Solid materials containing Li, Mg, P, S, and halogen elements

Abstract

The present invention relates to a compound having a high calculated ionic conductivity and represented by the following general formula (I): Li 7-2x-y Mg x S 6-y X y (I) wherein X is a halogen selected from the group consisting of F, Cl, I, and Br, or a combination thereof, and x is a number such that 0.01≦x≦0.4, and y is a number such that 0.5≦y≦1, and a method for making said solid material. The disclosure also relates to the use of this solid material, in particular as a solid electrolyte for electrochemical devices such as batteries.

Description

[Technical field]

[0001] This application claims priority to European Patent Application No. 21306819.0, filed December 17, 2021, the entire contents of which are incorporated herein by reference for all purposes.

[0002] The present invention relates to a compound having a high calculated ionic conductivity and represented by the following general formula (I): Li 7-2x-y Mg x P.S. 6-y X y (I) (In the formula, - X is a halogen selected from the group consisting of F, Cl, I and Br or a combination thereof; - x is a number such that 0.01≦x≦0.4, - y is a number such that 0.5≦y≦1. and a method for producing said solid material.

[0003] The present disclosure also relates to the use of this solid-state material, particularly as a solid-state electrolyte for electrochemical devices such as batteries. [Background technology]

[0004] 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 consisting of lithium salts dissolved in an organic solvent. The aforementioned system poses safety concerns since the organic solvent is flammable. If lithium dendrites form and pass through the liquid electrolyte medium, they can cause a short circuit and generate heat, which leads to accidents that can result in serious injuries. Since the electrolyte solution is a flammable liquid, there are concerns about leakage, fire, etc., when used in batteries. In light of such concerns, the development of a solid electrolyte with a higher degree of safety is expected as the electrolyte for next-generation lithium batteries.

[0005] Nonflammable inorganic solid electrolytes provide solutions to safety problems. Furthermore, their mechanical stability helps suppress lithium dendrite formation, prevent self-discharge and heating problems, and extend the battery life.

[0006] Solid sulfide 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, which eliminates 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 an increasing demand for solid electrolytes with high conductivity for lithium ions. An important class of such solid electrolytes is materials with the composition Li6PS5X (X = Cl, Br) having an argyrodite structure.

[0007] Sulfide-based solid electrolytes such as Li6PS5X (X = Cl, Br, I) with an argyrodite crystal structure are superionic conductors with high electrochemical stability and ionic conductivity. Due to these interesting properties, such materials have been the subject of numerous studies, some of which involve the use of dopants. U.S. Patent Application Publication No. 2021 / 047195 describes using chalcophilic metals such as Mn, Fe, Co, Ni, Cu, Zn, Hg, Mo to modify the structure of argyrodite, prevent the formation of H2S, and as a result, stabilize the material.

[0008] U.S. Patent Application Publication No. 2020 / 0194827 describes a sulfide-based solid electrolyte doped with alkaline earth metals to improve ionic conductivity and a method for manufacturing the same. The sulfide-based solid electrolyte represented by the formula Li 6-2x Me x PS5Ha (where Me is an alkaline earth rare earth element, Ha is a halogen element, and 0 < x ≦ 0.5) exhibits higher ionic conductivity than the undoped argyrodite of the formula Li6PS5Cl. However, the increase in ionic conductivity is rather limited.

[0009] International Publication No. 2021117869 pamphlet describes a sulfide-based solid electrolyte doped with a plurality of metals and a method for manufacturing the same in order to improve moisture resistance while maintaining ionic conductivity and reduce the generation of H2S. The sulfide-based solid electrolyte has the formula Li a M b PS c X d where 3.0 ≦ a ≦ 6.5, 0 < b ≦ 2.0, 3.5 ≦ c ≦ 5.5, 0.5 ≦ d ≦ 3.0, X is a halogen, and M may be Mg. However, even for the exemplified Mg-containing sulfides, the measured ionic conductivity is quite limited.

[0010] However, there is a need for new solid sulfide electrolytes with optimized performance such as higher ionic conductivity and lower activation energy without compromising other important properties such as chemical and mechanical stability.

Summary of the Invention

[0011] The ionic conductivity of the compound LiMgPSX, which is a solid sulfide corresponding to the formula Li 7-2x-y Mg x PS 6-y X y (where X is a halogen) was estimated by a computer over a wide range of compositions where x is from 0 to 0.5 and y is from 0.5 to 1.2. As a result, a conductivity map showing different compositions and their predicted lithium ion conductivity at room temperature was created by a molecular dynamics method based on a deep neural network potential.

[0012] Surprisingly, it has been found that the solid sulfide electrolytes of well-defined composition detailed below have higher calculated ionic conductivity compared to i) solid sulfides of other compositions, the compound LiMgPSX, ii) conventional Li6PS5Cl materials, and iii) LiMgPSX solid materials disclosed in the prior art. The LiCuPSX solid materials of the present invention also exhibit chemical and mechanical stability and processability at least similar to those of conventional lithium argyrodites. The solid materials of the present invention can also be produced with improved productivity and allow control of the morphology of the resulting products.

[0013] Thus, the present invention provides a polymer having the following general formula (I): Li 7-2x-y Mg x P.S. 6-y X y (I) (In the formula, - X is a halogen selected from the group consisting of F, Cl, I and Br or a combination thereof; - x is a number such that 0.01≦x≦0.4, - y is a number such that 0.5≦y≦1. This relates to solid materials.

[0014] The present invention also relates to a compound represented by the following general formula (I): Li 7-2x-y Mg x P.S. 6-y X y (I) (In the formula, - X is a halogen selected from the group consisting of F, Cl, I and Br or a combination thereof; - x is a number such that 0.01≦x≦0.4, - y is a number such that 0.5≦y≦1. 1. A method for producing a solid material of a) obtaining a composition by mixing ingredients, optionally in one or more solvents; b) optionally subjecting the composition obtained in step a) to a mechanical treatment; c) optionally removing at least a portion of the one or more solvents from the composition obtained in step b) to obtain a solid residue; d) optionally pressing the solid residue from step c) into pellets; e) heating the residue obtained in step c), for example in pellet form, to a temperature in the range of 350° C. to 580° C. for a time in the range of 1 hour to 12 hours, thereby forming a solid material; and f) optionally processing the solid material obtained in step e) to a desired particle size distribution; The present invention also relates to a method comprising the steps of:

[0015] The present invention also relates to a compound represented by the following general formula (I): Li 7-2x-y Mg x P.S. 6-y X y (I) (In the formula, - X is a halogen selected from the group consisting of F, Cl, I and Br or a combination thereof; - x is a number such that 0.01≦x≦0.4, - y is a number such that 0.5≦y≦1. 1. A method for producing a solid material of a') obtaining a solution by mixing the raw materials in one or more solvents; b') removing at least a portion of the one or more solvents from the composition obtained in step a') to obtain a solid residue; c') optionally pressing the solid residue from step b') into pellets; d') optionally heating the residue obtained in step b'), for example in pellet form, to a temperature in the range of 350°C to 580°C for a time in the range of 1 hour to 12 hours under an inert atmosphere, thereby forming a solid material; and e') optionally processing the solid material obtained in step d') to a desired particle size distribution; The present invention also relates to a method comprising the steps of:

[0016] The invention further relates to a solid material obtainable by said process.

[0017] The present invention relates to a compound represented by the following formula (I): Li 7-2x-y Mg x P.S. 6-y X y (I) (In the formula, - X is a halogen selected from the group consisting of F, Cl, I and Br or a combination thereof; - x is a number such that 0.01≦x≦0.4, - y is a number such that 0.5≦y≦1. The present invention also relates to the use of the solid material as a solid electrolyte.

[0018] The present invention also relates to a solid electrolyte comprising at least one solid material of formula (I) below: Li 7-2x-y Mg x P.S. 6-y X y (I) (In the formula, - X is a halogen selected from the group consisting of F, Cl, I and Br or a combination thereof; - x is a number such that 0.01≦x≦0.4, - y is a number such that 0.5≦y≦1.

[0019] The present invention also relates to an electrochemical device comprising at least one solid electrolyte comprising at least one solid material of formula (I) below: Li 7-2x-y Mg x P.S. 6-y X y (I) (In the formula, - X is a halogen selected from the group consisting of F, Cl, I and Br or a combination thereof; - x is a number such that 0.01≦x≦0.4, - y is a number such that 0.5≦y≦1.

[0020] The present invention also relates to a solid-state battery comprising at least one solid electrolyte comprising at least one solid material of formula (I) below: Li 7-2x-y Mg x P.S. 6-y X y (I) (In the formula, - X is a halogen selected from the group consisting of F, Cl, I and Br or a combination thereof; - x is a number such that 0.01≦x≦0.4, - y is a number such that 0.5≦y≦1.

[0021] 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 formula (I) below: Li 7-2x-y Mg x P.S. 6-y X y (I) (In the formula, - X is a halogen selected from the group consisting of F, Cl, I and Br or a combination thereof; - x is a number such that 0.01≦x≦0.4, - y is a number such that 0.5≦y≦1.

[0022] The present invention provides at least a metal substrate; at least one layer directly adhered to said metal substrate, (i) Formula (I): Li 7-2x-y Mg x P.S. 6-y X y (I) (In the formula, - X is a halogen selected from the group consisting of F, Cl, I and Br or a combination thereof; - x is a number such that 0.01≦x≦0.4, - y is a number such that 0.5≦y≦1. and (ii) at least one electroactive compound (EAC); (iii) optionally at least one lithium ion conducting material (LiCM) other than the solid-state material of the present invention; (iv) optionally at least one electrically conductive material (ECM); (v) an optional lithium salt (LIS); and (vi) optionally at least one polymeric binder material (P); At least one layer made from a composition comprising The present invention also relates to an electrode comprising:

[0023] The present invention comprises at least - the following formula (I): Li 7-2x-y Mg x P.S. 6-y X y (I) (In the formula, - X is a halogen selected from the group consisting of F, Cl, I and Br or a combination thereof; - x is a number such that 0.01≦x≦0.4, - y is a number such that 0.5≦y≦1. and - optionally at least one polymeric binding material (P); - optionally at least one metal salt, in particular a lithium salt, - optionally at least one plasticizer; The present invention also relates to a separator comprising:

[0024] definition Throughout this specification, unless the context requires otherwise, the terms "comprise" or "include" or variations such as "comprises," "comprising," "includes," "including" will be understood to imply the inclusion of a stated element or method step or group of elements or method steps, but not the exclusion of any other element or method step or group of elements or method steps. According to a preferred embodiment, the terms "comprise" and "comprises" and variations thereof mean "consisting only of".

[0025] As used herein, the singular forms "a", "an" and "the" include plural embodiments unless the context clearly indicates otherwise. The term "and / or" includes the meaning "and", "or" and also all other possible combinations of the elements associated with this term.

[0026] The term "to" should be understood to include the endpoints. Ratios, concentrations, amounts, and other numerical data may be presented in a range format herein. It should be understood that such range formats are used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values ​​explicitly recited as the endpoints of the range, but also to include all the individual numerical values ​​or subranges contained within the range, as if each numerical value and subrange were explicitly recited. For example, a temperature range of about 120°C to about 150°C should be interpreted to include not only the explicitly recited endpoints of about 120°C to about 150°C, but also subranges such as 125°C to 145°C, 130°C to 150°C, etc., and individual amounts, such as decimal points within the stated range, for example, 122.2°C, 140.6°C, and 141.3°C.

[0027] The term "electrolyte" refers in particular to an electrolyte through which ions, such as Li + An electrolyte is a material that allows the movement of ions, e.g. Li, through it, but does not conduct electrons. +The "solid electrolyte" according to the present invention is particularly useful for conducting ions, such as Li, while electrically insulating the cathode and anode of a battery. + By "material" we mean any type of material that can move around within it.

[0028] As used herein, the term "argyrodite" or "argyrodite crystal" refers to a crystal structure or crystal bonding arrangement based on the crystal structure for the naturally occurring mineral argyrodite, a silver germanium sulfide mineral characterized by the chemical formula Ag8GeS6. This crystal structure is also exemplified by the isomorphous argyrodite mineral, Ag8SnS6.

[0029] As used herein, the term "crystalline phase" refers to a fraction of a material that exhibits crystalline characteristics, for example, well-defined x-ray diffraction peaks as measured by x-ray diffraction (XRD).

[0030] As used herein, the term "peak" refers to a (2θ) position on the x-axis of an XRD powder pattern of intensity v, degrees (2θ), that has a peak intensity substantially greater than background. In a set of XRD powder pattern peaks, the main peak is the peak of highest intensity that is associated with the compound or phase under analysis. The second main peak is the second most intense peak. The third main peak is the third most intense peak.

[0031] The term "electrochemical device" refers in particular to devices that generate and / or store electrical energy, for example by electrochemical and / or electrostatic processes. Electrochemical devices can include electrochemical cells, such as batteries, especially solid-state batteries. Batteries can be primary (i.e., for single or "disposable" use) or secondary (i.e., rechargeable) batteries.

[0032] As used herein, the terms "cathode" and "anode" refer to the electrodes of a battery. During a charge cycle in a Li secondary battery, Li ions leave the cathode and move through the electrolyte to the anode. During a charge cycle, electrons leave the cathode and move through an external circuit to the anode. During a discharge cycle in a Li secondary battery, Li ions move through the electrolyte and from the anode toward the cathode. During a discharge cycle, electrons leave the anode and move through an external circuit to the cathode.

[0033] The terms "vehicle" or "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, aircraft, and include hybrid vehicles, electric vehicles, plug-in hybrid electric vehicles, hydrogen vehicles, and other alternative fuel vehicles (e.g., fuels derived from sources other than petroleum). As referred to herein, a hybrid vehicle is a vehicle that has two or more different power sources, such as a gasoline-powered and an electric-powered vehicle. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0034] The present invention therefore relates to compounds of the general formula (I) Li 7-2x-y Mg x P.S. 6-y X y (I) (In the formula, - X is a halogen selected from the group consisting of F, Cl, I and Br or a combination thereof; - x is a number such that 0.01≦x≦0.4, - y is a number such that 0.5≦y≦1. This relates to solid materials.

[0035] The solid material of the present invention is neutrally charged. It is understood that formula (I) is an empirical formula (gross formula) determined by elemental analysis. Therefore, formula (I) defines the composition averaged over all phases present in the solid material.

[0036] X is preferably Cl.

[0037] Typically, 0.01≦x≦0.4. In some embodiments, 0.01≦x≦0.125, and in some other embodiments, 0.125≦x≦0.4.

[0038] Typically, 0.5≦y<1. In some embodiments, 0.5≦y≦0.8, and in some other embodiments, 0.65≦x≦0.85.

[0039] Li 7-2x-y Mg x P.S. 6-y X y (I) Particularly high ionic conductivities have been calculated for (0.01≦x≦0.25 and 0.5≦y≦0.8). Thus, in some embodiments, 0.01≦x≦0.25 and 0.5≦y≦0.8.

[0040] Furthermore, Li 7-2x-y Mg x P.S. 6-y X y (I) However, particularly high ionic conductivities have been calculated where 0.125≦x≦0.4 and 0.65≦y≦0.8. Thus, in some further embodiments, 0.125≦x≦0.4 and 0.65≦y≦0.85.

[0041] The solid material of the present invention may be amorphous (glass) and / or crystallized (glass-ceramic). Only a part of the solid material may be crystallized. The crystallized part of the solid material may contain only one crystal structure or may contain multiple crystal structures. The crystallinity of the solid material (crystallinity of the crystal structure whose ionic conductivity is higher than that of the amorphous one) is preferably comprised between 80% and 100%.

[0042] The solid material of the present invention preferably comprises a fraction consisting of crystalline phases, where one of said crystalline phases has an argyrodite structure. Preferably, said crystalline phase having an argyrodite phase constitutes 90-100% of the total weight of the fraction consisting of crystalline phases. Such fractions can be determined by X-ray diffraction using Rietveld analysis of the total diffractogram. This refinement can be performed in the FullProf software by using the multi-step refinement option.

[0043] The solid material of the present invention has the structural unit PS4 3- and structural unit PO4 3- and preferably comprises the structural unit PS4 3- Amount of PO4 per structural unit 3- The ratio of the amounts ranges from 1000:1 to 9:1.

[0044] The solid material of the present invention, when analyzed by x-ray diffraction using CuKα radiation at 25°C, may comprise peaks at least at 15.65°±0.5°, 25.53°±0.5°, 30.16°±0.5° and 31.52°±0.5° (2θ).

[0045] The crystallographic space group of the solid material of the present invention is preferably space group 226

number

[0046] In some embodiments, the solid material of formula (I) according to the present invention may be as follows:

[0047] [Table 1]

[0048] In some alternative embodiments, the solid material of formula (I) according to the present invention may be as follows:

[0049] [Table 2]

[0050] [Table 3]

[0051] The composition of the compounds of formula (I) may be determined by chemical analysis using techniques well known to those skilled in the art, such as, for example, X-ray diffraction (XRD) and inductively coupled plasma-mass spectrometry (IPC-MS), among others.

[0052] The solid material of the present invention may be in the form of a powder. The powder may be characterized by its size or particle size distribution (PSD). The size of the particles of the powder, as measured by laser diffraction in paraxylene, is: - a d50 value of less than 50 μm, for example less than 40 μm, less than 30 μm or less than 20 μm; - a d10 value of more than 0.05 μm, and / or - a d90 value of less than 100 μm, for example less than 90 μm, less than 80 μm or less than 70 μm; It can be said that it shows.

[0053] The powder may be composed of agglomerated particles.

[0054] Particle size distribution (PSD) measurements, such as d50, d10, and d90 values, can be performed on a number of particles, at least 150, using a scanning electron microscope (SEM).

[0055] Alternatively, it can be performed by laser diffraction in paraxylene.

[0056] The d50 value has the usual meaning used in the field of particle size distribution. The dn value corresponds to the diameter of a particle where n% of the particles have a diameter less than dn. The d50 (median) is defined as the size value corresponding to the cumulative distribution at 50%. These parameters are usually determined from the volumetric distribution of diameters of a dispersion of particles of a solid material in a liquid, obtained with a laser diffractometer, using a standard procedure predefined by the instrument software. Laser diffractometers use the technique of laser diffraction to measure the size of particles by measuring the intensity of the light scattered when a laser beam passes through a dispersed particulate sample. The laser diffractometer can be, for example, a Mastersizer 3000 manufactured by Malvern.

[0057] D50 may be measured, inter alia, after treatment under ultrasound, which may include inserting an ultrasonic probe into a dispersion of a solid material in a liquid and subjecting the dispersion to ultrasonic treatment.

[0058] The particles of the powder may be spherical in shape.

[0059] The particles of the powder may exhibit a sphericity SR of 0.8 to 1.0, more specifically 0.85 to 1.0, even more specifically 0.90 to 1.0. SR may preferably be 0.90 to 1.0 or 0.95 to 1.0. The sphericity of the particles is determined by the following formula: SR=4πA / P 2 It is calculated from the measured circumference P and the measured projected area A of the particle using the following formula:

[0060] For an ideal sphere, SR is 1.0, and for spherical particles it is less than 1.0. SR can be determined by dynamic image analysis (DIA). Examples of devices that can be used to perform DIA are Retsch's CAMSIZER® P4 or Sympatec's QicPic®. More specifically, sphericity can be measured according to ISO 13322-2 (2006). DIA generally requires the analysis of a statistically meaningful large number of particles (e.g., at least 500 or even at least 1000).

[0061] The powders of the invention are also characterized by low release of H2S under given conditions, which can be measured by exposing the powder to a moist atmosphere and measuring the amount of H2S released during the first 50 minutes that the powder is in contact with said atmosphere.

[0062] The solid-state material may advantageously exhibit an ionic conductivity of at least 3.3 mS / cm, such as at least 3.4 mS / cm, such as from 3.5 to 15.0 mS / cm, or from 3.8 to 10.0 mS / cm, as measured on a pressed (500 MPa) pellet by impedance spectroscopy.

[0063] The measurement of ionic conductivity is carried out on pressed pellets. Typically, pressed pellets are produced using uniaxial or isostatic pressure. When pellets are formed by applying uniaxial pressure, a pressure of more than 100 MPa, advantageously more than 300 MPa, is applied for a time of at least 30 seconds. Measurements are typically carried out under uniaxial pressure of 2 MPa to 200 MPa.

[0064] The present invention also relates to a method for producing a solid material of general formula (I), comprising at least placing at least lithium sulfide, phosphorus sulfide, a halogen compound, and a magnesium compound, optionally in one or more solvents. One or more of lithium sulfide, phosphorus sulfide, a halogen compound, and a magnesium compound may be used.

[0065] In particular, the present invention also relates to a method for producing a solid material of general formula (I), which comprises at least reacting, optionally in one or more solvents, at least lithium sulfide, phosphorus sulfide, a halogen compound, and a magnesium compound. One or more of lithium sulfide, phosphorus sulfide, a halogen compound, and a magnesium compound may be used.

[0066] The solid materials of the present invention may be produced by any method known in the prior art for producing sulfide-based glass solid electrolytes, such as, for example, melt extrusion, full solution, mechanical milling, or slurry methods in which the raw materials are reacted, optionally in one or more solvents.

[0067] The present invention therefore relates to a process for the preparation of a solid material of general formula (I), comprising a) obtaining a composition by mixing ingredients, optionally in one or more solvents; b) optionally subjecting the composition obtained in step a) to a mechanical treatment; c) optionally removing at least a portion of the one or more solvents from the composition obtained in step b) to obtain a solid residue; d) optionally pressing the solid residue from step c) into pellets; e) heating the residue obtained in step c), for example in pellet form, under an inert atmosphere to a temperature in the range of 350° C. to 580° C. for a time in the range of 1 hour to 12 hours, thereby forming a solid material; and f) optionally processing the solid material obtained in step e) to a desired particle size distribution; The present invention relates to a method comprising the steps of:

[0068] In some embodiments, step a) is carried out under an inert atmosphere. The inert atmosphere used in step a) refers to the use of an inert gas; i.e., 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. Thus, an inert gas refers to a gas that does not chemically react with other reagents present in a particular chemical reaction. In the context of this disclosure, the term "inert gas" refers to a gas that does not react with the solid material precursor. Examples of "inert gases" include, but are not limited to, nitrogen, helium, argon, carbon dioxide, neon, xenon, H2S, O2 with less than 1000 ppm of water in liquid and suspended form, including condensation. The gas can also be pressurized.

[0069] It is preferable that the raw materials are stirred when they are contacted 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, particularly preferably -40°C or lower. The pressure can be 0.0001 Pa to 100 MPa, preferably 0.001 Pa to 20 MPa, preferably 0.01 Pa to 0.5 MPa.

[0070] Preferably in step a), the inert atmosphere comprises an inert gas such as H2S, dry N2, dry argon or dry air (dry may refer to a gas having less than 800 ppm water in liquid and suspended form, including condensation).

[0071] The composition ratio of each element can be controlled by adjusting the amount of the raw material compounds when the solid material is produced. The raw materials and their molar ratios are selected according to the target stoichiometric ratio, which defines the ratio between the elements Li, Mg, P, S, X that will be obtained from the applied amount of precursor under the condition of complete conversion without side reactions and other losses.

[0072] Lithium sulfide refers to a compound that contains one or more sulfur atoms and one or more lithium atoms, or alternatively, one or more sulfur-containing ionic groups and one or more lithium-containing ionic groups. In certain preferred embodiments, lithium sulfide can be composed of sulfur atoms and lithium atoms. Preferably, lithium sulfide is Li2S.

[0073] Phosphorus sulfide refers to a compound that contains one or more sulfur atoms and one or more phosphorus atoms, or alternatively, one or more sulfur-containing ionic groups and one or more phosphorus-containing ionic groups. In certain preferred embodiments, phosphorus sulfide can be composed of sulfur and phosphorus atoms. Non-limiting exemplary phosphorus sulfides include P2S5, P4S3, P4S 10 , P4S4, P4S5, P4S6, P4S7, P4S8 and P4S9.

[0074] A halogen compound refers to a compound that contains one or more halogen atoms, such as F, Cl, Br, or I, through a chemical bond (e.g., ionic or covalent bond) to other atoms that make up the compound. In certain preferred embodiments, the halogen compound may contain one or more of F, Cl, Br, I, or a combination thereof, and one or more metal atoms. In another preferred embodiment, the halogen compound may contain one or more of F, Cl, Br, I, or a combination thereof, and one or more non-metal atoms. Non-limiting examples may suitably include metal halides such as LiF, LiBr, LiCl, LiI, NaF, NaBr, NaCl, NaI, KaF, KBr, KCl, KI, and the like. In certain preferred embodiments, the halogen compound suitable for use in the solid electrolyte of the all-solid-state Li-ion battery may contain one or more halogen atoms and Li. Preferably, the halogen compound may be selected from the group consisting of lithium bromide (LiBr), lithium chloride (LiCl), lithium iodide (LiI), and combinations thereof.

[0075] A magnesium compound refers to a compound that contains one or more Mg atoms through chemical bonds (e.g., ionic or covalent bonds) with other atoms that make up the compound. In another embodiment, the magnesium compound can be metallic magnesium. In certain preferred embodiments, the magnesium compound can contain one or more Mg atoms and one or more non-metallic atoms, such as S, Cl, or B. The magnesium compound is preferably selected from the group consisting of MgS, MgCl2, and mixtures thereof. The magnesium compound of the present invention may be a blend of metallic magnesium and elemental sulfur.

[0076] In some embodiments, the lithium sulfide is Li2S, the phosphorus sulfide is P2S5, the halogen compound is LiCl, and the magnesium compound is selected from MgS, MgCl2, and mixtures thereof.

[0077] Preferably, the solid materials of the present invention are produced by using at least the following raw materials: Li2S, P2S5, and magnesium compounds selected from MgS, MgCl2, and mixtures thereof. In some embodiments, the solid materials of the present invention are produced by using at least the following raw materials: Li2S, P2S5, LiCl, and MgS. In some other embodiments, the solid materials of the present invention are produced by using at least the following raw materials: Li2S, P2S5, LiCl, and MgCl2.

[0078] Preferably, the lithium sulfide, phosphorus sulfide, halogen compound, and magnesium compound are in the form of powder having an average particle size comprised between 0.5 μm and 400 μm. The particle size can be evaluated by SEM image analysis or laser diffraction analysis.

[0079] The solvent may suitably be selected from one or more of polar or non-polar solvents capable of substantially dissolving at least one compound selected from lithium sulfide, phosphorus sulfide, halogen compounds, and magnesium compounds, and may also substantially suspend, dissolve, or mix the above components, such as lithium sulfide, phosphorus sulfide, halogen compounds, and magnesium compounds.

[0080] The solvent of the invention therefore constitutes in step a) the continuous phase in the dispersion of one or more of the abovementioned components.

[0081] Depending on the components and the solvent, some of the components may thus be rather dissolved, partially dissolved or in the form of a slurry (i.e., the components are not dissolved and thus form a slurry with the solvent).

[0082] In a particular preferred embodiment, the solvent is suitably a polar solvent, preferably selected from the group consisting of alkanols, particularly those having 1 to 6 carbon atoms, such as methanol, ethanol, propanol, and butanol, carbonates such as dimethyl carbonate, acetates such as ethyl acetate, ethers such as dimethyl ether, organic nitriles such as acetonitrile, aliphatic hydrocarbons such as hexane, pentane, 2-ethylhexane, heptane, decane, and cyclohexane, and aromatic hydrocarbons such as tetrahydrofuran, xylene, and toluene.

[0083] It will be understood that references herein to a "solvent" include one or more mixed solvents.

[0084] The powder mixture may be mixed in an amount of about 1% by weight to 80% by weight based on the total weight of the powder mixture and the solvent, and the solvent may be mixed in an amount of about 20% by weight to 99% by weight. Preferably, the powder mixture may be mixed in an amount of about 25% by weight to 75% by weight based on the total weight of the powder mixture and the solvent, and the solvent may be mixed in an amount of about 25% by weight to 75% by weight. In particular, the powder mixture may be mixed in an amount of about 40% by weight to 60% by weight based on the total weight of the powder mixture and the solvent, and the solvent may be mixed in an amount of about 40% by weight to 60% by weight.

[0085] The temperature of 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 where no undesirable reactivity between the solvent and the mixed compounds is found. Preferably, step a) is carried out at temperatures between -20°C and 40°C, more preferably between 15°C and 40°C. In the absence of a solvent, step a) is carried out at temperatures between -20°C and 200°C, preferably between 15°C and 40°C.

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

[0087] 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, in particular for a duration of 10 minutes to 80 hours, more preferably about 4 hours to 40 hours.

[0088] Said milling is also known as reactive milling in the conventional synthesis of lithium argyrodite.

[0089] Mechanical milling has the advantage that the 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 performed with or without balls such as ZrO2.

[0090] In such conditions, lithium sulfide, phosphorus sulfide, a halogen compound, and a magnesium compound are reacted, optionally in a solvent, for a period of time.

[0091] The temperature of 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 where no undesired reactivity between the solvent and the compound is found. Preferably, step b) is carried out at a temperature between -20°C and 80°C, more preferably between 15°C and 40°C. In the absence of a solvent, step a) is carried out at a temperature between -20°C and 200°C, preferably between 15°C and 40°C.

[0092] The mechanical treatment of the composition in step b) may also be carried out using techniques well known in the art, such as by stirring, especially by using a standard powder or slurry mixer.

[0093] Typically, a paste or a blend of paste and liquid vehicle may be obtained at the end of step b).

[0094] In step c) at least a portion of the solvent is removed, in particular by means of removing at least about 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 100% of the total weight of the solvent used, or any range included between these values. Solvent removal can be carried out by known methods used in the art, such as decantation, filtration, centrifugation, drying or a combination thereof.

[0095] The temperature in step c) is selected to allow the removal of the solvent. Preferably, if drying is selected as the method of solvent removal, the temperature is selected below the boiling temperature of the selected solvent and as a function of the partial vapor pressure of the selected solvent.

[0096] The duration of step c) is between 1 second and 100 hours, preferably between 1 hour and 20 hours. Such low durations can be obtained, for example, by using flash evaporation, such as by spray drying.

[0097] Step c) is preferably carried out under an atmosphere of an inert gas, such as nitrogen or argon. The dew point of the inert gas is preferably below -20°C, particularly preferably below -40°C. The pressure may be between 0.0001 Pa and 100 MPa, preferably between 0.001 Pa and 20 MPa, preferably between 0.01 Pa and 20 MPa. In particular, the pressure may be in the range of 0.0001 Pa to 0.001 Pa, in particular by using ultra-vacuum techniques. In particular, the pressure may be in the range of 0.01 Pa to 0.1 MPa, in particular by using primary vacuum techniques.

[0098] In step d), the solid residue from step c) can be pressed into pellets. For example, the solid residue can be pressed in a mold to form pellets. The molding can be carried out in equipment known to those skilled in the art. For example, molding can be carried out using a uniaxial press or a simplex tablet press.

[0099] In step e), heating or heat treatment of the residue obtained in step c), for example in the form of pellets, can make it possible, inter alia, to convert the amorphous powder mixture obtained above (glass) into a crystalline solid material or a mixture of glass and crystalline materials (glass ceramics).

[0100] The heat treatment is carried out at a temperature in the range of 350°C to 580°C, for example 370°C to 550°C or 390°C to 530°C, in particular for 1 min to 12 h, more particularly 2 h to 10 h or 3 h to 7 h. The heat treatment can start immediately at high temperature or by ramping the temperature at a rate comprised between 1°C / min and 20°C / min. The heat treatment can be finished by air quenching, or natural cooling from the heating temperature, or by a controlled ramp of the temperature at a rate comprised between 1°C / min and 20°C / min.

[0101] Preferably in step e), the inert atmosphere comprises an inert gas such as dry N2 or dry argon (dry may refer to gas with less than 800 ppm water in liquid and suspended form, including condensation). Preferably in step e), the inert atmosphere is a protective gas atmosphere used to minimize, preferably exclude, the access of oxygen and moisture.

[0102] The pressure during heating can be normal pressure or reduced pressure. The atmosphere can be an inert gas, such as nitrogen and argon. The dew point of the inert gas is preferably below -20°C, particularly preferably below -40°C. The pressure can be from 0.0001 Pa to 100 MPa, preferably from 0.001 Pa to 20 MPa, preferably from 0.01 Pa to 20 MPa. In particular, the pressure can be in the range of 0.0001 Pa to 0.001 Pa, in particular by using ultra-vacuum techniques. In particular, the pressure can be in the range of 0.01 Pa to 0.1 MPa by using primary vacuum techniques.

[0103] In step f), the solid material can be processed to the desired particle size distribution. If necessary, the solid material obtained by the method according to the present invention is ground (e.g., milled) into a powder. Preferably, the powder has a D50 value of the particle size distribution of less than 50 μm, more preferably less than 10 μm, and even more preferably less than 5 μm, as determined by dynamic light scattering or image analysis.

[0104] Preferably, the powder has a particle size distribution D90 value of less than 100 μm, more preferably less than 10 μm, even more preferably less than 5 μm, as determined by dynamic light scattering or image analysis. In particular, the powder has a particle size distribution D90 value comprised between 1 μm and 100.

[0105] The present invention therefore relates to a process for the preparation of a solid material of general formula (I), comprising a') obtaining a solution by mixing the raw materials in one or more solvents under an inert atmosphere; b') removing at least a portion of the one or more solvents from the composition obtained in step a') to obtain a solid residue; c') optionally pressing the solid residue from step b') into pellets; d') optionally heating the solid residue obtained in step b'), for example in pellet form, to a temperature in the range of 350°C to 580°C under an inert atmosphere, thereby forming a solid material; and e') optionally processing the solid material obtained in step d') to a desired particle size distribution; The present invention also relates to a method comprising the steps of:

[0106] The various features of step a') are basically similar to those of step a), e.g., with respect to precursors and solvents, etc. Preferably, the temperature in step a') is in the range of -200°C to 100°C, preferably -200°C to 10°C.

[0107] The characteristics of the removal of the solvent as described in step b') can be similar to those as shown in step c).Preferably in step b') the temperature is in the range of 30°C to 200°C under an inert atmosphere and preferably under a pressure of 0.0001 Pa to 100 MPa.

[0108] In step c'), the solid residue from step b') can be pressed into pellets, represented by step d).

[0109] The heating of step d') may be carried out with the characteristics as given in step e), preferably at a temperature ranging from 350°C to 580°C, under an inert atmosphere and preferably under a pressure ranging from 0.0001 Pa to 100 MPa.

[0110] The characteristics of the processing of the solid material as described in step e') may be similar to those as indicated in step f).

[0111] The present invention also relates to a solid electrolyte and a solid material of formula (I) as solid electrolyte comprising at least a solid material of formula (I).

[0112] Thus, the solid electrolyte comprises at least a solid material of formula (I) and optionally at least one lithium ion conducting material (LiCM) other than the solid material of the invention, such as lithium argyrodite, lithium thiophosphate, glass or glass ceramics Li3PS4, Li7PS 11 , and lithium conducting oxides, such as the lithium-filled garnet Li7La3Zr2O 12 (LLZO) and others.

[0113] The solid electrolyte may also optionally include a polymer, such as styrene butadiene rubber, an organic or inorganic stabilizer, or dispersant, such as SiO2.

[0114] The present invention also relates to an electrochemical device comprising a solid electrolyte comprising at least the solid material of formula (I).

[0115] Preferably, in an electrochemical device, particularly a rechargeable electrochemical device, the solid electrolyte is a solid structural component for the electrochemical device selected from the group consisting of the cathode, the anode and the separator.

[0116] A further aspect of the present invention relates to a battery, more preferably an alkali metal battery, in particular a lithium battery, comprising at least one, e.g., two or more, inventive electrochemical devices. The electrochemical devices can be combined, e.g., in series or parallel connection, with one another in an inventive alkali metal battery.

[0117] The present invention also relates to a solid-state battery comprising a solid electrolyte comprising at least the solid material of formula (I).

[0118] 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, wherein 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.

[0119] The cathode of an all-solid-state electrochemical device typically comprises a solid electrolyte as a further component in addition to the cathode active material, and the anode of an all-solid-state electrochemical device typically also comprises a solid electrolyte as a further component in addition to the anode active material.

[0120] The morphology of the solid-state structure for an electrochemical device, in particular an all-solid-state lithium battery, depends in particular on the morphology of the electrochemical device itself to be produced. The present invention further provides a solid-state structure for an electrochemical device, selected from the group consisting of a cathode, an anode and a separator, wherein the solid-state structure for an electrochemical device comprises a solid-state material according to the present invention.

[0121] Multiple electrochemical cells can be combined into an all-solid-state battery having both solid electrodes and a solid electrolyte.

[0122] The solid-state materials disclosed above may be used to manufacture electrodes. The electrodes may be positive or negative electrodes.

[0123] The electrodes are typically a metal substrate; at least one layer directly adhered to said metal substrate, (i) Formula (I): Li 7-2x-y Mg x P.S. 6-y X y (I) (In the formula, - X is a halogen selected from the group consisting of F, Cl, I and Br or a combination thereof; - x is a number such that 0.01≦x≦0.4, - y is a number such that 0.5≦y≦1. and (ii) at least one electroactive compound (EAC); (iii) optionally at least one lithium ion conducting material (LiCM) other than the solid-state material of the present invention; (iv) At least one optional conductive material (ECM), and (v) At least one optional lithium salt (LIS), and (vi) At least one optional polymeric binder material (P), and at least one layer made from a composition comprising the same. is included.

[0124] The numerical values x and y may belong to another range as described above.

[0125] The electroactive compound (EAC) means a compound that can incorporate or insert lithium ions into its structure and release them during the charging and discharging stages of an electrochemical device. The EAC can be a compound that can insert and desorb lithium ions into its structure. For the positive electrode (cathode), the EAC can be a complex metal chalcogenide of the formula LiMeQ2, where - 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) can be.

[0126] More specifically, the EAC can 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) and spinel structured LiMn2O4 and Li(Ni 0.5 Mn 1.5 )O4 is one example.

[0127] EAC is the formula M1M2(JO4) f E 1-f (In the formula, - M1 is lithium, which may be partially replaced by another alkali metal, which is less than 20% of M1; - M2 is a transition metal with an oxidation level of +2 selected from Fe, Co, Mn, Ni or mixtures thereof, which may be partially replaced by one or more additional metals with an oxidation level of +1 to +5, inclusive, and which is less than 35% of the M2 metal; - JO4 is any oxyanion where J is P, S, V, Si, Nb, Mo or any combination thereof; - E is a fluoride, hydroxide or chloride anion; - f is the mole fraction of JO4 oxyanions, typically between 0.75 and 1) The electroactive material may be a lithiated or partially lithiated transition metal oxyanion based material.

[0128] M1M2(JO4) as defined above f E 1-f The electroactive material is preferably phosphate-based. It may exhibit an ordered structure or a modified olivine structure.

[0129] For the positive electrode, the EAC may be sulfur or Li2S.

[0130] For the positive electrode, the EAC may also be a conversion type material such as FeS2, or FeF2, or FeF3.

[0131] For the negative electrode, the EAC may be selected from the group consisting of graphitic carbons capable of intercalating lithium. Further details regarding this type of EAC may be found in Carbon 2000, 38, 1031-1041. This type of EAC typically exists in the form of powders, flakes, fibers or spheres (e.g., mesocarbon microbeads).

[0132] EAC can be any of a variety of materials, including lithium metal; lithium alloy compositions (such as those described in U.S. Pat. No. 6,203,944 and WO 00 / 03444); generally of the formula Li4Ti5O 12 These compounds generally contain mobile ions, i.e., Li + Lithium-silicon alloys, commonly known as lithium silicides with high Li / Si ratios, and in particular the formula Li 4.4 Lithium silicide of formula Si; and Li 4.4 It can also be a lithium-germanium alloy containing a crystalline phase of Ge. The EAC can also be a composite material based on silicon and / or silicon oxide-loaded carbonaceous materials, especially graphitic carbon / silicon and graphite / silicon oxide, where the graphitic carbon is composed of one or several carbons capable of intercalating lithium.

[0133] The ECM is typically selected from the group consisting of conductive carbonaceous materials and metal powders or fibers. The 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 ketjen black and acetylene black. Metal powders or fibers include nickel and aluminum powders or fibers.

[0134] The lithium salt (LIS) may 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.

[0135] The function of the polymeric binder (P) is to bind the components of the composition. The polymeric binder is usually inert. It should also preferably be chemically stable and facilitate electronic and ionic transport. Polymeric binders are well known in the art. Non-limiting examples of polymeric materials (P) include, inter alia: (1) VDF or TFE based polymers, especially in the form of copolymers, block copolymers or graft copolymers; (2) hydrogenated or non-hydrogenated diene based rubber polymers, especially in the form of block copolymers and graft polymers, such as polyisobutylene (PIB), butadiene styrene rubber (SBR), (hydrogenated) acrylonitrile butadiene rubber ((h)NBR), styrene-ethylene-butylene-styrene (SEBS); (3) polymethyl methacrylate (PMMA), polybutyl acrylate (BA), styrene-butyl acrylate (ST-BA), styrene methyl acrylate (ST-MA), butyl acrylate-acrylonitrile (BA-CN), and the like. (4) polysaccharide-based polymers, copolymers, block copolymers and graft copolymers, such as carboxymethylcellulose (CMC), guar, etc.; (5) acrylonitrile-based polymers, especially in the form of copolymers, block copolymers and graft polymers, such as poly(acrylonitrile) (PAN), acrylonitrile-methylacrylate (PAN-MA), styrene-acrylonitrile (SAN), acrylonitrile-styrene-acrylate (ASA); (6) polyamide-imide (PAI) polymers, copolymers, block copolymers and graft polymers.

[0136] The polymeric material (P) can be selected from the list consisting of vinylidene fluoride (VDF) based (co)polymers. The polymeric material (P) can more particularly be a copolymer comprising or consisting of units of VDF and hexafluoropropylene (HFP).

[0137] The polymeric material (P) can be chosen from the list consisting of thermoplastic elastomers based on styrene, optionally hydrogenated, and more particularly can be butadiene-styrene rubber (SBR) or styrene-ethylene-butylene-styrene (SEBS).

[0138] The polymeric material (P) can be selected from the list consisting of polymers containing units of acrylonitrile. It can more particularly be a copolymer of acrylonitrile, butadiene and / or butyl acrylate.

[0139] 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, more particularly 5% to 30% by weight. The thickness of the electrode is not particularly limited and should be adjusted with respect to the energy and power required in the application. For example, the thickness of the electrode may be 0.01 mm to 1,000 mm.

[0140] The solid material of the present invention may also be used to manufacture a separator, which is an ion-permeable membrane placed between the anode and cathode of a battery. Its function is to allow the passage of lithium ions while blocking electrons and ensuring physical separation between the electrodes.

[0141] The separator of the present invention typically comprises at least - the following formula (I): Li 7-2x-y Mg x P.S. 6-y X y (I) (In the formula, - X is a halogen selected from the group consisting of F, Cl, I and Br or a combination thereof; - x is a number such that 0.01≦x≦0.4, - y is a number such that 0.5≦y≦1. and - optionally at least one polymeric binding material (P); - optionally at least one metal salt, in particular a lithium salt, - optionally at least one plasticizer; Includes.

[0142] The numbers x and y may fall within other ranges previously mentioned.

[0143] The electrodes and separators can be manufactured using methods well known to those skilled in the art, which typically involve mixing the components in a suitable solvent and removing the solvent. For example, the electrodes can be manufactured using the following steps: - applying a slurry comprising the components of the composition and at least one solvent onto a metal substrate; - Removing the solvent It can be produced by a method comprising:

[0144] Common techniques known to those skilled in the art are: coating and calendaring, dry and wet extrusion, 3D printing, sintering of porous foams followed by impregnation. Common manufacturing techniques for electrodes and separators are provided in Journal of Power Sources, 2018 382, ​​160-175. Other techniques may be used, such as extrusion, paste extrusion, (electrical) spraying, kneading followed by calendaring.

[0145] 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, personal digital assistants, cell phones, watches, camcorders, digital cameras, thermometers, calculators, laptop BIOS, communication equipment or remote car locks, and energy storage devices for power plants.

[0146] Electrochemical devices, especially batteries such as the solid-state batteries described herein, can be used in, among others, motorized vehicles, bicycles driven by electric motors, robots, aircraft (e.g. unmanned aerial vehicles such as drones), ships or stationary energy storage. Mobile devices such as vehicles, for example automobiles, bicycles, aircraft or water vehicles such as boats or ships, are preferred. Other examples of mobile devices are those that are portable, such as computers, especially laptops, telephones or power tools, for example from the construction sector, especially drills, battery-powered screwdrivers or battery-powered nailers.

[0147] To the extent that the disclosures of any patents, patent applications, and publications incorporated herein by reference conflict with the statements of this application to the extent that any term may be unclear, the statements of this application shall control.

[0148] Experimental section X-ray diffraction X-ray diffraction of the samples was collected using a Malvern Panalytical Aeris Research diffractometer (Cu, 600 W, 40 kV, 15 mA, Soller slits 0.02°). Diffraction was collected over a 2-h period in the range 10°-90°. Lattice parameters were determined by fitting of the diffraction profile using the Full-Prof Suite. Profile fitting was performed using the F-43M space group of argyrodite.

[0149] Conductivity and electrochemical impedance spectroscopy (EIS) To perform the impedance spectroscopy measurements, the powder was sandwiched between two dried carbon paper electrodes (Papyex soft graphite from Mersen, thickness 0.2 mm) and cold pressed at 500 MPa in a 6 mm die (Eurolabo uniaxial manual press MS15-MDD). The resulting pellet was then loaded into an airtight measurement cell (MTI EQ-PSC). All measurements were performed at a pressure of 40 MPa.

[0150] Ionic Conductivity: AC impedance spectra were collected using a Biologic VMP3, the temperature of the sample was controlled by a binder thermostat. The cell was connected to a galvanostat-potentiostat and PEIS spectra were recorded under conditions of a 20mV sinusoidal perturbation around the OCV from 1MHz to 10kHz, 25 points were recorded every 10 times, and each point was averaged from 50 measurements. A model circuit was used to fit the curve and extract the ionic resistance. Temperature tests were performed at each temperature with 2 hour steps and a spectrum recorded at the end. The temperature was set from -20°C to 60°C and back to 30°C.

[0151] The electronic conductivity is measured by DC measurements at 2 volts and is determined after 1 hour by the asymptotic method.

[0152] EIS measurements show that the LiPSMgX solid material according to the invention has improved ionic conductivity and lower or similar activation energy compared to the conductivity and activation energy of LiPSMgX materials according to the prior art.

[0153] modeling Conductivity maps showing different compositions and predicted room temperature lithium ion conductivities were generated by molecular dynamics based on deep neural network potentials. The method relies on a machine learning model of interatomic potentials to perform classical molecular dynamics simulations. The neural network potentials were trained with ab-initio molecular dynamics and the forces acting on the various atoms were fitted to those obtained directly from the ab-initio simulations. The training set consisted of Li ions with x=0, 0.5, y=0.5, 1.0, 1.2, containing 48–54 atoms. 7-2x-y Mg x P.S. 6-y Cl yThe simulations were run for approximately 120 ps at 1000 K, with snapshots (including the total energy and forces on each atom) taken approximately every 6 ps to generate a training set. Once trained, these neural network potentials are used to model systems that are much larger, lower temperature, or have more defects than are typically computable with ab-initio molecular dynamics. In this case, a 2 × 2 × 2 superlattice of a conventional unit cell containing 384 to 432 atoms was simulated for 200 ps, ​​250 ps, ​​300 ps, ​​400 ps, ​​and 800 ps at 1250 K, 1000 K, 830 K, 715 K, and 625 K, respectively, from which the Li-ion conductivity at room temperature (300 K) was extrapolated.

[0154] Formula Li where X is a halogen 7-2x-y Mg x P.S. 6-y X y We calculated the ionic conductivity of the compound LiMgPSX, which is the solid sulfide corresponding to LiMg, over a wide composition range, where x is from 0 to 0.5 and y is from 0.5 to 1.2.

[0155] Comparative Example 1: Synthesis of Li6PS5Cl Li2S (Lorad Chemical), LiCl (Sigma-Aldrich), and P2S5 (Sigma-Aldrich) were weighed and mixed in a stoichiometric ratio in an Ar-filled glove box to obtain 4 g of Li6PS5Cl of the desired composition. The mixture was then transferred into a 45 mL ZrO2 jar containing 5 mm zirconia (YSZ) balls. The ball to powder ratio was fixed at 16.5. The jar was sealed, removed from the glove box, and placed in a Fritsch Planetary Micro Mill Pulverisette7. The mixture was ball milled for 2 h at a rotation speed of 500 RPM with a 15 min break after every 30 min of grinding. The powder was collected in an Ar-filled glove box (<1 ppm H20, <1 ppm O2). The resulting powder was transferred into a sealed SiC crucible. The crucible was heated to 500 °C in a tube furnace with a N2 atmosphere at a heating rate of 5 °C / min and held at this temperature for 12 h. The sample was then cooled to room temperature. It was retrieved in an Ar-filled glove box and deagglomerated in a mortar.

[0156] The argyrodite phase was identified as pure, with a lattice parameter of 9.8519 Å.

[0157] The ionic conductivity at 30 °C was 3.2 mS / cm, which is associated with an activation energy of 0.38 eV. The electronic conductivity at 30 °C was 4 × 10 -9 It was S / cm.

[0158] Comparative example 2: Li 5,8 Mg 0.1 Synthesis of PS5Cl Li2S (Lorad Chemical), LiCl (Sigma-Aldrich), MgCl2 (Sigma-Aldrich), and P2S5 (Sigma-Aldrich) were weighed and mixed in a stoichiometric ratio in an Ar-filled glove box to prepare Li2S with the desired composition. 5.8 Mg 0.14 g of PS5Cl was obtained. The mixture was then transferred into a 45 mL ZrO2 jar containing 5 mm zirconia (YSZ) balls. The ball to powder ratio was fixed at 16.5. The jar was sealed, removed from the glove box and placed in a Fritsch Planetary Micro Mill Pulverisette7. The mixture was ball milled for 2 h at a rotation speed of 500 RPM with a 15 min break after every 30 min of grinding. The powder was collected inside an Ar filled glove box (<1 ppm H20, <1 ppm O2). The obtained powder was transferred into a sealed SiC crucible.

[0159] The crucible was heated to 500 °C in a tube furnace with a N2 atmosphere at a heating rate of 5 °C / min and held at this temperature for 12 h. The sample was then cooled to room temperature. It was retrieved in an Ar-filled glove box and deagglomerated in a mortar.

[0160] The argyrodite phase was identified as pure, with a lattice parameter of 9.8457 Å.

[0161] The ionic conductivity at 30 °C was 1.6 mS / cm, which corresponds to an activation energy of 0.38 eV. The electronic conductivity at 30 °C was 3.10 -9 S / cm.

[0162] Comparative example 3: Li 5.25 Mg 0.25 P.S. 4.75 Cl 1.25 Synthesis of Li2S (Lorad Chemical), LiCl (Sigma-Aldrich), MgCl2 (Sigma-Aldrich), and P2S5 (Sigma-Aldrich) were weighed and mixed in a stoichiometric ratio in an Ar-filled glove box to prepare Li2S with the desired composition. 5.25 Mg 0.25 P.S. 4.75 Cl 1.254 g of was obtained. The mixture was then transferred into a 45 mL ZrO2 jar containing 5 mm zirconia (YSZ) balls. The ball to powder ratio was fixed at 16.5. The jar was sealed, removed from the glove box and placed in a Fritsch Planetary Micro Mill Pulverisette7. The mixture was ball milled for 2 h at a rotation speed of 500 RPM with a 15 min break after every 30 min of grinding. The powder was collected in an Ar-filled glove box (<1 ppm H20, <1 ppm O2). The resulting powder was transferred into a sealed SiC crucible. The crucible was heated to 500 °C in a tube furnace with a N2 atmosphere at a heating rate of 5 °C / min and kept at this temperature for 12 h. The sample was then cooled to room temperature. It was collected in an Ar-filled glove box and deagglomerated in a mortar.

[0163] The argyrodite phase was identified and was nearly pure. Traces of MgS were also observed. The lattice parameter of argyrodite was 9.8188 Å.

[0164] The ionic conductivity at 30 °C was 2.6 mS / cm, which is associated with an activation energy of 0.38 eV. The electronic conductivity at 30 °C was 2 × 10 -9 S / cm.

Claims

1. The following general formula (I): Li ７－２ｘ－ｙ Mg ｘ PS ６－ｙ X ｙ (I) (In the formula, X is a halogen selected from the group consisting of F, Cl, I, and Br or a combination thereof; - x is a number such that 0.01≦x≦0.4, - y is a number such that 0.5≦y≦1) of solid materials.

2. 2. The solid material of claim 1, wherein X is Cl.

3. 0.01≦x≦0.125, and 0.5≦y≦0.8; The solid material of claim 1 .

4. 0.125≦x≦0.4, and 0.65≦y≦0.85; The solid material of claim 1 .

5. 10. The solid state material of claim 1, exhibiting an ionic conductivity of at least 3.3 mS / cm as measured in a compressed (500 MPa) pellet by impedance spectroscopy.

6. When measured by laser diffraction in paraxylene, - a d50 value of less than 50 μm, a d10 value of more than 0.05 μm, and / or - a d90 value of less than 100 μm, 2. The solid material of claim 1, in powder form having a particle size distribution exhibiting:

7. A method for producing the solid material of claim 1, comprising: a) obtaining a composition by mixing ingredients, optionally in one or more solvents; b) optionally subjecting the composition obtained in step a) to a mechanical treatment; c) optionally removing at least a portion of the one or more solvents from the composition obtained in step b) to obtain a solid residue; d) optionally pressing the solid residue from step c) into pellets; e) heating the residue obtained in step c), e.g., in pellet form, under an inert atmosphere to a temperature in the range of 350°C to 580°C for a time in the range of 1 hour to 12 hours, thereby forming the solid material; and f) optionally processing the solid material obtained in step e) to a desired particle size distribution; A method for producing a solid material comprising:

8. 8. The method according to claim 7, wherein in step b) the mechanical treatment is carried out by wet milling or dry milling.

9. A method for producing the solid material of claim 1, comprising: a') obtaining a solution by mixing raw materials in one or more solvents; b') removing at least a portion of the one or more solvents from the solution obtained in step a') to obtain a solid residue; c') optionally pressing said solid residue from step b') into pellets; d') optionally heating the residue obtained in step b'), for example in pellet form, to a temperature in the range of 350°C to 580°C for a time in the range of 1 hour to 12 hours under an inert atmosphere, thereby forming the solid material; and e') optionally processing the solid material obtained in step d') to a desired particle size distribution; A method for producing a solid material comprising:

10. The raw material is at least lithium sulfide (Li ２ S) and phosphorus sulfide (P ２ S ５ ), lithium chloride (LiCl), magnesium sulfide (MgS), magnesium chloride (MgCl ２ 10. The method according to claim 7, wherein the magnesium compound is selected from the group consisting of methyl methyl ketone, ...

11. A solid material obtainable by the method according to claim 7 or 9.

12. Use of the solid material according to any one of claims 1 to 6 as a solid electrolyte.

13. A solid electrolyte comprising at least the solid material according to claim 1.

14. An electrode comprising at least a metal substrate; at least one layer directly adhered to said metal substrate, (i) a solid material according to any one of claims 1 to 6; (ii) at least one electroactive compound (EAC); and (iii) optionally at least one lithium ion conducting material (LiCM) other than the solid material of the present invention; (iv) optionally at least one electrically conductive material (ECM); (v) an optional lithium salt (LIS); and (vi) optionally at least one polymeric binder material (P); At least one layer made from a composition comprising: An electrode comprising:

15. at least, - a solid material according to any one of claims 1 to 6; - optionally at least one polymeric binder material (P), optionally at least one metal salt, in particular a lithium salt, optionally at least one plasticizer; Contains separators.