGdCl4 and LiCl (tetragonal I41 / a phase). When the white portion of the powder was collected separately, it showed a large amount of precursors (GdCl3 and LiCl).

[0156] The transport characteristics of the gray powder were measured after pelletization: - Ionic conductivity measured at 20°C: 0.0009 mS / cm - Activation energy for lithium transport: 0.5 eV - Electronic conductivity at 20°C: 2E-09 S / cm

[0157] Example 3: Li3Y by dry mechanochemistry 0.9 Gd 0.1 Cl6 Precursor weighing and sample preparation were performed in an Ar-filled glove box with oxygen and moisture levels both below 1 ppm. In a typical experiment, LiCl (≧99.9%, Sigma Aldrich, 1.25 g), dried YCl3 (≧99.9%, Sigma Aldrich, 1.72 g), and dried GdCl3 (≧99%, Sigma Aldrich, 0.26 g) were mixed in a 30 mL glass vial to the target stoichiometry Li3Y 0.9 Gd 0.1 The sample was weighed according to Cl6. The sample was poured into a 20 mL ZrO2 milling jar containing 30 g of 5 mm diameter ZrO2 balls. The jar was sealed with a Viton seal (in an Ar atmosphere). The jar was removed from the glove box and placed in a planetary ball milling machine (Pluverisette 7 premium line, Fritsch). Mechanosynthesis was performed for 155 cycles at 600 rpm for 10 minutes each, with a 10-minute rest period between each cycle.

[0158] After mechanosynthesis was complete, the jar was placed in a glove box. The resulting gray powder was collected. The XRD pattern of this powder matched that of the reported original Li3YCl6. When the white portion of the powder was collected separately, it showed a large amount of precursors (YCl3 and LiCl).

[0159] The transport characteristics of the gray powder were measured after pelletization: - Ionic conductivity measured at 20°C: 0.31 mS / cm - Activation energy for lithium transport: 0.37 eV - Electronic conductivity at 20°C: 2.3E-9S / cm

[0160] Example 4: Li3Y by dry mechanochemistry 0.3 Er 0.3 Yb 0.3 Gd 0.1 Cl6 Precursor weighing and sample preparation were performed in an Ar-filled glove box with oxygen and moisture levels both below 1 ppm. In a typical experiment, LiCl (≧99.9%, Sigma Aldrich, 1.13 g), dried YCl3 (≧99.9%, Sigma Aldrich, 1.92 g), dried ErCl3 (≧99.9%, Sigma Aldrich, 1.92 g), dried YbCl3 (≧99.9%, Sigma Aldrich, 1.92 g), and dried GdCl3 (≧99%, Sigma Aldrich, 0.26 g) were weighed in 30 mL glass vials to the target stoichiometry of Li3Y 0.3 Er 0.3 Yb 0.3 Gd 0.1 The sample was weighed according to Cl6. The sample was poured into a 20 mL ZrO2 milling jar containing 30 g of 5 mm diameter ZrO2 balls. The jar was sealed with a Viton seal (in an Ar atmosphere). The jar was removed from the glove box and placed in a planetary ball milling machine (Pluverisette 7 premium line, Fritsch). Mechanosynthesis was performed for 155 cycles at 600 rpm for 10 minutes each, with a 10-minute rest period between each cycle.

[0161] After mechanosynthesis was complete, the jar was placed in a glove box. The resulting gray powder was collected. The XRD pattern of this powder matched that of the reported original Li3YCl6. The white portion of the powder was collected separately and revealed a large amount of precursors (YCl3, ErCl3, YbCl3, and LiCl).

[0162] The transport characteristics of the gray powder were measured after pelletization: - Ionic conductivity measured at 20°C: 0.20 mS / cm - Activation energy for lithium transport: 0.40 eV - Electronic conductivity at 20°C: 2.2E-9S / cm

[0163] Example 5: Li by dry mechanochemistry 2.7 YGd 0.1 Cl6 The weighing of the precursors and the preparation of the samples were carried out in an Ar-filled glove box where the levels of oxygen and moisture were both less than 1 ppm. In a typical experiment, a 30 mL glass vial was used to weigh LiCl (≥99.9%, Sigma Aldrich, 1.13 g), dried YCl3 (≥99.9%, Sigma Aldrich, 1.92 g), and dried GdCl3 (≥99%, Sigma Aldrich, 0.26 g) according to the stoichiometry of Li 2.7 YGd 0.1 Cl6. The sample was poured into a 20 mL ZrO2 milling jar containing 30 g of 5 mm diameter ZrO2 balls. The jar was fitted with a Viton seal and sealed (the inside of the jar was an Ar atmosphere). The jar was taken out of the glove box and set inside a planetary ball mill (Pluverisette 7 premium line, Fritsch). The mechanosynthesis was carried out for 10 minutes at 600 rpm for 155 cycles with a 10-minute rest period between each cycle.

[0164] After the mechanosynthesis was completed, the jar was placed inside the glove box. The obtained gray powder was recovered. This XRD was consistent with the reported pattern of the pristine Li3YCl6. When the white part of the powder was separately recovered, a large amount of the precursors (YCl3 and LiCl) was shown.

[0165] The transport properties of the gray powder were measured after pelletization: - Ionic conductivity measured at -20 °C: 0.44 mS / cm - Activation energy for lithium transport: 0.37 eV - Electronic conductivity at -20 °C: 9E-10 S / cm

[0166] Example 6: Li3Y by wet mechanochemistry 0.45 Er 0.45 Gd 0.1 Cl6 Precursor weighing and sample preparation were performed in an Ar-filled glove box with oxygen and moisture levels both below 1 ppm. In a typical experiment, LiCl (≧99.9%, Sigma Aldrich, 3.78 g), dried YCl3 (≧99.9%, Sigma Aldrich, 2.64 g), dried ErCl3 (≧99.9%, Sigma Aldrich, 3.65 g), and dried GdCl3 (≧99%, Sigma Aldrich, 0.77 g) were measured in 30 mL glass vials to the target stoichiometry of Li3Y 0.45 Er 0.45 Gd 0.1 The sample was weighed according to Cl6. The sample was poured into a 45 mL ZrO2 milling jar containing 30 g of 5 mm diameter ZrO2 balls. Then, 10.65 g of p-xylene (≧99%, Sigma-Aldrich, anhydrous) was added to the jar. A Viton seal was fitted to the jar and sealed (the jar was in an Ar atmosphere). The jar was removed from the glove box and placed in a planetary ball milling machine (Pluverisette 7 premium line, Fritsch). Mechanosynthesis was performed for 165 cycles at 800 rpm for 10 minutes each, with a 30 minute rest period between each cycle. After the mechanosynthesis was complete, the jar was placed back into the glove box. The products and balls were placed in two 30 mL glass vials (without caps), each containing the products themselves in a glass tube. The tubes were closed, removed from the glove box, and placed in a Buechi Glass Oven B-585. The sample was vacuum-dried at room temperature for 2 hours to evaporate the p-xylene. The resulting gray powder was collected. The XRD pattern was consistent with that of Li3YCl6 as reported.

[0167] The transport characteristics of the gray powder were measured after pelletization: - Ionic conductivity measured at 20°C: 0.39 mS / cm - Activation energy for lithium transport: 0.35 eV - Electronic conductivity at 20°C: 3E-9 S / cm

[0168] Example 7: Stability measurement in various solvents. Stability was confirmed by weighing 100 mg of Li3YCl6 from Example 1 into 2 g of a selected solvent for 7 days and filtering the solution. If any filter residue was present, it was vacuum-dried at 25°C and tested for conductivity.

[0169] [Table 5]

[0170] Subsequently, in the case of paraxylene, the filtrate was analyzed by ICP-MS and found that Y was present in the filtrate. 3+ and Li + The concentration was less than 1 ppm. The same procedure was performed on the starting materials LiCl and YCl3, but no solubility was observed (Y in the filtrate). 3+ + and Li + (It was less than 1 ppm).

[0171] These compounds appear to be stable in xylene and fluorinated solvents (Galden HT-135) (based on XRD and conductivity).

[0172] Example 8: Li3YCl6 by wet mechanochemistry Precursor weighing and sample preparation were performed in an Ar-filled glove box with oxygen and moisture levels both below 1 ppm. In a typical experiment, LiCl (≧99.9%, Sigma Aldrich, 2.45 g) and dried YCl3 (≧99%, Sigma Aldrich, 3.78 g) were weighed using a 30 mL glass vial according to the target stoichiometry of Li3YCl6. The sample was poured into a 45 mL ZrO2 milling jar containing 30 g of 5 mm diameter ZrO2 balls. Then, 6.05 g of p-xylene (≧99%, Sigma-Aldrich, anhydrous) was added to the jar.

[0173] A Viton seal was fitted to the jar, sealing the inside of the jar (with an Ar atmosphere). The jar was removed from the glove box and placed in a planetary ball milling machine (Pluverisette 7 premium line, Fritsch). Mechanosynthesis was performed for 165 cycles at 800 rpm for 10 minutes each, with a 30-minute rest period between each cycle. After the mechanosynthesis was complete, the jar was placed back into the glove box. The product and balls were placed in two 30 mL glass vials (without caps), each containing the product itself in a glass tube. The tubes were closed, removed from the glove box, and placed in a Buechi Glass Oven B-585. The sample was vacuum-dried at room temperature for 2 hours to evaporate the p-xylene. The resulting gray powder was collected. The XRD pattern was consistent with the reported Li3YCl6 pattern.

[0174] The transport characteristics of the gray powder were measured after pelletization: - Ionic conductivity measured at 20°C: 0.14 mS / cm - Activation energy for lithium transport: 0.38 eV - Electronic conductivity at 20°C: 6E-10S / cm

[0175] Example 9: Water-mediated synthesis of Li3YCl6 Li3YCl6 was prepared using the method described for producing Li3InCl6 by water-mediated synthesis (Angewandte Chemie, 131(46), 16579-16584).

[0176] In a typical experiment, a 50 mL glass beaker was used to weigh out LiCl (≧99.9%, Sigma Aldrich, 1.90 g) and an aqueous solution of YCl3 (>99%, 13.5 g, dry equivalent of YCl3 is 3.01 g) according to the target stoichiometry of Li3YCl6.

[0177] Next, the beaker was placed in a 120°C oven and the water was evaporated for 19 hours. The final product was a white, glassy solid. This product was then vacuum-dried for 4 hours at 120°C in a Buechi Glass Oven B-585. XRD of this sample showed the presence of LiCl, LiCl(H2O), YCl3, and YCl3·6H2O. 6、 In contrast to xH2O, the hydrated phase is Li3YCl 6、 There are no unknown phases that are thought to be caused by xH2O.

[0178] Next, the sample was heated under vacuum (Buechi's Glass Oven B-585) at 200°C for 4 hours, forming a mixture of LiCl and YCl3. In contrast to the reported Li3InCl6, Li3YCl6 was not present.

[0179] Example 10: Li by wet mechanochemistry 2.6 Zr 0.4 Y 0.54 Sm 0.06 Cl 5.82 Br 0.18 Precursor weighing and sample preparation are performed in an Ar-filled glove box with oxygen and moisture levels both below 1 ppm. In a typical experiment, a 30 mL glass vial is used to weigh LiCl (≧99.9%, Sigma Aldrich, 1.65 g), dried YCl3 (≧99.9%, Sigma Aldrich, 1.59 g), dried ZrCl4 (≧99.9%, Sigma Aldrich, 1.43 g), and dried SmBr3 (≧99%, Sigma Aldrich, 0.35 g) to the target stoichiometric level of Li. 2.6 Zr 0.4 Y 0.54 Sm 0.06 Cl 5.82 Br 0.18 Weigh according to the instructions.

[0180] The sample is poured into a 45 mL ZrO2 milling jar containing 66 g of Φ5 mm ZrO2 balls. Then, 5.0 g of p-xylene (≧99%, Sigma-Aldrich, anhydrous) is added to the jar.

[0181] A Viton seal was attached to the jar and sealed (the inside of the jar was in an Ar atmosphere). The jar was removed from the glove box and placed inside the planetary ball milling machine (Pluverisette 7 premium line, Fritsch). Mechanosynthesis was performed for 165 cycles at 800 rpm for 10 minutes, with a 15-minute rest period between each cycle.

[0182] After mechanosynthesis is complete, place the jar into the glove box. Set the product and balls into two 30 mL glass vials (without caps), each containing the product itself in a glass tube. Close the tube, remove it from the glove box, and place it in a Buechi Glass Oven B-585.

[0183] The sample was vacuum-dried at 110°C for 5 hours to evaporate p-xylene. The resulting powder was collected. XRD showed a pattern consistent with that of Li3YCl6, as reported.

[0184] The ionic conductivity measured at 30°C was 0.57 mS / cm, and the activation energy was 0.35 eV. [Table 6]

[0185] The results summarized in Table 1 show that the solid lithium rare earth halide obtained by the wet mechanochemistry process according to the present invention exhibits remarkably improved ionic conductivity at low temperatures compared to the solid lithium rare earth halide obtained by the dry mechanochemistry process (comparing Example 9 to Example 1 at 0°C and -20°C).

Claims

1. Solid materials of the following general formula (I): Li ６－３ｘ－４ｙ RE ｘ T ｙ X ６ (I) (In the formula, - X is a halogen; - 0 < x + (4 / 3)y < 2; preferably 0.8 ≤ x + (4 / 3)y ≤ 1.5; more preferably 0.95 ≤ x + (4 / 3)y ≤ 1.25; - 0 ≤ y ≤ 0.8; preferably 0.1 ≤ y ≤ 0.7; more preferably 0.2 ≤ y ≤ 0.6; - RE represents two or more different rare earth metals; - T is either Zr or Hf; (If y = 0 and RE represents two types of rare earth metals, then the condition is that if one rare earth metal is Y, the other is Yb.) The compounds are those of the following formulas (II) to (V): Li ６－３ｘ－４ｙ RE1 ａ RE2 ｂ T ｙ X ６ (II) (In the formula, a + b = x, and 0.05 ≤ a ≤ 0.95 and 0.0 < b ≤ 0.95; preferably 0.5 ≤ a ≤ 0.9 and 0.05 < b ≤ 0.5; if y = 0 and RE1 is Y, then RE2 is Yb); Li ６－３ｘ－４ｙ RE1 ａ RE2 ｂ RE3 ｃ T ｙ X ６ (III) (In the equation, a + b + c = x, and 0.05 ≤ a ≤ 0.95, 0.0 < b ≤ 0.95, 0.0 < c ≤ 0.95, and 0.05 ≤ b + c); Li ６－３ｘ－４ｙ RE1 ａ RE2 ｂ RE3 ｃ RE4 ｄ T ｙ X ６ (IV) (In the equation, a + b + c + d = x, and 0.05 ≤ a ≤ 0.95, 0.0 < b ≤ 0.95, 0.0 < c ≤ 0.95, 0.0 < d ≤ 0.95, and 0.05 ≤ b + c + d); Li ６－３ｘ－４ｙ RE1 ａ RE2 ｂ RE3 ｃ RE4 ｄ RE5 ｅ T ｙ X ６ (V) (In the equation, a + b + c + d + e = x, and 0.05 ≤ a ≤ 0.95, 0.0 < b ≤ 0.95, 0.0 < c ≤ 0.95, 0.0 < d ≤ 0.95, 0.0 < e ≤ 0.95, and 0.05 ≤ b + c + d + e); One of the following solid materials (In these formulas, - X is a halogen; - 0 < x + (4 / 3)y < 2; preferably 0.8 ≤ x + (4 / 3)y ≤ 1.5; more preferably 0.95 ≤ x + (4 / 3)y ≤ 1.25; - 0 ≤ y ≤ 0.8; preferably 0.1 ≤ y ≤ 0.7; more preferably 0.2 ≤ y ≤ 0.6; - RE1 is selected from the group consisting of Y, Yb, Ho, and Er; - RE2 is selected from the group consisting of Yb, Ho, Gd, Er, Sm, Dy, La, Nd, Ce, and Tb. - RE3 is selected from the group consisting of Ho, Gd, Er, Sm, Dy, La, Nd, Ce, and Tb; - RE4 is selected from the group consisting of Er, Gd, Sm, Dy, La, Nd, Ce, and Tb; - RE5 is selected from the group consisting of Gd, Sm, Dy, La, Nd, Ce, and Tb; RE1, RE2, R3, R4, and RE5 are different; (T is either Zr or Hf).

2. The solid material according to claim 1, wherein the average ionic radius of RE is less than 0.938 Å (Å).

3. The solid material according to claim 1 or 2, wherein X is Cl.

4. A solid material according to any one of claims 1 to 3, wherein 0.95 ≤ x + (4 / 3)y ≤ 1.

25.

5. A solid material according to any one of claims 1 to 4, wherein y = 0.

6. Li ３ Y ０．３ Er ０．３ Yb ０．３ Gd ０．１ Cl₆; Li ３ Y ０．４５ Er ０．４５ Gd ０．１ Cl ６ ; and Li ３ Y ０．４５ Er ０．４５ La ０．１ Cl ６ A solid material according to any one of claims 1 to 5, selected from the group consisting of the following.

7. A solid material according to any one of claims 1 to 6, comprising a fraction consisting of a glass phase.

8. The solid material according to any one of claims 1 to 7, which is in powder form having a particle size distribution containing D50 between 0.05 μm and 10 μm.

9. A method for producing a solid material according to any one of claims 1 to 8, comprising optionally reacting at least lithium halide with at least two different rare earth metal halides and optionally zirconium or hafnium halide in one or more solvents, wherein the rare earth metals in the rare earth metal halides are different from each other.

10. A method for preparing a solid material according to any one of claims 1 to 8, a) A step of obtaining a composition by mixing a stoichiometric amount of lithium halide, at least two different rare earth metal halides, and an optional zirconium or hafnium halide in an inert atmosphere and optionally one or more solvents, wherein the rare earth metals in the rare earth metal halides are different from each other; b) A step of performing a mechanical treatment on the composition obtained in step a) in order to obtain the solid material; and c) A step of optionally removing at least a portion of the one or more solvents from the composition obtained in step b) in order to obtain the solid material; A preparation method including the following.

11. The following general formula (I): Li ６－３ｘ－４ｙ RE ｘ T ｙ X ６ (I) (In the formula, - X is a halogen; - 0 < x + (4 / 3)y < 2; preferably 0.8 ≤ x + (4 / 3)y ≤ 1.5; more preferably 0.95 ≤ x + (4 / 3)y ≤ 1.25; - 0 ≤ y ≤ 0.8; preferably 0.1 ≤ y ≤ 0.7; more preferably 0.2 ≤ y ≤ 0.6; - RE represents one or more different rare earth metals; (T is either Zr or Hf) A method for preparing a solid material, a) A step of obtaining a composition by mixing a stoichiometric amount of lithium halide, at least one rare earth metal halide, and an optional zirconium or hafnium halide in one or more solvents under an inert atmosphere; b) A step of performing a mechanical treatment on the composition obtained in step a) in order to obtain the solid material; and c) A step of removing at least a portion of the one or more solvents from the composition obtained in step b) in order to obtain the solid material; A preparation method including the following.

12. The solid material is a compound of the following formulas (II) to (V): Li ６－３ｘ－４ｙ RE1 ａ RE2 ｂ T ｙ X ６ (II) (In the formula, a + b = x, and 0.05 ≤ a ≤ 0.95 and 0.0 < b ≤ 0.95; preferably 0.5 ≤ a ≤ 0.9 and 0.05 < b ≤ 0.5); Li ６－３ｘ－４ｙ RE1 ａ RE2 ｂ RE3 ｃ T ｙ X ６ (III) (In the equation, a + b + c = x, and 0.05 ≤ a ≤ 0.95, 0.0 < b ≤ 0.95, 0.0 < c ≤ 0.95, and 0.05 ≤ b + c); Li ６－３ｘ－４ｙ RE1 ａ RE2 ｂ RE3 ｃ RE4 ｄ T ｙ X ６ (IV) (In the equation, a + b + c + d = x, and 0.05 ≤ a ≤ 0.95, 0.0 < b ≤ 0.95, 0.0 < c ≤ 0.95, 0.0 < d ≤ 0.95, and 0.05 ≤ b + c + d); Li ６－３ｘ－４ｙ RE1 ａ RE2 ｂ RE3 ｃ RE4 ｄ RE5 ｅ T ｙ X ６ (V) (In the equation, a + b + c + d + e = x, and 0.05 ≤ a ≤ 0.95, 0.0 < b ≤ 0.95, 0.0 < c ≤ 0.95, 0.0 < d ≤ 0.95, 0.0 < e ≤ 0.95, and 0.05 ≤ b + c + d + e); The method according to claim 11, which is any one of the following: (In these formulas, - X is a halogen; - 0 < x + (4 / 3)y < 2; preferably 0.8 ≤ x + (4 / 3)y ≤ 1.5; more preferably 0.95 ≤ x + (4 / 3)y ≤ 1.25; - 0 ≤ y ≤ 0.8; preferably 0.1 ≤ y ≤ 0.7; more preferably 0.2 ≤ y ≤ 0.6; - RE1 is selected from the group consisting of Y, Yb, Ho, and Er; - RE2 is selected from the group consisting of Yb, Ho, Gd, Er, Sm, Dy, La, Nd, Ce, and Tb. - RE3 is selected from the group consisting of Ho, Gd, Er, Sm, Dy, La, Nd, Ce, and Tb; - RE4 is selected from the group consisting of Er, Gd, Sm, Dy, La, Nd, Ce, and Tb; - RE5 is selected from the group consisting of Gd, Sm, Dy, La, Nd, Ce, and Tb; RE1, RE2, RE3, RE4, and RE5 are different; (T is either Zr or Hf).

13. The method according to any one of claims 10 to 12, wherein the lithium halide is preferably selected from the group consisting of LiCl, LiBr, LiF, and LiI.

14. The rare earth metal halide is preferably YCl ３ ErCl ３ YbCl ３ GdCl ３ LaCl ３ YBr ３ ErBr ３ YbBr ３ GdBr ３ LaBr ３ , (Y, Yb, Er)Cl ３ , and (La,Y)Cl ３ A method according to any one of claims 10 to 13, selected from the group consisting of the following.

15. Zirconium halide is ZrCl ４ The method according to any one of claims 10 to 14.

16. The method according to any one of claims 10 to 15, wherein the solvent is selected from the group consisting of aliphatic hydrocarbons such as hexane, pentane, 2-ethylhexane, heptane, decane, and cyclohexane, and aromatic hydrocarbons such as xylene and toluene.

17. The method according to any one of claims 10 to 16, wherein in step b), the mechanical treatment is performed by wet or dry milling.

18. Use of the solid material according to any one of claims 1 to 8 as a solid electrolyte.

19. A solid electrolyte comprising at least one solid material as described in any one of claims 1 to 8.

20. An electrochemical device comprising at least one solid electrolyte comprising at least one solid material as described in any one of claims 1 to 8.

21. A solid battery comprising at least one solid electrolyte comprising at least one solid material as described in any one of claims 1 to 8.

22. A vehicle comprising at least one solid battery comprising at least one solid electrolyte comprising at least one solid material as described in any one of claims 1 to 8.

23. An electrode, and at least, - Metal substrate and, - At least one layer directly bonded to the metal substrate, (i) The solid material according to any one of claims 1 to 8; (ii) at least one electroactive compound (EAC); (iii) At least one lithium-ion conductive material (LiCM) other than the solid material of the present invention, which is optional; (iv) At least one optional conductive material (ECM); (v) Optional lithium salts (LIS); and (vi) at least one optional polymer binding material (P); A composition comprising at least one layer, An electrode containing an electrode.

24. A separator, and at least, - The solid material according to any one of claims 1 to 8; - At least one optional polymer binding material (P); - At least one optional metal salt, in particular a lithium salt; and - At least one optional plasticizer, A separator containing a separator.

Images