Polymer-inorganic particle composition, preparation processes, and use in electrochemical cells

Abstract

Compositions comprising a polymer and inorganic particles are described herein. The polymer in these compositions is the reaction product of at least one monomer comprising at least one polymerizable or crosslinkable function and an organic compound comprising one or more SH groups. Processes for preparing the compositions and uses thereof in the elements of an electrochemical cell are also described.

Description

[0001] POLYMER-INORGANIC PARTICLE COMPOSITION, METHODS OF MANUFACTURE AND USE IN ELECTROCHEMICAL CELLS

[0002] RELATED REQUEST

[0003] This application claims priority under applicable law from Canadian patent application number 3,145,586 filed on January 14, 2022, the contents of which are incorporated herein by reference in their entirety and for all purposes.

[0004] TECHNICAL FIELD

[0005] The present technology relates to compositions comprising a polymer and inorganic particles, the polymer being the product of the reaction of at least one monomer comprising at least one polymerizable or crosslinkable function and an organic compound comprising one or more SH groups.

[0006] STATE OF THE ART

[0007] Liquid electrolytes used in lithium-ion batteries are flammable and slowly degrade to form a passivation layer on the surface of the lithium film or solid electrolyte interface (SEI), irreversibly consuming lithium, which decreases the battery's Coulombic efficiency. In addition, lithium anodes undergo significant morphological changes during battery cycling, and lithium dendrites are formed. Since these typically migrate through the electrolyte, they can eventually cause short circuits.

[0008] Safety concerns and the requirement for higher energy density have stimulated research for the development of an all-solid-state lithium rechargeable battery with a polymer or ceramic (or ceramic-polymer composite) electrolyte, both of which are more stable towards metallic lithium and reduce the growth of lithium dendrites. However, some disadvantages result from the use of such solid electrolytes, e.g., loss of ionic reactivity or conductivity, poor contact between solid interfaces, etc.

[0009] Furthermore, manufacturing processes for solid electrolytes comprising a polymer, either as a solid polymer electrolyte or in a ceramic-polymer composite, generally require the presence of a polymerization initiator and polymerization conditions by heating or irradiation, which often requires additional equipment and longer manufacturing times. In addition, this polymerization initiator will remain trapped inside the film, which may, for example, interfere with the electrochemical reaction during cycling.

[0010] There is therefore a constant need for the development of new electrolyte compositions and processes for their manufacture.

[0011] SUMMARY

[0012] According to a first aspect, the present technology relates to a composition comprising a polymer and inorganic particles, the polymer being the product of the reaction of at least one monomer comprising at least one polymerizable or crosslinkable function and of an organic compound comprising one or more SH groups.

[0013] According to one embodiment, the monomer is a compound of formula R 2 (X) m , where R 2 is an organic group, X is a polymerizable or crosslinkable group, and m is a number in the range 1 to 8; or the monomer is a macromonomer comprising at least one crosslinkable segment comprising units of formula R 2 (X) m and optionally a non-crosslinkable polymer segment. In some embodiments, the non-crosslinkable polymer segment is present and is of Formula I:

[0014] Formula I in which,

[0015] R is a hydrogen atom, a C1-C group 10 alkyl, or a group -(CH2-OR a -R b );

[0016] R a is (CH2-CH2-O)j or (CH(CH3)-CH2-O)j;

[0017] R b is a hydrogen atom or a C1-C group 10 alkyl; i is an integer selected from the range of 2 to 200,000; and j is an integer selected from the range of 0 to 100. In another embodiment, X is a polymerizable or crosslinkable group comprising a double bond. In some embodiments, X is a group of formula -R 3 -C(R 4 )=CH2, WHERE R 3 is O, NH, OCH2, NHCH2, OC(O), NHC(O), or is absent and forms a covalent bond, and R 4 is H, C1-C 10 aCalkyl or C3-C 10 cycloalkyl.

[0018] According to one embodiment, the polymer units originating from the monomer comprise units of at least one of the formulas: in which R 2 , R 3 , R 4 and m are as defined previously, and where — when attached to C(R 3 R 4 ) or CH2represents a bond with a hydrogen or sulfur atom of the organic compound, a terminal group, or another unit of the polymer, and represents a macromonomer when adjacent to R 2 .

[0019] According to another embodiment, R 2 or the macromonomer comprising R 2 is chosen from the groups C 2-12 linear or branched alkyl, alkylene oxide or poly(alkylene oxide), alkylene sulfide or poly(alkylene sulfide), siloxane or polysiloxane, and mono or polyaromatic, e.g. R 2 is chosen from the groups C 2-12 linear or branched alkyl, alkylene oxide or poly(alkylene oxide), and phenyl.

[0020] In some embodiments, m is a number in the range of 2 to 4.

[0021] According to one embodiment, the monomer is chosen from branched poly(ethylene glycol) comprising acrylate groups at the end of the main and / or side chain and / or on the chains, poly(ethylene glycol) diacrylate, pentaerythritol tetraacrylate, triethylene glycol divinyl ether, ethylene glycol dimethacrylate, and divinylbenzene.

[0022] In some embodiments, the polymer units from the monomer comprise units of at least one of the formulas:

[0023] in which R 4 and — are as defined above, and p is a non-zero number.

[0024] According to one embodiment, R 4 is H or C1-C6alkyl, preferably H or C1-C3alkyl, preferably H or methyl.

[0025] In another embodiment, the monomer content (before reaction) in the composition is in the range of about 1 wt% to about 95 wt%, or about 2 wt% to about 90 wt%, or about 3 wt% to about 80 wt%, or about 4 wt% to about 50 wt%, or about 10 wt% to about 70 wt%, or about 20 wt% to about 65 wt%.

[0026] According to certain preferred embodiments, the organic compound is of formula R 1 (SH) n , where R 1 is an organic group linking the SH group(s), and where n is a number in the range 1 to 10, or the compound is a macromonomer comprising at least one segment comprising units of formula R 1 (SH) n .

[0027] According to another embodiment, the units of the polymer originating from the organic compound comprise units of at least one of the formulas: in which R 1 and n are as defined above and where — when attached to a sulfur atom represents a link to another unit of the polymer, such as a unit from the monomer, and represents a macromonomer when adjacent to R 1 .

[0028] In one embodiment, R 1 or the segment including R 1 is chosen from the groups C 2-12 linear or branched alkyl, ether or ester of C 2-12 linear or branched alkyl polyol, alkylene oxide or poly(alkylene oxide) optionally comprising one or more sulfur atoms in a chain, alkylene sulfide or poly(alkylene sulfide), siloxane or polysiloxane, mono or poly-cycloalkyl or heterocycloalkyl, mono or poly-aromatic or heteroaromatic fused or unfused optionally comprising a linking atom, or a combination thereof.

[0029] According to some embodiments, n is a number in the range of 1 to 4.

[0030] In one embodiment, the organic compound is selected from 1-(2-mercaptoethoxy-2-ethoxyethyl-2-thioethyl)-2-pyrrolidone, 2,2'-

[0031] (ethylenedioxy)diethanethiol, pentaerythritol tetrakis(3-mercaptopropionate), and 4,4'-thiobisbenzenethiol. For example, the polymer units from the organic compound include units of at least one of the formulas:

[0032] in which — is as previously defined.

[0033] In some preferred embodiments, the organic compound content in the composition (before reaction) is in the range of about 0.01 wt% to about 60 wt%, or about 0.05 wt% to about 50 wt%, or about 10 wt% to about 30 wt%, or about 15 wt% to about 40 wt%.

[0034] According to one embodiment, the polymer of the composition is a polymer of random, block, or alternating configuration.

[0035] According to another embodiment, the inorganic particles comprise an inorganic compound of amorphous, ceramic or glass-ceramic type, for example, based on oxide, sulfide or oxysulfide, the inorganic compound being natural or synthetic.

[0036] According to one embodiment, the inorganic particles comprise a natural or synthetic ceramic selected from inorganic compounds of formulas MLZO (for example, M7La3Zr2O 12 , M (7-a) La3Zr2AlbO 12 , M (7-a) La3Zr2Ga b O 12 , M(7- a )La3Zr (2-b) Your b O 12 , and M(7- a )La3Zr (2-b) NbbO 12 ); MLTaO (e.g., M7La3Ta2O 12 , MsLa3Ta2O 12 , and M6La3Ta1.5Y0.5O 12 ); MLSnO (e.g., M7LasSn2O 12); MAGP (e.g., M 1+a Al a Here 2-a (PO4)3); MATP (e.g., M 1+a Al a Ti 2-a (PO4)3,); MLTiO (e.g., M 3a The (2 / 3-a )TiO3); MZP (e.g., M a Zrb(PO4) c ); MCZP (e.g., M a Ca b Zr c (PO4)d); MGPS (e.g., M a GebP c S d such that M 10 GeP2S 12 ); MGPSO (e.g., M a GebP c S d OH e ); MSiPS (e.g., M a If b P c S d such that M 10 SiP2S 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 that M 10 SnP2S 12 ); MSnPSO (e.g., M a Sn b P c S d OH e ); MPS (e.g., M a P b Sc tel que M7P3S11); MPSO (par exemple, M a P b S c Od); MZPS (par exemple, M a Zn b P c S d ); MZPSO (par exemple, M a ZribP c S d O e ); xM2S-yP2S5; xM2S-yP2S5-zMX; xM2S-yP2S5-zP2O5; xM2S-yP2S5-zP2O5- wMX; xM2S-yM2O-zP2S5; xM2S-yM2O-zP2S5-wMX; xM2S-yM2O-zP2S5-wP2O5; XM2S- yM2O-zP2S5-wP2O5-vMX; xM2S-ySiS2; MPSX (par exemple, M a P b S c Xd tel que M7P3S11X, M7P2S8X, et MePS5X); MPSOX (par exemple, M a P b S c OdX e ); MGPSX (M a GebP c S d X e ); MGPSOX (M a Ge b P c S d O e X f ); MSiPSX (M a Si b P c S d X e ); MSiPSOX (M a Si b P c S d O e X f ); MSnPSX (M a SribP c Sd X e ); MSnPSOX (M a Sn b P c S d O e X f ); MZPSX (M a Zn b P c S d X e ); MZPSOX (M a ZribP 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:

[0037] M is an alkali metal, an alkaline earth metal, or a combination thereof, and wherein when M comprises an alkaline earth metal ion, then the number of M is adjusted to achieve electroneutrality;

[0038] X is selected from F, Cl, Br, I or a combination 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.

[0039] In another embodiment, the inorganic particles comprise a natural or synthetic ceramic selected from AI2O3, Mg2B2O5, Na2O 2B2O3, xMgO yB2O3zH2O, TiO2, ZrO2, ZnO, Ti2O3, SiO2, Cr2O3, CeO2, B2O3, B2O, SrBi4Ti40is, LLTO, LLZO, LAGP, LATP, Fe2O3, BaTiO3y-LiAIO2, molecular sieves and zeolites (e.g., aluminosilicate, mesoporous silica), sulfide ceramics (such as LiePS5CI, U7P3S11), glass-ceramics (such as LIPON, etc.), and other ceramics, as well as combinations thereof.

[0040] In some embodiments, the ceramic has the formula Li7-bLa3Zr2M'bO12 , where b is such that 0 < b < 1 and M' is Al, Ga, Ta, Fe or Nb or is absent, for example, b is 0 and M' is absent. In one embodiment, the ceramic is an aluminosilicate compound. In another embodiment, the ceramic is a sulfide or oxysulfide ceramic.

[0041] In one embodiment, the inorganic particles are in the form of spherical, rod-shaped, needle-shaped, nanotube-shaped particles, or a combination thereof. In a preferred embodiment, the content of inorganic particles in the composition is in the range of about 5 wt% to about 99 wt%, or about 5 wt% to about 90 wt%, or about 10 wt% to about 80 wt%, or about 15 wt% to about 40 wt%.

[0042] According to a preferred embodiment, the composition is solid. According to another preferred embodiment, the composition is free of polymerization initiator or crosslinking agent.

[0043] According to another aspect, the present technology relates to a process for preparing a composition as defined above, the process comprising a step of mixing inorganic particles, at least one monomer comprising at least one polymerizable or crosslinkable function and an organic compound comprising one or more SH groups.

[0044] According to one embodiment, the mixing step is carried out at a temperature in the range of 15°C to 50°C, or in the range of 20°C to 35°C, or in the range of 20°C to 30°C.

[0045] According to another embodiment, the mixing step is carried out in the presence of oxygen (e.g. in air). According to an alternative embodiment, the mixing step is carried out under an inert atmosphere.

[0046] According to a preferred embodiment, the process excludes the addition of a polymerization initiator or a crosslinking agent.

[0047] According to another embodiment, the method further comprises spreading the resulting mixture onto a support. In one embodiment, the support is an inert film and the method optionally comprises removing the film. In another embodiment, the support is an electrode film. In yet another embodiment, the support is a current collector or an electrolyte film.

[0048] In yet another aspect, the present technology relates to an electrolyte comprising the composition as defined herein, or obtained according to the present method. In a preferred embodiment, the electrolyte is in the form of a solid electrolyte film. In another aspect, the present technology relates to an electrode comprising the composition as defined herein or as obtained according to the present method, and an electrochemically active material. In one embodiment, the electrode further comprises a current collector. In one embodiment, the electrochemically active material is a positive electrode electrochemically active material, such as LiM'PO4 where M' is Fe, Ni, Mn, Co, or a combination thereof, LiV3O8, V2O5F, LiV2O5, LiMn2O4, LiM”O2, where M” is Mn, Co, Ni, or a combination thereof (such as NMC, LiMn s Co t Neither uO2with s+t+u = 1), Li(NiM'”)O2(where M'” is Mn, Co, Al, Fe, Cr, Ti, Zr, or a combination thereof), sulfur, elemental selenium or iodine, iron(lll) fluoride, copper(lll) fluoride, lithium iodide, carbon-based active materials such as graphite, organic cathode active materials, or a combination of two or more of these materials when compatible with each other. In another embodiment, the electrode further comprises an electronically conductive material, a binder, a salt, or a combination of two or more of these.

[0049] In one 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 above. In one embodiment, the positive electrode comprises a positive electrode electrochemically active material and optionally on a current collector. In another embodiment, the positive electrode electrochemically active material is selected from metal phosphates, lithiated metal phosphates, metal oxides, and lithiated metal oxides. In an alternative embodiment, the positive electrode electrochemically active material is LiM'PO4where M' is Fe, Ni, Mn, Co, or a combination thereof, LiVaOs, V2O5F, LiV2O5, LiMn2O4, LiM”O2, where M” is Mn, Co, Ni, or a combination thereof (such as NMC, LiMn s Co t Neither uO2with s+t+u = 1), Li(NiM”')O2(where M'” is Mn, Co, Al, Fe, Cr, Ti, Zr, or a combination thereof), sulfur, elemental selenium or iodine, iron(lll) fluoride, copper(lll) fluoride, lithium iodide, carbon-based active materials such as graphite, organic cathode active materials, or a combination of two or more of these materials when compatible with each other. In another embodiment, the positive electrode material further comprises an electronically conductive material, a binder, a salt, and / or inorganic particles. In another embodiment, the electrolyte is in direct contact with the positive electrode and / or the negative electrode, preferably with the positive electrode.

[0050] Alternatively, the present technology relates to an electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, wherein the positive electrode is as defined herein (and comprises the composition). In one embodiment, the electrolyte and the positive electrode are as defined above.

[0051] According to one embodiment, the negative electrode comprises an electrochemically active negative electrode material and optionally a current collector.

[0052] In another embodiment, the negative electrode electrochemically active material comprises a metal film comprising an alkali or alkaline earth metal or an alloy comprising an alkali or alkaline earth metal. In one embodiment, the alkali metal is selected from lithium and sodium or an alloy comprising one of these.

[0053] In another embodiment, the negative electrode electrochemically active material comprises 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., LiTi2(PO4)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 (SiOx-C), tin (Sn), a tin-carbon composite (Sn-C), a tin oxide (SnO x ), a tin oxide-carbon composite (SnO x -C), and their combinations, when compatible. According to one embodiment, the metal oxide is chosen from the compounds of formulas M””g Oh (where M”” is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination thereof; and g and h are numbers such that the h:g ratio is in the range 2 to 3) (e.g., MoO3MOO2, MoS2, V2O5, and TiNb2O7), spinel oxides (e.g., NiCo2O4, ZnCo2O4, MnCo2O4, CUCO2O4, and CoFe2O4) and LiM'””O (where M'”” is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination thereof) (e.g., a lithium titanate (such as Li4TisO 12 ) or a lithium molybdenum oxide (such as U2MO4O13)). In some embodiments, the negative electrode material further comprises an electronically conductive material, a binder, a salt, inorganic particles, or a combination of two or more thereof.

[0054] According to another aspect, the present technology also relates to a battery comprising at least one electrochemical cell as defined herein. According to one embodiment, the battery is selected from a lithium battery, a lithium-ion battery, a sodium battery, a sodium-ion battery, a potassium battery, a potassium-ion battery, a magnesium battery, and a magnesium-ion battery. According to another embodiment, the battery is a lithium battery. According to yet another embodiment, the battery is a lithium-ion battery.

[0055] BRIEF DESCRIPTION OF THE FIGURES

[0056] Figure 1 shows the NMR spectra (a) 6 Li of LLZO and TBT / LLZO mixture and (b) 13 C of TBT and TBT / LLZO mixture.

[0057] Figure 2 shows the results of impedance measurements for electrolytes comprising a sulfide ceramic, an ionic plastic salt, and a macromonomer with 0.5 wt% UV crosslinker (•), with 2 wt% TBT (A ), and with 4 wt% TBT (■).

[0058] Figure 3 shows the results of impedance measurements for electrolytes comprising a sulfide ceramic, an ionic plastic salt, and a macromonomer with 2 wt% TBT (A ), with an O:Li ratio of 30:1 LiFSI and 2 wt% TBT (★), and with an O:Li ratio of 20:1 LiFSI and 2 wt% TBT (▼).

[0059] DETAILED DESCRIPTION

[0060] 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.

[0061] 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.

[0062] Where 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. Where a range of values ​​is referred to in this application, then all intermediate ranges and sub-ranges, as well as individual values ​​included in ranges of values, are included in the definition.

[0063] When the article "a" is used to introduce an element in the present 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.

[0064] 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.

[0065] As used herein, the term "alkyl" refers to optionally substituted saturated hydrocarbon groups having from 1 to 20 carbon atoms (unless otherwise indicated), including straight or branched alkyl groups. Non-limiting examples of alkyl groups may include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, tert-butyl, sec-butyl, isobutyl, and the like. Similarly, an "alkylene" group refers to an alkyl group located between groups, e.g., methylene, ethylene, propylene, butylene, etc.

[0066] The term "cycloalkyl" herein refers to a group comprising a saturated or partially unsaturated carbon ring comprising from 3 to 15 members, which may be in the form of a monocycle or a polycyclic system, including spiro, fused, or bridged carbocycles and may be optionally substituted.

[0067] The term "heterocycloalkyl" herein refers to a monocyclic group having from 3 to 7 members or a bicyclic group having from 7 to 15 members and being chemically stable, being saturated or partially unsaturated, and having carbon atoms and from 1 to 4 heteroatoms selected from oxygen, nitrogen and sulfur. It is understood that when a nitrogen atom is used as a ring atom in a heterocycloalkyl, the nitrogen may also include a hydrogen atom or a substituent. The heterocycloalkyl group may be attached to the rest of the molecule by a carbon atom or a ring nitrogen atom.

[0068] As used herein, the term "aromatic" refers to an aromatic moiety having 4n+2 conjugated Tr(pi) electrons in which n is a number from 1 to 3, in a monocyclic group, or a fused or unfused bicyclic or tricyclic system having a total of six to 15 ring members, in which at least one of the rings in a system is aromatic.

[0069] The term "heteroaromatic" means an aromatic group having 4n+2 conjugated Tr(pi) electrons in which n is a number from 1 to 3, for example having from 5 to 18 ring atoms, preferably 5, 6, or 9 ring atoms; and having, in addition to carbon atoms, from 1 to 5 heteroatoms selected from oxygen, nitrogen and sulfur. It is understood that when a nitrogen atom is used as a ring atom in a heteroaryl, the nitrogen may also include a hydrogen atom or a substituent. The heteroaryl group may be attached to the rest of the molecule by a carbon atom or a ring nitrogen atom.

[0070] The term "monomer" as used herein refers to a molecule that can undergo polymerization. A monomer may include a macromonomer, that is, a macromolecule that can itself undergo polymerization.

[0071] A "macromonomer" as used herein refers more particularly to a macromolecule comprising a polymer chain. The polymer chain of the macromonomer may itself comprise a homopolymer or a copolymer and may comprise branches to form multi-branched macromonomers of the star, comb, etc. type.

[0072] The present document presents a composition, preferably solid, comprising a polymer and inorganic particles, the polymer being the product of the reaction of at least one monomer comprising at least one polymerizable or crosslinkable function and an organic compound comprising one or more SH groups. The combination of the monomer, the SH group(s) of the organic compound and the inorganic particles makes it possible to obtain polymerization and / or crosslinking and solidification without the addition of a polymerization initiator or crosslinking agent (for example, an agent activated by heat or by irradiation).

[0073] Non-limiting examples of the monomer include a compound of formula R 2 (X) m , where R 2 is an organic group, X is a polymerizable or crosslinkable group, and m is a number in the range 1 to 8; or the monomer is a macromonomer comprising at least one crosslinkable segment comprising units of formula R 2 (X) m and optionally a non-crosslinkable polymer segment.

[0074] For example, the non-crosslinkable polymer segment is present and is of Formula I:

[0075] Formula I in which,

[0076] R is a hydrogen atom, , a C1-C group 10 alkyl, or a group -(CH2-OR a - R b );

[0077] R a is (CH2-CH2-O)j or (CH(CH3)-CH2-O)j;

[0078] R b is a hydrogen atom or a C1-C group 10alkyl; i is an integer selected from the range 2 to 200,000; and j is an integer selected from the range 0 to 100.

[0079] In the formula R 2 (X) m , X can, for example, be a grouping of formula -R 3 - C(R 4 )=CH2, WHERE R 3 is O, NH, OCH2, NHCH2, OC(O), NHC(O), or is absent and forms a covalent bond, and R 4 is H, C1-C 10 alkyl or C3-C 10 cycloalkyl. R 2 or the macromonomer comprising R 2 can be chosen from the groups C 2-12 linear or branched alkyl, alkylene oxide or poly(alkylene oxide), alkylene sulfide or poly(alkylene sulfide), siloxane or polysiloxane, and mono or polyaromatic, preferably R 2 is chosen from the groups C 2-12linear or branched alkyl, alkylene oxide or poly(alkylene oxide), and phenyl. In some examples, m is a number in the range 2 to 4. For example, the polymer units from the monomer include units of at least one of the formulas: in which R 2 , R 3 , R 4 and m are as defined previously, and where — when attached to C(R 3 R 4 ) or CH2 represents a bond with a hydrogen or sulfur atom of the organic compound, a terminal group, or another unit of the polymer, and represents a macromonomer when adjacent to R 2 .

[0080] Examples of monomers include branched polyethylene glycol comprising acrylate groups at the end of the main and / or side chain and / or on the chains, polyethylene glycol diacrylate, pentaerythritol tetraacrylate, triethylene glycol divinyl ether, ethylene glycol dimethacrylate, and divinylbenzene. Other examples include macromonomers consisting of polyether chains and comprising crosslinkable groups (such as acrylates or methacrylates), the polyether chains being optionally branched (multi-branched). For example, the polymer units originating from the monomer comprise units of at least one of the formulas:

[0081] in which R 4 and — are as defined in the preceding formulas, and p is a non-zero number.

[0082] According to some examples, R 4is H or C1-C6alkyl, for example H or C1-C3alkyl, or H or methyl. Preferably, when R 4 is attached to a carbon adjacent to a carbonyl, R 4 may be hydrogen or C1-C6alkyl (such as C1-C3alkyl, or such as methyl), and when R 4 is not attached to a carbon adjacent to a carbonyl (e.g. from the polymerization of a vinyl group), R 4 can be a hydrogen atom.

[0083] The monomer content in the composition may be in the range of about 1 wt% to about 95 wt%, or about 2 wt% to about 90 wt%, or about 3 wt% to about 80 wt%, or about 4 wt% to about 50 wt%, or about 10 wt% to about 70 wt%, or about 20 wt% to about 65 wt%.

[0084] The organic compound comprising one or more SH groups generally comprises an organic group serving as a carrier group for the SH group(s). This may be a linear or branched alkyl, alkenyl, or alkynyl, optionally comprising heteroatoms (such as O, N, S, etc.) and / or being optionally substituted. The organic group may also be a monocyclic or polycyclic group optionally comprising heteroatoms (such as O, N, S, etc.) and / or being optionally substituted. The organic group may comprise an oligomeric or polymeric chain. The organic group may also comprise a combination of the preceding elements. For example, the organic compound is of formula R 1 (SH) n , where R 1is an organic group linking the SH group(s), and where n is a number in the range 1 to 10 (or 1 to 4), or the compound is a macromonomer comprising at least one segment comprising units of formula R 1 (SH) n . According to some examples, R 1 or the segment including R 1 can be chosen from the groups C 2-12 linear or branched alkyl, ether or ester of C 2-12linear or branched alkyl polyol, alkylene oxide or poly(alkylene oxide) optionally comprising one or more sulfur atoms in a chain, alkylene sulfide or poly(alkylene sulfide), siloxane or polysiloxane, mono or poly-cycloalkyl or heterocycloalkyl, mono or poly-aromatic or heteroaromatic fused or unfused optionally comprising a linking atom, or a combination thereof. Non-limiting examples of organic compounds include 1-(2-mercaptoethoxy-2-ethoxyethyl-2-thioethyl)-2-pyrrolidone, 2,2'-(ethylenedioxy)diethanethiol, pentaerythritol tetrakis(3-mercaptopropionate), and 4,4'-thiobisbenzenethiol.

[0085] In some examples, the polymer units from the organic compound comprise units of at least one of the formulas: in which R 1and n are as defined above and where — when attached to a sulfur atom represents a link to another unit of the polymer, such as a unit from the monomer, and represents a macromonomer when adjacent to R 1 .

[0086] For example, the polymer units from the organic compound include units of at least one of the formulas:

[0087] in which — is as defined for the two previous formulas.

[0088] The organic compound content in the composition is in the range of about 0.01 wt% to about 60 wt%, or about 0.05 wt% to about 50 wt%, or about 10 wt% to about 30 wt%, or about 15 wt% to about 40 wt%.

[0089] The polymer resulting from the reaction of the monomer and the organic compound can be a polymer of random, block, or alternating configuration.

[0090] The inorganic particles may comprise an inorganic compound of amorphous, ceramic or glass-ceramic type, for example, based on oxide, sulfide or oxysulfide, the inorganic compound being natural or synthetic. Examples of inorganic compounds include a natural or synthetic ceramic selected from inorganic compounds of formulae MLZO (for example, M7La3Zr2O 12 , M<7- a )La3Zr2AlbO 12 , M (7-a) La3Zr2Ga b O 12 , M(7- a )La3Zr (2-b) Your b O 12 , and M(7- a )La3Zr (2-b) NbbO 12 ); MLTaO (e.g., M7La3Ta2O 12 , MsLa3Ta2O 12 , and M6La3Ta1.5Y0.5O 12 ); MLSnO (e.g., M7LasSn2O 12 ); MAGP (e.g., M 1+a Al a Ge 2-a (PO4)3); MATP (e.g., M 1+a Al a Ti2- a (PO4)3,); MLTiO (e.g., M3aLa(2 / 3-a)TiO3); MZP (e.g., Ma Zrb(PO4) c ); MCZP (for example, M a Ca b Zr c (PO4)d); MGPS (par example, M a GebP c S d tel que M 10 GeP2S 12 ); MGPSO (for example, M a GebP c S d OR e ); MSiPS (for example, M a Yes b P c S d tel que M 10 SiP2S 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 M 10 SnP2S 12 ); MSnPSO (for example, M a Sn b P c S d OR e ); MPS (par exemple, M a P b S c phone M7P3S11); MPSO (for example, M a P b S c Od); MZPS (par exemple, M a Zn b P c S d ); MZPSO (for example, M a Zn b Pc S d O e ); xM2S-yP2S5; xM2S-yP2S5-zMX; xM2S-yP2S5-zP2O5; XM2S- yP2S5-zP2O5-wMX; xM2S-yM2O-zP2S5; xM2S-yM2O-zP2S5-wMX; xM2S-yM2O-zP2S5- WP2O5; xM2S-yM2O-zP2S5-wP2O5-vMX; xM2S-ySiS2; MPSX (par exemple, M a P b S c Xd tel que M7P3S11X, M7P2S8X, et MePS5X); MPSOX (par exemple, M a P b S c OdX e ); MGPSX (M a Ge b P c S d X e ); MGPSOX (M a Ge b P c S d O e X f ); MSiPSX (M a Si b P c S d X e ); MSiPSOX (M a Si b P c S d O e X f ); MSnPSX (M a Sn b P c S d X e ); MSnPSOX (M a Sn b P c S d O e X f ); MZPSX (M a ZribP c S d X e); MZPSOX (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

[0091] M is an alkali metal, an alkaline earth metal, or a combination thereof, and wherein when M comprises an alkaline earth metal ion, then the number of M is adjusted to achieve electroneutrality;

[0092] X is selected from F, Cl, Br, I or a combination 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.

[0093] According to another example, the inorganic particles comprise a natural or synthetic ceramic selected from AI2O3, Mg2B2O5, Na2O 2B2O3, xMgO yB2O3zH2O, TiO2, ZrO2, ZnO, Ti2O3, SiO2, Cr2O3, CeO2, B2O3, B2O, SrBi4Ti4O15, LLTO, LLZO, LAGP, LATP, Fe2O3, BaTiO3y-LiAIO2, molecular sieves and zeolites (e.g., aluminosilicate, mesoporous silica), sulfide ceramics (such as Li6PS5CI, Li7P3S11), glass ceramics (such as LIPON, etc.), and other ceramics, as well as combinations thereof.

[0094] According to one example, the ceramic has the formula Li7-bLa-Zr2M'bO 12 , where b is such that 0 < x < 1 and M' is Al, Ga, Ta, Fe or Nb or is absent, e.g., b is 0 and M is absent. In another example, the ceramic is an aluminosilicate compound. In yet another example, the ceramic is a sulfide or oxysulfide ceramic.

[0095] The inorganic particles may be in any form, for example, in the form of spherical particles, rods, needles, nanotubes, or any combination thereof. The content of inorganic particles in the composition is preferably in the range of about 5% by weight to about 99% by weight, or about 5% by weight to about 90% by weight, or about 10% by weight to about 80% by weight, or about 15% by weight to about 40% by weight.

[0096] The composition, after reaction of the monomer with the organic compound, is generally solid. The composition is also generally free of polymerization initiator or crosslinking agent, the polymerization and / or crosslinking taking place in situ, and mainly in the presence of the inorganic particles.

[0097] This document also describes a process for the preparation of a composition as defined herein, the process comprising a step of mixing inorganic particles, at least one monomer comprising at least one polymerizable or crosslinkable function and an organic compound comprising one or more SH groups.

[0098] The mixing step may be carried out at a temperature in the range of 15°C to 50°C, or in the range of 20°C to 35°C, or in the range of 20°C to 30°C. The temperature of the reaction mixture may be higher although the reaction may occur at a lower temperature or generally without heating (at room temperature).

[0099] The mixing step can be carried out in the presence of oxygen (e.g., in air) or under an inert atmosphere (e.g., argon, nitrogen). The choice of the type of atmosphere may depend on the sensitivity to air of the elements included in the composition or the type of process recommended. For example, a process carried out on a production line and followed by a contact step (spreading of the mixture or application of a solid film) directly or indirectly with a lithium film could be carried out in an anhydrous chamber or under an inert atmosphere. An inorganic compound used in the composition could also be more sensitive to air.

[0100] The method may further comprise spreading the composition onto a support before the composition is completely polymerized. The support may be a film that will optionally be removed after the composition has polymerized and / or hardened. The support may also be a film intended to remain in contact with the composition. For example, when the composition is used for the manufacture of an electrolyte, it may be spread directly onto one or other of the electrodes. Alternatively, when the composition is included in an electrode material, it may be applied to another element of the cell such as a current collector or an electrolyte film.

[0101] The present composition can be used in the manufacture of electrolyte films. The present document therefore also relates to an electrolyte comprising the composition as defined herein, or obtained according to the present method. Preferably, the electrolyte is in the form of a solid electrolyte film.

[0102] The composition as described herein could also be used in the manufacture of electrode material, by being mixed with an electrochemically active material and optionally applied to a current collector. The electrode material may also optionally comprise an electronically conductive material, a binder, a salt, or a combination of two or more thereof.

[0103] For example, the electrochemically active material may be a positive electrode electrochemically active material, such as LiM'PCL where M' is Fe, Ni, Mn, Co, or a combination thereof, LiVaOs, V2O5F, LiV2O5, LiM^CL, LiM”O2, where M” is Mn, Co, Ni, or a combination thereof (such as NMC, LiMn s Co t Neither u O2with s+t+u = 1), Li(NiM'”)O2(where M'” is Mn, Co, Al, Fe, Cr, Ti, Zr, or a combination thereof), elemental sulfur, selenium or iodine, iron(lll) fluoride, copper(lll) fluoride, lithium iodide, carbon-based active materials such as graphite, organic cathode active materials, or a combination of two or more of these materials when compatible with each other.

[0104] This document also relates to electrochemical cells comprising a negative electrode, a positive electrode and an electrolyte, wherein the electrolyte is as defined herein.

[0105] The positive electrode may then comprise an electrochemically active positive electrode material and optionally a current collector. The electrochemically active positive electrode material may be selected from metal phosphates, lithiated metal phosphates, metal oxides, and lithiated metal oxides. Alternatively, the electrochemically active positive electrode material may be selected from those described previously. The positive electrode may also optionally comprise an electronically conductive material, a binder, a salt, and / or inorganic particles.

[0106] For example, the electrolyte as defined herein or the composition intended to form this electrolyte may be deposited directly on the film of the positive or negative electrode during the formation of the cell. The electrolyte film thus formed is then in direct contact with the positive electrode and / or the negative electrode, preferably with the positive electrode.

[0107] Alternatively, the electrochemical cell comprises a negative electrode, a positive electrode, and an electrolyte, wherein the positive electrode is as defined above and comprises the composition, or both the positive electrode and the electrolyte comprise the present composition.

[0108] The negative electrode of electrochemical cells as described herein generally comprises an electrochemically active negative electrode material and optionally a current collector.

[0109] According to a variant of interest, the electrochemically active negative electrode material comprises a metal film comprising an alkali or alkaline-earth metal or an alloy comprising an alkali or alkaline-earth metal, preferably chosen from lithium or sodium or an alloy comprising one of these.

[0110] The metal film can therefore also be an alloy of lithium and an element chosen from alkali metals other than lithium (such as Na, K, Rb, and Cs), alkaline earth metals (such as Mg, Ca, Sr, and Ba), rare earth metals (such as S c , Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), zirconium, copper, silver, bismuth, cobalt, manganese, zinc, aluminum, silicon, tin, antimony, cadmium, mercury, lead, molybdenum, iron, boron, indium, thallium, nickel and germanium (e.g., Zr, Cu, Ag, Bi, Co, Zn, Al, Si, Sn, Sb, Cd, Hg, P b, Mn, B, In, Tl, Ni, or Ge), preferably the lithium alloy comprising at least 50%, or at least 75%, or at least 90%, or at least 95%, or at least 99% by weight of lithium.

[0111] In another embodiment, the negative electrode electrochemically active material comprises 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., LiTi2(PO4)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 (SnOx ), 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”” g Oh (where M”” is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination thereof; and g and h are numbers such that the h:g ratio is in the range 2 to 3) (e.g., MoO3MOO2, M0S2, V2O5, and TiNb2O7), spinel oxides (e.g., NiCo2O4, ZnCo2O4, MnCo2O4, CuCo2O4, and CoFe2O4) and LiM'””O (where M'”” is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination thereof) (e.g., a lithium titanate (such as Li4TisOi2) or a lithium molybdenum oxide (such as Li2Mo4Oi3)).

[0112] The negative electrode material may also optionally include an electronically conductive material, a binder, a salt, inorganic particles, or a combination of two or more of these.

[0113] This document also relates to electrochemical batteries or accumulators, comprising at least one of the electrochemical cells as defined above. For example, the battery may be chosen from a lithium battery, a lithium-ion battery, a sodium battery, a sodium-ion battery, a potassium battery, a potassium-ion battery, a magnesium battery, and a magnesium-ion battery, preferably a lithium or lithium-ion battery.

[0114] The electrochemical batteries and accumulators described here are intended, for example, for use in portable devices, such as mobile phones, cameras, tablets or laptops, in electric or hybrid vehicles, or in the storage of renewable energy.

[0115] EXAMPLES

[0116] 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. Example 1 - Preparation of compositions

[0117] Compositions 1, 2, and 4 (comparative) and the present compositions 3 and 5 to 19 are prepared with the elements and proportions indicated in Table 1, where the following abbreviations are used:

[0118] US'674: a multi-branched polyether (macromonomer) comprising crosslinkable acrylate units at the chain ends, as described in US Patent No. 7,897,674;

[0119] PEGDA: poly(ethylene glycol) diacrylate;

[0120] PETA: Pentaerythritol tetraacrylate;

[0121] TEGDVE: tri(ethylene glycol) divinyl ether;

[0122] EGDMA: ethylene glycol dimethacrylate;

[0123] DVB: divinylbenzene (approximately 80% 1,4-divinylbenzene, 20% 1,2-divinylbenzene);

[0124] HNT: a natural aluminosilicate ceramic (Halloysite nanotube);

[0125] LLZO: lithium lanthanum zirconium oxide (Li7La3Zr2O 12 );

[0126] MT: 1-(2-mercaptoethoxy-2-ethoxyethyl-2-thioethyl)-2-pyrrolidone, i.e.:

[0127] EDDET: 2,2'-(ethylenedioxy)diethanethiol;

[0128] PTM P: pentaerythritol tetrakis(3-mercaptopropionate); and TBT: 4,4'-thiobisbenzenethiol.

[0129] Table 1. Prepared compositions and polymer formation result

[0130] More particularly, compositions 1 to 19 of Table 1 are prepared according to the following procedures.

[0131] Composition 1:

[0132] 1.4 g of US'674 and 0.7 g of MT are mixed well in a flask at room temperature under air, the solution is stirred with a magnetic bar for 24 hours, there is no polymer formed.

[0133] Composition 2:

[0134] 1.4 g of US'674, 0.7 g of LiTFSI and 0.7 g of MT are well mixed in a flask at room temperature under air, the solution is stirred with a magnetic bar for 24 hours, there is no polymer formed.

[0135] Composition 3:

[0136] 1.4 g of US'674, 0.7 g of HNT and 0.7 g of MT are mixed well in a flask at room temperature under air, the solution is stirred with a magnetic bar. After 3 hours, the solution becomes solid, indicating the formation of polymer.

[0137] Composition 4:

[0138] 1.4 g of US'674, 0.7 g of HNT and 0.7 g of LiTFSI are well mixed in a flask at room temperature under air, the solution is stirred with a magnetic bar for 24 hours, there is no polymer formed.

[0139] Composition 5:

[0140] 1.5 g of US'674, 0.36 g of HNT and 0.76 g of MT are mixed well in a flask at room temperature under air, the solution is stirred with a magnetic bar. After 3 hours, the solution becomes solid, indicating the formation of polymer.

[0141] Composition 6: 1.5 g of US'674, 0.76 g of HNT and 0.36 g of MT are well mixed in a flask at room temperature under air, the solution is stirred with a magnetic bar. After 3 hours, the solution becomes solid, indicating the formation of polymer.

[0142] Composition 7:

[0143] 1.0 g of US'674, 1.0 g of HNT and 1.0 g of MT are mixed well in a flask at room temperature under air, the solution is stirred with a magnetic bar. After 1 hour, the solution becomes solid, indicating the formation of polymer.

[0144] Composition 8:

[0145] 1.5 g of US'674, 0.19 g of HNT and 0.75 g of MT are mixed well in a flask at room temperature under air, the solution is stirred with a magnetic bar. After 3 hours, the solution becomes solid, indicating the formation of polymer.

[0146] Composition 9:

[0147] 1.5 g of US'674, 0.75 g of HNT and 0.19 g of MT are mixed well in a flask at room temperature under air, the solution is stirred with a magnetic bar. After 3 hours, the solution becomes solid, indicating the formation of polymer.

[0148] Composition 10:

[0149] 0.6 g of US'674, 1.2 g of HNT and 1.2 g of MT are mixed well in a flask at room temperature under air, the solution is stirred with a magnetic bar. After 30 minutes, the solution becomes solid, indicating the formation of polymer.

[0150] Composition 11:

[0151] 1.4 g of PEGDA, 0.7 g of HNT and 0.7 g of MT are mixed well in a flask at room temperature under air, the solution is stirred with a magnetic bar. After 15 minutes, the solution becomes solid, indicating the formation of polymer.

[0152] Composition 12: 1.4 g of PETA, 0.7 g of HNT and 0.7 g of MT are mixed well in a flask at room temperature under air, the solution is stirred with a magnetic bar. After 15 minutes, the solution becomes solid, indicating the formation of polymer.

[0153] Composition 13:

[0154] 1.4 g of TEGDVE, 0.7 g of HNT and 0.7 g of MT are mixed well in a flask at room temperature under air, the solution is stirred with a magnetic bar. After 15 minutes, the solution becomes solid, indicating the formation of polymer.

[0155] Composition 14:

[0156] 1.4 g of EGDMA, 0.7 g of HNT and 0.7 g of MT are mixed well in a flask at room temperature under air, the solution is stirred with a magnetic bar. After 15 minutes, the solution becomes solid, indicating the formation of polymer.

[0157] Composition 15:

[0158] 1.4 g of DVB, 0.7 g of HNT and 0.7 g of MT are mixed well in a flask at room temperature under air, the solution is stirred with a magnetic bar. After 48 hours, the solution becomes solid, indicating the formation of polymer.

[0159] Composition 16:

[0160] 1.4 g of US'674, 0.7 g of HNT and 0.7 g of EDDET are mixed well in a flask at room temperature under air, the solution is stirred with a magnetic bar. After 15 minutes, the solution becomes solid, indicating the formation of polymer.

[0161] Composition 17:

[0162] 1.4 g of US'674, 0.7 g of HNT and 0.7 g of PTMP are mixed well in a flask at room temperature under air, the solution is stirred with a magnetic bar. After 15 minutes, the solution becomes solid, indicating the formation of polymer.

[0163] Composition 18: 1.2 g of US'674 and 0.3 g of TBT are mixed well in a flask at room temperature under air overnight. When the solution is homogeneous, 0.5 g of HNT is added with stirring. After 15 minutes, the solution becomes solid, indicating polymer formation.

[0164] Composition 19:

[0165] 1.4 g of US'674 and 0.2 g of TBT are mixed well in a flask at room temperature under air overnight. When the solution is homogeneous, 0.4 g of LLZO is added with stirring. After 15 minutes, the solution becomes solid, indicating polymer formation.

[0166] Example 2 - Characterization of compositions a) LLZO and TBT interactions

[0167] In order to study the polymerization mechanism, solid-state NMR analyses of TBT, LLZO and the TBT / LLZO mixture were performed on a 500 MHz NMR spectrometer equipped with a 4 mm triple resonance probe with MAS (magic angle spinning), up to 15 kHz. The TBT / LLZO mixture was prepared by grinding in a mortar. The NMR spectra 6 Li of LLZO and TBT / LLZO mixture and 13 C of TBT and TBT / LLZO mixture are shown in Figures 1(a) and (b).

[0168] Figure 1(a) shows that the signal intensity of LLZO in the mixture becomes weaker than that of LLZO, suggesting an interaction between LLZO and TBT that changes the chemical environment of Li ions in LLZO. Furthermore, in Figure 1(b) a shift of the peak corresponding to carbons next to the SH group in the TBT / LLZO mixture indicates the formation of -S' anion, which can initiate the polymerization by anionic route.

[0169] Example 3 - Preparation of electrolyte films and characterization a) Effect of crosslinking i. Preparation of films:

[0170] All manipulations are carried out in a glove box under argon (0.1 ppm H2O, 0.1 ppm O2). Two sizes (about 3 pm and less than 1 pm) of sulfide electrolyte particles (Li6PS5CI) are mixed in a 90 / 10 mass proportion by means of a vortex. The binder is formed by a 40 / 60 mass mixture respectively of (a) US'674 polymer with 0.5 wt% UV crosslinker, or (b) US'674 polymer with 2 wt% TBT, or (c) US'674 polymer with 4 wt% TBT; and ionic plastic salt (1,T-hexamethylene bis(l-methylpyrrolidinium) bis(trifluoromethanesulfonyl)imide) dissolved in dichloromethane (DCM).

[0171] The weight ratio between sulfide and binder is 90 / 10 by mass. The quantity of DCM is adjusted to achieve a good viscosity of the mixture. The mixture thus obtained is coated on a previously degreased aluminum sheet. After drying in a glove box, UV crosslinking is carried out for the film containing UV crosslinker. ii. Impedance measurements:

[0172] A 10 mm diameter puck of each film prepared in (i) was placed in a mold and compacted under 2.8 T of pressure, then transferred to a conductivity cell at a pressure of 5 MPa closed under Argon. The temperature was stabilized for approximately 1 hour. Two impedance measurements were recorded at each temperature from -10°C to 70°C and then back down to 20°C with 15 minutes between each measurement. The results are shown in Figure 2 for the electrolytes with 0.5 wt% UV crosslinker (•), with 2 wt% TBT (À) and with 4 wt% TBT (■).

[0173] After creep of the ionic plastic salt at 70°C (heating, bottom curves), which allows in situ densification of the sulfide ceramic film, and lowering the temperature (top curves), an increase in the ionic conductivity of the films can be observed with the use and increase in the TBT rate. Indeed, the crosslinking of the US'674 polymer as a monomer by UV crosslinking induces a polymer which participates in ionic conduction, but the intrinsic ionic conduction of this polymer is lower than that of the sulfide ceramic particle. The addition of TBT, which is fixed between the chains of the US'674 monomer polymer, increasingly inhibits ionic conduction through the US'674 polymer. Thus, ionic conduction only occurs through the sulfide particles and with the ionic plastic salt, explaining the increase in impedance after creep of the ionic plastic salt, creep allowing a better distribution of the ionic plastic salt around the particles.b) Effect of the presence of salt i. Preparation of films:.

[0174] The films are prepared as in Example 3(a)(i), where the binder is a 40 / 60 mass mixture respectively of (a) US'674 polymer with 2 wt% TBT, or (b) US'674 polymer with an O:Li ratio of 30:1 LiFSI and 2 wt% TBT, or (c) US'674 polymer with an O:Li ratio of 20:1 LiFSI and 2 wt% TBT, and ionic plastic salt (1,T-hexamethylene bis(1-methylpyrrolidinium) bis(trifluoromethanesulfonyl)imide) dissolved in DCM. The resulting mixture is coated onto previously degreased aluminum. ii. Impedance measurements:

[0175] After drying the films in a glove box, impedance measurements were performed as before. The results are shown in Figure 3 for US'674 polymer with 2 wt% TBT (A), US'674 polymer with an O:Li ratio of 30:1 LiFSI and 2 wt% TBT (★), and US'674 polymer with an O:Li ratio of 20:1 LiFSI and 2 wt% TBT (▼).

[0176] It can be seen that the ionic conductivity of the films decreases with the addition and increase of LiFSI salt. Normally, the addition of LiFSI salt increases the ionic conductivity of the US'674 polymer as described in US Patent No. 7,897,674. However, the opposite is observed here. This confirms that the TBT, by placing itself between the chains of the US'674 polymer as a monomer, inhibits its ionic conductive character. The product of the reaction of the US'674 polymer and the TBT then serves as a support for the film by bringing a flexible character to this film. Thus, the added LiFSI salt does not participate in the conduction and therefore blocks this conduction as dead matter because it does not react with the other constituents of the film.

[0177] 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

CLAIMS Composition comprising a polymer and inorganic particles, the polymer being the product of the reaction of at least one monomer comprising at least one polymerizable or crosslinkable function and an organic compound comprising one or more SH group(s). Composition according to claim 1, wherein the monomer is a compound of formula R 2 (X) m , where R 2 is an organic group, X is a polymerizable or crosslinkable group, and m represents the number of X group(s) bonded to R 2 and is a number in the range of 1 to 8; or the monomer is a macromonomer comprising at least one crosslinkable segment comprising units of formula R 2 (X) m and optionally a non-crosslinkable polymer segment. Composition according to claim 2, wherein the non-crosslinkable polymer segment is present and is of Formula I: Formula I in which, R is a hydrogen atom, a C1-C group 10 alkyl, or a -(CH2-OR) group a -R b ); R a is (CH2-CH2-O)j or (CH(CH3)-CH2-O)j; R b is a hydrogen atom or a C1-C group 10 alkyl; i is an integer from 2 to 200,000; and j is an integer from 0 to 100. Composition according to claim 2 or 3, wherein X is a polymerizable or crosslinkable group comprising a double bond. Composition according to claim 4, wherein X is a group of formula -R 3 -C(R 4 )=CH2, WHERE 3 is O, NH, OCH2, NHCH2, OC(O), NHC(O), or is absent and forms a covalent bond between R 2 and C(R 4 ), and R 4 is H, C1-C 10 alkyl or C3-C cycloalkyl.

6. Composition according to claim 5, wherein the polymer units derived from the monomer comprise units of at least one of the following formulas: in which R 2 , R 3 , R 4 and m are such as defined previously, and where — when attached to C(R 3 R 4 ) or CH2 represents a bond with a hydrogen or sulfur atom of the organic compound, a terminal group, or another unit of the polymer, and represents a macromonomer when adjacent to R 2 .

7. Composition according to any one of claims 2 to 6, wherein R 2 or the macromonomer comprising R 2 is chosen from among the groups C 2-12 linear or branched alkyl, alkylene oxide or poly(alkylene oxide), alkylene sulfide or poly(alkylene sulfide), siloxane or polysiloxane, and mono or polyaromatic.

8. Composition according to any one of claims 2 to 6, wherein R 2 is chosen from among the groups C 2-12 linear or branched alkyl, alkylene oxide or poly(alkylene oxide), and phenyl.

9. Composition according to any one of claims 2 to 8, wherein m is a number in the range of 2 to 4.

10. Composition according to claim 1, wherein the monomer is selected from branched poly(ethylene glycol) comprising acrylate groups at the end of the main and / or side chain and / or on the chains, poly(ethylene glycol) diacrylate, pentaerythritol tetraacrylate, triethylene glycol divinyl ether, ethylene glycol dimethacrylate, and divinylbenzene.

11. Composition according to claim 6, wherein the polymer units derived from the monomer comprise units of at least one of the following formulas: in which R 4 and — are as defined in claim 6, and p is a non-zero number. Composition according to any one of claims 5 to 9 and 11, wherein R 4 is H or C1-C6 alkyl, preferably H or C1-C3 alkyl, preferably H or methyl. Composition according to any one of claims 1 to 12, wherein the monomer content in the composition is in the range of about 1% by weight to about 95% by weight, or about 2% by weight to about 90% by weight, or about 3% by weight to about 80% by weight, or about 4% by weight to about 50% by weight, or about 10% by weight to about 70% by weight, or about 20% by weight to about 65% by weight.

14. Composition according to any one of claims 1 to 13, wherein the organic compound has the formula R 1 (SH) n , where R 1is an organic group linking the SH group(s), and where n represents the number of sulfur atom(s) bonded to R 1 and is a number in the range of 1 to 10, or the compound is a macromonomer comprising at least one segment comprising units of formula R 1 (SH) n .

15. Composition according to claim 14, wherein the polymer units derived from the organic compound comprise units of at least one of the following formulas: in which R 1 and n are as defined previously and where — when attached to a sulfur atom represents a bond with another unit of the polymer, such as a unit from the monomer, and represents a macromonomer when adjacent to R 1 .

16. Composition according to claim 14 or 15, wherein R 1 or the segment including R 1 is chosen from among the groups C 2-12linear or branched alkyl, ether or ester of C 2-12 linear or branched alkyl polyol, alkylene oxide or poly(alkylene oxide) possibly comprising one or more sulfur atom(s) in a chain, alkylene sulfide or poly(alkylene sulfide), siloxane or polysiloxane, heterocycle, mono- or poly-cycloalkyl or heterocycloalkyl, mono- or poly-aromatic or heteroaromatic fused or unfused possibly comprising a bonding atom, or a combination thereof.

17. Composition according to any one of claims 14 to 16, wherein n is a number in the range of 1 to 4.

18. Composition according to any one of claims 1 to 13, wherein the organic compound is selected from 1-(2-mercaptoethoxy-2-ethoxyethyl-2-thioethyl)-2-pyrrolidone, 2,2'-(ethylenedioxy)diethanethiol, pentaerythritol tetrakis(3-mercaptopropionate), and 4,4'-thiobisbenzenethiol. Composition according to claim 15, wherein the polymer units derived from the organic compound comprise units of at least one of the following formulas: in which — is as defined in claim 15. Composition according to any one of claims 1 to 19, wherein the organic compound content in the composition is in the range of approximately 0.01 wt% to approximately 60 wt%, or approximately 0.05 wt% to approximately 50 wt%, or approximately 10 wt% to approximately 30 wt%, or approximately 15 wt% to approximately 40 wt%. Composition according to any one of claims 1 to 19, wherein the polymer is a random, block, or alternating configuration polymer. Composition according to any one of claims 1 to 21, wherein the inorganic particles comprise an amorphous, ceramic, or glass-ceramic inorganic compound, for example, based on an oxide, sulfide, or oxysulfide, the inorganic compound being natural or synthetic. A composition according to any one of claims 1 to 22, wherein the inorganic particles comprise a natural or synthetic ceramic selected from inorganic compounds of formula MLZO (e.g., M7La3Zr2O 12 , M (7-a) La3Zr2Al b O 12 , M (7-a) La3Zr2Ga b O 12 , M (7-a) La3Zr (2-b) Your b O 12 , and M (7- a) La3Zr (2-b) Number b O 12 ); MLTaO (for example, M7La3Ta2O 12 , MsLa3Ta2O 12 , and M6La3Ta 1.5 Y 0.5 O 12 ); MLSnO (for example, M7La3Sn2O 12 ); MAGP (for example, M 1+a Al a Ge 2-a (PO4)3); MATP (for example, M 1+a Al a Ti 2-a (PO4)3,); MLTiO (for example, M 3a There (2 / 3-a) TiO3); MZP (for example, M a Zrb(PO4) c ); MCZP (for example, M a That b Zr c(PO4)d); MGPS (par example, M a GebP c S d tel que M 10 GeP2S 12 ); MGPSO (for example, M a GebP c S d OR e ); MSiPS (for example, M a Yes b P c S d tel que M 10 SiP2S 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 M 10 SnP2S 12 ); MSnPSO (for example, M a Sn b P c S d OR e ); MPS (par exemple, M a P b S c phone M7P3S11); MPSO (for example, M a P b S c Od); MZPS (par exemple, M a Zn b P c S d ); MZPSO (for example, M a Zn b P c S d OR e); xM2S-yP2S5; xM2S-yP2S5-zMX; xM2S-yP2S5- ZP2O5; xM2S-yP2S5-zP2O5-wMX; xM2S-yM2O-zP2S5; xM2S-yM2O-zP2S5-wMX; XM2S- yM2O-zP2S5-wP2O5; xM2S-yM2O-zP2S5-wP2O5-vMX; xM2S-ySiS2; MPSX (par exemple, M a P b S c X d tel que M7P3S11X, M7P2S8X, et MePS5X); MPSOX (par exemple, M a P b S c OdX e ); MGPSX (M a Ge b P c S d X e ); MGPSOX (M a Ge b P c S d O e X f ); MSiPSX ( M a Si b P c S d X e ); MSiPSOX (M a Si b P c S d O e X f ); MSnPSX (M a Sn b P c S d X e ); MSnPSOX (M a Sn b P c S d O e X f ); MZPSX (M a Zn b P c S d X e ); MZPSOX (Ma Zn b P c S d O e X f ); M3OX; M2HOX; M3PO4; M3PS4; and M a PObNc (where a = 2b + 3c - 5); in which M is an alkali metal, an alkaline earth metal, or one of their combinations, and in which, when M comprises an ion of an alkaline earth metal, then the number of M is adjusted to achieve electroneutrality; X is chosen from F, Cl, Br, I, or a combination thereof; a, b, c, d, e, and f are nonzero numbers and are, independently in each formula, selected to achieve electroneutrality; and v, w, x, y, and z are nonzero numbers and are, independently in each formula, selected to obtain a stable compound. Composition according to any one of claims 1 to 22, wherein the inorganic particles comprise a natural or synthetic ceramic chosen from Al2O3, Mg2B2O5, Na2O-2B2C>3, xMgO yB2O3 zH2O TiO2, ZrO2, ZnO, Ti2O3, SiO2, Cr2O3, CeO2, B2O3, B2O, SrBi4Ti40i5, LLTO, LLZO, LAGP, LATP, Fe2O3, BaTiO3Y-Li AlO2, molecular sieves and zeolites (e.g., aluminosilicate, mesoporous silica), sulfide ceramics (such as Li6PS5Cl, Li7P3S11), glass-ceramics (such as LIPON, etc.), and other ceramics, as well as their combinations.

25. Composition according to claim 23, wherein the MLZO ceramic has the formula where b is such that 0 < b < 1 and M' is Al, Ga, Ta, Fe or Nb or is absent, preferably b is 0 and M' is absent.

26. Composition according to claim 24, wherein the ceramic is an aluminosilicate compound.

27. Composition according to claim 23 or 24, wherein the ceramic is a sulfide or oxysulfide-based ceramic.

28. Composition according to any one of claims 1 to 27, wherein the inorganic particles are in the form of spherical particles, rods, needles, nanotubes, or any combination thereof.

29. Composition according to any one of claims 1 to 28, wherein the content of inorganic particles in the composition is in the range of about 5% by weight to about 99% by weight, or about 5% by weight to about 90% by weight, or about 10% by weight to about 80% by weight, or about 15% by weight to about 40% by weight.

30. Composition according to any one of claims 1 to 29, the composition being solid.

31. Composition according to any one of claims 1 to 30, the composition being free of polymerization initiator or crosslinking agent.

32. A method for preparing a composition as defined in any one of claims 1 to 31, the method comprising a step of mixing inorganic particles, of at least one monomer comprising at least one functional group a polymerizable or crosslinkable polymer and an organic compound comprising one or more SH groups. A process of claim 32, wherein the mixing step is carried out at a temperature in the range of 15°C to 50°C, or in the range of 20°C to 35°C, or in the range of 20°C to 30°C. A process of claim 32 or 33, wherein the mixing step is carried out in the presence of oxygen (e.g., under air). A process of claim 32 or 33, wherein the mixing step is carried out under an inert atmosphere. A process of any one of claims 32 to 35, which excludes the addition of a polymerization initiator or a crosslinking agent. A process according to any one of claims 32 to 36, further comprising spreading the resulting mixture onto a support. A method according to claim 37, wherein the support is an inert film and the method optionally includes the removal of the film.A method according to claim 37, wherein the support is an electrode film. A method according to claim 37, wherein the support is a current collector or an electrolyte film. An electrolyte comprising the composition as defined in any one of claims 1 to 31, or obtained according to the method as defined in any one of claims 32 to 39. An electrolyte according to claim 41, the electrolyte being in the form of a solid electrolyte film. An electrode comprising the composition as defined in any one of claims 1 to 31, or obtained according to the method as defined in any one of claims 32 to 38 and 40, and an electrochemically active material.

44. Electrode of claim 43, further comprising a current collector.

45. Electrode of claim 43 or 44, wherein the electrochemically active material is a positive electrode electrochemically active material, such as LiM'PO4 where M' is Fe, Ni, Mn, Co, or a combination thereof, LiVsOs, V2O5F, LiV2O5, LiMn2O4, LiM”O2, where M” is Mn, Co, Ni, or a combination thereof (such as NMC, LiMn s Co t Neither u O2(with s+t+u = 1), Li(NiM”')O2(where M'” is Mn, Co, Al, Fe, Cr, Ti, Zr, or a combination thereof), sulfur, selenium or elemental iodine, iron(III) fluoride, copper(II) fluoride, lithium iodide, carbon-based active materials such as graphite, organic cathode active materials, or a combination of two or more of these materials when they are compatible with each other.

46. ​​Electrode of any one of claims 43 to 45, further comprising an electronically conductive material, a binder, a salt, or a combination of two or more of these.

47. Electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, wherein the electrolyte is as defined in claim 41 or 42.

48. Electrochemical cell of claim 47, wherein the positive electrode comprises an electrochemically active positive electrode material and optionally a current collector.

49. Electrochemical cell of claim 48, wherein the electrochemically active positive electrode material is selected from metal phosphates, lithia metal phosphates, metal oxides, and lithia metal oxides.

50. Electrochemical cell of claim 48, wherein the electrochemically active positive electrode material is LiM'PO4 where M' is Fe, Ni, Mn, Co, or a combination thereof, LiV3O8, V2O5F, LiV2O5, LiMn2O4, LiM”O2, where M” is Mn, Co, Ni, or a combination thereof (such as NMC, LiMn s Co t Neither u O2 with s+t+u = 1), Li(NiM'”)O2 (where M'” is Mn, Co, Al, Fe, Cr, Ti, Zr, or a combination thereof), sulfur, selenium or elemental iodine, iron(III) fluoride, copper(ll) fluoride, lithium iodide, carbon-based active materials such as graphite, organic cathode active materials, or a combination of two or more of these materials when they are compatible with each other.

51. Electrochemical cell according to any one of claims 48 to 50, wherein the positive electrode material further comprises an electronically conductive material, a binder, a salt, and / or inorganic particles.

52. Electrochemical cell according to any one of claims 47 to 51, wherein the electrolyte is in direct contact with the positive electrode and / or the negative electrode, preferably with the positive electrode.

53. Electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, wherein the positive electrode is as defined in any one of claims 43 to 46.

54. Electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, wherein the electrolyte is as defined in claim 41 or 42 and the positive electrode is as defined in any one of claims 43 to 46.

55. Electrochemical cell of any one of claims 47 to 54, wherein the negative electrode comprises an electrochemically active negative electrode material and optionally a current collector.

56. Electrochemical cell of claim 55, wherein the electrochemically active negative electrode material comprises a metallic film comprising an alkali or alkaline earth metal or an alloy comprising an alkali or alkaline earth metal.

57. Electrochemical cell of claim 56, wherein the alkali metal is selected from lithium and sodium or an alloy comprising one of these.

58. Electrochemical cell of claim 55, wherein the electrochemically active negative electrode material comprises 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., LiTi2(PO4)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 (SiO2) x ), a silicon-carbon oxide composite (SiOx-C), tin (Sn), a tin-carbon composite (Sn-C), a tin oxide (SnO x ), a tin-carbon oxide composite (SnO x -C), and their combinations, when compatible. Electrochemical cell of claim 58, wherein the metal oxide is selected from compounds of formula M”” gOh (where M”” is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination thereof; and g and h are numbers such that the h:g ratio lies in the range of 2 to 3) (e.g., MoO3MOO2, M0S2, V2O5, and TiNb2O?), spinel oxides (e.g., NiCo2O4, ZnCo2O4, MnCo2O4, CuCO2O4, and CoFe2O4), and LiM'””O (where M'”” is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination thereof) (e.g., lithium titanate (such as Li4TisO 12) or a lithium molybdenum oxide (such as U2MO4O13). Electrochemical cell according to claim 58 or 59, wherein the negative electrode material further comprises an electronically conductive material, a binder, a salt, inorganic particles, or a combination of two or more of these. Battery comprising at least one electrochemical cell as defined in any one of claims 47 to 60. Battery according to claim 61, which is selected from a lithium battery, a lithium-ion battery, a sodium battery, a sodium-ion battery, a potassium battery, a potassium-ion battery, a magnesium battery, and a magnesium-ion battery. Battery according to claim 62, wherein said battery is a lithium battery.

64. Battery according to claim 62, wherein said battery is a lithium-ion battery.

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