Composite materials containing fluorinated amides and their use in electrochemical cells

Abstract

The present technology relates to a composite material comprising inorganic particles, a fluorinated amide compound, and optionally an electrolytic polymer, a plasticizer and / or a salt, and a method for preparing the composite material. Solid electrolytes and electrode materials comprising the composite material of the present invention, and their use in electrochemical cells and accumulators comprising them, are also described. The present application relates to polymer-ceramic composite electrolytes comprising organic additives, their production methods, and electrochemical cells comprising them.

Description

[Technical field]

[0001] Related Applications This application claims priority under applicable law to Canadian Patent Application No. 3,122,820, filed June 18, 2021, the contents of which are incorporated herein by reference in their entirety for all purposes.

[0002] Technical Field The present application relates to polymer-ceramic composite electrolytes containing organic additives, methods for their preparation, and electrochemical cells containing them. [Background technology]

[0003] background Lithium ion conducting polymer electrolytes enable the development of safer and more affordable manufacturing methods, and they are easily scaled up for large format all-solid-state batteries (see, for example, U.S. Patent No. 6,903,174). However, low ionic conductivity limits their application at room temperature, resulting in relatively low charge / discharge rates compared to conventional lithium ion batteries.

[0004] On the other hand, solid inorganic electrolytes are promising candidates for solid-state batteries since they offer higher lithium ion conductivity comparable to liquid electrolytes. In addition, the unique ion conducting properties of inorganic electrolytes allow lower concentration polarization at the lithium metal interface, allowing high-rate battery charging and discharging. Despite its high ionic conductivity in the dense bulk phase, complete cells using ceramic solid electrolytes suffer from poor electrochemical performance due to significant interfacial resistance at the grain boundaries of ceramic particles and between particles of composite electrodes made from a mixture of active material particles, carbon additives and solid electrolyte. Since Li+ ion conduction must take place in an interparticle mode, the electrochemical performance is limited by the poor distribution of solid electrolyte particles and by the presence of voids between the particles.

[0005] A recent review of various composite electrolytes, including polymers and solid electrolyte particles, was published by the group of S. Tang et al. (Adv. Energy Mater., 2021, 11, 2000802 (pp. 1-29)). To improve ionic conductivity, various 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 composites. However, these can reduce the mechanical strength, for example, if present in excessive amounts. With these composite electrolytes, problems of electrochemical instability may also be encountered, especially at the interface between the electrolyte layer and one of the electrodes, such as the lithium metal electrode. Indeed, according to Tang et al., despite the progress achieved in composite electrolytes, they still face various challenges in terms of ionic conductivity, electrochemical stability and interfacial interactions.

[0006] Zhu et al.'s team also recently described several strategies that can be used to increase the ionic conductivity and interfacial compatibility of solid inorganic-organic 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 the inorganic particles, modifying the surface of the inorganic particles (e.g., with polydopamine, silanes, etc.), or adding additives such as plasticizers in the form of small molecules (succinonitrile, TEGDME, etc.). Strategies described for improving the interfacial compatibility of solid composite electrolytes include symmetric or asymmetric multilayer arrangements, interactions between polymers (e.g., polycaprolactone) and inorganic particles, interactions between mixtures of two different polymers (e.g., poly(ethylene oxide) (PEO) and boronated poly(ethylene glycol) (BPEG)) and particles, etc. Thus, there is a continuing need for the development of solid electrolytes that improve upon at least one of the above-mentioned aspects while providing the advantages generally associated therewith. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] U.S. Patent No. 6,903,174 Summary of the Invention [Means for solving the problem]

[0008] overview According to a first aspect, the present technology provides a composite material comprising inorganic particles, a fluorinated compound and optionally a polymer, wherein the fluorinated compound is represented by formula I: [ka] [In the formula, R 1 and R 2 represents, independently at each occurrence, an optionally substituted linear or branched C 1~8 Alkyl groups, optionally substituted C 3~8 Cycloalkyl groups, optionally substituted C6 aryl groups, optionally substituted C 3~8 Heterocycloalkyl groups and optionally substituted C 5~6 heteroaryl groups; X 1 is selected from O and NH, or X 1 does not exist, X 2 are C(O), S(O)2 and Si(R 3 R 4 ), where R 3 and R 4 represents, independently at each occurrence, an optionally substituted linear or branched C 1~8 is an alkyl group or X 2 does not exist, Here, R 1 , R 2 , R 3 and R 4at least one of which is a group substituted with one or more fluorine atoms. The present invention relates to a composite material.

[0009] According to one embodiment, X 1 does not exist, and X 2 are C(O), S(O)2 and Si(R 3 R 4 ) or X 1 is selected from O and NH, and X 2 does not exist or X 1 and X 2 Neither of these exists.

[0010] According to another embodiment, R 1 is a group substituted with one or more fluorine atoms, e.g., R 1 can be a perfluorinated group. In one embodiment, R 1 is a linear or branched chain C 1~8 Alkyl group, or linear or branched C 1~4 Alkyl group, or C 1~2 It is an alkyl group.

[0011] In some embodiments, R 2 is a group substituted with one or more fluorine atoms, e.g., R 2 can be a perfluorinated group. According to one embodiment, R 2 is a linear or branched chain C 1~8 Alkyl group, or linear or branched C 1~4 Alkyl group, or C 1~2 is an alkyl group. Alternatively, R 2 is replaced as necessary 3~8 Cycloalkyl group or optionally substituted C 3~6 Cycloalkyl group or optionally substituted C 5~6 It is a cycloalkyl group.

[0012] In some embodiments, the fluorinated compound is selected from N-methyltrifluoroacetamide (NMTFAm), N-methylpentapropionamide (NMPPPAm), N-cyclopentyltrifluoroacetamide (NCPTFAm), N-trifluoromethylsulfonyltrifluoroacetamide (NTFMSTFAm), N-trimethylsilyltrifluoroacetamide (NTMSTFAm), and bistrifluoroacetamide (BTFAm).

[0013] 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.

[0014] 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 ion-conducting segments polyethers, polythioethers, polyesters, polythioesters, polycarbonates, polythiocarbonates, polyimides, polysulfonimides, polyamides, polysulfonamides, polyphosphazenes, and ion-nonconducting segments polyacrylates, polymethacrylates, polystyrenes, polysiloxanes, polyurethanes, polyethylenes, polypropylenes, or copolymers or combinations of two or more thereof.

[0015] According to another embodiment, the polymer comprises at least one polymer segment comprising a block copolymer having at least two different repeat units to reduce the crystallinity of the crosslinked polymer, for example, the polymer segment comprises a block copolymer comprising at least one alkali metal or alkaline earth metal ion solvation segment and a crosslinkable segment comprising a crosslinkable unit prior to crosslinking. According to an embodiment, the alkali metal or alkaline earth metal ion solvation segment is represented by Formula II: [ka] [In the formula, R is H, C1~C 10 Alkyl and -(CH2-OR a R b ), R a is (CH2-CH2-O) y and R b is C1~C 10 is an alkyl group. The repeat units are selected from homopolymers and copolymers containing the following repeat units:

[0016] In one embodiment, the crosslinkable units comprise functional groups selected from acrylate, methacrylate, allyl, vinyl, hydroxide, epoxide, aldehyde, carboxylic acid, halophenyl, halobenzyl, alkyne, azide, amine, thiol, and any combination thereof.

[0017] In some embodiments, the polymer is present in the composite 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.

[0018] According to another embodiment, the inorganic particles include an inorganic compound of an amorphous, ceramic or glass-ceramic type, such as an oxide, sulfide or oxysulfide. Preferably, the inorganic compound of an amorphous, ceramic or glass-ceramic type is an oxide. In another embodiment, the inorganic particles are Al2O3, Mg2B2O5, Na2O·2B2O3, xMgO·yB2O3·zH2O, TiO2, ZrO2, ZnO, Ti2O3, SiO2, Cr2O3, CeO2, B2O3, B2O, SrBi4Ti4O 15 , LLTO, LLZO, LAGP, LATP, Fe2O3, BaTiO3, γ-LiAlO2, molecular sieves and zeolites (e.g., aluminosilicates, mesoporous silica), sulfide ceramics (Li7P3S 11 etc.), glass-ceramics (e.g., LIPON etc.) and other ceramics, and combinations thereof. Preferably, the ceramic is selected from Al2O3, Mg2B2O5, Na2O·2B2O3, xMgO·yB2O3·zH2O, TiO2, ZrO2, ZnO, Ti2O3, SiO2, Cr2O3, CeO2, B2O3, B2O, SrBi4Ti4O 15 , LLTO, LLZO, LAGP, LATP, Fe2O3, BaTiO3, γ-LiAlO2, molecular sieves and zeolites (e.g., aluminosilicates, mesoporous silica), glass-ceramics (e.g., LIPON etc.), and combinations thereof.

[0019] According to one embodiment, the inorganic particles are in one form of spherical particles, rods, needles, nanotubes, or combinations thereof.

[0020] According to one embodiment, the inorganic particles are of the formula Li 1+z Al z M 2-z (PO4)3 [wherein M is Ti, Ge or a combination thereof, 0 < z < 1, and for example, here z can be in the range of 0.1 to 0.9, or 0.3 to 0.7, or 0.2 to 0.4] and include compounds selected from the compounds.

[0021] In another embodiment, the inorganic particles are of the formula Li 7-x La3Zr2M x x O 12 and Li 3y La (2 / 3)-y Ti 1-y’ M y y’ O3 [wherein M x is selected from Al, Ga, Ta, Fe and Nb; M y is selected from Ba, B, Al, Si and Ta; x is such that 0 ≦ x ≦ 1; y is such that 0 < y < 0.67; y' is such that 0 ≦ y' < 1] and are selected from compounds containing such compounds. For example, x may be in the range from 0 to 0.5, or x is zero and M x is absent.

[0022] According to one embodiment, the inorganic particle content is in the range from 1 wt% to 95 wt%, or from 5 wt% to 90 wt%, or from 5 wt% to 80 wt%, or from 5 wt% to 70 wt%, or from 5 wt% to 60 wt%, or from 5 wt% to 50 wt%, or from 5 wt% to 40 wt%, or from 5 wt% to 25 wt%, or from 5 wt% to 15 wt%.

[0023] According to another embodiment, the composite material comprises a polymer and an additional plasticizer. For example, the plasticizer may be selected from liquid glycol diethers (such as tetraethylene glycol dimethyl ether (TEGDME)), carbonate esters, ionic liquids, etc. In one embodiment, the plasticizer may be present in the composite material at a concentration in the range from 0.1 wt% to 50 wt%, or from 10 wt% to 50 wt%, or from 20 wt% to 40 wt%.

[0024] According to another embodiment, the composite material further comprises a salt. For example, the salt is a cation of an alkali metal or alkaline earth metal, preferably an alkali metal (preferably Li), and hexafluorophosphate (PF6 - ), bis(trifluoromethanesulfonyl)imide (TFSI- ), bis(fluorosulfonyl)imide (FSI - ), (fluorosulfonyl)(trifluoromethanesulfonyl)imide ((FSI)(TFSI) - ), 2-trifluoromethyl-4,5-dicyanoimidazolate (TDI - ), 4,5-dicyano-1,2,3-triazolate (DCTA - ), bis(pentafluoroethylsulfonyl)imide (BETI - ), difluorophosphate (DFP - ), tetrafluoroborate (BF4 - ), bis(oxalato)borate (BOB - ), nitrate ion (NO3 - ), chloride ion (Cl - ), bromide ion (Br - ), fluoride ion (F - ), perchlorate ion (ClO4 - ), hexafluoroarsenate (AsF6 - ), trifluoromethanesulfonate (SO3CF3 - )(Tf - ), fluoroalkyl phosphate [PF3(CF2CF3)3 - ](FAP - ), tetrakis(trifluoroacetoxy)borate [B(OCOCF3)4] - (TFAB - ), bis(1,2-benzenediolato(2-)-O,O')borate [B(C6O2)2] - (B.B.B. - ), difluoro(oxalato)borate (BF2(C2O4) - )(FOB - ), formula BF2O4R x - anion of (wherein R x =C 2~4 alkyl), and one of the combinations thereof, such as LiTFSI or LiFSI.

[0025] According to a second aspect, the present document relates to a solid electrolyte comprising a layer of a composite material as defined herein.

[0026] According to a third aspect, the present technology relates to an electrochemical cell comprising an anode, a cathode and a solid electrolyte, wherein at least one of the cathode, the anode and the electrolyte comprises a composite material as defined herein. According to one embodiment, the electrochemical cell comprises an anode, a cathode and a solid electrolyte, wherein the solid electrolyte is as defined herein. According to another embodiment, the solid electrolyte is as defined herein, and at least one of the anode and the cathode comprises a composite material as defined herein.

[0027] According to 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. According to another embodiment, the positive electrode electrochemically active material is selected from metal phosphates, lithiated metal phosphates, metal oxides, and lithiated metal oxides. According to yet another embodiment, the positive electrode electrochemically active material is selected from LiM'PO4, where M' is Fe, Ni, Mn, Co, or a combination thereof, LiV3O8, VO5F, LiV2O5, LiMn2O4, LiM''O2, where M'' is Mn, Co, Ni, or a combination thereof (NMC, LiMn x Co y Ni zO2, where x+y+z=1), Li(NiM''')O2 (where M''' is Mn, Co, Al, Fe, Cr, Ti, Zr, or a combination thereof), elemental sulfur, selenium or iodine, iron(III) fluoride, copper(II) fluoride, lithium iodide, carbon-based active materials such as graphite, organic cathode active materials (such as polyimides, poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl methacrylate) (PTMA), tetralithium perylene-3,4,9,10-tetracarboxylate (PTCLi4), naphthalene-1,4,5,8-tetracarboxylic dianhydride (NTCDA), perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA), pi-conjugated dicarboxylates and anthraquinones), or combinations of two or more of these materials, if compatible with each other.

[0028] According to one embodiment, the electrochemically active material of the positive electrode is in the form of particles that are optionally coated (e.g., with a polymer, ceramic, carbon, or a combination of two or more thereof).

[0029] According to another embodiment, the material of the positive electrode further comprises an electronically conductive material including, for example, at least one of carbon black (e.g., Ketjenblack™ or Super P™), acetylene black (e.g., Shawinigan black or Denka™ black), graphite, graphene, carbon fibers or nanofibers (e.g., vapor grown carbon fibers (VGCF)), carbon nanotubes (e.g., single-walled (SWNT), multi-walled (MWNT)), or metal powder.

[0030] In some embodiments, the positive electrode material further comprises a binder, for example a binder selected from a polymer as defined above, or a rubber-based binder (such as SBR (styrene-butadiene rubber), NBR (acrylonitrile-butadiene rubber), HNBR (hydrogenated NBR), CHR (epichlorohydrin rubber), ACM (acrylic acid rubber)) or a fluorinated polymer-based binder (such as PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), and combinations thereof), optionally including additives such as CMC (carboxymethyl cellulose). According to other embodiments, the positive electrode material further comprises a salt, inorganic particles of ceramic or glass type, or other suitable active materials (for example, sulfur), and / or the positive electrode material further comprises a composite material as defined herein.

[0031] In another embodiment, the negative electrode of the electrochemical cell comprises a negative electrode electrochemically active material.

[0032] According to one embodiment, the electrochemically active material of the negative electrode comprises a metal film containing an alkali metal or an alkaline earth metal, for example, the metal film comprises lithium containing less than 1000 ppm (or less than 0.1 wt %) of impurities. Alternatively, the metal film comprises an alloy of lithium with 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 preferably comprising at least 75% lithium by weight, or between 85% and 99.9% lithium by weight.

[0033] In another embodiment, the electrochemically active material of the negative electrode is selected from the group consisting of intermetallic compounds (e.g., SnSb, TiSnSb, CuSb, AlSb, FeSb2, FeSn2, and CoSn2), metal oxides, metal nitrides, metal phosphides, metal phosphates (e.g., LiTi2(PO4)3), metal halides (e.g., metal fluorides), metal sulfides, metal oxysulfides, carbon (e.g., graphite, graphene, reduced graphene oxide, hard carbon, soft carbon, expanded graphite, and amorphous carbon), silicon (Si), silicon-carbon composites (Si-C), silicon oxides (SiO x ), silicon oxide-carbon composite (SiO x -C), tin (Sn), tin-carbon composite (Sn-C), tin oxide (SnO x ), tin oxide-carbon composite (SnO x -C), and combinations thereof, where compatible. According to another embodiment, the metal oxide is represented by the formula M"" b O c where M'''' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination thereof; b and c are numbers such that the ratio of c:b is in the range of 2 to 3 (e.g., MoO3, MoO2, 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., lithium titanate (Li4Ti5O 12 etc.) or lithium molybdenum oxide (Li2Mo4O 13 etc.) are selected from.

[0034] In some embodiments, the electrochemically active material of the negative electrode is in the form of particles that are optionally coated (e.g., with a polymer, ceramic, carbon, or a combination of two or more thereof).

[0035] In one embodiment, the material of the negative electrode further comprises an electronically conductive material including, for example, at least one of carbon black (e.g., Ketjenblack™ or Super P™), acetylene black (e.g., Shawinigan black or Denka™ black), graphite, graphene, carbon fibers or nanofibers (e.g., vapor grown carbon fibers (VGCF)), carbon nanotubes (e.g., single-walled (SWNT), multi-walled (MWNT)), or metal powder.

[0036] In another embodiment, the material of the negative electrode further comprises a binder, for example a binder selected from a polymer as defined above, or a rubber-based binder (such as SBR (styrene-butadiene rubber), NBR (acrylonitrile-butadiene rubber), HNBR (hydrogenated NBR), CHR (epichlorohydrin rubber), ACM (acrylic acid rubber)) or a fluorinated polymer-based binder (such as PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), and combinations thereof), optionally including additives such as CMC (carboxymethylcellulose).

[0037] According to yet another embodiment, the material of the negative electrode further comprises a salt, inorganic particles of ceramic or glass type, or other suitable active material, and / or a composite material as defined herein.

[0038] 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.

[0039] According to a fifth aspect, the present document relates to the use of an electrochemical storage battery as defined herein in a mobile device, such as a mobile phone, a camera, a tablet or a laptop, in an electric or hybrid vehicle or in renewable energy storage.

[0040] 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 inorganic particles, a fluorinated compound and optionally a polymer. According to one embodiment, the mixing step comprises a polymer and optionally a crosslinking agent. According to another embodiment, the mixing step comprises a polymer and a crosslinking agent, and the method further comprises a polymer crosslinking step. [Brief description of the drawings]

[0041] [Figure 1] FIG. 1 shows infrared spectroscopy results for (a) LATP, (b) NMTFAm, (c) DAEDAm, (d) NMTFAm / LATP mixture, and (e) DAEDAm / LATP mixture.

[0042] [Diagram 2] FIG. 2 shows the solid-state NMR results: (a) 1H NMTFAm and NMTFAm / LATP mixture, (b) 6Li LATP, (c) 6Li NMTFAm / LATP mixture.

[0043] [Diagram 3] FIG. 3 shows the Young's modulus of the membrane prepared in Example 1(d).

[0044] [Figure 4] FIG. 4 shows the ionic conductivity results as a function of temperature for cells 1 to 6 and 8 to 15 in (a) and for cell 7 in (b) compared to LATP powder.

[0045] [Diagram 5] FIG. 5 shows the potential as a function of time for Cell 4 cycled at current densities ranging from C / 3 to 5C.

[0046] [Figure 6] FIG. 6 shows the electrochemical stability results for cell 4 performed at voltages ranging from 3.5V to 5V.

[0047] [Figure 7] FIG. 7 shows the capacity and coulombic efficiency as a function of cycle number for NMC / Li cells according to Example 3(e)(i).

[0048] [Figure 8] FIG. 8 shows galvanostatic charge and discharge curves at C / 6 as a function of cycle number of an LFP / Li cell according to Example 3(e)(ii). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0049] Detailed Description All technical and scientific terms and expressions used herein have the same meaning as commonly understood by those skilled in the art of the present invention. Nevertheless, some definitions of the terms and expressions used are provided below.

[0050] The term "about" as used in this document means approximately, in the region of, and around. When the term "about" is used in relation to a numerical value, the term modifies the numerical value up or down, for example, by a variance of 10% from the nominal value. This term may also take into account, for example, experimental error of a measuring device or rounding of values.

[0051] When a range of values ​​is stated in this application, the lower and upper limits of the range are always included in the definition, unless otherwise specified.

[0052] The chemical structures depicted herein are drawn according to conventions in the art, and when an atom, such as a drawn carbon atom, appears to contain incomplete valences, it will be assumed that the valences are satisfied by one or more hydrogen atoms, even if not explicitly drawn.

[0053] This document presents a composite material comprising inorganic particles, a fluorinated amide and optionally a polymer. Preferably, the fluorinated amide has formula I: [ka] [In the formula, R 1 and R 2 represents, independently at each occurrence, an optionally substituted linear or branched C 1~8 Alkyl groups, optionally substituted C 3~8 Cycloalkyl groups, optionally substituted C6 aryl groups, optionally substituted C 3~8 Heterocycloalkyl groups and optionally substituted C 5~6 heteroaryl groups; X 1 is selected from O and NH, or X 1 does not exist, X 2 are C(O), S(O)2 and Si(R 3 R 4 ), where R 3 and R 4 represents, independently at each occurrence, an optionally substituted linear or branched C 1~8 is an alkyl group or X 2 does not exist, Here, R 1 , R 2 , R 3 and R 4 at least one of which is a group substituted with one or more fluorine atoms. It is a compound of the formula: Some examples of compounds of formula I are: -X 1 does not exist and X 2 However, C(O), S(O)2 and Si(R 3 R 4 ), -X 1 is selected from O and NH, and X 2 does not exist, or -X 1 and X 2 does not exist Contains compounds.

[0054] According to some examples, R 1 is a group substituted with one or more fluorine atoms, for example, R 1 can be a perfluorinated group. This group can be a linear or branched C 1~8 Alkyl group, or linear or branched C 1~4 Alkyl group, or C 1~2 It may be an alkyl group.

[0055] R 2 The group may be a group substituted with one or more fluorine atoms, for example a perfluorinated group. The group may be a linear or branched C 1~8 Alkyl group, or linear or branched C 1~4 Alkyl group, or C 1~2 Alternatively, R 2 is replaced as necessary 3~8 Cycloalkyl group or optionally substituted C 3~6 Cycloalkyl group or optionally substituted C 5~6 It may be a cycloalkyl group.

[0056] Non-limiting examples of fluorinated compounds include the compounds N-methyltrifluoroacetamide (NMTFAm), N-methylpentaproprionamide (NMPPPAm), N-cyclopentyltrifluoroacetamide (NCPTFAm), N-trifluoromethylsulfonyltrifluoroacetamide (NTFMSTFAm), N-trimethylsilyltrifluoroacetamide (NTMSTFAm) and bistrifluoroacetamide (BTFAm).

[0057] The concentration of the compound in the composite material may be in the range of, for example, 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.

[0058] The polymer, when present in the composite, may comprise at least one polymer segment selected from ion-conducting segments polyethers, polythioethers, polyesters, polythioesters, polycarbonates, polythiocarbonates, polyimides, polysulfonimides, polyamides, polysulfonamides, polyphosphazenes, or from ion-nonconducting segments polyacrylates, polymethacrylates, polystyrenes, polysiloxanes, polyurethanes, polyethylenes, polypropylenes, or copolymers or combinations of two or more thereof. The polymer may be a copolymer comprising units of two or more of these segments, or combinations of two or more of these. The copolymer may be a random copolymer, a statistical copolymer, an alternating copolymer, a block copolymer, etc.

[0059] The polymer is preferably a crosslinked aprotic polymer and / or a branched polymer, preferably of the multi-branched type (star configuration, comb configuration, etc.). For example, the polymer comprises at least one polymer segment comprising a block copolymer having at least two different repeat units to reduce the crystallinity of the crosslinked polymer. For example, the polymer segment may comprise a block copolymer comprising at least one alkali metal or alkaline earth metal ion solvating segment and a crosslinkable segment comprising a crosslinkable unit prior to crosslinking. An example of an alkali metal or alkaline earth metal ion solvating segment is represented by Formula II: [ka] [In the formula, R is H, C1~C 10 Alkyl and -(CH2-OR a R b ), R a is (CH2-CH2-O) y and R b is C1~C 10 is an alkyl group. The repeat units are selected from homopolymers and copolymers containing the following repeat units:

[0060] Non-limiting examples of crosslinkable units include functional groups selected from acrylate, methacrylate, allyl, vinyl, hydroxide, epoxide, aldehyde, carboxylic acid, halophenyl, halobenzyl, alkyne, azide, amine, thiol, and any combination thereof. According to another example, the composite material includes a crosslinked polymer, where the crosslinkable group has been converted to its crosslinked version.

[0061] The polymer concentration 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.

[0062] The inorganic particles preferably comprise inorganic compounds of the amorphous, ceramic or glass-ceramic type, such as oxides, sulfides or oxysulfides, preferably oxides. The inorganic compounds may or may not be ionically conductive, preferably they are ionically conductive.

[0063] Non-limiting examples of inorganic compounds include compounds or ceramics such as Al2O3, Mg2B2O5, Na2O·2B2O3, xMgO·yB2O3·zH2O, TiO2, ZrO2, ZnO, Ti2O3, SiO2, Cr2O3, CeO2, B2O3, B2O, SrBi4Ti4O 15 , LLTO, LLZO, LAGP, LATP, Fe2O3, BaTiO3, γ-LiAlO2, molecular sieves and zeolites (e.g., aluminosilicates, mesoporous silica), sulfide ceramics (Li7P3S 11 ), glass ceramics (such as LIPON) and other ceramics, and combinations thereof, preferably Al2O3, Mg2B2O5, Na2O·2B2O3, xMgO·yB2O3·zH2O, TiO2, ZrO2, ZnO, Ti2O3, SiO2, Cr2O3, CeO2, B2O3, B2O, SrBi4Ti4O 15, LLTO, LLZO, LAGP, LATP, Fe2O3, BaTiO3, γ-LiAlO2, molecular sieves and zeolites (e.g., aluminosilicate, mesoporous silica), glass ceramics (such as LIPON), and combinations thereof. The inorganic compound is preferably in particulate form, and the particles are in one form of various shapes, such as spherical particles, rods, needles, nanotubes, or combinations thereof.

[0064] For example, the inorganic particles are of the formula Li 1+z Al z M 2-z (PO4)3 [wherein M is Ti, Ge, or a combination thereof, 0 < z < 1, for example, z can be in the range of 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] and is selected from compounds containing such compounds.

[0065] According to another example, the inorganic particles are of the formula Li 7-x La3Zr2M x x O 12 and Li 3y La (2 / 3)-y Ti 1-y’ M y y’ O3 [wherein M x is selected from Al, Ga, Ta, Fe, and Nb; M y is selected from Ba, B, Al, Si, and Ta; x is such that 0 ≤ x ≤ 1; y is such that 0 < y < 0.67; y’ is such that 0 ≤ y’ < 1] and is selected from compounds containing such compounds, preferably x is in the range of 0 to 0.5 or x is zero and M x is absent, preferably y’ is in the range of 0 to 0.5 or y’ is zero and M y is absent.

[0066] The content of inorganic particles in the composite material may be in the range of 1 wt% to 95 wt%, or 5 wt% to 90 wt%, or 5 wt% to 80 wt%, or 5 wt% to 70 wt%, or 5 wt% to 60 wt%, or 5 wt% to 50 wt%, or 5 wt% to 40 wt%, or 5 wt% to 25 wt%, or 5 wt% to 15 wt%.

[0067] According to some examples, the composite material includes a polymer and a plasticizer. Non-limiting examples of plasticizers include glycol diether based liquids (such as tetraethylene glycol dimethyl ether (TEGDME)), carbonate esters, ionic liquids, etc. When present, the concentration of the plasticizer in the composite material may range from 0.1% to 50% by weight, or from 10% to 50% by weight, or from 20% to 40% by weight.

[0068] According to a preferred embodiment, the composite material further comprises a lithium salt, for example a salt comprising a cation of an alkali metal or alkaline earth metal, preferably an alkali metal (preferably Li), and an anion. A non-limiting example of the anion is hexafluorophosphate (PF6 - ), bis(trifluoromethanesulfonyl)imide (TFSI - ), bis(fluorosulfonyl)imide (FSI - ), (fluorosulfonyl)(trifluoromethanesulfonyl)imide ((FSI)(TFSI) - ), 2-trifluoromethyl-4,5-dicyanoimidazolate (TDI - ), 4,5-dicyano-1,2,3-triazolate (DCTA - ), bis(pentafluoroethylsulfonyl)imide (BETI - ), difluorophosphate (DFP - ), tetrafluoroborate (BF4 - ), bis(oxalato)borate (BOB - ), nitrate ion (NO3 - ), chloride ion (Cl - ), bromide ion (Br - ), fluoride ion (F- ), perchlorate ion (ClO4 - ), hexafluoroarsenate (AsF6 - ), trifluoromethanesulfonate (SO3CF3 - )(Tf - ), fluoroalkyl phosphate [PF3(CF2CF3)3 - ](FAP - ), tetrakis(trifluoroacetoxy)borate [B(OCOCF3)4] - (TFAB - ), bis(1,2-benzenediolato(2-)-O,O')borate [B(C6O2)2] - (B.B.B. - ), difluoro(oxalato)borate (BF2(C2O4) - )(FOB - ), formula BF2O4R x - anion of (wherein R x =C 2~4 alkyl), and one of their combinations, such as LiTFSI or LiFSI.

[0069] The composite material of the present invention is prepared according to a method comprising at least one step of mixing inorganic particles, a fluorinated compound and optionally a polymer, as well as other optional components as described herein. The mixing step of the method may thus comprise a polymer and optionally a crosslinking agent. The mixing step of such a method may then be followed by a crosslinking step.

[0070] The composite material may be incorporated into the composition of the solid electrolyte layer or electrode material.

[0071] For example, the electrolyte comprises a composite material as defined herein in a solid layer. This layer may be formed by mixing, in any order, inorganic particles, an electrolytic polymer or a precursor thereof, a fluorinated amide and optionally a solvent, a plasticizer and / or a salt, and coating the mixture onto a support. The support may be temporary (such as a stainless steel, polypropylene, etc. support) and may be removed prior to assembly with the rest of the electrochemical cell. The support may be on the surface of an electrode material, which will have been previously prepared.

[0072] If a polymer precursor is used, the coated layer is treated to polymerize or crosslink the polymer, for example by heat treatment, irradiation (UV, microwave, gamma ray, X-ray, e-beam, etc.), or a combination of both, optionally in the presence of an initiator. If a solvent is present, the material is preferably dried, for example prior to crosslinking or assembly with other components of the electrochemical cell.

[0073] The composite material of the present invention is present in at least one of the electrolyte, the positive electrode or the negative electrode in an electrochemical cell, preferably in the electrolyte layer.

[0074] The positive electrode material generally comprises an electrochemically active material and may be free-standing or applied to a current collector. The positive electrode electrochemically active material may be selected from metal phosphates, lithiated metal phosphates, metal oxides, and lithiated metal oxides, among others.

[0075] Examples of electrochemically active materials are 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 (NMC, LiMn x Co y Ni zO2, where x+y+z=1), Li(NiM''')O2 (where M''' is Mn, Co, Al, Fe, Cr, Ti, Zr, or a combination thereof), elemental sulfur, selenium or iodine, iron(III) fluoride, copper(II) fluoride, lithium iodide, carbon-based active materials such as graphite, organic cathode active materials (such as polyimides, poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl methacrylate) (PTMA), tetralithium perylene-3,4,9,10-tetracarboxylate (PTCLi4), naphthalene-1,4,5,8-tetracarboxylic dianhydride (NTCDA), perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA), π-conjugated dicarboxylates and anthraquinones), or combinations of two or more of these materials, if compatible with each other.

[0076] The electrochemically active material of the positive electrode is preferably in the form of particles that are optionally coated (eg, with a polymer, ceramic, carbon, or a combination of two or more of these).

[0077] The electrode material may further comprise an electronically conductive material including, for example, at least one of carbon black (e.g., Ketjenblack™ or Super P™), acetylene black (e.g., Shawinigan black or Denka™ black), graphite, graphene, carbon fibers or nanofibers (e.g., vapor grown carbon fibers (VGCF)), carbon nanotubes (e.g., single walled (SWNT), multi-walled (MWNT)), or metal powder.

[0078] The electrode material may be prepared in the same manner as the electrolyte layer, except that the support for spreading may be the surface of the solid electrolyte layer or a current collector.

[0079] When the material of the positive electrode does not comprise a composite material, the material of the positive electrode may comprise an electrochemically active material as defined herein, a binder and optionally an electronically conductive material and / or a salt as defined herein.

[0080] Non-limiting examples of electrode material binders include the polymers described above in connection with the composite materials, as well as rubber-based binders (such as SBR (styrene-butadiene rubber), NBR (acrylonitrile-butadiene rubber), HNBR (hydrogenated NBR), CHR (epichlorohydrin rubber), ACM (acrylic acid rubber)) or fluorinated polymer-based binders (such as PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), and combinations thereof). Some binders, such as rubber binders, may include additives such as CMC (carboxymethyl cellulose).

[0081] Other additives may be present in the positive electrode material, such as inorganic particles, such as ceramic or glass, or other suitable active materials (eg, sulfur).

[0082] The negative electrode includes a negative electrochemically active material that may be formed, for example, from a metal film that includes an alkali metal or an alkaline earth metal. According to one example, the metal film is made of lithium containing less than 1000 ppm (or less than 0.1% by weight) of impurities. Alternatively, the metal film comprises an alloy of lithium with 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 weight, or between 85% and 99.9% lithium by weight.

[0083] Other examples of electrochemically active materials for the negative electrode include intermetallic compounds (e.g., SnSb, TiSnSb, CuSb, AlSb, FeSb2, FeSn2, and CoSn2), metal oxides, metal nitrides, metal phosphides, metal phosphates (e.g., LiTi2(PO4)3), metal halides (e.g., metal fluorides), metal sulfides, metal oxysulfides, carbon (e.g., graphite, graphene, reduced graphene oxide, hard carbon, soft carbon, expanded graphite, and amorphous carbon), silicon (Si), silicon-carbon composites (Si-C), silicon oxide (SiO x ), silicon oxide-carbon composite (SiO x -C), tin (Sn), tin-carbon composite (Sn-C), tin oxide (SnO x ), tin oxide-carbon composite (SnO x -C), and combinations thereof, where compatible. For example, the metal oxide can be represented by the formula M"" b O cwhere M'''' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination thereof; b and c are numbers such that the ratio of c:b is in the range of 2 to 3 (e.g., MoO3, MoO2, 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., lithium titanate (Li4Ti5O 12 etc.) or lithium molybdenum oxide (Li2Mo4O 13 etc.) may be selected from.

[0084] If the negative electrode is not in the form of a metal film, it rather comprises particles, optionally coated (e.g., with a polymer, ceramic, carbon, or a combination of two or more thereof), of the electrochemically active material of the negative electrode. The material of the negative electrode may comprise other components as described for the negative electrode (electronically conductive material, composite material of the invention, salt, binder, ceramic or glass type inorganic particles, or other suitable active materials, etc.).

[0085] This document also relates to an electrochemical accumulator comprising at least one electrochemical cell as defined herein, for example, the electrochemical accumulator being a lithium battery or a lithium-ion battery.

[0086] According to a fifth aspect, the use of the electrochemical accumulator of the present application is intended in a mobile device, such as a mobile phone, a camera, a tablet or a laptop, in an electric or hybrid vehicle or in renewable energy storage. EXAMPLES

[0087] The following examples are for illustrative purposes and should not be construed as limiting the scope of the invention as described.

[0088] Unless otherwise specified, the numbers expressing the amounts of ingredients, preparation conditions, concentrations, properties, and the like used herein should be interpreted in each instance as being modified by the term "about". At the very least, each numerical parameter should be interpreted in light of the number of reported significant digits and by applying ordinary rounding techniques. Thus, unless otherwise indicated, the numerical parameters recited herein are approximations that may vary depending on the properties sought. Nonetheless, while the parameters defining the broadest embodiments are approximations, the numerical values ​​presented in the following examples are reported as precisely as possible. However, any numerical value inherently contains certain limits of error resulting from variations in experiments, measurements, statistical analyses, and the like.

[0089] The crosslinkable polymers used in the following examples are polyethers containing crosslinkable units as described in U.S. Pat. No. 7,897,674 (hereinafter referred to as "Polymer US'674", which is a branched, hyperbranched polymer containing crosslinkable units) or U.S. Pat. No. 6,903,174 (hereinafter referred to as "Polymer US'174", which is linear and contains crosslinkable pendant groups). Example 1 Preparation of electrolyte (a) Polymer electrolyte (comparative example)

[0090] 2 g of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), 8 g of polymer US'674 and 0.08 g of Irgacure™ are mixed in a flask at room temperature. Once a homogeneous solution is obtained, the solution is coated onto a thin stainless steel plate. After 3 minutes of UV irradiation under nitrogen, a solid polymer electrolyte membrane is thus obtained. (b) Composite electrolyte using HNT and DAEDAm (comparative example)

[0091] 0.5 g LiTFSI, 0.77 g tetraethylene glycol dimethyl ether (TEGDME), 0.25 g N,N'-diacetylethylenediamine (DAEDAm) and 0.24 g halloysite nanotubes (HNT) are thoroughly mixed in a flask at room temperature. Once a homogeneous dispersion is obtained, 0.75 g polymer US'674 and 0.01 g Irgacure™ are added. After stirring for 1 hour at room temperature, the dispersion is coated onto a thin stainless steel plate. The composite electrolyte membrane thus obtained is cured by UV irradiation under nitrogen for 3 minutes. (c) Composite electrolyte using HNT and NMTFAm

[0092] 0.5 g LiTFSI, 0.69 g TEGDME, 0.44 g N-methyltrifluoroacetamide (NMTFAm) and 0.26 g HNT are thoroughly mixed in a flask at room temperature. Once a homogeneous dispersion is obtained, 0.67 g polymer US'674 and 0.01 g Irgacure™ are added. After stirring for 1 hour at room temperature, the dispersion is coated onto a thin stainless steel plate. The composite electrolyte membrane thus obtained is cured by UV irradiation under nitrogen for 3 minutes. (d) Composite electrolyte using LATP and NMTFAm

[0093] 0.5 g LiTFSI, 0.77 g TEGDME, 0.44 g NMTFAm and 0.26 g Li 1,3 Al 0,3 Ti 1,7 (PO4)3(LATP) is mixed thoroughly in a flask at room temperature. When a homogeneous dispersion is obtained, 0.67 g of polymer US'674 and 0.01 g of Irgacure™ are added. After stirring for 1 hour at room temperature, the dispersion is coated onto a thin stainless steel plate. The composite electrolyte membrane thus obtained is cured by UV irradiation under nitrogen for 3 minutes. (e) Composite electrolyte using LATP and DAEDAm (comparative example)

[0094] 0.5g LiTFSI, 0.77g TEGDME, 0.25g DAEDAm and 0.24g LATP are mixed thoroughly in a flask at room temperature. When a homogeneous dispersion is obtained, 0.75g polymer US'674 and 0.01g Irgacure are added. After stirring at room temperature for 1 hour, the dispersion is coated on a thin stainless steel plate. The composite electrolyte membrane thus obtained is cured by UV irradiation under nitrogen for 3 minutes. (f) Polymer electrolyte using NMTFAm (comparative example)

[0095] 0.5g LiTFSI, 0.77g TEGDME and 0.25g NMTFAm are mixed thoroughly in a flask at room temperature. When a homogeneous solution is obtained, 0.99g polymer US'674 and 0.01g Irgacure are added. After stirring at room temperature for 1 hour, the solution is coated onto a thin stainless steel plate. The polymer electrolyte membrane thus obtained is cured by UV irradiation under nitrogen for 3 minutes. (g) Ceramic electrolyte using LATP and NMTFAm

[0096] 0.35 g of LATP and 0.15 g of NMTFAm are thoroughly mixed and ground in a mortar at room temperature. The powder is then compressed into round pellets with a diameter of 16 mm and a thickness of 420 μm at a pressure of 120 psi. A comparative sample using pure LATP powder was also prepared in the same manner. (h) Composite electrolyte using LLZO and NMTFAm

[0097] 0.5g LiTFSI, 0.77g TEGDME, 0.44g NMTFAm and 0.26g Li7La3Zr2O 12(LLZO) is mixed thoroughly in a flask at room temperature. Once a homogeneous dispersion is obtained, 0.67 g of polymer US'674 and 0.01 g of Irgacure™ are added. After stirring for 1 hour at room temperature, the dispersion is coated onto a thin stainless steel plate. The composite electrolyte membrane thus obtained is cured by UV irradiation under nitrogen for 3 minutes. (i) Composite electrolyte using LATP, NMTFAm and polymer US'174

[0098] 0.5g LiTFSI, 0.77g TEGDME, 0.44g NMTFAm and 0.26g LATP are mixed thoroughly in a flask at room temperature. When a homogeneous dispersion is obtained, 0.67g polymer US'174 ​​and 0.01g Irgacure are added. After stirring at room temperature for 1 hour, the dispersion is coated on a thin stainless steel plate. The composite electrolyte membrane thus obtained is cured by UV irradiation under nitrogen for 3 minutes. (j) Composite electrolyte using LATP and NMPPPAm

[0099] 0.5g LiTFSI, 0.77g TEGDME, 0.44g N-methylpentaproprionamide (NMPPPAm) and 0.26g LATP are mixed thoroughly in a flask at room temperature. When a homogeneous dispersion is obtained, 0.67g polymer US'674 and 0.01g Irgacure™ are added. After stirring for 1 hour at room temperature, the dispersion is coated onto a thin stainless steel plate. The composite electrolyte membrane thus obtained is cured by UV irradiation under nitrogen for 3 minutes. (k) Composite electrolyte using LATP and NCPTFAm

[0100] 0.5g LiTFSI, 0.77g TEGDME, 0.44g N-cyclopentyltrifluoroacetamide (NCPTFAm) and 0.26g LATP are mixed thoroughly in a flask at room temperature. Once a homogeneous dispersion is obtained, 0.67g polymer US'674 and 0.01g Irgacure™ are added. After stirring for 1 hour at room temperature, the dispersion is coated onto a thin stainless steel plate. The composite electrolyte membrane thus obtained is cured by UV irradiation under nitrogen for 3 minutes. (l) Composite electrolyte using LATP and NTFMSTFAm

[0101] 0.5g LiTFSI, 0.77g TEGDME, 0.44g N-trifluoromethylsulfonyltrifluoroacetamide (NTFMSTFAm) and 0.26g LATP are mixed thoroughly in a flask at room temperature. When a homogeneous dispersion is obtained, 0.67g polymer US'674 and 0.01g Irgacure are added. After stirring for 1 hour at room temperature, the dispersion is coated on a thin stainless steel plate. The composite electrolyte membrane thus obtained is cured by UV irradiation under nitrogen for 3 minutes. (m) Composite electrolyte using LATP and NTMSTFAm

[0102] 0.5g LiTFSI, 0.77g TEGDME, 0.44g N-trimethylsilyltrifluoroacetamide (NTMSTFAm) and 0.26g LATP are mixed thoroughly in a flask at room temperature. When a homogeneous dispersion is obtained, 0.67g polymer US'674 and 0.01g Irgacure are added. After stirring for 1 hour at room temperature, the dispersion is coated on a thin stainless steel plate. The composite electrolyte membrane thus obtained is cured by UV irradiation for 3 minutes under nitrogen. (n) Composite electrolyte using LATP and BTFAm

[0103] 0.5g LiTFSI, 0.77g TEGDME, 0.44g bistrifluoroacetamide (BTFAm) and 0.26g LATP are mixed thoroughly in a flask at room temperature. When a homogeneous dispersion is obtained, 0.67g polymer US'674 and 0.01g Irgacure are added. After stirring for 1 hour at room temperature, the dispersion is coated on a thin stainless steel plate. The composite electrolyte membrane thus obtained is cured by UV irradiation under nitrogen for 3 minutes. (o) Composite electrolyte using LATP and less NMTFAm

[0104] 0.5 g LiTFSI, 0.65 g TEGDME, 0.37 g 1,1'-hexamethylenebis(1-methylpyrrolidinium)bis(trifluoromethanesulfonyl)imide, 0.11 g NMTFAm and 0.26 g LATP are thoroughly mixed in a flask at room temperature. Once a homogeneous dispersion is obtained, 0.60 g polymer US'674 and 0.01 g Irgacure™ are added. After stirring for 1 hour at room temperature, the dispersion is coated onto a thin stainless steel plate. The composite electrolyte membrane thus obtained is cured by UV irradiation for 3 minutes under nitrogen. Example 2 Physicochemical properties (a) Infrared spectroscopy of particle-amide mixtures

[0105] Chemical analysis was performed to better understand the effect of the presence of fluorinated amides. Solid-state infrared spectroscopy was performed on an Agilent-Cary 630® FTIR spectrometer. Particle-amide mixtures were prepared by grinding in a mortar using a 1.7:1 weight ratio for NMTFAm / LATP and a 1:1 weight ratio for DAEDAm / LATP. The infrared spectra of LATP, NMTFAm, DAEDAm, and of LATP / NMTFAm and LATP / DAEDAm mixtures are shown in Figure 1(a) to (e).

[0106] Figure 1(d) shows the peak at 3550 cm for the LATP / NMTFAm mixture.-1 It can be seen that a new signal was observed before and after, which was not present in the case of LATP / DAEDAm in FIG. 1(e). This new signal indicates that there is an interaction between the fluorinated amide and the LATP ceramic, which is not present in the case of the non-fluorinated amide DAEDAm. (b) NMR chemical structure of the NMTFAm / LATP mixture.

[0107] To confirm the results observed by infrared spectroscopy, solid-state NMR analysis of NMTFAm and NMTFAm / LATP mixtures was performed on a 500 MHz NMR spectrometer equipped with a 4 mm triple resonance probe using MAS (magic angle spinning) up to 15 kHz. The NMTFAm / LATP mixture was prepared as described in 2(a). The NMR spectra of NMTFAm, LATP, and the NMTFAm / LATP mixture were: 1 H and 6 The Li NMR spectra are shown in Figures 2(a) to (c).

[0108] Figure 2(a) shows that the NMTFAm signal is broader than that of the NMTFAm / LATP mixture, indicating an interaction between NMTFAm and LATP that significantly reduces the restriction of molecular mobility in NMTFAm. In addition, the shift of the peak corresponding to the NH protons of NMTFAm toward higher frequencies may indicate that more NH protons in the mixture are involved in hydrogen bonding.

[0109] Figure 2(c) shows, in comparison with Figure 2(b), that an additional signal at 1.2 ppm was observed in the mixture after 1 day of storage. 6 Li NMR spectrum, and new Li + This indicates that ions were produced. (c) Young's modulus of the membrane

[0110] The Young's modulus of the membrane prepared in Example 1(d) was evaluated at 20° C. with a TA Discovery DMA850. The film size for measurement was 10.7 mm×5.3 mm×0.167 mm (length×width×thickness). A rate-controlled strain ramp procedure was used. Figure 3 shows a graph of the Young's modulus of the membrane prepared in Example 1(d). (d) Diffusion coefficient

[0111] The ionic diffusion coefficients of various elements in the membrane prepared in Example 1(d) are 1 H, 7 Li and 19 The solid-state NMR experiments were performed using a Diff50™ probe as well as a double-resonance probe. 7 Li- 19 F and 1 H- 19 The measurements were performed on a 500 MHz NMR spectrometer equipped with a F RF insert.

[0112] Measurements were performed at 25° C. and 50° C. Gradient pulses ranged from 0.6 to 2.0 ms, and diffusion times were in the range of 40 to 100 ms depending on the nucleus. The gradient strength was varied from 100 G / cm to 2500 G / cm in 16 steps.

[0113] Diffusion measurements were accompanied by T2-related experiments using CPMG pulse trains with echo delays of 0.06 to 0.6 ms. Up to 64 echoes were collected per experiment. The results are presented in Table 1. [Table 1]

[0114] Most of the species were highly mobile in the samples, allowing for higher resolution in the NMR spectra.

[0115] 1 H and 19 The diffusion coefficients of NMTFAm measured by F NMR are in perfect agreement with each other.

[0116] The diffusion coefficients of Li in LATP at 25 and 50 °C are in agreement with values ​​obtained with other LATP-containing samples. This observation confirms that lithium diffusion in LATP is not dependent on the LATP particles being surrounded by a polymer, especially considering that the mean square displacement of the species during the NMR experiments is around 0.5 to 1 μm (much smaller than the LATP particle size, which is around 10 μm). Example 3 Electrochemical properties (a) Cell assembly (symmetric battery)

[0117] Symmetric coin cells of Li / electrolyte / Li type for critical current density (CCD) measurements and stainless steel / electrolyte / stainless steel type for ionic conductivity measurements were assembled. Polymer electrolyte membrane disks were cut to a diameter of 16 mm (for ionic conductivity measurements) and 14 mm (for CCD measurements) and sandwiched between two electrodes. The configuration of each cell is presented as follows: - Cell 1: electrode / Example 1(a) / electrode - Cell 2: electrode / Example 1(b) / electrode - 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 - Cell 14: electrode / Example 1(n) / electrode - Cell 15: electrode / Example 1(o) / electrode Electrodes = metallic lithium or stainless steel (b) Ionic conductivity

[0118] Electrochemical impedance spectroscopy was performed using a Bio-logic® VMP-300 system at an amplitude of 100 mV and a frequency range from 1 MHz to 200 mHz.

[0119] 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.

[0120] For example, LATP / fluorinated amide electrolyte (NMTFAm, 3.62 × 10 -4 The ionic conductivity in S / cm of LATP / non-fluorinated amide (DAEDAm, 9.29 × 10 -5 S / cm) and halloysite nanotube / NMTFAm (2.64 × 10 -5 It can be seen that the ionic conductivity at 20° C. is also generally higher for all electrolytes containing fluorinated amides compared to electrolytes without fluorinated amides. (c)Critical current density

[0121] The critical current density was evaluated using a Bio-logic® VMP-3 system. The test was performed at a current density of C / 24 (1C=3.0 mA / cm 2 ) and gradually increased. The same current density was applied to charge and discharge the battery.

[0122] FIG. 5 shows that cell 4, a symmetric Li / electrolyte / Li cell using the LATP / NMTFAm electrolyte from Example 1(d), achieved a maximum of 5 C (1 C=3.0 mA / cm) at 25° C. 2 The results are also summarized in Table 2 below. [Table 2-1] [Table 2-2] a. Polymer US'674, except for cell 9 where Polymer US'174 ​​was used. b.NM: Not measured c. The electrolyte also contains 15% by weight of 1,1'-hexamethylenebis(1-methylpyrrolidinium)bis(trifluoromethanesulfonyl)imide. (d) Electrochemical stability

[0123] To assess the electrochemical stability of the membrane prepared in Example 1(d), a solution containing 20 wt % carbon black (Ketjenblack™) was prepared.

[0124] 0.5 g LiTFSI, 0.77 g TEGDME, 0.44 g NMTFAm and 0.26 g Li 1.3 Al 0.3 Ti 1.7 (PO4)3(LATP) was mixed thoroughly in a flask at room temperature. Once a homogeneous dispersion was obtained, 0.67 g of polymer US'674, 0.01 g of azobisisobutyronitrile, and a dispersion of 0.528 g of carbon black in 6 mL of acetonitrile were added. After stirring for 1 hour 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 the film was then placed in an oven at 100°C under nitrogen for 10 minutes. A layer of electrolyte from Example 1(a) or Example 1(d) was coated onto the carbon film. The electrolyte layer was cured by UV irradiation under nitrogen for 3 minutes. A complete film for electrochemical stability measurements was thus obtained.

[0125] To assemble the coin cells, the membrane disks were cut with a diameter of 16 mm. The electrolyte side was covered with lithium foil. The cells thus formed, containing the membranes of Examples 1(a) and 1(d), respectively, are designated as Cell 8 and Cell 9.

[0126] Electrochemical stability was evaluated using a Bio-logic® VMP-3 system: the voltage was varied from 3.5 V to 5 V with an increment of 0.1 V every 2 h.

[0127] FIG. 6 shows the electrochemical stability for cell 9 containing the membrane prepared in Example 1(d) and for cell 8 containing the membrane prepared in Example 1(a).

[0128] In summary, the addition of N-methyltrifluoroacetamide (NMTFAm) to a composite electrolyte based on polymer US'674 and LATP (phosphate-type oxide ceramic) can significantly improve the ionic conductivity and stability at the Li / electrolyte interface at 25 °C (see Figure 1), and it can be observed that the oxidative stability reaches up to 4.5 V. This observation is supported by the ionic conductivity and critical current density (CCD) in symmetric cells containing the electrolyte compared to other ceramics or amides. (e) Complete cell assembly and performance

[0129] Complete cells using the electrolyte of Example 1(d) were assembled and their performance evaluated. (i) Cell: NMC811 / electrolyte / Li

[0130] The cathode contains 73.2% by weight of lithiated nickel manganese cobalt oxide (NMC811) active material, approximately 8 mg / cm 2 The electrolyte dispersion of Example 1(d) was directly coated onto the cathode and cured by UV irradiation for 3 minutes under nitrogen. The thickness of the electrolyte is approximately 40 μm. A lithium metal foil with a thickness of 50 μm was used as the anode. The thickness of the electrolyte is approximately 40 μm ... 2 A coin cell was assembled and its performance was evaluated.

[0131] The performance was evaluated on a Bio-Logic BCS-810 system at voltages of 2.75 to 4.2 V and C / 6 to 1 C (1 C = 1.2 mA / cm 2 ) at 45°C. The cell capacity was 4.4mAh (1.2mAh / cm 2 ) around.

[0132] FIG. 7 shows the cell capacity and coulombic efficiency as a function of cycle number. (ii) Cell LFP / electrolyte / Li

[0133] The LiFePO4 (LFP) cathode replaced NMC811 with LFP as the active material at a concentration of 70 wt%, approximately 12 mg / cm 2 The electrolyte dispersion of Example 1(d) was directly coated onto the cathode and cured under nitrogen by UV irradiation for 3 minutes. The thickness of the electrolyte is approximately 40 μm. A lithium metal foil with a thickness of 40 μm was used as the anode. The thickness of the electrolyte was approximately 40 μm ... 2 A coin cell was assembled and its performance was evaluated.

[0134] The performance was evaluated on a Bio-Logic BCS-810 system at voltages of 2 to 3.8 V and C / 6 to C / 6 (1 C = 1.2 mA / cm 2 ) at 45°C. The cell capacity was approximately 3mAh (0.8mAh / cm 2 )

[0135] FIG. 8 shows the galvanostatic charge and discharge curves at C / 6 charge and discharge rates.

[0136] Numerous modifications may be made to any of the above embodiments without departing from the scope of the invention as contemplated. All references, patents or scientific literature documents referred to in this application are incorporated herein by reference in their entirety for all purposes.

Claims

1. A composite material comprising inorganic particles, a fluorinated compound and optionally a polymer, wherein the fluorinated compound is represented by formula I: 【Chemistry 5】 [In the formula, R １ and R ２ represents independently at each occurrence an optionally substituted straight or branched chain C １～８ Alkyl group, optionally substituted C ３～８ Cycloalkyl group, optionally substituted C ６ Aryl group, optionally substituted C ３～８ Heterocycloalkyl groups and optionally substituted C ５～６ heteroaryl groups; X １ is selected from O and NH, or X １ does not exist, X ２ is C(O), S(O) ２ and Si(R ３ R ４ ), where R ３ and R ４ represents independently at each occurrence an optionally substituted straight or branched chain C １～８ is an alkyl group, or X ２ does not exist, Here, R １ , R ２ , R ３ and R ４ at least one of which is a group substituted with one or more fluorine atoms. A composite material.

2. -X １ does not exist, and X ２ But C(O), S(O) ２ and Si(R ３ R ４ ) or X 1 is selected from O and NH and X 2 is absent; or - X 1 and X 2 are absent; 2. The composite material of claim 1.

3. R １ is a group substituted by one or more fluorine atoms, preferably R 1 is a perfluorinated group and / or R 1 is a linear or branched C 1-8 alkyl group, or a linear or branched C 1-4 alkyl group, or a C 1-2 alkyl group.

4. R ２ is a group substituted by one or more fluorine atoms, preferably R 2 is a perfluorinated group, and / or R 2 is a linear or branched C 1-8 alkyl group, or a linear or branched C 1-4 alkyl group, or a C 1-2 alkyl group, or R 2 is an optionally substituted C 3-8 cycloalkyl group, or an optionally substituted C 3-6 cycloalkyl group, or an optionally substituted C 5-6 cycloalkyl group.

5. 2. The composite material of claim 1, wherein the compound is selected from N-methyltrifluoroacetamide (NMTFAm), N-methylpentapropionamide (NMPPPAm), N-cyclopentyltrifluoroacetamide (NCPTFAm), N-trifluoromethylsulfonyltrifluoroacetamide (NTFMSTFAm), N-trimethylsilyltrifluoroacetamide (NTMSTFAm) and bistrifluoroacetamide (BTFAm).

6. 6. The composite material of claim 1, 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, or 1% to 40% by weight, or 5% to 30% by weight, or 10% to 25% by weight, or 15% to 20% by weight.

7. 6. A composite material according to any one of claims 1 to 5, wherein the polymer is present, preferably the polymer is a crosslinked aprotic polymer and / or the polymer is a branched polymer, preferably of the multi-branched type.

8. 8. The composite material of claim 7, wherein the polymer comprises at least one polymer segment selected from ionically conductive segments polyethers, polythioethers, polyesters, polythioesters, polycarbonates, polythiocarbonates, polyimides, polysulfonimides, polyamides, polysulfonamides, polyphosphazenes, and ionically non-conductive segments polyacrylates, polymethacrylates, polystyrenes, polysiloxanes, polyurethanes, polyethylenes, polypropylenes, or copolymers or combinations of two or more thereof.

9. The polymer comprises at least one polymer segment comprising a block copolymer having at least two different repeat units to reduce the crystallinity of the crosslinked polymer, preferably the polymer segment comprises a block copolymer comprising, prior to crosslinking, at least one alkali metal or alkaline earth metal ion solvated segment and a crosslinkable segment comprising a crosslinkable unit, preferably said alkali metal or alkaline earth metal ion solvation segment having formula II: 【Chemistry 6】 [In the formula, R is selected from H, C 1 -C 10 alkyl, and —(CH 2 —O—R a R b ); R a is (CH 2 —CH 2 —O) y ; R b is a C 1 -C 10 alkyl group. and / or - said crosslinkable units comprise functional groups selected from acrylate, methacrylate, allyl, vinyl, hydroxide, epoxide, aldehyde, carboxylic acid, halophenyl, halobenzyl, alkyne, azide, amine, thiol and any combination thereof; 8. The composite material of claim 7.

10. 8. The composite material of claim 7, wherein the polymer is present in the composite material at a concentration in the range of 1 wt% to 80 wt%, 5 wt% to 70 wt%, or 10 wt% to 50 wt%, or 20 wt% to 40 wt%.

11. 6. The composite material according to claim 1 , wherein the inorganic particles comprise an inorganic compound of amorphous, ceramic or glass-ceramic type, such as an oxide, a sulfide or an oxysulfide, preferably the inorganic compound of amorphous, ceramic or glass-ceramic type is an oxide.

12. The inorganic particles are Al ２ O ３ , Mg ２ B ２ O ５ , Na ２ O・2B ２ O ３ , xMgO.yB ２ O ３ ・zH ２ O, TiO ２ , ZrO ２ , ZnO, Ti ２ O ３ , SiO ２ , Cr ２ O ３ , CeO ２ , B ２ O ３ , B ２ O, SrBi ４ Ti ４ O １５ , LLTO, LLZO, LAGP, LATP, Fe ２ O ３ , BaTiO ３ , γ-LiAlO ２ , molecular sieves and zeolites (e.g., aluminosilicates, mesoporous silica), sulfide ceramics (Li ７ P ３ S １１ and the like), glass-ceramics (e.g. LIPON, etc.) and other ceramics, and combinations thereof, preferably selected from Al 2 O 3 , Mg 2 B 2 O 5 , Na 2 O·2B 2 O 3 , xMgO·yB 2 O 3 ·zH 2 O, TiO 2 , ZrO 2 , ZnO, Ti 2 O 3 , SiO 2 , Cr 2 O 3 , CeO 2 , B 2 O 3 , B 2 O, SrBi 4 Ti 4 O 15 , LLTO, LLZO, LAGP, LATP, Fe 2 O 3 , BaTiO 3 , γ-LiAlO 2 6. The composite material of claim 1 , comprising a ceramic selected from: molecular sieves and zeolites (e.g., aluminosilicates, mesoporous silicas), glass-ceramics (e.g., LIPON, etc.), and combinations thereof.

13. 6. The composite material of claim 1, wherein the inorganic particles are in the form of one of spherical particles, rods, needles, nanotubes, or a combination thereof.

14. The inorganic particles are -formula: <h2 style=";text-align:left;direction:ltr">Li<h2 style=";text-align:left;direction:ltr"> １＋ｚ <h2 style=";text-align:left;direction:ltr"> Al<h2 style=";text-align:left;direction:ltr"> ｚ <h2 style=";text-align:left;direction:ltr"> 8<h2 style=";text-align:left;direction:ltr"> ２－ｚ <h2 style=";text-align:left;direction:ltr"> ((PO<h2 style=";text-align:left;direction:ltr"> ４ <h2 style=";text-align:left;direction:ltr"> )<h2 style=";text-align:left;direction:ltr"> ３ wherein M is Ti, Ge or a combination thereof, and z is such that 0<z<1, preferably z is in the range of 0.1 to 0.9, or 0.3 to 0.7, or 0.2 to 0.

4. or a compound selected from the group consisting of - Formula: Li 7-x La 3 Zr 2 M x x O 12 and Li 3y La (2 / 3)-y Ti 1-y' M y y' O 3 [In the formula, M x is selected from Al, Ga, Ta, Fe and Nb; M y is selected from Ba, B, Al, Si and Ta; x is such that 0≦x≦1; y is such that 0<y<0.67; y' is such that 0≦y'<1, Preferably, x is in the range of 0 to 0.5, and preferably x is zero and M x is absent. A compound selected from the compounds 6. The composite material of claim 1 , comprising:

15. 6. The composite material of any one of claims 1 to 5, wherein the inorganic particle content is in the range of from 1 wt% to 95 wt%, or from 5 wt% to 90 wt%, or from 5 wt% to 80 wt%, or from 5 wt% to 70 wt%, or from 5 wt% to 60 wt%, or from 5 wt% to 50 wt%, or from 5 wt% to 40 wt%, or from 5 wt% to 25 wt%, or from 5 wt% to 15 wt%.

16. 6. A composite material according to any one of claims 1 to 5, wherein the polymer is present and the composite material further comprises a plasticizer, preferably selected from glycol diether based liquids (such as tetraethylene glycol dimethyl ether (TEGDME)), carbonate esters, ionic liquids etc., preferably the plasticizer is present in the composite material at a concentration in the range of 0.1 wt.% to 50 wt.%, or 10 wt.% to 50 wt.%, or 20 wt.% to 40 wt.%.

17. The salt further comprises a salt, preferably the salt being a combination of a cation of an alkali metal or alkaline earth metal, preferably an alkali metal (preferably Li), and an anion such as hexafluorophosphate (PF 6 − ), bis(trifluoromethanesulfonyl)imide (TFSI − ), bis(fluorosulfonyl)imide (FSI − ), (fluorosulfonyl)(trifluoromethanesulfonyl)imide ((FSI)(TFSI) − ), 2-trifluoromethyl-4,5-dicyanoimidazolate (TDI − ), 4,5-dicyano-1,2,3-triazolate (DCTA − ), bis(pentafluoroethylsulfonyl)imide (BETI − ), difluorophosphate (DFP − ), tetrafluoroborate (BF 4 − ), bis(oxalato)borate (BOB − ), nitrate (NO 3 − ), chloride (Cl − ), or the like. ), bromide ion (Br − ), fluoride ion (F − ), perchlorate ion (ClO 4 − ), hexafluoroarsenate (AsF 6 − ), trifluoromethanesulfonate (SO 3 CF 3 − ) (Tf − ), fluoroalkylphosphate [PF 3 (CF 2 CF 3 ) 3 − ] (FAP − ), tetrakis(trifluoroacetoxy)borate [B(OCOCF 3 ) 4 ] − (TFAB − ), bis(1,2-benzenediolato(2-)-O,O′)borate [B(C 6 O 2 ) 2 ] − (BBB − ), difluoro(oxalato)borate (BF 2 (C 2 O 4 ) − ) (FOB − ), and the compounds of the formula BF 2 6. A composite material according to any one of claims 1 to 5, comprising an anion of O 4 R x - , where R x =C 2-4 alkyl, and one of the combinations thereof, such as LiTFSI or LiFSI.

18. A solid electrolyte comprising a layer of a composite material as defined in any one of claims 1 to 5.

19. - an anode, a cathode and a solid electrolyte, wherein at least one of the cathode, the anode and the electrolyte comprises a composite material as defined in any one of claims 1 to 5; or an anode, a cathode and a solid electrolyte, wherein the solid electrolyte and at least one of the anode and cathode comprise a composite material as defined in any one of claims 1 to 5.

1. An electrochemical cell comprising:

20. The positive electrode comprises a positive electrode material, optionally on a current collector, wherein the positive electrode material comprises a positive electrochemically active material, preferably the positive electrode electrochemically active material is selected from metal phosphates, lithiated metal phosphates, metal oxides and lithiated metal oxides, or the positive electrode electrochemically active material is selected from 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 (NMC, LiMnxCoyNizO2, etc., where x+y+z=1), Li(NiM'')O2 20. The electrochemical cell of claim 19, wherein M''' is Mn, Co, Al, Fe, Cr, Ti, Zr, or a combination thereof, elemental sulfur, selenium or iodine, iron (III) fluoride, copper (II) fluoride, lithium iodide, a carbon-based active material such as graphite, an organic cathode active material such as polyimide, poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl methacrylate) (PTMA), perylene-3,4,9,10-tetracarboxylate tetralithium (PTCLi 4 ), naphthalene-1,4,5,8-tetracarboxylic dianhydride (NTCDA), perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA), π-conjugated dicarboxylates and anthraquinones, or a combination of two or more of these materials if compatible with each other.

21. 21. The electrochemical cell of claim 20, wherein the positive electrode electrochemically active material is in the form of particles that are optionally coated (e.g., with a polymer, ceramic, carbon, or a combination of two or more thereof).

22. The material of the positive electrode is, for example, carbon black (e.g., Ketjenblack™ or Super P™), acetylene black (e.g. Shawinigan black or Denka™ black), graphite, graphene, carbon fibres or nanofibres (e.g. Vapor Grown Carbon Fibers (VGCF)), carbon nanotubes (e.g. Single Walled (SWNT), Multi Walled (MWNT)) or metal powder; and / or the positive electrode material further comprises a binder, preferably the binder being selected from a polymer as defined in claim 15, or a rubber-based binder (such as SBR (styrene-butadiene rubber), NBR (acrylonitrile-butadiene rubber), HNBR (hydrogenated NBR), CHR (epichlorohydrin rubber), ACM (acrylic rubber)) or a fluorinated polymer-based binder (such as PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), and combinations thereof), optionally including additives such as CMC (carboxymethyl cellulose); 21. The electrochemical cell of claim 20.

23. 21. The electrochemical cell of claim 20, wherein the material of the positive electrode further comprises a salt, inorganic particles of ceramic or glass type, or other suitable active material (e.g., sulfur), and / or the material of the positive electrode further comprises a composite material as defined in claim 1.

24. 20. The electrochemical cell of claim 19, wherein the negative electrode comprises a negative electrode electrochemically active material.

25. the negative electrode electrochemically active material comprises a metal film comprising an alkali metal or an alkaline earth metal, the metal film comprising: - Lithium containing less than 1000 ppm (or less than 0.1% by weight) of impurities, or - Lithium, alkali metals other than lithium (Na, K, Rb, Cs, etc.), alkaline earth metals (Mg, Ca, Sr, Ba, etc.), rare earth metals (Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, etc.), 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), said alloy preferably comprising at least 75% by weight of lithium, or between 85% and 99.9% by weight of lithium.

25. The electrochemical cell of claim 24, preferably comprising:

26. The electrochemically active material of the negative electrode is an intermetallic compound (e.g., SnSb, TiSnSb, Cu ２ Sb, AlSb, FeSb ２ , FeSn ２ and CoSn ２ ), metal oxides, metal nitrides, metal phosphides, metal phosphates (e.g., LiTi ２ (P.O. ４ ) ３ ), metal halides (e.g., metal fluorides), metal sulfides, metal oxysulfides, carbon (e.g., graphite, graphene, reduced graphene oxide, hard carbon, soft carbon, expanded graphite, and amorphous carbon), silicon (Si), silicon-carbon composites (Si—C), silicon oxide (SiO ｘ ), silicon oxide-carbon composite (SiO ｘ -C), tin (Sn), tin-carbon composite (Sn-C), tin oxide (SnO ｘ ), tin oxide-carbon composite (SnO ｘ -C), and, where compatible, combinations thereof, preferably said metal oxide is a compound of formula M'''' b O c , where M'''' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or combinations thereof; b and c are numbers such that the c:b ratio is in the range of 2 to 3 (e.g., MoO 3 , MoO 2 , MoS 2 , V 2 O 5 and TiNb 2 O 7 ), oxide spinels (e.g., NiCo 2 O 4 , ZnCo 2 O 4 , MnCo 2 O 4 , CuCo 2 O 4 and CoFe 2 O 4 ).

25. The electrochemical cell of claim 24, wherein the metal oxide is selected from 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 Li4Ti5O12) or lithium molybdenum oxide (such as Li2Mo4O13)).

27. 27. The electrochemical cell of claim 26, wherein the negative electrode electrochemically active material is in the form of particles that are optionally coated (e.g., with a polymer, ceramic, carbon, or a combination of two or more thereof).

28. The material of the negative electrode further comprises an electronically conductive material, for example comprising at least one of carbon black (e.g. Ketjenblack™ or Super P™), acetylene black (e.g. Shawinigan black or Denka™ black), graphite, graphene, carbon fibres or nanofibres (e.g. Vapor Grown Carbon Fibers (VGCF)), carbon nanotubes (e.g. Single Walled (SWNT), Multi-Walled (MWNT)) or metal powders, and / or the material of the negative electrode further comprises a binder, preferably the binder being a polymer as defined in claim 15, or 28. The electrochemical cell of claim 27, wherein the binder is selected from the group consisting of rubber-based binders (such as SBR (styrene-butadiene rubber), NBR (acrylonitrile-butadiene rubber), HNBR (hydrogenated NBR), CHR (epichlorohydrin rubber), ACM (acrylic rubber)) and fluorinated polymer-based binders (such as PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), and combinations thereof), and optionally includes additives such as CMC (carboxymethyl cellulose).

29. 28. The electrochemical cell of claim 27, wherein the material of the negative electrode further comprises a salt, inorganic particles of ceramic or glass type, or other suitable active material, and / or the material of the negative electrode further comprises a composite material as defined in claim 1.

30. 20. An electrochemical accumulator comprising at least one electrochemical cell as defined in claim 19, preferably said electrochemical accumulator being a lithium battery or a lithium ion battery.

31. 31. Use of an electrochemical accumulator battery according to claim 30 in a mobile device, such as a mobile phone, a camera, a tablet or a laptop, in an electric or hybrid vehicle or in renewable energy storage.

32. 6. A method for preparing a composite material as defined in any one of claims 1 to 5, comprising the step of mixing said inorganic particles, said fluorinated compound and optionally said polymer, said mixing step preferably comprising said polymer and optionally a crosslinking agent, preferably said mixing step comprising said crosslinking agent, said method further comprising a polymer crosslinking step.

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