Composite material comprising a fluorinated amide and uses thereof in electrochemical cells

Abstract

The present technology relates to a composite material comprising inorganic particles, a fluorinated amide compound and, optionally, an electrolyte polymer, a plasticizer and / or a salt, as well as to the method for preparing the composite material. Also disclosed are the solid electrolytes and electrode materials comprising the present composite material and their use in electrochemical cells and storage batteries containing them.

Description

[0001] COMPOSITE MATERIAL COMPRISING A FLUORINATED AMIDE AND USES IN ELECTROCHEMICAL CELLS

[0002] RELATED REQUEST

[0003] This application claims priority under applicable law from Canadian patent application number 3,122,820 filed on June 18, 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 polymer-ceramic composite electrolytes comprising an organic additive, to their manufacturing processes and to the electrochemical cells comprising them.

[0006] STATE OF THE ART

[0007] Lithium-ion conducting polymer electrolytes enable the development of safer and more affordable manufacturing processes, which are easily scaled up for large-format all-solid-state batteries (e.g., see U.S. Patent No. 6,903,174). However, the low ionic conductivity limits its application at room temperature and results in relatively low charge / discharge rates compared to conventional lithium-ion batteries.

[0008] On the other hand, solid inorganic electrolytes are promising candidates for solid-state batteries, as they provide higher lithium ion conductivity that is comparable to liquid electrolytes. In addition, the unique ion conduction property of inorganic electrolytes allows lower concentration polarization at the interface of metallic lithium and enables high-rate battery charging and discharging. Despite its high ionic conductivity in densified bulk phase, complete cells using ceramic solid electrolytes suffer from poor electrochemical performance due to significant interface resistance at the grain boundaries of ceramic particles and between the particles of composite electrodes consisting of a mixture of active material particles, carbon additive, and solid electrolyte. As Li ion conduction +must be carried out in particle-to-particle mode, the electrochemical performances are limited by the poor distribution of solid electrolyte particles as well as by the existence of voids between the particles.

[0009] A recent review of different composite electrolytes, comprising a polymer and solid electrolyte particles, was published by the group of S. Tang et al. (Adv. Energy Mater., 2021, 11, 2000802 (pages 1-29)). In order to improve ionic conductivity, different organic solvents (such as carbonate esters) and other plasticizers (such as 1-propene-1,3-sultone, glycerin, tetraethylene glycol dimethyl ether (TEGDME) or hexafluoropropylene (HFP)) can be added to the composite. However, these can reduce the mechanical strength, for example, if they are present in too large a quantity. Electrochemical instability problems can also be encountered with these composite electrolytes, particularly at the interface between the electrolyte layer and one of the electrodes, for example a lithium metal electrode. In fact, according to Tang et al., despite the progress made in composite electrolytes, they still face different challenges in terms of ionic conductivity, electrochemical stability and interfacial interactions.

[0010] Zhu et al.'s team also recently described some strategies that can be used to increase the ionic conductivity and interfacial compatibility of inorganic-organic solid composite electrolytes (see Energy Storage Materials, 2021, 36, 291-308). Strategies for increasing ionic conductivity include adjusting the inorganic particle content, optimizing particle size and morphology, orienting inorganic particles, modifying the surface of inorganic particles (such as with polydopamine, silanes, etc.), or adding additives such as small molecule plasticizers (such as succinonitrile, TEGDME, etc.).Strategies for improving the interfacial compatibility of solid composite electrolytes described include symmetric or asymmetric multilayer configurations, interactions between the polymer (such as polycaprolactone) and inorganic particles, blends of two different polymers (such as poly(ethylene oxide) (PEO) and boronized poly(ethylene glycol) (BPEG)) with the particles, etc.

[0011] There is therefore a constant need for the development of solid electrolytes that have the advantages associated with them in general while improving at least one of the aspects mentioned above. SUMMARY

[0012] According to a first aspect, the present technology relates to a composite material comprising inorganic particles, a fluorinated compound, and optionally a polymer, the fluorinated compound being of Formula I: Formula I in which:

[0013] R 1 and R 2are independently selected at each occurrence from an optionally substituted linear or branched C1-C1alkyl group, an optionally substituted C3-C1cycloalkyl group, an optionally substituted C1aryl group, an optionally substituted C3-C8heterocycloalkyl group, and an optionally substituted C5-C6heteroaryl group;

[0014] X 1 is chosen from O and NH or X 1 is absent;

[0015] X 2 is chosen from C(O), S(O)2, and Si(R 3 R 4 ), where R 3 and R 4 are independently at each occurrence a linear or branched optionally substituted Ci-salkyl group, or X 2 is absent; in which at least one of R 1 , R 2 , R 3 and R 4 is a group substituted by one or more fluorine atom(s).

[0016] According to one embodiment, X 1 is absent and X 2 is chosen from C(O), S(O)2, and Si(R3 R 4 ), or X 1 is chosen from O and NH and X 2 is absent, or even X 1 and X 2 are both absent.

[0017] According to another embodiment, R 1 is a group substituted by one or more fluorine atom(s), for example, R 1 may be a perfluorinated group. In one embodiment, R 1 is a linear or branched C 1-4 alkyl group, or a linear or branched C 1-4 alkyl group, or a C 1-2 alkyl group.

[0018] In some embodiments, R 2 is a group substituted by one or more fluorine atom(s), for example, R 2 may be a perfluorinated group. According to one embodiment, R 2 is a linear or branched Ci-salkyl group, or a linear or branched Ci-4alkyl group, or a Ci-2alkyl group. Alternatively, R 2is an optionally substituted C3-8cycloalkyl group, or an optionally substituted C3-6cycloalkyl group, or an optionally substituted C5-6cycloalkyl group.

[0019] In some embodiments, the fluorinated compound is selected from / V-methyltrifluoroacetamide (NMTFAm), / V-methylpentaproprionamide (NMPPPAm), / V-cylcopentyltrifluoroacetamide (NCPTFAm), N-trifluoromethylsulfonyl trifluoroacetamide (NTFMSTFAm), / V-trimethylsilyl trifluoroacetamide (NTMSTFAm), and bistrifluoroacetamide (BTFAm).

[0020] In one embodiment, the concentration of the compound in the composite material is in the range of 1% to 90% by weight, or 1% to 70% by weight, or 1% to 50% by weight, or 1% to 40% by weight, or 5% to 30% by weight, or 10% to 25% by weight, or 15% to 20% by weight.

[0021] In another embodiment, the polymer is present and may be a crosslinked aprotic polymer and / or a branched polymer, preferably of the multi-branched type. According to one embodiment, the polymer comprises at least one polymer segment selected from the ionically conductive segments polyether, polythioether, polyester, polythioester, polycarbonate, polythiocarbonate, polyimide, polysulfonimide, polyamide, polysulfonamide, polyphosphazene, and the ionically non-conductive segments polyacrylate, polymethacrylate, polystyrene, polysiloxane, polyurethane, polyethylene, polypropylene, or a copolymer or combination of two or more thereof.

[0022] According to another embodiment, the polymer comprises at least one polymer segment comprising a block copolymer with at least two different repeating units in order to reduce the crystallinity of the crosslinked polymer, for example, the polymer segment comprising, before crosslinking, a block copolymer comprising at least one alkali or alkaline earth metal ion solvating segment and a crosslinkable segment comprising crosslinkable units. According to one embodiment, the alkali or alkaline earth metal ion solvating segment is selected from homo- and copolymers comprising repeating units of Formula II:

[0023] -(CH2-CH-0) x - R

[0024] Formula II in which,

[0025] R is selected from Fl, Ci-Cioalkyl, and -(CFte-O-RaRb);

[0026] Ra is (CH2-CH2-0)y; and Rb is a Ci-Cioalkyl group.

[0027] In one embodiment, the crosslinkable units comprise functional groups selected from acrylates, methacrylates, allyls, vinyls, hydroxides, epoxides, aldehydes, carboxylic acids, halophenyls, halobenzyls, alkynes, azides, amines, thiols and a combination thereof. In some embodiments, the polymer is present in the composite material at a concentration in the range of 1% to 80% by weight, 5% to 70% by weight, or 10% to 50% by weight, or 20% to 40% by weight. In another embodiment, the inorganic particles comprise an inorganic compound of amorphous, ceramic or glass-ceramic type, for example, oxide, sulfide or oxysulfide. Preferably, the inorganic compound of amorphous, ceramic or glass-ceramic type is an oxide.In another embodiment, the inorganic particles comprise a ceramic selected from AI2O3, Mg2B20s, Na20-2B2C>3, xMg0 yB203-zH20, T1O2, ZrÜ2, ZnO, T12O3, S1O2, Cr203, Ce02, B2O3, B2O, SrBUTUOis, LLTO, LLZO, LAGP, LATP, Fe203, BaTi03, Y-L1AIO2, molecular sieves and zeolites (e.g., aluminosilicate, mesoporous silica), sulfide ceramics (such as U7P3S11), glass-ceramics (such as LIPON, etc.), and other ceramics, as well as combinations thereof. Preferably, the ceramic is selected from AI2O3, Mg2B20s, Na20-2B2C>3, xMg0 yB203-zH20, T1O2, ZrÜ2, ZnO, T12O3, S1O2, Cr203, Ce02, B2O3, B2O, SrBUTUOis, LLTO, LLZO, LAGP, LATP, Fe203, BaTiOs, Y-UAIO2, molecular sieves and zeolites (e.g., aluminosilicate, mesoporous silica), glass-ceramics (such as LIPON, etc.), as well as combinations thereof.

[0028] According to one embodiment, the inorganic particles are in the form of spherical, rod-shaped, needle-shaped, nanotube-shaped particles, or one of their combinations.

[0029] According to one embodiment, the inorganic particles comprise a compound chosen from the compounds of formula Lii+ z Al z M2-z(P04)3, where M is Ti, Ge or a combination thereof, and 0 < z < 1, for example, z may be in the range 0.1 to 0.9, or 0.3 to 0.7, or 0.2 to 0.4.

[0030] In another embodiment, wherein the inorganic particles comprise a compound selected from compounds of formulas L17- x La3Zr2lVl x xOi2 and Li3yLa(2 / 3)-yTii- y M y y 03 in which M x is selected from Al, Ga, Ta, Fe, and Nb; M yis chosen from Ba, B, Al, Si and Ta; x is such that 0 £ x £ 1 ; y is such that 0 < y < 0.67; and y' is such that 0 < y' < 1 . For example, x can be in the range 0 to 0.5, or x is zero and M x is absent. According to one embodiment, the content of inorganic particles is in the range of 1% to 95% by weight, or 5% to 90% by weight, or 5% to 80% by weight, or 5% to 70% by weight, or 5% to 60% by weight, or 5% to 50% by weight, or 5% to 40% by weight, or 5% to 25% by weight, or 5% to 15% by weight.

[0031] In another embodiment, the composite material comprises the polymer and further a plasticizing agent. For example, the plasticizing agent may be selected from glycol diether liquids (such as tetraethylene glycol dimethyl ether (TEGDME)), carbonate esters, ionic liquids, and the like. In one embodiment, the plasticizing agent may be present in the composite material at a concentration in the range of 0.1% to 50% by weight, or 10% to 50% by weight, or 20% to 40% by weight.

[0032] According to another embodiment, the composite material further comprises a salt. For example, the salt may comprise a cation of an alkali or alkaline earth metal, preferably an alkali metal (preferably Li), and an anion selected from hexafluorophosphate (PF6), bis(trifluoromethanesulfonyl)imide (TFSI), bis(fluorosulfonyl)imide (FSh), (flurosulfonyl)(trifluoromethanesulfonyl)imide ((FSI)(TFSI)), 2-trifluoromethyl-4,5-dicyanoimidazolate (TDh), 4,5-dicyano-1,2,3-triazolate (DCTA), bis(pentafluoroethylsulfonyl)imide (BETI), difluorophosphate (DFP), tetrafluoroborate (BF4), bis(oxalato)borate (BOB-), nitrate (NO3), chloride (Ch), bromide (Br), fluoride (F), perchlorate (CIO4), hexafluoroarsenate (AsF6), trifluoromethanesulfonate (SO3CF3) (Tf), fluoroalkylphosphate [PF3(CF2CF3)3] (FAP), tetrakis(trifluoroacetoxy)borate [B(OCOCF3)4] (TFAB-), bis(1,2-benzenediolato(2-)-0,0')borate [B(0QO2)2] (BBB), difluoro(oxalato)borate

[0033] (BF2(C2Ü4) ) (FOB ), an anion of formula BF2O4R X (where Rx = C2-4alkyl), and one of their combinations, e.g. LiTFSI or LiFSI.

[0034] In a second aspect, the present document relates to a solid electrolyte comprising a layer of the composite material as defined herein. In a third aspect, the present technology relates to an electrochemical cell comprising a negative electrode, a positive electrode, and a solid electrolyte, wherein at least one of the positive electrode, the negative electrode, and the electrolyte comprises a composite material as defined herein. In one embodiment, the electrochemical cell comprises a negative electrode, a positive electrode, and a solid electrolyte, wherein the solid electrolyte is as defined herein. In another embodiment, the solid electrolyte is as defined herein and at least one of the negative electrode and the positive electrode comprises a composite material as defined herein.

[0035] In one embodiment, the positive electrode comprises a positive electrode material optionally on a current collector, wherein the positive electrode material comprises a positive electrode electrochemically active material. In another embodiment, the positive electrode electrochemically active material is selected from metal phosphates, lithiated metal phosphates, metal oxides, and lithiated metal oxides. In yet another embodiment, the positive electrode electrochemically active material is LiM'PC where M' is Fe, Ni, Mn, Co, or a combination thereof, UV3O8, V2O5F, UV2O5, LiMn2C>4, LiM”C>2, where M” is Mn, Co, Ni, or a combination thereof (such as NMC, LiMn x Co yNiz02 with x+y+z = 1), Li(NiM'”)02 (where M'” is Mn, Co, Al, Fe, Cr, Ti, Zr, or a combination thereof), sulfur, selenium or elemental iodine, iron(lll) fluoride, copper(ll) fluoride, lithium iodide, carbon-based active materials such as graphite, organic cathode active materials (such as polyimide, poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl methacrylate) (PTMA), perylene-3,4,9,10-tetralithium tetracarboxylate (PTCU4), naphthalene-1,4,5,8-tetracarboxylic dianhydride (NTCDA), perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA), TT- dicarboxylates conjugated, and anthraquinone), or a combination of two or more of these materials when they are compatible with each other. According to one embodiment, the electrochemically active positive electrode material is in the form of optionally coated particles (for example, polymer, ceramic, carbon or a combination of two or more of these).

[0036] In another embodiment, the positive electrode material further comprises an electronically conductive material, e.g., comprising at least one of carbon blacks (e.g., Ketjenblack™ or Super P™), acetylene blacks (e.g., Shawinigan Black or Denka Black™), graphite, graphene, carbon fibers or nanofibers (e.g., gas-formed carbon fibers (VGCFs)), carbon nanotubes (e.g., single-walled (SWNT), multi-walled (MWNT)), or metal powders.

[0037] In some embodiments, the positive electrode material further comprises a binder, for example, the binder is a polymer as defined above, or a binder selected from rubber-type binders (such as SBR (styrene-butadiene rubber), NBR (acrylonitrile-butadiene rubber), HNBR (hydrogenated NBR), CHR (epichlorohydrin rubber), ACM (acrylate rubber)), or fluoropolymer-type binders (such as PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), and combinations thereof), optionally comprising an additive such as CMC (carboxymethylcellulose). In other embodiments, the positive electrode material further comprises a salt, inorganic particles of the ceramic or glass type, or other compatible active materials (e.g., sulfur), and / or the positive electrode material further comprises the composite material defined herein.

[0038] In another embodiment, the negative electrode of the electrochemical cell comprises an electrochemically active negative electrode material.

[0039] In one embodiment, the negative electrode electrochemically active material comprises a metal film comprising an alkali or alkaline earth metal. For example, the metal film comprises lithium comprising less than 1000 ppm (or less than 0.1% by mass) of impurities. Alternatively, the metal film comprises an alloy of lithium and an element selected 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 Sc, 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, Pb, Mn, B, In, Tl, Ni, or Ge), preferably, the alloy comprising at least 75% by mass of lithium, or between 85 % and 99.9% by mass of lithium.

[0040] 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., 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 (SiOx), a silicon oxide-carbon composite (SiOx-C), tin (Sn), a tin-carbon composite (Sn-C), an oxide tin (SnOx), a tin oxide-carbon composite (SnOx-C), and combinations thereof, when compatible.In another embodiment, the metal oxide is selected from compounds of formulas M””bOc (where M”” is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination thereof; and b and c are numbers such that the c:b ratio is in the range of 2 to 3) (e.g., M0O3, M0O2, M0S2, V2O5, and TiNb207), spinel oxides (e.g., N1C02O4, ZnCo204,.

[0041] MnCo204, CUC02O4, and CoFe204) and LiM . O (where M . is Ti, Mo, Mn, Ni, Co, Cu,

[0042] V, Fe, Zn, Nb, or a combination thereof) (e.g., lithium titanate (such as LUTisO^) or lithium molybdenum oxide (such as U2M04O13)). In some embodiments, the negative electrode electrochemically active material is in the form of optionally coated particles (e.g., polymer, ceramic, carbon, or a combination of two or more thereof).

[0043] In one embodiment, the negative electrode material further comprises an electronically conductive material, e.g., comprising at least one of carbon blacks (e.g., Ketjenblack™ or Super P™), acetylene blacks (e.g., Shawinigan Black or Denka Black™), graphite, graphene, carbon fibers or nanofibers (e.g., gas-formed carbon fibers (VGCFs)), carbon nanotubes (e.g., single-walled (SWNTs), multi-walled (MWNTs)), or metal powders.

[0044] In another embodiment, the negative electrode material further comprises a binder, for example, the binder is a polymer as defined above, or a binder selected from rubber-type binders (such as SBR (styrene-butadiene rubber), NBR (acrylonitrile-butadiene rubber), HNBR (hydrogenated NBR), CHR (epichlorohydrin rubber), ACM (acrylate rubber)), or fluoropolymer-type binders (such as PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), and combinations thereof), optionally comprising an additive such as CMC (carboxymethylcellulose).

[0045] According to yet another embodiment, the negative electrode material further comprises a salt, inorganic particles of the ceramic or glass type, or other compatible active materials, and / or the composite material as defined herein.

[0046] According to a fourth aspect, the present technology relates to an electrochemical accumulator comprising at least one electrochemical cell as defined herein. According to one embodiment, the electrochemical accumulator is a lithium battery or a lithium-ion battery. According to a fifth aspect, the present document relates to the use of an electrochemical accumulator as defined herein, in portable devices, for example mobile phones, cameras, tablets or laptops, in electric or hybrid vehicles, or in the storage of renewable energy.

[0047] According to a final aspect, the present technology also relates to a method for preparing a composite material as defined herein, comprising a step of mixing the inorganic particles, the fluorinated compound, and optionally the polymer. According to one embodiment, the mixing step comprises the polymer and optionally a crosslinking agent. According to another embodiment, the mixing step comprises the polymer and the crosslinking agent and the method further comprises a step of crosslinking the polymer.

[0048] BRIEF DESCRIPTION OF THE FIGURES

[0049] Figure 1 shows the infrared spectroscopy results of: (a) LATP; (b) NMTFAm; (c) DAEDAm; (d) NMTFAm / LATP mixture; and (e) DAEDAm / LATP mixture.

[0050] Figure 2 shows the solid-state NMR results: (a) 1 H of NMTFAm and NMTFAm / LATP mixture; (b) 6Li of LATP; (c) 6Li of NMTFAm / LATP mixture.

[0051] Figure 3 shows the Young's modulus of the membrane prepared in Example 1(d).

[0052] Figure 4 shows the ionic conductivity results as a function of temperature in (a) for Cells 1 to 6 and 8 to 15; and in (b) for Cell 7 compared to a LATP powder.

[0053] Figure 5 shows the potential versus time for Cell 4 cycled at current densities ranging from C / 3 to 5C.

[0054] Figure 6 shows the electrochemical stability results for Cell 4 performed at voltages ranging from 3.5 V to 5 V. Figure 7 shows the capacity and coulombic efficiency of an NMC / Li cell as a function of the number of cycles according to Example 3(e)(i).

[0055] Figure 8 shows the galvanostatic charge and discharge curves at C / 6 of an LFP / Li battery as a function of the number of cycles according to Example 3(e)(ii). DETAILED DESCRIPTION

[0056] All technical and scientific terms and expressions used herein have the same meaning as generally understood by the person skilled in the art of the present technology. Definitions of certain terms and expressions used are nevertheless provided below. The term "about" as used herein means approximately, in the region of, and around. When the term "about" is used in connection with a numerical value, it varies it, for example, above and below by a variation of 10% from the nominal value. This term may also take into account, for example, the experimental error of a measuring device or the rounding of a value.

[0057] 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.

[0058] 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 it will be assumed that the valence is satisfied by one or more hydrogen atoms even if they are not explicitly drawn.

[0059] This document discloses a composite material comprising inorganic particles, a fluorinated amide and optionally a polymer. Preferably, the fluorinated amide is a compound of Formula I:

[0060] Formula I in which:

[0061] R 1 and R 2are independently selected at each occurrence from an optionally substituted linear or branched C1-C10alkyl group, an optionally substituted C3-C12cycloalkyl group, an optionally substituted C13-C14aryl group, an optionally substituted C14-C16heterocycloalkyl group, and an optionally substituted C15-C16heteroaryl group;

[0062] X 1 is chosen from O and NH or X 1 is absent;

[0063] X 2 is chosen from C(O), S(O)2, and Si(R 3 R 4 ), where R 3 and R 4 are independently at each occurrence a linear or branched optionally substituted Ci-salkyl group, or X 2 is absent; in which at least one of R 1 , R 2 , R 3 and R 4 is a group substituted by one or more fluorine atom(s).

[0064] Some examples of compounds of Formula I include compounds in which:

[0065] - X1 is absent and X 2 is chosen from C(O), S(O)2, and Si(R 3 R 4 );

[0066] - X 1 is chosen from O and NH and X 2 is absent; or

[0067] - X 1 and X 2 are absent.

[0068] According to some examples, R 1 is a group substituted by one or more fluorine atom(s), for example, a perfluorinated group. This group may be a linear or branched C1-alkyl group, or a linear or branched C1-4alkyl group, or a C1-2alkyl group.

[0069] The R group 2 may be a group substituted by one or more fluorine atom(s), for example, a perfluorinated group. This group may be a linear or branched Ci-salkyl group, or a linear or branched Ci-4alkyl group, or a Ci-2alkyl group. Alternatively, R 2may be an optionally substituted C3-8cycloalkyl group, or an optionally substituted C3-6cycloalkyl group, or an optionally substituted C5-6cycloalkyl group.

[0070] Non-limiting examples of fluorinated compounds include N-methyltrifluoroacetamide (NMTFAm), / V-methylpentaproprionamide (NMPPPAm), / V-cylcopentyltrifluoroacetamide (NCPTFAm), / V-trifluoromethylsulfonyl trifluoroacetamide (NTFMSTFAm), / V-trimethylsilyl trifluoroacetamide (NTMSTFAm), and bistrifluoroacetamide (BTFAm).

[0071] The concentration of the compound in the composite material may be, for example, in the range of 1% to 90% by weight, or 1% to 70% by weight, or 1% to 50% by weight, or 1% to 40% by weight, or 5% to 30% by weight, or 10% to 25% by weight, or 15% to 20% by weight.

[0072] The polymer, when present in the composite material, may comprise at least one polymer segment selected from ionically conductive segments of the polyether, polythioether, polyester, polythioester, polycarbonate, polythiocarbonate, polyimide, polysulfonimide, polyamide, polysulfonamide, polyphosphazene type, or from non-ionically conductive segments polyacrylate, polymethacrylate, polystyrene, polysiloxane, polyurethane, polyethylene, polypropylene. The polymer may also be a copolymer comprising the units of two or more of these segments or a combination of two or more of these. The copolymer may be a random, statistical, alternating, block copolymer, etc.

[0073] The polymer is preferably a crosslinked aprotic polymer and / or a branched polymer, preferably of the multi-branched type (star, comb configuration, etc.). For example, the polymer comprises at least one polymer segment comprising a block copolymer with at least two different repeating units in order to reduce the crystallinity of the crosslinked polymer. For example, the polymer segment may comprise, before crosslinking, a block copolymer comprising at least one alkali or alkaline earth metal ion solvating segment and a crosslinkable segment comprising crosslinkable units. An example of an alkali or alkaline earth metal ion solvating segment is selected from homo- and copolymers comprising repeating units of Formula II:

[0074] -(CH2-CH-0) x -

[0075] R

[0076] Formula II in which,

[0077] R is selected from Fl, Ci-Cioalkyl, and -(CFte-O-RaRb);

[0078] Ra is (CH2-CH2-0) y ; And

[0079] Rb is a Ci-Cioalkyl group.

[0080] Non-limiting examples of crosslinkable units include functional groups selected from acrylates, methacrylates, allyls, vinyls, hydroxides, epoxides, aldehydes, carboxylic acids, halophenyls, halobenzyls, alkynes, azides, amines, thiols and any combination thereof. In another example, the composite material comprises the crosslinked polymer, wherein the crosslinkable group has been converted to its crosslinked version.

[0081] The concentration of the polymer in the composite material may generally be in the range of 1% to 80% by weight, 5% to 70% by weight, or 10% to 50% by weight, or 20% to 40% by weight.

[0082] The inorganic particles preferably comprise an inorganic compound of amorphous, ceramic or glass-ceramic type, for example, oxide, sulfide or oxysulfide, preferably an oxide. The inorganic compound may be ionically conductive or non-ionically conductive, preferably ionically conductive.

[0083] Non-limiting examples of inorganic compounds include AI2O3, Mg2B20s, Na2O-2B2C>3, xMg0 yB2C>3 zH20, T1O2, Zr02, ZnO, T12O3, S1O2, Cr203, Ce02, B2O3, B2O, SrBUTUOis, LLTO, LLZO, LAGP, LATP, Fe2Ü3, BaTiC>3, y-LiAICte, ​​molecular sieves and zeolites (e.g., aluminosilicate, mesoporous silica), sulfide ceramics (such as U7P3S11), glass-ceramics (such as LIPON, etc.), and other ceramics, as well as combinations thereof, preferably selected from AI2O3, Mg2B20s, Na2O-2B2C>3, xMgO 7B2O3 zhteO, T1O2, ZrÜ2, ZnO, T12O3, S1O2, Cr203, CeÜ2, B2O3, B2O, SrBUTUOis, LLTO, LLZO, LAGP, LATP, Fe203, BaTiOs, Y-UAIO2, molecular sieves and zeolites (e.g., aluminosilicate, mesoporous silica), glass-ceramics (such as LIPON, etc.), and combinations thereof.The inorganic compound is preferably in the form of particles, the particles being of various shapes, for example in the form of spherical particles, rods, needles, nanotubes, or any combination thereof.

[0084] For example, the inorganic particles comprise a compound selected from compounds of formula Lii+ z Al z M2-z(P04)3, where M is Ti, Ge or a combination thereof, and 0 < z < 1, for example, z can be in the range 0.1 to 0.9, or 0.3 to 0.7, or 0.4 to 0.6, or 0.2 to 0.5, or 0.2 to 0.4.

[0085] According to other examples, the inorganic particles comprise a compound selected from compounds of formulas LÎ7-xLa3Zr2M x x Oi2 and Li3yLa(2 / 3)-yTii- y M y y 03 in which M x is selected from Al, Ga, Ta, Fe, and Nb; M yis chosen from Ba, B, Al, Si and Ta; x is such that 0 < x < 1; y is such that 0 < y < 0.67; and y' is such that 0

[0086] £ y' < 1 , preferably x lies in the interval 0 to 0.5, or x is zero and M x is absent, preferably y' is in the range 0 to 0.5, or y' is 0 and M y is absent.

[0087] The content of inorganic particles in the composite material may be in the range of 1% to 95% by weight, or 5% to 90% by weight, or 5% to 80% by weight, or 5% to 70% by weight, or 5% to 60% by weight, or 5% to

[0088] 50% by weight, or from 5% to 40% by weight, or from 5% to 25% by weight, or from 5% to

[0089] 15% by weight.

[0090] In some examples, the composite material comprises the polymer and a plasticizing agent. Non-limiting examples of plasticizing agents include glycol diether liquids (such as tetraethylene glycol dimethyl ether (TEGDME)), carbonate esters, ionic liquids, and the like. When present, the concentration of plasticizing agent in the composite material may be in the range of 0.1% to 50% by weight, or 10% to 50% by weight, or 20% to 40% by weight.

[0091] According to a preferred example, the composite material further comprises a lithium salt, for example, a salt comprising a cation of an alkali or alkaline earth metal, preferably an alkali metal (preferably Li), and an anion.Non-limiting examples of anions include hexafluorophosphate (PFe-), bis(trifluoromethanesulfonyl)imide (TFSL), bis(fluorosulfonyl)imide (FSL), (flurosulfonyl)(trifluoromethanesulfonyl)imide ((FSI)(TFSI) ), 2- trifluoromethyl-4,5-dicyanoimidazolate (TDL), 4,5-dicyano-1 ,2,3-triazolate (DCTA ), bis(pentafluoroethylsulfonyl)imide (BETL), difluorophosphate (DFP ), tetrafluoroborate (BF4 ), bis(oxalato)borate (BOB ), nitrate (NO3 ), chloride (Ch), bromide (Br), fluoride (F ), perchlorate (CIO4 ), hexafluoroarsenate (AsF6 ), trifluoromethanesulfonate (SO3CF3 ) (Tf), fluoroalkylphosphate [PF3(CF2CF3)3] (FAP), tetrakis(trifluoroacetoxy)borate [B(OCOCF3)4] (TFAB-), bis(1,2-benzenediolato(2-)-0.0')borate [B(0QO2)2] (BBB), difluoro(oxalato)borate.

[0092] (BF2(C204) ) (FOB ), an anion of formula BF2O4R X (where Rx = C2-4alkyl), and one of their combinations, e.g. LiTFSI or LiFSI.

[0093] The present composite material is prepared according to a process comprising at least one step of mixing the inorganic particles, the fluorinated compound, and optionally the polymer and other optional elements as described herein. The mixing step of the process may therefore comprise the polymer and optionally a crosslinking agent. The mixing step of such a process may then be followed by a crosslinking step.

[0094] The composite material can be used in the composition of a solid electrolyte layer or an electrode material.

[0095] For example, the electrolyte comprises the composite material as defined herein in a solid layer. This layer may be formed by mixing, in any order, the inorganic particles, the electrolyte polymer or a precursor thereof, the fluorinated amide, and optionally a solvent, the plasticizer and / or a salt, and spreading the mixture on a support. The support may be temporary (such as a stainless steel, polypropylene, etc. support) and be removed before assembly with the rest of the electrochemical cell. The support may also be the surface of an electrode material, which will have been previously prepared.

[0096] When a polymer precursor is used, the spread layer is treated to polymerize or crosslink the polymer, for example, by heat treatment, irradiation (such as UV, microwave, gamma ray, X-ray, electron beam), or a combination of both, optionally in the presence of an initiator. When a solvent is present, the material is preferably dried, for example, before crosslinking or assembly with the other components of the electrochemical cell.

[0097] The present composite material is present in an electrochemical cell in at least one of the electrolyte, the positive electrode or the negative electrode, preferably in the electrolyte layer.

[0098] The positive electrode material generally comprises an electrochemically active material and may be self-supporting or applied to a current collector. The electrochemically active positive electrode material may, among others, be selected from metal phosphates, lithium metal phosphates, metal oxides, and lithium metal oxides.

[0099] Examples of electrochemically active materials include LiM'PC where M' is Fe, Ni, Mn, Co, or a combination thereof, LiVsOe, V2O5F, L1V2O5, LiMn2C>4, LiM”C>2, where M” is Mn, Co, Ni, or a combination thereof (such as NMC, LiMnxCo yNiz02 with x+y+z = 1), Li(NiM”')02 (where M'” is Mn, Co, Al, Fe, Cr, Ti, Zr, or a combination thereof), sulfur, selenium or elemental iodine, iron(lll) fluoride, copper(lll) fluoride, lithium iodide, carbon-based active materials such as graphite, organic cathode active materials (such as polyimide, poly(2,2,6,6- tetramethylpiperidinyloxy-4-yl methacrylate) (PTMA), perylene-3,4,9,10- tetralithium tetracarboxylate (PTCLU), naphthalene-1,4,5,8- tetracarboxylic dianhydride (NTCDA), perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA), dicarboxylates tt-conjugated, and anthraquinone), or a combination of two or more of these materials when they are compatible with each other.

[0100] The electrochemically active positive electrode material is preferably in the form of optionally coated particles (e.g., polymer, ceramic, carbon, or a combination of two or more thereof).

[0101] The electrode material may further comprise an electronically conductive material, for example, comprising at least one of carbon blacks (e.g., Ketjenblack™ or Super P™), acetylene blacks (e.g., Shawinigan Black or Denka Black™), graphite, graphene, carbon fibers or nanofibers (e.g., gas-formed carbon fibers (VGCFs)), carbon nanotubes (e.g., single-walled (SWNTs), multi-walled (MWNTs)), or metal powders.

[0102] The electrode material can be prepared in the same way as the electrolyte layer, except that the support for spreading can be the surface of a solid electrolyte layer or a current collector.

[0103] When the positive electrode material does not comprise the composite material, it may comprise the electrochemically active material as defined herein, a binder and optionally an electronically conductive material and / or a salt as defined herein.

[0104] Non-limiting examples of electrode material binders include the polymers described above in connection with the composite material, but also rubber-type binders (such as SBR (styrene-butadiene rubber), NBR (acrylonitrile-butadiene rubber), HNBR (hydrogenated NBR), CHR (epichlorohydrin rubber), ACM (acrylate rubber)), or fluoropolymer-type binders (such as PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), and combinations thereof). Some binders, such as rubber-type binders, may also include an additive such as CMC (carboxymethylcellulose).

[0105] Other additives may also be present in the positive electrode material, such as inorganic particles such as ceramic or glass, or other compatible active materials (e.g., sulfur).

[0106] The negative electrode comprises an electrochemically active negative electrode material that may be formed from a metal film, for example, comprising an alkali or alkaline earth metal. In one example, the metal film is made of lithium comprising less than 1000 ppm (or less than 0.1% by mass) of impurities. Alternatively, the metal film comprises an alloy of lithium and an element selected 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 Sc, 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, Pb, Mn, B, In, Tl, Ni, or Ge).The alloy may comprise at least 75% lithium by mass, or between 85% and 99.9% lithium by mass.

[0107] Other examples of negative electrode electrochemically active material include 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 (SiOx), a silicon oxide-carbon composite (SiOx-C), tin (Sn), a tin-carbon composite (Sn-C), a tin oxide (SnOx), a tin oxide-carbon composite (SnOx-C), and combinations thereof, when compatible.For example, the metal oxide may be selected from compounds of formulas M””bOc (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 TiNb2C>7), spinel oxides.

[0108] (e.g., N1C02O4, ZnCo2C>4, MnCo2C>4, CUC02O4, and CoFe2C>4) and LiM . O (where

[0109] M . is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination thereof)

[0110] (e.g., a lithium titanate (such as LUTisO^) or a lithium molybdenum oxide (such as U2M04O13)).

[0111] When the negative electrode is not in the form of a metal film, it instead comprises optionally coated particles of an electrochemically active negative electrode material (e.g., polymer, ceramic, carbon, or a combination of two or more thereof). The negative electrode material may also comprise other components such as those described for the negative electrode (such as an electronically conductive material, the present composite material, a salt, a binder, inorganic particles such as ceramic or glass, or other compatible active materials).

[0112] This document relates to an electrochemical accumulator comprising at least one electrochemical cell as defined herein. For example, the electrochemical accumulator is a lithium or lithium-ion battery.

[0113] In another aspect, the electrochemical accumulators of the present application are intended for use in portable devices, for example mobile phones, cameras, tablets or laptops, in electric or hybrid vehicles, or in the storage of renewable energy. EXAMPLES

[0114] The following examples are for illustration purposes and should not be construed as limiting the scope of the invention as described.

[0115] Unless otherwise indicated, numbers expressing component quantities, preparatory conditions, concentrations, properties, etc. used herein should be interpreted as modified in each instance by the term "approximately." At a minimum, each numerical parameter should be interpreted in light of the number of significant figures reported and by the application of customary rounding techniques. Therefore, unless otherwise indicated, the numerical parameters mentioned herein are approximations that may vary depending on the properties sought. Nevertheless, although the parameters defining the broadest embodiments are approximations, the numerical values ​​presented in the following examples are reported as precisely as possible. Any numerical value, however, inherently contains a certain margin of error resulting from variations in experiments, measurements, statistical analyses, etc.

[0116] The crosslinkable polymers used in the following examples are polyethers comprising crosslinkable units, as described in U.S. Patent No. 7,897,674 (hereinafter referred to as "Polymer US'674", which is a branched, multi-branch type polymer comprising crosslinkable units) or in U.S. Patent No. 6,903,174 (hereinafter referred to as "Polymer US'174", which is linear and comprises pendant crosslinkable groups).

[0117] Example 1 - Preparation of electrolytes

[0118] (a) Polymer electrolyte (Comparative)

[0119] 2 g of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), 8 g of US'674 polymer and 0.08 g of Irgacure MCare mixed in a flask at room temperature. Once a homogeneous solution is obtained, the solution is coated on a thin stainless steel sheet. After UV irradiation under nitrogen for 3 minutes, the solid polymer electrolyte membrane is thus obtained.

[0120] (b) Composite electrolyte with HNT and DAEDAm (Comparative)

[0121] 0.5g of LiTFSI, 0.77g of tetraethylene glycol dimethyl ether (TEGDME), 0.25g of L / , / V-diacetylethylenediamine (DAEDAm) and 0.24g of Halloysite nanotubes (HNT) are well mixed in a flask at room temperature. Once a homogeneous dispersion is obtained, 0.75g of US'674 polymer and 0.01g of Irgacure MC are added. After stirring for 1 hour at room temperature, the dispersion is coated onto a thin stainless steel sheet. The resulting composite electrolyte membrane is cured by UV irradiation under nitrogen for 3 minutes.

[0122] (c) Composite electrolyte with HNT and NMTFAm

[0123] 0.5g of LiTFSI, 0.69g of TEGDME, 0.44g of / V-methyltrifluoroacetamide (NMTFAm) and 0.26g of HNT are mixed well in a flask at room temperature. Once a homogeneous dispersion is obtained, 0.67g of polymer US'674 and 0.01g of lrgacure MC are added. After stirring for 1 hour at room temperature, the dispersion is coated onto a thin stainless steel sheet. The resulting composite electrolyte membrane is cured by UV irradiation under nitrogen for 3 minutes.

[0124] (d) Composite electrolyte with LATP and NMTFAm

[0125] 0.5g of LiTFSI, 0.77g of TEGDME, 0.44g of NMTFAm and 0.26g of Lii,3Alo,3Tii,7(P04)3 (LATP) are mixed well in a flask at room temperature. Once a homogeneous dispersion is obtained, 0.67g of polymer US'674 and 0.01g of lrgacure MCare added. After stirring for 1 hour at room temperature, the dispersion is coated onto a thin stainless steel sheet. The resulting composite electrolyte membrane is cured by UV irradiation under nitrogen for 3 minutes.

[0126] (e) Composite electrolyte with LATP and DAEDAm (Comparative)

[0127] 0.5g of LiTFSI, 0.77g of TEGDME, 0.25g of DAEDAm and 0.24g of LATP are mixed well in a flask at room temperature. Once a homogeneous dispersion is obtained, 0.75g of US'674 polymer and 0.01g of lrgacure MC are added. After stirring for 1 hour at room temperature, the dispersion is coated onto a thin stainless steel sheet. The resulting composite electrolyte membrane is cured by UV irradiation under nitrogen for 3 minutes.

[0128] (f) Polymer electrolyte with NMTFAm (Comparative)

[0129] 0.5g of LiTFSI, 0.77g of TEGDME, and 0.25g of NMTFAm are mixed well in a flask at room temperature. Once a homogeneous solution is obtained, 0.99g of US'674 polymer and 0.01g of Irgacure MC are added. After stirring for 1 hour at room temperature, the solution is coated onto a thin stainless steel sheet. The resulting polymer electrolyte membrane is cured by UV irradiation under nitrogen for 3 minutes.

[0130] (g) Ceramic electrolyte with LATP and NMTFAm

[0131] 0.35g of LATP and 0.15g of NMTFAm were mixed well and ground in a mortar at room temperature. Then the powder was compressed into round pellets at a pressure of 120 psi with a diameter of 16mm and a thickness of 420pm. A comparative sample with pure LATP powder was also prepared in the same way.

[0132] (h) Composite electrolyte with LLZO and NMTFAm

[0133] 0.5g of LiTFSI, 0.77g of TEGDME, 0.44g of NMTFAm and 0.26g of LÎ7La3Zr20i2 (LLZO) are mixed well in a flask at room temperature. Once a homogeneous dispersion is obtained, 0.67g of US'674 polymer and 0.01g of lrgacure MC are added. After stirring for 1 hour at room temperature, the dispersion is coated onto a thin stainless steel sheet. The resulting composite electrolyte membrane is cured by UV irradiation under nitrogen for 3 minutes.

[0134] (i) Composite electrolyte with LATP, NMTFAm and US'174 ​​polymer

[0135] 0.5g of LiTFSI, 0.77g of TEGDME, 0.44g of NMTFAm and 0.26g of LATP are mixed well in a flask at room temperature. Once a homogeneous dispersion is obtained, 0.67g of US'174 ​​polymer and 0.01g of lrgacure MCare added. After stirring for 1 hour at room temperature, the dispersion is coated onto a thin stainless steel sheet. The resulting composite electrolyte membrane is cured by UV irradiation under nitrogen for 3 minutes.

[0136] (j) Composite electrolyte with LATP and NMPPPAm

[0137] 0.5g of LiTFSI, 0.77g of TEGDME, 0.44g of / V-methylpentaproprionamide (NMPPPAm) and 0.26g of LATP are mixed well in a flask at room temperature. Once a homogeneous dispersion is obtained, 0.67g of polymer US'674 and 0.01g of lrgacure MC are added. After stirring for 1 hour at room temperature, the dispersion is coated onto a thin stainless steel sheet. The resulting composite electrolyte membrane is cured by UV irradiation under nitrogen for 3 minutes.

[0138] (k) Composite electrolyte with LATP and NCPTFAm

[0139] 0.5g of LiTFSI, 0.77g of TEGDME, 0.44g of / V-cylcopentyltrifluoroacetamide (NCPTFAm) and 0.26g of LATP are mixed well in a flask at room temperature. Once a homogeneous dispersion is obtained, 0.67g of polymer US'674 and 0.01g of lrgacure MC are added. After stirring for 1 hour at room temperature, the dispersion is coated onto a thin stainless steel sheet. The resulting composite electrolyte membrane is cured by UV irradiation under nitrogen for 3 minutes.

[0140] (L) Composite electrolyte with LATP and NTFMSTFAm 0.5g of LiTFSI, 0.77g of TEGDME, 0.44g of / V-trifluoromethylsulfonyl trifluoroacetamide (NTFMSTFAm) and 0.26g of LATP are mixed well in a flask at room temperature. Once a homogeneous dispersion is obtained, 0.67g of polymer US'674 and 0.01g of lrgacure MCare added. After stirring for 1 hour at room temperature, the dispersion is coated onto a thin stainless steel sheet. The resulting composite electrolyte membrane is cured by UV irradiation under nitrogen for 3 minutes.

[0141] (m) Composite electrolyte with LATP and NTMSTFAm

[0142] 0.5g of LiTFSI, 0.77g of TEGDME, 0.44g of / V-trimethylsilyl trifluoroacetamide (NTMSTFAm) and 0.26g of LATP are mixed well in a flask at room temperature. Once a homogeneous dispersion is obtained, 0.67g of polymer US'674 and 0.01g of lrgacure MC are added. After stirring for 1 hour at room temperature, the dispersion is coated onto a thin stainless steel sheet. The resulting composite electrolyte membrane is cured by UV irradiation under nitrogen for 3 minutes.

[0143] (n) Composite electrolyte with LATP and BTFAm

[0144] 0.5g of LiTFSI, 0.77g of TEGDME, 0.44g of bistrifluoroacetamide (BTFAm) and 0.26g of LATP are mixed well in a flask at room temperature. Once a homogeneous dispersion is obtained, 0.67g of US'674 polymer and 0.01g of lrgacure MC are added. After stirring for 1 hour at room temperature, the dispersion is coated onto a thin stainless steel sheet. The resulting composite electrolyte membrane is cured by UV irradiation under nitrogen for 3 minutes.

[0145] (o) Composite electrolyte with LATP and less NMTFAm

[0146] 0.5g of LiTFSI, 0.65g of TEGDME, 0.37g of 1,1'-hexamethylene bis(l-methylpyrrolidinium)bis(trifluoromethanesulfonyl)imide, 0.11g of NMTFAm and 0.26g of LATP are mixed well in a flask at room temperature. Once a homogeneous dispersion is obtained, 0.60g of US'674 polymer and 0.01g of lrgacure MCare added. After stirring for 1 hour at room temperature, the dispersion is coated onto a thin stainless steel sheet. The resulting composite electrolyte membrane is cured by UV irradiation under nitrogen for 3 minutes. Example 2 - Physicochemical properties

[0147] (a) Infrared spectroscopy of the particle-amide mixture

[0148] To better understand the effect of the presence of fluorinated amide, chemical analyses were carried out. Infrared spectroscopy was performed in the solid state on an Agilent-Cary 630 FTIR spectrometer. ® . The particle-amide mixtures were prepared with a weight ratio of 1.7:1 for NMTFAm / LATP and a weight ratio of 1:1 for DAEDAm / LATP by grinding in a mortar. The infrared spectra of LATP, NMTFAm, DAEDAm, and the LATP / NMTFAm and LATP / DAEDAm mixtures are shown in Figures 1(a) to (e).

[0149] Figure 1(d) shows that a new signal appeared around 3550 cm -1 for the LATP / NMTFAm mixture, this being absent in the case of LATP / DAEDAm in Figure 1(e). This new signal indicates that there is an interaction between the fluorinated amide and the LATP ceramic, this interaction not being present in the case of the non-fluorinated amide DAEDAm.

[0150] (b) NMR chemical structure of the NMTFAm / LATP mixture In order to confirm the results observed by infrared spectroscopy, solid-state NMR analyses of NMTFAm and the NMTFAm / LATP mixture were carried out on a 500 MHz NMR spectrometer equipped with a 4 mm triple resonance probe with MAS (magic angle spinning), up to 15 kHz. The preparation of the NMTFAm / LATP mixture is the same as that described in 2(a). The NMR spectra 1 H and 6Li of NMTFAm, LATP and NMTFAm / LATP mixture are shown in Figures 2(a) to (c). Figure 2(a) shows that the signals of NMTFAm are broader than those of NMTFAm / LATP mixture, indicating an interaction between NMTFAm and LATP that significantly decreases the restriction of molecular mobility in NMTFAm. Furthermore, a shift of the peak corresponding to NH protons of NMTFAm to a higher frequency may indicate that more NH protons in the mixture are involved in hydrogen bonding.

[0151] Figure 2(c) shows that an additional signal at 1.2 ppm appeared in the NMR spectrum 6 Li of the mixture after 1 day of storage compared to Figure 2(b), indicating that new Li ions + were generated by the interaction between NMTFAm and LATP.

[0152] (c) Young's modulus of the membrane

[0153] Young's modulus was evaluated for the membrane prepared in Example 1(d) on a Discovery DMA850 TA at 20 °C. The film size for measurement is 10.7 mm x 5.3 mm c 0.167 mm (length c width c thickness). The “Rate Control Strain Ramp” procedure was used. Figure 3 shows a graph of the Young's modulus of the membrane prepared in Example 1(d).

[0154] (d) Diffusion coefficient

[0155] The ion diffusion coefficient of the different elements of the membrane prepared in Example 1(d) was evaluated by pulsed field gradient solid state NMR spectroscopy of the nuclei 1 H, 7 Li, and 19 F. NMR experiments were performed on a 500 MHz NMR spectrometer equipped with a Diff50 probe MC and double resonance RF insertions 7 Li- 19 F and 1 H- 19 F.

[0156] Measurements were performed at 25°C and 50°C. The gradient pulse was in the range of 0.6 to 2.0 ms and the diffusion time was in the range of 40 to 100 ms depending on the nucleus. The gradient strength was varied in 16 steps from 100 G / cm to 2500 G / cm. Diffusion measurements were accompanied by T2 relation experiments using a CPMG pulse sequence with an echo delay of 0.06 to 0.6 ms. Up to 64 echoes were collected per experiment. The results are shown in Table 1. Table 1. Diffusion coefficients measured by NMR spectroscopy

[0157] Most species were highly mobile in the sample, which allowed for higher resolution of NMR spectra.

[0158] Diffusion coefficients of NMTFAm measured from NMR 1 H and 19 F match each other perfectly.

[0159] The diffusion coefficients of Li in LATP at 25 and 50 °C are consistent with the values ​​obtained with other samples containing LATP. This observation confirms that the diffusion of lithium in LATP is not dependent on the polymer-enclosed LATP particles, especially considering that the mean square displacement of the species during the NMR experiment is about 0.5 to 1 pm (much smaller than the size of LATP particles which is about 10 pm).

[0160] Example 3 - Electrochemical Properties

[0161] (a) Cell assembly (symmetrical cells) Symmetrical button cells of Li / Electrolyte / Li type for critical current density (CCD) measurement and Stainless steel / Electrolyte / Stainless steel type for ionic conductivity measurement were assembled. Polymer electrolyte membrane discs were cut with a diameter of 16 mm (for ionic conductivity measurement) or a diameter of 14 mm (for CCD measurement) and clamped between two electrodes. The configuration of each cell is shown as follows:

[0162] Cell 1: Electrode / Example 1 (a) / Electrode Cell 2: Electrode / Example 1 (b) / Electrode

[0163] Cell 3: Electrode / Example 1 (c) / Electrode Cell 4: Electrode / Example 1(d) / Electrode Cell 5: Electrode / Example 1 (e) / Electrode Cell 6: Electrode / Example 1 (f) / Electrode Cell 7: Electrode / Example 1(g) / Electrode Cell 8: Electrode / Example 1(h) / Electrode Cell 9: Electrode / Example 1(i) / Electrode Cell 10: Electrode / Example 1(j) / Electrode Cell 11: Electrode / Example 1(k) / Electrode Cell 12: Electrode / Example 1(l) / Electrode Cell 13: Electrode / Example 1(m) / Electrode

[0164] - Cell 14: Electrode / Example 1(n) / Electrode

[0165] - Cell 15: Electrode / Example 1(o) / Electrode

[0166] Electrode = Metallic lithium or stainless steel (b) Ionic conductivity Electrochemical impedance spectroscopy was performed with a Bio-logic system ® VMP-300 has an amplitude of 100 mV and the frequency range of 1 MHz to 200 mHz.

[0167] Figures 4(a) and 4(b) show the ionic conductivity results for Cells 1 to 15. The conductivity results at 50°C and 25°C are also shown in Table 2 below.

[0168] We see, for example, that the ionic conductivity in the LATP / fluorinated amide electrolyte (NMTFAm, 3.62 x 10 4 S / cm) at 20°C is much higher than that of LATP / non-fluorinated amide (DAEDAm, 9.29 x 10 5 S / cm) and Halloysite nanotubes / NMTFAm (2.64 x 10 5 S / cm). Ionic conductivity at 20°C is also generally higher for all electrolytes containing a fluorinated amide compared to the electrolyte without fluorinated amide.

[0169] (c) Critical current density The critical current density was evaluated using a Bio-logic system ® VMP-3. The test starts at a current density C / 24 (1C = 3.0 mA / cm 2), gradually increasing it. The same current density was applied to charge and discharge the battery.

[0170] Figure 5 shows that Cell 4, a symmetrical Li / electrolyte / Li cell with the LATP / NMTFAm electrolyte of Example 1(d), is stable up to 5C (1C = 3.0 mA / cm 2 ) at 25°C. The results are also summarized in Table 2 below.

[0171] Table 2. Electrolyte composition (wt%) and results for Cells 1 to 15 a. US'674 polymer except for Cell 9, where US'174 ​​polymer was used. b. NM: not measured c. The electrolyte also includes 15% by weight of 1,1'-hexamethylene bis(l-methylpyrrolidinium) bis(trifluoromethanesulfonyl)imide.

[0172] (d) Electrochemical stability

[0173] In order to evaluate the electrochemical stability of the membrane prepared in Example 1(d), a solution with 20 wt% carbon black (Ketjenblack™) was prepared.

[0174] 0.5g of LiTFSI, 0.77g of TEGDME, 0.44g of NMTFAm and 0.26g of Lii,3Alo,3Tii,7(PC>4)3 (LATP) were mixed well in a flask at room temperature. Once a homogeneous dispersion was obtained, 0.67g of US'674 polymer, 0.01g of azobisisobutyronitrile and a dispersion of 0.528g of carbon black in 6 mL of acetonitrile were added. After 1 hour of stirring at room temperature with a planetary centrifugal mixer, the dispersion was coated onto a conductive carbon-coated aluminum foil. The solvent was then evaporated under vacuum at 40°C, and then the membrane was placed in an oven at 100° under nitrogen for 10min. On the carbon membrane, a layer of the electrolyte of Example 1(a) or Example 1(d) is coated. The electrolyte layer is cured by UV irradiation under nitrogen for 3 minutes. The complete membrane for electrochemical stability measurement is thus obtained.

[0175] To assemble button cells, membrane discs with a diameter of 16 mm were cut. The electrolyte side was covered with a lithium foil. The cells thus formed are named Cell 8 and Cell 9 comprising the membranes of Examples 1(a) and 1(d) respectively. The electrochemical stability was evaluated using a Bio-logic system ® VMP- 3. The voltage varied from 3.5 V to 5 V with an increase rate of 0.1 V every 2 hours.

[0176] Figure 6 shows the electrochemical stability for Cell 9, comprising the membrane prepared in Example 1(d), and for Cell 8, comprising the membrane prepared in Example 1(a).

[0177] In summary, it can be observed that the addition of N-methyltrifluoroacetamide (NMTFAm) into a composite electrolyte based on US'674 polymer and LATP (a phosphate-type oxide ceramic) can greatly improve the ionic conductivity and stability at the Li / electrolyte interface (see Figure 1) at 25°C, with the oxidation stability reaching 4.5V. This observation is confirmed by the ionic conductivity and critical current density (CCD) in symmetric cells comprising the electrolytes compared to other ceramics or amide.

[0178] (e) Assembly and performance of complete batteries

[0179] Complete cells using the electrolyte of Example 1(d) were assembled and their performance was evaluated.

[0180] (i) NMC811 battery / electrolyte / Li

[0181] A cathode was prepared as described in patent application PCT / CA2022 / 050159 by including 73.2% by weight of lithium nickel manganese cobalt oxide (NMC811) active material, which gives a loading rate of approximately 8 mg / cm 2 . The electrolyte dispersion Example 1(d) was directly coated onto the cathode and cured by UV irradiation under nitrogen for 3 minutes. The electrolyte thickness is about 40 µm. A lithium metal foil with a thickness of 50 µm was used as the anode. A 3.8 cm coin cell 2 was therefore assembled to evaluate the performance. The performance evaluation was carried out on a Bio-Logic BCS-810 system with a voltage of 2.75 - 4.2 V and a charge-discharge rate of C / 6 - 1C (1C = 1.2 mA / cm 2 ) at 45°C. The battery capacity is around 4.4 mAh (1.2 mAh / cm 2 ).

[0182] Figure 7 shows the battery capacity and coulombic efficiency as a function of the number of cycles.

[0183] (ii) LFP / electrolyte / Li battery

[0184] A LiFePC>4 (LFP) cathode was prepared as in Example 3(e)(i) by replacing NMC811 with LFP as the active material at a weight concentration of 70%, which gives a loading rate of approximately 12 mg / cm 2 . The electrolyte dispersion Example 1(d) was directly coated onto the cathode and cured by UV irradiation under nitrogen for 3 minutes. The electrolyte thickness is about 40 μm. A lithium metal foil with a thickness of 40 μm was used as the anode. A 3.8 cm button cell 2 was assembled to evaluate the performance. The performance evaluation was carried out on a Bio-Logic BCS-810 system with a voltage of 2 - 3.8 V and a charge-discharge rate of C / 6 - C / 6 (1C = 1.2 mA / cm 2 ) at 45°C. The battery capacity is approximately 3 mAh (0.8 mAh / cm 2 ).

[0185] Figure 8 shows the galvanostatic charge and discharge curves at a charge and discharge rate of C / 6. 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. Composite material comprising inorganic particles, a fluorinated compound, and optionally a polymer, in which the fluorinated compound is of Formula I: Formula I in which: R 1 and R 2 are chosen independently at each occurrence from among a linear or branched Ci-ealkyl group possibly substituted, a C3-ecycloalkyl group possibly substituted, a Cearyl group possibly substituted, a C3-8 heterocycloalkyl group possibly substituted, and a C5-6 heteroaryl group possibly substituted; X 1 is chosen from O and NH or X 1 is absent; X 2 is chosen from C(O), S(0)2, and Si(R 3 R 4 ), where R 3 and R 4 are independently at each occurrence a linear or branched Ci-alkyl group, possibly substituted, or X 2 is absent; in which at least one of R 1, R 2 , R 3 and R 4 is a group substituted by one or more fluorine atom(s).

2. Composite material of claim 1, wherein X 1 is absent and X 2 is chosen from C(O), S(0)2, and Si(R 3 R 4 ).

3. Composite material of claim 1, wherein X 1 is chosen from O, NH, and X 2 is absent.

4. Composite material of claim 1, wherein X 1 and X 2 are absent.

5. Composite material of any one of claims 1 to 4, wherein R 1 is a group substituted by one or more fluorine atom(s).

6. Composite material of claim 5, wherein R 1 is a perfluorinated group.

7. Composite material of any one of claims 1 to 6, wherein R 1is a linear or branched Ci-ealkyl group, or a linear or branched Ci-4alkyl group, or a Ci-2alkyl group.

8. Composite material of any one of claims 1 to 7, wherein R 2 is a group substituted by one or more fluorine atom(s).

9. Composite material of claim 8, wherein R 2 is a perfluorinated group.

10. Composite material of any one of claims 1 to 9, wherein R 2 is a linear or branched Ci-salkyl group, or a linear or branched Ci-4-alkyl group, or a Ci-2-alkyl group.

11. Composite material of any one of claims 1 to 9, wherein R 2 is a C3-8cycloalkyl group possibly substituted, or a C3-6cycloalkyl group possibly substituted, or a C5-6cycloalkyl group possibly substituted.

12. A composite material of any one of claims 1 to 9, wherein the compound is selected from the compounds / V-methyltrifluoroacetamide (NMTFAm), / V-methylpentaproprionamide (NMPPPAm), N-cylcopentyltrifluoroacetamide (NCPTFAm), / V-trifluoromethylsulfonyl trifluoroacetamide (NTFMSTFAm), / V-trimethylsilyl trifluoroacetamide (NTMSTFAm), and bistrifluoroacetamide (BTFAm).

13. A composite material of any one of claims 1 to 12, wherein the concentration of the compound in the composite material is in the range of 1% to 90% by weight, or 1% to 70% by weight, or 1% to 50% by weight. weight, or from 1% to 40% by weight, or from 5% to 30% by weight, or from 10% to 25% by weight, or from 15% to 20% by weight.

14. Composite material of any one of claims 1 to 13, wherein the polymer is present.

15. Composite material of claim 14, wherein the polymer is a cross-linked aprotic polymer.

16. Composite material of claim 14 or 15, wherein the polymer is a branched polymer, preferably of the multi-branch type.

17. Composite material of any one of claims 14 to 16, wherein the polymer comprises at least one polymer segment selected from the ionically conductive segments polyether, polythioether, polyester, polythioester, polycarbonate, polythiocarbonate, polyimide, polysulfonimide, polyamide, polysulfonamide, polyphosphazene, and the ionically non-conductive segments polyacrylate, polymethacrylate, polystyrene, polysiloxane, polyurethane, polyethylene, polypropylene, or a copolymer or combination of two or more of these.

18. Composite material of any one of claims 14 to 17, wherein the polymer comprises at least one polymer segment comprising a block copolymer with at least two different repeating units in order to reduce the crystallinity of the crosslinked polymer.

19. Composite material of claim 18, wherein the polymer segment comprises, prior to crosslinking, a block copolymer comprising at least one alkali or alkaline earth metal ion solvating segment and a crosslinkable segment comprising crosslinkable units.

20. Composite material of claim 19, wherein the alkali or alkaline earth metal ion solvating segment is selected from homo- and copolymers comprising repeating units of Formula II: -(CH2-ÇH-0) x - R Formula II in which, R is chosen from H, Ci-Cioalkyl, and -(CFte-O-RaRb); Ra is (CH2-CH2-O) y ; And Rb is a Ci-Cioalkyl group.

21. Composite material of claim 19 or 20, wherein the crosslinkable units comprise functional groups selected from acrylates, methacrylates, allyls, vinyls, hydroxides, epoxides, aldehydes, carboxylic acids, halophenyls, halobenzyls, alkynes, azides, amines, thiols and any combination thereof.

22. Composite material of any one of claims 14 to 21, wherein the polymer is present in the composite material at a concentration in the range of 1% to 80% by weight, 5% to 70% by weight, or 10% to 50% by weight, or 20% to 40% by weight.

23. Composite material of any one of claims 1 to 22, wherein the inorganic particles comprise an amorphous, ceramic, or glass-ceramic inorganic compound, for example, an oxide, sulfide, or oxysulfide.

24. Composite material of claim 23, wherein the amorphous, ceramic, or glass-ceramic inorganic compound is an oxide.

25. A composite material of any one of claims 1 to 23, wherein the inorganic particles comprise a ceramic selected from Al2O3, Mg2B2C>5, Na2O-2B2C>3, xMgO yB2O3-zH2O, TiO2, ZrO2, ZnO, Ti2O3, SiO2, Cr2Os, CeO2, B2Os, B2O, SrBUTUOis, LLTO, LLZO, LAGP, LATP, Fe2Os, BaTiOs, y-LiAlO2, molecular sieves, and zeolites (e.g., aluminosilicate, silica). mesoporous), sulfide ceramics (such as U7P3S11), glass-ceramics (such as LIPON, etc.), and other ceramics, as well as their combinations.

26. Composite material of claim 25, wherein the ceramic is selected from Al2O3, Mg2B2Os, Na2O-2B2C>3, xMgO yB2O3-zH2O, T1O2, ZrÜ2, ZnO, T12O3, S1O2, Cr2O3, CeO2, B2O3, B2O, SrBUTUOis, LLTO, LLZO, LAGP, LATP, Fe2Ü3, BaTiO3, Y-L1AIO2, molecular sieves and zeolites (e.g., aluminosilicate, mesoporous silica), glass-ceramics (such as LIPON, etc.), as well as their combinations.

27. Composite material of any one of claims 1 to 26, wherein the inorganic particles are in the form of spherical particles, rods, needles, nanotubes, or any combination thereof.

28. A composite material of any one of claims 1 to 27, wherein the inorganic particles comprise a compound selected from the compounds of formula: Lii +z AlzM2-z(P04)3 in which M is Ti, Ge or a combination thereof, and z is such that 0 < z < 1.

29. Composite material of claim 28, wherein z is in the range of 0.1 to 0.9, or 0.3 to 0.7, or 0.2 to 0.

4.

30. Composite material of any one of claims 1 to 27, wherein the inorganic particles comprise a compound selected from the compounds of formulas: LÎ7-xLa3Zr2M x x Oi2 and Li3yLa(2 / 3)-yTii-yM y y03 in which: M x is chosen from Al, Ga, Ta, Fe, and Nb; M y is chosen from Ba, B, Al, Si and Ta; x is such that 0 ≤ x ≤ 1; y is such that 0 < y < 0.67; and y' is such that 0 < y' < 1.

31. Composite material of claim 30, wherein x is in the range from 0 to 0.5, preferably x is zero and M x is absent.

32. Composite material of any one of claims 1 to 31, wherein the inorganic particle content is in the range of 1% to 95% by weight, or 5% to 90% by weight, or 5% to 80% by weight, or 5% to 70% by weight, or 5% to 60% by weight, or 5% to 50% by weight, or 5% to 40% by weight, or 5% to 25% by weight, or 5% to 15% by weight.

33. Composite material of any one of claims 1 to 32, wherein the polymer is present and the composite material further comprises a plasticizing agent.

34. Composite material of claim 33, in the plasticizing agent is selected from liquids of the type glycol diethers (such as tetraethylene glycol dimethyl ether (TEGDME)), carbonate esters, ionic liquids, and others similar.

35. Composite material of claim 33 or 34, wherein the plasticizing agent is present in the composite material at a concentration in the range of 0.1% to 50% by weight, or 10% to 50% by weight, or 20% to 40% by weight.

36. Composite material of any one of claims 1 to 35, further comprising a salt.

37. Composite material of claim 36, wherein the salt comprises a cation of an alkali or alkaline earth metal, preferably an alkali metal (preferably Li), and an anion selected from the following anions: hexafluorophosphate (PF6), bis(trifluoromethanesulfonyl)imidide (TFSI), bis(fluorosulfonyl)imidide (FSI), (fluorosulfonyl)(trifluoromethanesulfonyl)imidide ((FSI)(TFSI)), 2-trifluoromethyl-4,5-dicyanoimidazolate (TDI), 4,5-dicyano-1,2,3-triazolate (DCTA-), bis(pentafluoroethylsulfonyl)imidide (BETI), difluorophosphate (DFP), tetrafluoroborate (BF4), bis(oxalato)borate (BOB-), nitrate (NO3), chloride (Ch), bromide (Br), fluoride (F), perchlorate (ClO4), hexafluoroarsenate (AsF6), trifluoromethanesulfonate (SO3CF3) (Tf), fluoroalkylphosphate [PF3(CF2CF3)3] (FAP), tetrakis(trifluoroacetoxy)borate [B(OCOCF3)4] (TFAB-), bis(1,2- benzenediolato(2-)-0.0')borate [B(0QO2)2] (BBB ), difluoro(oxalato)borate (BF2(C2O4) ) (FOB ), an anion of formula BF2O4R X (where Rx = C2-4alkyl), and one of their combinations, for example LiTFSI or LiFSI.

38. Solid electrolyte comprising a layer of the composite material as defined in any one of claims 1 to 37.

39. Electrochemical cell comprising a negative electrode, a positive electrode, and a solid electrolyte, wherein at least one of the positive electrode, the negative electrode and the electrolyte comprises a composite material as defined in any one of claims 1 to 37.

40. Electrochemical cell comprising a negative electrode, a positive electrode, and a solid electrolyte, wherein the solid electrolyte is as defined in claim 38.

41. Electrochemical cell comprising a negative electrode, a positive electrode, and a solid electrolyte, wherein the electrolyte is as defined in claim 38 and at least one of the negative electrode and the positive electrode comprises a composite material as defined in any one of claims 1 to 37.

42. Electrochemical cell of any one of claims 39 to 41, wherein the positive electrode comprises a positive electrode material optionally on a current collector, wherein the positive electrode material comprises an electrochemically active positive electrode material.

43. Electrochemical cell of claim 42, wherein the electrochemically active positive electrode material is selected from metal phosphates, lithia metal phosphates, metal oxides, and lithia metal oxides.

44. Electrochemical cell of claim 42, wherein the electrochemically active positive electrode material is LiM'PC where M' is Fe, Ni, Mn, Co, or a combination thereof, UV3O8, V2O5F, UV2O5, LiMn2C>4, LiM”C>2, where M” is Mn, Co, Ni, or a combination thereof (such as NMC, LiMn x Co y Neither zO2 with x+y+z = 1), Li(NiM'”)C>2 (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 (such as polyimide, poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl methacrylate) (PTMA), perylene-3,4,9,10-tetralithium tetracarboxylate (PTCU4), naphthalene-1,4,5,8-tetracarboxylic dianhydride (NTCDA), perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA), conjugated TT- dicarboxylates, and anthraquinone), or a combination of two or more of these materials when they are compatible with each other.

45. Electrochemical cell of any one of claims 42 to 44, wherein the electrochemically active positive electrode material is in the form of particles optionally coated (e.g., polymer, ceramic, carbon or a combination of two or more of these).

46. ​​An electrochemical cell of any one of claims 42 to 45, wherein the positive electrode material further comprises an electronically conductive material, for example, comprising at least one of the following: carbon blacks (e.g., Ketjenblack™ or Super P™), acetylene blacks (e.g., Shawinigan Black or Denka Black™), graphite, graphene, carbon fibers or nanofibers (e.g., phase-formed carbon fibers) gaseous (VGCFs)), carbon nanotubes (e.g., single-walled (SWNT), multi-walled (MWNT)) or metal powders.

47. Electrochemical cell of any one of claims 42 to 46, wherein the positive electrode material further comprises a binder.

48. Electrochemical cell of claim 47, wherein the binder is a polymer as defined in claims 15 to 21, or a binder selected from rubber-type binders (such as SBR (styrene-butadiene rubber), NBR (acrylonitrile-butadiene rubber), HNBR (hydrogenated NBR), CHR (epichlorohydrin rubber), ACM (acrylate rubber)), or fluoropolymer-type binders (such as PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), and combinations thereof), optionally comprising an additive such as CMC (carboxymethylcellulose).

49. Electrochemical cell of any one of claims 42 to 48, wherein the positive electrode material further comprises a salt, inorganic particles of the ceramic or glass type, or other compatible active materials (e.g., sulfur).

50. Electrochemical cell of any one of claims 42 to 48, wherein the positive electrode material further comprises the composite material defined in any one of claims 1 to 37.

51. Electrochemical cell of any one of claims 39 to 50, wherein the negative electrode comprises an electrochemically active negative electrode material.

52. Electrochemical cell of claim 51, wherein the electrochemically active negative electrode material comprises a metallic film including an alkali or alkaline earth metal.

53. Electrochemical cell of claim 52, wherein the metallic film comprises lithium comprising less than 1000 ppm (or less than 0.1% by mass) of impurities.

54. Electrochemical cell of claim 52, wherein the metal film comprises an alloy of lithium and an element selected 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 Sc, 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 (for example, Zr, Cu, Ag, Bi, Co, Zn, Al, Si, Sn, Sb, Cd, Hg, Pb, Mn, B, In, Tl, Ni, or Ge).

55. Electrochemical cell of claim 54, wherein the alloy comprises at least 75% by mass of lithium, or between 85% and 99.9% by mass of lithium. 56.Electrochemical cell of claim 51, 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, 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), silicon oxide (SiOx), a silicon-carbon composite (SiOx-C), tin (Sn), a tin-carbon composite (Sn-C), an oxide tin (SnOx), a tin-carbon oxide composite (SnOx-C), and their combinations, when compatible.

57. Electrochemical cell of claim 56, wherein the metal oxide is selected from compounds of formula M””bOc (where M”” is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination thereof; and b and c are numbers such that the c:b ratio is in the range of 2 to 3) (e.g., M0O3, M0O2, M0S2, V2O5, and TiNb2C>7), spinel oxides (e.g., N1CO2O4, 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) (for example, a lithium titanate (such as LUTisO^) or a lithium molybdenum oxide (such as U2MO4O13)).

58. Electrochemical cell of claim 56 or 57, wherein the electrochemically active negative electrode material is in the form of particles optionally coated (for example, of polymer, ceramic, carbon or a combination of two or more of these).

59. Electrochemical cell of claim 58, wherein the negative electrode material further comprises an electronically conductive material, for example, comprising at least one of the following: carbon blacks (e.g., Ketjenblack™ or Super P™), acetylene blacks (e.g., Shawinigan black or Denka black™), graphite, graphene, carbon fibers or nanofibers (e.g., gas-formed carbon fibers (VGCFs)), carbon nanotubes (e.g., single-walled (SWNT), multi-walled (MWNT)), or metal powders.

60. Electrochemical cell of claim 58 or 59, wherein the negative electrode material further comprises a binder.

61. Electrochemical cell of claim 60, wherein the binder is a polymer as defined in claims 15 to 21, or a binder selected from rubber-type binders (such as SBR (styrene-butadiene rubber), NBR (acrylonitrile-butadiene rubber), HNBR (hydrogenated NBR), CHR (epichlorohydrin rubber), ACM (acrylate rubber)), or fluoropolymer-type binders (such as PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), and combinations thereof), optionally comprising an additive such as CMC (carboxymethylcellulose).

62. An electrochemical cell of any one of claims 58 to 61, wherein the negative electrode material further comprises a salt, inorganic particles of the ceramic or glass type, or other compatible active materials.

63. An electrochemical cell of any one of claims 58 to 62, wherein the negative electrode material further comprises the composite material defined in any one of claims 1 to 37.

64. Electrochemical accumulator comprising at least one electrochemical cell as defined in any one of claims 39 to 63.

65. Electrochemical accumulator according to claim 64, wherein said electrochemical accumulator is a lithium battery or a lithium-ion battery.

66. Use of an electrochemical accumulator according to claim 64 or 65, in portable devices, for example mobile phones, cameras, tablets or laptops, in electric or hybrid vehicles, or in renewable energy storage.

67. A method for preparing a composite material as defined in any one of claims 1 to 37, comprising a step of mixing the inorganic particles, the fluorinated compound, and optionally the polymer.

68. A method according to claim 67, the mixing step comprising the polymer and optionally a crosslinking agent.

69. A process according to claim 68, wherein the mixing step comprises the crosslinking agent and the process further comprises a polymer crosslinking step.

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