CA3179099A1 - 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 type structure based on an alkali metal obtained by a preparation process comprising a step of grinding alkali metal sulfide, alkali metal sulfate, phosphorus pentasulfide and an alkali metal 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-state batteries.

Description

INORGANIC COMPOUNDS HAVING A LIKE STRUCTURE
ARGYRODITE, THEIR PREPARATION PROCESSES AND THEIR USES
IN ELECTROCHEMICAL APPLICATIONS
TECHNICAL AREA
The present application relates to the field of inorganic compounds based of oxysulphides having an argyrodite type structure and their uses in electrochemical applications. More particularly, the present request is relates to field of inorganic oxysulfide compounds having a structure Of type argyrodite, electrode materials and solid electrolytes understanding, to their production processes and their uses in cells electrochemical, particularly in so-called solid-state batteries.
STATE OF THE TECHNIQUE
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 electrochemical systems in the state all solid which are substantially safer.
Additionally, inorganic sulfide compounds exhibit a wide window of electrochemical stability and substantially higher ionic conductivity elevated to ambient temperature. Indeed, solid inorganic electrolytes including present 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, particularly due to the use of sulphide lithium (Li2S) as a precursor and source of sulfur and an annealing step at high temperature allowing interesting ionic conductivities to be obtained. One of the key elements of industrial requirements related to the production of this type of compounds inorganic is Date Received/Date Received 2022-10-12 therefore to minimize costs by lowering the rate of use of Li2S and the temperature of annealed while maintaining significantly high ionic conductivity.
In addition, inorganic compounds of the argyrodite type are associated with problems linked to their interfacial stability as well as their stability in ambient air and humidity. More precisely, these inorganic solid electrolytes generate sulfide hydrogen (H2S) gaseous 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 argyrodite type based on oxysulfide.
Indeed, a partial atomic substitution of sulfur and/or lithium in these compounds inorganic by oxygen would cause a significant reduction 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 electrochemical systems in their whole state solid excluding one or more of the disadvantages mentioned above.
SUMMARY
In some aspects, embodiments of the technology such as described here include the following items:
1. A process for preparing an inorganic compound having a structure of argyrodite type based on an alkali metal, the process comprising a step of grinding of alkali metal sulfide, alkali metal sulfate, pentasulfide phosphorus and an alkali metal halide, in which the alkali metal is chosen among lithium, sodium and potassium, for example, the alkali metal is THE
lithium.

2. Process according to item 1, in which the alkali metal halide is chosen from the alkali metal fluoride, alkali metal chloride, metal bromide alkaline, alkali metal iodide and a mixture of at least two of these.

3. Process according to item 2, in which the alkali metal halide is the chloride alkali metal.

Date Received/Date Received 2022-10-12

4. Process according to item 2, in which the alkali metal halide is the bromide of alkali metal.

5. Process according to item 2, in which the alkali metal halide is the iodide of alkali metal.

6. Process according to item 2, in which the alkali metal halide is a mix of alkali metal chloride and alkali metal bromide.

7. Process according to item 2, in which the alkali metal halide is a mix of alkali metal chloride, alkali metal bromide and metal iodide alkaline.

8. Method according to any one of items 1 to 7, in which the structure Of type argyrodite has the formula M6_õPS5_,_yOyZi,,, in which M is the metal alkaline chosen from Li, Na and K, for example M is Li, Z is a chosen halogen atom among F, Cl, Br and 1 and x and y are non-zero numbers selected for reach electroneutrality (for example, 0 <x 1 and 0 <y 1).

9. Method according to item 8, in which the argyrodite type structure is chosen from inorganic compounds having an argyrodite type structure of formulas M6,4PS4,300,1C11.6, M5,4PS4,100,30 1.6, M5.4PS3.900.501.6, M5.4PS3.6500.750 1.6, M5.7PS4.400.301.3, M5.4PS4.100.3C11.6, M5.4PS3.900.50 1.6, M5.4PS4.100.3Br1.6, M5,4PS4,1 00.30 Br0.6, M5,4PS4,100,300.8Br0.8, M5,4PS4,100,300,6Br, M5.4PS4.1 00.30 Br0.510.1, M5.4PS4.100.300.75Br0.7510.1, M5,4PS4,100,300,7Bro,710,2 and M5,4PS4,100,3CIBro,410,2, in which M is as defined here in item 8.

10. Method according to item 8, in which the argyrodite type structure is chosen from inorganic compounds having an argyrodite type structure of formulas Li6,4PB4,300,1C11,6, Li6,4PB4,100,3C11,6, Li5.4PS3.900.5C11.6, Li5.4PS3.6500.750 1.6, Li5,7PS4,400,3C11,3, Li5,4PS4,100,301,6, Li5.4PS3.900.50 1.6, Li5APS4.100.3Br1.6, Li5APS4,100,3CIBro,6, Li5APS4,100,3C10,8Bro,8, Li5APS4,100,3C10,6Br, Li5APS4,100,3C1Bro,5101, Li5APS4,100,3C10,75Bro,75101, Li5APS4,100,300,7Bro,710,2 and Li5,4PS4,100,3C1Bro,410,2.

11. Method according to any one of items 1 to 7, in which the structure of kind argyrodite has the formula M6_x_zyPS6_x_yOyZi+x, in which M is the metal alkaline chosen from Li, Na and K, for example M is Li, Z is a halogen atom selected Date Received/Date Received 2022-10-12 among F, Cl, Br and I and x and y are numbers other than zero (by example, 0 <
x 1 and 0 < y 1).

12. Method according to item 11, in which the argyrodite type structure deficient in lithium is chosen from inorganic compounds having a structure of argyrodite type with formulas M5,2PS4,300,1C11.6, M5.1 PS4,400,301.3 and M4,8PB4,100,3C11,6, in which M is as defined here in item 11.

13. Method according to item 12, in which the argyrodite type structure is chosen from inorganic compounds having an argyrodite type structure of formulas Li5,2PS4,300,1C11,6, Li5,1PB4,400,3C11,3 and Li4,8PS4,100,3C11,6.

14. Method according to any one of items 1 to 13, in which the step of grinding is carried out using a planetary mill.

15.
Process according to any one of items 1 to 14, in which the grinding step East carried out at a rotation speed included in the interval going about 500 rpm to approximately 700 rpm.

16. Method according to any one of items 1 to 14, in which the step of grinding is carried out at a rotation speed of approximately 600 rpm.

17. Method according to any one of items 1 to 15, in which the step of grinding is carried out for approximately 10 hours.

18. Method according to any one of items 1 to 17, in which the step of grinding is carried out in a grinding ball: precursor ratio of approximately 30.

19. Method according to any one of items 1 to 18, which further comprises a annealing step carried out at a maximum temperature of approximately 300 C.

20. Process according to any one of items 1 to 18, which is free from a stage of annealed.

21. An inorganic compound having an argyrodite type structure obtained according to the process as defined in any of items 1 to 20.

Date Received/Date Received 2022-10-12

22. An electrode material comprising an electrochemically active material and one inorganic compound having an argyrodite type structure as defined has item 21 or obtained according to the process as defined in any one of the items 1 to 20.

23. Electrode material according to item 22, in which the inorganic compound possessing an argyrodite-like structure is present as an additive.

24. Electrode material according to item 22 or 23, in which the compound inorganic having an argyrodite type structure is present as a material of coating.

25. Electrode material according to item 24, in which the material of shape covering a coating layer on the surface of the electrochemically active material.

26. Electrode material according to any one of items 22 to 25, in which THE
electrochemically active material is chosen from metal oxide, a sulfide of metal, a metal oxysulfide, a metal phosphate, a fluorophosphate of metal, a metal oxyfluorophosphate, a metal sulfate, a metal halide, A
metal fluoride, sulfur, selenium and a combination of two or more of these.

27. Electrode material according to item 26, in which the metal of the material electrochemically active is chosen from titanium (Ti), iron (Fe), manganese (Mn), vanadium (V), nickel (Ni), cobalt (Co), aluminum (AI), chromium (Cr), copper (Cu), zirconium (Zr), niobium (Nb) and a combination of au less two of these.

28. Electrode material according to item 26 or 27, in which the metal of the material electrochemically active further comprises an alkali or alkaline metal earthy chosen from lithium (Li), sodium (Na), potassium (K) and magnesium (Mg).

29. Electrode material according to any one of items 22 to 28, in which THE
electrochemically active material is a lithium metal oxide.

30. Electrode material according to item 29, in which the metal oxide and lithium is a mixed oxide of lithium, nickel, manganese and cobalt (NCM).

Date Received/Date Received 2022-10-12

31. Electrode material according to any one of items 22 to 25, in which THE
electrochemically active material is chosen from a non-alkaline metal or No-alkaline earth, 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), 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.

32. Electrode material according to any one of items 22 to 31, in which THE
electrochemically active material further comprises a doping element.

33. Electrode material according to any one of items 22 to 32, in which THE
electrochemically active material further comprises a coating material.

34. Electrode material according to item 33, in which the coating material is a electronic conductive material.

35. Electrode material according to item 34, in which the conductive material electronics is carbon.

36. Electrode material according to item 33, in which the material coating is chosen among Li2SiO3, LiTa03, LiA102, Li2O-ZrO2, LiNb03, other materials coating similar and a combination of at least two of these.

37. Electrode material according to any one of items 36, in which the material coating is LiNb03.

38. Electrode material according to any one of items 22 to 37, which includes in in addition to at least one electronic conductive material.

39. Electrode material according to item 38, in which the conductive material electronic is chosen from the group consisting of carbon black, black acetylene, graphite, graphene, carbon fibers, nanofibers of carbon, carbon nanotubes, and a mixture of at least two of these this.

Date Received/Date Received 2022-10-12

40. Electrode material according to item 39, in which the conductive material electronic is a mixture of carbon black and carbon fibers formed in gas phase (VGCFs).

41. Electrode material according to any one of items 22 to 40, which includes in in addition to at least one additive.

42. Electrode material according to item 41, in which the additive is chosen from inorganic ionic conductive materials, inorganic materials, glasses, glass ceramics, ceramics, nano ceramics, salts and a combination of at least two of these.

43. Electrode material according to any one of items 22 to 42, which includes in besides a binder.

44. Electrode material according to item 43, in which the binder is chosen from the group consisting of a polymer binder of the polyether, polycarbonate or polyester type, of a fluoropolymer and a water-soluble binder.

45. An electrode comprising the electrode material as defined in one any items 22 to 44 on a current collector.

46. A self-supporting electrode comprising the electrode material such as set to any of items 22 to 44.

47. An electrolyte comprising an inorganic compound having a structure of argyrodite type as defined in item 21 or obtained according to the process such as set to any of items 1 to 20.

48. Electrolyte according to item 47, which is a liquid electrolyte comprising a salt in a solvent.

49. Electrolyte according to item 47, which is a gel electrolyte comprising a salt in a solvent and optionally a solvating polymer.

50. Electrolyte according to item 47, which is a solid polymer electrolyte including a salt in a solvating polymer Date Received/Date Received 2022-10-12

51. Electrolyte according to any one of items 47 to 50, in which the compound inorganic having an argyrodite type structure is present as than additive.

52. Electrolyte according to item 47, which is a solid electrolyte inorganic.

53. Electrolyte according to item 47, which is a hybrid solid electrolyte polymer-ceramic.

54. Electrolyte according to item 52 or 53, in which the inorganic compound possessing an argyrodite-like structure is present as a material solid electrolyte inorganic.

55. Electrolyte according to any one of items 47 to 54, which comprises in besides the minus one additional component.

56. Electrolyte according to item 55, in which the additional component is chosen among ionic conductive materials, inorganic particles, particles glass or ceramic and a combination of at least two of these.

57. An electrochemical cell comprising a negative electrode, a electrode positive and an electrolyte, in which at least one of the electrode positive or the negative electrode is as defined in item 45 or 46 or includes a material electrode as defined in any of items 22 to 44.

58. An electrochemical cell comprising a negative electrode, a electrode positive and an electrolyte, in which the electrolyte is as defined in mon any of items 47 to 56.

59. Electrochemical cell according to item 57 or 58, in which the electrode negative comprises an electrochemically active material comprising an alkali metal, an alkaline earth metal, an alloy comprising at least one alkali metal or alkaline-earth, a non-alkaline and non-alkaline earth metal, or an alloy or a compound intermetallic.

Date Received/Date Received 2022-10-12

60. Electrochemical cell according to item 59, in which the material electrochemically active negative electrode includes lithium metallic or an alloy including or based on metallic lithium.

61. Electrochemical cell according to any one of items 57 to 60, in which the positive electrode is pre-lithiated and the negative electrode is substantially free of lithium.

62. Electrochemical cell according to item 61, in which the electrode negative is lithiated in situ during the cycling of said electrochemical cell.

63. An electrochemical accumulator comprising at least one cell electrochemical as defined in any of items 57 to 62.

64. Electrochemical accumulator according to item 63, in which said accumulator electrochemical is a battery is chosen from a lithium battery, a lithium-ion battery, a sodium battery, a sodium-ion battery, a battery magnesium, a magnesium-ion battery.

65. Electrochemical accumulator according to item 64, in which said battery is a lithium battery or a lithium-ion battery.

66. Electrochemical accumulator according to item 65, in which said accumulator electrochemical is a so-called all-solid-state battery.
BRIEF DESCRIPTION OF THE FIGURES
Figure 1 shows X-ray diffraction patterns obtained for THE
powders of Argyrodites 1 to 4 and 8, as described in Example 2.
Figure 2 shows X-ray diffraction patterns obtained for THE
powders of Argyrodites 2 and 5 to 7, as described in Example 2.
Figure 3 shows X-ray diffraction patterns obtained for THE
powders of Argyrodites 2, 3, 9 and 10, as described in Example 2.
Figure 4 shows X-ray diffraction patterns obtained for THE
powders of Argyrodites 2 and 12 to 15, as described in Example 2.

Date Received/Date Received 2022-10-12 Figure 5 shows X-ray diffraction patterns obtained for THE
powders of Argyrodites 16 to 19, as described in Example 2.
Figure 6 shows X-ray diffraction patterns obtained for THE
powders of Argyrodites 2, 13, 20 and 21, as described in Example 2.
Figure 7 shows nuclear magnetic resonance spectra of lithium (6Li NMR) obtained for Argyrodites 2 and 9, as described in Example 3.
Figure 8 shows nuclear magnetic resonance spectra of the phosphorus (31P
NMR) obtained for Argyrodites 2 and 9, as described in Example 3.
Figure 9 shows a nuclear magnetic resonance spectrum of lithium (6Li NMR) obtained for Argyrodite 7, as described in Example 3.
Figure 10 shows a nuclear magnetic resonance spectrum of the phosphorus (31P
NMR) obtained for Argyrodite 7, as described in Example 3.
Figure 11 shows nuclear magnetic resonance spectra of the lithium (6Li NMR) obtained for Argyrodites 13 and 16, as described in Example 3.
Figure 12 shows nuclear magnetic resonance spectra of the phosphorus (31P NMR) obtained for Argyrodites 13 and 16, as described in Example 3.
Figure 13 shows a graph of the volume of gaseous H2S normalized by mass of argyrodite generated over time for Argyrodites 2, 7, 8, 11, 13 and 16, such that described in Example 4.
Figure 14 is a graph showing the ionic conductivity results in function of the temperature for Cells 1 (.), 2 (A), 3 (#), 4 (*) and 8 (11), such as described in Example 5(b).
Figure 15 is a graph showing the ionic conductivity results in function of the temperature for Cells 2 (A), 5 (11), 6 (.) and 7 (#), such that described in the Example 5(b).
Date Received/Date Received 2022-10-12 Figure 16 is a graph showing the ionic conductivity results in function of the temperature for Cells 2 (11), 3 (.), 9 (A) and 10 (#), such that described in the Example 5(b).
Figure 17 is a graph showing the ionic conductivity results in function the temperature for Cells 2 (11), 12 (.), 13 (A), 14 (#) and 15 (*), as described in Example 5(b).
Figure 18 is a graph showing the ionic conductivity results in function of the temperature for Cells 16 (11), 17 (.), 18 (A) and 19 (#), such that described to Example 5(b).
Figure 19 is a graph showing the ionic conductivity results in function of the temperature for Cells 2 (11), 20 (.), 13 (A) and 21 (+), such that described in the Example 5(b).
Figure 20 presents cyclic voltammograms obtained for Cells 22 and 23 recorded at a slew rate of 0.05 mV/s between 2.5 V and 4.2 V vs Li/Li + to one temperature of approximately 30 C, as described in Example 6(b).
Figure 21 shows a graph of charge (.) and discharge capacity (11) and 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 of Cell 24 as a function of the capacity obtained at charge and discharge currents C/10, C/4 and C/2 and recorded vs Li/Li + at a temperature of 30 C.
Figure 23 shows the discharge profiles of Cell 24 as a function of time obtained at charge and discharge currents C/10, C/4 and C/2 and recorded vs Li/Li + at a temperature of 30 C.
DETAILED DESCRIPTION
The following detailed description and examples are presented for illustrative only and should not be construed as further limiting the scope of the invention. At otherwise, they are intended to cover all alternatives, modifications and equivalents Date Received/Date Received 2022-10-12 which may be included as defined by this description. THE
objects, advantages and other characteristics of the present inorganic compounds having a structure argyrodite type, their preparation processes, as well as materials electrode, electrodes, electrolytes, electrochemical cells and Accumulators electrochemicals including them will be more apparent and better understood at the reading of the following non-restrictive description and references to the figures attached.
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 approximately 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 example of the experimental error of a measuring device or rounding.
When a range of values is mentioned in this application, the terminals lower and upper ranges 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 subintervals, as well that the values individuals included in the value intervals, are included in the definition.
When article one is used to introduce an element 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 realization.
The term self-supporting electrode as used here refers to a electrode without collector of the metallic current.
The present technology relates to a process for preparing a compound inorganic having an argyrodite type structure based on M2S-P2S5-M2SO4-MZ (in which, Date Received/Date Received 2022-10-12 M is an alkali metal chosen from lithium (Li), sodium (Na), potassium (K), and a combination of at least two of these, and Z is a selected halogen atom among the fluorine (F), chlorine (Cl), bromine (Br) and iodine (I), or a combination of at least two of these), the process comprising a step of direct grinding of the precursors.
According to some examples, M is lithium. The precursors being made up of metal sulfide alkaline (M25), alkali metal sulfate (M2504), pentasulfide of phosphorus (P255) and an alkali metal halide, chosen from alkali metal fluoride, the chloride of alkali metal, alkali metal bromide, alkali metal iodide and a mixture of minus two of these.
According to one example, inorganic compounds having a structure of type argyrodite can be respectively of formulas M6,P55_x_y0yZi+x and M6_x_2,,P55,_yOyZi+x, in which Z and M are as defined here, and x and y are numbers different from zero, by example 0 <x 1 and 0< y 1. Inorganic compounds having a structure of argyrodite type can therefore be obtained by grinding from the precursors such as here defined respectively according to the following reaction equations:
(2.5-y/4-x) M25 + y/4 M2504+ 1/2 P255 +(1+x) MZ ¨> M6_xPS5_x_yOyZi-Fx + y S
Equation (1) (2.5-5/4y-x) M25 + y/4 M2504 + 1/2 P255 + (1+x) MZ ¨> M6_x_2,,P55_x_yOyZi+x Equation (2) in which, x, y, M and Z are as defined here.
According to one example, when the inorganic compound has a structure of type argyrodite, x and y are non-zero numbers selected for reach electroneutrality. Non-limiting examples of inorganic compounds possessing a argyrodite type structure according to Equation 1 include the compounds inorganic having an argyrodite type structure of formulas M5,4P54,300,1Z1,6, M5,4P54,100,3Z1,6, M5.4P53.900.5Z1.6, M5.4P53.6500.75Z1.6 and M5.7P54.400.3Z1.3, in which M
and Z are such as defined here. When the inorganic compound has a structure of type argyrodite including less of the alkali metal (i.e., an inorganic compound has a structure of argyrodite type according to Equation 2), x and y are different numbers of zero selected to obtain a desired stoichiometry. Non-limiting examples of compounds inorganic materials having an argyrodite type structure according to Equation 2 include the inorganic compounds having an argyrodite-like structure of formulas M5,1P54,400,3Z1,3 and M4,8P54,100,3Z1,6, in which M and Z are such as defined here.

Date Received/Date Received 2022-10-12 According to an example of interest, Z is a chlorine atom and the metal halide alkaline is the alkali metal chloride. For example, the inorganic compound having a structure of argyrodite type can be chosen from inorganic compounds having a argyrodite type structure of formulas M5.4P54.300.1 C11.6, M5.4P54.1 00.301.6, M5.4P53.900.5C11.6, M5.4P53.6500.75C11.6, M5.7P54.400.30 1.3, M5.1 P54,400,301.3 and M4,8P54,100,3C11,6, in which M is as defined here.
According to another example of interest, Z is a bromine atom and the halide of alkali metal is the alkali metal bromide. For example, the inorganic compound having a argyrodite type structure can be chosen from inorganic compounds possessing an argyrodite type structure with formulas M5,4P54,300,1Br1,6, M5,4P54,100,3Br1,6, M5.4P53.900.5Br1.6, M5.4P53.6500.75Br1.6, M5.7P54.400.311-1.3, M5.1 PS4,400,3Br1.3 and M4.8P54.100.3Br1.6, in which M is as defined here. For example, the compound inorganic material having an argyrodite type structure may be a compound inorganic having an argyrodite type structure of formula M5,4P54,100,3Br1,6, in which M
is as defined here.
According to another example of interest, Z is an iodine atom and the halide of alkali metal is alkali metal iodide. For example, the inorganic compound having a structure of argyrodite type can be chosen from inorganic compounds having a structure argyrodite type with formulas M5,4P54,300,111.6, M5,4P54,100,311.6, M5,4P53,900,511,6, M5.4P53.6500.7511.6, M5.7P54.400.3I1.3, M5.1 P54.400.311.3 and M4,8P54,100,311,6, in which M is as defined here.
According to an example of interest, Z is a combination including chlorine and bromine and Alkali metal halides are a mixture of alkali metal chloride and bromide alkali metal. For example, the inorganic compound having a structure Of type argyrodite can be chosen from inorganic compounds having a structure of argyrodite type with formulas M5,4P54,100,301,0Bro,6, M5,4P54,100,3C10,8Bro,8 and M5,4P54,100,3C10,6Br1,o, in which M is as defined here.
According to an example of interest, Z is a combination including chlorine, bromine and iodine and alkali metal halides are a mixture of metal chloride alkaline, alkali metal bromide and alkali metal iodide. For example, the compound inorganic material having an argyrodite type structure can be chosen from compounds Date Received/Date Received 2022-10-12 inorganic substances having an argyrodite type structure of formulas M5,4PS4,100,3C11,oBro,510,1, M5,4PS4,100,300,75Bro,7510,1, M5,4PS4,100,3C10,7Bro,710,2 and M5,4PS4,100,3C11,0Bro,410,2, in which M is as defined here.
According to an example of interest, the alkali metal is lithium and the compound inorganic having an argyrodite type structure is based on Li2S-P255-Li2SO4-LiZ
(in which, Z is a halogen atom chosen from F, Cl, Br and I, or a combination at least two of these), the process comprising a step of direct grinding of the precursors. THE
precursors consisting of lithium sulphide (Li2S), lithium sulphate lithium (Li2SO4), phosphorus pentasulfide (P255) and a lithium halide, chosen from fluoride lithium (LiF), lithium chloride (LiCI), lithium bromide (LiBr), lithium iodide (Lil) and a mixture of at least two of these.
Non-limiting examples of inorganic compounds having a structure Of type argyrodite according to Equation 1 include inorganic compounds having a structure argyrodite type with formulas Li5,4P54,300,1Z1,6, Li5,4P54,100,3Z1,6, 1-i5,41D53,90o,5Z1,6, Li5,4P53,6500,75Z1,6 and Li5,7P54,400,3Z1,3, in which Z is as here defined. Examples non-limiting inorganic compounds having a structure of the type argyrodite according to Equation 2 includes inorganic compounds having a structure of argyrodite type of formulas Li5,1P54,400,3Z1,3 and Li4,8P54,100,3Z1,6, in which Z is as defined here.
According to an example of interest, Z is a chlorine atom and the halide of lithium is LiCI.
For example, the inorganic compound having an argyrodite type structure maybe chosen from inorganic compounds having a structure of type argyrodite formulas Li5,4PS4,300,1C11.6, Li5,4P54,100,3C11.6, Li5,4P53,900,501.6, Li5,4P53,6500,75C11,6, Li5.7P54.400.3C11.3, Li5.1P54.400.3C11.3 and Li4.8P54.100.3C11.6.
According to another example of interest, Z is a bromine atom and the halide of lithium is the LiBr. For example, the inorganic compound having a structure of type argyrodite can be chosen from inorganic compounds having a structure of type argyrodite formulas Li5,4PS4,300,1Bri,6, Li5,4P54,100,3Br1.6, Li5,4P53,900.5Br1.6, Li5.4P53.6500.75Br1.6, Li6.7P54.400.3Br1.3, Li5.1P54.400.3Br1.3 and Li4.8P54.100.3Br1.6. For example, the compound inorganic material having an argyrodite type structure may be a compound inorganic having an argyrodite type structure with formula Li5.4P54.100.3Br1.6.
Date Received/Date Received 2022-10-12 According to another example of interest, Z is an iodine atom and the halide of lithium is the Lil.
For example, the inorganic compound having an argyrodite type structure maybe chosen from inorganic compounds having a structure of type argyrodite formulas Li5,4P54,300,111.6, Li5,4P54,100,311.6, Li5,4PS3,900,511.6, Li5,4PS3,6500,7511.6, Li5.7PS4,400,311.3, Li5.1PS4,400,311.3 and Li4.8PS4,100,311.6.
According to an example of interest, Z is a combination including chlorine and bromine and Lithium halides are a mixture of the alkali metal LiCl and LiBr.
For example, the inorganic compound having an argyrodite type structure can be chosen from inorganic compounds having an argyrodite type structure of formulas Li5,4PS4,10o,3Cli,oBro,6, Li5APS 0 CI Br e1 Li PS 0 CI Br . _4.1 _ 0.3 _ 0.8_ 0.8 _ _ _5.4_ _4.1 _ 0.3 - 0.6 - 1.0.
According to an example of interest, Z is a combination including chlorine, bromine and iodine and lithium halides are a mixture of LiCl, LiBr and LiI. By example, the inorganic compound having an argyrodite type structure can be chosen from among the inorganic compounds having an argyrodite-like structure of formulas Li5APS4,100,3C11,0Bro,5101, Li5AP54,100,3C10,75Bro,7510,1, Li5AP54.1 00.3C10.7Bro,710.2 and Li 5,4P64,100,3C11,oBro,410,2.
According to another example of interest, the process as defined here is carried out in a step. It is-that is to say that, preferably, the process does not include an annealing step.
Alternately, the process may include an optional annealing step at low temperature. By example, if the process includes an annealing step, this can be carried out at a maximum temperature of approximately 300 C.
According to another example, the grinding step can be carried out using a crusher planetary. For example, the grinding step can be carried out at a speed rotation, for a specific period and in a ratio of grinding balls: precursors allowing to obtain an inorganic compound having the argyrodite type structure desired. According to some examples, the ratio of grinding balls: precursors is approximately 30 and the stage of grinding is carried out at a rotation speed included in the interval ranging from around 500 rpm at about 700 rpm for about 10 hours in order to obtain a compound inorganic having the desired argyrodite type structure. For example, the step of grinding is carried out at a rotation speed of approximately 600 rpm.

Date Received/Date Received 2022-10-12 The use of an alkali metal sulfate (e.g., Li2SO4) as as a precursor in the process as defined here could make it possible to obtain a structure argyrodite type, and this, without annealing step or with a low temperature annealing step.
Furthermore, the process as defined here could make it possible to obtain compounds inorganic substances presenting ionic conductivities substantially similar to the conductivities ionic reported for inorganic compounds obtained by processes conventional to starting from different precursors and comprising an annealing step.
Certain properties of the present inorganic compounds as obtained according to some embodiments of the present method may also differ from those demonstrated by compounds prepared by conventional methods, for example, by methods using an alkali metal oxide (e.g. Li2O) as a replacement for sulfate alkali metal (e.g. Li2SO4) as precursor. For example, according to some embodiments, the compounds obtained here can present a more great stability electrochemical, reduced H2S emission, greater density current critical, or a reduced polarization in comparison with the compounds obtained from manner conventional. The inorganic compounds described here according to certain modes of realization can demonstrate greater purity of argyrodite structure by NMR of 6Li or 31P
and/or a reduction in the relative intensity of the peaks associated with the groups P0252, PO3S and/or PO4 in 31P NMR. For example, the relative intensity of peaks P0252, PO3S and PO4 can be locate 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 process such as defined here.
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 type argyrodite as defined herein may be present as an additive and/or as material of coating in the electrode material. For example, the inorganic compound Date Received/Date Received 2022-10-12 having an argyrodite type 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 chosen from a metal oxide, a sulfide metal, a metal oxysulfide, a metal phosphate, a fluorophosphate of metal, a metal oxyfluorophosphate, metal sulfate, metal halide (e.g.
example, a metal fluoride), sulfur, 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 (AI), chromium (Cr), copper (Cu), zirconium (Zr), niobium (Nb) and their combinations, when compatible. The electrochemically active material can possibly also comprising an alkali or alkaline earth metal, for example example, lithium (Li), sodium (Na), potassium (K) or magnesium (Mg).
Non-limiting examples of electrochemically active materials include of the lithium metal phosphates, complex oxides, such as LiM'PO4 (where I am 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 cobalt (NMC). According to a variant of interest, the material electrochemically 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 chosen 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 (e.g. LiTi2(PO4)3), a metal halide (e.g. a fluoride metal), a metal sulfide, a metal oxysulfide, a carbon (for example, graphite, graphene, reduced graphene oxide, hard carbon, soft carbon, graphite Date Received/Date Received 2022-10-12 exfoliated and amorphous carbon), silicon (Si), a silicon-composite carbon (Si-C), a silicon oxide (Si0x), a silicon oxide-carbon composite (SiOx-C), 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 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 2 to 3) (for example, Mo03, Mo02, MoS2, V205, and TiNb207), spinel oxides (for example, NiCo204, ZnCo204, MnCo204, CuCo204, and CoFe204) and LiM-0 (where M"¨ is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, No., 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 doped with other elements included in smaller quantities, e.g. for modulate or optimize its electrochemical properties. The material electrochemically active can 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 (e.g.
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 (for example, microparticles and/or nanoparticles) that can be freshly formed or from commercial sources. For example, the material electrochemically active can be in the form of particles coated with a layer of coating material. The coating material may be a conductive material electronic, for example a conductive carbon coating. Alternately, THE
coating 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 type structure as defined here). By example, the coating material can be chosen from Li2SiO3, LiTa03, LiA102, Li2O-ZrO2, LiNb03 their combinations, when compatible, and other similar materials.
According to one variant of interest, the coating material comprises LiNb03.

Date Received/Date Received 2022-10-12 According to another example, the electrode material as defined here includes in besides a material electronic conductor. 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 Denkam 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 a ratio mass in the interval from 65:35 to 85:15).
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 A1203, TiO2, 5i02 and other compounds similar), salts (e.g. lithium salts) and a combination of at least two of these this. By example, the additive can be an inorganic ionic conductor chosen from compounds LISICON type, thio-LISICON, argyrodites, garnets (garnet in English), NASICON, perovskites, oxides, sulphides, phosphides, fluorides, halides of 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 considered. By example, the binder can be chosen from a polymer binder of the polyether, polyester, polycarbonate, fluoropolymer and water-soluble binder (water-soluble). According to an example, the binder is a fluoropolymer 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 to another example, the binder is a polyether type polymer binder. By example, the binder Date Received/Date Received 2022-10-12 polyether type polymer is linear, branched and/or crosslinked and is based on poly(oxide ethylene) (POE), poly(propylene oxide) (POP) or a combination both (like an 0E/P0 copolymer), and possibly includes units crosslinkable. By example, the crosslinkable segment of the polymer can be a polymer segment comprising at least one crosslinkable functional group so 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 type structure as defined here or obtained according to process as defined here.
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 solvant. According to another alternative, the electrolyte comprises a material electrolyte inorganic solid, for example, the electrolyte may 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 it is 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 encore (pentafluoroethylsulfonyl)imide (LiBETI), lithium tetrafluoroborate lithium (LiBF4), lithium bis(oxalato)borate (LiBOB), lithium nitrate (LiNO3), chloride lithium (LiCI), lithium bromide (LiBr), lithium fluoride (LiF), perchlorate Date Received/Date Received 2022-10-12 lithium (LiCI04), lithium hexafluoroarsenate (LiAsF6), trifluoromethanesulfonate lithium (LiSO3CF3) (LiTf), lithium fluoroalkylphosphate Li[PF3(CF2CF3)3]
(LiFAP), the lithium tetrakis(trifluoroacetoxy)borate Li[B(OCOCF3)4] (LiTFAB), bis(1,2-benzenediolato(2-)-0.0')lithium borate Li[B(C602)2] (LiBBB) and a combination of minus two of these.
According to another example, the solvent, if it is present in the electrolyte, can be a solvent non-aqueous. Non-limiting examples of solvents include carbonates cyclical 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), carbon dioxide methyl and ethyl (EMC) and dipropyl carbonate (DPC); lactones like y-butyrolactone (y-BL) and y-valerolactone (y-VL); acyclic ethers like the 1,2-dimethoxyethane (DME), 1,2-diethoxyethane (DEE), ethoxy methoxy ethane (EME), trimethoxymethane and ethylmonoglyme; cyclic ethers like tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane and derivatives of dioxolane; and other solvents such as dimethyl sulfoxide, formamide, acetamide, dimethylformamide, acetonitrile, propylnitrile, nitromethane, acid triesters phosphoric acid, sulfolane, methylsulfolane, carbonate derivatives of 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 PCT patent applications published under the numbers W02009/111860 (Zaghib et al.) and W02004/068610 (Zaghib et al.
al.).
According to another example, a gel electrolyte or a liquid electrolyte such as 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-Date Received/Date Received 2022-10-12 polypropylene (PP/PE/PP). For example, the separator is a separator of polymer commercial type Celgard™.
According to another example, the electrolyte is a solid polymer electrolyte. By example, the solid polymer electrolyte can be chosen from all electrolytes solid polymers known and can be chosen for its compatibility with the various elements of a cell electrochemical. Solid polymer electrolytes generally include a salt as well as one or more solid polar polymer(s), optionally reticulated(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 crosslinked. 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 may include a copolymer sequence composed of at least one lithium ion solvation segment and possibly of at least one crosslinkable segment. Preferably, the solvation segment of ions lithium is chosen from homo- or copolymers having repeating units Formula I:
-(C H2-CH-O)-Formula I
in which, R is chosen from a hydrogen atom, and a C1-C1oalkyl group or ¨(CH2-0-RaRb);
Ra is (CH2-CH2-0)y;
Rb is selected from a hydrogen atom and a C1-C1oalkyl group;
x is an integer chosen from the range 10 to 200,000; And y is an integer chosen from the range 0 to 10.

Date Received/Date Received 2022-10-12 According to another example, the crosslinkable segment of the copolymer is a segment of polymer comprising at least one crosslinkable functional group so 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 argyrodite such that defined here may be present as an additive in the electrolyte.
When the electrolyte is a polymer-ceramic hybrid solid electrolyte or A
inorganic solid electrolyte of ceramic type, the inorganic compound possessing a argyrodite type structure as defined here may be present as material of inorganic solid electrolyte (ceramic).
According to another example, the electrolyte can also optionally include of the additional components such as ionic conductive materials, inorganic particles, glass or ceramic particles and other additives same type. The additional component can be chosen for its compatibility with the different elements of an electrochemical cell. According to one example, the component additional can be substantially dispersed in the electrolyte.
Alternatively, the Additional component may be in a separate layer.
The present technology also relates to an electrochemical cell including a negative electrode, a positive electrode and an electrolyte, in which at minus one of the positive electrode or the negative electrode is as defined here in or includes a electrode material as defined here.
According to one example, the negative electrode is as defined here or comprises a material electrode as defined here. For example, the material electrochemically the electrode negative can be chosen for its electrochemical compatibility with different elements of the electrochemical cell as defined here. For example, the material electrochemically of the negative electrode material may have a potential oxidation-reduction rate 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 defined here and the negative electrode includes a material Date Received/Date Received 2022-10-12 electrochemically active selected from all electrochemically active materials assets known compatibles. For example, the electrochemically active material of the electrode negative can be chosen for its electrochemical compatibility with different elements of the electrochemical cell as defined here. Examples no limitations of electrochemically active materials of the negative electrode include alkali metals, alkaline earth metals, alloys comprising at least one alkali metal or alkaline-earth, non-alkaline and non-alkaline earth metals (for example, 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 may be initially (i.e., before cell cycling electrochemical) substantially or completely free of lithium. The negative electrode maybe lithiated in situ during the cycling of said electrochemical cell, in particular when first charge. According to one example, metallic lithium can be deposited in located on the current collector (for example, a copper current collector) when of the cycling of the electrochemical cell, particularly during the first charge. According to a another example, an alloy including metallic lithium can be generated on the surface of a collector of current (e.g. aluminum current collector) when cycling of the cell electrochemical, especially during the first charge. It is understood that the electrode negative can be generated in situ during cell cycling electrochemical, especially during the first charge.
According to another example, the positive electrode and the negative electrode are both such as defined here or both include an electrode material as here defined.
The present technology also relates to an electrochemical cell including a negative electrode, a positive electrode and an electrolyte, in which the electrolyte is as defined here.
Date Received/Date Received 2022-10-12 The present technology also relates to an electrochemical cell including a negative electrode, a positive electrode and an electrolyte, in which the electrolyte is as defined here and at least one of the positive electrode or the electrode negative is such as here defined to or comprises an electrode material as defined here.
According to one example, the positive electrode is as defined here 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 may be a battery primary (battery) or secondary (accumulator). According to one example, the battery is chosen from the group consisting of a lithium battery, a lithium battery ion, of a sodium battery, a sodium-ion battery, a magnesium battery, of a magnesium-ion battery, a potassium battery and a battery potassium ion.
According to a variant of interest, the battery is a so-called solid-state battery.
According to one example, the use of an alkali metal sulfate (for example, Li2SO4) as that precursor in the process as defined here can make it possible to reduce the costs of production by a lower quantity of Li2S used and/or by the absence of a step of annealing or decreasing the annealing temperature.
According to another example, the process as defined here can allow obtaining compounds inorganic compounds exhibiting substantially ionic conductivities similar to ionic conductivities reported for inorganic compounds obtained by of the conventional processes using different precursors and comprising a stage of annealed.
According to another example, the process as defined here can allow obtaining compounds inorganic materials having improved electrochemical stability.
According to another example, the process 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.

Date Received/Date Received 2022-10-12 According to another example, the process as defined here can allow getting more high critical current density and therefore better contact stability with the negative metallic or alloy electrode.
EXAMPLES
The following examples are for illustrative purposes and should not be used interpreted as further limiting the scope of the invention as contemplated. These examples will be better understood by referring to the appended Figures.
Unless otherwise stated, all numbers expressing quantities of components, preparation conditions, concentrations, properties, etc. used here must be understood to be modified in all cases by the term approximately. At minimum, each numerical parameter must be interpreted in light of the number of numbers significant reported and applying rounding techniques communities. By Therefore, unless otherwise stated, the numerical parameters stated in THE
this document are approximations which may vary depending on the properties desired. Notwithstanding the fact that the intervals of numerical values and the settings defining the extent of the embodiments are approximations, the values numerical presented in the following examples are also reported precisely as possible. However, any numerical value inherently contains some errors resulting from variations in experiments, test measurements, analyzes statistics, etc.
Example 1 ¨ Synthesis of argyrodites Inorganic compounds having an argyrodite type structure of formulas Li5,4PS4,300,1C11,6, Li5,4P54,100,3C11,6, Li5,4P53,900,5C11,6, Li5,4P53,6500,75C11,6, Li5,7P54,400,301,3, Li5.1PS4.400.3C11.3, Li4.8P54.100.3CI 1.6, Li5.4P54.401.6, Li5.4P54.100.30 1.6, Li5.4P53,900,501.6, Li5,4P54,100,3Br1,6, Li5,4PS4,100,3Cli,oBro,6, Li5,4P54,100,300,8Bro,8, Li5,4P54,100,3C10,6Br1,o, Li5,4PS4,100,301,0Bro,510,1, Li5,4P54,100,3C10,75Bro,7510,1, Li5,4P54,100,3C10,75ro,710,2 Li5,4P54,100,3C11,oBro,410,2, and Li6PS5CI were fully prepared in glove box under inert atmosphere (H20 < 0.1 ppm; 02 < 0.1 ppm) by a reaction process at solid state without heat treatment. The inorganic compounds were obtained by grinding from Li2S, P255, Li2SO4 or Li2O precursors and at least one Li halide (LiCI, LiBr and/or Date Received/Date Received 2022-10-12 Lil) in order to obtain powders having the desired stoichiometries according to the equations of following reactions:
(3.5-y/4-tzw) Li2S + y/4 Li2SO4 + 1/2 P2S5 + t LiCI + z LiBr + w Lil ¨>
Lin z wPS6ty z wOyClerzlw + y S Equation (3) (3.5-5/4y-t) Li2S + y/4 Li2SO4 + 1/2 P2S5 + t LiCI ¨> Li74_2yPS6_t_yOyClt Equation (4) (3.5-yt) Li2S + y Li2O + 1/2 P2S5 + t LiCI ¨> Li7_tPS6_t_yOyClt Equation (5) The grinding of the powders was carried out by two different processes.
First powder grinding process (Process 1):
The grinding of the powders was carried out using a planetary mill.
SPRAY
.. 7.
1.7 g of powder as well as 15 grinding balls having a diameter of 10 mm in zirconia yttriated (mass ratio of balls: powder = 30) were placed in a jar of grinding in 45 mL yttriated zirconia. The powders were ground at a speed of approximately 600 rpm for about 10 hours to produce inorganic compounds having a argyrodite type structure.
Second powder grinding process (Process 2):
The grinding of the powders was carried out using a planetary mill PM100. 14g of powder as well as 16 grinding balls with a diameter of 20 mm in zirconia yttriate (ratio ball mass: powder = 30) were placed in a grinding jar in yttriated zirconia .. of 250 mL. The powders were ground at a speed of approximately 650 rpm during about 10 hours to produce inorganic compounds having a structure of kind argyrodite.
Argyrodite with formula Li5.4P54 300 iCli 6 (Argyrodite 1):
An inorganic compound having an argyrodite-like structure of formula Li5,4PS4,300,1C11,6 was obtained by Process 1 of the present example from of the precursors Li2S, P255, LiCI and Li2SO4 according to Equation 3 in which, t =
1.6;z=0;w =0; and y = 0.1.

Date Received/Date Received 2022-10-12 Arqyrodite with formula Li5.4PS41003C116 (Arqyrodite 2):
An inorganic compound having an argyrodite-like structure of formula Li5,4PS4,100,3C11,6 was obtained by Process 1 of the present example from of the precursors Li2S, P2S5, LiCI and Li2SO4 according to Equation 3 in which, t =
1.6; z = 0; w=
0 ; and y = 0.3.
Arqyrodite with formula Li5.4PS39005C116 (Arqyrodite 3):
An inorganic compound having an argyrodite-like structure of formula Li5,4PS3,900,5C11,6 was obtained by Process 1 of the present example from of the precursors Li2S, P2S5, LiCI and Li2SO4 according to Equation 3 in which, t =
1.6;z=0;w =0; and y = 0.5.
Arqyrodite with formula Li5.4PS3 6500 75C11 6 (Arqyrodite 4):
An inorganic compound having an argyrodite-like structure of formula Li5,4PS3,6500,75C11,6 was obtained by Process 1 of the present example at from precursors Li2S, P2S5, LiCI and Li2SO4 according to Equation 3 in which, t =
1.6;z=0; w = 0; and y = 0.75.
Arqyrodite with formula Li5.7PS44003C113 (Arqyrodite 5):
An inorganic compound having an argyrodite-like structure of formula Li5,7PS4,400,3C11,3 was obtained by Process 1 of the present example from of the precursors Li2S, P2S5, LiCI and Li2SO4 according to Equation 3 in which, t =
1.3;z=0; w = 0; and y = 0.3.
Arqvrodite of formula Li51PS44003C113 (Arqvrodite 6):
An inorganic compound having an argyrodite-like structure of formula Li5,1PS4,400,3C11,3 was obtained by Process 1 of the present example from of the precursors Li2S, P2S5, LiCI and Li2SO4 according to Equation 4 in which, t =
1.3;z=0; w = 0; and y = 0.3.
Arqyrodite with formula Li4.5PS41003C116 (Arqyrodite 7):

Date Received/Date Received 2022-10-12 An inorganic compound having an argyrodite-like structure of formula Li4.8PS4.100.3C11.6 was obtained by Process 1 of this example from of the precursors Li2S, P2S5, LiCI and Li2SO4 according to Equation 4 in which, t =
1.6; z = 0; w = 0; and y = 0.3.
Arqyrodite with formula Li54PS44C116 (Arqyrodite 8) (comparative example):
An inorganic compound having an argyrodite-like structure of formula Li5,4PS4,401,6 was obtained for comparison by Method 1 of the present example from precursors Li2S, P2S5 and LiCI according to Equation 3 in which, t = 1.6;
z = 0; w = 0 ; and y = 0.
Arqyrodite of formula Li54PS41003C116 (Arqyrodite 9) (comparative example):
An inorganic compound having an argyrodite-like structure of formula Li5,4PS4,100,3C11,6 was obtained for comparison by Method 1 of present example to from the precursors Li2S, P2S5, LiCI and Li2O according to Equation 5 in which, t = 1.6; z = 0;w= 0;ety= 0.3.
Arqyrodite of formula Li54PS39005C116 (Arqyrodite 10) (comparative example):
An inorganic compound having an argyrodite-like structure of formula Li5,4PS3,900,5C11,6 was obtained for comparison by Method 1 of present example to from the precursors Li2S, P2S5, LiCI and Li2O according to Equation 5 in which, t = 1.6; z = 0;w= 0;ety= 0.5.
Arqyrodite with formula Li6PS5C1 (Arqyrodite 11) (comparative example):
An inorganic compound having an argyrodite-like structure of formula Li6PS5CI
was obtained for comparison by Method 1 of the present example from of the precursors Li2S, P2S5 and LiCI according to Equation 3 in which, t = 1.0; z =
0 ; w = 0; and y = O.
Arqyrodite with formula Li5,4PS4,100,3C11,0Bro,6 (Arqyrodite 12):
An inorganic compound having an argyrodite-like structure of formula Li5,4PS4,100,3C11,0Bro,6 was obtained by Process 1 of the present example at from Date Received/Date Received 2022-10-12 precursors Li2S, P2S5, LiCI, LiBr and Li2SO4 according to Equation 3 in which, t = 1.0; z =
0.6; w = 0; and y = 0.3.
Arqyrodite with formula Li5.4PS41003C10813ro 8 (Arqyrodite 13):
An inorganic compound having an argyrodite-like structure of formula Li5,4PS4,100,3C10,8Bro,8 was obtained by Process 1 of the present example at from precursors Li2S, P2S5, LiCI, LiBr and Li2SO4 according to Equation 3 in which, t = 0.8; z =
0.8; w = 0; and y = 0.3.
Arqyrodite with formula Li5.4PS41003C106Br1 0 (Arqyrodite 14):
An inorganic compound having an argyrodite-like structure of formula Li5,4PS4,100,3C10,6Br1,0 was obtained by Process 1 of the present example at from precursors Li2S, P2S5, LiCI, LiBr and Li2SO4 according to Equation 3 in which, t = 0.6; z =
1; w = 0; and y = 0.3.
Arqyrodite with formula Li5.4PS41003Br1 6 (Arqyrodite 15):
An inorganic compound having an argyrodite-like structure of formula Li5,4PS4,100,3Br1,6 was obtained by Process 1 of the present example from of the precursors Li2S, P2S5, LiBr and Li2SO4 according to Equation 3 in which, t =
0; w = 0; z =
1.6; and y = 0.3.
Arqyrodite with formula Li5,4PS4,1003C11 oBrosloi (Arqyrodite 16):
An inorganic compound having an argyrodite-like structure of formula Li5,4PS4,100,3C11,0Bro,510,1 was obtained by Process 1 of the present example from precursors Li2S, P2S5, LiCI, LiBr, Lil and Li2SO4 according to Equation 3 in which, t = 1.0; z = 0.5; w = 0.1 and y = 0.3.
Arqvrodite of formula Lis 4PS41003C1075Bro 75101 (Arqvrodite 17):
An inorganic compound having an argyrodite-like structure of formula Li5,4PS4,100,3C10,75Bro,7510,1 was obtained by Method 1 of the present example from precursors Li2S, P2S5, LiCI, LiBr, Lil and Li2SO4 according to Equation 3 in which, t = 0.75;
z = 0.75; w = 0.1; and y = 0.3.

Date Received/Date Received 2022-10-12 Arqyrodite with formula Li5.4PS4.1003C107Br0710 2 (Arqyrodite 18):
An inorganic compound having an argyrodite-like structure of formula Li5,4PS4,100,3C10,7Bro,710,2 was obtained by Process 1 of this example from precursors Li2S, P2S5, LiCI, LiBr, Lil and Li2SO4 according to Equation 3 in which, t = 0.7; z = 0.7; w = 0.2; and y = 0.3.
Arqyrodite with formula Li5,4PS4,1003C11 oBro410 2 (Arqyrodite 19):
An inorganic compound having an argyrodite-like structure of formula Li5,4PS4,100,3Cli oBro,410,2 was obtained by Method 1 of the present example from precursors Li2S, P2S5, LiCI, LiBr, Lil and Li2SO4 according to Equation 3 in which, t = 1.0; z = 0.4; w = 0.2; and y = 0.3.
Arqyrodite with formula Li5.4PS41003C116 (Arqyrodite 20):
An inorganic compound having an argyrodite-like structure of formula Li5,4PS4,100,3C11,6 was obtained by Process 2 of the present example from of the precursors Li2S, P2S5, LiCI and Li2SO4 according to Equation 3 in which, t =
1.6; z = 0; w = 0; and y = 0.3.
Arqyrodite with formula Li5.4PS41003C108Bro 8 (Arqyrodite 21):
An inorganic compound having an argyrodite-like structure of formula Li5,4PS4,100,3C10,8Bro,8 was obtained by Process 2 of the present example at from precursors Li2S, P2S5, LiCI, LiBr and Li2SO4 according to Equation 3 in which, t = 0.8; z =
0.8; w = 0; and y = 0.3.
Example 2 ¨ Characterization by X-ray diffraction (XRD) of the compounds inorganic with an argyrodite type structure The crystal structure of the argyrodites prepared in Example 1 was studied by XRD.
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 a cobalt X-ray source.

Date Received/Date Received 2022-10-12 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 6, the pics corresponding to the impurities Li3PO4, Li2S and LiCI have been identified respectively by solid lines, dashed lines, and em-dash-dot-lines point. Peak D
comes from the dome used during the XRD analysis. The other peaks correspond to the argyrodite type structure.
Figure 1 shows the X-ray diffraction patterns obtained for THE
argyrodites (Argyrodites 1 to 4 and 8). Ray diffraction patterns X presented in Figure 1 show that the argyrodite type structure is well obtained for all compositions. It is possible to observe the presence of a quantity substantially more significant amount of impurities (LiCl, Li2S and Li3PO4) for the most compositions rich in oxygen (y> 0.3) (Argyrodites 3 and 4).
Figure 2 presents the X-ray diffraction patterns obtained for THE
argyrodites (Argyrodites 2 and 5 to 7). Figure 2 shows that the structure argyrodite has good was obtained for t = 1.3 and y = 0.3 (Argyrodites 5 and 6), for both syntheses (Equations 3 and 4). It is possible to observe in Figure 2, the presence of less Li2S
residual for the structure of Argyrodite 6 than for the structure of Argyrodite 5. Figure 2 also shows a degradation of the structure for the argyrodite of formula Li4.8PS4.100.3C11.6 in which, t = 1.6 and y = 0.3 (Argyrodite 7). He is possible to observe a substantially greater amount of residual LiCI, but no trace of Li2S. This indicates that an argyrodite type structure including less than lithium could induce a mixture of argyrodite type phases and parasitic phases (by example, LiCI).
Figure 3 shows the X-ray diffraction patterns for the argyrodites obtained from the precursors Li2SO4 (Argyrodites 2 and 3) and Li2O
(Argyrodites 9 and 10).
Figure 3 shows that for an oxygen level of 0.3 (Argyrodites 2 and 9) it there is no significant difference observable on the structure of argyrodite from compounds inorganic compounds obtained from the two different precursors. However, for a rate oxygen of 0.5 argyrodite prepared from Li2O (Argyrodite 10) contains Date Received/Date Received 2022-10-12 substantially more impurities (in particular LiCI) and has a structure substantially less well defined compared to argyrodite prepared at from Li2SO4 (Argyrodite 3). Thus, it is possible to obtain argyrodites oxidized substantially purer over a wide composition range from precursor Li2SO4 compared to the commonly used Li2O precursor.
Figure 4 shows the X-ray diffraction patterns for the argyrodites obtained from the precursor Li2SO4 and a mixture of halides including LiCI 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 peaks decrease when the Br level increases. This can be attributed to the increase in mesh parameter, a phenomenon known in the literature.
Figure 5 shows the X-ray diffraction patterns for the argyrodites obtained from the precursor Li2SO4 and a mixture of halides including LiCI, LiBr and Lil (Argyrodites 16 to 19). Figure 5 shows that the structure argyrodite is well preserved, even with the mixture of the three halides.
It is thus possible to obtain the compound with an oxidized argyrodite structure whatever they are halide composition and mixing with oxidation from precursor Li2SO4.
Figure 6 shows the X-ray diffraction patterns for the Argyrodites 2 and 13 obtained from the precursor Li2SO4 in small volume jars (according to Process 1 presented in Example 1) and Argyrodites 20 and 21 obtained in go from Li2SO4 precursor in larger volume jars (according to Process 2 introduced to 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 indeed preserved whatever the composition of the argyrodite and whatever the volume of synthesis demonstrating that the process thus described could be applied on a scale industrial.
Example 3 ¨ Characterization by nuclear magnetic resonance (NMR) of inorganic compounds with an argyrodite-like structure Date Received/Date Received 2022-10-12 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 (magic angle rotation) technique in using a Bruker Avance NEO 500 MHz spectrometer equipped with a triple resonance probe of 4 mm whose maximum rotation speed at the magic angle is 15 kHz.
Figures 7 and 8 respectively show 6Li NMR and 31P NMR spectra.
obtained for argyrodites of composition Li5,4P54,100,3C11,6 obtained from precursors Li2SO4 (Argyrodite 2) and Li20 (Argyrodite 9).
For the two argyrodites (Argyrodites 2 and 9), the main peak on the 6Li NMR spectra presented in Figure 7 corresponds to argyrodite, while the peak secondary corresponds to LiCl residues.
For Argyrodites 2 and 9, the main peak on the 31P NMR spectra shown in Figure 8 corresponds to argyrodite, while the secondary peaks correspond to phases P2564-, P0252, P035 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 Argyrodite 2 96.7 2.3 0.5 0.4 0.1 Argyrodite 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) makes it possible to significantly reduce the training of secondary phases P0252, P035 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 Li2SO4 precursor and therefore generates fewer phases additional.
This makes it possible to differentiate an argyrodite synthesized from Li2SO4 from an argyrodite prepared from Li20 or any other source of oxygen as precursor.
Figures 9 and 10 respectively show 6Li NMR and 31P NMR spectra.
obtained for argyrodite of formula Li4.8P54.100.3C11.6 obtained from Li2SO4 precursors (Argyrodite 7).
It is possible to observe on the 6Li NMR spectrum presented in Figure 9 a peak at 1.2 ppm corresponding to an argyrodite phase with six lithiums and one chlorine, a second peak at 0.2 Date Received/Date Received 2022-10-12 ppm corresponding to an argyrodite phase with a structure having an excess of chlorine and a third peak at -1.1 ppm corresponding to LiCI.
It is possible to observe on the 31P NMR spectrum presented in Figure 10 a main peak corresponding to argyrodite and three secondary peaks corresponding to phases of P2S64-, P02S2 and PO3S. Figure 10 also shows an enlargement of the peak main showing that it is decomposed into three peaks corresponding to a (P1), two (P2) and three (P3) chlorine in the secondary structure of phosphorus. The excess simultaneous of P1 and P3 confirm the presence of two types of argyrodites, with low and a strong chlorine fraction.
Thus, a substantial decrease in lithium levels can lead to presence of least two phases of argyrodites.
Figures 11 and 12 respectively show 6Li NMR and 31P NMR spectra.

obtained for argyrodite of formula Li5,4PS4,100,3C10,8Bro,8 (Argyrodite 13) and formula Li5,4PS4,100,3C11,0Bro,510,1 (Argyrodite 16) obtained from the precursor Li2SO4. Peak main on the 6Li NMR spectra presented in Figure 11 corresponds to argyrodite. He is possible to observe on the 31P NMR spectra presented in Figure 12 a main peak corresponding to argyrodite and the presence of weak secondary peaks corresponding to phases of P2S64- and P02S2. This confirms the results obtained by diffraction of X-rays, namely obtaining a pure oxidized argyrodite phase from Li2SO4 what whatever the halide composition.
Example 4 ¨ Generation of H2S during exposure of inorganic compounds having an argyrodite type structure in air Security tests were carried out to assess the impact of argyrodite on the generation of H2S. Approximately 10 mg (3 mg) of argyrodite powder was placed in a sealed cell under an inert atmosphere.
A flow of air was introduced into the sealed cell at a flow 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 gaseous H2S
generated at been measured approximately every 15 seconds with a multigas detector (MSA
ALTAIR™

Date Received/Date Received 2022-10-12 5X) previously calibrated and placed at the cell outlet. From these data, the volume of H2S gas generated normalized by the mass of argyrodite was calculated.
The results of these analyzes are presented in Figure 13. Figure 13 shows a graph of the volume of H2S gas generated per gram of argyrodite powder (mL/g) as a function of time (hours) for Argyrodites 2 (Li5,4PS4,100,3C11,6) (dotted line), 7 (Li4,8PS4,100,3C11,6) (em-dash-dot line), 8 (Li5,4PS4,401,6) (dashed line), 11 (Li6PS5CI) (solid line), 13 (Li5,4PS4,100,3C10,8Bro,8) (dot dash line point) and 16 (Li5,4PS4,100,3C11,0Bro,510,1) (small dash line) prepared in Example 1.
It is possible to observe that a classic argyrodite of the Li6PS5CI type (Argyrodite 11) generates a substantially higher volume of H2S gas than an argyrodite doped with chlorine of type Li5,4PS4,4C11,6 (Argyrodite 8), demonstrating the interest of chlorine doping on security. It is also possible to observe that argyrodites at basis of Li2SO4 precursor also makes it possible to reduce the volume of gaseous H2S
as this is the case for argyrodite Li5,4PS4,100,3C11,6 (Argyrodite 2). The addition of bromine and/or iodine from the previous composition while maintaining the same rate oxygen and lithium makes it possible to once again reduce the generation of H2S. Finally, the Figure 13 shows that an argyrodite type structure generated from the precursor Li2SO4 comprising a significant reduction in lithium (Argyrodite 7) makes it possible to reduce increase the volume of gaseous H2S generated, and thus improve safety while in reducing production costs through a lower quantity of Li2S
used and by the absence or reduction of the annealing step.
Example 5 ¨ Ionic conductivity of inorganic compounds having a argyrodite-like structure a) Preparation of symmetrical cells for conductivity measurements ionic Symmetrical cells were assembled according to the following procedure in order to to measure the ionic conductivity of inorganic compounds having a structure of kind argyrodite prepared in Example 1.
Pellets were prepared by compressing 160 mg of compound powder inorganic material having an argyrodite type structure prepared in Example 1 between two stainless steel electrodes under a pressure of 360 MPa. The pellets placed between Date Received/Date Received 2022-10-12 two stainless steel electrodes were then assembled into cells of conductivity sealed in glove box under maintained inert atmosphere to one pressure of 20 M Pa.
The symmetrical cells were assembled according to the indicated configurations At Table 2.
Table 2. Symmetric cell configurations Value Value Value Value Symmetric Cell Argyrodite Argyrodite of t of w of z of y Cell 1 Argyrodite 1 Li5.4PS4.300.1C11.6 1.6 0 0 0.1 Cell 2 Argyrodite 2 Li5.4PS4.100.3C11.6 1.6 0 0 0.3 Cell 3 Argyrodite 3 Li5.4PS3.900.5C11.6 1.6 0 0 0.5 Cell 4 Argyrodite 4 Li5.4PS3.6500.75C11.6 1.6 0 0 0.75 Cell 5 Argyrodite 5 Li5.7PS4.400.3C11.3 1.3 0 0 0.3 Cell 6 Argyrodite 6 Li5.1PS4.400.3C11.3 1.3 0 0 0.3 Cell 7 Argyrodite 7 Li4.8PS4.100.3C11.6 1.6 0 0 0.3 Cell 8 1.6 0 0 0 Argyrodite 8 Li5,4PS4,4C11,6 (comparative cell) Cell 9 1.6 0 0 0.3 Argyrodite 9 Li5,4PS4,100,3C11,6 (comparative cell) Cell 10 1.6 0 0 0.5 Argyrodite 10 Li5.4PS3.900.5Cl1.6 (comparative cell) Cell 12 Argyrodite 12 Li5,4PS4,100,3C11,oBro,6 1.0 0 0.6 0.3 Cell 13 Argyrodite 13 Li5,4PS4,100,3Clo,8Bro,8 0.8 0 0.8 0.3 Cell 14 Argyrodite 14 Li5,4PS4,100,3Clo,6Br1,o 0.6 0 1.0 0.3 Cell 15 Argyrodite 15 Li5.4PS4.100.3Br1.6 0 0 1.6 .. 0.3 Cell 16 Argyrodite 16 Li5,4PS4,100,3C11,0Bro,510,1 1.0 0.1 0.5 0.3 Cell 17 Argyrodite 17 Li5,4PS4,100,3C10,75Bro,7510,1 0.75 0.1 0.75 0.3 Cell 18 Argyrodite 18 Li5.4PS4.100.3C10.7Bro.710.2 0.7 0.2 0.7 0.3 Cell 19 Argyrodite 19 Li5,4PS4,100,3C11,0Bro,410.2 1.0 0.2 0.4 0.3 Cell 20 Argyrodite 20 Li5.4PS4.100.3C11.6 1.6 0 0 0.3 Cell 21 Argyrodite 21 Li5,4PS4,100,3Clo,8Bro,8 0.8 0 0.8 0.3 b) Measurement of ionic conductivity of symmetric cells Ionic conductivity measurements of symmetrical cells assembled at The example 5(a) were carried out with a VMP-300 multichannel potentiostat (BioLogic).
THE
measurements were carried out 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 ionic conductivity measurement was obtained after stabilization of approximately one hour from oven temperature to temperature. Conductivity ionic was extracted based on an equivalent circuit used to extract the resistance associated with Date Received/Date Received 2022-10-12 measured pellet. The lines were obtained for the symmetrical cells prepared for Example 5(a). The slope of these lines corresponds to the activation energy and has a value of approximately 0.3 eV.
Figure 14 presents the results of ionic conductivity measured in function of the temperature for Cells 1 (.), 2 (A), 3 (*), 4 (*) and 8 (o). He is possible to observe in Figure 14 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 argyrodite of formula Li5,4PS4,100,3C11,6 (Cell 2) prepared from Li2SO4 is substantially identical to that of argyrodite free of oxide (Cell 8).
Figure 15 presents the results of ionic conductivity measured in function of the temperature for Cells 2 (A), 5 (o), 6 (.) and 7 (*). Figure 15 shows values of substantially similar ionic conductivity for Cells 5 and 6 including respectively Argyrodites 5 and 6 (t = 1.3 and y = 0.3) obtained by two syntheses different (respectively Equations (3) and (4)). For t = 1.6 and y =
0.3, Figure 15 also shows substantially higher ionic conductivity values Weak To Cell 7 including Argyrodite 7 in comparison with those of Cell 2 including Argyrodite 2. As can be observed, thanks to the precursor Li2SO4, it is possible to modulate the composition (for example, the level of lithium, oxygen and of sulfur) of an oxysulfurized lithium argyrodite while remaining substantially in the same range of ionic conductivity. It is also possible to observe that one significant lithium deficiency induces a reduction in conductivity ionic.
Figure 16 presents the results of ionic conductivity measured in function of the temperature for Cells 2 (o), 3 (.), 9 (A) and 10 (*). Figure 16 shows that for the same composition, the ionic conductivity of the argyrodites obtained at go from precursor Li2SO4 (Argyrodites 2 and 3) is significantly greater than that of argyrodites obtained from the Li2O precursor (Argyrodites 9 and 10). As demonstrated in Figure 8, the use of Li2SO4 type precursor allows better incorporation oxygen within the argyrodite structure and this results in a increase of conductivity as demonstrated by the results in Figure 16.

Date Received/Date Received 2022-10-12 Figure 17 presents the results of ionic conductivity measured in function of the temperature for Cells 2 (.), 12 (.), 13 (A), 14 (#) and 15 (*). There Figure 17 shows that the modulation of composition from the two halogens (i.e., the chlorine and bromine) does not substantially modify the ionic conductivity, in now from high conductivities. It should be noted that the Argyrodite 14 presents the best conductivity.
Figure 18 presents the results of ionic conductivity measured in function of the temperature for Cells 16 (.), 17 (.), 18 (A) and 19 (*). Figure 18 show that incorporation of the three halogens (i.e., chlorine, bromine and iodine) in the presence of Li2SO4 does not substantially modify the ionic conductivity, in now from high conductivities. It is possible to observe that an iodine level of 0.1 provides better conductivity than at a higher rate.
Thus by combining the different analyses, thanks to the Li2SO4 precursor, it is possible to obtain oxysulfurized argyrodites having the same conductivities ionic that those without oxide and improved compared to the use of the precursor Li2O. Moreover, he is possible to modulate the composition of argyrodites based on Li2SO4 with different halide rate and type while maintaining high ionic conductivity.
Moreover, this modulation makes it possible to improve security while maintaining good properties of conduction.
Figure 19 presents the ionic conductivity results measured in function of the temperature for Cells 2 (o), 20 (.), 13 (A) and 21 (*). Figure 19 show that whatever the composition of the argyrodite based on Li2SO4, the increase in volume synthesis makes it possible to slightly increase the ionic conductivity. This demonstrates that the proposed solutions can be easily applied at scale industrial, and this, without loss of performance.
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.
Date Received/Date Received 2022-10-12 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 reactions redox tests substantially representative of the final compositions 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 negative metallic lithium electrode were then compressed and assembled in sealed cells closed in a glove box under atmosphere inert.
The pseudo-batteries were assembled according to the configurations presented in the Table 3.
Table 3. Pseudo-battery configurations Composition of the pseudo-composite positive electrode Composition Composition Pseudo-battery Material argyrodite the electrolyte the electrode Conductive Argyrodite negative solid electronic Li5,4PS4,100,3C11,6 VGCFs Li5.4PS4.100.3C11.6 Lithium Cell 22 (Argyrodite 2) 5 cYo (Argyrodite 2) metallic 95 c/o mass mass Li5,4PS4,100,3C11,6 VGCFs Cell 23 Li5.4PS4.100.3C11.6 Lithium (Argyrodite 9) 5 cYo (Comparative cell) (Argyrodite 9) metallic 95 c/o mass mass b) Cyclic voltammetry The electrochemical stability in oxidation of pseudo-batteries such as described in Example 6(a) was measured using a VMP-300 multichannel potentiostat (BioLogic).
Figure 20 presents the cyclic voltammetry results obtained for the cell 22 and for Cell 23 (comparative battery) recorded at a speed of scan of 0.05 mV/s in the potential range of lithium oxide, nickel oxide, manganese and of cobalt (NMC), i.e. between 2.5 V and 4.2 V vs Li/Li + at a temperature about 30 C. The Date Received/Date Received 2022-10-12 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 the lithium metallic. In the potential range of the NMC, it is possible to observe a weak redox reaction for the two pseudo-batteries, with a density of fluent weaker generated for Cell 22 including 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 argyrodite obtained using Li2SO4 as a precursor. Thus, argyrodite obtained in 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 type structure The electrochemical properties of Argyrodite 2 prepared in Example 1 have been studied.
a) Preparation of composite positive electrode material 35% by weight of Argyrodite 2 powder prepared in Example 1 were mixed at 65%
mass of LiNi particles0.6M no.2Co0.202 (NMC 622) and 5% by mass of a blend carbon black Li400 (Denkamc) and VGCFs (75:25 mass ratio). THE
powders dry were mixed using a vortex mixer (from vortex type) then with mortar in order to homogenize the positive electrode material composite.
b) Configuration of the electrochemical cell (Cell 24) The electrochemical cell was assembled according to the following procedure.
A solid electrolyte was prepared in 80 mg of argyrodite 2 powder prepared for Example 1 in a mold of 10mm in diameter under a pressure of 200 M Pa.
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 aluminum current.

Date Received/Date Received 2022-10-12 The contents of the mold including the solid electrolyte layer, the layer positive electrode composite and the aluminum current collector were then compressed under a pressure of 360 MPa for approximately 10 minutes. A lithium electrode metallic mm diameter on a stainless steel current collector was then added 5 facing the solid electrolyte layer and the whole was compressed under a pressure of 120 MPa for approximately 5 minutes.
The electrochemical cell was then assembled, in a cell of waterproof cycling closed in a glove box under an inert atmosphere maintained at a pressure of 20 MPa.
c) Electrochemical behavior of the electrochemical cell 10 Cell 24 assembled in Example 7(b) was cycled between 2.5 V and 4.5 V vs. Li/Li. THE
first five cycles were carried out at C/10, followed by four cycles at C/4, then the Aging experiments were carried out at a load current and dump constant of C/2 at a temperature of 30 C for a surface capacity of 1.8 mAh/cm2.
Figure 21 shows a graph of charge (.) and discharge capacity (o) and the coulombic efficiency (A) as a function of the number of cycles per 100 cycles.
Figures 22 and 23 show the discharge profiles at different charging currents and of dump. More particularly, Figures 22 and 23 respectively show A
graph of potential versus discharge capacity and time hours.
It is possible to observe that the electrochemical cell has C/10, C/4 and C/2 provided respectively a capacity of approximately 170 mAh.g-1, 160 mAh.g-1 and 150 mAh.g-1.
It is possible to observe substantial capacity retention after 100 cycles, thus allowing stability of performance in aging as demonstrated to the Figure 22. It is possible to observe adequate cyclability of the cell electrochemical at C/2 in charge and discharge at a temperature of 30 C demonstrating the beautiful stability electrochemical of Argyrodite 2 in potential and with respect to the material driver electronic (i.e., the mixture of Li400 carbon black and VGCFs) and the 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 Date Received/Date Received 2022-10-12 than envisaged. References, patents or scientific literature documents referred in this application are incorporated herein by reference in their completeness and all purposes.

Date Received/Date Received 2022-10-12

Claims (66)

1. A process for preparing an inorganic compound having a structure of argyrodite type based on an alkali metal, the process comprising a step of grinding of alkali metal sulfide, alkali metal sulfate, pentasulfide phosphorus and an alkali metal halide, in which the alkali metal is chosen among lithium, sodium and potassium, for example, the alkali metal is THE
lithium. 2. Method according to claim 1, in which the metal halide alkaline is chosen from alkali metal fluoride, alkali metal chloride, bromide of alkali metal, alkali metal iodide and a mixture of at least two of these this. 3. Method according to claim 2, in which the metal halide alkaline is the alkali metal chloride. 4. Method according to claim 2, in which the metal halide alkaline is the alkali metal bromide. 5. Method according to claim 2, in which the metal halide alkaline is alkali metal iodide. 6. Method according to claim 2, in which the metal halide alkaline is a mixture of alkali metal chloride and alkali metal bromide. 7. Method according to claim 2, in which the metal halide alkaline is a mixture of alkali metal chloride, alkali metal bromide and the iodide of alkali metal. 8. Method according to any one of claims 1 to 7, in which the structure of argyrodite type has the formula M6_,PS5_,_yOyZi+x, in which M is the metal alkaline chosen from Li, Na and K, for example M is Li, Z is an atom halogen chosen from F, Cl, Br and I and x and y are non-zero numbers selected to achieve electroneutrality (e.g., 0 < x ~ 1 and 0 < y ~ 1). 9. Method according to claim 8, in which the type structure argyrodite is chosen from inorganic compounds having a structure of type argyrodite Date Received/Date Received 2022-1 0-1 2 of formulas M5.4PS4.300.1Cl 1.6, M5.4P54.100.3C11.6, M5.4PS3.900.50 1.6, M5,4P53,6500,75C11,6, M5,7PS4,400,3C11,3, M5,4P54,100,3C11,6, M5,4 PS3,900,5C11,6, M5,4P54,100,3Br1,6, M5,4P54,100,30Bro,6, M5,4P54,100,3C10,8BrO,8, M5,4P54,100,3C10,6B r, M5,4P54,100,30B r0,510,1, M5,4P54,100,300,7513r0,7510,1, M5.4 P54.100.30 0.7 Bro.710.2 and IV15,4P54,100,3C1Bro,410,2, in which M is as defined here in claim 8. 10. Method according to claim 8, in which the type structure argyrodite is chosen from inorganic compounds having a structure of type argyrodite of formulas Lis,4P54,300,1Cl 1.6, I¨
is,4P54,100,3C11,6,Li5APS3,900,50 1.6, LisAP53,6500,75C11.6, Li5.7PS4,400,3C11.3, LisAP54,100,3C11,6, Lis,4 P53,900,501,6, LisAP54,100,3B ri ,6, LisAP54,100,3CIBro,6, LisAP54,100,3C10,8Bro,8, LisAP54,100,3C10,6Br, LisAP54,100,3CIBro,510,1, LisAP54,100,3C10,75Bro,7510,1, LisAP54,100,3C10,7Bro,710,2 and ReadAP54,100,3CIBro,410,2. 11. Method according to any one of claims 1 to 7, in which the structure argyrodite type has formula M
¨ -6-x-2yPS5-x-yOyZ1+x, in which M is the metal alkaline chosen from Li, Na and K, for example M is Li, Z is an atom halogen chosen from F, Cl, Br and I and x and y are numbers other than zero (by example, 0 < x ~ 1 and 0 < y ~ 1). 12. Method according to claim 11, in which the type structure argyrodite deficient in lithium is chosen from inorganic compounds possessing a argyrodite type structure of formulas M5,2P54,300,1C11,6, M5,1P54,400,3C11,3 and M4,8P54,100,3C11,6, in which M is as defined here in claim 11. 13. Method according to claim 12, in which the type structure argyrodite is chosen from inorganic compounds having a structure of type argyrodite of formulas Lis,2P54,300,1 CI 1.6, 1-I5,1PS4,400,301.3 and Li4.8P54.100.3C11.6. 14. Method according to any one of claims 1 to 13, in which the stage of Grinding is carried out using a planetary mill. 15. Method according to any one of claims 1 to 14, in which the stage of grinding is carried out at a rotation speed included in the interval going from about 500 rpm to about 700 rpm.

Date Received/Date Received 2022-1 0-1 2 16. Method according to any one of claims 1 to 14, in which the stage of Grinding is carried out at a rotation speed of approximately 600 rpm. 17. Method according to any one of claims 1 to 15, in which the stage of Grinding is carried out for approximately 10 hours. 18. Method according to any one of claims 1 to 17, in which the stage of grinding is carried out in a grinding ball: precursor ratio of approximately 30. 19. Method according to any one of claims 1 to 18, which comprises in in addition to an annealing step carried out at a maximum temperature of around 300 vs. 20. Method according to any one of claims 1 to 18, which is free from a annealing step. 21. An inorganic compound having an argyrodite type structure obtained according to the process as defined in any one of claims 1 to 20. 22. An electrode material comprising an electrochemically active material and one inorganic compound having an argyrodite type structure as defined to the claim 21 or obtained according to the process as defined in any one of the claims 1 to 20. 23. Electrode material according to claim 22, in which the compound inorganic having an argyrodite type structure is present as an additive. 24. Electrode material according to claim 22 or 23, in which the compound inorganic having an argyrodite type structure is present as covering material. 25. Electrode material according to claim 24, in which the material of coating forms a coating layer on the surface of the material electrochemically active. 26. Electrode material according to any one of claims 22 to 25, in which the electrochemically active material is chosen from metal oxide, a sulfide metal, a metal oxysulfide, a metal phosphate, a fluorophosphate of metal, a metal oxyfluorophosphate, a metal sulfate, a metal halide, A

Date Received/Date Received 2022-1 0-1 2 metal fluoride, sulfur, selenium and a combination of two or more of these. 27. Electrode material according to claim 26, in which the metal of the material 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), niobium (Nb) and a combination of au less two of these. 28. Electrode material according to claim 26 or 27, in which 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). 29. Electrode material according to any one of claims 22 to 28, In wherein the electrochemically active material is a metal and carbon oxide lithium. 30. Electrode material according to claim 29, in which the oxide of metal and lithium is a mixed oxide of lithium, nickel, manganese and cobalt (NCM). 31. Electrode material according to any one of claims 22 to 25, in which the electrochemically active material is chosen from a non-alkaline metal or No-alkaline earth, 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), composite tin-carbon (Sn-C), a tin oxide (SnO,), a tin oxide-carbon composite (SnOx-C), and a combination of at least two of these. 32. Electrode material according to any one of claims 22 to 31, In wherein the electrochemically active material further comprises an element doping. 33. Electrode material according to any one of claims 22 to 32, In wherein the electrochemically active material further comprises a material coating.

Date Received/Date Received 2022-1 0-1 2 34. Electrode material according to claim 33, in which the material coating is an electronic conductive material. 35. Electrode material according to claim 34, in which the material driver electronics is carbon. 36. Electrode material according to claim 33, in which the material coating is chosen from Li2SiO3, LiTa03, LiAl02, Li20-Zr02, LiNb03, others materials similar coatings and a combination of at least two of these. 37. Electrode material according to any one of claims 36, in whichone coating material is LiNb03. 38. Electrode material according to any one of claims 22 to 37, which further comprises at least one electronic conductive material. 39. Electrode material according to claim 38, in which the material driver electronic is chosen from the group consisting of carbon black, black acetylene, graphite, graphene, carbon fibers, nanofibers of carbon, carbon nanotubes, and a mixture of at least two of these this. 40. Electrode material according to claim 39, in which the material driver electronic is a mixture of carbon black and carbon fibers formed in gas phase (VGCFs). 41. Electrode material according to any one of claims 22 to 40, which further comprises at least one additive. 42. Electrode material according to claim 41, in which 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. 43. Electrode material according to any one of claims 22 to 42, which further comprises a binder.

Date Received/Date Received 2022-1 0-1 2 44. Electrode material according to claim 43, in which the binder is chosen from the group consisting of a polymer binder of the polyether, polycarbonate or polyester, a fluoropolymer and a water-soluble binder. 45. An electrode comprising the electrode material as defined in one any of claims 22 to 44 on a current collector. 46. A self-supporting electrode comprising the electrode material such as set to any one of claims 22 to 44. 47. An electrolyte comprising an inorganic compound having a structure of argyrodite type as defined in claim 21 or obtained according to process such as defined in any one of claims 1 to 20. 48. Electrolyte according to claim 47, which is an electrolyte liquid comprising a salt in a solvent. 49. Electrolyte according to claim 47, which is a gel electrolyte including a salt in a solvent and optionally a solvating polymer. 50. Electrolyte according to claim 47, which is a polymer electrolyte solid comprising a salt in a solvating polymer 51. Electrolyte according to any one of claims 47 to 50, in which THE
inorganic compound having an argyrodite type structure is present in as an additive. 52. Electrolyte according to claim 47, which is a solid electrolyte inorganic. 53. Electrolyte according to claim 47, which is a solid electrolyte hybrid polymer-ceramic. 54. Electrolyte according to claim 52 or 53, in which the compound inorganic having an argyrodite type structure is present as a material of inorganic solid electrolyte. 55. Electrolyte according to any one of claims 47 to 54, which includes in in addition to at least one additional component.
Date Received/Date Received 2022-1 0-1 2 56. Electrolyte according to claim 55, 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. 57. An electrochemical cell comprising a negative electrode, a electrode positive and an electrolyte, in which at least one of the electrode positive or the negative electrode is as defined in claim 45 or 46 or understand an electrode material as defined in any one of the claims 22 to 44. 58. An electrochemical cell comprising a negative electrode, a electrode positive and an electrolyte, in which the electrolyte is as defined in moon any of claims 47 to 56. 59. Electrochemical cell according to claim 57 or 58, in which the electrode negative comprises an electrochemically active material comprising a metal alkaline, 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 intermetallic compound. 60. Electrochemical cell according to claim 59, in which the material electrochemically active negative electrode includes lithium metallic or an alloy including or based on metallic lithium. 61. Electrochemical cell according to any one of claims 57 to 60, In in which the positive electrode is pre-lithiated and the negative electrode is substantially free of lithium. 62. Electrochemical cell according to claim 61, in which the negative electrode is lithiated in situ during the cycling of said electrochemical cell. 63. An electrochemical accumulator comprising at least one cell electrochemical as defined in any one of claims 57 to 62. 64. Electrochemical accumulator according to claim 63, in which said electrochemical accumulator is a battery is chosen from a battery At Date Received/Date Received 2022-1 0-1 2 lithium, a lithium-ion battery, a sodium battery, a sodium-ion, a magnesium battery, a magnesium-ion battery. 65. Electrochemical accumulator according to claim 64, in which said battery is a lithium battery or lithium-ion battery. 66. Electrochemical accumulator according to claim 65, in which said An electrochemical accumulator is a so-called solid-state battery.

Date Received/Date Received 2022-1 0-1 2