Lithium rare earth halides

Abstract

The present invention relates to lithium rare earth halides which can be used as solid electrolytes or in electrochemical devices. The present invention also relates to dry-wet processes for the synthesis of such lithium rare earth halides and to lithium rare earth halides readily obtained from these processes.

Description

[0001] This application claims priority to applications filed in Europe on April 14, 2020, under numbers 20169464.3 and 20169467.6, the full contents of which are incorporated herein by reference for all purposes.

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

[0003] Lithium-ion batteries are used to power portable electronic devices and electric vehicles due to their high energy and power densities. Conventional lithium-ion batteries utilize a liquid electrolyte formed from lithium salts dissolved in an organic solvent. This system presents safety concerns because the organic solvent is flammable. The formation of lithium dendrites and their penetration through the liquid electrolyte medium can cause short circuits and generate heat, leading to accidents that can result in serious damage. Since the electrolyte solution is a flammable liquid, there are concerns about leakage, ignition, or similar problems when used in batteries. Considering these concerns, there is a desire to develop a solid electrolyte with high safety for use in next-generation lithium-ion batteries.

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

[0005] Glass and glass-ceramic electrolytes are advantageous for lithium-ion battery applications due to their high ionic conductivity and mechanical properties. These electrolytes can be pelletized and attached to electrode materials via cold pressing, eliminating the need for high-temperature assembly steps. Removing the high-temperature sintering step eliminates one of the challenges of using lithium metal anodes in lithium-ion batteries. With the widespread use of all solid-state lithium batteries, there is an increasing demand for solid-state electrolytes with high lithium-ion conductivity.

[0006] Recent reports have demonstrated that rare earth halides, Li3YCl6, produced via dry mechanical synthesis, exhibit enhanced oxidative stability at high potentials, particularly compared to thiophosphate-based electrolytes. However, improvements in ionic conductivity remain necessary.

[0007] Therefore, there is a need for solid electrolytes with optimized properties (such as higher ionic conductivity and lower activation energy) without compromising other important properties (such as chemical and mechanical stability). Summary of the Invention

[0008] Surprisingly, it has been found that solid lithium rare earth halides with higher ionic conductivity and lower activation energy compared to the commonly used Li3YCl6 material can be obtained by using at least two rare earth metals. The LiREX solid materials of the present invention also exhibit at least similar chemical and mechanical stability and processability to conventional lithium halides. The solid materials of the present invention can also be prepared with improved productivity and allow control of the morphology of the obtained products. Additionally, rare earth metal materials, especially those used as raw materials for producing lithium rare earth halides, are shown to be cheaper and have better scalability than commonly used rare earth halide materials.

[0009] The present invention thus relates to a solid material according to the following general formula (I):

[0010] Li 6-3x-4y RE x T y X6(I)

[0011] where:

[0012] - X is a halogen selected from the group consisting of F, Cl, I, and Br;

[0013] - 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;

[0014] - 0 ≤ y ≤ 0.8; preferably 0.1 ≤ y ≤ 0.7; more preferably 0.2 ≤ y ≤ 0.6;

[0015] - RE represents two or more rare earth metals; these rare earth metals are different from each other; and

[0016] - T is Zr or Hf;

[0017] provided that when y = 0 and RE represents two rare earth metals, if one rare earth metal is Y, then the other rare earth metal is selected from the group consisting of Gd, Yb, Ho, Er, Dy, Ce, Tb, and Nd.

[0018] The present invention also relates to a method for producing a solid material according to the following general formula (I):

[0019] Li 6-3x-4y RE x T y X6(I)

[0020] where X, x, y, RE, and T are as defined above;

[0021] The method includes reacting at least lithium halide and at least two different rare earth metal halides, optionally in one or more solvents, wherein the rare earth metals in the at least two different rare earth metal halides are different from each other and optionally are zirconium halide or hafnium halide.

[0022] The present invention also relates to a process for preparing solid materials according to the following general formula (I):

[0023] Li 6-3x-4y RE x T y X6(I)

[0024] Where X, x, y, RE, and T are defined as above;

[0025] The process includes the following steps:

[0026] a) A composition is obtained by mixing stoichiometric amounts of lithium halide and at least two different rare earth metal halides, optionally in one or more solvents under an inert atmosphere, wherein the rare earth metals in the at least two different rare earth metal halides are different from each other and optionally are zirconium halide or hafnium halide.

[0027] b) Apply mechanical treatment to the composition obtained in step a) to obtain the solid material; and

[0028] c) Optionally, remove at least a portion of the one or more solvents from the composition obtained in step b) to obtain the solid material.

[0029] The present invention also relates to a solid material that is readily obtained by the process described.

[0030] The present invention also relates to the use of solid materials of the following formula (I):

[0031] Li 6-3x-4y RE x T y X6(I)

[0032] Where X, x, y, RE, and T are defined as above;

[0033] The solid material is used as a solid electrolyte.

[0034] The present invention also relates to a solid electrolyte, said solid electrolyte comprising at least a solid material of formula (I):

[0035] Li 6-3x-4y RE x T y X6(I)

[0036] X, x, y, RE, and T are defined as above.

[0037] The present invention also relates to an electrochemical device comprising at least a solid electrolyte, the solid electrolyte comprising at least a solid material of formula (I):

[0038] Li 6-3x-4y RE x T y X6(I)

[0039] X, x, y, RE, and T are defined as above.

[0040] The present invention also relates to a solid-state battery, the solid-state battery comprising at least a solid electrolyte, the solid electrolyte comprising at least a solid material of the following formula (I):

[0041] Li 6-3x-4y RE x T y X6(I)

[0042] X, x, y, RE, and T are defined as above.

[0043] The present invention also relates to a vehicle, the vehicle comprising at least a solid-state battery, the solid-state battery comprising at least a solid electrolyte, the solid electrolyte comprising at least a solid material of the following formula (I):

[0044] Li 6-3x-4y RE x T y X6(I)

[0045] X, x, y, RE, and T are defined as above.

[0046] Surprisingly, it has been found that the new process for producing solid lithium rare earth halides allows for improved ionic conductivity and lower activation energies compared to conventional processes. The LiREX solid materials of this invention also exhibit at least similar chemical and mechanical stability and handleability to those of conventional lithium halides. The solid materials of this invention can also be prepared with improved productivity and allow for control over the morphology of the obtained products.

[0047] The present invention also relates to a process for preparing solid materials according to the following general formula (I):

[0048] Li 6-3x-4y RE x T y X6(I)

[0049] in:

[0050] -X represents a halogen;

[0051] -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;

[0052] -0 ≤ y ≤ 0.8; preferably 0.1 ≤ y ≤ 0.7; more preferably 0.2 ≤ y ≤ 0.6;

[0053] - RE represents one or more rare earth metals; these rare earth metals are different from each other; and

[0054] - T is Zr or Hf;

[0055] The process comprises the following steps:

[0056] a) obtaining a composition by mixing stoichiometric amounts of lithium halide, at least one rare earth metal halide and optionally zirconium halide or hafnium halide in one or more solvents under an inert atmosphere;

[0057] b) subjecting the composition obtained in step a) to mechanical treatment in order to obtain the solid material; and

[0058] c) removing at least a portion of the one or more solvents from the composition obtained in step b), thereby obtaining the solid material.

[0059] The present invention further relates to a solid material readily obtainable by the process.

[0060] Finally, the present invention also relates to the use of the previously described solid material as a solid electrolyte. The present invention also relates to a solid electrolyte comprising at least the previously described solid material. The present invention also relates to an electrochemical device comprising at least a solid electrolyte comprising at least the previously described solid material. The present invention also relates to a solid-state battery comprising at least a solid electrolyte comprising at least the previously described solid material. The present invention also relates to a vehicle comprising at least a solid-state battery comprising at least a solid electrolyte comprising at least the previously described solid material.

[0061] Definitions

[0062] Unless the context otherwise requires, throughout this specification, the word "comprise" or "include" or variations such as "comprises", "comprising", "includes", "including" will be understood to imply the inclusion of the stated element or method step or group of elements or group of method steps, but not the exclusion of any other element or method step or group of elements or group of method steps. According to a preferred embodiment, the terms "comprising" and "including" and variations thereof are meant to mean "consisting exclusively of".

[0063] As used herein, unless the context clearly indicates otherwise, the singular forms “a / an” and “the” include the plural aspect. The term “and / or” includes the meaning of “and”, “or”, and all other possible combinations of the elements associated with this term.

[0064] The term “between” should be understood to include the limit.

[0065] Ratios, concentrations, quantities, and other numerical data may be presented in range format herein. It should be understood that this range format is used merely for convenience and brevity, and should be flexibly interpreted to include not only the values ​​explicitly mentioned as range limits, but also all individual values ​​or subranges covered within this range, as if each value and subrange were explicitly mentioned. For example, a temperature range of approximately 120°C to approximately 150°C should be interpreted to include not only the explicitly mentioned 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 within the specified range, including fractional quantities, such as 122.2°C, 140.6°C, and 141.3°C.

[0066] The term "electrolyte" specifically refers to electrolytes that allow ions, such as Li, to pass through. + Materials through which electrons migrate but are not allowed to conduct electricity. Electrolytes are useful for electrically insulating the cathode and anode of a battery while allowing ions such as Li to migrate through. + Transported through the electrolyte. The "solid electrolyte" according to the invention specifically refers to the electrolyte in which ions (e.g., Li) are transported. + Any kind of material that can move while remaining in a solid state.

[0067] As used herein, the term "crystalline phase" refers to a material or fraction of material that exhibits crystalline properties (e.g., well-defined x-ray diffraction peaks as measured by X-ray diffraction (XRD)).

[0068] As used herein, the term "peak" refers to the (2θ) position on the x-axis of an XRD powder spectrum with a significantly higher intensity than the background. In a series of XRD powder spectrum peaks, the dominant peak is the highest intensity peak associated with the analyzed compound or related components. The second dominant peak is the peak with the second highest intensity. The third dominant peak is the peak with the third highest intensity.

[0069] The term "electrochemical device" specifically refers to a device that generates and / or stores electrical energy through, for example, electrochemical and / or electrostatic processes. Electrochemical devices can include electrochemical cell units such as batteries, especially solid-state batteries. The battery can be a primary (i.e., single-use or "disposable") battery or a secondary (i.e., rechargeable) battery.

[0070] As used herein, the terms "cathode" and "anode" refer to the electrodes of a battery. During the charging cycle of a Li secondary battery, Li ions leave the cathode and move through the electrolyte to the anode. During the charging cycle, electrons leave the cathode and move through the external circuit to the anode. During the discharging cycle of a Li secondary battery, Li ions migrate from the anode and through the electrolyte to the cathode. During the discharging cycle, electrons leave the anode and move through the external circuit to the cathode.

[0071] It should be understood that, as used herein, the term "vehicle" or "vehicular" or other similar terms encompass motor vehicles in general such as passenger cars including sport utility vehicles (SUVs), buses, trucks, various commercial vehicles, watercraft including various small boats and ships, aircraft, etc., and encompass hybrid vehicles, electric vehicles, plug-in hybrid electric vehicles, hydrogen vehicles, and other alternative fuel vehicles (e.g., fuels derived from other resources than petroleum). As referred to herein, a hybrid vehicle is a vehicle having two or more different power sources, such as a vehicle powered by gasoline and electricity simultaneously. Detailed Description

[0072] The present invention relates to a solid material of the following formula (I):

[0073] Li 6-3x-4y RE x T y X6(I)

[0074] Where:

[0075] - X is a halogen;

[0076] - 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;

[0077] - 0 ≤ y ≤ 0.8; preferably 0.1 ≤ y ≤ 0.7; more preferably 0.2 ≤ y ≤ 0.6;

[0078] - RE represents two or more rare earth metals; these rare earth metals are different from each other; and

[0079] - T is Zr or Hf;

[0080] The prerequisite is that when y = 0 and RE represents two rare earth metals, if one rare earth metal is Y, then the other rare earth metal is selected from the group consisting of Gd, Yb, Ho, Er, Dy, Ce, Tb, and Nd.

[0081] In the first embodiment of the present invention, y = 0 and the solid material has the formula (Ia)

[0082] Li 6-3x RE x X6(Ia)

[0083] Where:

[0084] - X is a halogen;

[0085] - 0 ≤ x ≤ 2; preferably 0.8 ≤ x ≤ 1.5; more preferably 0.95 ≤ x ≤ 1.25; and

[0086] - RE represents two or more rare earth metals; these rare earth metals are different from each other; the prerequisite is that when RE represents two rare earth metals, if one rare earth metal is Y, then the other rare earth metal is selected from the group consisting of Gd, Yb, Ho, Er, Dy, Ce, Tb, and Nd.

[0087] The solid material of the present invention is electrically neutral. It should be understood that the formula (I) / (Ia) is an empirical formula (approximate formula) determined by elemental analysis. Therefore, the formula (I) defines the composition averaged over all phases present in the solid material.

[0088] These 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).

[0089] X is a halogen selected from the group consisting of F, Cl, I, and Br, and X is preferably Cl or Br.

[0090] In the formula (Ia): 0 < x < 2; preferably 0.8 ≤ x ≤ 1.5; more preferably 0.95 ≤ x ≤ 1.25. Specifically, 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 formed by these values.

[0091] The solid materials of the present invention can be amorphous (glass) and / or crystalline (glass-ceramic). The solid materials can only be partially crystalline. The crystalline part of the solid materials can include only one crystal structure or can include multiple crystal structures. The contents of the amorphous and crystalline components in the solid materials can be evaluated by the whole powder pattern fitting (WPPF) technique with Al2O3 crystals, which are typical reference materials, as described in "RSC Adv., 2019, 9, 14465". The solid materials of the present invention preferably include a fraction composed of a glass phase.

[0092] The composition of the compounds of formula (I) / (Ia) can be determined by chemical analysis, for example, X-ray diffraction (XRD) and inductively coupled plasma mass spectrometry (ICP-MS), by techniques well-known to those skilled in the art.

[0093] Preferably, the average ionic radius of RE, i.e., the average ionic radius value of the rare earth metals, exhibits a value lower than the ionic radius value (in terms of ). Each of the rare earth metals constituting RE (e.g., RE1 and RE2) 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-fold coordination number 3+ ) in the compound. For example, according to the present invention, the average radius can be equal to:

[0094] where RE1 is Y (90% mol) and RE2 is Gd (10% mol);

[0095] where RE1 is Y (50% mol) and RE2 is Er (50% mol);

[0096] The solid materials of the present invention can have the following formula (II):

[0097] Li 6-3x-4y RE1 a RE2 b T y X6(II)

[0098] where:

[0099] - X is a halogen;

[0100] - 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;

[0101] - 0 ≤ y ≤ 0.8; preferably 0.1 ≤ y ≤ 0.7; more preferably 0.2 ≤ y ≤ 0.6;

[0102] -a + b = x, where 0.05 ≤ a ≤ 0.95 and 0.0 < b ≤ 0.95; preferably 0.5 ≤ a ≤ 0.9 and 0.05 < b ≤ 0.5;

[0103] - RE1 is selected from the group consisting of: Y, Yb, Ho, Er;

[0104] - RE2 is selected from the group consisting of: Yb, Ho, Gd, Er, Sm, Dy, La, Nd, Ce, Tb; where RE1 and RE2 are different; and

[0105] - T is Zr or Hf,

[0106] 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.

[0107] When y = 0, the solid material has the following formula (IIa):

[0108] Li 6-3x RE1 a RE2 b X6 (IIa)

[0109] where:

[0110] - X is a halogen; ​​​​​​​​​​​​​​​​​​​​​​​Preferably, the solid material of formula (II) / (IIa) according to the present invention may be as follows:

[0118]

[0119] The solid material may also be a compound of formula (III) as follows:

[0120] Li 6-3x-4y RE1 a RE2 b RE3 c T y X6(III)

[0121] Where:

[0122] - X is a halogen;

[0123] - 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;

[0124] - 0 ≤ y ≤ 0.8; preferably 0.1 ≤ y ≤ 0.7; more preferably 0.2 ≤ y ≤ 0.6;

[0125] - a + b + c = x, where 0.05 ≤ a ≤ 0.95, 0.0 < b ≤ 0.95 and 0.0 < c ≤ 0.95, where 0.05 ≤ b + c;

[0126] - RE1 is selected from the group consisting of: Y, Yb, Ho, Er;

[0127] - RE2 is selected from the group consisting of: Yb, Ho, Gd, Er, Sm, Dy, La, Nd, Ce, Tb;

[0128] - RE3 is selected from the group consisting of: Ho, Gd, Er, Sm, Dy, La, Nd, Ce, Tb;

[0129] Where RE1, RE2 and RE3 are different; and

[0130] - T is Zr or Hf.

[0131] When y = 0, the solid material is a compound of formula (IIIa) as follows:

[0132] Li 6-3x RE1 a RE2 b RE3 c X6(IIIa)

[0133] Where:

[0134] - X is a halogen;

[0135] -0 < x < 2; preferably 0.8 ≤ x ≤ 1.5; more preferably 0.95 ≤ x ≤ 1.25;

[0136] -a + b + c = x, where 0.05 ≤ a ≤ 0.95, 0.0 < b ≤ 0.95 and 0.0 < c ≤ 0.95, where 0.05 ≤ b + c;

[0137] -RE1 is selected from the group consisting of: Y, Yb, Ho, Er;

[0138] -RE2 is selected from the group consisting of: Yb, Ho, Gd, Er, Sm, Dy, La, Nd, Ce, Tb; and

[0139] -RE3 is selected from the group consisting of: Ho, Gd, Er, Sm, Dy, La, Nd, Ce, Tb; where RE1, RE2 and RE3 are different.

[0140] Preferably, the average ionic radius of RE, i.e., the average ionic radius values of rare earth metals RE1, RE2 and RE3, exhibit a value lower than of the ionic radius value (in terms of).

[0141] Preferably, the solid material of formula (III) / (IIIa) according to the present invention can be as follows:

[0142]

[0143] The solid material of the present invention can also be a compound of formula (IV) as follows:

[0144] Li 6-3x-4y RE1 a RE2 b RE3 c RE4 d T y X6(IV)

[0145] where:

[0146] -X is a halogen;

[0147] -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;

[0148] -0 ≤ y ≤ 0.8; preferably 0.1 ≤ y ≤ 0.7; more preferably 0.2 ≤ y ≤ 0.6;

[0149] -a + b + c + d = x, where 0.05 ≤ a ≤ 0.95, 0.0 < b ≤ 0.95, 0.0 < c ≤ 0.95, and 0.0 < d ≤ 0.95, and 0.05 ≤ b + c + d;

[0150] - RE1 is selected from the group consisting of: Y, Yb, Ho, Er;

[0151] - RE2 is selected from the group consisting of: Yb, Ho, Gd, Er, Sm, Dy, La, Nd, Ce, Tb;

[0152] - RE3 is selected from the group consisting of: Ho, Gd, Er, Sm, Dy, La, Nd, Ce, Tb;

[0153] - RE4 is selected from the group consisting of: Er, Gd, Sm, Dy, La, Nd, Ce, Tb; where RE1, RE2, RE3, and RE4 are different; and

[0154] - T is Zr or Hf.

[0155] When y = 0, the solid material is a compound of formula (IVa) as follows:

[0156] Li 6-3x RE1 a RE2 b RE3 c RE4 d X6(IVa)

[0157] where

[0158] - X is a halogen;

[0159] - 0 < x < 2; preferably 0.8 ≤ x ≤ 1.5; more preferably 0.95 ≤ x ≤ 1.25;

[0160] - a + b + c + d = x, where 0.05 ≤ a ≤ 0.95, 0.0 < b ≤ 0.95, 0.0 < c ≤ 0.95, and 0.0 < d ≤ 0.95, and 0.05 ≤ b + c + d;

[0161] - RE1 is selected from the group consisting of: Y, Yb, Ho, Er;

[0162] - RE2 is selected from the group consisting of: Yb, Ho, Gd, Er, Sm, Dy, La, Nd, Ce, Tb;

[0163] - RE3 is selected from the group consisting of: Ho, Gd, Er, Sm, Dy, La, Nd, Ce, Tb; and

[0164] - RE4 is selected from the group consisting of: Gd, Er, Sm, Dy, La, Nd, Ce, Tb; wherein RE1, RE2, R3 and RE4 are different.

[0165] Preferably, the average ionic radius of RE, i.e., the average ionic radius values of rare earth metals RE1, RE2, RE3 and RE4, exhibit a value lower than the ionic radius value (in terms of).

[0166] Preferably, the solid material of formula (IV) / (IVa) according to the present invention can be as follows:

[0167]

[0168] The solid material of the present invention can also be a compound of formula (V) as follows:

[0169] Li 6-3x-4y RE1 a RE2 b RE3 c RE4 d RE5 e T y X6(V)

[0170] Wherein:

[0171] - X is a halogen,

[0172] - 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;

[0173] - 0 ≤ y ≤ 0.8; preferably 0.1 ≤ y ≤ 0.7; more preferably 0.2 ≤ y ≤ 0.6;

[0174] - 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 and 0.0 < e ≤ 0.95, where 0.05 ≤ b + c + d + e;

[0175] - RE1 is selected from the group consisting of: Y, Yb, Ho, Er;

[0176] - RE2 is selected from the group consisting of: Yb, Ho, Gd, Er, Sm, Dy, La, Nd, Ce, Tb;

[0177] - RE3 is selected from the group consisting of: Ho, Gd, Er, Sm, Dy, La, Nd, Ce, Tb;

[0178] - RE4 is selected from the group consisting of: Er, Gd, Sm, Dy, La, Nd, Ce, Tb; and

[0179] - RE5 is selected from the group consisting of: Gd, Sm, Dy, La, Nd, Ce, Tb; wherein RE1, RE2, RE3, RE4 and RE5 are different; and

[0180] - T is Zr or Hf.

[0181] When y = 0, the solid material is a compound of the following formula (Va):

[0182] Li 6-3x RE1 a RE2 b RE3 c RE4 d RE5 e X6(Va)

[0183] wherein

[0184] - X is a halogen;

[0185] - 0 < x < 2; preferably 0.8 ≤ x ≤ 1.5; more preferably 0.95 ≤ x ≤ 1.25;

[0186] - 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 and 0.0 < e ≤ 0.95, where 0.05 ≤ b + c + d + e;

[0187] - RE1 is selected from the group consisting of: Y, Yb, Ho, Er;

[0188] - RE2 is selected from the group consisting of: Yb, Ho, Gd, Er, Sm, Dy, La, Nd, Ce, Tb;

[0189] - RE3 is selected from the group consisting of: Ho, Gd, Er, Sm, Dy, La, Nd, Ce, Tb;

[0190] - RE4 is selected from the group consisting of: Er, Gd, Sm, Dy, La, Nd, Ce, Tb; and

[0191] - RE5 is selected from the group consisting of: Gd, Sm, Dy, La, Nd, Ce, Tb; wherein RE1, RE2, R3, R4 and RE5 are different.

[0192] Preferably, the average ionic radius of RE, i.e., the average ionic radius values of rare earth metals RE1, RE2, RE3, RE4 and RE5, exhibit lower than ionic radius values ​​(in terms of count).

[0193] Preferably, the solid material according to the formula (V) / (Va) of the present invention can be as follows:

[0194]

[0195]

[0196] Preferably, the solid material of the present invention is selected from the group consisting of: Li3Y 0.9 Gd 0.1 Cl6;Li3Y 0.3 Er 0.3 Yb 0.3 Gd 0.1 Cl6, Li 2.7 Y1Gd 0.1 Cl6;Li3Y 0.5 Er 0.5 Cl6;Li3Y 0.45 Er 0.45 Gd 0.1 Cl6; and Li3Y 0.45 Er 0.45 La 0.1 Cl6.

[0197] The solid material of the present invention can be in powder form having a particle diameter distribution with a D50 preferably included between 0.05 μm and 10 μm. The particle size can be estimated using SEM image analysis or laser diffraction analysis.

[0198] D50 has a commonly used meaning in the field of particle size distribution. Dn corresponds to a particle diameter for which n% of the particles have a diameter smaller than Dn. D50 (median) is defined as the size value corresponding to the 50% of the cumulative distribution. These parameters are typically determined by the volume distribution of the diameter of a dispersion of solid material particles in solution, obtained using a laser diffractometer and a standard procedure pre-defined in the instrument software. A laser diffractometer measures particle size by measuring the intensity of diffracted light as a laser beam passes through a dispersed particulate sample. A laser diffractometer can be, for example, the Mastersizer 3000 manufactured by Malvern.

[0199] In particular, D50 can be measured after ultrasonic treatment. Ultrasonic treatment involves inserting an ultrasonic sample into a dispersion of a solid material in a solution and subjecting the dispersion to ultrasound.

[0200] The present invention also relates to a method for producing the solid materials of the present invention, particularly solid materials of formulas (I), (Ia), (II), (IIa), (III), (IIIa), (IV), (IVa), (V), and (Va) as previously described, the method comprising reacting at least lithium halide and at least two different rare earth metal halides optionally in one or more solvents, wherein the rare earth metals in the at least two different rare earth metal halides are different from each other and optionally are zirconium halide or hafnium halide.

[0201] In particular, one or more lithium halides can be used.

[0202] The solid material of the present invention can be produced by any method known in the art for producing glass solid electrolytes, such as melt extraction, mechanical milling, or slurry method in which the raw materials are optionally reacted in one or more solvents.

[0203] Preferably, the solid materials of formulas (I), (Ia), (II), (IIa), (III), (IIIa), (IV), (IVa), (V) and (Va) as previously described can be produced by dry or wet mechanical synthesis.

[0204] The present invention then relates to a process for preparing solid materials as previously described, particularly solid materials according to formulas (I), (Ia), (II), (IIa), (III), (IIIa), (IV), (IVa), (V), and (Va), said process comprising the following steps:

[0205] a) A composition is obtained by mixing stoichiometric amounts of lithium halide and at least two different rare earth metal halides, optionally in one or more solvents under an inert atmosphere, wherein the rare earth metals in the at least two different rare earth metal halides are different from each other and optionally are zirconium halide or hafnium halide.

[0206] b) Apply mechanical treatment to the composition obtained in step a) to obtain the solid material; and

[0207] c) Optionally, remove at least a portion of the one or more solvents from the composition obtained in step b) to obtain the solid material.

[0208] The inert atmosphere used in step a) refers to the use of an inert gas, i.e., a gas that does not undergo an unfavorable chemical reaction under reaction conditions. Inert gases are generally used to avoid unwanted chemical reactions, such as oxidation and hydrolysis reactions with oxygen and water vapor in the air. Therefore, an inert gas means a gas that does not react chemically with other reactants present in a particular chemical reaction. In the context of 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, which contain water (including condensation) in liquid and gaseous forms below 1000 ppm. The gas may also be pressurized.

[0209] Preferably, stirring is performed when the raw materials are brought into contact with each other in an inert gas atmosphere such as nitrogen or argon. The dew point of the inert gas is preferably -20°C or lower, particularly preferably -40°C or lower. The pressure can be from 0.0001 Pa to 100 MPa, preferably from 0.001 Pa to 20 MPa, and more preferably from 0.01 Pa to 0.5 MPa.

[0210] Preferably, in step a), the inert atmosphere includes an inert gas such as dry N2, dry argon, or dry air (dry can refer to a gas having less than 800 ppm of water (including condensation) in both liquid and gaseous forms).

[0211] The composition ratio of each element can be controlled by adjusting the amount of raw material compounds during the production of solid materials. The precursors and their molar ratios are selected based on the target stoichiometry. The target stoichiometry defines the ratio between elements Li, RE, T, and X, and can be derived from the amount of precursors applied under conditions of complete conversion without side reactions and other losses.

[0212] Lithium halides are compounds comprising one or more sulfur atoms and one or more halogen atoms, or alternatively, one or more halogen-containing ionic groups and one or more lithium-containing ionic groups. In some preferred aspects, lithium halides may consist of halogen atoms and lithium atoms. Preferably, lithium halides are LiCl, LiBr, LiF, and LiI.

[0213] Rare earth metal halide compounds are compounds containing one or more halogen atoms (such as F, Cl, Br, or I) bonded via chemical bonds (e.g., ionic or covalent bonds) to other atoms constituting the compound. In some preferred aspects, the halogen compound may contain one or more of F, Cl, Br, and I, or combinations thereof, and one or more rare earth metal atoms. Non-limiting examples may suitably include YCl3, ErCl3, YbCl3, GdCl3, LaCl3, YBr3, ErBr3, YbBr3, GdBr3, and LaBr3. Mixed rare earth halides REX3 may also be used as precursors; non-limiting examples are (Y, Yb, Er)Cl3 and (La, Y)Cl3. Rare earth metal halide compounds are 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.

[0214] It is entirely possible to use one or more rare earth metal halides, where the rare earth metals are particularly different from one another.

[0215] Lithium halides and rare earth halides preferably have an average particle diameter ranging from 0.5 μm to 400 μm. The particle size can be estimated using SEM image analysis or laser diffraction analysis.

[0216] Dopants, preferably anisovalent dopants such as zirconium and hafnium, can also be added to the composition in step a) to create lithium vacancies. Any zirconium halide or hafnium halide containing one or more halogen atoms (such as F, Cl, Br, or I) added to the composition in step a) is suitable for this purpose. ZrCl4 is preferred to be added to the composition in step a).

[0217] The composition in step a) may also include one or more solvents. The solvent may be suitably selected from one or more polar or nonpolar solvents that do not dissolve lithium halides and rare earth metal halides.

[0218] Then, in step a), the solvent of the present invention forms a continuous phase having one or more of the above-mentioned components.

[0219] Then, depending on the components and solvent, some of these components are dissolved, partially dissolved, or in the form of a slurry. (That is, one or more components remain undissolved and then form a slurry with the solvent).

[0220] In a preferred aspect, the solvent may suitably 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.

[0221] It should be understood that the term "solvent" as used in this article includes one or more mixed solvents.

[0222] Based on the total weight of the powder mixture and the solvent, approximately 1 wt% to 80 wt% of the powder mixture and approximately 20 wt% to 99 wt% of the solvent can be mixed. Preferably, based on the total weight of the powder mixture and the solvent, approximately 25 wt% to 75 wt% of the powder mixture and approximately 25 wt% to 75 wt% of the solvent can be mixed. In particular, based on the total weight of the powder mixture and the solvent, approximately 40 wt% to 60 wt% of the powder mixture and approximately 40 wt% to 60 wt% of the solvent can be mixed.

[0223] In the presence of a solvent, the temperature of step a) is preferably between the melting temperature and boiling temperature of the selected solvent, a temperature at which there is no undesirable reactivity between the solvent and the mixed compound. Step a) is preferably performed between -20°C and 40°C, and more preferably between 15°C and 40°C. In the absence of a solvent, step a) is performed at a temperature between -20°C and 200°C, and preferably between 15°C and 40°C.

[0224] The duration of step a) is preferably between 1 minute and 1 hour.

[0225] The mechanical treatment of the composition in step b) can be carried out by wet or dry milling; in particular by adding the powder mixture to a solvent and then milling at about 100 rpm to 1000 rpm, especially for a duration of from 10 minutes to 80 hours, more preferably for a duration of about 4 hours to 40 hours.

[0226] The milling process is also known as reactive milling in the conventional synthesis of lithium rare earth halides.

[0227] Mechanical milling also has the advantage that pulverization occurs simultaneously with the production of the glass mixture. Various methods can be used in mechanical milling, such as rotary ball milling, drum ball milling, vibratory ball milling, and planetary ball milling. Mechanical milling can be carried out with or without ZrO2 balls.

[0228] Under these conditions, lithium halides and rare earth halides are allowed to react for a predetermined period of time.

[0229] In the presence of a solvent, the temperature of step b) is between the melting temperature and boiling temperature of the selected solvent, a temperature at which there is no undesirable reactivity between the solvent and the compound. Step b) is preferably performed at a temperature between -20°C and 80°C, and more preferably between 15°C and 40°C. In the absence of a solvent, step a) is performed at a temperature between -20°C and 200°C, and preferably between 15°C and 40°C.

[0230] At the end of step b), a paste or a blend of paste and liquid solvent is usually obtained.

[0231] Optionally, in step c), at least a portion of the solvent may be completely removed, for example, to remove at least about 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, or 100% of the total weight of the solvent used, or any range between these values, such as from 30% to 100% or 50% to 90%. Solvent removal can be carried out by methods known in the art, such as decantation, filtration, centrifugation, drying, or combinations thereof.

[0232] When filtration is chosen as the method for removing solvent, it is preferable to select a temperature below the boiling point and as a function of the vapor partial pressure of the selected solvent.

[0233] The duration is between 1 second and 100 hours, preferably between 1 hour and 20 hours. Such a short duration can be obtained, for example, by using flash evaporation, such as by spray drying.

[0234] Solvent removal can be carried out in an inert gas atmosphere such as nitrogen or argon. The dew point of the inert gas is preferably -20°C or lower, particularly preferably -40°C or lower. The pressure can be from 0.0001 Pa to 100 MPa, preferably from 0.001 Pa to 20 MPa, and even more preferably from 0.01 Pa to 20 MPa. The pressure range is particularly from 0.0001 Pa to 0.001 Pa, especially by using ultravacuum techniques. By using primary vacuum techniques, the pressure range is particularly from 0.01 Pa to 0.1 MPa.

[0235] It is also entirely possible to heat the solid material after step b) or step c). Heating or heat treatment, in particular, can allow the amorphous powder mixture (glass) obtained as above to be transformed into a solid material crystal or a mixture of glass and crystal (glass ceramic).

[0236] Heat treatment is performed at temperatures ranging from 50°C to 700°C, particularly for durations from 1 minute to 100 hours, preferably from 30 minutes to 20 hours. In some embodiments, heat treatment is performed at temperatures ranging from 100°C to 400°C. In some other embodiments, heat treatment is performed at temperatures ranging from 150°C to 300°C. Heat treatment can be initiated directly at high temperatures or through a temperature gradient at a rate between 1°C / minute and 20°C / minute. Heat treatment can be performed using quenching with air, natural cooling from the heating temperature, or through a controlled temperature gradient at a rate between 1°C / minute and 20°C / minute.

[0237] The treatment can be carried out under an inert atmosphere, including, for example, dry N2 or dry argon (dry can refer to a gas having less than 800 ppm of water in liquid and gaseous forms (including condensation)). Preferably, the inert atmosphere is a protective gas atmosphere used to minimize, and preferably exclude, the ingress of oxygen and water vapor.

[0238] The pressure during heating can be normal pressure or reduced pressure. The atmosphere can be an inert gas, such as nitrogen or argon. The dew point of the inert gas is preferably -20°C or lower, particularly preferably -40°C or lower. The pressure can be from 0.0001 Pa to 100 MPa, preferably from 0.001 Pa to 20 MPa, and even more preferably from 0.01 Pa to 20 MPa. The pressure range can be particularly from 0.0001 Pa to 0.001 Pa, especially by using ultravacuum techniques. By using primary vacuum techniques, the pressure range can be particularly from 0.01 Pa to 0.1 MPa.

[0239] The solid material can also be processed to a desired particle size distribution, especially after step b), step c), or heat treatment. If necessary, the solid material obtained by the process of the present invention as described above is ground (milled) into powder. 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 determined by means of dynamic light scattering or image analysis.

[0240] Preferably, the powder has a D90 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 determined by means of dynamic light scattering or image analysis. The powder particularly has a D90 value encompassing a particle size distribution from 1 μm to 100 μm.

[0241] In some embodiments of the process in which the process 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 mechanical synthesis.

[0242] Then, the present invention relates to a process for preparing the solid materials described, in particular solid materials according to formulas (I), (Ia), (II), (IIa), (III), (IIIa), (IV), (IVa), (V) and (Va), the process comprising the following steps:

[0243] a) obtaining a composition by mixing a stoichiometric amount of lithium halide, at least one rare earth metal halide and optionally zirconium halide or hafnium halide in one or more solvents under an inert atmosphere;

[0244] b) subjecting the composition obtained in step a) to mechanical treatment in order to obtain the solid material; and

[0245] c) removing at least a portion of the one or more solvents from the composition obtained in step b) to obtain the solid material.

[0246] The present invention also relates to a process for preparing a solid material according to the following general formula (I):

[0247] Li 6-3x-4y RE x T y X6(I)

[0248] where:

[0249] - X is a halogen;

[0250] - 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;

[0251] - 0 ≤ y ≤ 0.8; preferably 0.1 ≤ y ≤ 0.7; more preferably 0.2 ≤ y ≤ 0.6;

[0252] - RE represents one or more rare earth metals; these rare earth metals are different from each other; and

[0253] - T is Zr or Hf;

[0254] The process comprises the following steps:

[0255] a) obtaining a composition by mixing a stoichiometric amount of lithium halide, at least one rare earth metal halide and optionally zirconium halide or hafnium halide in one or more solvents under an inert atmosphere;

[0256] b) subject the composition obtained in step a) to a mechanical treatment in order to obtain the solid material; and

[0257] c) remove at least a portion of the one or more solvents from the composition obtained in step b), thereby obtaining the solid material.

[0258] Thus, the present invention also relates to a process for preparing a solid material according to any of the following general formulas (II) to (V):

[0259] Li 6-3x-4y RE1 a RE2 b T y X6(II)

[0260] where a + b = x, where 0.05 ≤ a ≤ 0.95 and 0.0 < b ≤ 0.95; preferably 0.5 ≤ a ≤ 0.9 and 0.05 < b ≤ 0.5;

[0261] Li 6-3x-4y RE1 a RE2 b RE3 c T y X6(III)

[0262] where a + b + c = x, where 0.05 ≤ a ≤ 0.95, 0.0 < b ≤ 0.95 and 0.0 < c ≤ 0.95, where 0.05 ≤ b + c;

[0263] Li 6-3x-4y RE1 a RE2 b RE3 c RE4 d T y X6(IV)

[0264] where a + b + c + d = x, where 0.05 ≤ a ≤ 0.95, 0.0 < b ≤ 0.95, 0.0 < c ≤ 0.95 and 0.0 < d ≤ 0.95, where 0.05 ≤ b + c + d;

[0265] Li 6-3x-4y RE1 a RE2 b RE3 c RE4 d RE5 e T y X6(V)

[0266] where 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 and 0.0 < e ≤ 0.95, where 0.05 ≤ b + c + d + e; and

[0267] where

[0268] - X is a halogen;

[0269] - 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;

[0270] - 0 ≤ y ≤ 0.8; preferably 0.1 ≤ y ≤ 0.7; more preferably 0.2 ≤ y ≤ 0.6;

[0271] - RE1 is selected from the group consisting of: Y, Yb, Ho, Er;

[0272] - RE2 is selected from the group consisting of: Yb, Ho, Gd, Er, Sm, Dy, La, Nd, Ce, Tb;

[0273] - RE3 is selected from the group consisting of: Ho, Gd, Er, Sm, Dy, La, Nd, Ce, Tb;

[0274] - RE4 is selected from the group consisting of: Er, Gd, Sm, Dy, La, Nd, Ce, Tb; and

[0275] - RE5 is selected from the group consisting of: Gd, Sm, Dy, La, Nd, Ce, Tb; where RE1, RE2, RE3, RE4 and RE5 are different; and

[0276] - T is Zr or Hf;

[0277] The process comprises the following steps:

[0278] a) obtaining a composition by mixing stoichiometric amounts of lithium halide, at least two different rare earth metal halides in one or more solvents under an inert atmosphere, wherein the rare earth metals in the at least two different rare earth metal halides are different from each other and optionally zirconium halide or hafnium halide;

[0279] b) subjecting the composition obtained in step a) to mechanical treatment in order to obtain the solid material; and

[0280] c) removing at least a portion of the one or more solvents from the composition obtained in step b), thereby obtaining the solid material.

[0281] The present invention also relates to a solid material that is readily obtained by the process described.

[0282] The present invention also relates to a solid material as previously described and obtainable by the process according to the present invention, such as solid materials of formula (I), (Ia), (II), (IIa), (III), (IIIa), (IV), (IVa), (V), and (Va), as a solid electrolyte, and to a solid electrolyte comprising at least the solid material as previously described and obtainable by the process according to the present invention, such as solid materials of formula (I), (Ia), (II), (IIa), (III), (IIIa), (IV), (IVa), (V), and (Va).

[0283] Then, the solid electrolyte comprises at least solid materials of formulas (I), (Ia), (II), (IIa), (III), (IIIa), (IV), (IVa), (V), and (Va) and optionally comprises another solid electrolyte, such as lithium silver germanium sulfide, lithium thiophosphate, such as glass or glass-ceramic sulfides Li3PS4 and Li7PS4. 11 And lithium-conducting oxides such as lithium-filled garnet Li7La3Zr2O 12 (LLZO).

[0284] The solid electrolyte may optionally include polymers such as styrene-butadiene rubber, organic or inorganic stabilizers such as SiO2, or dispersants.

[0285] The present invention also relates to an electrochemical device comprising a solid electrolyte comprising at least a solid material as previously described and obtainable by the process according to the present invention, such as solid materials of formulas (I), (Ia), (II), (IIa), (III), (IIIa), (IV), (IVa), (V), and (Va).

[0286] Preferably, in the electrochemical device, particularly the rechargeable electrochemical device, the solid electrolyte is a component of the solid structure of the electrochemical device selected from the group consisting of a cathode, an anode, and a diaphragm.

[0287] Preferably, the solid electrolyte is a component of the solid structure of the electrochemical device, wherein the solid structure is selected from the group consisting of a cathode, an anode, and a diaphragm. Therefore, the solid material according to the invention can be used alone or in combination with additional components for producing solid structures (such as cathodes, anodes, or diaphragms) of electrochemical devices.

[0288] The electrode that exhibits a net negative charge during discharge is called the anode, while the electrode that exhibits a net positive charge during discharge is called the cathode. A diaphragm electronically isolates the cathode and anode from each other in an electrochemical device.

[0289] 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-type carbon, metallic lithium, silicon compounds such as Si, SiO x , lithium titanate such as Li4Ti5O 12 or a metal alloy such as Sn including lithium as the anode active material.

[0290] In the electrochemical device according to the present invention, the anode preferably comprises a metal chalcogenide having the formula LiMQ2, wherein M is at least one metal selected from transition metals such as Co, Ni, Fe, Mn, Cr and V, and Q is a chalcogen element such as O or S. Among these, lithium-based composite metal oxides having the formula LiMO2, wherein M is as defined above, are preferably used. Preferred examples thereof may include LiCoO2, LiNiO2, LiNi x [[ID=e11]]Co 1-x O2 (0 < x < 1) and spinel-structured LiMn2O4. Another preferred example thereof may include a lithium-nickel-manganese-cobalt-based metal oxide having the formula LiNi x Mn y Co z O2 (x + y + z = 1, referred to as NMC) such as 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 having the formula LiNi x Co y Al z O2 (x + y + z = 1, referred to as NCA) such as LiNi 0.8 Co 0.15 Al 0.05 O2. The cathode may comprise a material based on lithiated or partially lithiated transition metal oxyanions, such as LiFePO4.

[0291] For example, the electrochemical device has a cylindrical or prismatic shape. The electrochemical device may comprise a housing that may be formed of steel or aluminum or a multilayer film polymer / metal foil.

[0292] Another aspect of the present invention relates to a battery, more preferably to an alkali metal battery, and specifically to a lithium battery comprising at least one (e.g., two or more) electrochemical devices of the present invention. The electrochemical devices may be combined with each other in the alkali metal battery of the present invention, for example, connected in series or in parallel.

[0293] The present invention also relates to a solid-state battery comprising a solid electrolyte comprising at least a solid material as previously described and obtainable by the process according to the present invention, such as solid materials of formulas (I), (Ia), (II), (IIa), (III), (IIIa), (IV), (IVa), (V), and (Va).

[0294] 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 includes a solid electrolyte as defined above.

[0295] In addition to the active cathode material, the cathode of an all-solid-state electrochemical device typically includes a solid electrolyte as another component. Similarly, in addition to the active anode material, the anode of an all-solid-state electrochemical device typically also includes a solid electrolyte as another component.

[0296] The form of the solid structure of an electrochemical device, particularly an all-solid-state lithium battery, depends specifically on the form of the resulting electrochemical device itself. The present invention also provides a solid structure for an electrochemical device, wherein the solid structure is selected from the group consisting of a cathode, an anode, and a separator, and wherein the solid structure for the electrochemical device comprises a solid material according to the present invention.

[0297] Multiple electrochemical cell units can be combined to form an all-solid-state battery with both solid electrodes and solid electrolytes.

[0298] The solid materials disclosed above can be used to prepare electrodes. The electrodes can be positive or negative electrodes.

[0299] This electrode typically includes at least:

[0300] -Metal substrate;

[0301] - At least one layer directly attached to the metal substrate, said layer being made of a composition comprising:

[0302] (i) Solid materials as previously described and obtainable by the process according to the invention, such as solid materials having formulas (I), (Ia), (II), (IIa), (III), (IIIa), (IV), (IVa), (V) and (Va);

[0303] (ii) at least one electroactive compound (EAC);

[0304] (iii) Optionally at least one lithium-ion conductive material (LiCM) other than the solid material of the present invention;

[0305] (iv) Optionally, at least one electroconductive material (ECM);

[0306] (v) Optionally, a lithium salt (LIS); and

[0307] (vi) Optionally, at least one polymeric binder material (P).

[0308] An electroactive compound (EAC) means a compound that can incorporate or insert lithium ions into its structure and release lithium ions during the charging and discharging stages of an electrochemical device. The EAC can be a compound that can intercalate lithium ions into its structure and deintercalate lithium ions. For the positive electrode, the EAC can be a complex metal chalcogenide having the formula LiMeQ2, where:

[0309] - Me is at least one metal selected from the group consisting of Co, Ni, Fe, Mn, Cr, Al, and V;

[0310] - Q is a chalcogen element such as O or S.

[0311] More specifically, the EAC can have 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), such as 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) and spinel-structured LiMn2O4 and Li(Ni 0.5 Mn 1.5 )O4.

[0312] The EAC can also be an electroactive material based on lithiated or partially lithiated transition metal oxyanions having the formula M1M2(JO4) f E 1-f where:

[0313] - M1 is lithium, which can be partially replaced by another alkali metal representing less than 20% of M1;

[0314] -M2 is a transition metal selected from Fe, Co, Mn, Ni or mixtures thereof with an oxidation state of +2, which may be partially replaced by one or more additional metal portions with an oxidation state between +1 and +5 and representing less than 35% (inclusive) of the M2 metal.

[0315] -JO4 is any oxygen anion in which J is P, S, V, Si, Nb, Mo or a combination thereof;

[0316] -E is a fluoride anion, hydroxide anion, or chloride anion;

[0317] -f is the mole fraction of the JO4 oxoanion, which is usually included between 0.75 and 1.

[0318] As defined above, M1M2(JO4) f E 1-f Electroactive materials are preferably phosphate-based. They can exhibit ordered or modified olivine structures.

[0319] For the positive electrode, EAC can also be sulfur or Li2S.

[0320] For the cathode, EAC can also be a conversion material such as FeS2, FeF2, or FeF3.

[0321] For the negative electrode, EAC can be selected from the group consisting of graphitic carbon capable of lithium intercalation. More details about such EACs can be found in Carbon 2000, 38, 1031-1041. Such EACs typically exist in the form of powder, flakes, fibers, or spheres (e.g., mesophase carbon microspheres).

[0322] EAC can also be: lithium metal; lithium alloy compositions (e.g., described in US 6,203,944 and WO 00 / 03444); lithium titanate, typically in the form of Li4Ti5O 12 These compounds are generally considered to be "zero-strain" intercalation materials, absorbing mobile ions, i.e., Li... + It exhibits low levels of physical expansion; lithium-silicon alloys, often referred to as lithium silicides with high Li / Si ratios, are particularly suitable for lithium with the formula Li 4.4 Lithium silicide of Si, and lithium-germanium alloys, including those with the formula Li 4.4 The crystal phase of Ge. EAC can also be based on composite materials of carbon-containing materials with silicon and / or silicon oxides, especially graphitic carbon / silicon and graphitic / silicon oxide, wherein the graphitic carbon consists of one or more carbons capable of lithium intercalation.

[0323] Electrically conductive carbon-containing materials (ECMs) are typically selected from the group consisting of electrically conductive carbon-containing materials and metal powders or fibers. Electrically conductive carbon-containing materials can be selected, for example, from the group consisting of carbon black, carbon nanotubes, graphite, graphene, and graphite fibers, and combinations thereof. Examples of carbon black include Ketjen black and acetylene black. Metal powders or fibers include nickel and aluminum powders or fibers.

[0324] Lithium salts (LIS) can be selected from the group consisting of: LiPF6, lithium bis(trifluoromethanesulfonate)imide, lithium bis(fluorosulfonate)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-dicyanimidazolium.

[0325] The function of a polymeric binder (P) is to hold the components of a composition together. Polymeric binders are typically inert. They are preferably also chemically stable and conducive to electron and ion transport. Polymeric binders are well known in the art. Non-limiting examples of polymeric binders include, in particular, (co)polymers based on vinylidene fluoride (VDF), styrene-butadiene rubber (SBR), styrene-ethylene-butene-styrene (SEBS), carboxymethyl cellulose (CMC), polyamide-imide (PAI), poly(tetrafluoroethylene) (PTFE), and poly(acrylonitrile) (PAN) (co)polymers.

[0326] The proportion of the solid material in the composition of this invention can be between 0.1 wt% and 80 wt% based on the total weight of the composition. Specifically, this proportion can be between 1.0 wt% and 60 wt%, more specifically between 5 wt% and 30 wt%. The thickness of the electrode is not particularly limited and should be adapted to the energy and power required in the application. For example, the thickness of the electrode can be between 0.01 mm and 1,000 mm.

[0327] Inorganic material M can also be used to prepare separators. A separator is a membrane that allows ions to pass through, 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.

[0328] The diaphragm of the present invention typically comprises at least:

[0329] - Solid materials as previously described and obtainable by the process according to the invention, such as solid materials of formulas (I), (Ia), (II), (IIa), (III), (IIIa), (IV), (IVa), (V) and (Va);

[0330] -Optionally at least one polymeric bonding material (P);

[0331] -Optionally at least one metal salt, especially a lithium salt; and

[0332] -Optionally, at least one plasticizer.

[0333] Electrodes and membranes can be prepared using methods well known to those skilled in the art. Typically, the components are mixed in a suitable solvent and then the solvent is removed. A suitable solvent is inert to the solid materials of the present invention and therefore does not dissolve the solid materials. Solvents used to prepare the solid materials of the present invention can also be used to prepare electrode or membrane layers; for example, xylene.

[0334] For example, electrodes can be fabricated using a process that includes the following steps:

[0335] - Apply a slurry comprising the components of the composition and at least one solvent onto a metal substrate;

[0336] - Remove the solvent.

[0337] Commonly used techniques known to those skilled in the art include coating and calendering, dry and wet extrusion, 3D printing, and sintering of porous foam followed by impregnation. Common techniques for fabricating electrodes and diaphragms are described in the Journal of Power Sources, 2018, 382, ​​160-175.

[0338] Electrochemical devices, especially batteries (such as solid-state batteries as described herein), can be used in the manufacture or operation of automobiles, computers, personal digital assistants, mobile phones, watches, portable video cameras, digital cameras, thermometers, calculators, laptop BIOS, communication equipment or remote car locks, as well as stationary applications such as energy storage devices for power plants.

[0339] Electrochemical devices, particularly batteries (such as solid-state batteries as described herein), can be used in motor vehicles, electrically operated bicycles, robots, aircraft (e.g., unmanned aerial vehicles including drones), ships, or stationary energy storage devices. Preferred are mobile devices, such as vehicles, bicycles, aircraft, or water vehicles such as boats or ships. Other examples of mobile devices are portable mobile devices, such as computers, especially laptops, telephones, or power tools, such as those from the construction industry, especially drill bits, battery-powered screwdrivers, or battery-powered nailers.

[0340] If any disclosure of any patent, patent application, or publication incorporated herein by reference conflicts with the specification of this application to the extent that it may cause ambiguity in the terminology, then this specification shall take precedence. Attached Figure Description

[0341] Figure 1 : Powder XRD pattern of Li3YCl6 obtained by dry mechanochemistry in Example 1.

[0342] Figure 2 : Powder XRD pattern of Li3GdCl6 obtained by dry mechanochemistry in Example 2.

[0343] Figure 3 Li3Y obtained by dry mechanochemistry in Example 3 0.9 Gd 0.1 Powder XRD pattern of Cl6.

[0344] Figure 4 Li3Y obtained by dry mechanochemistry in Example 4 0.3 Er 0.3 Yb 0.3 Gd 0.1 Powder XRD pattern of Cl6.

[0345] Figure 5 In Example 5, Li was obtained via dry mechanochemistry. 2.7 YGd 0.1 Powder XRD pattern of Cl6.

[0346] Figure 6 In Example 6, Li3(Y) was obtained by wet mechanical chemistry. 0.45 Er 0.45 Gd 0.1 XRD pattern of Cl6 powder.

[0347] Figure 7 : Powder XRD pattern of Li3YCl6 obtained by wet mechanical chemistry in Example 8.

[0348] Experimental Section

[0349] The following examples are used to illustrate the present invention, but are not intended to be limiting.

[0350] X-ray diffraction

[0351] Using a Cu X-ray tube (Cu Kα wavelength is...) XRD diffraction patterns of the powder are obtained on an XRD goniometer with Bragg-Brentano geometry. This setup can be used in various optical configurations, i.e., with variable or fixed diverging slits (or Soler slits). Filtering devices on the master side, such as monochromators or Bragg-Brentano HD optics from Panalytical, can also be used. If a variable diverging slit is used, the typical illumination area is 10 mm x 10 mm. The sample holder is mounted on the rotator; the rotation speed during sampling is typically 60 rpm. For variable slit sampling, the tube is set to operate at 40 kV / 30 mA, while for fixed slit sampling with incident Bragg-Brentano HD optics, the tube is set to operate at 45 kV / 40 mA. The sampling step size is 0.017° per step. The angular range is typically 5° to 90° or greater in terms of 2θ. The total sampling time is typically 30 min or longer. The powder is covered with a Kapton film to prevent it from reacting with air and moisture.

[0352] Conductivity measurement

[0353] Conductivity was obtained on the pellets using a uniaxial press operating at 500 MPa. Pelletizing was performed using a laboratory-scale uniaxial press in a glovebox filled with anhydrous argon atmosphere. Two carbon paper foils (Papyex soft graphite N998 from Mersen, reference number: 496300120050000, 0.2 mm thick) were used as current collectors. Measurements were performed in a Swagelock cell with a manual spring-closed mechanism. Impedance spectra were acquired on a Biologic VMP3 apparatus, and temperature control was ensured via a Binder climate chamber. A two-hour duration was set to allow temperature equilibration between measurements. Impedance spectroscopy was performed in PEIS mode with an amplitude of 10 mV and a frequency range of 1 MHz to 1 kHz (25 points per decibel, with each frequency point representing the average of 50 measurements). Electronic conductivity was obtained by applying a potential difference of 1 V over a 2-minute period and measuring the resulting current to determine the electronic resistance of the pellets.

[0354] Example 1: Comparison - Li3YCl6 obtained by dry mechanochemistry

[0355] Precursor weighing and sample preparation were performed in an Ar-filled glovebox with oxygen and moisture levels below 1 ppm. In a typical experiment, 30 mL glass vials were used to weigh LiCl (≥99.9%, Sigma Aldrich, 1.98 g) and dry YCl3 (≥99%, Sigma Aldrich, 3.004 g) according to the target stoichiometric ratio Li3YCl6. The precursor used here was a powder with an average particle diameter ranging from 10 μm to 400 μm.

[0356] The sample was poured into a 20 mL ZrO2 grinding jar containing 30 g of ZrO2 balls with a diameter of 5 mm. The jar was equipped with a Viton seal and sealed with an Ar atmosphere. The jar was removed from the glove box and placed in a planetary ball mill (Pulverisette 7 premium line, Fritsch). Mechanical synthesis was performed for 207 cycles at 600 rpm for 10 min, with a 10 min rest period between each cycle.

[0357] After mechanical synthesis, the container was placed in a glove box. The resulting gray powder was recovered, and XRD analysis was consistent with the reported Li3YCl6 spectrum (orthorhombic phase). The white portion of the powder was recovered separately, revealing a large amount of precursor.

[0358] The transport properties of the gray powder were measured after pelletizing:

[0359] - Ionic conductivity measured at 20°C: 0.16 mS / cm

[0360] - Activation energy for lithium transport: 0.42 eV

[0361] Electron conductivity at -20℃: 3.17E-09S / cm

[0362] Example 2: Comparison - Li3GdCl6 obtained by dry mechanochemistry

[0363] Precursor weighing and sample preparation were performed in an Ar-filled glovebox with oxygen and moisture levels below 1 ppm. In a typical experiment, 30 mL glass vials were used to weigh LiCl (≥99.9%, Sigma-Aldrich, 1.24 g) and dry GdCl3 (≥99%, Sigma-Aldrich, 2.58 g) according to the target stoichiometric ratio Li3GdCl6. The sample was poured into a 20 mL ZrO2 grinding jar containing 30 g of ZrO2 balls with a diameter of 5 mm. The jar was fitted with a Viton seal and was sealed (to the Ar atmosphere). The jar was removed from the glovebox and placed in a planetary ball mill (Pulverisette 7 premium line, Fritsch). Mechanical synthesis was performed for 155 cycles at 600 rpm for 10 min, with a 10 min rest period between each cycle.

[0364] After mechanical synthesis, the container was placed in a glove box. The resulting gray powder was recovered, and XRD patterns were consistent with reported LiGdCl4 and LiCl (tetragonal I41 / a phase). The white portion of the powder was recovered separately, revealing abundant precursors (GdCl3 and LiCl).

[0365] The transport properties of the gray powder were measured after pelletizing:

[0366] - Ionic conductivity measured at 20°C: 0.0009 mS / cm

[0367] - Activation energy for lithium transport: 0.5 eV

[0368] Electron conductivity at -20℃: 2E-09S / cm

[0369] Example 3: Li3Y obtained by dry mechanochemistry 0.9 Gd 0.1 Cl6

[0370] 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, 30 mL glass vials were used according to the target stoichiometric ratio of Li3Y. 0.9 Gd 0.1Weigh out 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). Pour the sample into a 20 mL ZrO2 grinding jar containing 30 g of ZrO2 balls with a diameter of 5 mm. The jar is equipped with a Viton seal and is sealed (with an Ar atmosphere). Remove the jar from the glove box and place it in a planetary ball mill (Pulverisette 7 premium line, Fritsch). Perform mechanical synthesis for 155 cycles at 600 rpm for 10 min, with a 10 min rest period between each cycle.

[0371] After mechanical synthesis, the container was placed in a glove box. The obtained gray powder was recovered, and XRD analysis was performed compared with the reported parent Li3YCl6 spectrum. Figure 1 The white portion of the powder was recovered separately and a large amount of precursors (YCl3 and LiCl) were observed.

[0372] The transport properties of the gray powder were measured after pelletizing:

[0373] - Ionic conductivity measured at 20°C: 0.31 mS / cm

[0374] - Activation energy for lithium transport: 0.37 eV

[0375] Electron conductivity at -20℃: 2.3E-9S / cm

[0376] Example 4: Li3Y obtained by dry mechanochemistry 0.3 Er 0.3 Yb 0.3 Gd 0.1 Cl6

[0377] 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, 30 mL glass vials were used according to the target stoichiometric ratio of Li₃Y. 0.3 Er 0.3 Yb 0.3 Gd 0.1The following samples were weighed: 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). The samples were poured into a 20 mL ZrO2 grinding jar containing 30 g of ZrO2 balls with a diameter of 5 mm. The jar was equipped with a Viton seal and was sealed (with an Ar atmosphere). The jar was removed from the glove box and placed in a planetary ball mill (Pulverisette 7 premium line, Fritsch). Mechanical synthesis was performed for 155 cycles at 600 rpm for 10 min, with a 10 min rest period between each cycle.

[0378] After mechanical synthesis, the container was placed in a glove box. The obtained gray powder was recovered, and XRD analysis was performed compared with the reported parent Li3YCl6 spectrum. Figure 1 The white portion of the powder was recovered separately and a large amount of precursors (YCl3, ErCl3, YbCl3, and LiCl) were observed.

[0379] The transport properties of the gray powder were measured after pelletizing:

[0380] - Ionic conductivity measured at 20℃: 0.20 mS / cm

[0381] - Activation energy for lithium transport: 0.40 eV

[0382] Electron conductivity at -20℃: 2.2E-9S / cm

[0383] Example 5: Li obtained by dry mechanochemistry 2.7 YGd 0.1 Cl6

[0384] Precursor weighing and sample preparation were performed in an Ar-filled glovebox with oxygen and moisture levels below 1 ppm. In a typical experiment, 30 mL glass vials were used according to the target stoichiometric ratio of Li. 2.7 YGd 0.1Weigh out 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). Pour the sample into a 20 mL ZrO2 grinding jar containing 30 g of ZrO2 balls with a diameter of 5 mm. The jar is equipped with a Viton seal and is sealed (with an Ar atmosphere). Remove the jar from the glove box and place it in a planetary ball mill (Pulverisette 7 premium line, Fritsch). Perform mechanical synthesis for 155 cycles at 600 rpm for 10 min, with a 10 min rest period between each cycle.

[0385] After mechanical synthesis, the container was placed in a glove box. The obtained gray powder was recovered, and XRD analysis was performed compared with the reported parent Li3YCl6 spectrum. Figure 1 The white portion of the powder was recovered separately and a large amount of precursors (YCl3 and LiCl) were observed.

[0386] The transport properties of the gray powder were measured after pelletizing:

[0387] - Ionic conductivity measured at 20℃: 0.44 mS / cm

[0388] - Activation energy for lithium transport: 0.37 eV

[0389] Electron conductivity at -20℃: 9E-10S / cm

[0390] Example 6: Li3Y obtained by wet mechanochemistry 0.45 Er 0.45 Gd 0.1 Cl6

[0391] 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, 30 mL glass vials were used according to the target stoichiometric ratio of Li₃Y. 0.45 Er 0.45 Gd 0.1Weigh out 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). Pour the sample into a 45 mL ZrO2 grinding jar containing 30 g of ZrO2 balls with a diameter of 5 mm. Then add 10.65 g of p-xylene (≥99%, Sigma-Aldrich, anhydrous). The jar is equipped with a Viton seal and is sealed (with an Ar atmosphere). Remove the jar from the glove box and place it in a planetary ball mill (Pulverisette 7 premium line, Fritsch). Mechanical synthesis was performed over 165 cycles at 800 rpm for 10 min, with a 30 min rest period between each cycle. After mechanical synthesis, the container was placed in a glove box. The product and spheres were placed in two 30 mL glass vials (uncapped), with the vials themselves placed in a glass test tube. The test tube was sealed, removed from the glove box, and placed in a glass oven B-585 from Büchi. The sample was dried under vacuum at room temperature for 2 h to evaporate the p-xylene. The obtained gray powder was recovered, and XRD was performed in accordance with the reported Li3YCl6 spectrum. Figure 1 To.

[0392] The transport properties of the gray powder were measured after pelletizing:

[0393] - Ionic conductivity measured at 20℃: 0.39 mS / cm

[0394] - Activation energy for lithium transport: 0.35 eV

[0395] Electron conductivity at -20℃: 3E-9S / cm

[0396] Example 7: Stability measurements in various solvents.

[0397] Stability was examined by weighing 100 mg of Li3YCl6 from Example 1 into 2 g of the selected solvent for 7 days and filtering the solution. When filtration residue was present, it was dried under vacuum at 25°C to test conductivity.

[0398]

[0399] The filtrate was then analyzed by ICP-MS in the presence of p-xylene, and less than 1 ppm of Y was found in the filtrate. 3+ and Li +The same procedure was performed on the starting reagents LiCl and YCl3, and there was no solubility (YCl3 concentration less than 1 ppm in the filtrate). 3+ and Li + ).

[0400] These compounds are stable in xylene and fluorinated solvents (Galden HT-135) (as shown by XRD and conductivity).

[0401] Example 8: Li3YCl6 obtained by wet mechanochemistry

[0402] Precursor weighing and sample preparation were performed in an Ar-filled glovebox with oxygen and moisture levels below 1 ppm. In a typical experiment, 30 mL glass vials were used to weigh LiCl (≥99.9%, Sigma-Aldrich, 2.45 g) and dry YCl3 (≥99%, Sigma-Aldrich, 3.78 g) according to the target stoichiometric ratio Li3YCl6. The sample was poured into a 45 mL ZrO2 grinding jar containing 30 g of ZrO2 balls with a diameter of 5 mm. Then, 6.05 g of p-xylene (≥99%, Sigma-Aldrich, anhydrous) was added to the jar.

[0403] The jar was equipped with a Viton seal and was sealed (with an Ar atmosphere). The jar was removed from the glove box and placed in a planetary ball mill (Pulverisette 7 premium line, Fritsch). Mechanical synthesis was performed over 165 cycles at 800 rpm for 10 min, with a 30 min rest period between each cycle. After mechanical synthesis, the jar was placed back into the glove box. The product and the balls were placed in two 30 mL glass vials (uncapped), with the vials themselves placed in a glass test tube. The test tube was sealed, removed from the glove box, and placed in a glass oven B-585 from Büchner. The sample was dried under vacuum at room temperature for 2 h to evaporate the p-xylene. The obtained gray powder was recovered, and XRD was performed compared with the reported Li3YCl6 spectrum. Figure 1 To.

[0404] The transport properties of the gray powder were measured after pelletizing:

[0405] - Ionic conductivity measured at 20°C: 0.14 mS / cm.

[0406] - Activation energy for lithium transport: 0.38 eV

[0407] Electron conductivity at -20℃: 6E-10S / cm

[0408] Example 9: Water-mediated synthesis of Li3YCl6

[0409] The method described is used to produce Li3YCl6, and Li3InCl6 is produced by water-mediated synthesis (Angewandte Chemie, 131(46), 16579-16584).

[0410] In a typical experiment, a 50 mL glass beaker is used to weigh an aqueous solution of LiCl (≥99.9%, Sigma-Aldrich, 1.90 g) and YCl3 (≥99%, 13.5 g, dry equivalent of YCl3 equal to 3.01 g) according to the target stoichiometric ratio Li3YCl6.

[0411] The beaker was then placed in a furnace at 120°C to evaporate the water for 19 hours. The final product was a white, glassy solid. This product was then vacuum dried at 120°C in a glass furnace B-585 from Buchi Company over a period of 4 hours. XRD analysis of this sample showed the presence of LiCl, LiCl(H₂O), YCl₃, and YCl₃·6H₂O. No unknown phase, possibly attributable to the hydrated phase Li₃YCl₆,xH₂O (different from the reported Li₃InCl₆,xH₂O), was present.

[0412] Subsequent heating of the sample at 200°C under vacuum (from a glass furnace B-585 from Bucher) over a 4-hour period resulted in the formation of a mixture of LiCl and YCl3. No Li3YCl6, different from the reported Li3InCl6, was found.

[0413] Example 10: Li obtained by wet mechanochemistry 2.6 Zr 0.4 Y 0.54 Sm 0.06 Cl 5.82 Br 0.18

[0414] Precursor weighing and sample preparation were performed in an Ar-filled glovebox with oxygen and moisture levels below 1 ppm. In a typical experiment, 30 mL glass vials were used according to the target stoichiometric ratio of Li. 2.6 Zr 0.4 Y 0.54 Sm 0.06 Cl 5.82 Br 0.18 Weigh LiCl (≥99.9%, Sigma-Aldrich, 1.65g), dried YCl3 (≥99.9%, Sigma-Aldrich, 1.59g), dried ZrCl4 (≥99.9%, Sigma-Aldrich, 1.43g), and dried SmBr3 (≥99%, Sigma-Aldrich, 0.35g).

[0415] The sample was poured into a 45mL ZrO2 grinding jar, which contained 66g of ZrO2. ZrO2 spheres. Then add 5.0g of p-xylene (≥99%, Sigma-Aldrich, anhydrous) to the jar.

[0416] The jar is equipped with a Viton seal and is sealed (with an Ar atmosphere inside). The jar is removed from the glove box and placed in a planetary ball mill (Pulverisette 7premium line, Fritsch). Mechanical synthesis is performed over 165 cycles at 800 rpm for 10 minutes each, with a 15-minute rest period between each cycle.

[0417] After mechanical synthesis, place the jar in a glove box. Place the product and spheres in two 30 mL glass vials (uncapped), with the vials themselves placed in a glass test tube. Seal the test tube, remove it from the glove box, and place it in a glass oven B-585 from Buchner.

[0418] The sample was dried under vacuum at 110 °C for 5 h to evaporate the p-xylene. The obtained powder was recovered and XRD was compared with the reported Li3YCl6 spectrum. Figure 1 To.

[0419] The ionic conductivity measured at 30℃ was 0.57 mS / cm, and the activation energy was 0.35 eV.

[0420] Table 1: Conductivity at 20°C and lower temperatures

[0421]

[0422]

[0423] The results summarized in Table 1 show that, compared with solid lithium rare earth halides obtained by dry mechanochemical processes (Comparative Example 9 and Example 1 at 0°C and -20°C), solid lithium rare earth halides obtained by wet mechanochemical processes according to the present invention unexpectedly have improved ionic conductivity at low temperatures.

Claims

1. A solid material according to the following general formula (I): Li 6-3x-4y RE x T y X6 (I) in: - X is a halogen; - 0 < x + (4 / 3)y < 2; - 0 ≤ y ≤ 0.8； - RE indicates two or more rare earth metals; these rare earth metals are distinct from one another; and -T is Zr or Hf; The prerequisite is that when y = 0 and RE represents two rare earth metals, if one rare earth metal is Y, then the other rare earth metal is Yb.

2. The solid material according to claim 1, wherein, In equation (I), 0.8 ≤ x + (4 / 3)y ≤ 1.

5.

3. The solid material according to claim 1, wherein, In equation (I), 0.95 ≤ x + (4 / 3)y ≤ 1.

25.

4. The solid material according to claim 1, wherein, In equation (I), 0.1 ≤ y ≤ 0.

7.

5. The solid material according to claim 1, wherein, In equation (I), 0.2 ≤ y ≤ 0.

6.

6. The solid material according to claim 1, wherein, The solid material is any one of the compounds having the following formulas (II) to (V): Li 6-3x-4y RE1 a RE2 b T y X6 (II) Where a + b = x, where 0.05 ≤ a ≤ 0.95 and 0.0 < b ≤ 0.95; and when y = 0 and RE1 is Y, RE2 is Yb; The 6-3x-4y RE1 a RE2 b RE3 c T y X6 (III) Where a + b + c = x, where 0.05 ≤ a ≤ 0.95, 0.0 < b ≤ 0.95 and 0.0 < c ≤ 0.95, where 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, where 0.05 ≤ a ≤ 0.95, 0.0 < b ≤ 0.95, 0.0 < c ≤ 0.95 and 0.0 < d ≤ 0.95, where 0.05 ≤ b+c+d; Li 6-3x-4y RE1 a RE2 b RE3 c RE4 d RE5 e T y X6 (V) Where 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 and 0.0 < e ≤ 0.95, where 0.05 ≤ b + c + d + e; and - X is a halogen; - 0 < x + (4 / 3)y < 2; - 0 ≤ y ≤ 0.8； - RE1 can be selected from the following groups: Y, Yb, Ho, Er; - RE2 can be selected from the following groups: Yb, Ho, Gd, Er, Sm, Dy, La, Nd, Ce, Tb; - RE3 can be selected from the following groups: Ho, Gd, Er, Sm, Dy, La, Nd, Ce, Tb; - RE4 selects from the following groups: Er, Gd, Sm, Dy, La, Nd, Ce, Tb; and - RE5 is selected from the following groups: Gd, Sm, Dy, La, Nd, Ce, Tb; where RE1, RE2, R3, R4, and RE5 are different; and - T is Zr or Hf.

7. The solid material according to claim 6, wherein, In equation (II), 0.5 ≤ a ≤ 0.9 and 0.05 < b ≤ 0.

5.

8. The solid material according to claim 6, wherein, In equation (V), 0.8 ≤ x + (4 / 3)y ≤ 1.

5.

9. The solid material according to claim 6, wherein, In equation (V), 0.95 ≤ x + (4 / 3)y ≤ 1.

25.

10. The solid material according to claim 6, wherein, In equation (V), 0.1 ≤ y ≤ 0.

7.

11. The solid material according to claim 6, wherein, In equation (V), 0.2 ≤ y ≤ 0.

6.

12. The solid material according to any one of claims 1 to 11, wherein, The average ionic radius of RE exhibits an ionic radius value below 0.938 oz.

13. The solid material according to any one of claims 1 to 11, wherein, X is Cl.

14. The solid material according to any one of claims 1 to 11, wherein, y = 0。 15. The solid material according to any one of claims 1 to 11, wherein, The solid material is selected from the group consisting of: Li3Y 0.3 Er 0.3 Yb 0.3 Gd 0.1 Cl6, Li3Y 0.45 Er 0.45 Gd 0.1 Cl6; and Li3Y 0.45 Er 0.45 La 0.1 Cl6.

16. The solid material according to any one of claims 1 to 11, wherein, The solid material comprises fractions consisting of a glass phase.

17. The solid material according to any one of claims 1 to 11, wherein, The solid material is in the form of a powder with a particle diameter distribution having a D50 between 0.05 µm and 10 µm.

18. A method for producing a solid material according to any one of claims 1 to 17, the method comprising reacting at least lithium halide, at least two different rare earth metal halides optionally in one or more solvents, wherein the rare earth metals in the at least two different rare earth metal halides are different from each other, and further comprising optionally zirconium halide or hafnium halide.

19. A process for preparing a solid material according to any one of claims 1 to 17, the process comprising the following steps: a) A composition is obtained by mixing stoichiometric amounts of lithium halide, at least two different rare earth metal halides optionally in one or more solvents under an inert atmosphere, wherein the rare earth metals in the at least two different rare earth metal halides are different from each other, and also optionally contains zirconium halide or hafnium halide. b) Apply mechanical treatment to the composition obtained in step a) to obtain the solid material; as well as c) Optionally, remove at least a portion of the one or more solvents from the composition obtained in step b) to obtain the solid material.

20. A process for preparing solid materials according to the following general formula (I): Li 6-3x-4y RE x T y X6 (I) in: - X is a halogen; - 0 < x + (4 / 3)y < 2; - 0 ≤ y ≤ 0.8； - RE indicates two or more rare earth metals; these rare earth metals are different from each other; and - T is either Zr or Hf; The prerequisite is that when y = 0 and RE represents two rare earth metals, if one rare earth metal is Y, then the other rare earth metal is Yb. The process includes the following steps: a) A composition is obtained by mixing stoichiometric amounts of lithium halide, at least two rare earth metal halides, and optionally zirconium halide or hafnium halide in one or more solvents under an inert atmosphere; b) Applying mechanical treatment to the composition obtained in step a) to obtain the solid material; and c) Remove at least a portion of the one or more solvents from the composition obtained in step b) to obtain the solid material.

21. The process according to claim 20, wherein, In equation (I), 0.8 ≤ x + (4 / 3)y ≤ 1.

5.

22. The process according to claim 20, wherein, In equation (I), 0.95 ≤ x + (4 / 3)y ≤ 1.

25.

23. The process according to claim 20, wherein, In equation (I), 0.1 ≤ y ≤ 0.

7.

24. The process according to claim 20, wherein, In equation (I), 0.2 ≤ y ≤ 0.

6.

25. The process according to claim 24, wherein, The solid material is any one of the compounds having the following formulas (II) to (V): Li 6-3x-4y RE1 a RE2 b T y X6 (II) Where a + b = x, where 0.05 ≤ a ≤ 0.95 and 0.0 < b ≤ 0.95; and when y = 0 and RE1 is Y, RE2 is Yb; The 6-3x-4y RE1 a RE2 b RE3 c T y X6 (III) Where a + b + c = x, where 0.05 ≤ a ≤ 0.95, 0.0 < b ≤ 0.95, and 0.0 < c ≤ 0.95, where 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, where 0.05 ≤ a ≤ 0.95, 0.0 < b ≤ 0.95, 0.0 < c ≤ 0.95 and 0.0 < d ≤ 0.95, where 0.05 ≤ b + c + d; Li 6-3x-4y RE1 a RE2 b RE3 c RE4 d RE5 e T y X6 (V) Where 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 and 0.0 < e ≤ 0.95, where 0.05 ≤ b + c + d + e; and in - X is a halogen. - 0 < x + (4 / 3)y < 2; - 0 ≤ y ≤ 0.8； - RE1 can be selected from the following groups: Y, Yb, Ho, Er; - RE2 can be selected from the following groups: Yb, Ho, Gd, Er, Sm, Dy, La, Nd, Ce, Tb; - RE3 can be selected from the following groups: Ho, Gd, Er, Sm, Dy, La, Nd, Ce, Tb; - RE4 selects from the following groups: Er, Gd, Sm, Dy, La, Nd, Ce, Tb; and - RE5 is selected from the following groups: Gd, Sm, Dy, La, Nd, Ce, Tb; where RE1, RE2, RE3, RE4, and RE5 are different; and - T is Zr or Hf.

26. The process according to claim 25, wherein, In equation (II), 0.5 ≤ a ≤ 0.9 and 0.05 < b ≤ 0.

5.

27. The process according to claim 25, wherein, In equation (V), 0.8 ≤ x + (4 / 3)y ≤ 1.

5.

28. The process according to claim 25, wherein, In equation (V), 0.95 ≤ x + (4 / 3)y ≤ 1.

25.

29. The process according to claim 25, wherein, In equation (V), 0.1 ≤ y ≤ 0.

7.

30. The process according to claim 25, wherein, In equation (V), 0.2 ≤ y ≤ 0.

6.

31. The process according to any one of claims 20 to 30, wherein, Lithium halides are selected from the group consisting of LiCl, LiBr, LiF, and LiI.

32. The process according to any one of claims 20 to 30, wherein, Rare earth metal halides are selected from the group consisting of: YCl3, ErCl3, YbCl3, GdCl3, LaCl3, YBr3, ErBr3, YbBr3, GdBr3, LaBr3, (Y, Yb, Er)Cl3, and (La, Y)Cl3.

33. The process according to any one of claims 20 to 30, wherein, Zirconium halide is ZrCl4.

34. The process according to any one of claims 20 to 30, wherein, The solvent is selected from the group consisting of: aliphatic hydrocarbons; and aromatic hydrocarbons.

35. The process according to claim 34, wherein, The aliphatic hydrocarbon is selected from hexane, pentane, 2-ethylhexane, heptane, decane, and cyclohexane.

36. The process according to claim 34, wherein, The aromatic hydrocarbon is selected from xylene and toluene.

37. The process according to any one of claims 20 to 30, wherein, The mechanical treatment described in step b) is performed by wet grinding or dry grinding.

38. A solid material obtained by the process according to any one of claims 20 to 37.

39. Use of the solid material according to any one of claims 1 to 17 or according to claim 38 as a solid electrolyte.

40. A solid electrolyte comprising at least one of claims 1 to 17 or the solid material according to claim 38.

41. An electrochemical device comprising at least a solid electrolyte, the solid electrolyte comprising at least a solid material according to any one of claims 1 to 17 or according to claim 38.

42. A solid-state battery, the solid-state battery comprising at least a solid electrolyte, the solid electrolyte comprising at least a solid material according to any one of claims 1 to 17 or according to claim 38.

43. A vehicle comprising at least a solid-state battery, the solid-state battery comprising at least a solid electrolyte, the solid electrolyte comprising at least a solid material according to any one of claims 1 to 17 or according to claim 38.

44. An electrode comprising at least: - Metal substrate; - At least one layer directly attached to the metal substrate, said layer being made of a composition comprising: (i) The solid material according to any one of claims 1 to 17 or according to claim 38; (ii) at least one electroactive compound; (iii) Optionally at least one lithium-ion conductive material other than the solid material of the present invention; (iv) Optionally at least one electrically conductive material; (v) Lithium salts, optionally; and (vi) Optionally, at least one polymeric bonding material.

45. A diaphragm comprising at least: - The solid material according to any one of claims 1 to 17 or according to claim 38; - Optionally at least one polymer-type bonding material; - Optionally at least one metal salt; and - Optionally at least one plasticizer.

46. ​​The diaphragm according to claim 45, wherein the at least one metal salt is a lithium salt.

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