Method for preparing particles of sulfide solid material

Abstract

This disclosure relates to a method for preparing particles of a sulfide solid material containing at least elements Li, P, S, and X, comprising: a) a D50 value in the range of 20 μm to 500 μm measured by laser diffraction in paraxylene and a 5m value measured by nitrogen gas adsorption according to the Brunauer-Emmet-Teller (BET) method. 2 The present invention relates to a method comprising the steps of: a) preparing a lithium sulfide (Li2) powder having a specific surface area of ​​1 / g or more; b) reacting the Li2S powder from step a) with at least P2S5 and LiX to obtain sulfide solid material particles containing Li, P, S, and X (where X is selected from a list consisting of F, Cl, I, Br, CN, NC, OCN, NCO, SCN, NCS, N3, or combinations thereof). The present invention also relates to the particles obtained by the method, and their use in the manufacture of electrodes, electrolyte layers of electrodes, or separators.

Description

[Technical Field]

[0001] Cross-reference of related patent applications This application claims priority under European Patent Application No. 23305326.3 filed on 10 March 2023, and the entire contents of this application are incorporated herein by reference for any purpose.

[0002] This disclosure relates to a method for preparing particles of a sulfide solid material containing at least Li, P, S, and X elements, a) D50 values ​​in the range of 20 μm to 500 μm measured by laser diffraction in paraxylene, and 5 m measured by nitrogen gas adsorption according to the Brunauer-Emmet-Teller (BET) method. 2 A step of preparing lithium sulfide (Li2S) powder having a specific surface area of ​​1 / g or more, b) A step in which the Li2S powder from step a) is reacted with at least P2S5 and LiX to obtain sulfide solid material particles containing Li, P, S, and X. (X is selected from a list consisting of F, Cl, I, Br, CN, NC, OCN, NCO, SCN, NCS, N3, or combinations thereof) Regarding methods including

[0003] The present invention also relates to particles obtained by the above method, and their use in the manufacture of electrodes, electrolyte layers of electrodes, or separators. [Background technology]

[0004] Lithium-ion batteries are widely used, especially as power sources for household appliances. In such rechargeable batteries, organic solvents are used as the organic liquid electrolyte, and lithium ions move from one electrode to the other depending on whether the battery is charging or discharging.

[0005] Since the solvent used as an electrolyte is flammable, all-solid-state lithium-ion batteries that do not use organic solvents are very attractive. Such all-solid-state lithium-ion batteries are formed, for example, by solidifying the entire battery using a solid electrolyte containing Li, P, S, and optionally also a halogen.

[0006] One of the starting materials for preparing such sulfide solid electrolytes (SSEs) is lithium sulfide (Li2S), which is generally available as a powder. Although it is well known that the purity of lithium sulfide (Li2S) powder is important for obtaining a high-purity sulfide solid electrolyte, little is known about the influence of the particle size and porosity of such starting materials on the properties of the resulting SSE. Various methods for manufacturing Li2S have been disclosed in the art, which generally involve raw materials such as LiOH or Li2CO3 as a lithium source and H2S as a sulfur source.

[0007] In some examples, the production of Li2S is carried out in a solution, for example, in an organic solvent, so this is a gas-liquid reaction between a gaseous H2S stream and LiOH or Li2CO3 in the solution. However, performing a gas-solid reaction between a gaseous H2S stream and LiOH or Li2CO3 solid particles is considered environmentally and economically advantageous, at least because it requires less wastewater management.

[0008] The overall equilibration reaction between LiOH and H2S can be represented by the following reaction scheme 1:

Equation

[0009] Sulfide solid electrolytes (SSEs) are typically synthesized by a solid-state reaction (mechanosynthesis) involving various raw materials, such as Li2S and P2S5, and optionally also LiX (where X is a halogen or pseudohalogen). The conditions of mechanosynthesis can affect the basic properties of SSEs, such as phase purity, particle size, and ionic conductivity.

[0010] Among these, the particle size is an important characteristic because it ultimately determines the final thickness of the separator layer and the denseness of the cathode electrode. If an appropriate particle size cannot be obtained during the synthesis of the SSE, a milling process is performed later. However, this post-treatment step generally causes a decrease in ionic conductivity due to the deterioration of the final SSE surface. Furthermore, this results in additional costs for the entire process of manufacturing the separator or electrode.

[0011] For example, European Patent No. 2732451 B1 discloses a method for producing a sulfide solid electrolyte material, which includes adding an ether compound to a coarse-grained material of the sulfide solid electrolyte material and making the coarse-grained material into fine particles by a fine pulverization process.

[0012] Japanese Patent Application Laid-Open No. 2019-102412 A2 discloses a method for reducing the size of coarse-grained particles of a sulfide by a spray process.

[0013] Therefore, there is a need for a method for producing a sulfide solid electrolyte powder having a particle size distribution that does not require a subsequent milling process after synthesis.

[0014] There is also a need for a method for producing a sulfide solid electrolyte powder having a high phase purity.

[0015] Finally, there is a need for a method for producing a sulfide solid electrolyte powder having a high ionic conductivity.

Summary of the Invention

[0016] All of these and more requirements are met by the first aspect of the present invention. This aspect is a method for preparing particles of a sulfide solid material containing at least Li, P, S, and X elements, a) The D50 value in the range of 20 μm to 500 μm measured by laser diffraction in p-xylene and 5 m measured by nitrogen gas adsorption according to the Brunauer-Emmet-Teller (BET) method 2A step of preparing lithium sulfide (Li2S) powder having a specific surface area of ​​1 / g or more, b) A step in which the Li2S powder from step a) is reacted with at least P2S5 and LiX to obtain sulfide solid material particles containing Li, P, S, and X. (X is selected from a list consisting of F, Cl, I, Br, CN, NC, OCN, NCO, SCN, NCS, N3, or combinations thereof) Regarding methods including

[0017] Another object of the present invention is a sulfide solid material particle obtained by the method according to the present invention, comprising at least elements Li, P, S, and X, characterized in that it has a D50 value in the range of 0.5 μm to 8 μm and a D90 value of 20 μm or less, as measured by analytical centrifugation analysis after deaggregation.

[0018] Another object of the present invention relates to the use of sulfide solid material particles according to the present invention for preparing a composition (C) comprising (i) a sulfide solid material and (ii) at least one polymer-based material (P).

[0019] The present invention also relates to the use of sulfide solid material particles according to the present invention for manufacturing an electrolyte layer of an electrode or separator. [Modes for carrying out the invention]

[0020] Currently, the influence of the characteristics of the raw materials involved in synthesis on the final SSE properties is not fully understood, nor has it been adequately reported in the literature.

[0021] The inventors have found that the specific surface area and particle size, which are important properties of Li2S powder produced by solid-gas reaction, enable the production of sulfide solid materials with smaller particle sizes while maintaining the same level of phase purity and excellent ionic conductivity as those produced from Li2S powder that does not possess the aforementioned properties.

[0022] Advantageously, the inventors have found that the method according to the present invention makes it possible to prepare particles of sulfide solid material having smaller particle sizes, which can be achieved simply by deaggregating the resulting powder without requiring additional milling or grinding.

[0023] Deaggregation refers to the process of breaking down weakly bound particle clusters (aggregates) of powder or crystal without further disintegration of the powder or crystal particles themselves, thereby reducing their size.

[0024] While not bound by any particular theory, this result is thought to be due to the increased reactivity of Li2S resulting from the larger specific surface area.

[0025] Surprisingly, it was found that lithium sulfide (Li2S) powder with relatively large particle sizes, for example, D50 values ​​in the range of 20 μm to 500 μm, is advantageous for the production of sulfide solid materials with small particle sizes.

[0026] Therefore, the method according to the present invention is a method for preparing particles of a sulfide solid material containing at least Li, P, S, and X elements, a) D50 values ​​in the range of 20 μm to 500 μm measured by laser diffraction in paraxylene, and 5 m measured by nitrogen gas adsorption according to the Brunauer-Emmet-Teller (BET) method. 2 A step of preparing lithium sulfide (Li2S) powder having a specific surface area of ​​1 / g or more, b) A step in which the Li2S powder from step a) is reacted with at least P2S5 and LiX to obtain sulfide solid material particles containing Li, P, S, and X. (X is selected from a list consisting of F, Cl, I, Br, CN, NC, OCN, NCO, SCN, NCS, N3, or combinations thereof) This method includes [something].

[0027] The Li2S powder used in this invention is typically 5 μm in size. 2 / g or more; preferably 7μm 2 It has a specific surface area of ​​8m² or more.2 Good results were obtained with Li2S powder showing a specific surface area of / g. The specific surface area is determined by nitrogen gas adsorption according to the Brunauer-Emmet-Teller (BET) method.

[0028] The Li2S powder used in the present invention usually has a specific surface area not exceeding 50 m 2 / g, for example not exceeding 20 m 2 / g, and in some cases not exceeding 15 m 2 / g.

[0029] The Li2S powder used in the present invention usually has a specific surface area in the range of 5 m 2 / g to 20 m 2 / g, and in some cases in the range of 7 m 2 / g to 15 m 2 / g.

[0030] The Li2S powder used in the present invention usually has a D50 value in the range of 20 μm to 500 μm, in some cases in the range of 50 μm to 500 μm, in many cases in the range of 100 μm to 500 μm, and typically in the range of 250 μm to 450 μm.

[0031] For example, the Li2S powder in step a) may have a particle size distribution showing a D50 value in the range of 20 μm to 400 μm or 50 μm to 400 μm.

[0032] The Li2S powder used in the present invention usually has a D90 value less than 1000 μm, and in some cases less than 700 μm.

[0033] The particle size distribution can be measured by laser diffraction from a dispersion in which the powder is dispersed in p-xylene.

[0034] The Dx value represents a value determined with respect to the volume-based distribution of particle sizes, where x% of the particles have a size less than or equal to this value Dx. For example, for D10, 10% of the particles have a size less than D10. Again, for example, for D90, 90% of the particles have a size less than D90. D50 corresponds to the median of the volume-based distribution.

[0035] The high reactivity of Li2S powder can be evaluated from the viewpoint of its reactivity to moisture. Therefore, when the Li2S powder used in this invention is exposed to 23°C and 30-40% relative humidity for 60 minutes, it typically exhibits an H2S release of more than 200 ml / g, preferably more than 350 ml / g, and more preferably more than 500 ml / g. Furthermore, the H2S release does not typically exceed 700 ml / g.

[0036] In some embodiments, the Li2S powder used in the present invention has a D50 value in the range of 20 μm to 500 μm and 5 m 2 It has a specific surface area of ​​1 / g or more and exhibits an H2S emission of more than 200 ml / g when exposed to 23°C at 30-40% relative humidity for 60 minutes.

[0037] In some other embodiments, the Li2S powder used in the present invention has a D50 value in the range of 20 μm to 400 μm and 5 m 2 It has a specific surface area of ​​1 / g or more and exhibits an H2S emission of more than 200 ml / g when exposed to 23°C at 30-40% relative humidity for 60 minutes.

[0038] The Li2S powder used in this invention can be obtained by any synthesis route. For example, it can be obtained by a gas-liquid reaction between a gaseous H2S stream and LiOH or Li2CO3 in solution. However, it is considered advantageous to perform a gas-solid reaction between a gaseous H2S stream and solid LiOH or Li2CO3 particles, at least because it requires less waste management. Generally, a gas-solid reaction between gaseous H2S and LiOH is preferred.

[0039] The method according to the present invention includes step b), which involves reacting the Li2S powder from step a) with at least P2S5 and LiX to obtain sulfide solid material particles containing Li, P, S, and X.

[0040] Preferably, the phosphorus sulfide (P2S5) is in the form of a powder with an average particle size ranging from 0.5 μm to 400 μm. The particle size can be evaluated by SEM image analysis or laser diffraction analysis.

[0041] Typically, halogen compounds or pseudohalogen compounds (LiX) are in the form of powders with an average particle size ranging from 0.5 μm to 400 μm.

[0042] In some preferred embodiments, X is selected from a list consisting of F, Cl, I, Br, and mixtures thereof.

[0043] Typically, step b) of the method according to the present invention includes the following steps: i) A step of obtaining a composition by mixing Li2S from at least step a), P2S5, and LiX in one or more solvents, optionally; ii) A step of performing mechanical treatment on the composition obtained in step i); iii) Optionally, remove at least a portion of one or more solvents from the composition obtained in step ii) to obtain a sulfide solid material precursor; iv) Optionally, press the sulfide solid material precursor from step iii) into pellets; v) A step of heating the precursor obtained in step iii) in, for example, pellet form, in an inert atmosphere at a temperature in the range of 350°C to 580°C for a time in the range of 1 to 12 hours, thereby forming sulfide solid material particles; and vi) A step of optionally processing the sulfide solid material obtained in step v) to a desired particle size distribution.

[0044] In some embodiments, step i) is carried out under an inert atmosphere. The inert atmosphere used in step i) refers to the use of an inert gas, i.e., a gas that does not undergo chemical reactions that would adversely affect the reaction conditions. Inert gases are generally used to avoid undesirable chemical reactions, such as oxidation and hydrolysis reactions with oxygen and moisture in the air. Therefore, an inert gas means a gas that does not chemically react with other reagents present in a particular chemical reaction. In relation to this disclosure, the term “inert gas” means a gas that does not react with the sulfide solid material precursor. Examples of “inert gases” include, but are not limited to, nitrogen, helium, argon, neon, and xenon, including water in liquid and suspended forms at less than 1000 ppm, including condensed gases. The gas may also be pressurized.

[0045] In step i), it is preferable that stirring is performed when the raw materials are brought into contact with each other under an inert gas atmosphere such as nitrogen or argon. The pressure may be 0.0001 Pa to 100 MPa, preferably 0.001 Pa to 20 MPa, and preferably 0.01 Pa to 0.5 MPa.

[0046] Preferably, in step i), the inert atmosphere includes an inert gas such as H2S, dry N2, dry argon, or dry air (dry may refer to a gas containing less than 800 ppm of liquid and suspended water, including condensed water).

[0047] The composition ratio of each element can be controlled by adjusting the amounts of Li2S, P2S5, and LiX when producing the sulfide solid material. The raw materials containing Li2S, P2S5, and LiX, and their molar ratios, are selected according to the target stoichiometric ratio. The target stoichiometric ratio determines the ratio between the elements Li, P, S, and X, obtained from the amount of precursor applied under conditions of complete conversion without side reactions and other losses. As an example, 2 moles of Li3PS4 can be obtained from 3 moles of Li2S and 1 mole of P2S5. Similarly, 2 moles of Li7P3S can be obtained from 7 moles of Li2S and 3 moles of P2S5. 11This can be obtained. Furthermore, similarly, 2 moles of Li6PS5Cl can be obtained from 5 moles of Li2S, 1 mole of P2S5, and 2 moles of LiCl.

[0048] The solvent in step i) can be appropriately selected from one or more polar or nonpolar solvents capable of substantially dissolving at least one compound selected from lithium sulfide, phosphorus sulfide, and other compounds that may be introduced in step i), if present. The solvent can also substantially suspend, dissolve, or otherwise mix the above components, e.g., lithium sulfide, phosphorus sulfide, and other compounds that may be introduced in step i).

[0049] Subsequently, in step i), the solvent of the present invention constitutes a continuous phase in which one or more of the above components are dispersed.

[0050] Depending on the components and solvent, some of the components may therefore be dissolved, partially dissolved, or in the form of a slurry (i.e., the components are not dissolved and, as a result, form a slurry with the solvent).

[0051] In certain preferred embodiments, the solvent can preferably be a polar solvent. The solvent is preferably a polar solvent selected from the group consisting of: alkanols 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.

[0052] It is understood that references to "solvent" in this specification include one or more mixed solvents.

[0053] A mixture may be prepared by combining approximately 1% to 80% by weight of the powder mixture and solvent, based on the total weight of the powder mixture and solvent, with approximately 20% to 99% by weight of the solvent. Preferably, a mixture may be prepared by combining approximately 25% to 75% by weight of the powder mixture and solvent, based on the total weight of the powder mixture and solvent, with approximately 25% to 75% by weight of the solvent. In particular, a mixture may be prepared by combining approximately 40% to 60% by weight of the powder mixture and solvent, based on the total weight of the powder mixture and solvent, with approximately 40% to 60% by weight of the solvent.

[0054] The temperature in step i) in the presence of a solvent is preferably between the melting point and boiling point of the selected solvent, a temperature at which no undesirable reactions occur between the solvent and the compound mixed. Preferably, step i) is carried out at -20°C to 40°C, more preferably 15°C to 40°C. Without a solvent, step i) is carried out at a temperature of -20°C to 200°C, preferably 15°C to 40°C.

[0055] The duration of step i) is preferably 1 minute to 1 hour.

[0056] The mechanical treatment of the composition in step ii) may 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 about 10 minutes to 80 hours, more preferably about 4 hours to 40 hours.

[0057] The milling described above is also known as reactive milling in the conventional synthesis of lithium argyrodites.

[0058] Mechanical milling also has the advantage that grinding occurs simultaneously with the formation of the glass mixture. Various methods can be used in mechanical milling, such as rotary ball mills, tumbling ball mills, vibrating ball mills, and planetary ball mills. Mechanical milling can be carried out with or without balls such as ZrO2.

[0059] Under such conditions, lithium sulfide, phosphorus sulfide, LiX, and other compounds that may be introduced in step i) are reacted in a solvent, optionally, for a predetermined time.

[0060] The temperature in step ii) in the presence of a solvent is a temperature between the melting point and boiling point of the selected solvent, where no undesirable reaction occurs between the solvent and the compound. Preferably, step ii) is carried out at a temperature of -20°C to 80°C, more preferably 15°C to 40°C. Without a solvent, step a) is carried out at -20°C to 200°C, preferably 15°C to 40°C.

[0061] The mechanical treatment of the composition in step ii) can also be carried out by stirring, in particular by using a standard powder mixer or slurry mixer, or by using other techniques well known in the art.

[0062] Typically, a paste, or a blend of the paste and a liquid solvent, can be obtained at the end of step ii).

[0063] In step iii), at least a portion of the solvent is removed by means of removing, in particular, at least about 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 100%, or any range falling between these values, of the total weight of the solvent used. Solvent removal can be carried out by known methods used in the art, such as decantation, filtration, centrifugation, drying, or a combination thereof.

[0064] The temperature in step iii) is selected to allow for the removal of the solvent. Preferably, if drying is selected as the method for solvent removal, the temperature is selected as a function of the vapor partial pressure of the selected solvent and is below the boiling point of the selected solvent.

[0065] The duration of step iii) is 1 second to 100 hours, preferably 1 hour to 20 hours. Such short durations can be achieved by using flash evaporation, for example, by spray drying.

[0066] Step iii) 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 -20°C or lower, and particularly preferably -40°C or lower. The pressure may be 0.0001 Pa to 100 MPa, preferably 0.001 Pa to 20 MPa, and preferably 0.01 Pa to 20 MPa. In particular, the pressure may be in the range of 0.0001 Pa to 0.001 Pa by using ultra-vacuum technology. In particular, the pressure may be in the range of 0.01 Pa to 0.1 MPa by using primary vacuum technology.

[0067] The sulfide solid material precursor in step iii) is usually a glassy (PS4) 3- The species contains at least 85 mol%, preferably at least 88 mol%, of P species in species form. 31 (Determined by 3P NMR).

[0068] In step iv), the sulfide solid material precursor from step iii) can be press-molded into pellets. For example, the sulfide solid material precursor can be pressed in a mold to form pellets. Molding can be carried out using equipment known to those skilled in the art. For example, molding can be carried out using a uniaxial press or a single-screw tablet press.

[0069] In step v), heating or heat treatment of the precursor obtained in step iii) (for example, in the form of pellets) makes it possible to convert the amorphous powder mixture (glass) obtained above into a crystalline sulfide solid material or a mixture of glass and crystalline material (glass ceramics).

[0070] The heat treatment is carried out at temperatures in the range of 350°C to 580°C, for example, 370°C to 550°C, or 390°C to 530°C, particularly for durations of 1 minute to 12 hours, preferably 2 hours to 10 hours or 3 hours to 7 hours. The heat treatment may be started immediately at a high temperature, or by heating at a rate including 1°C / min to 20°C / min. The heat treatment may be terminated by rapid cooling, natural cooling from the heating temperature, or by a controlled temperature gradient at a rate including 1°C / min to 20°C / min.

[0071] Preferably, in step v), the inert atmosphere contains an inert gas such as dry N2 or dry argon ("dry" may refer to a gas containing water in liquid and suspended forms, including condensed water, at a concentration of less than 800 ppm). Preferably, in step e), the inert atmosphere is a protective gas atmosphere used to minimize, preferably eliminate, the approach of oxygen and moisture.

[0072] The pressure during heating may be standard pressure or reduced pressure. The atmosphere may be an inert gas such as nitrogen and argon. The dew point of the inert gas is preferably -20°C or lower, and particularly preferably -40°C or lower. The pressure may be 0.0001 Pa to 100 MPa, preferably 0.001 Pa to 20 MPa, and preferably 0.01 Pa to 20 MPa. In particular, the pressure may be in the range of 0.0001 Pa to 0.001 Pa by using ultra-vacuum technology. In particular, the pressure may be in the range of 0.01 Pa to 0.1 MPa by using primary vacuum technology.

[0073] In step vi), the sulfide solid material can be processed to a desired particle size distribution. In fact, the sulfide solid material obtained by the method according to the present invention described above may contain aggregates that can be reduced to a powder with a desired particle size distribution by deaggregation.

[0074] Deaggregation refers to the process of breaking down weakly bound particle clusters (aggregates) of powder or crystal without further disintegration of the powder or crystal particles themselves, thereby reducing their size.

[0075] In some preferred embodiments, step vi) comprises deaggregating the sulfide solid material obtained in step v) to a desired particle size distribution.

[0076] Typically, the powder has a D50 value with a particle size distribution in the range of 0.5 μm to 8 μm, preferably 1 μm to 6 μm, and more preferably 1 μm to 5 μm, as determined by analytical centrifugation analysis.

[0077] Typically, the powder has a D90 value with a particle size distribution of 20 μm or less, preferably 15 μm or less, and more preferably 10 μm or less, as determined by analytical centrifugation analysis.

[0078] Typically, the powder has a D10 value with a particle size distribution of 2 μm or less, preferably 1.5 μm or less, as determined by analytical centrifugation analysis.

[0079] In some embodiments, step b) includes the following steps: i') A step of obtaining a composition by mixing Li2S from at least step a), P2S5, and LiX in one or more solvents under an inert atmosphere; ii') A step of obtaining a sulfide solid material precursor by removing at least a portion of one or more solvents from the composition obtained in step i'); iii') Optionally, press the sulfide solid material precursor from step ii') into pellets; iv') A step of heating the precursor obtained in step ii') for example in pellet form in an inert atmosphere at a temperature in the range of 350°C to 580°C for a time in the range of 1 to 12 hours, thereby forming sulfide solid material particles; and v') A step of optionally processing the sulfide solid material particles obtained in step iv') to a desired particle size distribution.

[0080] The various characteristics of step i'), such as Li2S, P2S5, LiX, other compounds that may be introduced in step i), and the solvent, are essentially the same as those of step i). Preferably, the temperature in step i') is in the range of -200°C to 100°C, preferably -200°C to 10°C.

[0081] In some embodiments, during step i'), a solution of Li2S, P2S5, and LiX is obtained before any other compound is introduced and further solubilized.

[0082] The solvent removal characteristics described in step ii') may be the same as those shown in step iii). Preferably, in step ii'), 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.

[0083] The sulfide solid material precursor in step ii') is usually a glassy (PS4) 3- The species contains at least 85 mol%, preferably at least 88 mol%, of P species in species form. 31 (Determined by 3P NMR).

[0084] In step iii'), the sulfide solid material precursor from step ii') can be pressed into pellets as shown in step iv).

[0085] The heating in step iv') can be carried out having the characteristics described in step v). Preferably, the heating is carried out in an inert atmosphere and preferably at a temperature in the range of 350°C to 580°C under a pressure of 0.0001 Pa to 100 MPa.

[0086] The characteristics of the sulfide solid material treatment described in step v') may be the same as those shown in step vi).

[0087] In some embodiments, the sulfide solid material obtained by the method according to the present invention corresponds to formula (I): Li 7-y PS6-y X y (I) (In the formula, y is a number such as 0.5 ≤ y < 2, preferably 1.0 ≤ y ≤ 1.8, more preferably 1.2 ≤ y ≤ 1.6, etc.)

[0088] Therefore, step b) is a step of reacting the Li2S powder from step a) with at least P2S5 and LiX, where X is selected from a list consisting of F, Cl, I, Br, CN, NC, OCN, NCO, SCN, NCS, N3, or combinations thereof.

[0089] Similarly, step i) is to obtain the composition by optionally mixing Li2S, P2S5, and LiX from at least step a) in one or more solvents. Step i') is to obtain a solution by mixing Li2S, P2S5, and LiX from at least step a) in one or more solvents under an inert atmosphere.

[0090] Therefore, the composition ratio of each element can be controlled by adjusting the amounts of Li2S, P2S5, and LiX in step b). The starting materials containing Li2S, P2S5, and LiX, and their molar ratios, are selected according to the target stoichiometric ratio. The target stoichiometric ratio determines the ratio between the elements Li, P, S, and X, obtained from the amount of precursor applied under conditions of complete conversion without side reactions and other losses. As an example, 2 moles of Li6PS5Cl can be obtained from 5 moles of Li2S, 1 mole of P2S5, and 2 moles of LiCl.

[0091] In some preferred embodiments, X is selected from the list consisting of F, Cl, I, Br, and mixtures thereof.

[0092] Preferably, phosphorus sulfide (P2S5), halogen compounds, or pseudohalogen compounds (LiX) are in the form of powders having an average particle size of 0.5 μm to 400 μm.

[0093] In some cases, the sulfide solid material obtained by the method according to the present invention corresponding to formula (I) can be doped with an alkaline earth metal element.

[0094] Therefore, in some embodiments, the sulfide solid material obtained by the method according to the present invention corresponds to formula (II): Li 7-2x-y M x PS 6-y X y (II) (X is selected from the list consisting of F, Cl, I, Br, CN, NC, OCN, NCO, SCN, NCS, N3, or combinations thereof) M is an alkaline earth metal element selected from Sr, Ca, Mg, and Ba. x is a number such as 0.01 ≤ y < 0.5, y is a number such as 0.5 ≤ y < 2, preferably 1.0 ≤ y ≤ 1.8, more preferably 1.2 ≤ y ≤ 1.6, etc.

[0095] Therefore, step b) is to react the Li2S powder from step a) with a compound selected from at least P2S5, LiX, MX2, MS, and mixtures thereof.

[0096] Similarly, step i) is to obtain a composition by optionally mixing compounds selected from Li2S, P2S5, LiX, and MX2 from at least step a), MS, and mixtures thereof in one or more solvents, and step i') is to obtain a solution by mixing compounds selected from Li2S, P2S5, LiX, and MX2 from at least step a), MS, and mixtures thereof in one or more solvents under an inert atmosphere.

[0097] Therefore, the composition ratio of each element can be controlled by adjusting the amounts of Li2S, P2S5, LiX, MX2, MS, or mixtures thereof in step b). The starting materials containing Li2S, P2S5, LiX, MX2, MS, or mixtures thereof, and their molar ratios, are selected according to the target stoichiometric ratio. The target stoichiometric ratio determines the ratio between the elements Li, P, S, X, and M, obtained from the amount of precursor applied under conditions of complete conversion without side reactions and other losses.

[0098] Preferably, phosphorus sulfide (P2S5), halogen compounds or pseudohalogen compounds (LiX), and alkaline earth metal compounds (MX2 or MS) are in the form of powders with an average particle size ranging from 0.5 μm to 400 μm.

[0099] In some cases, the sulfide solid material obtained by the method according to the present invention corresponding to formula (I) can be doped with an element selected from Na, K, Rb, Cs, Cu, and Ag.

[0100] Therefore, in some embodiments, the sulfide solid material obtained by the method according to the present invention corresponds to formula (III): Li 7-x’-y M' x’ PS 6-y X y (III) (X is selected from the list consisting of F, Cl, I, Br, CN, NC, OCN, NCO, SCN, NCS, N3, or combinations thereof) M' is selected from Na, K, Rb, Cs, Cu, and Ag. x' is a number such as 0.01 ≤ y < 0.5, y is a number such as 0.5 ≤ y < 2, preferably 1.0 ≤ y ≤ 1.8, more preferably 1.2 ≤ y ≤ 1.6, etc.

[0101] Therefore, step b) is to react the Li2S powder from step a) with a compound selected from at least P2S5, LiX, M'X, M'2S, and mixtures thereof.

[0102] Similarly, step i) is to obtain a composition by optionally mixing a compound selected from Li2S, P2S5, LiX, and M'X from at least step a), M'2S, and mixtures thereof in one or more solvents, and step i') is to obtain a solution by mixing a compound selected from Li2S, P2S5, LiX, and M'X from at least step a), M'2S, and mixtures thereof in one or more solvents under an inert atmosphere.

[0103] Therefore, the composition ratio of each element can be controlled by adjusting the amounts of Li2S, P2S5, LiX, M'Cl, M'2S, or mixtures thereof in step b). The starting materials containing Li2S, P2S5, LiX, M'Cl, M'2S, or mixtures thereof, and their molar ratios, are selected according to the target stoichiometric ratio. The target stoichiometric ratio determines the ratio between the elements Li, P, S, X, and M', obtained from the amount of precursor applied under conditions of complete conversion without side reactions and other losses.

[0104] Preferably, lithium sulfide, phosphorus sulfide (P2S5), halogen compounds or pseudohalogen compounds (LiX), and compounds of Na, K, Rb, Cs, Cu, and Ag (M'X or M'2S) are in the form of powders having an average particle size between 0.5 μm and 400 μm.

[0105] Another object of the present invention relates to sulfide solid material particles obtained by the method according to the present invention, comprising at least elements Li, P, S, and X, wherein the particles have a D50 value in the range of 0.5 μm to 8 μm and a D90 value of 20 μm or less, as measured by analytical centrifugation analysis after deaggregation.

[0106] Therefore, the present invention also relates to particles of sulfide solid materials corresponding to the above formulas (I), (II), or (III).

[0107] Another object of the present invention relates to the use of particles according to the present invention for preparing a composition (C) comprising (i) a sulfide solid material of formula (I), (II), or (III) and (ii) at least one polymer material (P).

[0108] Composition (C) of the present invention may be used for the manufacture of electrodes. Composition (C) of the present invention may also be used for the manufacture of the electrolyte layer of an electrode. The electrode may be a positive electrode or a negative electrode. Composition (C) of the present invention may also be used for the manufacture of a separator.

[0109] Composition (C) is, in more detail, (i) Sulfide solid material according to formula (I), (II), or (II), (ii) at least one polymer material (P), (iii) at least one optional electroactive compound (EAC), (iv) At least one lithium-ion conductive material (LiCM) other than the sulfide solid material of the present invention, optionally selected. (v) at least one optional conductive material (ECM), and (vi) Optional lithium salts (LIS) Includes.

[0110] Another object of the present invention relates to the use of the particles according to the present invention for the manufacture of electrodes or for the manufacture of electrolyte layers of electrodes.

[0111] A further object of the present invention relates to the use of particles according to the present invention for the manufacture of separators.

[0112] If any disclosure of a patent, patent application, or publication incorporated herein by reference conflicts with the description of this application to such an extent that it obscures certain terms, the description herein shall prevail. [Brief explanation of the drawing]

[0113] [Figure 1] This is the solid-state 31P NMR spectrum of the argyrodite precursor after step a). [Examples]

[0114] XRD analysis Powder XRD diffractograms were acquired using an XRD goniometer (Malvern-Panalytical Aeris) with Bragg Brentano geometry and a Cu X-ray tube (Cu Kα wavelength of 1.5406 Å). The tube was operated at 40 kV / 15 mA, 600 W. This configuration used a fixed slit and a 0.02 rad Soller slit. Filtering devices such as nickel filters, monochromators, or Panalytical's Bragg Brentano HD optics could also be used on the primary side. The sample holder was mounted on a spinner, and the rotation speed during acquisition was typically 60 rpm. The acquisition step was 0.0108° per step. The angular range was typically 10° to 90° with two or more thetas. The total acquisition time was typically 30 minutes or more. Measurements were performed in a drying room.

[0115] solid 31 P NMR Solid-state NMR spectra were recorded using a Bruker Avance 400 spectrometer equipped with a high-speed DVT4 probe. 31 P measurements were performed using magic angle spinning (MAS) at a speed of 10 kHz, single pulse mode, and a relaxation time of D1 = 60 seconds. 31 The reference for the 3P NMR spectrum was 85% H3PO4.

[0116] Measurement of particle size distribution The particle size distribution (PSD) of Li2S powder was evaluated using laser diffraction measurements. For this purpose, the powder was stirred in para-xylene. The solution was filtered through an 800 μm sieve and introduced into a Malvern Mastersizer 3000. The data were processed using Fraunhofer's optical model.

[0117] For the sulfide solid electrolyte (SSE) powder of formula Li6PS5Cl, a second method was used to measure the particle size distribution. For this purpose, an analytical centrifuge LUMiSizer® (LUM) and an airtight quartz tube were used. First, the powder was deaggregated using an Ultra-Turrax® Tube Drive P (IKA) with a tube ST-20 (IKA). 45 mg of SSE powder was packed into the tube. Next, 15 g of p-xylene, pre-dried in a molecular sieve, was added to the tube. Then, the tube was inserted into the Ultra-Turrax® tool, and the SSE powder was deaggregated at 6000 rpm for 29 minutes. At the end of the deaggregation process, a small sample was taken with gentle stirring and placed in an airtight quartz tube. The sample was then analyzed, and the particle size distribution was determined using the Rosin-Rammler-Sperling-Bennet model.

[0118] Specific surface area of ​​particles by the BET method The specific surface area of ​​the particles was measured by nitrogen gas adsorption according to the Brunauer-Emet-Teller (BET) method described in "The Journal of the American Chemical Society," vol. 60, page 309, February 1938. The instrument used was a Micromeritics® TriStar 3000. Samples were pre-treated in a vacuum at 200°C for 2 hours before analysis. The specific surface area was calculated by considering a P / P° range of 0.05 to 0.2. To obtain a good correlation coefficient, at least 6 points were selected within this P / P° range.

[0119] Determination of H2S emissions Sample preparation is performed in a dry Ar glove box (moisture level < 5 ppm, O2 level < 5 ppm). The sample (350-700 mg of powder) is placed in a 4.02 cm³ container. 2The sample is placed in an open circular holder having a circular surface. Next, the holder is placed on top of the zirconia pot, where it can be isolated from the atmosphere. The zirconia pot is moved from the dry argon glove box to an indoor air glove box used for the H2S quantification test. The relative humidity is set to 35% at room temperature (23°C) (corresponding to a dew point of 6.7°C). Humidity is measured by a dew point probe (EA2-TX-100) from Mitchell Instruments. Humidity inside the glove box can be controlled by an inlet of pre-dried compressed air. The atmosphere inside the glove box is homogenized by two fans. Once the atmosphere is stable, the zirconia pot is opened and the sample is exposed to a controlled humid atmosphere. H2S quantification is performed by a Sensorcon sensor (Industrial Pro-H2S Pro). The experiment is carried out for 60 minutes, at which point the zirconia pot is closed again.

[0120] Conductivity and electrochemical impedance spectroscopy (EIS) Sample preparation and measurement were performed in a drying room. Before impedance spectroscopy, powder samples were cold-pressed at 500 MPa. Conductivity was obtained for pellets prepared using a uniaxial press operating at 500 MPa. Pelletization was performed using a lab-scale uniaxial press. Two carbon paper foils (Mersen Papyex soft graphite N998 Ref: 496300120050000, 0.2 mm thick) were used as current collectors. The pellets with these carbon electrodes attached were then filled into an airtight sample holder, and a pressure of 40 MPa was applied to the sample holder for measurement. Impedance spectra were acquired using a Biologic VMP3 device. The samples were placed in a binder thermostat and impedance measurements were performed at different temperatures. Each spectrum was acquired after 2 hours of stabilization at the target temperature. The temperature range was from -20°C to 60°C in 10°C increments. Impedance spectroscopy is performed in PEIS mode with an amplitude of 20 mV and a frequency range of 1 MHz to 1 kHz (average of 25 points per 10x multiplier and 50 measurements per frequency point).

[0121] material Dry LiOH was obtained from Supelco, and LiOH-H2O from Chengdu. Dry H2S was obtained from Air Liquide (purity >99.5 vol%). Li2S Lorad 200 and 40 were supplied by Lorad Chemical Corporation.

[0122] Preparation of Li2S Sulfidation procedure The reaction was carried out in a 200 mL stirred quartz reactor capable of operating in an inert atmosphere and at high temperatures. The reaction system included a gas inlet and outlet, a stirrer, and a counter blade. The reactor had a system for heating the reactor and its lid. The temperature was measured by placing a probe in the powder introduced into the reactor. A pump connected to the reactor allowed for the introduction of reagent gases through the inlet tube. The outlet tube was connected to a Dean-Stark apparatus for recovering the water produced in the reaction, and further to a scrubber containing NaOH for neutralizing unreacted H2S. The reactor was inactivated with nitrogen by applying a cycle of purging under vacuum followed by refilling with nitrogen.

[0123] LiOH drying LiOH-H2O was added to a reactor set to 200°C under a flow of dry nitrogen for 3 hours. Mechanical stirring was set to 100 rpm.

[0124] Preparation of Li2S powder (A) Three moles of dry LiOH powder were placed in the reactor. The reactor was inactivated by purging under vacuum and then refilling with nitrogen for three cycles. Then, mechanical stirring was set to 100 rpm and the temperature to 200°C. Dry H2S was passed through a molecular sieve and then introduced into the reactor from the inlet tube at a flow rate of 10 NL / h until it reached 2.5 equivalents relative to the present LiOH. Unreacted H2S and the formed water vapor were extracted from the outlet tube, and the condensed water was recovered using a Dean-Stark apparatus while neutralizing the H2S with a scrubber containing NaOH.

[0125] Preparation of Li2S powder (B) Three moles of dry LiOH powder were placed in the reactor. The reactor was inactivated by purging under vacuum and then refilling with nitrogen for three cycles. Mechanical stirring was then set to 100 rpm and the temperature to 240°C. Dry H2S was passed through a molecular sieve and then introduced into the reactor from the inlet tube at a flow rate of 20 NL / h until its concentration reached 2.0 equivalents relative to the present LiOH. Unreacted H2S and the formed water vapor were extracted from the outlet tube, and the condensed water was recovered using a Dean-Stark apparatus while neutralizing the H2S with a scrubber containing NaOH.

[0126] Li2S powder having the characteristics described in Table 1 was used as the raw material.

[0127] [Table 1]

[0128] As can be seen from Table 1, which shows that a large amount of H2S is released when exposed to moisture, Li2S powder exhibits high reactivity to water vapor.

[0129] LiCl and P2S5 were supplied from Altichem and Italmatch, respectively (purity > 99%).

[0130] Preparation of a sulfide solid electrolyte with formula Li6PS5Cl (argyrodite) Step a): 7.7 g of LiCl, 20.1 g of P2S5, and 20.8 g of Li2S were weighed in sequence and placed in a glass container. The powders were homogenized by gently mixing them by hand. These were then placed in a zirconia bowl (Across) containing 440 g of ZrO2 balls (5 mm, Across). Next, 113.5 g of xylene isomer (Carlo Erba, purity >99%, dry) was added and used to directly wash the powder from the glass container into the zirconia bowl. The bowl was quickly sealed to prevent evaporation of the xylene isomer. Wet ball milling was performed using a Retsch™ PM400 planetary ball mill. After milling at 350 rpm for 14 hours, a pale yellow / beige paste was obtained.

[0131] The paste was transferred to a dry alumina crucible and dried under dynamic vacuum at 130°C to remove xylene. The xylene was condensed in ice water, and drying was continued until no more xylene could be recovered. After drying for 5 hours, milling balls were separated from the pale beige powder by sieving with a 4 mm sieve.

[0132] The powder obtained after step a) corresponds to a sulfide solid electrolyte precursor, and is solid 31 Large amounts of glassy (PS4) are measured by 1P NMR. 3- It contains seeds. This fact reflects that the reaction producing the desired sulfide solid electrolyte proceeded to a high degree.

[0133] 31 The composition of the precursor, as measured by 1P NMR, is shown in Table 2. 31 In the 1P NMR method, the glassy (PS4) 3- The species is attributed to a large peak centered around a chemical shift of approximately 84 ppm. This peak is attributed to the crystal (PS4) centered around a peak of approximately 86.4 ppm. 3- The presence of species may result in asymmetry. If necessary, deconvolution of the peaks can be performed for each (PS4) 3- The relative proportion of species can be obtained. Furthermore, (P2S7) 4- and (P2S6)2- Other species, such as those mentioned above, can be seen at 94 ppm and 106 ppm (see Figure 1).

[0134] [Table 2]

[0135] The inventors of the present invention have determined that precursors obtained from Li2S according to the present invention generally have a D50 of less than, for example, 20 μm and / or 5 μm. 2 (PS4) is more abundant than that obtained from precursors (PS4) from Li2S with a specific surface area of ​​less than / g. 3- Includes parts or an equivalent amount of glassy material (PS4) 3- It was observed that the site was included. Therefore, the reaction involving Li2S according to the present invention proceeds further or to the same extent at this stage.

[0136] Step b): The dried mixture was placed in a quartz reactor in dry air (dew point <-40°C). Next, the reactor was placed in a rotary furnace and the product was crystallized at 490°C for 12 hours under a N2 flow (30 L / h) and rotation at 9 rpm (heating increase of 1.5°C / min). It was then cooled to 50°C under the same N2 flow and rotation. The final product was slightly deaggregated to obtain a sulfide solid electrolyte of formula Li6PS5Cl. Its properties are reported in Table 3.

[0137] [Table 3]

[0138] As can be seen from Table 3, the argyrodite powder obtained from Li2S in the present invention has a D50 of less than 20 μm and / or 5 μm, for example. 2The particle size is smaller than that of argyrodite powder obtained from Li2S having a specific surface area of ​​less than / g. Therefore, while the D50 of argyrodite powder obtained from Li2S powder (A) and Li2S powder (B) is 4.7 μm and 6 μm, respectively, the D50 of argyrodite powder obtained from Li2S powder Lorad 40 and Li2S powder Lorad 200 is 8.6 μm and 7.4 μm, respectively. Furthermore, while the D90 of argyrodite powder obtained from Li2S powder (A) and Li2S powder (B) is 9.7 μm and 12 μm, respectively, the D90 of argyrodite powder obtained from Li2S powder Lorad 40 and Li2S powder Lorad 200 is 15.9 μm and 15.3 μm, respectively.

[0139] This reduction in particle size does not adversely affect the ionic conductivity of the resulting argyrodite (greater than or near 3 mS / cm at 30°C). This is advantageous because the properties of the SSE particles, particularly their particle size, determine the difficulty in manufacturing thin separators and compact cathode electrodes. Using small-sized SSE particles allows for the manufacture of separators and cathodes without milling, which typically impairs the ionic conductivity of the material.

Claims

1. A method for preparing particles of a sulfide solid material containing at least Li, P, S, and X elements, a) D50 values ​​in the range of 20 μm to 500 μm measured by laser diffraction in paraxylene, and 5 m measured by nitrogen gas adsorption according to the Brunauer-Emmet-Teller (BET) method. ２ Lithium sulfide (Li) having a specific surface area of ​​1 / g or more ２ The process of preparing the powder of S) b) Li of process a) ２ S powder contains at least P ２ S ５ The process involves reacting LiX with Li, P, S, and X to obtain sulfide solid material particles. (X is F, Cl, I, Br, CN, NC, OCN, NCO, SCN, NCS, N ３ (or selected from a list consisting of combinations thereof), A method that includes this.

2. Step a) Lithium sulfide (Li ２ When the powder in S) is exposed to 23°C and 30-40% relative humidity for 60 minutes, it contains more than 200 ml / g of H ２ The method according to claim 1, which shows the amount of sulfur released.

3. Step b) is, i) At least Li in step a) ２ S, and P ２ S ５ and LiX are optionally mixed in one or more solvents to obtain a composition; ii) A step of performing a mechanical treatment on the composition obtained in step i); iii) Optionally, remove at least a portion of one or more solvents from the composition obtained in step ii) to obtain a sulfide solid material precursor; iv) Optionally, press the sulfide solid material precursor of step iii) into pellets; v) A step of heating the precursor obtained in step iii) for example in pellet form in an inert atmosphere at a temperature in the range of 350°C to 580°C for a time in the range of 1 to 12 hours, thereby forming sulfide solid material particles; and vi) optionally, a step of treating the sulfide solid material obtained in step v) to a desired particle size distribution; The method according to claim 1 or 2, including the method described in claim 1 or 2.

4. The method according to claim 3, wherein in step ii), the mechanical treatment is performed by wet milling or dry milling.

5. Process b) is the following process: i') At least Li of step a) ２ S and P ２ S ５ A step of obtaining a solution by mixing LiX in one or more solvents under an inert atmosphere; ii') A step of obtaining a sulfide solid material precursor by removing at least a portion of the one or more solvents from the composition obtained in step i'); iii') Optionally, a step of pressing the sulfide solid material precursor of step ii') into pellets; A step of heating the precursor obtained in step iv') ii') in, for example, pellet form, in an inert atmosphere at a temperature in the range of 350°C to 580°C for a time in the range of 1 to 12 hours, thereby forming sulfide solid material particles; and v') A step of optionally processing the sulfide solid material particles obtained in step iv') to a desired particle size distribution. The method according to claim 1 or 2, including the method described in claim 1 or 2.

6. The sulfide solid material precursor of step iii) or step ii') is ３１ When determined by P NMR, the glassy (PS ４ ) ３－ The method according to any one of claims 3 to 5, comprising at least 85 mol% of species P in species form.

7. The sulfide solid material is given by formula (I): Li ７－ｙ PS ６－ｙ X ｙ (I) (In the formula, y is a number such as 0.5 ≤ y < 2, preferably 1.0 ≤ y ≤ 1.8, more preferably 1.2 ≤ y ≤ 1.6,) X is F, Cl, I, Br, CN, NC, OCN, NCO, SCN, NCS, N ３ (or selected from a list consisting of combinations thereof), The method according to any one of claims 1 to 6, corresponding to the present invention.

8. The sulfide solid material further contains an alkaline earth metal element, and formula (II): Li ７－２ｘ－ｙ 7. ｘ PS ６－ｙ 8 ｙ (99) (X is F, Cl, I, Br, CN, NC, OCN, NCO, SCN, NCS, N ３ , or selected from a list consisting of combinations thereof, M is an alkaline earth metal element selected from Be, Sr, Ca, Mg, and Ba. x is a number such as 0.01 ≤ y < 0.5, (y is a number such as 0.5 ≤ y < 2, preferably 1.0 ≤ y ≤ 1.8, more preferably 1.2 ≤ y ≤ 1.6, etc.) In response to, Step b) is the Li of step a) ２ S powder, at least P ２ S ５ LiX, MX ２ The method according to any one of claims 1 to 7, comprising the step of reacting a compound selected from, MS, and a mixture thereof.

9. The sulfide solid material further comprises an element selected from Na, K, Rb, Cs, Cu, and Ag, and the formula (III) Li ７－ｘ’－ｙ M' ｘ’ PS ６－ｙ X ｙ (III) (X is F, Cl, I, Br, CN, NC, OCN, NCO, SCN, NCS, N ３ , or selected from a list consisting of combinations thereof, M' is selected from Na, K, Rb, Cs, Cu, and Ag. x' is a number such as 0.01 ≤ y < 0.5, (y is a number such as 0.5 ≤ y < 2, preferably 1.0 ≤ y ≤ 1.8, more preferably 1.2 ≤ y ≤ 1.6, etc.) In response to, Step b) is the Li of step a) ２ S powder, at least P ２ S ５ A compound selected from LiX, M'X, M' ２ The method according to any one of claims 1 to 7, comprising the step of reacting with S and a mixture thereof.

10. The method according to any one of claims 1 to 9, wherein the sulfide solid material particles have a D50 value in the range of 0.5 μm to 8 μm and a D90 value of 20 μm or less, as measured by analytical centrifugal separation.

11. Particles of a sulfide solid material containing at least elements Li, P, S, and X, characterized in that they have a D50 value in the range of 0.5 μm to 8 μm and a D90 value of 20 μm or less, as measured by analytical centrifugation analysis after deaggregation, obtained by the method of any one of claims 1 to 10.

12. The particle according to claim 11, wherein the sulfide solid material corresponds to formula (I), (II), or (III).

13. Use of sulfide solid material particles according to claim 11 or 12 for the preparation of a composition (C) comprising (i) the product of formula (I), (II), or (II), and (ii) at least one polymer material (P).

14. Use of sulfide solid material particles according to claim 11 or 12 for the manufacture of an electrode or for the manufacture of an electrolyte layer of an electrode.

15. Use of sulfide solid material particles according to claim 11 or 12 for the manufacture of a separator.

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