New solid sulfide electrolytes

Abstract

The present invention relates to a compound having the following general formula (I): Li 6-x-2y Cu x PS 5-y The present invention relates to a method for producing a solid material according to formula X(I), wherein X is selected from the group consisting of F, Cl, I and Br; 0.005≦x≦5; and 0≦y≦0.5, the method comprising at least the step of bringing at least lithium sulfide, phosphorus sulfide, a halogen compound and a copper compound, optionally in one or more solvents. The present invention also refers to said solid material and its use, inter alia, as a solid electrolyte for electrochemical devices.

Description

[Technical Field]

[0001] This application claims priority to European Patent Application Publication No. 20164967.0, filed March 23, 2020, the entire contents of which are incorporated herein by reference for all purposes.

[0002] The present invention relates to a compound of the general formula (I): Li 6-x-2y Cu x PS 5-y X (I) wherein X is a halogen, 0.005≦x≦5; and 0≦y≦0.5. The present invention also relates to a method for producing a solid material according to claim 1, which method comprises at least the step of bringing at least lithium sulfide, phosphorus sulfide, a halogen compound and a copper compound, optionally in one or more solvents. The present invention also refers to said solid material and its use, in particular as a solid electrolyte for electrochemical devices. [Background technology]

[0003] Lithium batteries are used to power portable electronics and electric vehicles due to their high energy and power density. Conventional lithium batteries utilize a liquid electrolyte composed of a lithium salt dissolved in an organic solvent. This system poses safety concerns because the organic solvent is flammable. Lithium dendrites can form and pass through the liquid electrolyte medium, causing short circuits and generating heat, which can lead to accidents that can result in serious injury. Because the electrolyte solution is a flammable liquid, there are concerns about leakage, fire, and other issues when used in batteries. In light of these concerns, the development of a solid electrolyte with a higher level of safety is anticipated as the electrolyte for next-generation lithium batteries.

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

[0005] 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 challenges to 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-state electrolytes with high conductivity for lithium ions. An important class of such solid electrolytes is materials with the composition Li6PS5X (X = Cl, Br) having the argyrodite structure. Argyrodite has been known for a long time and originates from argyrodite Ag8GeS6, first described by C. Winkler in 1886, the analysis of which led to the discovery of germanium. The argyrodite family consists of over 100 crystalline solids, including those in which silver is replaced by copper, germanium by gallium or phosphorus, and sulfur by selenium. Thus, Nitsche, Kuhs, Krebs, Evain, Boucher, Pfitzner and Nilges describe compounds such as Cu9GaS6, Ag7PSe6 and Cu8GaS5Cl, among others, whose solid-state structures are derived from argyrodite.

[0006] As reported in the literature, most lithium argyrodites, especially most Li6PS5Cl, are prepared by dry or wet mechanochemical routes.

[0007] 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

[0008] It has been unexpectedly discovered that new solid sulfide electrolytes with higher ionic conductivity and lower activation energy than conventional Li6PS5Cl materials can be obtained by using copper dopants. The new LiCuPSX solid materials of the present invention also exhibit chemical and mechanical stability and processability similar to those of conventional lithium argyrodites. The solid materials of the present invention can also be prepared with improved productivity and allow for control of the morphology of the resulting products. Furthermore, the solid materials of the present invention exhibit lower amounts of raw material impurities, such as Li2S and LiCl impurities. The solid materials of the present invention also exhibit lower amounts of undesired phases, such as gamma-Li3PS4.

[0009] The present invention therefore provides compounds of the general formula (I): Li 6-x-2y Cu x PS 5-y X (I) (In the formula, - X is selected from the group consisting of F, Cl, I and Br; 0.005≦x≦5; preferably 0.015≦x≦1.5; and - 0≦y≦0.5, preferably 0≦y≦0.25) This refers to solid materials according to

[0010] The present invention relates to a compound of the general formula (I): Li 6-x-2y Cu x PS 5-y X (I) (In the formula, - X is selected from the group consisting of F, Cl, I and Br; 0.005≦x≦5; preferably 0.015≦x≦1.5; and - 0≦y≦0.5, preferably 0≦y≦0.25) The present invention also relates to a method for producing a solid material according to claim 1, comprising at least the step of bringing at least lithium sulfide, phosphorus sulfide, a halogen compound and a copper compound, optionally in one or more solvents.

[0011] The present invention relates to a compound of the general formula (I): Li 6-x-2y Cu x PS 5-y X (I) (In the formula, - X is selected from the group consisting of F, Cl, I and Br; 0.005≦x≦5; preferably 0.015≦x≦1.5; and - 0≦y≦0.5, preferably 0≦y≦0.25) A process for the preparation of a solid material according to the method of claim 1, comprising at least a) mixing stoichiometric amounts of lithium sulfide, phosphorus sulfide, a halogen compound, and a copper compound under an inert atmosphere, optionally in one or more solvents, to obtain a composition; b) a process step of subjecting the composition of step a) to a mechanical treatment; c) optionally, a process step of removing at least a portion of the one or more solvents from the composition obtained in step b), thereby obtaining a solid residue; d) heating the resulting residue obtained in step c) at a temperature in the range of 100°C to 700°C under an inert atmosphere, thereby forming said solid material; e) optionally processing the solid material obtained in step d) to a desired particle size distribution; It also refers to a process that includes

[0012] The invention further relates to a solid material obtainable by said first process.

[0013] The solid materials of the present invention can also be prepared by a complete solution process. In particular, the present invention provides a compound of the general formula (I): Li 6-x-2y Cu x PS 5-y X (I) (In the formula, - X is selected from the group consisting of F, Cl, I and Br; 0.005≦x≦5; preferably 0.015≦x≦1.5; and - 0≦y≦0.5, preferably 0≦y≦0.25) A process for the preparation of a solid material according to the method of claim 1, comprising at least a') a process step of mixing stoichiometric amounts of lithium compounds, sulfide compounds, phosphorus compounds, halogen compounds and copper compounds in one or more solvents under an inert atmosphere to obtain a solution; b') a process step of removing at least a portion of the one or more solvents from the composition as obtained in step a'), preferably under an inert atmosphere and at a temperature in the range of 30°C to 200°C, thereby obtaining a solid material; c') optionally a process step of heating the solid material as obtained in step b') at a temperature in the range of 100°C to 700°C under an inert atmosphere; d') optionally processing the solid material obtained in step c') to a desired particle size distribution; It also refers to a process that includes

[0014] The invention further relates to a solid material obtainable by said second process.

[0015] The present invention relates to a compound of formula (I): Li 6-x-2y Cu x PS 5-y X (I) (In the formula, - X is selected from the group consisting of F, Cl, I and Br; 0.005≦x≦5; preferably 0.015≦x≦1.5; and - 0≦y≦0.5, preferably 0≦y≦0.25) The present invention also refers to the use of the solid material as a solid electrolyte.

[0016] The present invention relates to a compound of formula (I): Li 6-x-2y Cu x PS 5-y X (I) (In the formula, - X is selected from the group consisting of F, Cl, I and Br; 0.005≦x≦5; preferably 0.015≦x≦1.5; and - 0≦y≦0.5, preferably 0≦y≦0.25) Also referred to is a solid electrolyte comprising at least one solid material.

[0017] The present invention relates to a compound of formula (I): Li 6-x-2y Cu x PS 5-y X (I) (In the formula, - X is selected from the group consisting of F, Cl, I and Br; 0.005≦x≦5; preferably 0.015≦x≦1.5; and - 0≦y≦0.5, preferably 0≦y≦0.25) The present invention also relates to an electrochemical device including at least a solid electrolyte containing at least the solid material described above.

[0018] The present invention relates to a compound of formula (I): Li 6-x-2y Cu x PS 5-y X (I) (In the formula, - X is selected from the group consisting of F, Cl, I and Br; 0.005≦x≦5; preferably 0.015≦x≦1.5; and - 0≦y≦0.5, preferably 0≦y≦0.25) It also refers to a solid-state battery comprising at least a solid electrolyte comprising at least a solid material of the formula:

[0019] The present invention relates to a compound of formula (I): Li 6-x-2y Cu x PS 5-y X (I) (In the formula, - X is selected from the group consisting of F, Cl, I and Br; 0.005≦x≦5; preferably 0.015≦x≦1.5; and - 0≦y≦0.5, preferably 0≦y≦0.25) The present invention also relates to a vehicle including at least a solid-state battery including at least a solid electrolyte including at least the solid material.

[0020] definition Throughout this specification, unless the context requires otherwise, the words "comprise" or "include" or variations such as "comprises," "including," "includes," "comprising," and the like, are 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 words "comprise" and "comprises" and variations thereof mean "consisting only of."

[0021] As used herein, the singular forms "a," "an," and "the" include plural references unless the context clearly dictates otherwise. The term "and / or" includes the meaning "and," "or," and also all other possible combinations of the elements associated with this term.

[0022] The term "~" should be understood to be inclusive.

[0023] Ratios, concentrations, amounts, and other numerical data may be presented in range format herein. It should be understood that such range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values ​​explicitly recited as the limits of the range, but also all individual numerical values ​​or subranges subsumed within that 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 limits 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 fractions within a stated range, e.g., 122.2°C, 140.6°C, and 141.3°C.

[0024] The term "electrolyte" refers in particular to the electrolyte through which ions, such as Li + An electrolyte is a material that allows ions to move through it, but does not conduct electrons. + "Solid electrolytes" according to the present invention are particularly useful for conducting ions, such as Li, while electrically insulating the cathode and anode of a battery. + means any kind of material that can move around in it.

[0025] 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 AgGeS. This crystal structure is also exemplified by the isomorphous argyrodite mineral, AgSnS.

[0026] 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).

[0027] As used herein, the term "peak" refers to a (2Θ) position on the x-axis of an XRD powder pattern of intensity v, in degrees (2Θ), that has a peak intensity substantially greater than background. In a set of XRD powder pattern peaks, the major peak is the peak of highest intensity associated with the compound or phase under analysis. The second major peak is the second most intense peak. The third major peak is the third most intense peak.

[0028] The term "electrochemical device" refers, inter alia, 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.

[0029] 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.

[0030] 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 watercraft, aircraft, and the like, and to 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 having two or more different power sources, e.g., a gasoline-powered and an electric-powered vehicle.

[0031] The present invention therefore provides compounds of general formula (I) Li 6-x-2y Cu x PS 5-y X (I) (In the formula, X is a halogen preferably selected from the group consisting of F, Cl, I and Br; 0.005≦x≦5; preferably 0.015≦x≦1.5; and - 0≦y≦0.5, preferably 0≦y≦0.25)

[0010] This relates to solid materials according to

[0032] 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) clearly defines the composition averaged over all phases present in the solid material.

[0033] X is preferably Cl, preferably 0.02≦x≦0.8, more preferably 0.03≦x≦0.6, especially 0.03≦x≦0.06. More preferably, x is 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, and 0.1, or any range formed therein. More preferably, y is 0, 0.1, 0.2, 0.3, 0.4, and 0.5, or any range formed therein.

[0034] The solid material of the present invention can be amorphous (glass) and / or crystallized (glass ceramics). Only a portion of the solid material can be crystallized. The crystallized portion of the solid material can contain only one crystalline structure, or it can contain multiple crystalline structures. The crystallinity of the solid material (the crystallinity of the crystalline structure whose ionic conductivity is higher than that of the amorphous material) is preferably between 80% and 100%.

[0035] The crystallinity can be measured using an NMR spectrometer. 31A P-NMR spectrum is measured, and for the resulting spectrum, the resonance lines observed between 70 and 120 ppm are separated into Gaussian curves using a nonlinear least-squares method, and the ratio of the areas of each curve is obtained.

[0036] The solid material of the present invention preferably comprises a fraction consisting of crystalline phases, one of which has an argyrodite structure. Preferably, the crystalline phase having the argyrodite structure 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 refinement of the full diffractogram. This refinement can be performed in the FullProf software using the multi-step refinement option.

[0037] The solid material of the present invention comprises the structural unit PS4 3- and structural unit PO4 3- wherein preferably the structural unit PS4 3- Amount and structural unit of PO4 3- The ratio between the amounts of is in the range of 1000:1 to 9:1. The solid material of the present invention, when analyzed by X-ray diffraction using CuKα radiation at 25°C, may comprise peaks at positions of at least 15.65°±0.5°, 25.53°±0.5°, 30.16°±0.5° and 31.52°±0.5° (2θ).

[0038] The crystalline space group of the solid material of the present invention is preferably space group 226

number

[0039] Preferably, the solid material of formula (I) according to the present invention may be:

[0040] [Table 1]

[0041] 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.

[0042] The solid material of the present invention may preferably be in the form of a powder having a particle size distribution with a D50 comprised between 0.05 μm and 10 μm. The particle size can be evaluated by SEM image analysis or laser diffraction analysis.

[0043] D50 has the usual meaning used in the field of particle size distribution. Dn corresponds to the diameter of particles where n% of the particles have a diameter less than Dn. D50 (median) is defined as the size value corresponding to the cumulative distribution at 50%. These parameters are usually determined from the volumetric diameter distribution of a dispersion of particles of a solid material in a liquid obtained with a laser diffractometer using a standard procedure predetermined by the instrument software. Laser diffractometers use the technique of laser diffraction to measure particle size by measuring the intensity of 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.

[0044] D50 can be measured, inter alia, after treatment under ultrasound, which can include inserting an ultrasound probe into a dispersion of a solid material in a liquid and subjecting the dispersion to ultrasound treatment.

[0045] The present invention also refers to a method for producing a solid material according to general formula (I), which comprises at least the step of bringing at least lithium sulfide, phosphorus sulfide, a halogen compound and a copper compound, optionally in one or more solvents. One or more of lithium sulfide, phosphorus sulfide, a halogen compound and a copper compound may be used.

[0046] In particular, the present invention also relates to a method for producing a solid material according to general formula (I), comprising at least the step of reacting at least lithium sulfide, phosphorus sulfide, a halogen compound and a copper compound, optionally in one or more solvents. One or more of lithium sulfide, phosphorus sulfide, a halogen compound and a copper compound may be used.

[0047] The solid materials of the present invention may be produced by any method known in the prior art for producing sulfide-based glassy solid electrolytes, such as, for example, melt extrusion, complete solution, mechanical milling, or slurry methods in which raw materials are reacted, optionally in one or more solvents.

[0048] The present invention therefore relates to a process for the preparation of a solid material according to general formula (I), comprising at least a) mixing stoichiometric amounts of lithium sulfide, phosphorus sulfide, a halogen compound, and a copper compound under an inert atmosphere, optionally in one or more solvents, to obtain a composition; b) a process step of subjecting the composition obtained in step a) to a mechanical treatment; c) optionally, a process step of removing at least a portion of the one or more solvents from the composition obtained in step b), thereby obtaining a solid residue; d) heating the resulting residue obtained in step c) at a temperature in the range of 100°C to 700°C under an inert atmosphere, thereby forming said solid material; e) optionally processing the solid material obtained in step d) to a desired particle size distribution; This refers to a process that includes:

[0049] 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 prevent undesirable chemical reactions, such as oxidation and hydrolysis reactions with oxygen and moisture in the air. Therefore, 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, and O2 with less than 1000 ppm of water in liquid and suspended form, including condensed form. The gas can also be pressurized.

[0050] Preferably, stirring is carried out when the raw materials are brought into contact with each other under an atmosphere of an inert gas such as nitrogen or argon. The dew point of the inert gas is preferably -20°C or lower, particularly preferably -40°C or lower. The pressure may be 0.0001 Pa to 100 MPa, preferably 0.001 Pa to 20 MPa, preferably 0.01 Pa to 0.5 MPa. 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 of water in liquid and suspended form, including condensation).

[0051] The composition ratio of each element can be controlled by adjusting the amount of raw material compounds when the solid material is produced. The precursors and their molar ratios are selected according to a target stoichiometry, which defines the ratio between the elements Li, Cu, P, S, and M that can be obtained from the applied amount of precursor under conditions of complete conversion without side reactions and other losses.

[0052] Lithium sulfide refers to a compound containing 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 LiS.

[0053] Phosphorus sulfide refers to a compound containing 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, the phosphorus sulfide may be composed of sulfur atoms and phosphorus atoms. Non-limiting exemplary phosphorus sulfides include P2S5, P4S3, P4S 10 , P4S4, P4S5, P4S6, P4S7, P4S8 and P4S9.

[0054] A halogen compound refers to a compound containing one or more halogen atoms, such as F, Cl, Br, or I, chemically bonded (e.g., ionic or covalently) to other atoms constituting the compound. In certain preferred embodiments, the halogen compound may contain one or more or a combination of F, Cl, Br, and I and one or more metal atoms. In another preferred embodiment, the halogen compound may contain one or more or a combination of F, Cl, Br, and I and one or more non-metal atoms. Non-limiting examples may include metal halides such as LiF, LiBr, LiCl, LiI, NaF, NaBr, NaCl, NaI, KaF, KBr, KCl, KI, etc. In certain preferred embodiments, the halogen compound suitable for use in the solid electrolyte of an 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.

[0055] A copper compound refers to a compound containing one or more copper atoms through chemical bonds (e.g., ionic or covalent bonds) to other atoms that make up the compound. In another embodiment, the copper compound can be metallic copper. In certain preferred embodiments, the copper compound can contain one or more Cu atoms and one or more non-metallic atoms, such as S, Cl, or B. The copper compound is preferably CuS, CuS, Cu 2-xS (where x is between 0 and 1, in particular x=0.06 (durletite), x=0.1, x=0.2 (digenite)) and CuCl. The copper compound of the present invention can also be a blend of metallic copper and elemental sulfur.

[0056] Preferably, the solid material of the present invention is produced by using at least the following precursors: Li2S, P2S5, LiCl and Cu2S. The lithium sulfide is therefore Li2S, the phosphorus sulfide is therefore P2S5, the halide compound is therefore LiCl, and the copper compound is therefore Cu2S.

[0057] Preferably, the lithium sulfide, phosphorus sulfide, halogen compounds and copper compounds have 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.

[0058] The solvent may suitably be selected from one or more polar or non-polar solvents capable of substantially dissolving at least one compound selected from lithium sulfide, phosphorus sulfide, halogen compounds, and copper compounds, and the solvent may also substantially suspend, dissolve, or otherwise mix the above components, such as lithium sulfide, phosphorus sulfide, halogen compounds, and copper compounds.

[0059] The solvent of the present invention therefore constitutes in step a) the continuous phase in the dispersion of one or more of the above components.

[0060] Depending on the components and the solvent, some of the components may therefore 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).

[0061] In certain preferred embodiments, the solvent is suitably a polar solvent preferably selected from the group consisting of alkanols, especially 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.

[0062] It is understood that references herein to a "solvent" include one or more mixed solvents.

[0063] The powder mixture may be mixed in an amount of about 1% to 80% by weight based on the total weight of the powder mixture and the solvent, and about 20% to 99% by weight of the solvent. Preferably, the powder mixture may be mixed in an amount of about 25% to 75% by weight based on the total weight of the powder mixture and the solvent, and about 25% to 75% by weight of the solvent. In particular, the powder mixture may be mixed in an amount of about 40% to 60% by weight based on the total weight of the powder mixture and the solvent, and about 40% to 60% by weight of the solvent.

[0064] 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 undesired 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. The duration of step a) is preferably between 1 minute and 1 hour.

[0065] 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 for a duration of 10 minutes to 80 hours, more preferably about 4 hours to 40 hours.

[0066] Said milling is also known as reactive milling in the conventional synthesis of lithium argyrodite.

[0067] Mechanical milling also has the advantage that grinding occurs simultaneously with the formation of the glass mixture. Various methods can be used in mechanical milling, such as rotary ball mills, tumbling ball mills, vibrating ball mills, and planetary ball mills. Mechanical milling can be performed with or without balls such as ZrO2.

[0068] Under such conditions, lithium sulfide, phosphorus sulfide, a halogen compound, and a copper compound are reacted in a solvent for a predetermined period of time.

[0069] 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 of -20°C to 80°C, more preferably 15°C to 40°C. In the absence of a solvent, step a) is carried out at a temperature of -20°C to 200°C, preferably 15°C to 40°C. The mechanical treatment of the composition in step b) can also be carried out by using techniques well known in the art, such as by stirring, especially by using a standard powder mixer or slurry mixer.

[0070] Typically, a paste or a blend of paste and liquid vehicle can be obtained at the end of step b).

[0071] In step c), at least a portion of the solvent is removed, particularly 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 therebetween. Solvent removal can be carried out by known methods used in the art, such as decantation, filtration, centrifugation, drying, or a combination thereof.

[0072] The temperature in step c) is selected to allow the removal of the solvent, preferably when 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 solvent.

[0073] The duration of step c) is between 1 second and 100 hours, preferably between 1 hour and 20 hours. Such short durations can be obtained, for example, by using flash evaporation, such as by spray drying.

[0074] 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 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 may be in the range of 0.0001 Pa to 0.001 Pa, especially by using ultra-vacuum techniques. In particular, the pressure may be in the range of 0.01 Pa to 0.1 MPa by using primary vacuum techniques.

[0075] In step d), the heating or heat treatment may, inter alia, convert the amorphous powder mixture obtained above (glass) into a crystalline solid material or a mixture of glass and crystalline (glass ceramics).

[0076] The heat treatment is carried out in particular for a duration of 1 minute to 100 hours, preferably 30 minutes to 20 hours, at a temperature ranging from 100°C to 700°C, preferably from 250°C to 600°C. 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 completed by air quenching, or natural cooling from the heating temperature, or by controlled ramping of the temperature at a rate comprised between 1°C / min and 20°C / min.

[0077] Preferably, in step d), the inert atmosphere comprises an inert gas such as dry N2 or dry argon (dry may refer to a gas containing less than 800 ppm of water, including condensed, in liquid and suspended form). Preferably, in step d), the inert atmosphere is a protective gas atmosphere used to minimize, preferably exclude, the access of oxygen and moisture.

[0078] The pressure during heating may be normal pressure or reduced pressure. The atmosphere may 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 may be 0.0001 Pa to 100 MPa, preferably 0.001 Pa to 20 MPa, and more preferably 0.01 Pa to 20 MPa. In particular, the pressure may be in the range of 0.0001 Pa to 0.001 Pa, especially by using ultra-vacuum technology. In particular, the pressure may be in the range of 0.01 Pa to 0.1 MPa by using primary vacuum technology.

[0079] In step e), the solid material can be processed to the desired particle size distribution. If necessary, the solid material obtained by the process according to the invention as described above is ground (e.g., milled) into a powder. Preferably, the powder has a particle size distribution D50 value of less than 100 μm, more preferably less than 10 μm, and most preferably less than 5 μm, as measured by dynamic light scattering or image analysis.

[0080] Preferably, the powder has a particle size distribution D90 value of less than 100 μm, more preferably less than 10 μm, most preferably less than 5 μm, as measured by dynamic light scattering or image analysis. In particular, the powder has a particle size distribution D90 value comprised between 1 μm and 100.

[0081] The present invention therefore relates to a process for the preparation of a solid material according to general formula (I), comprising at least a') a process step of mixing stoichiometric amounts of lithium compounds, sulfide compounds, phosphorus compounds, halogen compounds and copper compounds in one or more solvents under an inert atmosphere to obtain a solution; b') a process step of removing at least a portion of the one or more solvents from the composition as obtained in step a'), thereby obtaining a solid material; c') optionally a process step of heating the solid material as obtained in step b') at a temperature in the range of 100°C to 700°C under an inert atmosphere; d') optionally processing the solid material obtained in step c') to a desired particle size distribution; It also refers to a process that includes

[0082] 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.

[0083] The characteristics of the solvent removal as described in step b') can be similar to those as described 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.

[0084] The heating of step c') can be carried out with the characteristics as given in step d), preferably at a temperature in the range of 100°C to 700°C, under an inert atmosphere and preferably under a pressure of 0.0001 Pa to 100 MPa.

[0085] The characteristics of the processing of the solid material as described in step d') can be similar to those as indicated in step e).

[0086] The present invention also refers to a solid electrolyte and a solid material of formula (I) as a solid electrolyte comprising at least a solid material of formula (I).

[0087] The solid electrolyte may therefore comprise a solid material of formula (I) and, optionally, other solid electrolytes such as lithium argyrodite, lithium thiophosphates such as glasses or glass ceramics, Li3PS4, Li7PS 11 and lithium-filled garnet Li7La3Zr2O 12 The solid electrolyte may also optionally contain a polymer such as styrene butadiene rubber, an organic or inorganic stabilizer or dispersant such as SiO2, and / or a sulfide.

[0088] The present invention also relates to an electrochemical device comprising a solid electrolyte comprising at least the solid material of formula (I).

[0089] Preferably, in electrochemical devices, particularly rechargeable electrochemical devices, the solid electrolyte is a solid structural component for the electrochemical device selected from the group consisting of the cathode, anode and separator.

[0090] In this specification, preferably, the solid electrolyte is a component of a solid structure for an electrochemical device, where the solid structure is selected from the group consisting of a cathode, an anode, and a separator. Thus, the solid materials according to this specification can be used alone or in combination with additional components for manufacturing a solid structure for an electrochemical device, such as a cathode, an anode, or a separator.

[0091] The electrode where a net negative charge is generated during discharge is called the anode, and the electrode where a net positive charge is generated during discharge is called the cathode. The separator electrically separates the cathode and the anode from each other in an electrochemical device.

[0092] 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 contains graphite carbon, metallic lithium, Si, silicon compounds such as SiO x and lithium titanium oxides such as Li4Ti5O 12 or metal alloys containing lithium as an anode active material such as Sn.

[0093] In the electrochemical device according to the present invention, the electrode preferably contains a metal chalcogenide of the formula LiMQ2 (where M is at least one metal selected from transition metals such as Co, Ni, Fe, Mn, Cr, and V, and Q is a chalcogen such as O or S). Among these, it is preferable to use a lithium-based composite metal oxide of the formula LiMO2 (where M is the same as defined above). Preferred examples thereof include LiCoO2, LiNiO2, LiNi x Co 1-x O2 (0 < x < 1) and spinel-structured LiMn2O4. Another preferred example thereof includes the formula LiNi x Mn y Co z O2 (x + y + z = 1, referred to as NMC), for example, LiNi 1 / 3 Mn 1 / 3 Co1 / 3 O2, LiNi 0,6 Mn 0,2 Co 0,2 O2 lithium-nickel-manganese-cobalt metal oxides and the formula LiNi x Co y Al z O2 (x+y+z=1, called NCA), e.g. LiNi 0,8 Co 0,15 Al 0,05 The cathode may include a lithiated or partially lithiated transition metal oxyanion-based material such as LiFePO4.

[0094] For example, the electrochemical device has a cylindrical-like shape or a prismatic shape.The electrochemical device can include a housing that can be made of steel or aluminum or a multi-layer film polymer / metal foil.

[0095] A further aspect of the present invention refers to a battery, more preferably an alkali metal battery, especially a lithium battery, comprising at least one, e.g., two or more, inventive electrochemical devices. The electrochemical devices can be combined with one another, e.g., in series or parallel connection, in an inventive alkali metal battery.

[0096] The present invention also relates to a solid state battery comprising a solid electrolyte comprising at least the solid material of formula (I).

[0097] 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.

[0098] The cathode of an all-solid-state electrochemical device typically includes 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 includes a solid electrolyte as a further component in addition to the anode active material.

[0099] The morphology of the solid-state structure for an electrochemical device, in particular an all-solid-state lithium battery, depends inter alia on the morphology of the electrochemical device itself to be produced. The present invention further provides a solid-state structure for an electrochemical device, the solid-state structure being 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.

[0100] Multiple electrochemical cells can be combined into an all-solid-state battery having both solid electrodes and a solid electrolyte.

[0101] The solid materials disclosed above can be used to prepare electrodes. The electrodes can be positive or negative electrodes. Electrodes typically include: - Metal substrate; at least one layer adhered directly onto said metal substrate, comprising at least (i) Formula (I) as follows: Li 6-x-2y Cu x PS 5-y X (I) (In the formula, - X is selected from the group consisting of F, Cl, I and Br; 0.005≦x≦5; preferably 0.015≦x≦1.5; and - 0≦y≦0.5, preferably 0≦y≦0.25) of solid materials; (ii) at least one electroactive compound (EAC); (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) optionally, a lithium salt (LIS); (vi) optionally, at least one polymeric binder material (P) At least one layer made of a composition comprising Includes:

[0102] An 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, 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) and can be.

[0103] 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) as well as spinel-structured LiMn2O4 and Li(Ni 0.5 Mn 1.5 )O4.

[0104] The EAC has the formula M1M2(JO4) f E 1-f (where - M1 is lithium that can be partially substituted by another alkali metal representing 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, representing 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 in the range of 0.75 to 1. The present invention can also be a lithiated or partially lithiated transition metal oxyanion based electroactive material.

[0105] M1M2(JO4) as defined above f E 1-f The electroactive material is preferably phosphate-based and may exhibit an ordered or modified olivine structure.

[0106] For the positive electrode, the EAC can also be sulfur or Li2S.

[0107] For the positive electrode, the EAC can also be a conversion-type material such as FeS2, or FeF2, or FeF3.

[0108] For the negative electrode, the EAC can be selected from the group consisting of graphitic carbons capable of intercalating lithium. Further details regarding this type of EAC can be found in Carbon 2000, 38, 1031-1041. This type of EAC typically exists in the form of powder, flakes, fibers, or spheres (e.g., mesocarbon microbeads).

[0109] EACs include lithium metal; lithium alloy compositions (such as those described in U.S. Pat. No. 6,203,944 and WO 00 / 03444); generally, lithium alloys of the formula Li4Ti5O 12 These compounds generally contain mobile ions, i.e., Li +considered a "zero strain" insertion material that exhibits low levels of physical expansion upon incorporation of lithium; lithium-silicon alloys, commonly known as lithium silicides with high Li / Si ratios, especially those of 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-filled carbonaceous materials, especially graphite carbon / silicon and graphite / silicon oxide, where the graphite carbon is composed of one or several carbons capable of intercalating lithium.

[0110] 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 carbon black, carbon nanotubes, graphite, graphene, 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.

[0111] The lithium salt (LIS) may be selected from the group consisting of LiPF, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, LiB(C2O4), LiAsF6, LiClO4, LiBF4, LiAlO4, LiNO3, LiCF3SO3, LiN(SO2CF3), LiN(SO2C2F5), LiC(SO2CF3), LiN(SO3CF3), LiC4F9SO3, LiCF3SO3, LiAlCl4, LiSbF6, LiF, LiBr, LiCl, LiOH, and lithium 2-trifluoromethyl-4,5-dicyanoimidazole.

[0112] The function of the polymeric binder (P) is to bind the components of the composition. The polymeric binder is usually inert. It should preferably be chemically stable and facilitate electronic and ionic transport. Polymeric binder materials are well known in the art. Non-limiting examples of polymeric binder materials include vinylidene fluoride (VDF)-based (co)polymers, styrene-butadiene rubber (SBR), styrene-ethylene-butylene-styrene (SEBS), carboxymethyl cellulose (CMC), polyamideimide (PAI), poly(tetrafluoroethylene) (PTFE), and poly(acrylonitrile) (PAN) (co)polymers, among others.

[0113] 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 according 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.

[0114] Inorganic materials M can also be used to prepare the separator. The separator is an ion-permeable membrane placed between the anode and cathode of a battery. Its function is to block electrons and ensure physical separation between the electrodes while allowing lithium ions to pass through.

[0115] The separator of the present invention typically comprises at least - Formula (I) such as: Li 6-x-2y Cu x PS 5-y X (I) (In the formula, - X is selected from the group consisting of F, Cl, I and Br; 0.005≦x≦5; preferably 0.015≦x≦1.5; and - 0≦y≦0.5, preferably 0≦y≦0.25) of solid materials; - optionally at least one polymeric binder material (P); - optionally at least one metal salt, in particular a lithium salt; optionally at least one plasticizer Includes:

[0116] The electrodes and separators can be prepared 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, electrodes can be prepared by the following steps: - applying a slurry comprising the components of the composition and at least one solvent onto a metal substrate; - Removal of the solvent It can be prepared by a process comprising:

[0117] Typical 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. Typical preparation techniques for electrodes and separators are given in Journal of Power Sources, 2018 382, ​​160-175.

[0118] Electrochemical devices, particularly batteries such as the solid-state batteries described herein, can be used to manufacture or operate stationary applications such as automobiles, computers, mobile devices, cell phones, watches, camcorders, digital cameras, thermometers, calculators, laptop BIOS, communication equipment or remote car locks, and energy storage devices for power plants.

[0119] Electrochemical devices, particularly batteries such as the solid-state batteries described herein, can be used in, among other things, motorized vehicles, bicycles driven by electric motors, robots, aircraft (e.g., unmanned aerial vehicles such as drones), ships, or stationary energy storage stations. Mobile devices such as vehicles, e.g., automobiles, bicycles, aircraft, or water vehicles such as boats or ships, are preferred. Other examples of mobile devices are portable, such as computers, particularly laptops, telephones, or power tools, e.g., from the construction sector, particularly drills, battery-powered screwdrivers, or battery-powered nailers.

[0120] If the disclosure of any patent, patent application, or publication incorporated herein by reference contradicts the statement of this application to the extent that it may render a term unclear, the statement shall control. [Brief explanation of the drawings]

[0121] [Figure 1] Powder XRD patterns of Li6-x-2yCuxPS5-yCl. Sample A: x=0; Sample B: x=0.03; Sample C: x=0.06; Sample D: x=0.3; Sample E: x=0.6; Sample F: x=1.5. [Figure 2] 31P NMR data for Li6-x-2yCuxPS5-yCl with x = 0.3 and y = 0. The star symbol indicates the signature of a PS4 3-entity, the pentagon symbol indicates the signature of a P2S7 4-entity, and the hexagon symbol indicates the signature of a PO4 3-entity. [Figure 3] 7Li NMR data for Li6-x-2yCuxPS5-yCl with x=0.3 and y=0. DETAILED DESCRIPTION OF THE INVENTION

[0122] The following examples serve to illustrate the invention but do not have a limiting character.

[0123] X-ray diffraction XRD diffractograms of the powders were acquired with an XRD goniometer in Bragg Brentano geometry using a Cu X-ray tube (Cu Kalpha wavelength of 1.5406 Å). The setup can be used in different optical configurations, i.e., with a variable or fixed divergence slit or Soller slit. Primary filtering devices such as a Panalytical monochromator or Bragg Brentano HD optics can also be used. When a variable divergence slit is used, the typical irradiation area is 10 mm x 10 mm. The sample holder was loaded onto a spinner; the rotation speed was typically 60 rpm during acquisition. The tube settings were operated at 40 kV / 30 mA for variable slit acquisition and 45 kV / 40 mA for fixed slit acquisition using incident Bragg Brentano HD optics. The acquisition step was 0.017° per step. The angular range was typically 5° to 90° over 2 theta. The total acquisition time was typically more than 30 min. The powder is covered with a Kapton film to prevent reaction with moisture in the air.

[0124] Conductivity and electrochemical impedance spectroscopy (EIS) Conductivity measurements were performed on the pellets using a uniaxial press operating at 500 MPa. Measurements were performed under a load of 40 MPa, using two carbon paper foils as current collectors in an MTI pressure cell (BATTE-CELL-0067 EQ-PSC-15-P). Impedance spectra were acquired with a Biologic VMP3 device, and temperature control was ensured by a Binder climate chamber. A duration of 2 h was set to allow temperature equilibration between two measurements. Impedance spectroscopy was acquired in PEIS mode at an amplitude of 10 mV and a frequency range of 1 MHz to 1 kHz (25 points every 10 times, 50 measurements averaged per frequency point).

[0125] solid state NMR Solid-state NMR spectra were recorded on a Bruker Avance 400 spectrometer equipped with a high-speed DVT4 probe. 31 P and6 Li measurements were performed by magic angle spinning (MAS) at a rate of 10 kHz in single pulse mode with relaxation time D1 depending on the experiment (see Examples below). 7 Li measurements were performed in static single pulse mode with a relaxation time D1 = 120 seconds. 31 The standard for P NMR was 85% H3PO4. 6 The standard for Li NMR is 5 mol / L. -1 It was an aqueous LiCl solution.

[0126] Example 1: Synthesis Precursor weighing and sample preparation are both performed in an Ar-filled glovebox with oxygen and moisture levels below 1 ppm. In a typical experiment, 30 mL glass vials are used to prepare Li with the target stoichiometry. 6-x-2y Cu x PS 5-y Weigh out LiS (≥99.9%, Albemarle), P2S5 (≥99%, Sigma Aldrich), LiCl (≥99%, Sigma Aldrich), and CuS (≥99.5%, Alfa Aesar) according to Cl (0.015 ≤ x ≤ 1.5 and 0 ≤ y ≤ 0.25) (total mass of 8 g). For example, the solid material Li 5.94 Cu 0.06 For PS5Cl (x = 0.06 and y = 0), 3.34 g of Li2S, 3.27 g of PS2S5, 1.25 g of LiCl, and 0.14 g of Cu2S were used. The precursors used here are powders with an average particle size between 10 μm and 400 μm.

[0127] The glass vial is sealed, removed from the glove box, and mixed in a Turbula mixer for 20 minutes. The glass vial is placed in the glove box, and the sample is poured into a 45 mL ZrO2 milling jar containing 66.4 g of Φ5 mm diameter ZrO2 balls. 8 g of p-xylene (≥99%, Sigma-Aldrich, anhydrous) is then added to the jar. The jar is equipped with a Viton seal and sealed under an Ar atmosphere inside the jar. The jar is removed from the glove box and placed in a planetary ball mill (Pluverisette 7 Premium Line, Fritsch). Mechanosynthesis is carried out at 800 rpm for 80 cycles of 15 minutes each. The jar is allowed to cool naturally for 30 minutes between cycles.

[0128] After mechanosynthesis is complete, the jar is placed in a glove box. The product and balls are placed in two 30 mL glass vials (without caps) that are themselves placed in glass tubes. The tubes are closed, removed from the glove box, and placed in a Büchi Glass Oven B-585. The samples are dried under vacuum at room temperature (25 °C) for 2 h, then heated to 110 °C for 5 h to evaporate the p-xylene. The tubes are then closed (inside a vacuum) and placed in a glove box. The powder is sieved and separated from the milling burs. The powder is placed in 30 mL glass vials without caps that are themselves placed in glass tubes. The tubes are closed, removed from the glove box, and placed in a Büchi Glass Oven B-585. The samples are heated under vacuum at 150 °C for 1 h, then at 280 °C for 1 h, and finally at 300 °C for 12 h. The tube is closed (inside vacuum) and placed in a glove box. A sample is removed from the tube and stored for further analysis.

[0129] Example 2: Properties For all compositions within the selected range, powder XRD (Figure 1) shows a predominance of the argyrodite phase with trace amounts of LiS when x < 0.06. Even for the higher copper contents in the selected range (x = 1.5), copper-containing impurities are not visible from the powder XRD. Powder XRD also shows that increasing copper content (x) decreases the amount of LiS impurity.

[0130] Lattice parameters were calculated using Le Bail refinement on the diffractogram of the Kapton substrate, which was performed using Fullprof software.

[0131] [Table 2]

[0132] x=0.3 sample 31 P NMR (Figure 2) shows traces of P2S7 4- and PS4 with potentially small amounts of Li3PO4 impurity 3- This confirms the superiority of chemical species.

[0133] x=0.3 sample 7 The Li NMR (Figure 3) shows the presence of a single Li environment with a displacement close to 1.38 ppm, in very good agreement with the displacements of the Li6PS5Cl phase found in the literature.

[0134] Electrochemical impedance spectroscopy measurements were performed on 6 mm diameter pellets compressed under 500 MPa. The pellet thickness was close to 1 mm. EIS measurements show that a low copper content improves the conductivity of the material. Thus, samples with 0.03≦x≦0.06 benefit from higher conductivity than samples with x=0. Furthermore, the activation energy of samples with 0.03≦x≦0.06 remains below 0.40 eV from 20°C to 60°C. For higher copper contents (x≧0.3), the conductivity decreases and the activation energy increases, as shown in the table below.

[0135] Table 3

Claims

1. General formula (I) as follows: Li ６－ｘ－２ｙ Cổ ｘ PS ５－ｙ X (I) (In the formula, X is selected from the group consisting of F, Cl, I and Br; 0.005≦x≦5; and - 0≦y≦0.5) Solid materials according to.

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

3. 3. The solid material according to claim 1, wherein 0.02≦x≦0.

8.

4. 4. Solid material according to any one of claims 1 to 3, wherein the crystallinity of said solid material is comprised between 80% and 100%.

5. 5. The solid material according to claim 1, which, when analysed by X-ray diffraction using CuKα radiation at 25°C, comprises peaks at positions at least 15.65°±0.5°, 25.53°±0.5°, 30.16°±0.5° and 31.52°±0.5° (2θ).

6. 6. A solid material according to any one of claims 1 to 5, in powder form having a particle size distribution with a D50 comprised between 0.05 μm and 10 μm.

7. A method for preparing a solid material according to any one of claims 1 to 6, comprising at least a) mixing stoichiometric amounts of lithium sulfide, phosphorus sulfide, a halogen compound, and a copper compound in one or more solvents under an inert atmosphere to obtain a composition; b) subjecting the composition obtained in step a) to a mechanical treatment; c) a process step of removing at least a portion of said one or more solvents from the composition obtained in step b), thereby obtaining a solid residue; d) heating the solid residue obtained in step c) at a temperature in the range of 100°C to 700°C under an inert atmosphere, thereby forming a solid material; A method comprising:

8. The copper compound is CuS, Cu ２ S, Cu ２－ｘ S (wherein x is in the range of 0 to 1) and CuCl ２ 8. The method of claim 7, wherein the compound is selected from the group consisting of:

9. Lithium sulfide is Li ２ S, and phosphorus sulfide is P ２ S ５ wherein the halogen compound is LiCl and the copper compound is Cu ２ The method according to claim 7 or 8, wherein S is

10. The method of any one of claims 7 to 9, wherein the solvent is selected from the group consisting of alkanols; carbonates; acetates; ethers; organic nitriles; aliphatic hydrocarbons; and aromatic hydrocarbons.

11. 11. The method according to any one of claims 7 to 10, wherein in step b) the mechanical treatment is carried out by wet or dry milling.

12. A method for preparing a solid material according to any one of claims 1 to 6, comprising at least a') mixing stoichiometric amounts of a lithium compound, a sulfide compound, a phosphorus compound, a halide compound and a copper compound in one or more solvents under an inert atmosphere to obtain a solution; b') removing at least a portion of the one or more solvents from the solution obtained in step a'), thereby obtaining a solid material; c') heating the solid material obtained in step b') at a temperature in the range of 100°C to 700°C under an inert atmosphere; A method comprising:

13. Formula (I) as follows: Li ６－ｘ－２ｙ Cổ ｘ PS ５－ｙ X (I) (In the formula, X is selected from the group consisting of F, Cl, I and Br; 0.005≦x≦5; and - 0≦y≦0.5) of solid materials as solid electrolytes.

14. Formula (I) as follows: Li ６－ｘ－２ｙ Cổ ｘ PS ５－ｙ X (I) (In the formula, X is selected from the group consisting of F, Cl, I and Br; 0.005≦x≦5; and - 0≦y≦0.5) A solid electrolyte comprising at least the solid material.

15. Formula (I) as follows: Li ６－ｘ－２ｙ Cổ ｘ PS ５－ｙ X (I) (In the formula, X is selected from the group consisting of F, Cl, I and Br; 0.005≦x≦5; and - 0≦y≦0.5) An electrochemical device comprising a solid electrolyte comprising a solid material of

16. Formula (I) as follows: Li ６－ｘ－２ｙ Cổ ｘ PS ５－ｙ X (I) (In the formula, X is selected from the group consisting of F, Cl, I and Br; 0.005≦x≦5; and - 0≦y≦0.5) A solid-state battery comprising a solid electrolyte comprising a solid material.

17. Formula (I) as follows: Li ６－ｘ－２ｙ Cổ ｘ PS ５－ｙ X (I) (In the formula, X is selected from the group consisting of F, Cl, I and Br; 0.005≦x≦5; and - 0≦y≦0.5) A vehicle including a solid-state battery including a solid electrolyte including a solid material.

18. An electrode comprising at least - Metal substrate; at least one layer adhered directly onto said metal substrate, (i) Formula (I) as follows: Li ６－ｘ－２ｙ Cổ ｘ PS ５－ｙ X (I) (In the formula, X is selected from the group consisting of F, Cl, I and Br; 0.005≦x≦5; and - 0≦y≦0.5) solid materials; (ii) at least one electroactive compound (EAC); At least one layer made of a composition comprising An electrode comprising:

19. A separator comprising at least Formula (I) such as: Li ６－ｘ－２ｙ Cổ ｘ PS ５－ｙ X (I) (In the formula, X is selected from the group consisting of F, Cl, I and Br; 0.005≦x≦5; and - 0≦y≦0.5) Solid materials Contains separators.

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