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  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B25/00—Phosphorus; Compounds thereof
  • C01B25/14—Sulfur, selenium, or tellurium compounds of phosphorus
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
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  • C01B17/00—Sulfur; Compounds thereof
  • C01B17/22—Alkali metal sulfides or polysulfides
• • C—CHEMISTRY; METALLURGY
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  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B25/00—Phosphorus; Compounds thereof
  • C01B25/16—Oxyacids of phosphorus; Salts thereof
• • C—CHEMISTRY; METALLURGY
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  • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
  • C01D15/00—Lithium compounds
  • C01D15/04—Halides
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
  • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
  • H01B1/10—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances sulfides
• • H—ELECTRICITY
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  • H01M10/05—Accumulators with non-aqueous electrolyte
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  • H01M10/00—Secondary cells; Manufacture thereof
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  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
  • H01M10/0562—Solid materials
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  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0566—Liquid materials
  • H01M10/0567—Liquid materials characterised by the additives
• • H—ELECTRICITY
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/04—Processes of manufacture in general
• • H—ELECTRICITY
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/04—Processes of manufacture in general
  • H01M4/0402—Methods of deposition of the material
  • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
• • H—ELECTRICITY
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  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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  • H01M4/00—Electrodes
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  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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  • H01M10/00—Secondary cells; Manufacture thereof
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  • H01M10/052—Li-accumulators
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  • H01M10/00—Secondary cells; Manufacture thereof
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  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• • H—ELECTRICITY
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  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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  • H01M2300/00—Electrolytes
  • H01M2300/0017—Non-aqueous electrolytes
  • H01M2300/0065—Solid electrolytes
  • H01M2300/0068—Solid electrolytes inorganic
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the present application relates to the field of inorganic compounds based on oxysulphides having an argyrodite type structure and their uses in electrochemical applications. More particularly, the present application relates to the field of inorganic compounds based on oxysulphide having an argyrodite-like structure, to electrode materials and to solid electrolytes comprising them, to their methods of production and to their uses in electrochemical cells. , especially in so-called all-solid-state batteries.
• Inorganic compounds such as sulphide-based ceramics, glasses and glass-ceramics are promising materials for many technological applications since they allow the development of all-solid-state electrochemical systems that are substantially safer.
• inorganic sulfide compounds exhibit a wide window of electrochemical stability and substantially higher ionic conductivity at room temperature. Indeed, the inorganic solid electrolytes comprising them exhibit ionic conductivities at room temperature comparable to those of liquid organic electrolytes, and therefore substantially higher than those of their counterparts based on the use of solid polymer electrolytes.
• argyrodite of formula LiePSsX in which X is Cl, Br or I has an ionic conductivity at ambient temperature of the order of mS.cnr 1 .
• inorganic compounds of the argyrodite type is limited by their high production cost, in particular due to the use of lithium sulphide (U2S) as a precursor and source of sulfur and a high-temperature annealing step. temperature allowing the obtaining of interesting ionic conductivities.
• U2S lithium sulphide
• One of the key elements of the industrial requirements related to the production of this type of inorganic compounds is therefore to minimize the costs by lowering the U2S utilization rate and the annealing temperature while maintaining a considerably high ionic conductivity.
• argyrodite-like inorganic compounds are associated with problems related to their interfacial stability as well as their stability in ambient air and humidity. More precisely, these inorganic solid electrolytes generate hydrogen sulphide (H2S) gas in contact with humid air and must therefore be prepared, assembled and operated under an inert atmosphere.
• H2S hydrogen sulphide
• One strategy employed to solve this problem involves the use of an inorganic argyrodite compound based on oxysulfide. Indeed, a partial atomic substitution of sulfur and/or lithium in these inorganic compounds by oxygen would lead to a significant reduction in the generation of H2S in the presence of humidity.
• embodiments of the technology as described herein include the following:
• a process for preparing an inorganic compound having an argyrodite-like structure based on an alkali metal comprising a step of grinding alkali metal sulfide, alkali metal sulfate, phosphorus pentasulfide and an alkali metal halide, wherein the alkali metal is selected from lithium, sodium and potassium, for example the alkali metal is lithium.
• the alkali metal halide is chosen from alkali metal fluoride, alkali metal chloride, alkali metal bromide, alkali metal iodide and a mixture of au least two of these.
• alkali metal halide is a mixture of alkali metal chloride, alkali metal bromide and alkali metal iodide.
• the argyrodite-like structure is of the formula in which M is the alkali metal chosen among Li, Na and K, for example M is Li, Z is a halogen atom chosen from F, Cl, Br and I, x denotes the number of Z in excess of 1 or is equal to zero, and y is a nonzero number (for example, 0 ⁇ x ⁇ 1 and 0 ⁇ y ⁇ 1 ).
• An inorganic compound having an argyrodite-like structure obtained according to the process as defined in any one of items 1 to 29.
• An electrode material comprising an electrochemically active material and an inorganic compound having an argyrodite type structure as defined in item 30 or obtained according to the process as defined in any one of items 1 to 29.
• Electrode material according to item 31 in which the inorganic compound having an argyrodite-like structure is present as an additive.
• Electrode material according to item 33 wherein the coating material forms a coating layer on the surface of the electrochemically active material.
• Electrode material according to item 35 in which the metal of the electrochemically active material is chosen from among titanium (Tl), iron (Fe), manganese (Mn), vanadium (V), nickel ( Ni), cobalt (Co), aluminum (Al), chromium (Cr), copper (Cu), zirconium (Zr), niobium (Nb), molybdenum (Mo), tungsten (W ) and a combination of at least two of these.
• an alkali or alkaline-earth metal chosen from lithium (Li), sodium (Na), potassium (K ) and magnesium (Mg).
• the electrochemically active material is chosen from a non-alkaline or non-alkaline-earth metal, an intermetallic compound, a metal oxide, a nitride of metal, metal phosphide, metal phosphate, metal halide, metal fluoride, metal sulfide, metal oxysulfide, carbon, silicon (Si), silicon-carbon composite (Si-C ), silicon oxide (SIO X ), silicon oxide-carbon composite (SIOx-C), tin (Sn), tin-carbon composite (Sn-C), tin oxide (SnO x ), a tin oxide-carbon (SnOx-C) composite, and a combination of at least two of these.
• Electrode material according to item 43 in which the electronic conductive material is carbon.
• Electrode material according to item 42 in which the coating material is chosen from , other similar potting materials and a combination of two or more thereof.
• Electrode material according to item 45 in which the coating material is LiNbO 3 .
• Electrode material according to any one of items 31 to 46 which further comprises at least one electronically conductive material.
• Electrode material according to item 47 in which the electronically conductive material is chosen from the group consisting of carbon black, acetylene black, graphite, graphene, carbon fibers, carbon nanofibers , carbon nanotubes, and a mixture of at least two thereof.
• the electronically conductive material is a mixture of carbon black and gas phase formed carbon fibers (VGCFs).
• Electrode material according to any one of items 31 to 49, which further comprises at least one additive.
• Electrode material according to item 50 in which the additive is chosen from inorganic ionic conducting materials, inorganic materials, glasses, glass ceramics, ceramics, nano ceramics, salts and a combination of at least two of these.
• Electrode material according to any of items 31 to 51 which further comprises a binder.
• Electrode material according to item 52 in which the binder is chosen from the group consisting of a polymer binder of the polyether, polycarbonate or polyester type, a fluorinated polymer and a water-soluble binder .
• An electrode comprising the electrode material as defined in any of items 31 to 53 on a current collector.
• a self-supporting electrode comprising the electrode material as defined in any of items 31 to 53.
• An electrolyte comprising an inorganic compound having an argyrodite-like structure as defined in item 30 or obtained by the process as defined in any one of items 1 to 29.
• Electrolyte according to item 56 said electrolyte being a liquid electrolyte comprising a salt in a solvent.
• Electrolyte according to item 56 said electrolyte being a gel electrolyte comprising a salt in a solvent and optionally a solvating polymer.
• Electrolyte according to item 56 said electrolyte being a solid polymer electrolyte comprising a salt in a solvating polymer.
• Electrolyte according to item 56 said electrolyte being an inorganic solid electrolyte.
• Electrolyte according to item 56 said electrolyte being a polymer-ceramic hybrid solid electrolyte.
• Electrolyte according to item 64 in which the additional component is chosen from ionic conductive materials, inorganic particles, glass or ceramic particles and a combination of at least two of these.
• An electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, in which at least one of the positive electrode or the negative electrode is as defined in item 54 or 55 or comprises a material electrode as defined in any of items 31 to 53.
• An electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, in which the electrolyte is as defined in any one of items 56 to 65.
• Electrochemical cell according to item 66 or 67 in which the negative electrode comprises an electrochemically active material comprising an alkali metal, an alkaline earth metal, an alloy comprising at least one alkali or alkaline earth metal, a non -alkaline and non-alkaline-earth metal, or an alloy or intermetallic compound.
• Electrochemical cell according to item 70 in which the negative electrode is lithiated in situ during the cycling of said electrochemical cell.
• An electrochemical accumulator comprising at least one electrochemical cell as defined in any one of items 66 to 71.
• Electrochemical battery according to item 72 wherein said electrochemical battery is a battery selected from a lithium battery, a lithium-ion battery, a sodium battery, a sodium-ion battery, a magnesium battery, and a magnesium-ion.
• Electrochemical accumulator according to item 73 wherein said battery is a lithium battery or a lithium-ion battery.
• Figure 1 presents X-ray diffraction patterns obtained for the powders of Argyrodites 1 to 4 and 8, as described in ('Example 2.
• Figure 2 presents X-ray diffraction patterns obtained for the powders of Argyrodites 2 and 5 to 7, as described in ('Example 2.
• Figure 3 presents X-ray diffraction patterns obtained for the powders of Argyrodites 2, 3, 9 and 10, as described in Example 2.
• Figure 4 presents X-ray diffraction patterns obtained for the powders of Argyrodites 2 and 12 to 15, as described in ('Example 2.
• Figure 5 presents X-ray diffraction patterns obtained for the powders of Argyrodites 16 to 19, as described in Example 2.
• Figure 6 presents X-ray diffraction diagrams obtained for the powders of Argyrodites 2, 13, 20 and 21, as described in Example 2.
• Figure 7 presents lithium nuclear magnetic resonance spectra ( 6 Li NMR) obtained for Argyrodites 2 and 9, as described in Example 3.
• Figure 8 presents phosphorus nuclear magnetic resonance spectra ( 31 P NMR) obtained for Argyrodites 2 and 9, as described in ('Example 3.
• Figure 9 shows a lithium nuclear magnetic resonance spectrum ( 6 Li NMR) obtained for Argyrodite 7, as described in Example 3.
• Figure 10 shows a phosphorus nuclear magnetic resonance spectrum ( 31 P NMR) obtained for Argyrodite 7, as described in Example 3.
• Figure 11 presents lithium nuclear magnetic resonance spectra ( 6 Li NMR) obtained for Argyrodites 13 and 16, as described in Example 3.
• Figure 12 shows phosphorus nuclear magnetic resonance spectra ( 31 P NMR) obtained for Argyrodites 13 and 16, as described in Example 3.
• Figure 13 shows a plot of the volume of gaseous H2S normalized by the mass of argyrodite generated as a function of time for Argyrodites 2, 7, 8, 11, 13 and 16, as described in Example 4.
• Figure 14 is a graph showing the results of ionic conductivity versus temperature for Cells, as described in Example 5(b).
• Figure 15 is a graph showing the results of ionic conductivity as a function of temperature for Cells, as described in Example 5(b).
• Figure 16 is a graph showing the results of ionic conductivity versus temperature for Cells as described in Example 5(b).
• Figure 17 is a graph showing the results of ionic conductivity versus temperature for Cells, as described in Example 5(b).
• Figure 18 is a graph showing the results of ionic conductivity versus temperature for Cells, as described in Example 5(b).
• Figure 19 is a graph showing the results of ionic conductivity versus temperature for Cells as described in Example 5(b).
• Figure 20 presents cyclic voltammograms obtained for Cells 22 and 23 recorded at a sweep rate of 0.05 mV/s between 2.5 V and 4.2 V vs Li/Li* at a temperature of approximately 30° C, as described in Example 6(b).
• Figure 21 shows a graph of charge (•) and discharge capacity and the coulombic efficiency (A) as a function of the number of cycles per 100 cycles obtained for Cell 24, as described in (Example 7(c).
• Figure 22 presents the discharge profiles obtained for Cell 24 as a function of the capacity obtained at charge and discharge currents of C/10, C/4 and C/2 and recorded vs Li/Li* at a temperature of 30°C, as described in (Example 7(c).
• Figure 23 presents the discharge profiles obtained for Cell 24 as a function of time obtained at charge and discharge currents of C/10, C/4 and C/2 and recorded vs Li/Li* at a temperature of 30 °C, as described in Example 7(c).
• self-supporting electrode refers to an electrode without a metallic current collector.
• the present technology relates to a process for preparing an inorganic compound having an argyrodite-like structure based on M2S-P2S5-M2SO4-MZ (wherein, M is an alkali metal selected from lithium (Li), sodium (Na), potassium (K), and a combination of at least two thereof, and Z is a halogen atom selected from fluorine (F), chlorine (Cl), bromine (Br) and iodine (I), or a combination of at least two of these), the method comprising a step of direct grinding of the precursors.
• M is lithium.
• the precursors consist of alkali metal sulphide (M2S), alkali metal sulphate (M2SO4), phosphorus pentasulphide (P2S5) and an alkali metal halide, chosen from alkali metal fluoride, alkali, alkali metal bromide, alkali metal iodide and a mixture of at least two of these.
• M2S alkali metal sulphide
• M2SO4 alkali metal sulphate
• P2S5 phosphorus pentasulphide
• an alkali metal halide chosen from alkali metal fluoride, alkali, alkali metal bromide, alkali metal iodide and a mixture of at least two of these.
• the inorganic compounds possessing an argyrodite-like structure can respectively be of formulas in in which Z and M are such quid defined, x designates the number of Z in excess of 1 or is equal to zero, and y is a number different from zero, for example 0 ⁇ x ⁇ 1 and 0 ⁇ y ⁇ 1 . According to an example, x is a non-zero number (for example, 0 ⁇ x ⁇ 1).
• the inorganic compounds having an argyrodite type structure can therefore be obtained by grinding from precursors such as quid respectively defined according to the following reaction equations: in which, x, y, M and Z are such quid defined.
• x designates the number of Z in excess of 1 or is equal to zero
• y is a number different from zero
• x and y are selected to obtain a desired stoichiometry or to achieve electroneutrality.
• inorganic compounds having an argyrodite-like structure according to Equation 1 include inorganic compounds having an argyrodite-like structure of formulas in which M and Z are such quid defined.
• the inorganic compound has an argyrodite-like structure including less of the alkali metal (i.e., an inorganic compound having an argyrodite-like structure according to Equation 2)
• x denotes the number of Zs in excess of 1 or is zero
• y is a non-zero number
• x and y are selected to get desired stoichiometry.
• Non-limiting examples of inorganic compounds having an argyrodite-like structure according to Equation 2 include inorganic compounds having an argyrodite-like structure of formulas wherein M and Z are as defined herein.
• Z is a chlorine atom and the alkali metal halide is the alkali metal chloride.
• the inorganic compound having an argyrodite-like structure can be chosen from inorganic compounds having an argyrodite-like structure of formulas in which M is as defined here.
• Z is a bromine atom and the alkali metal halide is the alkali metal bromide.
• the inorganic compound having an argyrodite-like structure can be chosen from inorganic compounds having an argyrodite-like structure of formulas in which M is as defined here.
• the compound compound having an argyrodite-like structure may be an inorganic compound having an argyrodite-like structure of formula wherein M is as defined here.
• Z is an iodine atom and the alkali metal halide is the alkali metal iodide.
• the inorganic compound having an argyrodite-like structure can be chosen from inorganic compounds having an argyrodite-like structure of formulas , in which M is as defined here.
• Z is a combination including chlorine and bromine and the alkali metal halides are a mixture of alkali metal chloride and alkali metal bromide.
• the inorganic compound having an argyrodite-like structure can be chosen from inorganic compounds having an argyrodite-like structure of formulas in which M is as defined here.
• Z is a combination including chlorine, bromine and iodine and the alkali metal halides are a mixture of alkali metal chloride, alkali metal bromide and alkali metal iodide .
• the inorganic compound having an argyrodite-like structure can be chosen from inorganic compounds having an argyrodite-like structure of formulas in which M is as defined here.
• the alkali metal is lithium and the inorganic compound having an argyrodite-like structure is based on (in which, Z is a halogen atom chosen from F, Cl, Br and I, or a combination of at least two of these), the method comprising a step of direct grinding of the precursors.
• the precursors consisting of lithium sulphide (Li 2 S), lithium sulphate (Li 2 SO 4 ), phosphorus pentasulphide (P2S5) and a lithium halide, chosen from lithium fluoride (LiF), lithium chloride (LiCl), lithium bromide (LiBr), lithium iodide (Lil) and a mixture of at least two of these.
• Non-limiting examples of inorganic compounds having an argyrodite-like structure according to Equation 1 include inorganic compounds having an argyrodite-like structure of formulas in which Z is as defined herein.
• Examples non-limiting inorganic compounds having an argyrodite-like structure according to Equation 2 include inorganic compounds having an argyrodite-like structure of formulas , where Z is as herein defined.
• Z is a chlorine atom and the lithium halide is LiCl.
• the inorganic compound having an argyrodite-like structure can be chosen from inorganic compounds having an argyrodite-like structure of formulas
• Z is a bromine atom and the lithium halide is LiBr.
• the inorganic compound having an argyrodite-like structure can be chosen from inorganic compounds having an argyrodite-like structure of formulas
• the inorganic compound having an argyrodite-like structure may be an inorganic compound having an argyrodite-like structure of formula
• Z is an iodine atom and the lithium halide is Lil.
• the inorganic compound having an argyrodite-like structure can be chosen from inorganic compounds having an argyrodite-like structure of formulas
• Z is a combination including chlorine and bromine and the lithium halides are a mixture of LICI and LiBr.
• the inorganic compound having an argyrodite-like structure can be chosen from inorganic compounds having an argyrodite-like structure of formulas
• Z is a combination including chlorine, bromine and iodine and the lithium halides are a mixture of LiCl, LiBr and Lil.
• the inorganic compound having an argyrodite-like structure can be chosen from inorganic compounds having an argyrodite-like structure of formulas
• the method as defined here is carried out in one step. That is to say that, preferably, the method does not include an annealing step.
• the method may include an optional low temperature annealing step. For example, if the process includes an annealing step, this can be carried out at a maximum temperature of around 400°C or at a maximum temperature of around 300°C.
• the grinding step can be carried out using a grinder, for example a planetary grinder. Any type of known compatible grinder is envisaged.
• the grinding step can be carried out at a speed of rotation, for a determined duration and in a grinding ball:precursor ratio making it possible to obtain an inorganic compound having the desired argyrodite type structure.
• the grinding step can be carried out at a rotational speed comprised in the range ranging from approximately 300 rpm to approximately 800 rpm, or ranging from approximately 400 rpm to approximately 700 rpm, or ranging from about 500 rpm to about 700 rpm.
• the grinding step can be carried out at a rotational speed of around 600 rpm.
• the milling step can be carried out for a duration ranging from about 5 hours to about 20 hours.
• the grinding step can be done for about 10 hours.
• the grinding step can be carried out in a grinding balls: precursors ratio comprised in the range going from about 10 to about 30.
• the grinding step can be carried out in a balls ratio grinding: precursors of about 30.
• the ratio of grinding balls: precursors is approximately 30 and the grinding step is carried out at a rotational speed included in the interval going from approximately 500 rpm to approximately 700 rpm for approximately 10 hours in order to obtaining an inorganic compound having the desired argyrodite-like structure.
• the grinding step is performed at a rotational speed of approximately 600 rpm.
• the parameters of the grinding step making it possible to obtain an inorganic compound having the desired argyrodite-type structure can be selected and/or optimized depending on the type of mill used.
• an alkali metal sulphate for example, Li 2 SO 4
• the method as defined here could make it possible to obtain inorganic compounds exhibiting ionic conductivities substantially similar to the ionic conductivities reported for inorganic compounds obtained by conventional methods from different precursors and comprising an annealing step.
• Certain properties of the present inorganic compounds as obtained according to certain embodiments of the present process may also differ from those demonstrated by compounds prepared by conventional methods, for example, by methods using an alkali metal oxide (for example, Li 2 O) replacing the alkali metal sulphate (for example, Li 2 SO 4 ) as precursor.
• the id compounds obtained may exhibit greater electrochemical stability, reduced H2S emission, greater critical current density, or reduced polarization compared to compounds obtained conventionally. .
• the inorganic compounds described here according to certain embodiments can demonstrate a greater purity of argyrodite structure by 6 Li or 31 P NMR and/or a reduction in the relative intensity of the peaks associated with the PO2S2, PO3S and/or PO4 groups in 31 P NMR.
• the relative intensity of the PO2S2, PO3S and PO4 peaks can be respectively below 1.5, below 0.8 and below 0.3.
• the present technology also relates to an inorganic compound having an argyrodite type structure as defined here obtained according to the method as defined here.
• the present technology also relates to an electrode material comprising an electrochemically active material and an inorganic compound having an argyrodite type structure as defined here or obtained according to the process as defined here.
• the inorganic compound having an argyrodite-like structure as defined herein may be present as an additive and/or as a coating material in the electrode material.
• the inorganic compound having an argyrodite-like structure can form a coating layer on the surface of the electrochemically active material.
• said electrode material is a positive electrode material and the electrochemically active material is chosen from a metal oxide, a metal sulphide, a metal oxysulphide, a metal phosphate, a metal fluorophosphate, metal oxyfluorophosphate, metal sulfate, metal halide (eg, metal fluoride), sulfur, selenium, and a combination of two or more of these.
• the electrochemically active material is chosen from a metal oxide, a metal sulphide, a metal oxysulphide, a metal phosphate, a metal fluorophosphate, metal oxyfluorophosphate, metal sulfate, metal halide (eg, metal fluoride), sulfur, selenium, and a combination of two or more of these.
• the metal of the electrochemically active material is chosen from titanium (Tl), iron (Fe), manganese (Mn), vanadium (V), nickel (Ni), cobalt (Co), aluminum (Al), chromium (Cr), copper (Cu), zirconium (Zr), niobium (Nb), molybdenum (Mo), tungsten (W) and their combinations, when compatible.
• the electrochemically active material may optionally further comprise a metal alkaline or alkaline-earth, for example, lithium (Li), sodium (Na), potassium (K) or magnesium (Mg).
• Non-limiting examples of electrochemically active materials include lithium and metal phosphates, complex oxides, such as or a combination thereof), is Mn, Co, Ni, or a combination thereof), L or a combination thereof) and combinations thereof, where compatible.
• the electrochemically active material is an oxide as described above.
• the electrochemically active material may be a lithium manganese oxide, wherein the manganese may be partially substituted by a second transition metal, such as a lithium nickel manganese cobalt oxide (NMC ).
• NMC lithium nickel manganese cobalt oxide
• the electrochemically active material is the
• said electrode material is a negative electrode material and the electrochemically active material is chosen from a non-alkaline and non-alkaline-earth metal (for example, indium (In), germanium ( Ge) and bismuth (Bi)), an intermetallic compound (for example, ), a metal oxide, a metal nitride, a metal phosphide, a metal phosphate (for example, , a metal halide (for example, a fluoride of metal), metal sulfide, metal oxysulfide, carbon (e.g.
• a non-alkaline and non-alkaline-earth metal for example, indium (In), germanium ( Ge) and bismuth (Bi)
• an intermetallic compound for example, a metal oxide, a metal nitride, a metal phosphide, a metal phosphate (for example, , a metal halide (for example, a fluoride of metal), metal sulfide,
• the metal oxide can be chosen from compounds of formulas or a combination thereof; and b and c are numbers such that the ratio c:b lies in the interval from 2 to 3) (for example, MoO3, MoO2, M0S2, ), spinel oxides (e.g., a combination thereof) (for example, a lithium titanate (such as Li4Ti5O12) or a lithium molybdenum oxide
• the electrochemically active material can optionally be doped with other elements included in smaller quantities, for example to modulate or optimize its electrochemical properties.
• the electrochemically active material can be doped by the partial substitution of the metal by other ions.
• the electrochemically active material can be doped with a transition metal (eg Tl, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, W or Y) and/or a metal other than a transition metal (for example, Mg, Al or Sb).
• a transition metal eg Tl, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, W or Y
• a metal other than a transition metal for example, Mg, Al or Sb.
• the electrochemically active material can be in the form of particles (eg, microparticles and/or nanoparticles) which can be freshly formed or from a commercial source.
• the electrochemically active material can be in the form of particles coated with a layer of coating material.
• the potting material may be an electronically conductive material, for example a conductive carbon potting.
• the coating material can make it possible to substantially reduce the interfacial reactions at the interface between the electrochemically active material and an electrolyte, for example, a solid electrolyte, and in particular, an inorganic solid electrolyte of ceramic type based on sulphide.
• the coating material can be chosen from combinations thereof, where compatible, and other similar materials.
• the coating material comprises LiNbO3.
• the electrode material as defined here further includes an electronically conductive material.
• electronically conductive material include a carbon source such as carbon black (e.g., carbon and carbon Super ), acetylene black (for example, Shawinigan carbon and Denka carbon black ), graphite, graphene, carbon fibers (e.g., gas-phase formed carbon fibers (VGCFs)), carbon nanofibers, carbon nanotubes (CNTs), and a combination of at least two of these.
• electronic conductive material is a mixture of carbon black and VGCFs (preferably at a weight ratio in the range of 65:35 to 85:15).
• the electrode material as defined here further includes an additive.
• the additive is chosen from inorganic ionic conducting materials, inorganic materials, glasses, glass ceramics, ceramics, including nanoceramics (such as and other similar compounds), salts (eg, lithium salts) and a combination of two or more thereof.
• the additive may be an inorganic ion conductor chosen from compounds of the LISICON, thio-LISICON, argyrodite, garnet (“ga and” in English) type, NASICON, perovskites, oxides, sulphides, phosphides, fluorides, sulfur halides, phosphates, thio-phosphates, in crystalline and/or amorphous form, and a combination of at least two of these.
• the electrode material as defined here further includes a binder.
• the binder is chosen for its compatibility with the different elements of an electrochemical cell. Any known compatible binder is contemplated.
• the binder can be chosen from a polymer binder of the polyether, polyester, polycarbonate type, a fluorinated polymer and a water-soluble (water-soluble) binder.
• the binder is a fluorinated polymer such as polyvinylidene fluoride (PVdF) or polytetrafluoroethylene (PTFE).
• the binder is a water-soluble binder such as styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), hydrogenated NBR (HNBR), epichlorohydrin rubber (CHR) , or acrylate rubber (ACM), and optionally comprising a thickening agent such as carboxymethylcellulose (CMC), or a polymer such as poly(acrylic adde) (PAA), poly(methyl methacrylate) (PMMA) or a combination thereof.
• the binder is a polyether-type polymer binder.
• the polyether type polymer binder is linear, branched and/or cross-linked and is based on poly(ethylene oxide) (POE), poly(propylene oxide) (POP) or a combination of the two (such as an EO/PO copolymer), and optionally comprises crosslinkable units.
• the crosslinkable segment of the polymer can be a polymer segment comprising at least one functional group crosslinkable in a multidimensional manner by irradiation or heat treatment.
• the present technology also relates to an electrode comprising an electrode material as defined herein.
• the electrode may be on a current collector (eg, aluminum or copper foil).
• the electrode can be self-supporting.
• the present technology also relates to an electrolyte comprising an inorganic compound having an argyrodite type structure as defined here or obtained according to the process as defined here.
• the electrolyte can be chosen for its compatibility with the various elements of an electrochemical cell. Any type of compatible electrolyte is envisaged.
• the electrolyte is a liquid electrolyte comprising a salt in a solvent.
• the electrolyte is a gel electrolyte comprising a salt in a solvent and optionally a solvating polymer.
• the electrolyte is a solid polymer electrolyte comprising a salt in a solvating polymer.
• the electrolyte comprises an inorganic solid electrolyte material, for example, the electrolyte can be an inorganic solid electrolyte of the ceramic type.
• the electrolyte is a polymer-ceramic hybrid solid electrolyte.
• the solvent if present in the electrolyte, can be a non-aqueous solvent.
• solvents include cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and vinylene carbonate (VC); acyclic carbonates such as dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC) and dipropyl carbonate (DPC); lactones like y- butyrolactone ( ⁇ -BL) and ⁇ -valerolactone ( ⁇ -VL); acyclic ethers such as 1,2-dimethoxyethane (DME), 1,2-diethoxyethane (DEE), ethoxy methoxy ethane (EME), trimethoxymethane and ethylmonoglyme; cyclic ethers such as tetrahydrofuran, 2-methyltetrahydroftirane,
• the electrolyte is a gel electrolyte or a polymer gel electrolyte.
• the gel polymer electrolyte may comprise, for example, a polymer precursor and a salt (for example, a salt as defined above), a solvent (for example, a solvent as defined above) and a polymerization initiator and / or crosslinking, if necessary.
• examples of gel electrolyte include, without limitation, gel electrolytes such as those described in PCT patent applications published under the numbers WO2009/111860 (Zaghib et al.) and WO2004/068610 (Zaghib et al.).
• a gel electrolyte or a liquid electrolyte as defined above can also impregnate a separator such as a polymer separator.
• separators include, without limitation, polyethylene (PE), polypropylene (PP), cellulose, polytetrafluoroethylene (PTFE), poly(vinylidene fluoride) (PVDF) and polypropylene-polyethylene-polypropylene (PP) separators. /PE/PP).
• the separator is a type commercial polymer separator.
• the electrolyte is a solid polymer electrolyte.
• the solid polymer electrolyte can be chosen from all known solid polymer electrolytes and can be chosen for its compatibility with the various elements of an electrochemical cell.
• Solid polymer electrolytes generally comprise a salt as well as one or more solid polar polymer(s), optionally crosslinked.
• Polyether type polymers such as those based on poly(ethylene oxide) (POE)
• POE poly(ethylene oxide)
• the polymer can be cross-linked. Examples of such polymers include branched polymers, for example, star polymers or comb polymers such as those described in the PCT patent application published under the number W02003/063287 (Zaghib et al.).
• the solid polymer electrolyte can include a block copolymer composed of at least one solvation segment of lithium ions and optionally of at least one crosslinkable segment.
• the lithium ion solvation segment is chosen from homo- or copolymers having repeating units of Formula
• the crosslinkable segment of the copolymer is a polymer segment comprising at least one functional group crosslinkable in a multidimensional manner by irradiation or heat treatment.
• the electrolyte is a liquid electrolyte, a gel electrolyte or a solid polymer electrolyte
• the inorganic compound having an argyrodite-like structure as herein defined may be present as an additive in the electrolyte.
• the electrolyte is a polymer-ceramic hybrid solid electrolyte or a ceramic-like inorganic solid electrolyte
• the inorganic compound having an argyrodite-like structure as herein defined may be present as the inorganic solid electrolyte (ceramic) material.
• the electrolyte may also optionally include additional components such as ionic conductive materials, inorganic particles, glass or ceramic particles and other similar additives.
• the additional component can be chosen for its compatibility with the different elements of an electrochemical cell.
• the additional component can be substantially dispersed in the electrolyte.
• the additional component may be in a separate layer.
• the present technology also relates to an electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, in which at least one of the positive electrode or the negative electrode is as defined herein or comprises a material of electrode as defined here.
• the negative electrode is as defined herein or comprises an electrode material as defined herein.
• the electrochemically active material of the negative electrode can be chosen for its electrochemical compatibility with the different elements of the electrochemical cell as defined here.
• the electrochemically active material of the negative electrode material may possess a substantially lower oxidation-reduction potential than that of the electrochemically active material of the positive electrode.
• the positive electrode is as defined herein or comprises an electrode material as defined herein and the negative electrode includes an electrochemically active material chosen from all known compatible electrochemically active materials.
• the electrochemically active material of the negative electrode can be chosen for its electrochemical compatibility with the various elements of the electrochemical cell as defined here.
• Non-limiting examples of electrochemically active materials of the negative electrode include alkali metals, alkaline-earth metals, alloys comprising at least one alkali or alkaline-earth metal, non-alkaline and non-alkaline-earth metals (for example, indium (In), germanium (Ge) and bismuth (Bi)), and alloys or intermetallic compounds (eg, ).
• the material electrochemically active of the negative electrode can be in the form of a film.
• the electrochemically active material of the negative electrode can comprise a film of metallic lithium or of an alloy including or based on metallic lithium.
• the positive electrode can be pre-lithiumated and the negative electrode can be initially (ie, before cycling the electrochemical cell) substantially or completely free of lithium.
• the negative electrode can be lithiated in situ during the cycling of said electrochemical cell, in particular during the first charge.
• metallic lithium can be deposited in situ on the current collector (for example, a copper current collector) during the cycling of the electrochemical cell, in particular during the first charge.
• an alloy including metallic lithium can be generated at the surface of a current collector (for example, an aluminum current collector) during the cycling of the electrochemical cell, in particular during the first charge. It is understood that the negative electrode can be generated in situ during the cycling of the electrochemical cell, in particular during the first charge.
• the positive electrode and the negative electrode are both as defined id or both comprise an electrode material as defined herein.
• the present technology also relates to an electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, in which the electrolyte is as defined herein.
• the present technology also relates to an electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, in which the electrolyte is as defined herein and at least one of the positive electrode or the negative electrode is such defined herein or includes an electrode material as defined herein.
• the positive electrode is as defined herein or comprises an electrode material as defined herein.
• the present technology also relates to a battery comprising at least one electrochemical cell as defined here.
• the battery can be a primary or secondary battery.
• the battery is chosen from the group consisting of a lithium battery, a lithium-ion battery, a sodium battery, a sodium-ion battery, a magnesium battery, a a magnesium-ion battery, a potassium battery and a potassium-ion battery.
• the battery is a so-called all-solid battery.
• an alkali metal sulphate for example, Li 2 SO 4
• the use of an alkali metal sulphate can make it possible to reduce the production costs by a lower quantity of Li 2 S used and/or by the absence of an annealing step or the reduction of the annealing temperature.
• the method as defined here can make it possible to obtain inorganic compounds having ionic conductivities substantially similar to the ionic conductivities reported for inorganic compounds obtained by conventional methods from different precursors and comprising an annealing step .
• the method as defined here can make it possible to obtain inorganic compounds having improved electrochemical stability.
• the process as defined here can make it possible to obtain an inorganic compound having improved safety, for example, by substantially reducing the volume of H2S generated by the exposure of the inorganic compound to humidity or Ambiant air.
• the method as defined here can make it possible to obtain a greater critical current density and therefore better stability in contact with the metallic or metallic alloy negative electrode.
• Example 1 - Synthesis of argyrodites were fully prepared in a glove box under an inert atmosphere by a solid state reaction process without heat treatment.
• the inorganic compounds were obtained by a grinding process from the precursors and at least one halide of Li (LiCI, LiBr and/or Lil) in order to obtain powders having the desired stoichiometries according to the following reaction equations:
• the grinding of the powders was carried out by two different methods.
• Example 2 Characterization by X-ray diffraction (XRD) of inorganic compounds having an argyrodite-type structure
• the crystal structure of the argyrodites prepared in Example 1 was studied by XRD. The analysis was carried out entirely in an anhydrous chamber and the X-ray spectra were obtained using a Rigaku X-ray diffractometer equipped with a cobalt x-ray source.
• Pellets were prepared by compressing 80 mg of argyrodite powder prepared in Example 1. The pellets were then placed in sealed sample holders which were closed in a glove box, under an inert atmosphere.
• Figure 1 presents the X-ray diffraction patterns obtained for argyrodites (Argyrodites 1 to 4 and 8).
• the X-ray diffraction patterns presented in Figure 1 show that the argyrodite-like structure is indeed obtained for all the compositions. It is possible to observe the presence of a substantially greater quantity of impurities for the compositions richest in oxygen (y > 0.3) (Argyrodites 3 and 4).
• Figure 2 presents the X-ray diffraction diagrams obtained for Argyrodites 2 and 5 to 7.
• Figure 3 presents the X-ray diffraction diagrams for the argyrodites obtained from the precursors Li 2 SO 4 (Argyrodites 2 and 3) and Li 2 O (Argyrodites 9 and 10).
• Figure 3 shows that for an oxygen level of 0.3 (Argyrodites 2 and 9) there is no significant difference observable on the structure of the argyrodite of the inorganic compounds obtained from the two different precursors.
• argyrodite prepared from Li 2 O Arbubble-containing substantially more impurities (notably LiCI) and has a substantially less well-defined structure compared to argyrodite prepared from Li 2 SO 4 (Argyrodite 3).
• Figure 4 presents the X-ray diffraction diagrams for the argyrodites obtained from the precursor Li 2 SO 4 and a mixture of halides including LiCl and LiBr (Argyrodites 12 to 14) compared to those of the same compositions obtained from LiCI (Argyrodite 2) or LiBr (Argyrodite 15).
• Figure 4 shows that the argyrodite structure is well preserved whatever the level of Br and Cl. The position of the peaks decreases when the level of Br increases. This can be attributed to the increase in the lattice parameter, a phenomenon known in the literature.
• Figure 5 presents the X-ray diffraction patterns for argyrodites obtained from the precursor Li 2 SO 4 and a mixture of halides including LiCl, LiBr and Lil (Argyrodites 16 to 19).
• Figure 5 shows that the argyrodite structure is well preserved, even with the mixture of the three halides.
• Figure 6 presents the X-ray diffraction patterns for Argyrodites 2 and 13 obtained from the precursor Li 2 SO 4 in small volume jars (according to the Process 1 presented in (Example 1) and Argyrodites 20 and 21 obtained from the precursor Li 2 SO 4 in larger volume jars (according to Process 2 presented in (Example 1).
• the composition of Argyrodites 2 and 20 are similar as well as those of argyrodites 13 and 21.
• Figure 5 shows that the argyrodite structure is well preserved whatever the composition of the argyrodite and whatever the volume of synthesis demonstrating that the method thus described could be applied to the industrial scale.
• the composition of the argyrodites prepared in Example 1 was studied by NMR.
• the nuclear magnetic resonance spectra of lithium ( 6 Li NMR) and phosphorus ( 31 P NMR) were obtained by the MAS technique (magic angle rotation) using a Bruker Avance NEO 500 MHz spectrometer fitted with a probe 4 mm triple resonance whose maximum speed of rotation at the magic angle is 15 kHz.
• Figures 7 and 8 show respectively 6 Li NMR and 31 P NMR spectra obtained for argyrodites of composition obtained from precursors
• Figures 9 and 10 respectively show 6 Li NMR and 31 P NMR spectra obtained for the argyrodite of formula obtained from Li 2 SO 4 precursors (Argyrodite 7).
• Figures 11 and 12 show respectively 6 Li NMR and 31 P NMR spectra obtained for the argyrodites of formula (Argyrodite 13) and formula (Argyrodite 16) obtained from the Li 2 SO 4 precursor.
• the main peak on the 6 Li NMR spectra presented in Figure 11 corresponds to argyrodite. It is possible to observe on the 31 P NMR spectra presented in Figure 12 a main peak corresponding to argyrodite and the presence of weak secondary peaks corresponding to phases of This confirms the results obtained by X-ray diffraction, namely the obtaining of a pure oxidized argyrodite phase from Li 2 SO 4 whatever the halide composition.
• Example 4 Generation of H2S upon exposure of Inorganic compounds having an argyrodite-like structure to air Safety tests were carried out to assess the impact of argyrodite on the generation of H2S.
• An airflow was introduced into the sealed cell at a flow rate of approximately 0.3 L/min, at a controlled temperature of approximately 24.5°C ( ⁇ 0.5°C) and at a controlled hygrometry with one with a humidity level of 50% ( ⁇ 5%).
• the concentration of gaseous H2S generated was measured approximately every 15 seconds with a multigas detector (MSA ALTAIR MC 5X) previously calibrated and placed at the outlet of the cell. From these data, the volume of gaseous H2S generated normalized by the mass of argyrodite was calculated.
• Figure 13 shows a graph of the volume of H2S gas generated per gram of argyrodite powder (mL/g) against time (hours) for Argyrodites 2 (dotted line ), (em-dash-dot line), (dashed line), 11 (solid line), 13 (line dash dot dot) and 16 (line small dash) prepared in Example 1.
• Figure 13 shows that an argyrodite type structure generated from the precursor Li 2 SO 4 comprising a significant reduction in lithium (Argyrodite 7) makes it possible to further reduce the volume of gaseous H2S generated, and thus improve safety while by reducing the production costs by a lower quantity of Li 2 S used and by the absence or reduction of the annealing step.
• Example 5 Ionic Conductivity of Inorganic Compounds Having an Argyrodite-Type Structure a) Preparation of Symmetrical Cells for Ionic Conductivity Measurements Symmetrical cells were assembled according to the following procedure in order to measure the ionic conductivity of inorganic compounds possessing an argyrodite-like structure prepared in ('Example 1.
• Pellets were prepared by compressing 160 mg of inorganic compound powder having an argyrodite-like structure prepared in Example 1 between two stainless steel electrodes under a pressure of 360 MPa. The pellets placed between two stainless steel electrodes were then assembled in sealed conductivity cells closed in a glove box under an inert atmosphere maintained at a pressure of 20 MPa.
• Symmetrical cells were assembled according to the configurations shown in Table 2.
• Ion conductivity measurements of the symmetric cells assembled in Example 5(a) were performed with a VMP-300 multi-channel potentiostat (BioLogic). THE measurements were made in the frequency range from 7 MHz to 200 mHz under an amplitude of 50 mV in a temperature range from -10°C to 70°C (uphill and downhill, every 10°C).
• Figure 14 presents the results of ionic conductivity measured as a function of temperature for Cells It is possible to observe in Figure 14 that the ionic conductivity of the most oxygen-poor (y ⁇ 0.3) argyrodites (Cells 1 and 2) is similar to that of the oxide-free argyrodite (Cell 8) . A decrease in conductivity is observed for the most oxygen-rich argyrodites (y > 0.3) (Cells 3 and 4). It should be noted that the ionic conductivity of argyrodite of formula (Cell 2) prepared from Li 2 SO 4 is substantially identical to that of oxide-free argyrodite (Cell 8).
• Figure 15 presents the results of measured ionic conductivity as a function of temperature for Cells .
• the precursor Li 2 SO 4 it is possible to modulate the composition (for example, the lithium, oxygen and sulfur levels) of an oxysulphide lithium argyrodite while remaining substantially in the same range of ionic conductivity. It is also possible to observe that a significant lithium deficiency induces a reduction in ionic conductivity.
• Figure 16 presents the results of measured ionic conductivity as a function of temperature for Cells.
• Figure 16 shows that for the same composition, the ionic conductivity of the argyrodites obtained from the Li 2 SO 4 precursor (Argyrodites 2 and 3) is significantly higher than that of the argyrodites obtained from the Li 2 O precursor (Argyrodites 9 and 10).
• the use of a precursor of the Li 2 SO 4 type allows better incorporation of oxygen within the argyrodite structure and this results in an increase in conductivity as demonstrated by the results in Figure 16.
• Figure 17 presents the results of ionic conductivity measured as a function of temperature for Cells .
• Figure 17 shows that the composition modulation from the two halogens (ie, chlorine and bromine) does not substantially modify the ionic conductivity, while maintaining high conductivities. It should be noted that Argyrodite 14 has the best conductivity.
• Figure 18 presents the results of measured ionic conductivity as a function of temperature for Cells .
• Figure 18 shows that the incorporation of the three halogens (i.e., chlorine, bromine and iodine) in the presence of Li 2 SO 4 does not substantially modify the ionic conductivity, and this, while maintaining high conductivities. It is possible to observe that an iodine rate of 0.1 makes it possible to obtain better conductivity than at a higher rate.
• the three halogens i.e., chlorine, bromine and iodine
• Figure 19 presents the results of measured ionic conductivity as a function of temperature for Cells.
• Figure 19 shows that whatever the composition of the argyrodite based on Li 2 SO 4 , the increase in synthesis volume makes it possible to slightly increase the ionic conductivity. This demonstrates that the proposed solutions can be easily applied on an industrial scale, without loss of performance.
• Example 6 Electrochemical Stability of Inorganic Compounds Having an Argyrodite-Type Structure a) Preparation of Pseudo-batteries for Electrochemical Stability Measurements
• Pseudo-batteries were assembled according to the following procedure in order to determine the electrochemical stability of Argyrodites 2 and 9 prepared in Example 1.
• VGCFs 5% by mass of VGCFs were mixed with 95% by mass of Argyrodites 2 and 9 in order to obtain composite positive pseudo-electrodes, and thus observe oxidation-reduction reactions substantially representative of the final compositions of composite positive electrodes that can be used in battery configuration.
• Solid electrolytes composed of the same argyrodites were then placed on the surface of the composite positive pseudo-electrodes. Negative electrodes of metallic lithium were then deposited on the surface of the solid electrolytes.
• the assemblies comprising a composite positive pseudo-electrode, a solid electrolyte and a metallic lithium negative electrode were then compressed and assembled in sealed cells closed in a glove box under an inert atmosphere.
• the pseudo-batteries were assembled according to the configurations presented in Table 3.
• Figure 20 presents the cyclic voltammetry results obtained for Cell 22 and for Cell 23 (comparative battery) recorded at a sweep rate of 0.05 mV/s in the potential range of lithium oxide, nickel , manganese and cobalt (NMC), i.e. between 2.5 V and 4.3 V vs Li/Li* at a temperature of around 30°C.
• Figure 20 presents the results obtained during the first four cycles for each of the two pseudo-batteries.
• Figure 20 shows that no reaction with lithium metal could be observed, demonstrating the chemical and electrochemical stability of argyrodites with lithium metal.
• a weak oxidation-reduction reaction for the two pseudo-batteries with a weaker current density generated for Cell 22 comprising the argyrodite obtained by using Li 2 SO 4 as a precursor (0.3 pA/cm 2 ) and a lower polarization hysteresis. It is also possible to observe that this reaction is reversible.
• Argyrodites would therefore be substantially electrochemically stable in the NMC potential range with substantially improved electrochemical stability for argyrodite obtained using Li 2 SO 4 as a precursor.
• the argyrodite obtained by using Li 2 SO 4 as a precursor is substantially stable over the entire potential range of a lithium metal battery.
• Example 7 Electrochemical Properties of Inorganic Compounds Possessing an Argyrodite-like Structure
• the electrochemical cell was assembled according to the following procedure.
• a solid electrolyte was prepared by placing 80 mg of argyrodite 2 powder prepared in Example 1 in a 10 mm diameter mold under a pressure of 200 MPa. 13 mg of the composite positive electrode material prepared in Example 7(a) were then added into the mold on top of the solid electrolyte followed by an aluminum current collector The contents of the mold including the solid electrolyte layer, the composite positive electrode layer and the current collector aluminum current were then compressed under a pressure of 360 MPa for about 10 minutes. A 10 mm diameter metallic lithium electrode on a stainless steel current collector was then added facing the solid electrolyte layer and the The assembly was compressed under a pressure of 120 MPa for approximately 5 minutes.
• Cell 24 assembled in Example 7(b) was cycled between 2.5 V and 4.3 V vs Li/ Li*. The first five cycles were performed at C/10, followed by four cycles at C/ 4, then the aging experiments were carried out at a constant charge and discharge current of C/2 at a temperature of 30° C. for a surface capacity of 1.8 mAh/cm 2 .
• Figure 21 shows a graph of charge and discharge capacity and the coulombic efficiency (A) as a function of the number of cycles for 100 cycles.
• Figures 22 and 23 show the discharge profiles at different charge and discharge currents. More specifically, Figures 22 and 23 show a graph of potential versus discharge capacity and time in hours, respectively.
• the electrochemical cell respectively provides a capacity of approximately 170 mAh.g' 1 , 160 mAh.g' 1 and 150 mAh.g' 1 .

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