Coating materials based on unsaturated aliphatic hydrocarbons and uses thereof in electrochemical applications

Abstract

The present technology relates to a coating material comprising at least one branched or linear unsaturated aliphatic hydrocarbon having 10 to 50 carbon atoms and having at least one carbon-carbon double or triple bond for use in electrochemical applications, in particular in electrochemical storage cells such as batteries referred to as all-solid-state batteries. The present technology also relates to coated particles comprising the coating material and methods for manufacturing same. The invention also describes electrode materials, electrodes, electrolytes, coating materials for current collectors and current collectors comprising the coated particles, and the use thereof in electrochemical cells, for example, in electrochemical storage cells, in particular in batteries referred to as all-solid-state batteries.

Description

[0001] COATING MATERIALS BASED ON UNSATURATED ALIPHATIC HYDROCARBONS AND THEIR USES IN APPLICATIONS

[0002] ELECTROCHEMICAL

[0003] RELATED APPLICATION This application claims priority under applicable law from Canadian Provisional Patent Application No. 3,120,989 filed on June 3, 2021, the contents of which are incorporated herein by reference in their entirety and for all purposes.

[0004] TECHNICAL FIELD

[0005] The present application relates to the field of coatings and their use in electrochemical applications. More particularly, the present application relates to coatings for particles of ionically conductive inorganic material, of electrochemically active material, of electronic conductor, to their manufacturing processes and to their uses in electrochemical cells, in particular in so-called all-solid-state batteries. STATE OF THE ART

[0006] All-solid-state electrochemical systems are substantially safer, lighter, more flexible, and more efficient than their counterparts based on the use of liquid electrolytes. However, the scope of application of solid electrolytes is still limited.

[0007] Indeed, solid polymer electrolytes have problems related to their limited electrochemical stability, low transport number and relatively low ionic conductivity at room temperature.

[0008] Ceramic-based solid electrolytes exhibit a wide window of electrochemical stability and substantially higher ionic conductivity at room temperature. However, they are associated with problems related to their interfacial stability as well as their stability in ambient air and humidity.

[0009] Furthermore, the manufacture of solid electrolytes and electrode materials for all-solid-state electrochemical systems very frequently encounter dispersion problems, especially when forming composite electrodes and electrolytes. More specifically, since the nature of the elements in a composite, for example, polymers and inorganic particles, is different, solid elements may tend to form agglomerates within a polymer matrix or electrode binder, which may adversely affect the performance, efficiency, or stability of the system.

[0010] These dispersion problems can also be significantly reduced through the use of binders, additives or dispersion media resulting in better particle dispersion.

[0011] Examples of dispersion media are described in the European patent published under number EP 3 467 845, these being present in the composition of the solid electrolyte.

[0012] The manufacture of ceramic-based solid electrolytes is associated with cracking problems following the dry pressing process. One strategy employed to address this problem involves encapsulating the ceramic-based solid electrolyte particles with a substantially flexible (or elastic) polymer. For example, Korean Patent Publication No. KR 10-2003300 describes a polymer coating layer comprising an acrylic-, fluorine-, diene-, silicone-, or cellulose-based polymer coated on the surface of sulfide-based crystalline electrolyte particles. In addition to minimizing the risk of cracking of the solid electrolyte, the polymer coating layer also allows for aggregation of the electrolyte particles without lowering their ionic conductivity and helps absorb volume changes during cycling.Although this strategy allows to obtain interesting properties, it does not allow to solve the dispersion problems mentioned previously.

[0013] Therefore, there is a need for the development of all-solid-state electrochemical systems that exclude one or more of the disadvantages of conventional all-solid-state electrochemical systems.

[0014] SUMMARY

[0015] In one aspect, the present technology relates to a coating material comprising at least one branched or linear unsaturated aliphatic hydrocarbon having from 10 to 50 carbon atoms and having at least one carbon-carbon double or triple bond for use in an electrochemical cell.

[0016] In one embodiment, the boiling temperature of the unsaturated aliphatic hydrocarbon is greater than 150°C. For example, the boiling temperature of the unsaturated aliphatic hydrocarbon is in the range of about 150°C to about 675°C, or about 155°C to about 670°C, or about 160°C to about 665°C, or about 165°C to about 660°C, or about 170°C to about 655°C, inclusive.

[0017] In another embodiment, the unsaturated aliphatic hydrocarbon is selected from the group consisting of decene, dodecene, undecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, 1,9-decadiene, docosene, hexacosene, eicosene, tetracosene, squalene, farnesene, b-carotene, pinenes, dicyclopentadiene, camphene, a-phellandrene, b-phellandrene, terpinenes, b-myrcene, limonene, 2-carene, sabinene, a-cedrene, copaene, b-cedrene, decyne, dodecyne, octadecyne, hexadecyne, tridecyne, tetradecyne, docosyne, and a combination of at least two of these. In one embodiment of interest, the unsaturated aliphatic hydrocarbon comprises squalene. In another embodiment of interest, the unsaturated aliphatic hydrocarbon comprises farnesene.According to another variant of interest, the unsaturated aliphatic hydrocarbon comprises squalene and farnesene.

[0018] In another embodiment, the coating material is a mixture comprising the unsaturated aliphatic hydrocarbon and an additional component. For example, the additional component is an alkane or a mixture comprising an alkane and a polar solvent.

[0019] In another aspect, the present technology relates to coated particles for use in an electrochemical cell, said coated particle comprising: a core comprising an electrochemically active material, an electronically conductive material or an ionically conductive inorganic material; and a coating material as defined herein, the coating material being disposed on the surface of the core. In another aspect, the present technology relates to a method of manufacturing coated particles as defined herein, the method comprising at least one step of coating at least a portion of the surface of the core with the coating material.

[0020] In one embodiment, the method further comprises a step of grinding the electrochemically active material, the electronically conductive material or the ionically conductive inorganic material of the core of the coated particle.

[0021] In another aspect, the present technology relates to an electrode material comprising: coated particles as defined herein, wherein the core of the coated particle comprises an electrochemically active material; and / or an electrochemically active material and coated particles as defined herein.

[0022] In one embodiment, the core of the coated particle comprises the electrochemically active material. In one example, the electrochemically active material is selected from a metal oxide, a metal sulfide, a metal oxysulfide, a metal phosphate, a metal fluorophosphate, a metal oxyfluorophosphate, a metal sulfate, a metal halide, a metal fluoride, sulfur, selenium, and a combination of at least two thereof. For example, the metal of the electrochemically active material is selected from titanium (Ti), iron (Fe), manganese (Mn), vanadium (V), nickel (Ni), cobalt (Co), aluminum (Al), chromium (Cr), copper (Cu), zirconium (Zr), niobium (Nb), and a combination of at least two thereof. According to one example, the electrochemically active material further comprises an alkali or alkaline earth metal selected from lithium (Li), sodium (Na), potassium (K) and magnesium (Mg).According to another example, the electrochemically active material is selected from a non-alkaline or non-alkaline earth metal, an intermetallic compound, a metal oxide, a metal nitride, a metal phosphide, a metal phosphate, a metal halide, a metal fluoride, a metal sulfide, a metal oxysulfide, a carbon, silicon (Si), a silicon-carbon (Si-C) composite, a silicon oxide (SiO. x ), a silicon oxide-carbon composite (SiO x -C), tin (Sn), a tin-carbon composite (Sn-C), a tin oxide (SnO x ), a tin oxide-carbon composite (SnO x-C), and a combination of at least two thereof. In another embodiment, the electrode material further comprises at least one electronically conductive material. In a variant of interest, the core of the coated particle comprises the electronically conductive material. For example, the electronically conductive material is selected from the group consisting of carbon black, acetylene black, graphite, graphene, carbon fibers, carbon nanofibers, carbon nanotubes, and a combination of at least two thereof.

[0023] In another embodiment, the electrode material further comprises at least one additive. According to a variant of interest, the core of the coated particle comprises the additive. According to one example, the additive is selected from inorganic ionic conductive materials, inorganic materials, glasses, glass-ceramics, ceramics, nanoceramics, salts, and a combination of at least two of these. According to another example, the additive comprises ceramic, glass or glass-ceramic particles based on fluoride, phosphide, sulfide, oxysulfide or oxide. According to another example, the additive is selected from compounds of the LISICON, thio-LISICON, argyrodites, garnets, NASICON, perovskites, oxides, sulfides, oxysulfides, phosphides, fluorides, in crystalline and / or amorphous form, and a combination of at least two of these.According to another example, the additive is selected from inorganic compounds of formulas MLZO (e.g., M7La3Zr20i2, M. (7 - a) La3Zr2AlbOi2, M(7- a) La3Zr2GabOi2, M(7- a) La3Zr(2-b)TabOi2, and M(7- a) La3Zr(2-b>NbbOi2); MLTaO (e.g., M7La3Ta20i2, M5La3Ta20i2, and M6La3Ta1.5Y0.5O12); MLSnO (e.g., M7La3Sn20i2); MAGP (e.g. Mi +a Al a Ge2- a (P04)3); MATP (e.g. Mi +a Al a TÎ2- a (P04)3,); MLTiO (for example, M3aLa(2 / 3-a>Ti03); MZP (for example, M a Zrb(P04) c ); MCZP (e.g., M a CabZr c (P04)d); MGPS (e.g., M a GebP c Sd such as MioGeP2Si2); MGPSO (e.g., M a Ge b P c S d O e ); MSiPS (e.g., M a If b P c S d such as M 10 S1P2S 12 ); MSiPSO (e.g., M aIf b P c S d O e ); MSnPS (e.g., M a Sn b P c S d such as MioSnP2Si2); MSnPSO (e.g., M a Sn b P c S d O e ); MPS (e.g., M a P b S c such as M7P3S 11 ); MPSO (e.g., M a P b S c O d ); MZPS (e.g., M a Zn b P c S d ); MZPSO (e.g., M a Zn b P c S d O e ); xM2S-yP2S5; xM2S-yP2S5-zMX; xM2S-yP2S5-zP205; XM2S- yP2S5-zP205-wMX; xM2S-yM20-zP2S5; xM2S-yM20-zP2S5-wMX; xM2S-yM20-zP2S5-WP2O5; xM2S-yM20-zP2S5-wP205-vMX; xM2S-ySiS2; MPSX (e.g., M a P b S c X d such as M7P3S 11 X, M7P2S8X, and M6PS5X); MPSOX (e.g., M a P b S c O d X e); MGPSX (e.g., M a Ge b P c S d X e ); MGPSOX (e.g., M a Ge b P c S d O e X f ); MSiPSX (e.g., M a If b P c S d X e ); MSiPSOX (e.g., M a If b P c S d O e X f ); MSnPSX (e.g., MaSri b PCS d Xe); MSnPSOX (e.g., M a Sn b PCS d O e X f ); MZPSX (e.g., MaZribPcSdXe); MZPSOX (e.g., M a ZnbPcSdO e Xf); M3OX; M2HOX; M3PO4; M3PS4; and M a PO b N c (where a = 2b + 3c - 5); in which:

[0024] M is an alkali metal ion, an alkaline earth metal ion, or a combination thereof, and wherein when M comprises an alkaline earth metal ion, then the number of M is adjusted to achieve electroneutrality;

[0025] X is selected from F, Cl, Br, I or a combination of at least two thereof; a, b, c, d, e and f are non-zero numbers and are, independently in each formula, selected to achieve electroneutrality; and v, w, x, y and z are non-zero numbers and are, independently in each formula, selected to obtain a stable compound.

[0026] According to a variant of interest, the additive is chosen from inorganic compounds of the argyrodite type of formula LÎ6PS5X, in which X is Cl, Br, I or a combination of at least two of these. For example, the additive is LÎ6PS5CI.

[0027] In another aspect, the present technology relates to an electrode comprising the electrode material as defined herein on a current collector. In another aspect, the present technology relates to a self-supporting electrode comprising the electrode material as defined herein. In one embodiment, said electrode is a positive electrode.

[0028] In another aspect, the present technology relates to an electrolyte comprising coated particles as defined herein, wherein the core of the coated particle comprises an ionically conductive inorganic material. In one example, the ionically conductive inorganic material is selected from glasses, glass-ceramics, ceramics, nanoceramics and a combination of at least two thereof. In another example, the ionically conductive inorganic material comprises a fluoride, phosphide, sulfide, oxysulfide or oxide based ceramic, glass or glass-ceramic. According to another example, the ionically conductive inorganic material is selected from compounds of the LISICON, thio-LISICON, argyrodites, garnets, NASICON, perovskites, oxides, sulfides, oxysulfides, phosphides, fluorides, in crystalline and / or amorphous form, and a combination of at least two of these.According to another example, the ionically conductive inorganic material is selected from inorganic compounds of formulas MLZO (for example,. M (7 - a) La3Zr2AlbOi2, M(7- a) La3Zr2GabOi2, M(7- a) La3Zr(2-b)TabOi2, and M(7- a >La3Zr(2-b)NbbOi2); MLTaO (e.g., M7La3Ïa20i2, M5La3Ta20i2, and M6La3Ta1.5Y0.5O12); MLSnO (e.g., M7La3Sn20i2); MAGP (e.g. Mi +a Al a Ge2- a (P04)3); MATP (e.g. Mi +a Al a TÎ2- a (P04)3,); MLTiO (e.g., M3aLa(2 / 3-a)TiO3); MZP (for example, M a Zrb(P04) c ); MCZP (e.g., M a CabZr c (P04)d); MGPS (e.g., M a GebP c Sd such as MioGeP2Si2); MGPSO (e.g., M a Ge b P c S d O e ); MSiPS (e.g., M a If b P c S d such as M 10 S1P2S 12); MSiPSO (e.g., M a If b P c S d O e ); MSnPS (e.g., M a Sn b P c S d such as MioSnP2Si2); MSnPSO (e.g., M a SnbPcSdO e ); MPS (e.g., M a PbS c such as M7P3S 11 ); MPSO (e.g., M a P b S c O d ); MZPS (e.g., M a Zn b P c S d ); MZPSO (e.g., M a Zn b P c S d O e ); xM2S-yP2S5; xM2S-yP2S5-zMX; xM2S-yP2S5-zP205; XM2S- yP2S5-zP205-wMX; xM2S-yM20-zP2S5; xM2S-yM20-zP2S5-wMX; xM2S-yM20-zP2S5-WP2O5; xM2S-yM20-zP2S5-wP205-vMX; xM2S-ySiS2; MPSX (e.g., M a P b S c X d such as M7P3S 11 X, M7P2S8X, and M6PS5X); MPSOX (e.g., M a P b S c O d X e ); MGPSX (e.g., Ma Ge b P c S d X e ); MGPSOX (e.g., M a Ge b P c S d O e X f ); MSiPSX (e.g., M a If b P c S d X e ); MSiPSOX (e.g., M a If b P c S d O e X f ); MSnPSX (e.g., M a Sn b P c S d X e ); MSnPSOX (e.g., M a Sn b P c S d O e X f ); MZPSX (e.g., M a Zn b PcSdXe); MZPSOX (e.g., M a ZnbP c SdO e Xf); M3OX; M2HOX; M3PO4; M3PS4; and M a PO b N c (where a = 2b + 3c - 5); in which:

[0029] M is an alkali metal ion, an alkaline earth metal ion, or a combination thereof, and wherein when M comprises an alkaline earth metal ion, then the number of M is adjusted to achieve electroneutrality;

[0030] X is selected from F, Cl, Br, I or a combination of at least two thereof; a, b, c, d, e and f are non-zero numbers and are, independently in each formula, selected to achieve electroneutrality; and v, w, x, y and z are non-zero numbers and are, independently in each formula, selected to obtain a stable compound. According to an alternative embodiment of interest, the ionically conductive inorganic material is selected from argyrodite-type inorganic compounds of formula LÎ6PS5X, wherein X is Cl, Br, I or a combination of at least two thereof. For example, the ionically conductive inorganic material is LÎ6PS5CI. According to another aspect, the present technology relates to a coating material for a current collector comprising coated particles as defined herein, wherein the core of the coated particle comprises an electronically conductive material.For example, the electronically conductive material is carbon.

[0031] In another aspect, the present technology relates to a current collector comprising a coating material as defined herein, disposed on a metal foil.

[0032] In another aspect, the present technology relates to an electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, wherein at least one of the positive electrode or the negative electrode is as defined herein or comprises an electrode material as defined herein. In another aspect, the present technology relates to an electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, wherein the electrolyte is as defined herein.

[0033] In another aspect, the present technology relates to an electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, wherein at least one of the positive electrode and the negative electrode is on a current collector as defined herein or comprising a coating material as defined herein.

[0034] According to another aspect, the present technology relates to an electrochemical accumulator comprising at least one electrochemical cell as defined herein.

[0035] In one embodiment, the electrochemical accumulator is a battery selected from a lithium battery, a lithium-ion battery, a sodium battery, a sodium-ion battery, a magnesium battery, a magnesium-ion battery.

[0036] In another embodiment, the electrochemical accumulator is a so-called all-solid-state battery. BRIEF DESCRIPTION OF THE FIGURES

[0037] Figure 1 shows scanning electron microscopy (SEM) images of (A) Li6PS5CI particles before the milling and coating step, and (B) LiePSsCI particles coated with a mixture of decane and squalene, as described in Example 3(a).

[0038] Figure 2 shows results of thermogravimetric analyses for squalene (¨; curve 1) and for Ü6PS5CI particles coated with a mixture of decane and squalene (o; curve 2), as described in Example 3(b).

[0039] Figure 3 shows respectively in (A) and (B) proton nuclear magnetic resonance (NMR) spectra 1 H) and carbon (NMR 13 C) obtained for particles of

[0040] LiePSsCI coated with the mixture of decane and squalene, as described in Example 3(c).

[0041] Figure 4 shows proton nuclear magnetic resonance (NMR) spectra 1H) obtained for pure farnesene as well as for Ü6PS5CI particles coated with a mixture of decane and farnesene, as described in Example 3(c). Figure 5 shows proton nuclear magnetic resonance (NMR) spectra

[0042] 1 H) obtained for pure farnesene and squalene as well as for particles of

[0043] LiePSsCI coated with a mixture of decane, squalene and farnesene, as described in Example 3(c).

[0044] Figure 6 shows in (A) and (B) SEM images and energy dispersive X-ray spectroscopy (EDS) Ni and S element mapping images obtained for Films 1 and 2, respectively, as described in Example 4(b).

[0045] Figure 7 shows in (A) and (B) backscattered electron SEM images and enlargements of these images for Films 3 and 4, respectively, as described in Example 4(b). Figure 8 shows in (A) a plot of discharge capacity (mAh / g) and coulombic efficiency (%) versus number of cycles, and in (B) a plot of average charge and discharge potential (V) versus number of cycles for Cell 1 (A) and for Cell 2 ( ■ ), as described in Example 5(b). Figure 9 shows in (A) a graph of discharge capacity and coulombic efficiency versus number of cycles, and in (B) a graph of average charging and discharging potential (V) versus number of cycles for Cell 2 (■), Cell 3 (A), Cell 4 (T) and Cell 5 (·), as described in Example 5(b).

[0046] Figure 10 shows a plot of discharge capacity and coulombic efficiency versus cycle number for Cell 2 (■), Cell 6 (·) and Cell 7 (★), as described in Example 5(b).

[0047] Figure 11 shows proton nuclear magnetic resonance (NMR) spectra 1 H) for the solution samples of Film 4 before cycling (blue) and after cycling (red), as described in Example 6(a).

[0048] Figure 12 shows a graph of the amount of hydrogen sulfide (H2S) gas generated (mL / g) versus time (hours) for decane-coated (dashed line), decane:squalene (85:15 by volume) coated (dashed-dot-dot line), and decane:squalene (75:25 by volume) coated (solid line) LÎ6PS5CI powder, as described in Example 6(b).

[0049] DETAILED DESCRIPTION

[0050] All technical and scientific terms and expressions used herein have the same definitions as those generally understood by those skilled in the art of the present technology. Definitions of certain terms and expressions used are nevertheless provided below.

[0051] When the term "about" is used here, it means approximately, in the region of, or around. For example, when the term "about" is used in connection with a numerical value, it modifies it above and below by a variation of 10% from its nominal value. This term may also take into account, for example, the experimental error of a measuring device or rounding.

[0052] When a range of values ​​is referred to in this application, the lower and upper bounds of the range are, unless otherwise indicated, always included in the definition. When a range of values ​​is referred to in this application, then all intermediate ranges and subranges, as well as individual values ​​included in the ranges of values, are included in the definition. When the article "a" is used to introduce an element in this application, it does not have the meaning of "a single one," but rather of "one or more." Of course, where the description states that a particular step, component, element, or feature "may" or "could" be included, that particular step, component, element, or feature is not required to be included in every embodiment.

[0053] The chemical structures described here are drawn according to the conventions of the field. Also, when an atom, such as a carbon atom, as drawn appears to include an incomplete valence, then the valence is assumed to be satisfied by one or more hydrogen atoms even if they are not explicitly drawn.

[0054] The present technology relates to a coating material comprising at least one branched or linear unsaturated aliphatic hydrocarbon having from 10 to 50 carbon atoms and having at least one carbon-carbon double or triple bond for use in an electrochemical cell.

[0055] In one example, the unsaturated aliphatic hydrocarbon as defined herein is characterized by a boiling point above about 150°C. For example, the unsaturated aliphatic hydrocarbon is characterized by a boiling point in the range of about 150°C to about 675°C, or about 155°C to about 670°C, or about 160°C to about 665°C, or about 165°C to about 660°C, or about 170°C to about 655°C, inclusive.

[0056] In another example, the unsaturated aliphatic hydrocarbon as defined herein includes a single carbon-carbon double or triple bond, e.g., an alkene, an alkyne, or an acyclic olefin. Alternatively, the unsaturated aliphatic hydrocarbon includes at least two conjugated or non-conjugated carbon-carbon double bonds, e.g., an alkadiene, an alcatriene, and so on, or a polyene. Alternatively, the unsaturated aliphatic hydrocarbon includes at least two carbon-carbon triple bonds, e.g., or an alkadiyne, an alkatriyne, and so on, or a polyyne. Alternatively, the unsaturated aliphatic hydrocarbon includes at least one carbon-carbon double bond and at least one carbon-carbon triple bond.Non-limiting examples of unsaturated aliphatic hydrocarbons having at least one carbon-carbon double bond as defined herein include decene, dodecene, undecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, 1,9-decadiene, docosene, hexacosene, eicosene, tetracosene, squalene, farnesene, b-carotene, pinenes, dicyclopentadiene, camphene, Ga-phellandrene, b-phellandrene, terpinenes, b-myrcene, limonene, 2-carene, sabinene, Ga-cedrene, copaene, b-cedrene, and combinations thereof. In one example, the unsaturated aliphatic hydrocarbon is selected from decene, dodecene, undecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, 1,9-decadiene, docosene, hexacosene, eicosene, tetracosene, squalene, b-carotene, and combinations thereof.According to another example, the unsaturated aliphatic hydrocarbon is selected from decene, undecene, squalene, octadecene, b-carotene and a combination of at least two thereof. According to one variant of interest, the unsaturated aliphatic hydrocarbon includes squalene. According to another variant of interest, the unsaturated aliphatic hydrocarbon includes farnesene. According to another variant of interest, the unsaturated aliphatic hydrocarbon includes a mixture including squalene and farnesene.

[0057] Non-limiting examples of unsaturated aliphatic hydrocarbons having at least one carbon-carbon triple bond as defined herein include decyne, dodecyne, octadecyne, hexadecyne, tridecyne, tetradecyne, docosyne, and a combination of at least two thereof. In another example, the coating material as defined herein is a mixture comprising the unsaturated aliphatic hydrocarbon as defined herein and at least one additional component. In one example, the additional component may be an alkane, e.g., an alkane having from 10 to 50 carbon atoms. In another example, the additional component may be a mixture comprising an alkane as defined herein and a polar solvent. Non-limiting examples of polar solvents include tetrahydrofuran, acetonitrile, / V, / V-dimethylformamide, and a miscible combination of at least two thereof. According to a variant of interest, the additional component is decane.

[0058] The present technology also relates to coated particles for use in an electrochemical cell. More particularly, the coated particles comprise: a core comprising an electrochemically active material, an electronically conductive material or an ionically conductive inorganic material; and a coating material as defined herein disposed on the surface of said core.

[0059] According to one example, the coating material may form a homogeneous coating layer on the surface of the core. That is, it may form a substantially uniform coating layer on the surface of the core.

[0060] In another example, the coating material may form a coating layer on at least a portion of the surface of the core. In other words, it may be heterogeneously dispersed over the surface of the core.

[0061] It should be understood that the volume or mass ratio of the coating material and the material of said core as well as the conditions of the coating process influence the degree of coverage of the surface of said core by the coating material and / or the homogeneity of the coated particle samples.

[0062] The use of coated particles as defined herein in electrochemical applications is also contemplated. For example, the coated particles may be used in electrochemical cells, electrochemical accumulators, and in particular in so-called all-solid-state batteries. For example, the coated particles may be used in an electrode material, in an electrolyte, or at the interface between the two as an additional layer.

[0063] The present technology also relates to a method for manufacturing coated particles as defined herein, the method comprising at least one step of coating at least a portion of the surface of the core with the coating material. The coating step may be carried out by any compatible coating method. For example, the coating step may be carried out by a dry or wet coating method. According to an alternative form of interest, the coating step may be carried out by a wet coating method, for example, by a mechanical coating method, such as a mixing, grinding, or mechanosynthesis method.

[0064] According to one example, the method further comprises a step of grinding (or pulverizing) the electrochemically active material, the electronically conductive material or the ionically conductive inorganic material of said core of the coated particle. For example, the coating and grinding steps may be performed simultaneously, sequentially, or may partially overlap in time. When the coating and grinding steps are performed sequentially, the grinding step may be performed before the coating step. According to a variant of interest, the coating and grinding steps are performed simultaneously, for example, using a planetary mill or a planetary micromill.

[0065] In another example, the coating and grinding steps may be performed at a rotational speed and for a determined duration to achieve an optimal particle size or diameter, a desired degree of coverage of the particle core surface by the coating material, and / or a desired homogeneity of the coated particle samples.

[0066] In some examples, the particles are sulfide-based ceramic particles (e.g., Li6PS5CI argyrodite particles). The coating and grinding steps are performed at a rotational speed of about 300 rpm for about 7.5 hours to obtain coated Li6PS5CI particles having a final particle size of about 1 μm or less.

[0067] In another example, the method further comprises a step of drying the coated particles. In one example, the drying step may be performed to remove moisture and / or residual solvent. In another example, the drying process may be performed at a low temperature and for a determined time to dry the coated particles without evaporating the coating material or without significantly evaporating the coating material. For example, the drying step may be performed at a temperature below the boiling point of the unsaturated aliphatic hydrocarbon of the coating material and for a determined time to not evaporate it or not significantly evaporate it.It is understood that, when the coating material comprises a mixture, at least one unsaturated aliphatic hydrocarbon does not evaporate entirely during the drying step, and therefore, it remains present in the coating layer disposed on the surface of the core of the particle. For example, when the mixture comprises an additional component (for example, an alkane or a mixture comprising an alkane and a polar solvent as defined above), this may be partially or completely evaporated during the drying step. According to one example, the drying step may be carried out at a temperature of approximately 80°C for a duration of approximately 5 hours.

[0068] According to another example, when the coating material comprises a mixture, the composition of said mixture comprises at least about 2% by volume of the unsaturated aliphatic hydrocarbon as defined herein, during the coating step. For example, the composition of said mixture comprises at least about 3%, or at least about 4%, or at least about 5% by volume of the unsaturated aliphatic hydrocarbon as defined herein, during the coating step.

[0069] According to another example, the method further comprises a step of coating (also called spreading) a suspension comprising said coated particles, said coating step being carried out, for example, by at least one doctor-blade coating method, a comma coating method, a reverse-comma coating method, a printing method such as gravure coating, or a slot-die coating method. According to an alternative embodiment of interest, said coating step is carried out by a doctor-blade coating method. According to one example, the suspension comprising said coated particles may be coated onto a substrate or support film, said substrate or support film being subsequently removed.According to another example, the suspension comprising said particles can be coated directly onto a current collector.

[0070] The present technology also relates to an electrode material comprising: coated particles as defined herein, wherein the core comprises an electrochemically active material; and / or an electrochemically active material and coated particles as defined herein.

[0071] According to another example, said electrode material is a positive electrode material and the electrochemically active material is selected from a metal oxide, a metal sulfide, a metal oxysulfide, a metal phosphate, a metal fluorophosphate, a metal oxyfluorophosphate, a metal sulfate, a metal halide (e.g., a metal fluoride), sulfur, selenium, and a combination of at least two thereof. According to another example, the metal of the electrochemically active material is selected from titanium (Ti), iron (Fe), manganese (Mn), vanadium (V), nickel (Ni), cobalt (Co), aluminum (Al), chromium (Cr), copper (Cu), zirconium (Zr), niobium (Nb), and combinations thereof, when compatible. The electrochemically active material may optionally further comprise an alkali or alkaline earth metal, for example, lithium (Li), sodium (Na), potassium (K) or magnesium (Mg).

[0072] Non-limiting examples of electrochemically active materials include lithium metal phosphates, complex oxides, such as LiM'PC (where M' is Fe, Ni, Mn, Co, or a combination thereof), UV3O8, V2O5, LiM^C, 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, where compatible.

[0073] According to a variant of interest, the electrochemically active material is an oxide or a phosphate such as those described above.

[0074] For example, the electrochemically active material is a lithium manganese oxide, wherein the manganese may be partially substituted by a second transition metal, such as a lithium nickel manganese cobalt (NMC) oxide. Alternatively, the electrochemically active material is lithium iron phosphate. Alternatively, the electrochemically active material is a manganese-containing lithium metal phosphate such as those described above, e.g., the manganese-containing lithium metal phosphate is a lithium iron manganese phosphate (LiMni- x Fe x P04, where x is between 0.2 and 0.5).

[0075] According to another example, said electrode material is a negative electrode material and the electrochemically active material is selected from a non-alkali and non-alkaline earth metal (e.g., indium (In), germanium (Ge) and bismuth (Bi)), an intermetallic compound (e.g., SnSb, TiSnSb, Cu2Sb, AlSb, FeSb2, FeSn2 and CoSn2), a metal oxide, a metal nitride, a metal phosphide, a metal phosphate (e.g., LiTÎ2(P04)3), a metal halide (e.g., a metal fluoride), a metal sulfide, a metal oxysulfide, a carbon (e.g., graphite, graphene, reduced graphene oxide, hard carbon, soft carbon, exfoliated graphite and amorphous carbon), silicon (Si), a silicon-carbon composite (Si-C), a silicon oxide (SiO x ), a silicon oxide-carbon composite (SiO x -C), tin (Sn), a tin-carbon composite (Sn-C), a tin oxide (SnO x), a tin oxide-carbon composite (SnO x -C), and combinations thereof, when compatible. For example, the metal oxide may be chosen from compounds of formulas M”” b O c (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) (e.g., M0O3, M0O2, M0S2, V2O5, and TiNb207), spinel oxides (e.g., NίOq2q4, ZhOq2q4, MnCo204, CUC02O4, and CoFe2C>4) and LiM””O (where M'”” is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination of two or more thereof) (e.g., a lithium titanate (such as Li4Ti5Oi2) or a lithium molybdenum oxide (such as U2M04O 13 )).

[0076] According to another example, the electrochemically active material may optionally be doped with other elements included in smaller amounts, for example to modulate or optimize its electrochemical properties. The electrochemically active material may be doped by partial substitution of the metal with other ions. For example, the electrochemically active material may be doped with a transition metal (e.g., Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, or Y) and / or a metal other than a transition metal (e.g., Mg, Al, or Sb).

[0077] In another example, the electrochemically active material may be in the form of particles (e.g., microparticles and / or nanoparticles) that may be freshly formed or commercially sourced. For example, the coating material forms a coating layer on the surface of the electrochemically active material and the coating material is disposed on the surface of the coating layer. For example, the electrochemically active material may be in the form of particles coated with a layer of coating material. The coating material may be an electronically conductive material, e.g., a conductive carbon coating.Alternatively, the coating material may substantially reduce interfacial reactions at the interface between the electrochemically active material and an electrolyte, for example, a solid electrolyte, and in particular, a sulfide-based ceramic-type solid electrolyte (for example, based on Li6PS5CI). For example, the coating material may be selected from LhSiOs, LiTa03, UAIO2, LhO-ZrC^, LiNbC>3, combinations thereof, when compatible, and other similar materials. According to an alternative of interest, the coating material comprises LiNbOs. According to another example, the electrode material as defined herein further includes a conductive material. According to an alternative of interest, the core of the coated particle comprises the electronically conductive material.

[0078] Non-limiting examples of electronically conductive material include a carbon source such as carbon black (e.g., Ketjen carbon MCand Super P carbon MC ), acetylene black (e.g., Shawinigan carbon and Denka carbon black MC ), graphite, graphene, carbon fibers (e.g., gas-formed carbon fibers (VGCFs)), carbon nanofibers, carbon nanotubes (CNTs), and a combination of two or more thereof. In another example, the electronically conductive material, if present in the electrode material, may be a modified electronically conductive material such as those described in PCT patent application published under number WO2019 / 218067 (Delaporte et al.). For example, the modified electronically conductive material may be grafted with at least one aryl group of Formula I:

[0079] Formula I in which:

[0080] FG is a hydrophilic functional group; and n is a natural integer in the range from 1 to 5, preferably n is in the range from 1 to 3, preferably n is 1 or 2, and more preferably n is 1.

[0081] Examples of hydrophilic functional groups include hydroxyl, carboxyl, sulfonic acid, phosphonic acid, amine, amide, and other similar groups. For example, the hydrophilic functional group is a carboxyl or sulfonic acid functional group. The functional group may optionally be lithiated by the exchange of a hydrogen with a lithium. Preferred examples of an aryl group of Formula I are p-benzoic acid or p-benzenesulfonic acid. According to one variant of interest, the electronically conductive material is carbon black optionally grafted with at least one aryl group of Formula I. According to another variant of interest, the electronically conductive material may be a mixture comprising at least one modified electronically conductive material.For example, a mixture of carbon black grafted with at least one aryl group of Formula I and carbon fibers (e.g., gas-formed carbon fibers (VGCFs)), carbon nanofibers, carbon nanotubes (CNTs) or a combination of at least two of these.

[0082] According to another example, the electrode material as defined herein further includes an additive. For example, the core of the coated particle comprises the additive. For example, the additive is selected from inorganic ionic conductive materials, inorganic materials, glasses, glass-ceramics, ceramics, including nanoceramics (e.g., AI2O3, T1O2, S1O2 and other similar compounds), salts (e.g., lithium salts) and a combination of at least two thereof. For example, the additive may be an inorganic ionic conductor selected from compounds of the LISICON, thio-LISICON, argyrodites, garnets, NASICON, perovskites, oxides, sulfides, phosphides, fluorides, sulfur halides, phosphates, thio-phosphates, in crystalline and / or amorphous form, and a combination of at least two of these.

[0083] In one embodiment, the additive, if present in the electrode material, may be ceramic, glass, or glass-ceramic particles based on fluoride, phosphide, sulfide, oxysulfide, oxide, or a combination of two or more thereof. Non-limiting examples of ceramic, glass, or glass-ceramic particles include inorganic compounds of formulas MLZO (e.g., M7La3Zr20i2, M(7- a) La3Zr2AlbOi2, M(7- a) La3Zr2GabOi2, M(7- a) La3Zr(2-b)TabOi2, and M(7- a >La3Zr(2- b)Nb b Oi2); MLTaO (e.g., M7La3Ta2Oi2, M5La3Ta20i2, and M6La3Ta1.5Y0.5O12); MLSnO (e.g., M7La3Sn20i2); MAGP (e.g. Mi +a Al a Ge2- a (P04)3); MATP (e.g. Mi +a Al a TÎ2- a (P04)3,); MLTiO (e.g., M3 a The(2 / 3- a >Ti03); MZP (e.g., M a Zrb(P04) c ); MCZP (e.g., M a CabZrc (P04)d); MGPS (par example, M a Ge b P c S d tel que MioGeP2Si2); MGPSO (see example, M a Ge b P c S d OR e ); MSiPS (for example, M a Yes b P c S d tel que M 10 S1P2S 12 ); MSiPSO (for example, M a Yes b P c S d OR e ); MSnPS (for example, M a Sn b P c S d tel que MioSnP2Si2); MSnPSO (see example, M a Sn b P c S d OR e ); MPS (par exemple, M a P b S c tel que M7P3S 11 ); MPSO (par exemple, M a P b S c OR d ); MZPS (for example, M a Zri b P c S d ); MZPSO (for example, M a Zn b P c S d OR e); xlVbS-yPaSs; xlVbS-yPaSs- zMX; xM2S-yP2S5-zP205; xM2S-yP2S5-zP205-wMX; xM2S-yM20-zP2S5; xM2S-yM20- ZP2S5-WMX; xM2S-yM20-zP2S5-wP205; xM2S-yM20-zP2S5-wP205-vMX; xM2S-ySiS2; MPSX (par exemple, M a P b S c X d tel que M7P3S 11 X, M7P2S8X, et MePS5X (tel que LiePSsCI)); MPSOX (par exemple, M a P b S c O d X e ); MGPSX (par exemple, M a Ge b P c S d X e ); MGPSOX (par exemple, M a Ge b P c S d O e X f ); MSiPSX (par exemple, M a Si b P c S d X e ); MSiPSOX (par exemple, M a Si b P c S d O e X f ); MSnPSX (par exemple, M a Sn b P c S d X e ); MSnPSOX (par exemple, M a Sn b P c S d Oe X f ); MZPSX (e.g., M a Zn b P c S d X e ); MZPSOX (e.g., M a Zri b P c S d O e X f ); M3OX; M2HOX; M3PO4; M3PS4; and M a PO b N c (where a = 2b + 3c - 5); in which:

[0084] M is an alkali metal ion, an alkaline earth metal ion, or a combination thereof, and wherein when M comprises an alkaline earth metal ion, then the number of M is adjusted to achieve electroneutrality;

[0085] X is selected from F, Cl, Br, I or a combination of at least two thereof; a, b, c, d, e and f are non-zero numbers and are, independently in each formula, selected to achieve electroneutrality; and v, w, x, y and z are non-zero numbers and are, independently in each formula, selected to obtain a stable compound.

[0086] For example, M is selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba or a combination of at least two thereof. According to a variant of interest, M comprises Li and may further comprise at least one of Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba or a combination of at least two thereof. According to a variant of interest, M comprises Na, K, Mg or a combination of at least two thereof.

[0087] For example, the additive, if present in the electrode material, may be sulfide-based ceramic particles, for example, argyrodite-type ceramic particles of formula Li6PS5X (where X is Cl, Br, I or a combination of at least two of these). In a variant of interest, the additive is argyrodite LiePSsCI.

[0088] According to another example, the electrode material as defined herein further includes a binder. For example, the binder is chosen for its compatibility with the various elements of an electrochemical cell. Any known compatible binder is contemplated. For example, the binder may be selected from a polymer binder such as polyether, polyester, polycarbonate, fluoropolymer, and water-soluble (water-soluble) binder. According to one example, the binder is a fluoropolymer such as polyvinylidene fluoride (PVDF) or polytetrafluoroethylene (PTFE).In another example, the binder is a water-soluble binder such as styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), hydrogenated NBR (HNBR), epichlorohydrin rubber (CHR), or acrylate rubber (ACM), and optionally comprising a thickening agent such as carboxymethylcellulose (CMC), or a polymer such as poly(acrylic acid) (PAA), poly(methyl methacrylate) (PMMA), or a combination of two or more thereof. In another example, the binder is a polyether polymer binder. For example, the polyether polymer binder is linear, branched, and / or crosslinked and is based on poly(ethylene oxide) (PEO), poly(propylene oxide) (POP), or a combination of both (such as an EO / PO copolymer), and optionally comprises crosslinkable units.For example, the crosslinkable segment of the polymer may be a polymer segment comprising at least one functional group that can be crosslinked multidimensionally by irradiation or by heat treatment.

[0089] According to a variant of interest, the binder, if present in the electrode material, may comprise a mixture including a polymer based on polybutadiene and a polymer comprising norbornene-based monomer units derived from the polymerization of a compound of Formula II: in which,

[0090] R 1 and R 2 are independently and at each occurrence chosen from a hydrogen atom, a carboxyl group (-COOH), a sulfonic acid group (-SO3H), a hydroxyl group (-OH), a fluorine atom and a chlorine atom.

[0091] According to one example, at least one of R 1 or R 2is chosen from -COOH, -SO3H, -OH, -F and -Cl which means that at least one of R 1 or R 2 is different from a hydrogen atom. In another example, R 1 is a -COOH and R group 2 is a hydrogen atom.

[0092] According to another example, at least one of R 1 or R 2 is a -COOH group and the norbornene-based monomer units are norbornene-based monomer units functionalized by a carboxylic acid. According to a variant of interest, R 1 is a -COOH and R group 2 is a hydrogen atom. According to another variant of interest, R 1 and R 2 are both -COOH groups.

[0093] According to another variant of interest, the binder, if present in the electrode material, may comprise a mixture including a polymer based on polybutadiene and a polymer of Formula III: in which,

[0094] R 1 and R 2 are as defined above, and n is a natural integer chosen such that the mass average molecular weight of the polymer of Formula III is between about 10,000 g / mol and about 100,000 g / mol as determined by gel permeation chromatography (GPC), upper and lower bounds inclusive.

[0095] In another example, the mass average molecular weight of the polymer of Formula III is between about 12,000 g / mol and about 85,000 g / mol, or between about 15,000 g / mol and about 75,000 g / mol, or between about 20,000 g / mol and about 65,000 g / mol, or between about 25,000 g / mol and about 55,000 g / mol, or between about 25,000 g / mol and about 50,000 g / mol as determined by GPC, upper and lower bounds inclusive.

[0096] According to a variant of interest R 1 and R 2 are -COOH groups. According to one example, the polymer is of Formula III(a):

[0097]

[0098] Formula lll(a) in which,

[0099] R 2 and n are as defined above. According to another example, the polymer is of Formula III(b):

[0100] Formula III(b) wherein n is as defined above. In another example, the norbornene-based polymer of Formula II, or the polymer of Formula III, III(a) or III(b) is a homopolymer.

[0101] According to another example, the polymerization of the norbornene-based monomer of Formula II can be carried out by all known and compatible polymerization methods. According to an alternative of interest, the polymerization of the compound of Formula II can be carried out by the synthetic method described by Commarieu, B. et al. (Commarieu, Basile, et al. "Ultrahigh T gEpoxy Thermosets Based on Insertion Polynorbornenes", Macromolecules, 49.3 (2016): 920-925). For example, the polymerization of the compound of Formula II can also be carried out by an addition polymerization process. For example, norbornene-based polymers produced by an addition polymerization process are substantially stable under severe conditions (e.g., acidic and basic conditions). Addition polymerization of norbornene-based polymers can be carried out using inexpensive norbornene-based monomers. The glass transition temperature (T v ) obtained with norbornene-based polymers produced by this polymerization route may be equal to or greater than about 300°C, e.g., as high as 350°C.

[0102] According to another example, the polybutadiene-based polymer may be characterized by substantially higher elasticity or flexibility and / or by a glass transition temperature (T v ) substantially lower than those of the norbornene-based polymer of Formulas III, III(a) or III(b).

[0103] In another example, the polybutadiene-based polymer may be polybutadiene. Alternatively, the polybutadiene-based polymer may be functionalized polybutadiene or a polybutadiene-derived polymer. For example, compared to non-functionalized polybutadiene, the functionalized polybutadiene or the polybutadiene-derived polymer may be characterized by substantially higher elasticity or flexibility, and / or by a glass transition temperature (T v) substantially lower and / or may improve the mechanical or cohesive properties of the electrode binder. According to another example, the polybutadiene-based polymer is selected from epoxidized polybutadienes, for example, epoxidized polybutadienes having reactive end groups. For example, the reactive end groups may be hydroxyl groups. The epoxidized polybutadiene may comprise repeating units of Formulas IV, V and VI:

[0104] Formula IV Formula V Formula VI and two hydroxyl end groups. In another example, the mass average molecular weight of the epoxidized polybutadiene comprising repeating units of Formulas IV, V and VI may be between about 1000 g / mol and about 1500 g / mol as determined by GC, inclusive of upper and lower limits. In another example, the epoxide equivalent weight of the epoxidized polybutadiene comprising repeating units of Formulas IV, V and VI is between about 100 g / mol and about 600 g / mol as determined by GC, inclusive of upper and lower limits. The epoxide equivalent weight corresponds to the mass of resin which contains 1 mole of epoxide functional groups. In a variant of interest, the epoxidized polybutadiene is of Formula VII: wherein, m is a natural integer selected such that the mass average molecular weight of the epoxidized polybutadiene of Formula VII is between about 1,000 g / mol and about 1,500 g / mol as determined by GPC, inclusive of the upper and lower limits; and the epoxide equivalent weight is between about 100 g / mol and about 600 g / mol as determined by GPC, inclusive of the upper and lower limits. In another example, the mass average molecular weight of the epoxidized polybutadiene comprising repeating units of Formulas IV, V and VI or the epoxidized polybutadiene of Formula VII is between about 1050 g / mol and about 1450 g / mol, or between about 1100 g / mol and about 1400 g / mol, or between about 1150 g / mol and about 1350 g / mol, or between about 1200 g / mol and about 1350 g / mol, or between about 1250 g / mol and about 1350 g / mol as determined by GPC, upper and lower bounds inclusive.In one embodiment of interest, the mass average molecular weight of epoxidized polybutadiene comprising repeating units of Formulas IV, V and VI or epoxidized polybutadiene of Formula VII is about 1300 g / mol, as determined by GPC.

[0105] In another example, the epoxide equivalent weight of the epoxidized polybutadiene comprising repeating units of Formulas IV, V and VI or the epoxidized polybutadiene of Formula VII is between about 150 g / mol and about 550 g / mol, or between about 200 g / mol and about 550 g / mol, or between about 210 g / mol and about 550 g / mol, or between about 260 g / mol and about 500 g / mol as determined by GPC, upper and lower bounds inclusive. In a variant of interest, the epoxide equivalent weight of the epoxidized polybutadiene comprising repeating units of Formulas IV, V and VI or the epoxidized polybutadiene of Formula VII is between about 400 g / mol and about 500 g / mol, or between about 260 g / mol and about 330 g / mol as determined by GPC, upper and lower bounds inclusive.

[0106] For example, epoxidized polybutadiene of Formula VII is a commercial epoxidized polybutadiene resin having hydroxyl end groups of the Poly bd type MC 600E or 605E marketed by Cray Valley. The physicochemical properties of these resins are presented in Table 1.

[0107] Table 1. Physicochemical properties of Poly bd 600E or 605E type resins

[0108] It is understood that the electrode binder comprises a polymer blend comprising at least a first polymer and at least a second polymer. The first polymer is the polybutadiene-based polymer and the second polymer is the polymer comprising norbornene-based monomer units derived from the polymerization of the compound of Formula II or the polymer of Formula III, III(a) or III(b).

[0109] In another example, the ratio of "first polymer:second polymer" is in the range of about 6:1 to about 2:3, inclusive. For example, the ratio of "first polymer:second polymer" is in the range of about 5.5:1 to about 2:3, or about 5:1 to about 2:3, or about 4.5:1 to about 2:3, or about 4:1 to about 2:3, or about 6:1 to about 1:1, or about 5.5:1 to about 1:1, or about 5:1 to about 1:1, or about 4.5:1 to about 1:1, or about 4:1 to about 1:1, inclusive. According to a variant of interest, the ratio “first polymer: second polymer” is in the range from about 4:1 to about 1:1, upper and lower limits inclusive.

[0110] The present technology also relates to an electrode comprising an electrode material as defined herein. In one example, the electrode may be on a current collector (e.g., aluminum or copper foil). Alternatively, the electrode may be self-supporting.

[0111] The present technology also relates to an electrolyte comprising coated particles as defined herein, wherein the core of the coated particle comprises an ionically conductive inorganic material.

[0112] In one example, the electrolyte may be chosen for its compatibility with the various elements of the electrochemical cell. Any type of compatible electrolyte is considered. In one example, the electrolyte is a liquid electrolyte comprising a salt in a solvent. In one alternative, the electrolyte is a gel electrolyte comprising a salt in a solvent and optionally a solvating polymer. In another alternative, the electrolyte is a solid polymer electrolyte comprising a salt in a solvating polymer. In another alternative, the electrolyte comprises an inorganic solid electrolyte material, for example, the electrolyte may be a ceramic-type solid electrolyte. In another alternative, the electrolyte is a polymer-ceramic hybrid solid electrolyte.

[0113] According to another example, the ionically conductive inorganic material is selected from inorganic ionically conductive materials, glasses, glass-ceramics, ceramics, nano-ceramics and a combination of at least two of these.

[0114] According to another example, the ionically conductive inorganic material comprises a ceramic, glass or glass-ceramic in crystalline and / or amorphous form. For example, the ceramic, glass or glass-ceramic particles may be based on fluoride, phosphide, sulfide, oxysulfide, oxide, or a combination thereof. According to another example, the ionically conductive inorganic material is selected from compounds of the LISICON, thio-LISICON, argyrodites, garnets, NASICON, perovskites, oxides, sulfides, oxysulfides, phosphides, fluorides, in crystalline and / or amorphous form, and a combination of at least two of these.

[0115] According to another example, the ionically conductive inorganic material is selected from inorganic compounds of formulas MLZO (e.g., M7La3Zr20i2, M ( 7- a) La3Zr2Al b Oi2, M(7-a)La3Zr2GabOi2, M ( 7-a)La3Zr(2-b)TabOi2, and M ( 7-a)La3Zr ( 2-b)NbbOi2); MLTaO (e.g., M7La3Ta20i2, M5La3Ta20i2, and M6La3Ta1.5Y0.5O12); MLSnO (e.g., M7La3Sn20i2); MAGP (e.g. Mi +a Al a Ge 2-a (P04)3); MATP (e.g. Mi +a Al a You 2-a (P04) 3, ); MLTiO (e.g., M 3a La(2 / 3-a)Ti03); MZP (for example, M a Zrb(P04) c ); MCZP (e.g., M a CabZr c (P04)d); MGPS (e.g., M a GebP c Sd such as MioGeP2Si2); MGPSO (e.g., M a Ge b P c S d O e ); MSiPS (e.g., M a If b P c S d such as M10 S1P2S 12 ); MSiPSO (e.g., M a If b P c S d O e ); MSnPS (e.g., M a Sn b P c S d such as MioSnP2Si2); MSnPSO (e.g., M a Sn b P c S d O e ); MPS (e.g., M a P b S c such as M7P3SII); MPSO (e.g., M a P b S c O d ); MZPS (e.g., M a Zn b P c S d ); MZPSO (e.g., M a Zn b P c S d O e ); xM2S-yP2S5; xM2S-yP2S5-zMX; xM2S-yP2S5-zP205; XM2S- yP2S5-zP205-wMX; xM2S-yM20-zP2S5; xM2S-yM20-zP2S5-wMX; xM2S-yM20-zP2S5-WP2O5; xM2S-yM20-zP2S5-wP205-vMX; xM2S-ySiS2; MPSX (e.g., M a P b S c X d such as M7P3SHX, M7P2S8X, and MePS5X); MPSOX (e.g., M a P b S c Od X e ); MGPSX (e.g., M a Ge b P c S d X e ); MGPSOX (e.g., M a Ge b P c S d O e X f ); MSiPSX (e.g., M a If b P c S d X e ); MSiPSOX (e.g., M a If b P c S d O e X f ); MSnPSX (e.g., M a Sn b P c S d X e ); MSnPSOX (e.g., M a Sn b P c S d O e X f ); MZPSX (e.g., MaZn b PcSdXe); MZPSOX (e.g., M a ZnbP c SdO e Xf); M3OX; M2HOX; M3PÜ4; M3PS4; and M a PO b N c (where a = 2b + 3c - 5); in which:

[0116] M is an alkali metal ion, an alkaline earth metal ion, or a combination thereof, and wherein when M comprises an alkaline earth metal ion, then the number of M is adjusted to achieve electroneutrality;

[0117] X is selected from F, Cl, Br, I or a combination of at least two thereof; a, b, c, d, e and f are non-zero numbers and are, independently in each formula, selected to achieve electroneutrality; and v, w, x, y and z are non-zero numbers and are, independently in each formula, selected to obtain a stable compound.

[0118] According to a variant of interest, the ionically conductive inorganic material is chosen from inorganic compounds of the argyrodite type of formula LÎ6PS5X, in which X is Cl, Br, I or a combination of at least two of these. For example, the ionically conductive inorganic material is LÎ6PS5CI.

[0119] As another example, the salt, if present in the electrolyte, may be an ionic salt, such as a lithium salt. Non-limiting examples of lithium salts include lithium hexafluorophosphate (LiPFe), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium 2-trifluoromethyl-4,5-dicyanoimidazolate (LiTDI), lithium 4,5-dicyano-1,2,3-triazolate (LiDCTA), lithium bis(pentafluoroethylsulfonyl)imide (LiBETI), lithium difluorophosphate (LiDFP), lithium tetrafluoroborate (L1BF4), lithium bis(oxalato)borate (LiBOB), lithium nitrate (UNO3), lithium chloride (LiCl), lithium bromide (LiBr), lithium fluoride (LiF), lithium perchlorate (UCIO4), lithium hexafluoroarsenate (LiAsFe), lithium trifluoromethanesulfonate (USO3CF3) (LiOTf), lithium fluoroalkylphosphate Li[PF3(CF2CF3)3] (LiFAP),lithium tetrakis(trifluoroacetoxy)borate Li[B(OCOCF3)4] (LiTFAB), lithium bis(1,2-benzenediolato(2-)-0.0')borate Li[B(C602)2] (LiBBB), lithium difluoro(oxalato)borate (LiBF2(C204)) (LiFOB), a salt of formula LiBF204R, x (in which, R x = C2- C4alkyl), and a combination of at least two of these.

[0120] In another example, the solvent, if present in the electrolyte, may be a non-aqueous solvent. Non-limiting examples of solvents include cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and vinylene carbonate (VC); acyclic carbonates such as dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), and dipropyl carbonate (DPC); lactones such as γ-butyrolactone (g-BL) and γ-valerolactone (g-VL); acyclic ethers such as 1,2-dimethoxyethane (DME), 1,2-diethoxyethane (DEE), ethoxy methoxy ethane (EME), trimethoxymethane, and ethylmonoglyme; cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane and dioxolane derivatives;and other solvents such as dimethyl sulfoxide, formamide, acetamide, dimethylformamide, acetonitrile, propylnitrile, nitromethane, phosphoric acid triesters, sulfolane, methylsulfolane, propylene carbonate derivatives and mixtures thereof.;

[0121] In another example, the electrolyte is a gel electrolyte or a gel polymer electrolyte. The gel polymer electrolyte may comprise, for example, a polymer precursor and a salt (e.g., a salt as defined above), a solvent (e.g., a solvent as defined above), and a polymerization and / or crosslinking initiator, if desired. Examples of gel electrolyte include, but are not limited to, gel electrolytes such as those described in PCT patent applications published under numbers WO2009 / 111860 (Zaghib et al.) and WO2004 / 068610 (Zaghib et al.).

[0122] In another example, a gel electrolyte or a liquid electrolyte as defined above may also impregnate a separator such as a polymer separator. Examples of separators include, but are not limited to, polyethylene (PE), polypropylene (PP), cellulose, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), and polypropylene-polyethylene-polypropylene (PP / PE / PP) separators. For example, the separator is a commercial polymer separator such as Celgard. MC .

[0123] In another example, the electrolyte is a solid polymer electrolyte. For example, the solid polymer electrolyte may be selected from any known solid polymer electrolyte and may be chosen for its compatibility with the various elements of an electrochemical cell. Solid polymer electrolytes generally comprise a salt as well as one or more solid polar polymer(s), optionally crosslinked. Polyether-type polymers, such as those based on polyethylene oxide (PEO), may be used, but several other compatible polymers are also known for the preparation of solid polymer electrolytes and are also contemplated. The polymer may be crosslinked. Examples of such polymers include branched polymers, for example, star polymers or comb polymers such as those described in PCT patent application published under number WO2003 / 063287 (Zaghib et al.).

[0124] According to another example, the solid polymer electrolyte may include a block copolymer composed of at least one lithium ion solvation segment and optionally at least one crosslinkable segment. Preferably, the lithium ion solvation segment is selected from homo- or copolymers having repeating units of Formula VIII:

[0125] -(CH2-CH-0) x -

[0126] R

[0127] Formula VIII in which,

[0128] R is chosen from a hydrogen atom, and a C1-C10alkyl group or a -(CH2-O-R a R b );

[0129] R a is (CH2-CH2-0) y ;

[0130] R b is selected from a hydrogen atom and a C1-C10alkyl group; x is an integer selected from the range of 10 to 200,000; and y is an integer selected from the range of 0 to 10.

[0131] According to another example, the crosslinkable segment of the copolymer is a polymer segment comprising at least one functional group crosslinkable multidimensionally by irradiation or by heat treatment. When the electrolyte is a liquid electrolyte, a gel electrolyte or a solid polymer electrolyte, the coated particles as defined herein may be present as an additive in the electrolyte.

[0132] Where the electrolyte is a polymer-ceramic hybrid solid electrolyte or a ceramic-type solid electrolyte, the coated particles as defined herein may be present as an inorganic (ceramic) solid electrolyte material.

[0133] In another example, the electrolyte may also optionally include additional components such as ionically conductive materials, inorganic particles, glass or ceramic particles as defined above, and other additives of the same type. In another example, the additional component may be a dicarbonyl compound such as those described in PCT patent application published under number WO2018 / 116529 (Asakawa et al.). For example, the additional component may be poly(ethylene-alt-maleic anhydride) (PEMA). The additional component may be chosen for its compatibility with the various elements of an electrochemical cell. In one example, the additional component may be substantially dispersed in the electrolyte. Alternatively, the additional component may be present in a separate layer.

[0134] The present technology also relates to a coating material for a current collector comprising coated particles as defined herein, wherein the core of the coated particle comprises an electronically conductive material. For example, the coated particles may be coated conductive carbon particles that may be coated onto a metal current collector foil (e.g., aluminum or copper foil). A current collector comprising the coating material coated onto a metal foil is also contemplated.

[0135] The present technology also relates to an electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, wherein at least one of the positive electrode or the negative electrode is as defined herein or comprises an electrode material as defined herein.

[0136] According to an alternative embodiment of interest, the negative electrode is as defined herein or comprises an electrode material as defined herein. For example, the electrochemically active material of the negative electrode may be chosen for its electrochemical compatibility with the various elements of the electrochemical cell as defined herein. For example, the electrochemically active material of the negative electrode material may have a substantially lower oxidation-reduction potential than that of the electrochemically active material of the positive electrode.

[0137] According to another variant of interest, the positive electrode is as defined herein or comprises an electrode material as defined herein and the negative electrode includes an electrochemically active material selected from all known compatible electrochemically active materials. For example, the electrochemically active material of the negative electrode may be chosen for its electrochemical compatibility with the various elements of the electrochemical cell as defined herein. Non-limiting examples of electrochemically active materials of the negative electrode include alkali metals, alkaline earth metals, alloys comprising at least one alkali or alkaline earth metal, non-alkali and non-alkaline earth metals (e.g., indium (In), germanium (Ge) and bismuth (Bi)), and alloys or intermetallic compounds (e.g., SnSb, TiSnSb, Cii2Sb, AlSb, FeSb2, FeSri2 and CoSri2).For example, the electrochemically active material of the negative electrode may be in the form of a film having a thickness in the range of about 5 μm to about 500 μm and preferably in the range of about 10 μm to about 100 μm, upper and lower limits inclusive. According to an alternative embodiment of interest, the electrochemically active material of the negative electrode may comprise a film of metallic lithium or of an alloy including or based on metallic lithium.

[0138] According to another example, the positive electrode may be prelithiated and the negative electrode may be initially (i.e., before cycling of the electrochemical cell) substantially or completely free of lithium. The negative electrode may be lithiated in situ during cycling of said electrochemical cell, in particular during the first charge. According to one example, metallic lithium may be deposited in situ on the current collector (e.g., a copper current collector) during cycling of the electrochemical cell, in particular during the first charge. According to another example, an alloy including metallic lithium may be generated on the surface of a current collector (e.g., an aluminum current collector) during cycling of the electrochemical cell, in particular during the first charge. It is understood that the negative electrode may be generated in situ during cycling of the electrochemical cell, in particular during the first charge.

[0139] According to another embodiment of interest, the positive electrode and the negative electrode are both as defined herein or both comprise an electrode material as defined herein.

[0140] The present technology also relates to an electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, wherein the electrolyte is as defined herein.

[0141] The present technology also relates to an electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, wherein at least one of the positive electrode and the negative electrode is on a current collector as defined herein or comprising a coating material as defined herein.

[0142] The present technology also relates to a battery comprising at least one electrochemical cell as defined herein. For example, the battery may be a primary (cell) or secondary (accumulator) battery. According to one example, the battery is selected from the group consisting of a lithium battery, a lithium-ion battery, a sodium battery, a sodium-ion battery, a magnesium battery, a magnesium-ion battery, a potassium battery and a potassium-ion battery. According to a variant of interest, the battery is a so-called all-solid-state battery.

[0143] In another example, the coating material may allow a substantial reduction in the number and size of particle agglomerates in the dispersion. For example, the coating material allows a substantial reduction in the number and size of particle agglomerates of electronically conductive material or ceramic-type electrolyte material. Without wishing to be bound by theory, for example, repulsive interactions related to the coating material may allow a better dispersion of the constituents of the positive electrode in the dispersion, whether or not the other constituents allowing this type of interaction are modified. For example, the repulsive interactions may be pp-type and / or polar interactions.

[0144] According to another example, the coating material can also substantially limit parasitic reactions with other constituents of the electrochemical cell, and thus improve the cycling and aging stability of the electrochemical cell.

[0145] In another example, the coating material may also substantially limit charge transfer resistance and may substantially improve ionic and / or electronic conductivity due to the double or triple bonds present in the coating material. Without wishing to be bound by theory, the p orbitals of the coating material as defined herein may allow orbital delocalization and thus orbital interactions with ions and / or electrons.

[0146] In another example, the coating material may also substantially improve the safety of the electrochemical cell, for example, by reducing gas generation. For example, when applied to a sulfide-based ceramic-type electrolyte material particle, the coating may substantially reduce the amount of hydrogen sulfide (H2S) generated by exposure of the coated material to moisture or ambient air. In one example, the coating material may also include organic compounds or molecules for trapping gas molecules (e.g., H2S) and / or for forming a barrier to reduce the introduction of moisture to decrease H2S formation. EXAMPLES

[0147] The following examples are for illustrative purposes and should not be construed as further limiting the scope of the invention as contemplated. These examples will be better understood by reference to the accompanying Figures.

[0148] Example 1 - Preparation of argyrodite-type ceramic particles of formula LiePSsCI

[0149] The coating of LiePSsCI particles was carried out by a wet particle grinding process.

[0150] Coating of LiePSsCI particles was carried out using a PULVERISETTE planetary micromill MC 7. 4 g of LiePSsCI particles were placed in an 80 ml zirconium oxide (or zirconia) grinding jar. A mixture comprising 20 ml of anhydrous decane and 7 ml of squalene (75:25 by volume) and grinding balls with a diameter of 2 mm were added to the jar. The LiePSsCI particles and the mixture of decane and squalene were combined by grinding at a speed of about 300 rpm for about 7.5 hours to produce LiePSsCI particles coated with the mixture of decane and squalene. The resulting particles were subsequently dried under vacuum at a temperature of about 80 °C.

[0151] The same coating procedure was carried out (i) with decane, (ii) with a mixture of decane and squalene (90:10 by volume), (iii) with a mixture of decane and farnesene (85:15 by volume), and (iv) with a mixture of decane, farnesene and squalene (85:7.5:7.5 by volume).

[0152] Example 2 - Preparation of the modified electronically conductive material a) Coating of the electronically conductive material particles with a mixture of decane and squalene (75:25 by volume) The coating method described in Example 1 is used to coat the electronically conductive material. More specifically, the wet particle grinding method is used to coat the coating material comprising a mixture of decane and squalene (75:25 by volume) with carbon black. b) Grafting of the electronically conductive material particles with at least one aryl group of Formula I

[0153] The following process for the production of electronic conductive material was applied to carbon black.

[0154] 5 g of carbon black were dispersed in 200 ml of 0.5 M aqueous sulfuric acid (H2SO4) solution, then 0.01 equivalent of aniline p-substituted with a hydrophilic substituent (-SO3H which was then lithiated in order to exchange hydrogen with lithium) was added to the mixture (i.e. 0.01 equivalent of aniline relative to the carbon black). The mixture was then stirred vigorously until the amine was completely dissolved.

[0155] After addition of 0.03 equivalents of sodium nitrite (NaNO2) relative to carbon black (e.g., 3 equivalents of NaNO2 relative to aniline), the corresponding aryl diazonium ion was generated in situ and reacted with the carbon black. The resulting mixture was left to react overnight at room temperature.

[0156] After the reaction was completed, the mixture was vacuum filtered using a vacuum filtration assembly (Büchner type) and a nylon filter with a pore size of 0.22 μm. The modified carbon black powder thus obtained was then washed successively with deionized water until a neutral pH was reached, and then with acetone. Finally, the modified carbon black powder was then dried under vacuum at 100 °C for at least one day before use.

[0157] Example 3 - Characterization of coated particles a) Scanning electron microscopy (SEM)

[0158] The Li6PS5CI particles coated with the mixture of decane and squalene (75:25 by volume) prepared in Example 1 were characterized by SEM imaging. Figure 1 shows in (A) an SEM image of Ü6PS5CI particles before the milling and coating step and in (B) an SEM image of LiePSsCI particles coated with the mixture of decane and squalene (75:25 by volume) prepared in Example 1. The scale bars represent 20 pm.

[0159] Figure 1(B) confirms the reduction in the size of the LÎ6PS5CI particles as well as the presence of the coating on them and does not show any agglomeration of said particles following the coating. b) Thermogravimetric analysis (TGA)

[0160] The squalene-coated LÎ6PS5CI particles prepared in Example 1 were characterized by TGA imaging.

[0161] Thermogravimetric curves of squalene (¨; curve 1) and squalene-coated Ü6PS5CI particles prepared in Example 1 (o; curve 2) are shown in Figure 2. Thermogravimetric analyses were performed at a temperature ramp rate of 10 °C / min. Figure 2 shows that squalene remains stable up to about 254 °C, at which temperature the onset of thermal degradation can be observed. Figure 2 also shows a mass variation for the sample comprising squalene-coated Ü6PS5CI particles at a similar temperature. Indeed, a mass loss can be observed starting at a temperature of about 233 °C, which is the signature of thermal evaporation of squalene adsorbed on the particle surface. A slight temperature difference can be observed because unlike pure squalene which is free, the squalene which constitutes the coating of the particles is adsorbed in a thin layer.Figure 2 confirms the presence of squalene coating on LÎ6PS5CI particles. c) Nuclear magnetic resonance (NMR).

[0162] Proton and carbon nuclear magnetic resonance (NMR) spectra 1 H and 13 C) were obtained by the MAS (magic angle spinning) technique using a Bruker Avance spectrometer MC NEO 500 MHz equipped with a 4 mm triple resonance probe with a maximum magic angle rotation speed of 15 kHz.

[0163] Figure 3 shows in (A) an NMR spectrum 1 H, and in (B) an NMR spectrum 13 C both obtained for Li6PS5CI particles coated with the mixture of decane and squalene (75:25 by volume) prepared in Example 1 and dried at a temperature of about 80 °C under vacuum for about 5 hours.

[0164] NMR signals 1 H as well as the value of the integral of these signals (in red) of the NMR spectra 1H and 13 C presented in Figure 3(A) confirm the presence of squalene, even after the drying step at a temperature of approximately 80 °C.

[0165] Assignment of NMR signals 13 C presented in Figure 3(B) was carried out based on the data reported by Nam et al. (Nam, AM, et al. "Quantification of squalene in olive oil using 13 C nuclear magnetic resonance spectroscopy", Magnetochemistry 3.4 (2017): 34). These signals confirm the presence of squalene on the surface of the particles without modification of its structure.

[0166] Figure 4 shows an NMR spectrum 1 H obtained for the LÎ6PS5CI particles coated with the mixture of decane and farnesene (85:15 by volume) prepared in Example 1 and dried at a temperature of about 80 °C under vacuum for about 5 hours. Figure 4 also shows an NMR spectrum 1H, obtained for pure farnesene. By comparing the spectrum obtained for Ü6PS5CI particles coated with the mixture of decane and farnesene (85:15 by volume) with the spectrum obtained for pure farnesene, it is possible to confirm the presence of farnesene on the surface of the particles, without modification of its structure.

[0167] Figure 5 shows an NMR spectrum 1 H obtained for the Ü6PS5CI particles coated with the mixture of decane and squalene and farnesene (85:7.5:7.5 by volume) prepared in Example 1 and dried at a temperature of about 80 °C under vacuum for about 5 hours. Figure 5 also shows an NMR spectrum 1 H, obtained for pure farnesene and squalene.

[0168] By comparing the spectrum obtained for the Ü6PS5CI particles coated with the mixture of decane and squalene and farnesene with the spectra obtained for pure farnesene and squalene, it is possible to confirm the presence of squalene and farnesene on the surface of the particles, without modification of their structure.

[0169] Thus, it is possible to coat different unsaturated aliphatic hydrocarbons on the surface of particles, without modifying their structure. Example 4 - Preparation and characterization of positive electrode films a) Preparation of positive electrode films

[0170] 1.55 g of LiNio particles ,6 Mno ,2 Coo ,2O2(NMC 622) coated with commercially sourced LiNbOs type oxide having an average diameter of about 4 pm were mixed with 0.40 g of Li6PS5CI particles prepared in Example 1 having an average diameter of about 200 nm and 0.5 g of carbon black or modified carbon black to form a dry powder mixture. The dry powders were mixed for about 10 minutes using a vortex mixer. A polymer solution was prepared separately by dissolving 0.04 g of polybutadiene and 0.01 g of polynorbornene in 0.94 g of tetrahydrofuran.

[0171] The polymer solution was added to the dry powder mixture. The resulting mixture was mixed for approximately 5 minutes using a planetary centrifugal mixer (Thinky Mixer). An additional solvent, methoxybenzene, was added to the mixture to achieve an optimal viscosity for coating, approximately 10,000 cP. The resulting suspension was coated onto aluminum foil using a doctor blade coating method to obtain a positive electrode film applied to a current collector. The positive electrode film was then dried under vacuum at a temperature of approximately 120 °C for approximately 5 hours.

[0172] A positive electrode film with uncoated Ü6PS5CI particles as an additive was also obtained for comparison by the method of the present example.

[0173] The aluminum foil could also be unmodified carbon-coated aluminum foil or carbon-coated aluminum foil coated with the coating material as defined herein.

[0174] The composition of the positive electrode films is shown in Table 2. Table 2. Composition of the positive electrode films

[0175] ** PB: polybutadiene; PNB: polynorbornene. b) Characterization of the positive electrode films prepared in Example 4(a) Morphological studies of the different positive electrode films were carried out using a scanning electron microscope (SEM) equipped with a detector equipped with an energy dispersive X-ray spectrometer (EDS).

[0176] Figure 6 shows in (A) and (B) images obtained by SEM and elemental microanalyses by EDS allowing the analysis of the distribution of the elements (Ni and S) by mapping obtained respectively for Films 1 and 2 prepared in Example 4(a). The scale bars represent 100 pm.

[0177] It is possible to observe in Figure 6(A) the presence of sulfide agglomerates on the section of the reference positive electrode film comprising uncoated U6PS5CI particles (Film 1). Comparatively, Figure 6(B) confirms the absence of these agglomerates when analyzing the section of Film 2 including U6PS5CI particles coated with the decane:squalene mixture (75:25 by volume). Thus, the coating of the U6PS5CI particles with unsaturated aliphatic hydrocarbons comprising at least one double or triple bond allows their good dispersion and the absence of agglomerates.

[0178] Figure 7 shows in (A) an SEM image for Movie 3 and an enlargement of this image, and in (B) an SEM image for Movie 4 and an enlargement of this image. The scale bars of the SEM images and their enlargement represent 300 pm and 100 pm, respectively.

[0179] In Figure 7(A), it is possible to observe the presence of carbon agglomerates on the section of Film 3 composed of a reference positive electrode film comprising LiePSsCI particles coated with decane. The presence of these carbon agglomerates could cause a decrease in electrochemical performance, particularly from the point of view of electronic percolation, and therefore, stability and cycling performance. Comparatively, Figure 7(B) confirms the absence of these agglomerates on the surface of Film 4 including LiePSsCI particles coated with the mixture of decane:squalene (75:25 by volume).

[0180] Thus the coating of ionically conductive inorganic particles with unsaturated aliphatic hydrocarbons comprising at least one double or triple bond coupled with the surface modification of the electronically conductive material by polar groups allows a repulsion of these two types of particles and thus ensures good dispersion and homogeneity of the composition in thickness and on the surface of the films.

[0181] Example 5 - Electrochemical Properties

[0182] The electrochemical properties of the positive electrode films prepared in Example 4(a) were studied. a) Electrochemical cell configurations The electrochemical cells were assembled according to the following procedure.

[0183] Pellets of 10 mm diameter were taken from the positive electrode films prepared in Example 4(a). Sulfide-based ceramic-type inorganic solid electrolytes were prepared by placing 80 mg of LiePSsCl sulfide-based ceramic on the surface of the positive electrode film pellets. The positive electrode film pellets including the inorganic solid electrolyte layer were then compressed under a pressure of 2.8 tons using a press. They were then assembled, in a glove box, in CR2032-type coin cell cases facing 10 mm diameter lithium metal electrodes on aluminum and copper current collectors. The electrochemical cells were assembled according to the configurations shown in Table 3.

[0184] Table 3. Electrochemical cell configurations b) Behavior of positive electrode films

[0185] This example illustrates the electrochemical behavior of electrochemical cells as described in Example 5(a).

[0186] The electrochemical cells assembled in Example 5(a) were cycled between 4.3 V and 2.5 V vs Li / Li + at a temperature of 50 °C. The formation cycle was carried out at a constant charge and discharge current of C / 15. Then four cycles were carried out at a constant charge and discharge current of C / 10 followed by four cycles at a constant charge and discharge current of C / 5. Finally, the aging experiments were carried out at a constant charge and discharge current of C / 3.

[0187] Figure 8 shows in (A) a graph of discharge capacity (mAh / g) and coulombic efficiency (%) as a function of the number of cycles, and in (B) a graph of the average potential in charge and discharge (V) as a function of the number of cycles for Cell 1 (A) and for Cell 2 ( ■), as described in Example 3(a).

[0188] It can be observed that the cycling performances are substantially improved by coating the electronically conductive material with the coating materials as defined herein. Indeed, as can be observed, Cell 2 exhibits improved capacity retention during long cycling experiments in comparison with Cell 1. Thus, the coating of the ionically conductive inorganic particles with unsaturated aliphatic hydrocarbons comprising at least one double or triple bond coupled with the surface modification of the electronically conductive material with polar groups allows repulsion of these two types of particles and ensures better ionic and electronic percolation which results in better capacity retention and coulombic efficiency as well as a decrease in the average potential due to the decrease in charge transfer resistance.

[0189] Figure 9 shows in (A) a graph of discharge capacity (mAh / g) and coulombic efficiency (%) as a function of the number of cycles, and in (B) a graph of the average charge and discharge potential (V) as a function of the number of cycles for the

[0190] Cell 2 ( ■ ), Cell 3 (A), Cell 4 (T) and Cell 5 (·), as described in Example 3(a).

[0191] As can be observed, among all the cells tested, a better capacity retention is obtained for Cells 2 and 5 comprising LÎ6PS5CI particles coated with a mixture of decane and squalene.

[0192] Figure 10 shows a graph of discharge capacity (mAh / g) and coulombic efficiency (%) versus cycle number for Cell 2 ( ■), Cell 6 (·), Cell 7 (★), as described in Example 3(a). As can be observed, Cell 7 comprising LÎ6PS5CI particles coated with a mixture of decane, squalene and farnesene exhibits better cycling aging. This demonstrates the feasibility and the interest of coating the surface of particles with a mixture of several unsaturated aliphatic hydrocarbons. It is also possible to vary the ratios of these unsaturated aliphatic hydrocarbons in the mixture.

[0193] Example 6 - Characterization of coating properties a) Characterization of coating properties after cycling by proton nuclear magnetic resonance (NMR) 1 H)

[0194] Figure 11 shows results of proton nuclear magnetic resonance (NMR) analysis 1H) for liquid samples obtained by extraction of Film 4 before cycling (blue) and after cycling (red) with tetrahydrofuran. The NMR spectra 1 H were obtained using a Bruker Avance spectrometer MC NEO NanoBay 300 MHz equipped with a 5 mm wideband dual resonance probe. The solvent used was deuterated tetrahydrofuran (THF-d8).

[0195] The two enlargements presented in Figure 11 confirm the presence of squalene, both before and after cycling, without modification of the squalene signal even after 160 cycles. Thus, the particles coated with the coating material as defined here do not degrade during aging, thus allowing the stability of the aging performances as demonstrated in Figure 9. b) Generation of hydrogen sulfide (H2S) The safety test was carried out to evaluate the impact of the coating of Li6PS5CI particles on the generation of hydrogen sulfide (H2S). Approximately 80 mg of decane-coated (dashed line), decane:squalene (85:15 by volume) coated (dashed-dot-dot line), and decane:squalene (75:25 by volume) coated (solid line) U6PS5CI particles powder were each placed separately in a pre-dried cell.

[0196] A quantity of ambient air at a controlled temperature of approximately 20 °C and controlled humidity was introduced into the cell. The amount of H2S gas generated was measured with a portable detector. The results of these analyses are presented in Figure 12. Figure 12 shows a graph of the volume of H2S gas generated per gram of powder (mL / g) versus time (hours). Sulfide coating could therefore significantly reduce the amount of H2S generated, and thus improve the safety of electrochemical systems.

[0197] Several modifications could be made to any of the embodiments described above without departing from the scope of the present invention as contemplated. The references, patents or scientific literature documents referred to in this application are incorporated herein by reference in their entirety and for all purposes.

Claims

DEMANDS 1. Coating material comprising at least one branched or linear unsaturated aliphatic hydrocarbon having 10 to 50 carbon atoms and having at least one carbon-carbon double or triple bond for use in an electrochemical cell.

2. Coating material according to claim 1, in which the boiling point of the unsaturated aliphatic hydrocarbon is greater than 150 °C.

3. Coating material according to claim 1 or 2, wherein the boiling point of the unsaturated aliphatic hydrocarbon is in the range of approximately 150 °C to approximately 675 °C, or from approximately 155 °C to approximately 670 °C, or ranging from about 160 °C to about 665 °C, or ranging from about 165 °C to about 660 °C, or ranging from about 170 °C to about 655 °C, inclusive upper and lower bounds.

4. Coating material according to any one of claims 1 to 3, wherein the unsaturated aliphatic hydrocarbon is selected from the group consisting of decene, dodecene, undecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, 1,9-decadiene, docosene, hexacosene, eicosene, tetracosene, squalene, farnesene, β-carotene, pinenes, dicyclopentadiene, camphene, α-phellandrene, β-phellandrene, terpinenes, β-myrcene, limonene, 2-carene, sabinene, α-cedrene, copaene, β-cedrene, decyne, dodecyne, octadecyne, hexadecyne, tridecyne, tetradecyne, docosyne, and a combination of at least two of these.

5. Coating material according to any one of claims 1 to 4, wherein the unsaturated aliphatic hydrocarbon is selected from the group consisting of decene, dodecene, undecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, 1,9-decadiene, docosene, hexacosene, eicosene, tetracosene, squalene, farnesene, β-carotene, and a combination of at least two of these.

6. Coating material according to any one of claims 1 to 5, wherein the unsaturated aliphatic hydrocarbon is selected from the group consisting of decene, undecene, octadecene, squalene, farnesene, β-carotene, and a combination of at least two of these.

7. Coating material according to any one of claims 1 to 6, wherein the unsaturated aliphatic hydrocarbon comprises squalene.

8. Coating material according to any one of claims 1 to 6, wherein the unsaturated aliphatic hydrocarbon comprises farnesene.

9. Coating material according to any one of claims 1 to 6, wherein the unsaturated aliphatic hydrocarbon comprises squalene and farnesene.

10. Coating material according to any one of claims 1 to 9, which is a mixture comprising the unsaturated aliphatic hydrocarbon and an additional component.

11. Coating material according to claim 10, wherein the additional component is an alkane or a mixture comprising an alkane and a polar solvent.

12. Coating material according to claim 11, wherein the alkane comprises from 10 to 50 carbon atoms.

13. Coating material according to claim 11 or 12, wherein the alkane is decane.

14. Coating material according to any one of claims 11 to 13, wherein the polar solvent is selected from tetrahydrofuran, acetonitrile, N,N-dimethylformamide and a miscible combination of at least two of these.

15. Coating material according to claim 14, wherein the polar solvent is tetrahydrofuran.

16. Coated particles for use in an electrochemical cell, said coated particle comprising: a core comprising an electrochemically active material, an electronically conductive material, or an ionically conductive inorganic material; and a coating material as defined in claims 1 to 15, the coating material being disposed on the surface of the core.

17. Coated particles according to claim 16, in which the coating material forms a homogeneous coating layer on the surface of the core.

18. Coated particles according to claim 16, wherein the coating material forms a coating layer over at least a portion of the core surface.

19. Coated particles according to claim 18, wherein the coating material is heterogeneously dispersed over the core surface.

20. Coated particles according to any one of claims 16 to 19, which are used in an electrode material.

21. Coated particles according to any one of claims 16 to 19, which are used in an electrolyte.

22. Coated particles according to any one of claims 16 to 19, which are used in a current collector.

23. A method for manufacturing coated particles as defined in any one of claims 16 to 19, the method comprising at least one step of coating at least a part of the surface of the core with the coating material.

24. A process according to claim 23, wherein the coating step is carried out by a dry coating process.

25. A method according to claim 23, wherein the coating step is carried out by a wet coating process.

26. A method according to claim 25, wherein the wet coating process is a mechanical coating process.

27. A process according to claim 26, wherein the mechanical coating process is a mechanosynthesis or mechanofusion process.

28. A method according to any one of claims 23 to 27, further comprising a step of grinding the electrochemically active material, the electronically conductive material or the ionically conductive inorganic material of the nucleus of the coated particle.

29. A method according to claim 28, wherein the coating and grinding steps are carried out simultaneously, sequentially, or partially overlapping in time.

30. A method according to claim 29, wherein the coating and grinding steps are carried out simultaneously.

31. Electrode material comprising: coated particles as defined in any one of claims 16 to 19, wherein the core of the coated particle comprises an electrochemically active material; and / or an electrochemically active material and coated particles as defined in any one of claims 16 to 19.

32. Electrode material according to claim 31, wherein the core of the coated particle comprises the electrochemically active material.

33. Electrode material according to claim 31 or 32, wherein the electrochemically active material is selected from a metal oxide, a metal sulfide, a metal oxysulfide, a metal phosphate, a metal fluorophosphate, a metal oxyfluorophosphate, a metal sulfate, a metal halide, a metal fluoride, sulfur, selenium, and a combination of at least two of these.

34. Electrode material according to claim 33, wherein the metal of the electrochemically active material is selected from titanium (Ti), iron (Fe), manganese (Mn), vanadium (V), nickel (Ni), cobalt (Co), aluminum (Al), chromium (Cr), copper (Cu), zirconium (Zr), niobium (Nb) and a combination of at least two of these.

35. Electrode material according to claim 33, wherein the metal of the electrochemically active material further comprises an alkali or alkaline earth metal selected from lithium (Li), sodium (Na), potassium (K) and magnesium (Mg).

36. Electrode material according to any one of claims 31 to 35, wherein the electrochemically active material is a metal and lithium oxide.

37. Electrode material according to claim 36, wherein the lithium metal oxide is a mixed oxide of lithium, nickel, manganese, and cobalt (NCM).

38. Electrode material according to any one of claims 31 to 35, wherein the electrochemically active material is a lithium metal phosphate.

39. Electrode material according to claim 38, wherein the lithium metal phosphate is lithium iron phosphate.

40. Electrode material according to claim 31 or 32, wherein the electrochemically active material is selected from a non-alkali or non-alkaline-earth metal, an intermetallic compound, a metal oxide, a metal nitride, a metal phosphide, a metal phosphate, a metal halide, a metal fluoride, a metal sulfide, a metal oxysulfide, carbon, silicon (Si), a silicon-carbon composite (Si-C), or silicon dioxide (SiO₂). x ), a silicon-carbon oxide composite (SiO₂) x -C), tin (Sn), a tin-carbon composite (Sn- C), a tin oxide (SnO x ), a tin-carbon oxide composite (SnO x -C), and a combination of at least two of these.

41. Electrode material according to any one of claims 31 to 40, wherein the electrochemically active material further comprises a doping element.

42. Electrode material according to any one of claims 31 to 41, wherein the electrochemically active material further comprises a coating material.

43. Electrode material according to claim 42, wherein the coating material forms a coating layer on the surface of said electrochemically active material and the encapsulating material is disposed on the surface of the coating layer.

44. Electrode material according to claim 42 or 43, wherein the coating material is selected from LhSiOs, LiTaOs, UAIO2, LhO-ZrOa, LiNbOs, other similar coating materials, and a combination of at least two of these.

45. Electrode material according to any one of claims 42 to 44, wherein the coating material is LiNbOs.

46. ​​Electrode material according to claim 42 or 43, wherein the coating material is an electronically conductive material.

47. Electrode material according to claim 46, wherein the electronically conductive material is carbon.

48. Electrode material according to any one of claims 31 to 47, further comprising at least one electronically conductive material.

49. Electrode material according to claim 48, wherein the core of the coated particle comprises the electronically conductive material.

50. Electrode material according to claim 48 or 49, wherein the electronically conductive material is selected from the group consisting of carbon black, acetylene black, graphite, graphene, carbon fibers, carbon nanofibers, carbon nanotubes, and a combination of at least two of these.

51. Electrode material according to claim 50, wherein the electronically conductive material is carbon black.

52. Electrode material according to any one of claims 48 to 51, wherein the surface of said electronically conductive material is grafted with at least one aryl group of Formula I: Formula I in which, FG is a hydrophilic functional group; and n is a natural number in the range of 1 to 5, preferably n is in the range of 1 to 3, preferably n is 1 or 2, and more preferably n is 1.

53. Electrode material according to claim 52, wherein the hydrophilic functional group is a carboxylic acid or sulfonic acid functional group.

54. Electrode material according to claim 52, wherein the aryl group of Formula I is p-benzoic acid or p-benzenesulfonic acid.

55. Electrode material according to any one of claims 31 to 54, further comprising at least one additive.

56. Electrode material according to claim 55, wherein the core of the coated particle comprises the additive.

57. Electrode material according to claim 55 or 56, wherein the additive is selected from inorganic ion-conducting materials, inorganic materials, glasses, glass-ceramics, ceramics, nano-ceramics, salts, and a combination of at least two of these.

58. Electrode material according to any one of claims 55 to 57, wherein the additive comprises ceramic, glass, or glass-ceramic particles based on fluoride, phosphide, sulfide, oxysulfide, or oxide.

59. Electrode material according to any one of claims 55 to 58, wherein the additive is selected from compounds of the type LISICON, thio-LISICON, argyrodites, garnets, NASICON, perovskites, oxides, sulfides, oxysulfides, phosphides, fluorides in crystalline and / or amorphous form, and a combination of at least two of these.

60. Electrode material according to any one of claims 55 to 59, wherein the additive is selected from inorganic compounds of the following formulas: MLZO (for example, M7La3Zr20i2, M(7- a) La3Zr2AlbOi2, M(7- a) La3Zr2GabOi2, M(7- a >La3Zr(2-b)TabOi2, and M(7- a >La3Zr(2-b)NbbOi2); MLTaO (for example, M7La3Ïa20i2, M5La3Ta20i2, and M6La3Ta1.5Y0.5O12); MLSnO (for example, M7La3Sn20i2); MAGP (for example, Mi +a Al a Ge2- a (P04)3); MATP (for example, Mi +a Al a TÎ2- a (P04)3,); - MLTiO (e.g., M 3a The (2 / 3-a) Ti03); MZP (e.g., M a Zrb(P04) c ); MCZP (e.g., M a CabZr c (P04)d); MGPS (e.g., M a Here b P c S d such as MioGeP2Si2); MGPSO (e.g., M a Here b P c S d OH e ); MSiPS (e.g., M a If b P c S d such that M 10 S1P2S 12 ); MSiPSO (e.g., M a If b P c S d OH e ); MSnPS (e.g., M a Sn b P c S d such as MioSnP2Si2); MSnPSO (e.g., M a Sn b P c S d OH e ); MPS (e.g., M a P b S c such as M7P3S 11 ); MPSO (for example, M a P b S c O d ); MZPS (for example, M a Zn b P c S d ); MZPSO (for example, M a Zn b P c S d O e ); - xM2S-yP2S5; - xM2S-yP2S5-zMX; xM2S-yP2S5-zP205; - xM2S-yP2S5-zP205-wMX; - xM2S-yM20-zP2S5; - xM2S-yM20-zP2S5-wMX; - xM2S-yM20-zP2S5-wP205; - xM2S-yM20-zP2S5-wP205-vMX; - xM2S-ySiS2; MPSX (for example, M a P b S c X d such as M7P3S 11 X, M7P2S8X, and M6PS5X); MPSOX (for example, M a PbS c OdX e ); MGPSX (for example, M a GebP c SdX e ); MGPSOX (for example, M a Ge b P c S d O e X f ); MSiPSX (for example, Ma SibP c SdXe); MSiPSOX (for example, M a If b P c S d O e X f ); MSnPSX (for example, M a SnbP c SdXe); - MSnPSOX (for example, M a SribPcSdOeXf); MZPSX (for example, M a ZnbP c SdXe); MZPSOX (for example, M a Zn b P c S d O e X f ); - M3OX; - M2HOX; - M3PO4; M3PS4; and M a PO b Nc (where a = 2b + 3c - 5); in which, M is an alkali metal ion, an alkaline earth metal ion, or a combination thereof, and in which, when M comprises an alkaline earth metal ion, then the number of M is adjusted to achieve electroneutrality; X is chosen from F, Cl, Br, I or a combination of at least two of these; a, b, c, d, e and f are non-zero numbers and are, independently in each formula, selected to achieve electroneutrality; and v, w, x, y and z are non-zero numbers and are, independently in each formula, selected to obtain a stable compound.

61. Electrode material according to claim 60, wherein M is selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba or a combination of at least two of these.

62. Electrode material according to claim 61, wherein M is Li.

63. Electrode material according to any one of claims 55 to 62, wherein the additive is selected from argyrodite-type inorganic compounds of formula LiePSsX, wherein X is Cl, Br, I or a combination thereof.

64. Electrode material according to any one of claims 55 to 63, wherein the additive is Li6PS5Cl.

65. Electrode material according to any one of claims 31 to 64, further comprising a binder.

66. Electrode material according to claim 65, wherein the binder is selected from the group consisting of a polymer binder of the type polyether, polycarbonate or polyester, a fluorinated polymer and a water-soluble binder.

67. Electrode material according to claim 65, wherein the binder comprises a mixture of a polybutadiene-based polymer and a polymer comprising norbornene-based monomer units derived from the polymerization of a Formula II compound: Formula II in which, R 1 and R 2are independently and at each occurrence chosen from among a hydrogen atom, a carboxyl group (-COOH), a sulfonic acid group (-SO3H), a hydroxyl group (-OH), a fluorine atom and a chlorine atom.

68. Electrode material according to claim 67, wherein the polymer is a Formula III polymer: Formula III in which, R 1 and R 2 are as defined in claim 67, and n is a natural integer chosen so that the average molecular weight by mass of the Formula II polymer is between approximately 10000 g / mol and approximately 100,000 g / mol, inclusive upper and lower bounds.

69. Electrode material according to claims 67 and 68, wherein R 1 and R 2 are independently and at each occurrence chosen from a hydrogen atom and a -COOH group.

70. Electrode material according to claim 69, wherein R 1 is a group -COOH and R 2 is a hydrogen atom.

71. Electrode material according to claim 69, wherein R 1 and R 2 are both -COOH groups.

72. Electrode material according to any one of claims 67 to 71, wherein the polybutadiene-based polymer is polybutadiene.

73. Electrode material according to any one of claims 67 to 71, wherein the polybutadiene-based polymer is selected from epoxidized polybutadienes.

74. Electrode material according to claim 73, wherein the epoxy-coated polybutadiene comprises repeating units of Formulas IV, V and VI: and two terminal hydroxyl groups.

75. Electrode material according to claim 74, wherein the epoxy-coated polybutadiene is of Formula VII: in which, m is a natural number chosen so that the average molecular weight by mass of epoxidized polybutadiene of Formula VI is between about 1000 g / mol and about 1500 g / mol, upper and lower bounds inclusive; and the equivalent weight of epoxide is between about 100 g / mol and about 600 g / mol, upper and lower bounds inclusive.

76. Electrode material according to claim 75, wherein the average molecular weight by mass of epoxidized polybutadiene of Formula VII is about 1300 g / mol.

77. Electrode material according to claim 75 or 76, wherein the equivalent weight of epoxy is between approximately 210 g / mol and approximately 550 g / mol, inclusive of the upper and lower ends.

78. Electrode material according to any one of claims 75 to 77, wherein the epoxy-coated polybutadiene of Formula VII is a Poly bd resin MC600E having a mass average molecular weight of about 1300 g / mol and an equivalent epoxy weight of between about 400 g / mol and about 500 g / mol, inclusive upper and lower bounds.

79. Electrode material according to any one of claims 75 to 77, wherein the epoxy-coated polybutadiene of Formula VII is a Poly bd resin MC 605E having a mass average molecular weight of about 1300 g / mol and an equivalent epoxide weight between about 260 g / mol and about 330 g / mol, upper and lower bounds inclusive.

80. Electrode material according to any one of claims 67 to 79, wherein the weight ratio of polybutadiene-based polymer to polymer comprising norbornene-based monomer units derived from the polymerization of the Formula II compound is in the range of approximately 6:1 to approximately 2:3, inclusive upper and lower bounds.

81. Electrode material according to claim 80, wherein the weight ratio is within the range of about 5.5:1 to about 2:3, or about 5:1 to about 2:3, or about 4.5:1 to about 2:3, or about 4:1 to about 2:3, or about 6:1 to about 1:1, or about 5.5:1 to about 1:1, or about 5:1 to about 1:1, or about 4.5:1 to about 1:1, or about 4:1 to about 1:1, inclusive of upper and lower bounds.

82. Electrode material according to claim 81, wherein the weight ratio is in the range of approximately 4:1 to approximately 1:1, inclusive of the upper and lower terminals.

83. Electrode comprising the electrode material as defined in any one of claims 31 to 82 on a current collector.

84. Self-supporting electrode comprising the electrode material as defined in any one of claims 31 to 82.

85. Electrode according to claim 83 or 84, said electrode being a positive electrode.

86. Electrolyte comprising coated particles as defined in any one of claims 16 to 19, wherein the nucleus of the coated particle comprises an ionically conductive inorganic material.

87. Electrolyte according to claim 86, wherein the ionically conductive inorganic material is selected from glasses, glass-ceramics, ceramics, nano-ceramics and a combination of at least two of these.

88. Electrolyte according to claims 86 and 87, wherein the ionically conductive inorganic material comprises a ceramic, a glass or a glass-ceramic based on fluoride, phosphide, sulfide, oxysulfide or oxide.

89. Electrolyte according to any one of claims 86 to 88, wherein the ionically conductive inorganic material is selected from compounds of the type LISICON, thio-LISICON, argyrodites, garnets, NASICON, perovskites, oxides, sulfides, oxysulfides, phosphides, fluorides in crystalline and / or amorphous form, and a combination of at least two of these.

90. Electrolyte according to any one of claims 86 to 89, wherein the ionically conductive inorganic material is selected from inorganic compounds of formulas: MLZO (for example, M(7- a) La3Zr(2-b)TabOi2, and M(7- a >La3Zr(2-b)NbbOi2); MLTaO (for example, M7La3Ïa20i2, M5La3Ta20i2, and M6La3Ta1.5Y0.5O12); MLSnO (for example, M7La3Sn20i2); MAGP (for example, Mi +a Al a Ge2- a (P04)3); MATP (for example, Mi +a Al a Ti2- a (P04)3,); - MLTiO (e.g., M 3a The (2 / 3-a) Ti03); MZP (e.g., M a Zrb(P04) c ); MCZP (e.g., M a CabZr c (P04)d); MGPS (e.g., M a Here b P c S d such as MioGeP2Si2); MGPSO (e.g., M a Here b P c S d OH e ); MSiPS (e.g., M a If b P c S d such that M 10 S1P2S 12 ); MSiPSO (e.g., M a If b P c S d OH e ); MSnPS (e.g., M a Sn b P c S d such as MioSnP2Si2); MSnPSO (e.g., M a Sn b P c S d OH e ); MPS (e.g., M a P b S c such as M7P3S11); MPSO (for example, M a P b S c O d ); MZPS (for example, M a Zn b P c S d ); MZPSO (for example, M a Zn b P c S d O e ); - xM2S-yP2S5; - xM2S-yP2S5-zMX; xM2S-yP2S5-zP205; - xM2S-yP2S5-zP205-wMX; - xM2S-yM20-zP2S5; - xM2S-yM20-zP2S5-wMX; - xM2S-yM20-zP2S5-wP205; - xM2S-yM20-zP2S5-wP205-vMX; - xM2S-ySiS2; MPSX (for example, M a P b S c X d such as M7P3S 11 X, M7P2S8X, and M6PS5X); MPSOX (for example, M a PbS c OdX e ); MGPSX (for example, M a GebP c SdX e ); MGPSOX (for example, M a Ge b P c S d O e X f ); MSiPSX (for example, Ma SibP c SdXe); MSiPSOX (for example, M a If b P c S d O e X f ); MSnPSX (for example, M a SribPcSdXe); MSnPSOX (for example, M a Sn b P c S d O e X f ); MZPSX (for example, M a ZnbP c SdXe); MZPSOX (for example, M a Zn b P c S d O e X f ); - M3OX; - M2HOX; - M3PO4; M3PS4; and M a PO b N c (where a = 2b + 3c - 5); in which, M is an alkali metal ion, an alkaline earth metal ion, or a combination thereof, and in which, when M comprises an alkaline earth metal ion, then the number of M is adjusted to achieve electroneutrality; X is chosen from F, Cl, Br, I or a combination of at least two of these; a, b, c, d, e and f are non-zero numbers and are, independently in each formula, selected to achieve electroneutrality; and v, w, x, y and z are non-zero numbers and are, independently in each formula, selected to obtain a stable compound.

91. Electrolyte according to claim 90, wherein M is selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba or a combination of at least two of these.

92. Electrolyte according to claim 91, wherein M is Li.

93. Electrolyte according to any one of claims 86 to 92, wherein the ionically conductive inorganic material is selected from argyrodite-type inorganic compounds of formula L16PS5X, where X is Cl, Br, I, or a combination of at least two of these.

94. Electrolyte according to any one of claims 86 to 93, wherein the ionically conductive inorganic material is L16PS5Cl.

95. Electrolyte according to any one of claims 86 to 94, which is a liquid electrolyte comprising a salt in a solvent.

96. Electrolyte according to any one of claims 86 to 94, which is a solid polymer electrolyte comprising a salt in a solvating polymer.

97. Electrolyte according to any one of claims 86 to 94, which is a solid hybrid polymer-ceramic electrolyte.

98. Electrolyte according to any one of claims 86 to 94, which is an inorganic solid electrolyte.

99. Electrolyte according to claim 98, which is an inorganic solid electrolyte of the ceramic type.

100. Coating material for a current collector comprising coated particles as defined in any one of claims 16 to 19, wherein the core of the coated particle comprises an electronically conductive material.

101. Coating material according to claim 100, wherein the electronically conductive material is carbon.

102. Current collector comprising a coating material as defined in claim 100 or 101 disposed on a metal foil.

103. Electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte, wherein at least one of the positive or negative electrodes is as defined in claim 83 or 84 or comprises an electrode material as defined in any one of claims 31 to 82.

104. Electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, wherein the electrolyte is as defined in any one of claims 86 to 99.

105. An electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte, wherein at least one of the positive and negative electrodes is on a current collector as defined in claim 102 or comprising a coating material as defined in claim 100 or 101.

106. An electrochemical cell according to claim 104 or 105, wherein the negative electrode comprises an electrochemically active material comprising an alkali metal, an alkaline earth metal, an alloy comprising at least one alkali or alkaline earth metal, a non-alkaline and non-alkaline earth metal, or an intermetallic alloy or compound.

107. An electrochemical cell according to claim 106, wherein the electrochemically active material of the negative electrode comprises metallic lithium or an alloy including or based on metallic lithium.

108. Electrochemical cell according to claim 106 or 107, wherein the electrochemically active material of the negative electrode is in the form of a film having a thickness in the range of about 5 pm to about 500 pm, inclusive of upper and lower terminals.

109. Electrochemical cell according to claim 108, wherein the thickness of the film of electrochemically active material of the negative electrode is in the range of about 10 pm to about 100 pm, inclusive of upper and lower terminals.

110. Electrochemical cell according to any one of claims 104 to 106, wherein the positive electrode is pre-lithiumized and the negative electrode is substantially lithium-free.

111. Electrochemical cell according to any one of claims 110, wherein the negative electrode is lithiated in situ during the cycling of said electrochemical cell.

112. An electrochemical accumulator comprising at least one electrochemical cell as defined in any one of claims 104 to 111.

113. Electrochemical accumulator according to claim 112, wherein said electrochemical accumulator is a battery selected from a lithium battery, a lithium-ion battery, a sodium battery, a sodium-ion battery, a magnesium battery, or a magnesium-ion battery.

114. Electrochemical accumulator according to claim 112, wherein said battery is a lithium battery or a lithium-ion battery.

115. Electrochemical accumulator according to claim 112, wherein said electrochemical accumulator is a so-called all-solid battery.

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