CA3136069A1 - Inorganic compounds with an argyrodite-type structure, their preparation methods and their use in electrochemical applications - Google Patents

Abstract

The present technology relates to inorganic compounds having an argyrodite-like structure obtained by a preparation process comprising a step of grinding lithium sulphide, lithium sulphate, phosphorus pentasulphide and a lithium halide. Also described are electrode materials, electrodes, electrolytes comprising said inorganic compound having an argyrodite type structure and their uses in electrochemical cells, for example, in electrochemical accumulators, in particular in so-called all-solid batteries.

Description

INORGANIC COMPOUNDS HAVING A STRUCTURE LIKE
ARGYRODITE, THEIR PREPARATION PROCESSES AND THEIR USES
IN ELECTROCHEMICAL APPLICATIONS
TECHNICAL AREA
This application relates to the field of inorganic compounds based oxysulfides having an argyrodite-like structure and to their uses in electrochemical applications. More specifically, this application is reports to field of inorganic oxysulfide compounds having a structure Of type argyrodite, electrode materials and solid electrolytes including, to their production methods and uses thereof in cells electrochemical, especially in so-called all-solid batteries.
STATE OF THE ART
Inorganic compounds such as ceramics, glasses and glass-ceramics base of sulfide are promising materials for many applications technological since they allow the development of state-of-the-art electrochemical systems all solid which are substantially safer.
In addition, inorganic sulfide compounds exhibit a wide window of electrochemical stability and substantially higher ionic conductivity raised to ambient temperature. Indeed, inorganic solid electrolytes including 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. By example, the argyrodite of formula Li6PS5X (in which, X is Cl, Br or I) presents a conductivity ionic at room temperature of the order of mS.cm-1.
However, the use of inorganic compounds of the argyrodite type is limited by their high production cost, in particular due to a high-temperature annealing step temperature allowing the obtaining of interesting ionic conductivities. One of the key elements of industrial requirements related to the production of this type of compound inorganic is thus minimizing costs by lowering the annealing temperature while retaining a considerably high ionic conductivity.

Date received/date received 2021-10-27 In addition, argyrodite-like inorganic compounds are associated with problems related to their interfacial stability as well as their stability in ambient air and humidity. More specifically, these inorganic solid electrolytes generate sulfide hydrogen (H2S) gas in contact with humid air and must therefore be prepared, assembled and operated under inert atmosphere. A strategy used to solve this problem understand the use of an inorganic compound of the oxysulfide-based argyrodite type.
Indeed, a partial atomic substitution of sulfur and/or lithium in these compounds inorganic by oxygen would lead to a significant decrease in the generation of H2S in presence of humidity.
Therefore, there is still a need for the development of compounds inorganic compounds for use in whole-state electrochemical systems solid excluding one or more of the disadvantages mentioned above.
SUMMARY
In one aspect, the present technology relates to a process for preparing of one inorganic compound having an argyrodite-like structure, the method including a step of grinding lithium sulphide, lithium sulphate, pentasulfide phosphorus and a lithium halide.
In another embodiment, the argyrodite-like structure is not deficient in lithium. According to a variant of interest, the argyrodite type structure not deficient in lithium has the formula Li6_xPS5_x_yOyZi+x, in which Z is an atom selected halogen among F, Cl, Br and I and x and y are non-zero numbers selected to achieve electroneutrality (for example, 0 < x 1 and 0 < y 1). According to a mode achievement, structure of non-lithium deficient argyrodite type is selected from the group made of Li5.4P54.300.1CI 1.6 , Li5.4P54.100.30 1.6, Li5.4P53.900.50 1.6, Li5,4P53,6500,750 1.6 and Li5.7P54.400.30 1.3 =
In another embodiment, the argyrodite-like structure is lithium deficient.
According to a variant of interest, the structure of the argyrodite type deficient in lithium is formula Li6_x_zyPS5_x_yOyZi+x, where Z is a chosen halogen atom among F, Cl, Br and I and x and y are nonzero numbers (for example, 0 < x 5 1 and 0 < y 1).
For example, the lithium-deficient argyrodite-like structure is chosen among the group consisting of Li5,4PS4,300,1Cli,6, Li5,1PS4,400,3C11,3 and Li4.8PS4.100.3C11.6.

2 Date received/date received 2021-10-27 In another embodiment, the grinding step is carried out by using a planetary micromill. According to a variant of interest, the grinding step is performed at a rotational speed of approximately 600 rpm. According to another variant of interest, the step of grinding is carried out for about 10 hours. According to another variant of interest, the grinding step is carried out in a ratio of grinding balls: precursors of about 30.
In another embodiment, the method further comprises a step of annealed carried out at a maximum temperature of approximately 300 C. Alternatively, the process is free of an annealing step.
In another aspect, the present technology relates to an inorganic compound having an argyrodite type structure obtained according to the method as here defined.
In another aspect, the present technology relates to a material electrochemically active and an inorganic compound having a structure of kind argyrodite as defined here or obtained according to the process as defined here.
In one embodiment, the inorganic compound having a structure of kind argyrodite is present as an additive and/or as a material of coating. By example, the coating material forms a coating layer on the surface of electrochemically active material.
In another embodiment, the electrochemically active material is chosen from metal oxide, metal sulfide, metal oxysulfide, metal phosphate metal, a metal fluorophosphate, metal oxyfluorophosphate, metal sulfate, A
metal halide, a metal fluoride, sulfur, selenium and a combination at least two of these. For example, the material metal electrochemically active is chosen from titanium (Ti), iron (Fe), manganese (Mn), vanadium (V), nickel (Ni), cobalt (Co), aluminum (Al), chromium (Cr), copper (Cu), zirconium (Zr), the niobium (Nb) and a combination of two or more thereof. According to a variant of interest, the metal of the electrochemically active material further comprises a metal alkaline or alkaline-earth metal chosen from lithium (Li), sodium (Na), potassium (K) and the magnesium (Mg).

3 Date received/date received 2021-10-27 In another embodiment, the electrochemically active material is an oxide of metal and lithium. For example, lithium metal oxide is an oxide mixed of lithium, nickel, manganese and cobalt (NCM).
In another embodiment, the electrochemically active material is chosen from .. a non-alkaline or non-alkaline-earth metal, an intermetallic compound, an oxide of metal, a metal nitride, a metal phosphide, a metal phosphate, a halide of metal, a metal fluoride, a metal sulphide, a metal oxysulphide, a carbon, silicon (Si), silicon-carbon composite (Si-C), silicon oxide (Si0x), a silicon oxide-carbon composite (SiOx-C), tin (Sn), a composite tin-carbon (Sn-C), a tin oxide (SnOx), a tin oxide-carbon composite (SnOx-C), and a combination of at least two of these.
In another embodiment, the electrode material further comprises at least an electronically conductive material. For example, the conductive material electronic is selected from the group consisting of carbon black, acetylene black, graphite, graphene, carbon fibers, carbon nanofibers, nanotubes of carbons, and a combination of two or more thereof. According to a variant of interest, the electronic conductive material is a mixture of carbon black and fiber carbon formed in the gas phase (VGCFs).
According to another aspect, the present technology relates to an electrode including the electrode material as herein defined on a current collector.
According to another aspect, the present technology relates to an electrode self-supported comprising the electrode material as herein defined.
In another aspect, the present technology relates to an electrolyte including a inorganic compound having an argyrodite-like structure such as here defined or obtained according to the method as defined here.
In one embodiment, the electrolyte is a liquid electrolyte comprising a salt in a solvent. Alternatively, the electrolyte is a gel electrolyte comprising a salt in a solvent and optionally a solvating polymer. Alternately, the electrolyte is a solid polymer electrolyte comprising a salt in a polymer solvating. By

4 Date received/date received 2021-10-27 For example, the inorganic compound possessing an argyrodite-like structure is here as an additive.
In another embodiment, the electrolyte is a solid electrolyte inorganic.
Alternatively, the electrolyte is a hybrid polymer-solid electrolyte ceramic. By For example, the inorganic compound possessing an argyrodite-like structure is here as an inorganic solid electrolyte material.
In another aspect, the present technology relates to a cell electrochemical comprising a negative electrode, a positive electrode and an electrolyte, in which at least one of the positive electrode or the negative electrode is such here defined or includes an electrode material as defined herein.
In another aspect, the present technology relates to a cell electrochemical comprising a negative electrode, a positive electrode and an electrolyte, in which the electrolyte is as herein defined.
In one embodiment, the negative electrode comprises a material electrochemically active comprising an alkali metal, an alkaline metal earthy, a alloy comprising at least one alkali metal or alkaline-earth metal, a non-alkaline and non-alkaline earth, or an alloy or intermetallic compound. By example, the electrochemically active material of the negative electrode comprises lithium metal or alloy including or based on metallic lithium.
In another embodiment, said electrochemical accumulator is a battery is selected from a lithium battery, a lithium-ion battery, a sodium battery, a sodium-ion battery, a magnesium battery, a magnesium-ion. By example, said battery is a lithium battery or a lithium-ion. According to one variant of interest, said electrochemical accumulator is a so-called battery all solid.
BRIEF DESCRIPTION OF FIGURES
Figure 1 presents X-ray diffraction patterns obtained for THE
powders of Argyrodites from 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.

5 Date received/date received 2021-10-27 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 nuclear magnetic resonance spectra of lithium (6Li NMR) obtained for Argyrodites 2 and 9, as described in Example 3.
Figure 5 presents nuclear magnetic resonance spectra of the phosphorus (31P
NMR) obtained for Argyrodites 2 and 9, as described in Example 3.
Figure 6 shows a nuclear magnetic resonance spectrum of lithium (6Li NMR) obtained for Argyrodite 7, as described in Example 3.
Figure 7 shows a nuclear magnetic resonance spectrum of phosphorus (31P
.. NMR) obtained for Argyrodite 7, as described in Example 3.
Figure 8 shows a graph of the volume of gaseous H2S generated as a function of the time for Argyrodites 2, 7, 8 and 11, as described in Example 4.
Figure 9 is a graph showing the ion conductivity results active temperature for Cells 1 (.), 2 (A), 3 (+), 4 (*) and 8 (3), as than described to .. Example 5(b).
Figure 10 is a graph showing the ion conductivity results active temperature for Cells 2 (A), 5 (3), 6 (.) and 7 (+), such as described in Example 5(b).
Figure 11 is a graph showing the ion conductivity results active temperature for Cells 2 (3), 3 (.), 9 (A) and 10 (+), such as described in Example 5(b).
Figure 12 presents cyclic voltammograms obtained for Cells (green lines) and 12 (blue lines) recorded at a scan rate of 0.05mV/s between 2.5 V and 4.2 V vs Li/Li+ at a temperature of about 30 C, such as described in Example

6(b).
Figure 13 shows a graph of charge (.) and discharge capacity (3) and the coulombic efficiency (A) as a function of the number of cycles for 100 cycles got for Cell 13, as described in Example 7(c).

Date received/date received 2021-10-27 Figure 14 shows the discharge profiles of Cell 13 as a function of the capacity obtained at charge and discharge currents C/10, C/4 and C/2 and saved vs.
Li/Li + at a temperature of 30 C.
Figure 15 shows the discharge profiles of Cell 13 as a function of the time .. obtained at charge and discharge currents C/10, C/4 and C/2 and saved vs.
Li/Li + at a temperature of 30 C.
DETAILED DESCRIPTION
All technical and scientific terms and expressions used here have the same definitions as those generally understood of the person versed in art of this technology. The definition of certain terms and expressions used is nevertheless provided below.
When the term approximately is used here, it means approximately, In the region of, or around. For example, when the term environ is used in link with a numerical value, it modifies it above and below by a variation of 10% per .. compared to its nominal value. This term can also take into account, for example of experimental error of a measuring device or rounding.
When a range of values is mentioned in this application, the terminals lower and upper of the interval are, unless otherwise indicated opposites, always included in the definition. When a range of values is mentioned in this request, then all intermediate intervals and sub-intervals, as well as that the values individual values included in the intervals of values, are included in the definition.
When item one is used to introduce an item into the this request, it does not have the meaning of just one, but rather of one or more. GOOD
heard, when the description states that a step, component, element or characteristic particular can or could be included, this step, this component, this element or this particular feature is not required to be included in every mode of achievement.
The term self-supporting electrode as used herein refers to a electrode without metallic current collector.

7 Date received/date received 2021-10-27 The chemical structures described here are drawn according to the conventions of the domain.
Also, when an atom, such as a carbon atom, as drawn seems include a incomplete valence, then the valence is assumed to be satisfied by one or several hydrogen atoms even if they are not explicitly drawn.
The present technology relates to a process for the preparation of a compound inorganic having an argyrodite type structure deficient or not in lithium based of Li2S-P2S5-Li2SO4-LiZ (in which, Z is a halogen atom selected from F, Cl, Br and I), the process comprising a step of direct grinding of the precursors. THE
precursors being consisting of lithium sulphide (Li2S), lithium sulphate (Li2SO4), pentasulfide .. phosphorus (P2S5) and a lithium halide, chosen from fluoride of lithium (LiF), lithium chloride (LiCI), lithium bromide (LiBr) and lithium iodide lithium (LH).
According to another example, inorganic compounds having a structure of kind non-deficient and lithium-deficient argyrodite can be respectively formulas Li6_xPS5_x_yOyZi+x and Li6_x_2yPS5_x_yOyZi+x, in which Z is such as here defined, and x and y are non-zero numbers, for example 0 < x 5 1 and 0 < y 1. Compounds inorganic materials possessing a non-deficient argyrodite-like structure or deficient in lithium can therefore be obtained by grinding from precursors such as here defined respectively according to the following reaction equations:
(2.5-y/4-x) Li2S + y/4 Li2SO4+ 1/2 P255 +(1+x) LiZ ¨> Li6_xPS5_x_yOyX1-,x + y S Equation (1) (2.5-514y-x) Li2S + y/4 Li2SO4 + 1/2 P255 + (1+x) LiZ ¨>
Li6_x_2,,PS5_x_yOyCli+x Equation (2) wherein x, y and Z are as defined herein.
According to another example, when the inorganic compound has a structure Of type non-lithium deficient argyrodite, y and z are different numbers from zero selected to achieve electroneutrality. Non-limiting examples of compounds inorganic having an argyrodite-like structure not deficient in lithium include Li5,4P54,300,1Z1,6, Li5,4PS4,100,3Z1,6, Li5,4P53,900,5Z1,6, Li5.4P53.6500.75Z1.6 and Li5.7P54.400.3Z1.3, in which Z is as defined herein. Alternatively, when the compound inorganic has a lithium-deficient argyrodite-like structure, y and z are numbers different from zero selected to obtain a desired stoichiometry. Of the examples no .. limitation of inorganic compounds having a structure of the type deficient argyroditis

8 Date received/date received 2021-10-27 in lithium include Li5,IPS4,400,3Z1,3 and Li4,8PS4,100,3Z1,6, in which Z is such that here defined.
According to an example of interest, Z is a chlorine atom and the halide of lithium is LiCI.
For example, the inorganic compound possessing an argyrodite-like structure No deficient in lithium can be chosen from Li5,4P54,300,1C11,6, Li5.4P54.100.3C11.6, Li5.4P53.900.5C11.6, Li5.4P53.6500.75C11.6 and Li5.7P54.400.3C11.3 and the inorganic compound possessing a lithium-deficient argyrodite-like structure can be chosen from Li5.1PS4.400.3C11.3 and Li4.8PS4.100.3C11.6.
According to another example of interest, the method as defined here is carried out in a step. It is-that is, the method preferably does not include an annealing step.
Alternately, the method may include an optional step of annealing at low temperature. By example, if the process includes an annealing step, this can be performed at a maximum temperature of about 300 C.
According to another example, the grinding step can be carried out using a microgrinder planetary. For example, the grinding step can be performed at a speed rotation, for a determined period and in a ratio of grinding balls: precursors allowing to obtain an inorganic compound having the argyrodite-like structure desired. According some examples, the ratio of grinding balls: precursors is about 30 and the step of grinding is carried out at a rotational speed of approximately 600 rpm for around 10 hours to obtain an inorganic compound having the type structure argyroditis desired.
Without wishing to be bound by theory, the use of Li2SO4 as a pioneer in the process as defined here could make it possible to obtain a structure of the type argyroditis, and this, without an annealing step or with a low temperature annealing step. Moreover, the process as defined here could make it possible to obtain inorganic compounds presenting ionic conductivities substantially similar to ionic conductivities reported for inorganic compounds obtained by conventional processes at from different precursors and comprising an annealing step.
Certain properties of the present inorganic compounds as obtained according to some embodiments of this method may also differ from those demonstrated by compounds prepared by conventional methods, for example, by methods

9 Date received/date received 2021-10-27 using Li20 to replace Li2SO4 as a precursor. For example, according to some embodiments, the compounds obtained here can exhibit a higher great stability electrochemical, a reduction in the emission of H2S, or a polarization reduced to comparison of compounds obtained conventionally. Compounds inorganic substances described herein according to certain embodiments may demonstrate one more high purity of argyrodite structure by 6Li or 31P NMR and/or a reduction of the relative intensity of the peaks associated with the P0252, P035 and/or PO4 groups in 31P NMR.
For example, the relative intensity of the P02S2, 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 a argyrodite type structure as defined here obtained according to the method as than here defined.
The present technology also relates to an electrode material comprising A
electrochemically active material and an inorganic compound having a structure of argyrodite type as defined here or obtained according to the process as here defined.
.. According to one example, the inorganic compound having a structure of the type argyroditis as herein defined may be present as an additive and/or as a material coating in the electrode material. For example, the inorganic compound possessing an argyrodite-like structure can form a layer of coating on the surface of the electrochemically active material.
According to another example, said electrode material is an electrode material positive and the electrochemically active material is selected from a metal oxide, a sulfide metal, a metal oxysulfide, a metal phosphate, a fluorophosphate of metal, a metal oxyfluorophosphate, a metal sulphate, a metal halide (for example, a metal fluoride), sulphur, selenium, and a combination of at least two of these. According to another example, the metal of the material electrochemically active is chosen among titanium (Ti), iron (Fe), manganese (Mn), vanadium (V), nickel (Ni), cobalt (Co), aluminum (Al), chromium (Cr), copper (Cu), zirconium (Zr), niobium (Nb) and their combinations, when compatible. The electrochemically active material can optionally further comprising an alkali or alkaline-earth metal, for example, lithium (Li), sodium (Na), potassium (K) or magnesium (Mg).
Date received/date received 2021-10-27 Non-limiting examples of electrochemically active materials include of the lithium and metal phosphates, complex oxides, such as LiM'PO4 (where me is Fe, Ni, Mn, Co, or a combination thereof), LiV308, V205, LiMn204, LiM"02 (where M"
is Mn, Co, Ni, or a combination thereof), Li(NiM¨)02 (where M" is Mn, Co, Al, Fe, Cr, Ti, or Zr, or a combination thereof) and combinations thereof, when compatible.
According to an example of interest, the electrochemically active material is an oxide such as described above. For example, the electrochemically active material can be an oxide of lithium and manganese, in which the manganese can be partially substituted by a second transition metal, such as an oxide of lithium, nickel, manganese and of cobalt (NMC). According to a variant of interest, the electrochemically material active is LiNi0.6Mn0.2C00.202 (NMC 622).
According to another example, said electrode material is an electrode material negative and the electrochemically active material is selected from a non-alkaline metal and no-alkaline earth (e.g. indium (In), germanium (Ge) and bismuth (Bi)), a intermetallic compound (e.g., SnSb, TiSnSb, Cu2Sb, AlSb, FeSb2, FeSn2 And CoSn2), a metal oxide, a metal nitride, a metal phosphide, a phosphate metal (for example, LiTi2(PO4)3), a metal halide (for example, a fluoride metal), a metal sulphide, a metal oxysulphide, a carbon (for example, graphite, graphene, reduced graphene oxide, hard carbon, soft carbon, graphite exfoliated and amorphous carbon), silicon (Si), a silicon-carbon (Si-C), a silicon oxide (Si0x), a silicon oxide-carbon composite (SiOx-C), of tin (Sn), a tin-carbon composite (Sn-C), a tin oxide (SnOx), an oxide composite tin-carbon (SnOx-C), and their combinations, when compatible. For example, the oxide of metal can be chosen from the compounds of formulas M¨b0, (where M" is Ti, Mo, Mn, Ni, .. Co, Cu, V, Fe, Zn, Nb, or a combination thereof; and b and c are numbers such that the c:b ratio is in the range of 2 to 3) (for example, Mo03, Mo02, MoS2, V205, and TiNb207), spinel oxides (e.g., NiCo204, ZnCo204, MnCo204, CuCo204, and CoFe204) and LiM-0 (where M"¨ is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination thereof) (for example, a lithium titanate (such as Li4Ti5012) or a lithium molybdenum oxide (such as Li2Mo4013)).
According to another example, the electrochemically active material can possibly be spiked with other elements included in smaller amounts, e.g. for modulate or optimize its electrochemical properties. The material electrochemically active can Date received/date received 2021-10-27 be doped by the partial substitution of the metal by other ions. By example, the material electrochemically active can be doped with a transition metal (for example Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn or Y) and/or a metal other than a metal of transition (by example, Mg, Al or Sb).
According to another example, the electrochemically active material can be under made of particles (e.g. microparticles and/or nanoparticles) that can be freshly formed or from a commercial source. For example, the material electrochemically active can be in the form of particles coated with a layer of coating material. The potting material can be a conductive material electronics, for example a conductive carbon coating. Alternately, THE
potting material can substantially reduce reactions interfacial at the interface between the electrochemically active material and a electrolyte, by example, a solid electrolyte, and in particular, a solid electrolyte inorganic type ceramic based on sulfide or oxysulfide (for example, based on the compound inorganic having an argyrodite-like structure as defined here). By example, the coating material can be chosen from Li2SiO3, LiTa03, LiA102, Li2O-ZrO2, LiNb03 combinations thereof, where compatible, and other similar materials.
According to one variant of interest, the coating material comprises LiNb03.
According to another example, the electrode material as defined here includes in besides a material electronic driver. Non-limiting examples of conductive material electronics include a carbon source such as carbon black (by example, Ketjen™ carbon and Super P™ carbon), acetylene black (For example, Shawinigan carbon and Denkamc carbon black), graphite, graphene, fibers carbon (for example, carbon fibers formed in the gas phase (VGCFs)), the carbon nanofibers, carbon nanotubes (CNTs) and a combination of at less two of these. According to a variant of interest, conductive material electronic is a mixture of carbon black Li400 (Denkamc) and VGCFs (preferably at a ratio in the range of 65:35 to 85:15 by weight).
According to another example, the electrode material as defined here includes in besides an additive.
For example, the additive is chosen from ionic conductive materials inorganic, inorganic materials, glasses, glass-ceramics, ceramics, including the nano ceramics (such as Al2O3, TiO2, 5iO2 and other compounds similar), salts Date received/date received 2021-10-27 (e.g., lithium salts) and a combination of at least two of these this. By example, the additive may be an inorganic ionic conductor selected from compounds type LISICON, thio-LISICON, argyrodites, garnets (garnet in English), NASICON, perovskites, oxides, sulphides, phosphides, fluorides, halides .. sulfur, phosphates, thio-phosphates, in crystalline form and/or amorphous, and a combination of at least two of these.
According to another example, the electrode material as defined here includes in besides a binder.
For example, the binder is chosen for its compatibility with the different elements of a electrochemical cell. Any known compatible binder is contemplated. By example, the binder can be chosen from a polymer binder of the polyether, polyester, polycarbonate, fluorinated polymer and water-soluble binder (water-soluble). According to an example, the binder is a fluorinated polymer such as polyvinylidene fluoride (PVdF) or polytetrafluoroethylene (PTFE). According to another example, the binder is a binder soluble in water such as styrene-butadiene rubber (SBR), rubber acrylonitrile-butadiene (NBR), hydrogenated NBR (HNBR), epichlorohydrin rubber (CHR), or acrylate rubber (ACM), and optionally comprising an agent thickener such such as carboxymethylcellulose (CMC), or a polymer such as poly(acid acrylic) (PAA), poly(methyl methacrylate) (PMMA) or a combination thereof.
According another example, the binder is a polyether-type polymer binder. By example, the binder .. polyether-type polymer is linear, branched and/or cross-linked and is based on the poly(oxide of ethylene) (POE), poly(propylene oxide) (POP) or on a combination both (such as an OE/P0 copolymer), and optionally comprises units cross-linkable. By example, the crosslinkable segment of the polymer can be a polymer segment comprising at least one crosslinkable functional group in such a way multidimensional by irradiation or heat treatment.
The present technology also relates to an electrode comprising a material electrode as defined here. According to one example, the electrode can be on a collector of current (for example, aluminum or copper foil). Alternately, the electrode can be self-supporting.
The present technology also relates to an electrolyte comprising a compound inorganic having an argyrodite-like structure as herein defined or obtained according to process as defined here.

Date received/date received 2021-10-27 According to one example, the electrolyte can be chosen for its compatibility with the different elements of an electrochemical cell. Any type of compatible electrolyte is considered.
According to one example, the electrolyte is a liquid electrolyte comprising a salt in a solvent. According to an alternative, the electrolyte is a gel electrolyte comprising a salt in a solvent and optionally a solvating polymer. According to another alternative, the electrolyte is a solid polymer electrolyte comprising a salt in a polymer solvating. According to another alternative, the electrolyte comprises a material electrolyte inorganic solid, for example, the electrolyte can be a solid electrolyte inorganic ceramic type. According to another alternative, the electrolyte is a solid electrolyte polymer-ceramic hybrid.
According to another example, the salt, if present in the electrolyte, can be an ionic salt, such as a lithium salt. Non-limiting examples of lithium salts include lithium hexafluorophosphate (LiPF6), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), 2-trifluoromethyl1-4,5-dicyano-lithium imidazolate (LiTDI), lithium 4,5-dicyano-1,2,3-triazolate (LiDCTA), the bis lithium (pentafluoroethylsulfonyl)imide (LiBETI), lithium tetrafluoroborate lithium (LiBF4), lithium bis(oxalato)borate (LiBOB), lithium nitrate (LiNO3), chloride lithium (LiC1), lithium bromide (LiBr), lithium fluoride (LiF), perchlorate lithium (LiC104), lithium hexafluoroarsenate (LiAsF6), trifluoromethanesulfonate lithium (LiSO3CF3) (LiTf), lithium fluoroalkylphosphate Li[PF3(CF2CF3)3]
(LiFAP), the lithium tetrakis(trifluoroacetoxy)borate Li[B(OCOCF3)4] (LiTFAB), the bis(1,2-lithium benzenediolato(2-)-0.01)borate Li[B(0602)2] (LiBBB) and a combination of least two of these.
According to another example, the solvent, if present in the electrolyte, can be a solvent non-aqueous. Non-limiting examples of solvents include carbonates cyclic such as ethylene carbonate (EC), propylene carbonate (PC), carbonate butylene (BC) and vinylene carbonate (VC); acyclic carbonates as the dimethyl carbonate (DMC), diethyl carbonate (DEC), carbonate of methyl and ethyl (EMC) and dipropyl carbonate (DPC); lactones like y-butyrolactone (γ-BL) and γ-valerolactone (γ-VL); acyclic ethers like the 1,2-dimethoxyethane (DME), 1,2-diethoxyethane (DEE), ethoxy methoxy ethane (EME), trimethoxymethane and ethylmonoglyme; cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane and derivatives of Date received/date received 2021-10-27 dioxolane; and other solvents like dimethyl sulfoxide, formamide, acetamide, dimethylformamide, acetonitrile, propylnitrile, nitromethane, acid triesters phosphoric acid, sulfolane, methylsulfolane, carbonate derivatives propylene and their mixtures.
According to another example, the electrolyte is a gel electrolyte or a polymer electrolyte in gel. The gel polymer electrolyte may comprise, for example, a precursor of polymer and a salt (for example, a salt as defined above), a solvent (by example, a solvent as defined previously) and an initiator of polymerization and/or crosslinking, if necessary. Examples of gel electrolyte include, without limitation, gel electrolytes such as those described in the PCT patent applications published under numbers W02009/111860 (Zaghib et aL) and W02004/068610 (Zaghib et par.).
According to another example, a gel electrolyte or a liquid electrolyte such than defined previously can also impregnate a separator such as a separator in polymer. Examples of separators include, without limitation, separators polyethylene (PE), polypropylene (PP), cellulose, polytetrafluoroethylene (PTFE), poly(vinylidene fluoride) (PVDF) and polypropylene-polyethylene-polypropylene (PP/PE/PP). For example, the separator is a separator of polymer commercial type Celgardtm.
According to another example, the electrolyte is a solid polymer electrolyte. By example, the solid polymer electrolyte can be selected from all electrolytes solid polymers known and can be chosen for its compatibility with the various elements of a cell electrochemical. Solid polymer electrolytes typically include a salt as well as one or more solid polar polymer(s), optionally reticular(s). Of the polyether type polymers, such as those based on poly(ethylene oxide) (POE), can be used, but several other compatible polymers are also known for the preparation of solid polymer electrolytes and are also considered.
The polymer can be cross-linked. Examples of such polymers include polymers branched, for example, star polymers or comb polymers such that those described in the PCT patent application published under number W02003/063287 (Zaghib et al.).
According to another example, the solid polymer electrolyte can include a copolymer sequence composed of at least one solvation segment of lithium ions and Most often is "possibly"
Date received/date received 2021-10-27 of at least one crosslinkable segment. Preferably, the solvation segment ions lithium is chosen from homo- or copolymers having repeating units of Formula I:
-(CH2-CH-0),-To Formula I
in which, R is chosen from a hydrogen atom, and a C1-C1oalkyl group or ¨(CH2-0-RaRb), Ra is (CH2-CH2-O)y;
Rb is selected from hydrogen and C1-C1oalkyl;
x is an integer selected from the range of 10 to 200,000; And y is an integer chosen from the range 0 to 10.
According to another example, the crosslinkable segment of the copolymer is a segment of polymer comprising at least one crosslinkable functional group in a manner multidimensional by irradiation or heat treatment.
When the electrolyte is a liquid electrolyte, a gel electrolyte or a electrolyte solid polymer, the inorganic compound having a structure of the type argyroditis such as herein defined may be present as an additive in the electrolyte.
When the electrolyte is a polymer-ceramic hybrid solid electrolyte or A
ceramic type inorganic solid electrolyte, the inorganic compound possessing a argyrodite-like structure as herein defined may be present as material inorganic solid electrolyte (ceramic).
According to another example, the electrolyte may also optionally include of the additional components such as ionic conductive materials, inorganic particles, glass or ceramic particles and other additives same kind. The additional component can be chosen for its compatibility with the different elements of an electrochemical cell. According to one example, the component Date received/date received 2021-10-27 additional can be substantially dispersed in the electrolyte.
Alternatively, the additional component can be in a separate layer.
The present technology also relates to an electrochemical cell including a negative electrode, a positive electrode and an electrolyte, wherein at minus one of the positive electrode or of the negative electrode is as herein defined at or includes a electrode material as defined herein.
According to one example, the negative electrode is as defined herein or comprises a material electrode as defined here. For example, the electrochemically material of the electrode negative can be chosen for its electrochemical compatibility with the different elements of the electrochemical cell as defined here. For example, the material electrochemically of the negative electrode material may possess a potential oxidation-reduction substantially lower than that of the material electrochemically active of the positive electrode.
According to another example, the positive electrode is as defined here or includes a electrode material as herein defined and the negative electrode includes a material electrochemically active selected from all electrochemically assets known compatible. For example, the electrochemically active material of the electrode negative can be chosen for its electrochemical compatibility with the different elements of the electrochemical cell as defined here. Examples no limiting of electrochemically active materials of the negative electrode include the alkali metals, alkaline-earth metals, alloys comprising at least one alkali metal or alkaline-earth, non-alkaline and non-alkaline-earth metals (e.g., indium (In), germanium (Ge) and bismuth (Bi)), and alloys or compounds intermetallic (by example, SnSb, TiSnSb, Cu2Sb, AlSb, FeSb2, FeSn2 and CoSn2). For example, the material electrochemically active of the negative electrode can be in the form of movie. According to one variant of interest, the electrochemically active material of the electrode negative can comprise a film of metallic lithium or an alloy including or based on lithium metallic.
According to another example, the positive electrode can be prelithiated and the negative electrode can be initially (ie before the cycling of the electrochemical cell) substantially or completely lithium-free. The negative electrode can be lithiated in located during Date received/date received 2021-10-27 cycling of said electrochemical cell, in particular during the first charge. According an example, metallic lithium can be deposited in situ on the collector of current (by example, a copper current collector) when cycling the cell electrochemical, especially during the first charge. According to another example, an alloy including metallic lithium can be generated at the surface of a current collector (For example, an aluminum current collector) when cycling the cell electrochemical, especially during the first charge. It is understood that the negative electrode maybe generated in situ during the cycling of the electrochemical cell, in particular during of the first charge.
According to another example, the positive electrode and the negative electrode are both such as defined herein or both include an electrode material as herein defined.
The present technology also relates to an electrochemical cell including a negative electrode, a positive electrode and an electrolyte, wherein the electrolyte is as defined here.
The present technology also relates to an electrochemical cell including a negative electrode, a positive electrode and an electrolyte, wherein the electrolyte is as herein defined and at least one of the positive electrode or the electrode negative is such as herein defined to or includes an electrode material as herein defined.
According to one example, the positive electrode is as defined herein or comprises a material electrode as defined here.
The present technology also relates to a battery comprising at least a electrochemical cell as defined here. For example, the battery can be a battery primary (battery) or secondary (accumulator). In one example, the battery is chosen from the group consisting of a lithium battery, a lithium-ion, of a sodium battery, sodium-ion battery, magnesium battery, of one magnesium-ion battery, a potassium battery and a battery potassium-ion.
According to a variant of interest, the battery is a so-called all-solid battery.
According to one example, the use of Li2SO4 as a precursor in the process as here defined can make it possible to reduce production costs by lowering number of Date received/date received 2021-10-27 Li2S used and/or by the absence of an annealing step or the reduction of the temperature of annealed.
According to another example, the method as defined here can allow obtaining compounds inorganic materials exhibiting ionic conductivities substantially similar to ionic conductivities reported for inorganic compounds obtained by of the conventional processes from different precursors and comprising a stage of annealed.
According to another example, the method as defined here can allow obtaining compounds inorganic materials with improved electrochemical stability.
According to another example, the method as defined here can allow obtaining a inorganic compound having improved safety, for example, by reducing substantially the volume of H25 generated by exposure of the compound inorganic to humidity or ambient air.
EXAMPLES
The following examples are for illustrative purposes and should not be interpreted as further limiting the scope of the invention as contemplated. These examples will be better understood by referring to the appended Figures.
Example 1 ¨ Synthesis of argyrodites Inorganic compounds possessing an argyrodite-like structure of formulas Li5,4P54,300,1C11,6, Li5,4P54,100,3C11,6, Li5,4P53,900,5C11,6, Li5.4P53,6500,7501.6, Li5.7P54,400,301.3, Li5,1PS4,400,3C11,3, Li4,8P54,100,3C11,6, Li5,4P54,401,6, Li5,4P54,100,301,6, Li5.4P53.900.5C11.6, and Li6PS5CI were fully prepared in a glove box under an inert atmosphere (H20 <
0.1ppm; 02 < 0.1 ppm) by a solid state reaction process without thermal treatment.
The inorganic compounds were obtained by grinding from the precursors Li2S, .. P255, LiCl, and Li2SO4 or Li2O according to the following reaction equations:
(2.5-y/4-x) Li2S + y/4 Li2SO4+1/2 P255+(1+x) LiCI ¨> Li6_xPS5_x_yOyCli+x + y S
Equation (1) (2.5-514y-x) Li2S + y/4 Li2SO4 +1/2 P255 + (1+x) LiCI ¨>
Li6_x_2yPS5_x_yOyCli+x Equation (2) (2.5-yx) Li2S + y Li2O +1/2 P255 + (1+x) LiCI ¨> Li6_xPS5_x_yOyCli+x Equation (3) Date received/date received 2021-10-27 The respective precursors (Li2S, P2S5, LiCI, and Li2SO4 or Li2O) were weighed in order to get powders having the desired stoichiometries. The grinding of the powders was carried out using a PULVERISETTE 7 planetary micromill. 1.7 g of powder have been placed in a 45 mL yttria-zirconia (Y-TZP) grinding jar.
1.7 g of powder as well as 15 grinding balls with a diameter of 10 mm in zirconia yttria (ratio in ball weight: powder = 30) were placed in a grinding jar in yttria zirconia of 45ml. The powders were ground at a speed of approximately 600 rpm for approximately hours to produce the inorganic compounds possessing a type structure argyroditis.

10 Non-lithium deficient arovrodite of formula Li5.4PS4,300.1C11.6 (Arovrodite 1):
An inorganic compound possessing an argyrodite-like structure not deficient in lithium of formula Li5,4PS4,300,1C11,6 was obtained by the process of the present example to from the precursors Li2S, P255, LiCl and Li2SO4 according to Equation 1 in which, x = 0.6 and y = 0.1.
Arovrodite not deficient in lithium of formula Li54PS41003Cl1 6 (Arovrodite 2):
An inorganic compound possessing an argyrodite-like structure not deficient in lithium of formula Li5,4PS4,100,3C11,6 was obtained by the process of the present example to from the precursors Li2S, P255, LiCl and Li2SO4 according to Equation 1 in which, x = 0.6 and y = 0.3.
Arovrodite not deficient in lithium of formula Lis_ P=S n fA rlif 4- -3 9 - 0 5-1 6:
An inorganic compound possessing an argyrodite-like structure not deficient in lithium of formula Li5,4PS3,900,5C11,6 was obtained by the process of the present example to from the precursors Li2S, P255, LiCl and Li2SO4 according to Equation 1 in which, x = 0.6 and y = 0.5.
Non-lithium deficient argyrodite with the formula Li5APS3, n 65- 0.75-1.6 (Ar qVrOdite 4):
An inorganic compound possessing an argyrodite-like structure not deficient in lithium of formula Li5.4PS3.6500.75C11.6 was obtained by the process of this example to Date received/date received 2021-10-27 from the precursors Li2S, P2S5, LiCl and Li2SO4 according to Equation 1 in which, x = 0.6 and y = 0.75.
Non-lithium deficient Arqyrodite of formula Li57PS44003C113 (Arqyrodite 5) :
An inorganic compound possessing an argyrodite-like structure not deficient in lithium of formula Li5,7PS4,400,3C11,3 was obtained by the process of the present example to from the precursors Li2S, P2S5, LiCl and Li2SO4 according to Equation 1 in which, x = 0.3 and y = 0.3.
Lithium-deficient Arqyrodite with the formula Li5iPS4,400.3C11.3 (Arqyrodite 6) :
An inorganic compound possessing a deficient argyrodite-like structure lithium .. of formula Li5,1PS4,400,3C11,3 was obtained by the method of the present example from precursors Li2S, P2S5, LiCl and Li2SO4 according to Equation 2 in which, x =
0.3 and y = 0.3.
Arqyrodite deficient in lithium of formula Li4,8PS4,100,3C11,6(Argyrodite 7) :
An inorganic compound possessing a deficient argyrodite-like structure lithium of formula Li4.8PS4.100.3C11.6 was obtained by the method of this example from precursors Li2S, P2S5, LiCl and Li2SO4 according to Equation 2 in which, x =
0.6 and y=0.3.
Arqyrodite of formula Li5.4PS4.4C11.6 (Arqyrodite 8) (comparative example):
An inorganic compound having an argyrodite-like structure of the formula Li5.4PS4.401.6 was obtained for comparison by the method of the present example from Li2S, P2S5 and LiCl precursors according to Equation 1 in which, x = 0.6 and y = 0.
Arqyrodite of formula Li54PS41003Cl16 (Arqyrodite 9) (comparative example):
An inorganic compound having an argyrodite-like structure of the formula Li5.4PS4.100.3C11.6 was obtained for comparison by the method of the present example from Li2S, P2S5, LiCl and Li2O precursors according to Equation 3 in which, x =
0.6 and y =
0.3.
.. Arqyrodite of formula Li5,4PS3,900,5C11,6(Arqyrodite 10) (example comparison):

Date received/date received 2021-10-27 An inorganic compound having an argyrodite-like structure of the formula Li5.4PS3.900.5C11.6 was obtained for comparison by the method of the present example from Li2S, P2S5, LiCl and Li2O precursors according to Equation 3 in which, x =
0.6 and y =
0.5.
Arovrodite of formula Li6PS5C1 (Arovrodite 11) (comparative example):
An inorganic compound having an argyrodite-like structure of the formula Li6PS5CI
was obtained for comparison by the process of the present example from the precursors Li2S, P2S5 and LiCI according to Equation 1 in which, x = 0 and y = 0.
Example 2 ¨ Characterization by X-ray diffraction (XRD) of the compounds inorganic compounds having an argyrodite-like structure The crystal structure of the argyrodites prepared in Example 1 was studied by DRX.
The analysis was entirely carried out in an anhydrous chamber and the spectra of x-rays have were obtained using a Rigaku MiniFlex™ X-ray diffractometer equipped of one cobalt x-ray source.
Pellets were prepared by compressing 80 mg of argyrodite powder prepared to Example 1. The pellets were then placed in holders waterproof samples which were closed in a glove box, under an inert atmosphere.
In the X-ray diffraction patterns shown in Figures 1 to 3, the pics corresponding to the impurities Li3PO4, Li2S and LiCI have been identified respectively by red solid lines, black dashed lines and dashed lines dial-dot-blue dots. Peak D identified by a solid gray line comes from the dome used during XRD analysis. The other peaks correspond to the type structure argyroditis.
Figure 1 presents the X-ray diffraction patterns obtained for THE
argyrodites not deficient in lithium (Argyrodites 1 to 4 and 8). THE
diagrams of X-ray diffraction presented in Figure 1 show that the structure of kind argyrodite is well obtained for all compositions. It is possible to observe the presence of a substantially larger amount of impurities (LiCI, Li2S and Li3PO4) for the most oxygen-rich compositions (y > 0.3) (Argyrodites 3 and 4).

Date received/date received 2021-10-27 Figure 2 presents the X-ray diffraction patterns obtained for THE
lithium-deficient and non-deficient argyrodites (Argyrodites 2 and 5 to 7). Figure 2 shows that the argyrodite structure has indeed been obtained for x = 0.3 and y = 0.3 (Argyrodites and 6), for both syntheses (Equations 1 and 2). It is possible to observe at the 5.. Figure 2, the presence of less residual Li2S for the structure deficient argyroditis lithium (Argyrodite 6) than for the structure not deficient in lithium (Argyrodite 5). There Figure 2 also shows structural degradation for argyrodite deficient in lithium of formula Li4,8PS4,100,3C11,6 in which, x = 0.6 and y = 0.3 (Argyrodite 7). He is possible to observe a substantially larger amount of LiCI
residual, but no trace of Li2S. This indicates that an argyrodite-like structure substantially deficient in lithium could induce an argyrodite-like phase mixture and of parasitic phases (for example, LiCI).
Figure 3 presents the X-ray diffraction patterns obtained for THE
argyrodites obtained from Li2SO4 and Li2O precursors (Argyrodites 2, 3, 9 and 10).
Figure 3 shows that for an oxygen level of 0.3 (Argyrodites 2 and 9) there there is no significant difference observable on the structure of the argyrodite of the compounds inorganic compounds obtained from the two different precursors. However, for a rate oxygen of 0.5 argyrodite prepared from Li2O (Argyrodite 10) contains substantially more impurities (notably LiCI) and has a structure substantially less well defined compared to argyrodite prepared at from Li2SO4(Argyrodite 3).
Example 3 ¨ Characterization by nuclear magnetic resonance (NMR) of inorganic compounds having an argyrodite-like structure The composition of the argyrodites prepared in Example 1 was studied by NMR.
THE
nuclear magnetic resonance spectra of lithium (6Li NMR) and phosphorus (31P
NMR) were obtained by the MAS technique (magic angle rotation) in using a Bruker Avance NE0 500 MHz spectrometer equipped with a triple resonance probe of 4 mm whose maximum speed of rotation at the magic angle is 15 kHz.
Figures 4 and 5 present respectively 6Li NMR and 31P NMR spectra obtained .. for argyrodites obtained from Li2SO4 precursors (Argyrodite 2) (gray) and Li2O
(Argyrodite 9) (black).

Date received/date received 2021-10-27 For the two argyrodites (Argyrodites 2 and 9), the main peak on the 6Li NMR spectra presented in Figure 4 corresponds to argyrodite, while the peak secondary matches to LiCI residues.
For Argyrodites 2 and 9, the main peak on the 31P NMR spectra shown in Figure 5 corresponds to argyrodite, while the secondary peaks correspond to stages P2S64-, P02S2, PO3S and PO4. The relative intensity of the 31P NMR peaks is indicated to the blackboard 1.
Table 1. Relative intensity of 31P NMR peaks Argyrodite Argyrodite P2S64 P02S2 PO3S PO4 Argyroditis 2 96.7 2.3 0.5 0.4 0.1 Argyroditis 9 95.3 1.7 1.7 0.9 0.4 The relative intensity of the peaks presented in Table 1 shows that the use of Li2SO4 as a precursor (Argyrodite 2) significantly reduces the training of secondary phases P02S2, PO3S and PO4 compared to the use of Li20 (Argyrodite 9).
It is therefore possible to observe that oxygen is better incorporated into the structure argyrodite thanks to the precursor Li2SO4 and therefore generates fewer phases additional.
This may explain the observed differences, in particular an improvement in there ionic conductivity as well as electrochemical stability and allows differentiate a argyrodite synthesized from Li2SO4 of an argyrodite prepared from of Li20 or any other source of oxygen as a precursor.
Figures 6 and 7 present respectively 6Li NMR and 31P NMR spectra obtained for the argyrodite of formula Li4,8PS4,100,3C11,6 obtained from the Li2SO4 precursors (Argyrodite 7).
It is possible to observe on the 6Li NMR spectrum presented in Figure 6 a peak at 1.2 ppm corresponding to an argyrodite phase with six lithiums and one chlorine, a second peak at 0.2 ppm corresponding to an argyrodite phase with a structure deficient in lithium and a excess chlorine and a third peak at -1.1 ppm corresponding to LiCl.
It is possible to observe on the 31P NMR spectrum presented in Figure 7 a main peak corresponding to argyrodite and three secondary peaks corresponding to phases of P2S64-, P02S2 and PO3S. Figure 7 also shows an enlargement of the peak main showing that it breaks down into three peaks corresponding to a (P1), two Date received/date received 2021-10-27 (P2) and three (P3) chlorine in the secondary structure of phosphorus. Excess simultaneous P1 and P3 confirms the presence of two types of argyrodites, with low and a strong fraction of chlorine.
Example 4 ¨ Generation of H2S upon exposure of inorganic compounds having an air argyrodite-like structure Security tests have been performed to assess the impact of argyroditis on the generation of H2S. About 10mg (3mg) of argyrodite powder has been placed in a sealed cell under an inert atmosphere.
An airflow was introduced into the sealed cell at a rate of approximately 0.3 Umin, to a controlled temperature of approximately 24.5 C (0.5 C) and has a hygrometry controlled with one with a humidity level of 50% (5%). The concentration of H2S gas generated at was measured approximately every 15 seconds with a multi-gas detector (MSA
ALTAIR™
5X) placed at the exit of the cell. From these data, the volume of H2S
gaseous generated normalized by the mass of argyrodite was calculated.
The results of these analyzes are shown in Figure 8. Figure 8 shows A
graph of the volume of gaseous H2S generated per gram of argyrodite powder (mL/g) as a function of time (hours) for Argyrodites 2 (blue dotted line), 7 (dash line dial-dot green), 8 (red dashed line) and 11 (solid black line) prepared to Example 1.
It is possible to observe that a classical argyrodite of Li6PS5CI type (Argyrodite 11) generates a substantially higher volume of gaseous H2S than an argyrodite spiked chlorine type Li5,4PS4,4C11,6 (Argyrodite 8), demonstrating the interest of chlorine doping on security. It is also possible to observe that the argyrodites at basis of precursor Li2SO4 also reduce the volume of gaseous H2S
as this is the case for the argyrodite Li5,4PS4,100,3C11,6 (Argyrodite 2). Eventually, Figure 8 shows that a lithium-deficient argyrodite-like structure generated at go from precursor Li2SO4 (Argyrodite 7) would further reduce the volume of gas generated, and thus, improve safety while reducing the costs of production by a lower quantity of Li2S used and by the absence or step reduction annealed.
Date received/date received 2021-10-27 Example 5 ¨ Ionic conductivity of inorganic compounds having a argyrodite-like structure To) Preparation of symmetric cells for ion conductivity measurements Symmetrical cells were assembled according to the following procedure in order to to measure the ionic conductivity of inorganic compounds possessing a structure of kind argyrodite prepared in Example 1.
Pellets were prepared by compressing 80 mg of compound powder inorganic possessing an argyrodite type structure prepared in Example 1 between two electrodes of stainless steel under a pressure of 360 MPa. The pellets placed between two stainless steel electrodes were then assembled into cells of sealed conductivity closed in glove box under maintained inert atmosphere to one pressure of 20 MPa.
The symmetrical cells were assembled according to the configurations indicated At Table 2.
Table 2. Balanced Cell Configurations Composition Values Argyrodite Argyrodite symmetrical cell in lithium of x and y argyroditis x = 0.6 and Cell 1 Argyrodite 1 Li5.4PS4.300.1C11.6 y=
0.1 Cell 2 Argyrodite 2 Li5,4PS4,100,3C11,6 x = 0.6 and y =0.3 Not deficient x =
0.6 and Cell 3 Argyrodite 3 Li5.4PS3.900.5C11.6 in lithium y = 0.5 x = 0.6 and Cell 4 Argyrodite 4 Li5,4PS3,6500,75C11,6 y = 0.75 Cell 5 Argyrodite 5 Li5.7PS4.400.3C11.3 x = 0.3 and y =0.3 x = 0.3 and Cell 6 Argyrodite 6 Li5,1PS4,400,3C11,3 Deficient in y =
0.3 lithium x =
0.6 and Cell 7 Argyrodite 7 Li4.8PS4.100.3C11.6 y=
0.3 Cell 8x =
0.6 and Argyrodite 8 Li5.4PS4.4C11.6 (comparative cell) y = 0 Argyroditis no Cell 9 x =
0.6 and Argyrodite 9 Li5,4PS4,100,3C11,6 deficient in (comparative cell) y =
0.3 lithium Cell 10x =
0.6 and Argyrodite 10 Li5.4PS3.900.5Cli.6 (comparative cell) y =
0.5 Date received/date received 2021-10-27 b) Measurement of the ionic conductivity of symmetrical cells Ion conductivity measurements of symmetric cells assembled at The example 5(a) were performed with a VMP-300 multichannel potentiostat (BioLogic).
THE
measurements were performed frequency range from 7 MHz to 200 mHz under a .. amplitude of 50 mV in a temperature range from -10 C to 70 C (uphill and downhill, every 10 C).
Each ion conductivity measurement was obtained after stabilization of about one hour from oven temperature to room temperature. conductivity ionic was extracted based on an equivalent circuit used to extract the resistance associated with measured pellet. Lines were obtained for symmetric cells prepared to Example 5(a). The slope of these lines corresponds to the activation energy and has a value of about 0.3 eV.
Figure 9 presents the results of ionic conductivity measured as a function of of the temperature for Cells 1 (.), 2 ( A), 3 (+), 4 (*) and 8 (a). He is possible to observe in Figure 9 that the ionic conductivity of the poorest argyrodites in oxygen (y 0.3) (Cells 1 and 2) is similar to that of oxide-free argyrodite (Cell 8). A
decrease in conductivity is observed for the most argyrodites rich in oxygen (y > 0.3) (Cells 3 and 4). It should be noted that the ionic conductivity of argyroditis formula Li5,4PS4,100,3C11,6 (Cell 2) prepared from Li2SO4 is substantially .. identical to that of oxide-free argyrodite (Cell 8).
Figure 10 presents the results of ionic conductivity measured in function of the temperature for Cells 2 ( A), 5 (3), 6 (.) and 7 (+). Figure 10 shows values of substantially similar ionic conductivity for Cells 5 and 6 including respectively Argyrodites 5 and 6 (x = 0.3 and y = 0.3) obtained by two syntheses .. different. For x = 0.6 and y = 0.3, Figure 10 also shows values of Substantially lower ionic conductivity for Cell 7 including argyrodite deficient in lithium (Argyrodite 7) in comparison with those of Cell 2 including non-lithium deficient argyrodite (Argyrodite 2). As we can observe it, thanks to precursor Li2SO4, it is possible to modulate the composition (for example, the rate .. lithium, oxygen and sulfur) of an oxysulfide lithium argyrodite while remaining substantially in the same ionic conductivity range. he is also possible Date received/date received 2021-10-27 to observe that a significant lithium deficiency induces a reduction in the conductivity ionic.
Figure 11 presents the results of ionic conductivity measured in function of the temperature for Cells 2 (3), 3 (.), 9(A) and 10 (+). Figure 11 shows that for the same composition, the ionic conductivity of the argyrodites obtained at go from precursor Li2SO4 is significantly higher than that of argyrodites obtained at from the Li2O precursor.
Example 6 ¨ Electrochemical stability of inorganic compounds having a argyrodite-like structure a) Preparation of pseudo-batteries for stability measurements electrochemical 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.
5% by weight of VGCFs were mixed with 95% by weight of Argyrodites 2 and 9 in order to to obtain composite positive pseudo-electrodes, and thus observe reactions redox substantially representative of the final compositions of electrodes composite positives 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. electrodes negative of metallic lithium were then deposited on the surface of the electrolytes solid.
Assemblies comprising a composite positive pseudo-electrode, a electrolyte solid and a metallic lithium negative electrode were then compressed and assembled in airtight cells closed in a glove box under atmosphere inert.
The pseudo-batteries were assembled according to the configurations presented in the Table 3.

Date received/date received 2021-10-27 Table 3. Pseudo-battery configurations Composition of the pseudo-composite positive electrode Composition of Composition argyroditis Pseudo-battery Material the electrolyte the electrode conductive argyrodite solid negative electronic Li5,4PS4,100,3C11,6 VGCFs Li5,4PS4,100,3C11,6 Lithium Cell 11 (Argyrodite 2) 95 wt% 5 wt% (Argyrodite 2) metallic Li5.4PS4.100.3C11.6 Cell 12 VGCFs Li5,4PS4,100,3C11,6 Lithium (Comparative cell) (Argyrodite 9) 5 wt% (Argyrodite 9) metallic 95% by weight b) Cyclic voltammetry The electrochemical oxidation stability of pseudo-batteries such as described at Example 6(a) was measured using a VMP-300 multi-channel potentiostat (BioLogic).
Figure 12 presents the cyclic voltammetry results obtained for the cell

11 (green lines) and for Cell 12 (comparative battery) (lines blue) recorded at a slew rate of 0.05 mV/s in the oxide potential range lithium, of nickel, manganese and cobalt (NMC), i.e. between 2.5 V and 4.2 V vs Li/Li + to one temperature of approximately 30 C. Figure 12 presents the results obtained during of the four first cycles for each of the two pseudo-batteries.
Figure 12 shows that no reaction with lithium metal could be observed, demonstrating the chemical and electrochemical stability of argyrodites with the lithium metallic. In the potential range of the NMC, it is possible to observe a weak oxidation-reduction reaction for the two pseudo-batteries, with a density of fluent lowest generated for Cell 11 comprising the argyrodite obtained in using Li2SO4 as precursor (0.3 pA/cm2) and polarization hysteresis weaker. He It is also possible to observe that this reaction is reversible. THE
argyrodites would therefore be substantially electrochemically stable in the range of potential of NMC with substantially improved electrochemical stability for argyroditis obtained using Li2SO4 as a precursor. Thus, argyroditis obtained in Date received/date received 2021-10-27 using Li2SO4 as a precursor is substantially stable on full range potential of a lithium metal battery.
Example 7 ¨ Electrochemical properties of inorganic compounds possessing an argyrodite-like structure The electrochemical properties of Argyrodite 2 prepared in Example 1 have been studied.
a) Preparation of the composite positive electrode material 35% by weight of Argyrodite 2 powder prepared in Example 1 were 65% mixed by weight of particles of LiNi0.6Mn0.2Coo.202 (NMC 622) and at 5% by weight of a blend carbon black Li400 (Denkamc) and VGCFs (ratio 75:25 by weight). THE
powders were mixed for a while using a vortex mixer (from vortex type) then with a mortar in order to homogenize the positive electrode material composite.
b) Configuration of the electrochemical cell (Cell 13) The electrochemical cell was assembled according to the following procedure.
A solid electrolyte was prepared in 80 mg of argyrodite powder 2 prepared to Example 1 in a mold 10 mm in diameter under a pressure of 200 MPa. 13 mg of the composite positive electrode material prepared in Example 7(a) have then been added in the mold on the solid electrolyte followed by a collector of aluminum current.
The contents of the mold including the solid electrolyte layer, the positive electrode composite and the aluminum current collector were then compressed under a pressure of 360 MPa for about 10 minutes. A lithium electrode metallic 10 mm diameter on a stainless steel current collector then been added facing the layer of solid electrolyte and the assembly was compressed under a pressure of 120 MPa for about 5 minutes.
The electrochemical cell was then assembled, in a cell of sealed cycling closed in a glove box under an inert atmosphere maintained at a pressure of 20 MPa.
c) Electrochemical behavior of the electrochemical cell Cell 13 assembled in Example 7(b) was cycled between 2.5 V and 4.5 V vs Lili. THE
five first cycles were performed at C/10, followed by four cycles at C/4, then the Date received/date received 2021-10-27 aging experiments were carried out at a charging current and dump constant of C/2 at a temperature of 30 C for a surface capacity of 1.8 mAh/cm2.
Figure 13 shows a graph of charge (.) and discharge capacity (3) and the coulombic efficiency (A) as a function of the number of cycles for 100 cycles.
Figures 14 and 15 the discharge profiles at different charging currents and of dump. More particularly, Figures 14 and 15 respectively show A
graph of potential as a function of discharge capacity and time in hours.
It is possible to observe that at C/10, C/4 and C/2 the electrochemical cell provided respectively a capacity of approximately 170 mAh.g-1, 160 mAh.g-1 and 150 mAh.g-1.
It is possible to observe a substantial retention of capacity after 100 cycles, thus allowing the stability of the performances in aging as demonstrated at the Figure 14. Adequate cyclability of the cell can be observed electrochemical at C/2 in charge and discharge at a temperature of 30 C demonstrating the beautiful stability electrochemistry of Argyrodite 2 in potential and with respect to the material driver electronics (i.e., the mixture of carbon black Li400 and VGCFs) and material electrochemically active (ie, NCM).
Several modifications could be made to either mode of achievements described above without departing from the scope of the present invention such than envisaged. References, patents or scientific literature documents referred in the present application are incorporated herein by reference in their completeness and to all purposes.

Date received/date received 2021-10-27

Claims (61)

1. A process for preparing an inorganic compound having a structure of argyrodite type, the method comprising a step of grinding sulphide of lithium, lithium sulphate, phosphorus pentasulphide and a halide of lithium. 2. Process according to claim 1, in which the lithium halide is chosen from lithium fluoride, lithium chloride, lithium bromide and iodide of lithium. 3. Process according to claim 2, in which the lithium halide is chloride of lithium. 4. Method according to any one of claims 1 to 3, in which the structure argyrodite type is not deficient in lithium. 5. Method according to claim 4, in which the structure of the type argyroditis no deficient in lithium has the formula Li6_,PS5_x_yOyZi-ix, in which Z is an atom of halogen selected from F, Cl, Br and I and x and y are different numbers from zero selected to achieve electroneutrality (for example, 0 < x E 1 and 0 <
y E 1). 6. Method according to claim 5, in which the structure of the type argyroditis no deficient in lithium is selected from the group consisting of Li5.4P54.300.101.6, Li5,4P54,100,3C11,6, U5,41'53,900,501,6, Li5,4P53,6500,75Clu and Li5.7P54.400.301.3. 7. Method according to any one of claims 1 to 3, in which the structure argyrodite type is deficient in lithium. 8. Method according to claim 7, in which the structure of the type argyroditis deficient in lithium has the formula Li =6-x-2yPS5-x-yOyZ1+x where Z is an atom of halogen selected from F, Cl, Br and I and x and y are different numbers from zero (for example, 0 < x É 1 and 0 < y É 1). 9. Method according to claim 8, in which the structure of the type argyroditis deficient in lithium is selected from the group consisting of LisAP54,300,101,6, 1_15.1FS4.400.3Ch.3 and Li4.8PS4.100.3Ch.6. 10. Method according to any one of claims 1 to 9, in which the step of Grinding is performed using a planetary micromill. 11. Method according to any one of claims 1 to 10, in which the step of grinding is carried out at a rotational speed of about 600 rpm. 12. Method according to any one of claims 1 to 11, in which the step of grinding is carried out for about 10 hours. 13. Method according to any one of claims 1 to 12, in which the step of grinding is carried out in a ratio of grinding balls: precursors of approximately 30. 14. A method according to any one of claims 1 to 13, which comprises in in addition to an annealing step carried out at a maximum temperature of approximately 300 vs. 15. Method according to any one of claims 1 to 13, which is free of a annealing step. 16. An inorganic compound having an argyrodite-like structure obtained according the method as defined in any one of claims 1 to 15. 17. An electrode material comprising an electrochemically active material and one inorganic compound having an argyrodite-like structure as defined to the claim 16 or obtained by the process as defined in any of the claims 1 to 15. 18. Electrode material according to claim 17, in which the compound inorganic having an argyrodite-like structure is present as an additive. 19. Electrode material according to claim 17 or 18, wherein the compound inorganic material possessing an argyrodite-like structure is present as coating material. 20. An electrode material according to claim 19, wherein the electrode material coating forms a coating layer on the surface of the material electrochemically active. 21. Electrode material according to any one of claims 17 to 20, in which the electrochemically active material is selected from metal oxide, a sulfide metal, a metal oxysulfide, a metal phosphate, a fluorophosphate of metal, a metal oxyfluorophosphate, a metal sulphate, a metal halide, A
metal fluoride, sulfur, selenium and a combination of two or more of these. 22. An electrode material according to claim 21, wherein the metal of the material electrochemically active is selected from titanium (Ti), iron (Fe), manganese (Mn), vanadium (V), nickel (Ni), cobalt (Co), aluminum (Al), chromium (Cr), copper (Cu), zirconium (Zr), niobium (Nb) and a combination of at less two of these. 23. Electrode material according to claim 21 or 22, wherein the metal of electrochemically active material further comprises an alkali metal or alkaline-earth chosen from lithium (Li), sodium (Na), potassium (K) and magnesium (Mg). 24. Electrode material according to any one of claims 17 to 23, In wherein the electrochemically active material is an oxide of metal and lithium. 25. An electrode material according to claim 24, wherein the oxide of metal and lithium is a mixed oxide of lithium, nickel, manganese and cobalt (NCM). 26. Electrode material according to any one of claims 17 to 20, in which the electrochemically active material is selected from a non-alkaline metal or No-alkaline earth metal, an intermetallic compound, a metal oxide, a nitride of metal, a metal phosphide, a metal phosphate, a metal halide, A
metal fluoride, metal sulfide, metal oxysulfide, carbon, silicon (Si), a silicon-carbon composite (Si-C), a silicon oxide (Si0x), a silicon oxide-carbon composite (SiOx-C), tin (Sn), a composite tin-carbon (Sn-C), a tin oxide (SnOx), a tin oxide-carbon composite (SnOx-C), and a combination of two or more thereof. 27. Electrode material according to any one of claims 17 to 26, In wherein the electrochemically active material further comprises an element doping. 28. Electrode material according to any one of claims 17 to 27, In wherein the electrochemically active material further comprises a material coating. 29. An electrode material according to claim 28, wherein the material coating is an electronic conductive material. 30. An electrode material according to claim 29, wherein the material driver electronics is carbon. 31. An electrode material according to claim 28, wherein the material coating is selected from Li2SiO3, LiTa03, LiAl02, Li20-Zr02, LiNb03, others materials coatings and a combination of two or more thereof. 32. Electrode material according to any one of claims 31, in whichone embedding material is LiNbO3. 33. Electrode material according to any one of claims 17 to 32, which further comprises at least one electronically conductive material. 34. An electrode material according to claim 33, wherein the material driver electronics is selected from the group consisting of carbon black, black acetylene, graphite, graphene, carbon fibers, nanofibers of carbon, carbon nanotubes, and a combination of at least two of these. 35. An electrode material according to claim 48, wherein the material driver electronics is a mixture of carbon black and formed carbon fibers in gas phase (VGCFs). 36. Electrode material according to any one of claims 17 to 35, which further comprises at least one additive. 37. An electrode material according to claim 36, wherein the additive is chosen from inorganic ionic conductive materials, inorganic materials, THE
glasses, glass-ceramics, ceramics, nano-ceramics, salts and a combination of at least two of these. 38. Electrode material according to any one of claims 17 to 37, which further comprises a binder. 39. An electrode material according to claim 38, wherein the binder is chosen from the group consisting of a polymer binder of the polyether, polycarbonate or polyester, a fluorinated polymer and a water-soluble binder. 40. An electrode comprising the electrode material as defined in one any of claims 17 to 39 on a current collector. 41. A self-supporting electrode comprising the electrode material such as set to any of claims 17 to 39. 42. An electrolyte comprising an inorganic compound having a structure of argyrodite type as defined in claim 16 or obtained according to process as as defined in any one of claims 1 to 15. 43. An electrolyte according to claim 42, which is an electrolyte liquid comprising a salt in a solvent. 44. An electrolyte according to claim 42, which is a gel electrolyte including a salt in a solvent and optionally a solvating polymer. 45. An electrolyte according to claim 42, which is a polymer electrolyte solid comprising a salt in a solvating polymer 46. Electrolyte according to any one of claims 42 to 45, in which THE
inorganic compound possessing an argyrodite-like structure is present in as an additive. 47. Electrolyte according to claim 42, which is a solid electrolyte inorganic. 48. Electrolyte according to claim 42, which is a solid electrolyte hybrid polymer-ceramic. 49. Electrolyte according to claim 47 or 48, in which the compound inorganic having an argyrodite-like structure is present as a material inorganic solid electrolyte. 50. Electrolyte according to any one of claims 42 to 49, which includes in besides at least one additional component. 51. Electrolyte according to claim 50, in which the component additional is chosen from ionic conductive materials, inorganic particles, THE
glass or ceramic particles and a combination of at least two of these this. 52. An electrochemical cell comprising a negative electrode, a electrode positive and an electrolyte, wherein at least one of the electrode positive or the negative electrode is as defined in claim 40 or 41 or understand an electrode material as defined in any one of the claims 17 to 41. 53. An electrochemical cell comprising a negative electrode, a electrode positive and an electrolyte, wherein the electrolyte is as defined in moon any of claims 42 to 51. 54. Electrochemical cell according to claim 52 or 53, in which the electrode negative comprises an electrochemically active material comprising a metal alkali, an alkaline-earth metal, an alloy comprising at least one metal alkaline or alkaline-earth metal, a non-alkaline and non-alkaline-earth metal, or a alloy or a intermetallic compound. 55. Electrochemical cell according to claim 54, in which the material electrochemically active negative electrode comprises lithium metallic or an alloy including or based on metallic lithium. 56. Electrochemical cell according to any one of claims 52 to 55, In which the positive electrode is pre-lithium and the negative electrode is substantially free of lithium. 57. Electrochemical cell according to claim 56, in which the negative electrode is lithiated in situ during the cycling of said electrochemical cell. 58. An electrochemical accumulator comprising at least one cell electrochemical as defined in any one of claims 52 to 57. 59. Electrochemical accumulator according to claim 58, wherein said electrochemical accumulator is a battery is selected from a battery At lithium, a lithium-ion battery, a sodium battery, a sodium-ion, a magnesium battery, a magnesium-ion battery. 60. Electrochemical accumulator according to claim 59, in which said battery is a lithium battery or a lithium-ion battery. 61. Electrochemical accumulator according to claim 59, wherein said electrochemical accumulator is a so-called all-solid battery.