Classifications

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• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
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  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
  • C08K5/109—Esters; Ether-esters of carbonic acid, e.g. R-O-C(=O)-O-R
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  • C08K5/00—Use of organic ingredients
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  • C08K5/21—Urea; Derivatives thereof, e.g. biuret
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  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/43—Compounds containing sulfur bound to nitrogen
  • C08K5/435—Sulfonamides
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  • C08K5/00—Use of organic ingredients
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  • C08K5/544—Silicon-containing compounds containing nitrogen
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  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
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  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• • H—ELECTRICITY
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
  • H01M10/0562—Solid materials
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/362—Composites
  • H01M4/366—Composites as layered products
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  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
• • H—ELECTRICITY
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
  • H01M4/40—Alloys based on alkali metals
  • H01M4/405—Alloys based on lithium
• • H—ELECTRICITY
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
  • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
• • H—ELECTRICITY
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/621—Binders
  • H01M4/622—Binders being polymers
• • H—ELECTRICITY
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  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/624—Electric conductive fillers
  • H01M4/625—Carbon or graphite
• • H—ELECTRICITY
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  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
  • H01M2004/027—Negative electrodes
• • H—ELECTRICITY
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  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
  • H01M2004/028—Positive electrodes
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  • H01M2300/00—Electrolytes
  • H01M2300/0017—Non-aqueous electrolytes
  • H01M2300/0065—Solid electrolytes
  • H01M2300/0068—Solid electrolytes inorganic
• • H—ELECTRICITY
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M2300/00—Electrolytes
  • H01M2300/0088—Composites
  • H01M2300/0091—Composites in the form of mixtures
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the present application relates to polymer-ceramic composite electrolytes comprising an organic additive, to their manufacturing processes and to the electrochemical cells comprising them.
• Lithium ion-conducting polymer electrolytes enable the development of safer and more affordable manufacturing processes that are easily scaled up for large format all-solid-state batteries (for example, see US patent number 6,903,174) .
• the low ionic conductivity limits its application at room temperature and results in relatively low charge/discharge rates compared to conventional lithium-ion batteries.
• solid inorganic electrolytes are promising candidates for solid state batteries, as they provide higher lithium ion conductivity which is comparable to liquid electrolytes.
• the unique ion conduction property of inorganic electrolytes enables lower concentration polarization at the interface of metallic lithium and enables high speed battery charging and discharging.
• complete cells using solid ceramic electrolytes suffer from poor electrochemical performance due to significant interface resistance at the cell boundaries.
• grains of the ceramic particles and between the particles of the composite electrodes made up of a mixture of particles of active material, carbon additive and solid electrolyte.
• the conduction of Li + ions must be carried out in particle-to-particle mode, the electrochemical performance is limited by the poor distribution of the solid electrolyte particles as well as by the existence of a vacuum between the particles.
• Electrochemical instability problems can also be encountered with these composite electrolytes, in particular at the interface between the electrolyte layer and one of the electrodes, for example a metallic lithium electrode.
• these composite electrolytes in particular at the interface between the electrolyte layer and one of the electrodes, for example a metallic lithium electrode.
• they still face different challenges in terms of ionic conductivity, electrochemical stability and interfacial interactions.
• 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:
• R 1 and R 2 are independently selected at each occurrence from an optionally substituted linear or branched C1-ealkyl group, an optionally substituted C3-ecycloalkyl group, an optionally substituted Cearyl group, an optionally substituted C3-8 heterocycloalkyl group, and an optionally substituted C5- optionally substituted 6heteroaryl;
• X 1 is selected from O and NH or X 1 is absent;
• X 2 is selected from C(O), S(0)2, and Si(R 3 R 4 ), where R 3 and R 4 are independently at each occurrence an optionally substituted linear or branched Ci-salkyl group, or X 2 is absent; wherein at least one of R 1 , R 2 , R 3 and R 4 is a group substituted by one or more fluorine atoms.
• X 1 is absent and X 2 is chosen from C(O), S(0)2, and Si(R 3 R 4 ), or X 1 is chosen from O and NH and X 2 is absent , or else X 1 and X 2 are both absent.
• R 1 is a group substituted by one or more fluorine atoms, for example, R 1 can be a perfluorinated group.
• R 1 is a linear or branched C1-ealkyl group, or a linear or branched C1-4alkyl group, or a C1-2alkyl group.
• R 2 is a group substituted by one or more fluorine atoms, for example, R 2 can be a perfluorinated group.
• R 2 is a linear or branched Ci-salkyl group, or a linear or branched Ci-4alkyl group, or a Ci-2alkyl group.
• R 2 is an optionally substituted C3-8cycloalkyl group, or an optionally substituted C3-6cycloalkyl group, or an optionally substituted C5-6cycloalkyl group.
• the fluorinated compound is chosen from the compounds /V-methyltrifluoroacetamide (NMTFAm), /V-methylpentaproprionamide (NMPPPAm), /V-cylcopentyltrifluoroacetamide (NCPTFAm), N-trifluoromethylsulfonyl trifluoroacetamide (NTFMSTFAm), /V-trimethylsilyl trifluoroacetamide (NTMSTFAm), and bistrifluoroacetamide (BTFAm).
• NMTFAm /V-methyltrifluoroacetamide
• NMPPPAm /V-methylpentaproprionamide
• NCPTFAm /V-cylcopentyltrifluoroacetamide
• NFMSTFAm N-trifluoromethylsulfonyl trifluoroacetamide
• NTMSTFAm /V-trimethylsilyl trifluoroacetamide
• BTFAm bistrifluoroace
• 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 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.
• the polymer is present and may be a cross-linked aprotic polymer and/or a branched polymer, preferably of the multi-branched type.
• the polymer comprises at least one polymer segment chosen from polyether ionic conductive segments, 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.
• 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.
• blocks comprising at least one alkali or alkaline earth metal ion solvating segment and a crosslinkable segment comprising crosslinkable units.
• the alkali or alkaline-earth metal ion solvating segment is chosen from homo- and copolymers comprising repeating units of Formula II:
• R is selected from F1, C1-C10alkyl, and -(CFte-O-RaRb);
• Ra is (CH 2 -CH 2 -0)y; and Rb is a C1-C10alkyl group.
• the crosslinkable units comprise functional groups chosen from acrylates, methacrylates, allyls, vinyls, hydroxides, epoxides, aldehydes, carboxylic acids, halophenyls, halobenzyls, alkynes, azides, amines, thiols and one of their combinations.
• 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 from 20% to 40% by weight.
• the inorganic particles comprise an inorganic compound of the amorphous, ceramic or glass-ceramic type, for example, oxide, sulphide or oxysulphide.
• the inorganic compound of the amorphous, ceramic or glass-ceramic type is an oxide.
• the inorganic particles comprise a ceramic chosen from Al2O3, Mg2B2Os, Na20-2B2C>3, xMg0 yB203-zH20, T1O2, ZrO2, ZnO, T12O3, S1O2, Cr 2 0 3 , Ce0 2 , B2O3, B2O, SrBUTUOis, LLTO, LLZO, LAGP, LATP, Fe 2 0 3 , BaTiO3, Y-L1AIO2, molecular sieves and zeolites (e.g.
• the ceramic is chosen from Al2O3, Mg2B20s, Na20-2B2C>3, xMg0 yB203-zH20, T1O2, ZrO2, ZnO, T12O3, S1O2, Cr203, Ce02, B2O3, B2O, SrBUTUOis, LLTO, LLZO, LAGP, LATP , Fe 2 0 3 , BaTiOs, Y-UAIO2, molecular sieves and zeolites (for example, aluminosilicate, mesoporous silica), glass-ceramics (such as LIPON, etc.), as well as their combinations.
• the ceramic is chosen from Al2O3, Mg2B20s, Na20-2B2C>3, xMg0 yB203-zH20, T1O2, ZrO2, ZnO, T12O3, S1O2, Cr203, Ce02, B2O3, B2O, SrBUTUOis, LLTO,
• the inorganic particles are in the form of spherical particles, rods, needles, nanotubes, or one of their combinations.
• the inorganic particles comprise a compound chosen from the compounds of formula Lii+ z Al z M2-z (P0 4 ) 3, where M is Ti, Ge or a combination thereof, and 0 ⁇ z ⁇ 1 , for example, z possibly being in the range of 0.1 to 0.9, or 0.3 to 0.7, or 0.2 to 0.4.
• the inorganic particles comprise a compound selected from compounds of formula L17- x La3Zr2lVl x xOi2 and Li3yLa(2/3)-yTii- y M y y 03 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 £; y is such that 0 ⁇ y ⁇ 0.67; and y' is such that 0 ⁇ y' ⁇ 1 .
• x can be in the range 0 to 0.5, or x is zero and M x is absent.
• 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 from 5% to 60% by weight, or from 5% to 50% by weight, or from 5% to 40% by weight, or from 5% to 25% by weight, or from 5% at 15% by weight.
• the composite material comprises the polymer and in addition a plasticizer.
• the plasticizer can be chosen from liquids of glycol diether types (such as tetraethylene glycol dimethyl ether (TEGDME)), carbonate esters, ionic liquids, and the like.
• the plasticizer 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% at 40% by weight.
• the composite material further comprises a salt.
• the salt can comprise a cation of an alkali or alkaline-earth metal, preferably an alkali metal (preferably Li), and an anion chosen from hexafluorophosphate (PF6), bis(trifluoromethanesulfonyl)imide (TFSI) anions , 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-), nit
• PF6
• this document relates to a solid electrolyte comprising a layer of the composite material as defined here.
• the present technology relates to an electrochemical cell comprising a negative electrode, a positive electrode, and a solid electrolyte, in which at least one of the positive electrode, the negative electrode and the electrolyte comprises a material composite as defined here.
• the electrochemical cell comprises a negative electrode, a positive electrode, and a solid electrolyte, in which the solid electrolyte is as defined herein.
• the solid electrolyte is as defined here and at least one of the negative electrode and the positive electrode comprises a composite material as defined here.
• 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.
• the positive electrode electrochemically active material is chosen from metal phosphates, lithiated metal phosphates, metal oxides, and lithiated metal oxides.
• M'PC
• the positive electrode material further comprises an electronically conductive material, for example, comprising at least one of carbon blacks (for example, KetjenblackTM or Super PTM), acetylene blacks (e.g., Shawinigan black in DenkaTM black), graphite, graphene, carbon fibers or nanofibers (e.g., gas-phase formed carbon fibers (VGCFs)), carbon nanotubes (e.g., single-walled ( SWNT), multi-wall (MWNT)) or metal powders.
• carbon blacks for example, KetjenblackTM or Super PTM
• acetylene blacks e.g., Shawinigan black in DenkaTM black
• graphite graphene
• carbon fibers or nanofibers e.g., gas-phase formed carbon fibers (VGCFs)
• VGCFs gas-phase formed carbon fibers
• SWNT single-walled
• MWNT multi-wall
• the positive electrode material further comprises a binder, for example, the binder is a polymer as defined above, or a binder chosen from rubber-type binders (such as SBR (styrene rubber - butadiene), NBR (acrylonitrile-butadiene rubber), HNBR (hydrogenated NBR), CHR (epichlorohydrin rubber), ACM (acrylate rubber)), or fluorinated polymer type binders (such as PVDF (polyvinylidene fluoride ), PTFE (polytetrafluoroethylene), and their combinations), optionally comprising an additive such as CMC (carboxymethylcellulose).
• the positive electrode material further comprises a salt, inorganic particles of the ceramic or glass type, or even other compatible active materials (for example, sulfur), and/or the material positive electrode further comprises the composite material defined here.
• the negative electrode of the electrochemical cell comprises a negative electrode electrochemically active material.
• the negative electrode electrochemically active material comprises a metal film comprising an alkali or alkaline-earth metal.
• the metallic film comprises lithium comprising less than 1000 ppm (or less than 0.1% by mass) of impurities.
• the metal film comprises an alloy of lithium and an element chosen from alkali metals other than lithium (such as Na, K, Rb, and Cs), alkaline-earth metals (such as Mg, Ca, Sr, and Ba), rare earth metals (such as 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.
• the alloy comprising at least 75% by weight of lithium, or between 85% and 99, 9% by mass of lithium.
• the negative electrode electrochemically active material comprises an intermetallic compound (eg, SnSb, TiSnSb, Cu2Sb, AlSb, FeSb2, FeSn2, and CoSn2), a metal oxide, a metal nitride, a phosphide metal, metal phosphate (e.g., LiT2(P04)3), metal halide (e.g., metal fluoride), metal sulfide, metal oxysulfide, carbon (e.g., graphite , graphene, reduced graphene oxide, hard carbon, soft carbon, exfoliated graphite and amorphous carbon), silicon (Si), silicon-carbon composite (Si-C), silicon oxide ( SiOx), silicon oxide-carbon composite (SiOx-C), tin (Sn), tin-carbon composite (Sn-C), tin oxide (SnOx), tin oxide composite -carbon (SnOx-C), and their combinations, when compatible
• the metal oxide is chosen 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 TiNb207), the spinel oxides (e.g., N1C02O4, ZnCo204,
• MnCo 2 0 4 , CUC02O4, and CoFe 2 0 4 and LiM . O (where M . is Ti, Mo, Mn, Ni, Co, Cu,
• the electrochemically active negative electrode material is in the form of optionally coated particles (eg, polymer, ceramic, carbon, or a combination of two or more thereof).
• the negative electrode material further comprises an electronically conductive material, for example, comprising at least one of carbon blacks (eg, KetjenblackTM or Super PTM), acetylene blacks (e.g., Shawinigan Black in DenkaTM Black), graphite, graphene, carbon fibers or nanofibers (e.g., gas-phase formed carbon fibers (VGCFs)), carbon nanotubes (e.g., single-walled (SWNTs) ), multi-wall (MWNT)) or metal powders.
• carbon blacks eg, KetjenblackTM or Super PTM
• acetylene blacks e.g., Shawinigan Black in DenkaTM Black
• graphite graphene
• carbon fibers or nanofibers e.g., gas-phase formed carbon fibers (VGCFs)
• SWNTs single-walled
• MWNT multi-wall
• the negative electrode material further comprises a binder
• the binder is a polymer as defined above, or a binder chosen from rubber type binders (such as SBR (rubber styrene-butadiene rubber), NBR (acrylonitrile-butadiene rubber), HNBR (hydrogenated NBR), CHR (epichlorohydrin rubber), ACM (acrylate rubber)), or fluorinated polymer type binders (such as PVDF (fluoride polyvinylidene), PTFE (polytetrafluoroethylene), and their combinations), optionally comprising an additive such as CMC (carboxymethylcellulose).
• rubber type binders such as SBR (rubber styrene-butadiene rubber), NBR (acrylonitrile-butadiene rubber), HNBR (hydrogenated NBR), CHR (epichlorohydrin rubber), ACM (acrylate rubber)
• fluorinated polymer type binders such as PVDF (fluoride poly
• the negative electrode material further comprises a salt, inorganic particles of ceramic or glass type, or other compatible active materials, and/or the composite material as defined here.
• the present technology relates to an electrochemical accumulator comprising at least one electrochemical cell as defined here.
• the electrochemical accumulator is a lithium battery or a lithium-ion battery.
• this document relates to the use of an electrochemical accumulator as defined here, in portable devices, for example mobile telephones, cameras, tablets or portable computers, in electric vehicles or hybrids, or in the storage of renewable energy.
• the present technology also relates to a method for preparing a composite material as defined here, comprising a step of mixing the inorganic particles, the fluorinated compound, and optionally the polymer.
• the mixing step comprises the polymer and optionally a crosslinking agent.
• the mixing step comprises the polymer and the crosslinking agent and the method further comprises a polymer crosslinking step.
• Figure 1 shows the results of infrared spectroscopy: (a) LATP; (b) NMTFAm; (c) DAEDAm; (d) NMTFAm/LATP mixture; and (e) DAEDAm/LATP mixture.
• Figure 2 shows the solid state NMR results: (a) 1 H NMTFAm and NMTFAm/LATP mixture; (b) 6Li of LATP; (c) 6Li of the NMTFAm/LATP mixture.
• Figure 3 shows the Young's modulus of the membrane prepared in Example 1(d).
• Figure 4 shows the ionic conductivity versus temperature results in (a) for Cells 1-6 and 8-15; and in (b) for Cell 7 compared to LATP powder.
• Figure 5 presents the potential as a function of time for Cell 4 cycled at current densities ranging from C/3 to 5C.
• 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).
• Figure 8 shows the C/6 galvanostatic charge and discharge curves of an LFP/Li cell as a function of the number of cycles according to Example 3(e)(ii).
• the fluorinated amide is a compound of Formula I:
• R 1 and R 2 are independently selected at each occurrence from an optionally substituted linear or branched C1-ealkyl group, an optionally substituted C3-scycloalkyl group, an optionally substituted Cearyl group, an optionally substituted C3-8 heterocycloalkyl group, and an optionally substituted C5- optionally substituted 6heteroaryl;
• X 1 is selected from O and NH or X 1 is absent;
• X 2 is selected from C(O), S(0)2, and Si(R 3 R 4 ), where R 3 and R 4 are independently at each occurrence an optionally substituted linear or branched Ci-salkyl group, or X 2 is absent; wherein at least one of R 1 , R 2 , R 3 and R 4 is a group substituted by one or more fluorine atoms.
• X 1 is absent and X 2 is chosen from C(O), S(0)2, and Si(R 3 R 4 );
• - X 1 is chosen from O and NH and X 2 is absent;
• R 1 is a group substituted by one or more fluorine atoms, for example, a perfluorinated group.
• This group can be a linear or branched C1-salkyl group, or a linear or branched C1-4alkyl group, or else a C1-2alkyl group.
• the R 2 group can be a group substituted by one or more fluorine atoms, for example a perfluorinated group.
• This group can be a Ci-salkyl group linear or branched, or a linear or branched C1-4alkyl group, or a C1-2alkyl group.
• R 2 can be an optionally substituted C3-8cycloalkyl group, or an optionally substituted C3-6cycloalkyl group, or an optionally substituted C5-6cycloalkyl group.
• 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).
• NMTFAm N-methyltrifluoroacetamide
• NMPPPAm /V-methylpentaproprionamide
• NCPTFAm /V-cylcopentyltrifluoroacetamide
• NFMSTFAm /V-trifluoromethylsulfonyl trifluoroacetamide
• NTMSTFAm /V-trimethylsilyl trifluoroacetamide
• BTFAm bistrifluor
• 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.
• the polymer when it is present in the composite material, may comprise at least one polymer segment chosen from ionic conductor segments of the polyether, polythioether, polyester, polythioester, polycarbonate, polythiocarbonate, polyimide, polysulfonimide, polyamide, polysulfonamide, polyphosphazene, or from polyacrylate, polymethacrylate, polystyrene, polysiloxane, polyurethane, polyethylene, polypropylene ionically non-conductive segments.
• the polymer can 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 can be a random, random, alternating, block, etc. copolymer.
• the polymer is preferably a cross-linked aprotic polymer and/or a branched polymer, preferably of the multi-branched type (star, comb configuration, etc.).
• the polymer includes at least one polymer segment comprising a block copolymer with at least two different repeating units to reduce the crystallinity of the crosslinked polymer.
• the polymer segment can comprise, before crosslinking, a block copolymer comprising at least one an 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:
• R is selected from F1, C1-C10alkyl, and -(CFte-O-RaRb);
• Ra is (CH2-CH 2 -0) y ;
• Rb is a Ci-Cioalkyl group.
• Non-limiting examples of crosslinkable units include functional groups chosen from acrylates, methacrylates, allyls, vinyls, hydroxides, epoxides, aldehydes, carboxylic acids, halophenyls, halobenzyls, alkynes, azides, amines, thiols and one of their combinations.
• the composite material comprises the crosslinked polymer, where the crosslinkable group has been converted into its crosslinked version.
• the concentration of the polymer in the composite material can 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 % in weight.
• the inorganic particles preferably comprise an inorganic compound of the amorphous, ceramic or glass-ceramic type, for example, oxide, sulphide or oxysulphide, preferably an oxide.
• the inorganic compound may or may not be ionically conductive, preferably ionically conductive.
• Non-limiting examples of inorganic compounds include the compounds or ceramics Al2O3, Mg2B20s, Na20-2B2C>3, xMg0 yB2C>3 zH20, T1O2, Zr0 2 , ZnO, T12O3, S1O2, Cr 2 0 3 , Ce0 2 , 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 their combinations, preferably chosen from Al2O3, Mg2B20s, Na20-2B2C>3, xMgO 7B2O3 zhteO, T1O
• the inorganic particles comprise a compound chosen from compounds of formula Lii+ z Al z M2-z(P0 4 )3, where M is Ti, Ge or a combination thereof, and 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 from 0.2 to 0.4.
• the inorganic particles comprise a compound chosen from the compounds of formulas LÎ7-xLa3Zr2M x x Oi2 and Li3yLa(2/3)-yTii- y M y y 03 in which M x is chosen 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; and y' is such that 0
• 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 0 and M y is absent.
• the content of inorganic particles in the composite material can range from 1% to 95% by weight, or from 5% to 90% by weight, or from 5% to 80% by weight, or from 5% to 70% by weight, or from 5% to 60% by weight, or from 5% to
• the composite material comprises the polymer and a plasticizing agent.
• plasticizing agents include glycol diether type liquids (such as tetraethylene glycol dimethyl ether (TEGDME)), carbonate esters, ionic liquids, and the like.
• TEGDME tetraethylene glycol dimethyl ether
• the plasticizer concentration 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% in weight.
• 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.
• 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.
• 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)imi
• This 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 here.
• the mixing step of the process can therefore include the polymer and optionally a crosslinking agent.
• the mixing step of such a process can then be followed by a crosslinking step.
• the composite material can enter into the composition of a layer of solid electrolyte or of an electrode material.
• the electrolyte comprises the composite material as defined here in a solid layer.
• This layer can be formed by mixing, in any order, inorganic particles, electrolyte polymer or precursor thereof, fluorinated amide, and optionally solvent, plasticizer and/or salt, and spreading the mixture on a stand.
• Support may be temporary (such as stainless steel, polypropylene, etc.) and removed prior to assembly with the rest of the electrochemical cell.
• the support can also be the surface of an electrode material, which will have been prepared beforehand.
• the spread layer is treated in order to polymerize or crosslink the polymer, for example, by heat treatment, by irradiation (such as by UV, microwaves, gamma rays, X-rays, beam of 'electrons), or a combination of the two, optionally in the presence of an initiator.
• irradiation such as by UV, microwaves, gamma rays, X-rays, beam of 'electrons
• the material is preferably dried, for example, before crosslinking or assembling with the other components of the electrochemical cell.
• 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.
• the positive electrode material generally comprises an electrochemically active material and can be self-supporting or applied to a current collector.
• the positive electrode electrochemically active material may, inter alia, be chosen from metal phosphates, lithiated metal phosphates, metal oxides, and lithiated metal oxides.
• the positive electrode electrochemically active material is preferably in the form of optionally coated particles (eg, polymer, ceramic, carbon or a combination of two or more thereof).
• the electrode material may further comprise an electronically conductive material, for example, comprising at least one of carbon blacks (eg, KetjenblackTM or Super PTM), acetylene blacks (eg, Shawinigan black in DenkaTM black), graphite, graphene, carbon fibers or nanofibers (e.g., gas-phase formed carbon fibers (VGCFs)), carbon nanotubes (e.g., single-walled (SWNT), multi-walled ( MWNT)) or metal powders.
• carbon blacks eg, KetjenblackTM or Super PTM
• acetylene blacks eg, Shawinigan black in DenkaTM black
• graphite graphene
• carbon fibers or nanofibers e.g., gas-phase formed carbon fibers (VGCFs)
• SWNT single-walled
• MWNT multi-walled
• 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.
• the positive electrode material does not include the composite material
• the latter may include the electrochemically active material as defined here, a binder and optionally an electronic conductive material and/or a salt as defined here.
• 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). Certain binders, such as those of the rubber type, may also include an additive such as CMC (carboxymethylcellulose).
• CMC carboxymethylcellulose
• additives may also be present in the positive electrode material, such as inorganic particles of the ceramic or glass type, or even other compatible active materials (for example, sulfur).
• the negative electrode comprises a negative electrode electrochemically active material which may be formed from a metal film, for example, comprising an alkali or alkaline earth metal.
• the metallic film consists of lithium comprising less than 1000 ppm (or less than 0.1% by mass) of impurities.
• the metallic film comprises an alloy of lithium and of an element chosen from alkali metals other than lithium (such as Na, K, Rb, and Cs), alkaline-earth metals (such as Mg, Ca, Sr, and Ba), rare earth metals (such as 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.
• 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
• the alloy may comprise at least 75% by weight lithium, or between 85% and 99.9% by weight lithium.
• negative electrode electrochemically active material examples include an intermetallic compound (e.g., SnSb, TiSnSb, Cu2Sb, AlSb, FeSb2, FeSn2, and CoSn2), metal oxide, metal nitride, metal phosphide, metal phosphate (eg, LiT2(PO4)3), metal halide (eg, metal fluoride), metal sulfide, metal oxysulfide, carbon (eg, graphite, graphene , reduced graphene oxide, hard carbon, soft carbon, exfoliated graphite and amorphous carbon), silicon (Si), silicon-carbon composite (Si-C), silicon oxide (SiOx), a silicon oxide-carbon composite (SiOx-C), tin (Sn), a tin-carbon composite (Sn-C), a tin oxide (SnOx), an oxide composite tin-carbon (SnOx-C), and combinations thereof, when compatible.
• intermetallic compound
• the metal oxide can be selected from compounds of formula M””bOc (where M”” is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination of these; and b and c are numbers such that the ratio c:b is in the range from 2 to 3) (for example, M0O3, M0O2, M0S2, V2O5, and TiNb2C>7), the oxides spinels
• M. is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination thereof
• lithium titanate such as LUTisO4
• lithium molybdenum oxide such as U2MO4O13
• the negative electrode when it is not in the form of a metallic film, it instead comprises particles of an electrochemically active negative electrode material optionally coated (e.g., polymer, ceramic, carbon or a combination of two or more of these).
• the negative electrode material may also include 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 of the ceramic or glass type, or other compatible active materials).
• an electrochemical accumulator comprising at least one electrochemical cell as defined here.
• the electrochemical accumulator is a lithium or lithium-ion battery.
• the electrochemical accumulators of the present application are intended for use in portable devices, for example mobile telephones, cameras, tablets or portable computers, in electric or hybrid vehicles, or in the renewable energy storage.
• crosslinkable polymers used in the examples which follow are polyethers comprising crosslinkable units, as described in United States Patent No. 7,897,674 (referred to below as “polymer US'674", which is a branched polymer of the multibranched type comprising crosslinkable units) or in U.S. Patent No. 6,903,174 (referred to below as “polymer US'174", which is linear and includes pendant crosslinkable groups).
• LiTFSI lithium bis(trifluoromethanesulfonyl)imide
• US'674 polymer 0.08 g of Irgacure MC
• LiTFSI LiTFSI
• TEGDME tetraethylene glycol dimethyl ether
• DAEDAm L/,/V-diacetylethylenediamine
• HNT Halloysite nanotubes
• 0.5g of LiTFSI, 0.69g of TEGDME, 0.44g of N-methyltrifluoroacetamide (NMTFAm) and 0.26g of HNT are mixed well in a flask at room temperature. Once a homogeneous dispersion has been obtained, 0.67 g of US'674 polymer and 0.01 g of Irgacure MC are added. After 1 hour of stirring at room temperature, the dispersion is coated on a thin stainless steel sheet. The composite electrolyte membrane thus obtained is hardened by UV irradiation under nitrogen for 3 minutes.
• LiTFSI LiTFSI
• TEGDME 0.77g of TEGDME
• NMTFAm 0.26g of Li1,3Alo,3Ti1,7(PO4)3 (LATP)
• 0.67 g of US'674 polymer and 0.01 g of Irgacure MC are added. After 1 hour of stirring at room temperature, the dispersion is coated on a thin stainless steel sheet. The composite electrolyte membrane thus obtained is hardened by UV irradiation under nitrogen for 3 minutes.
• LiTFSI 0.5g LiTFSI, 0.77g TEGDME, 0.25g DAEDAm and 0.24g LATP are mixed well in a flask at room temperature. Once a homogeneous dispersion has been obtained, 0.75 g of US'674 polymer and 0.01 g of Irgacure MC are added. After 1 hour of stirring at room temperature, the dispersion is coated on a thin stainless steel sheet. The composite electrolyte membrane thus obtained is hardened by UV irradiation under nitrogen for 3 minutes.
• LiTFSI, 0.77g TEGDME, 0.44g NMTFAm and 0.26g L17La3Zr2012 (LLZO) are mixed well in a flask at room temperature.
• 0.67 g of US'674 polymer and 0.01 g of Irgacure MC are added. After 1 hour of stirring at room temperature, the dispersion is coated on a thin sheet of stainless steel. The composite electrolyte membrane thus obtained is hardened by UV irradiation under nitrogen for 3 minutes.
• LiTFSI, 0.77g TEGDME, 0.44g NMTFAm and 0.26g LATP are mixed well in a flask at room temperature. Once a homogeneous dispersion has been obtained, 0.67 g of US'174 polymer and 0.01 g of Irgacure MC are added. After 1 hour of stirring at room temperature, the dispersion is coated on a thin stainless steel sheet. The composite electrolyte membrane thus obtained is hardened by UV irradiation under nitrogen for 3 minutes.
• 0.5g LiTFSI, 0.77g TEGDME, 0.44g N-trimethylsilyl trifluoroacetamide (NTMSTFAm) and 0.26g LATP are mixed well in a flask at room temperature. Once a homogeneous dispersion has been obtained, 0.67 g of US'674 polymer and 0.01 g of Irgacure MC are added. After 1 hour of stirring at room temperature, the dispersion is coated on a thin stainless steel sheet. The composite electrolyte membrane thus obtained is hardened by UV irradiation under nitrogen for 3 minutes.
• 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.
• Figure 2(a) shows that the signals from NMTFAm are broader than those from the NMTFAm/LATP mixture, indicating an interaction between NMTFAm and LATP that significantly decreases the molecular mobility restriction in NMTFAm. Also, a shift of the peak corresponding to the NH protons of NMTFAm to a higher frequency may indicate that more NH protons in the mixture are involved in hydrogen bonds.
• Figure 2(c) shows that an additional signal at 1.2 ppm appeared in the 6 Li NMR spectrum of the mixture after 1 day of storage compared to Figure 2(b), indicating that new Li + ions have were generated by the interaction between NMTFAm and LATP.
• Example 1(d) The ionic diffusion coefficient of the various elements of the membrane prepared in Example 1(d) was evaluated by pulsed-field gradient solid-state NMR spectroscopy of the 1 H, 7 Li, and 19 F nuclei.
• the NMR experiments were carried out on a 500 MHz NMR spectrometer equipped with a Diff50 MC probe and 7 Li -19 F and 1 H -19 F double resonance RF insertions.
• the measurements were carried out 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 core.
• the strength of the gradient was varied in 16 steps from 100 G/cm to 2500 G/cm.
• Diffusion measurements were accompanied by T2 relationship experiments using a CPMG pulse sequence with echo delay of 0.06 to 0.6 ms. Up to 64 echoes were collected per experiment. The results are presented in Table 1. Table 1. Diffusion coefficients measured by NMR spectroscopy
• the diffusion coefficients of Li in LATP at 25 and 50°C correspond to the values obtained with other samples containing LATP. This observation confirms that the diffusion of lithium in LATP is not dependent on the LATP particles surrounded by polymer, in particular considering that the mean square displacement of the species during the NMR experiment is approximately 0.5 to 1 pm (much smaller than the particle size of LATP which is about 10 pm).
• Cell 1 Electrode/Example 1 (a)/Electrode
• Cell 2 Electrode/Example 1 (b)/Electrode
• 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
• Electrode Metallic Lithium or Stainless Steel (b) Ion Conductivity Electrochemical impedance spectroscopy was performed with a Bio- logic® VMP-300 system at an amplitude of 100 mV and the frequency range of 1 MHz to 200 mHz.
• Figures 4(a) and 4(b) show the ionic conductivity results for Cells 1 through 15. Conductivity results at 50°C and 25°C are also shown in Table 2 below.
• the ionic conductivity in the electrolyte LATP/fluorinated amide (NMTFAm, 3.62 x 10 4 S/cm) at 20° C. is much higher than that of non-fluorinated LATP/amide (DAEDAm , 9.29 x 10 5 S/cm) and Halloysite nanotubes/NMTFAm (2.64 ⁇ 10 5 S/cm).
• the ionic conductivity at 20°C is also generally higher for all electrolytes comprising a fluorinated amide compared to the electrolyte without fluorinated amide.
• Table 2 The results are also summarized in Table 2 below.
• Electrolyte composition (% by weight) and results of Cells 1 to 15 has. US'674 polymer except Cell 9, where US'174 polymer was used. b. NM: not measured c.
• the electrolyte also comprises 15% by weight of bis(trifluoromethanesulfonyl)imide of 1,1'-hexamethylene bis(l-methylpyrrolidinium).
• LiTFSI LiTFSI
• TEGDME 0.77g of TEGDME
• NMTFAm 0.26g of Lii,3Alo,3Tii,7(PC>4)3 (LATP)
• 0.67 g of US'674 polymer 0.01 g of azobisisobutyronitrile and a dispersion of 0.528 g 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 on a conductive carbon coated aluminum foil.
• Example 1(a) or Example 1(d) was coated on the carbonaceous membrane.
• the electrolyte layer is hardened by UV irradiation under nitrogen for 3 minutes. The complete membrane for the measurement of electrochemical stability is thus obtained.
• Electrochemical stability was evaluated using a Bio- logic® VMP-3 system. The voltage ranged from 3.5 V to 5 V with a rate of increase of 0.1 V every 2 hours.
• FIG 6 shows the electrochemical stability for Cell 9, including the membrane prepared in Example 1(d), and for Cell 8, including the membrane prepared in Example 1(a).
• N-methyltrifluoroacetamide (NMTFAm) in a composite electrolyte based on US'674 polymer and LATP (a phosphate type oxide ceramic) can greatly improve the ionic conductivity and the stability to the Li/electrolyte interface (see Figure 1) at 25°C, oxidation stability up to 4.5V.
• NMTFAm N-methyltrifluoroacetamide
• LATP a phosphate type oxide ceramic
• a cathode was prepared as described in patent application PCT/CA2022/050159 by including 73.2% by weight of lithium manganese cobalt nickel oxide active material (NMC811), which gives a loading rate of approximately 8 mg /cm 2 .
• the Example 1(d) electrolyte dispersion was coated directly onto the cathode and cured by UV irradiation under nitrogen for 3 minutes. The electrolyte thickness is about 40 ⁇ m.
• a metallic lithium foil with a thickness of 50 ⁇ m was used as the anode.
• a 3.8cm 2 button cell was therefore assembled to evaluate the performance.
• the battery capacity is around 4.4 mAh (1.2 mAh/cm 2 ).
• Figure 7 shows the capacity and coulombic efficiency of the cell as a function of the number of cycles.
• a LiFePC>4 (LFP) cathode was prepared as in Example 3(e)(i) replacing NMC811 with LFP as the active material at a concentration by weight of 70%, which gives a loading rate of about 12 mg/cm 2 .
• the Example 1(d) electrolyte dispersion was coated directly onto the cathode and cured by UV irradiation under nitrogen for 3 minutes. The electrolyte thickness is about 40 ⁇ m.
• a metallic lithium foil with a thickness of 40 ⁇ m was used as the anode.
• a 3.8 cm 2 button cell was assembled to evaluate performance.
• the battery capacity is approximately 3 mAh (0.8 mAh/cm 2 ).
• Figure 8 shows the galvanostatic charge and discharge curves at a charge and discharge rate of C/6.

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