Classifications

• • H—ELECTRICITY
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  • 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
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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  • 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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• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
  • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
  • C07D295/037—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements with quaternary ring nitrogen atoms
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  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0566—Liquid materials
  • H01M10/0567—Liquid materials characterised by the additives
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  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0566—Liquid materials
  • H01M10/0568—Liquid materials characterised by the solutes
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  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/058—Construction or manufacture
  • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
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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
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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  • 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
  • H01M4/381—Alkaline or alkaline earth metals elements
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  • 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
  • H01M4/381—Alkaline or alkaline earth metals elements
  • H01M4/382—Lithium
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  • 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
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  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
  • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
  • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
• • H—ELECTRICITY
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  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
  • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
  • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
• • H—ELECTRICITY
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  • 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
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  • 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
  • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/624—Electric conductive fillers
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  • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
  • H01M2004/027—Negative electrodes
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  • H01M2004/028—Positive electrodes
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  • H01M2300/00—Electrolytes
  • H01M2300/0017—Non-aqueous electrolytes
  • H01M2300/0065—Solid electrolytes
• • 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 the field of hybrid solid electrolytes comprising a ceramic and to their uses in electrochemical applications. More particularly, the present application relates to ionic compounds, to their manufacturing processes and to their uses in electrochemical cells, in particular in so-called all-solid-state batteries.
• the liquid electrolytes used in lithium-ion batteries are flammable and slowly degrade to form a passivation layer on the surface of the lithium film or solid electrolyte interface (SEI for "solid electrolyte interface” or “solid electrolyte interphase” in English) irreversibly consuming lithium, which decreases the coulombic efficiency of the battery.
• SEI solid electrolyte interface
• solid electrolyte interphase solid electrolyte interphase
• solid electrolytes have problems related to their electrochemical stability. limited, their limited interfacial stability, their relatively low ionic conductivity, loss of reactivity, poor contact between solid interfaces, etc.
• the present technology relates to a solid electrolyte comprising inorganic particles and an ionic bifunctional molecule of Formulas I or II:
• A' is a delocalized anion
• R + is selected from -N + (RIR2R3) and -P + (RIR2R3) groups;
• R1, R2, and R3 are independently selected from a linear or branched, substituted or unsubstituted C1-12alkyl group; or R1 and R2 with the nitrogen or phosphorus atom together form a heterocycle with one or more rings and having from 3 to 12 members and R3 is as previously defined; or R1, R2, and R3 together with the nitrogen or phosphorus atom together form a heteroaromatic or partially unsaturated heterocycle with one or more rings and having from 5 to 12 members;
• L is linear or branched C2-4 alkylene
• the present technology relates to a solid electrolyte comprising inorganic particles and an ionic bifunctional molecule of Formulas I or II:
• A- is a delocalized anion
• R + is chosen from the groups -N + (RIR2R3) and -PXR1R2R3) excluding the cations derived from amidine, guanidine and phosphazene superbases;
• R1, R2, and R3 are independently selected from a linear or branched, substituted or unsubstituted C1-12alkyl group; or R1 and R2 with the nitrogen or phosphorus atom together form a heterocycle with one or more rings and having from 3 to 12 members and R3 is as previously defined; or R1, R2, and R3 together with the nitrogen or phosphorus atom together form a heteroaromatic or partially unsaturated heterocycle with one or more rings and having from 5 to 12 members;
• L is linear or branched C2-4alkylene
• the delocalized anion is chosen from hexafluorophosphate (PF6-), bis(trifluoromethanesulfonyl)imide (TFSI-), bis(fluorosulfonyl)imide (TDI-), (flurosulfonyl)(trifluoromethanesulfonyl) imide (TFSI-), 2-trifluoromethyl-4,5-dicyanoimidazolate (TDI-), 4,5-dicyano-1,2,3-triazolate (DCTA-), bis(pentafluoroethylsulfonyl)imide (BEIT), difluorophosphate (DFP'), tetrafluoroborate (BF4'), bis(oxalato)borate (BOB'), nitrate (NOs'), perchlorate (CIO4'), hexafluoroarsenate (AsFe'), trifluoromethanesulfonate (CF3
• the delocalized anion is chosen from hexafluorophosphate (PF6-), bis(trifluoromethanesulfonyl)imide (TFSI′), bis(fluorosulfonyl)imide (FSI), (flurosulfonyl)(trifluoromethanesulfonyl)imide (FTFSI '), tetrafluoroborate (BF4-), and trifluoromethanesulfonate (CF3SO3- or -OT.f)
• the delocalized anion is bis(trifluoromethanesulfonyl)imide (TFSI').
• R + is a -N + (RI R2R3) group.
• R1, R2, and R3 are independently chosen from linear or branched, substituted or unsubstituted C1-12alkyl groups.
• Ri, R2, and R3 are independently chosen from linear or branched C1-12alkyl groups, or at least one of Ri, R2, or R3 is substituted by a halogen atom or an alkoxy group, ether, ester or siloxy.
• R1 and R2 with the nitrogen atom together form a heterocycle with one or more rings and having 3 to 12 members and R3 is as previously defined, preferably R3 is a C1-12alkyl, or a C1-4alkyl.
• R1, R2, and R3 with the nitrogen atom together form a heteroaromatic or partially unsaturated heterocycle with one or more rings and having from 5 to 12 members.
• R + is chosen from: in which R3 is as previously defined, R 4 is a linear or branched, substituted or unsubstituted C1-12alkyl, C1-12alkenyl or C1-12alkynyl group, R5 is a hydrogen atom, or a C1-12alkyl, C1 -12alkenyl or C1-12alkynyl linear or branched, substituted or unsubstituted, and the heterocycle is optionally substituted.
• R 4 is a C1-4alkyl group.
• R5 is a C1-4alkyl group.
• R3 is an unsubstituted C1-4alkyl group. According to an example of interest, R3 is chosen from a methyl group, an ethyl group, an n- or i-propyl group, and an n-, i-, s- or t-butyl group.
• R + is a -P + group (RIR2R3).
• R1, R2, and R3 are independently chosen from linear or branched, substituted or unsubstituted C1-12alkyl groups.
• Ri, R2, and R3 are independently chosen from linear or branched C1-12alkyl groups, or at least one of Ri, R2, or R3 is substituted by a halogen atom or an alkoxy group, ether, ester or siloxy.
• n is a number in the range of 2 to 10, or 3 to 8, or 4 to 6.
• the ionic bifunctional molecule is 1,1′-(1,6-hexamethylene)bis(1-methylpyrrolidinium) bis(trifluoromethanesulfonyl)imide.
• the ionic bifunctional molecule is 1,1'-(1,12-dodecamethylene)bis(1-methylpyrrolidinium) bis(trifluoromethanesulfonyl)imide. According to another embodiment, the ionic bifunctional molecule is 1,1′-(2,2′-(ethylenedioxy)diethane)bis(1-methylpyrrolidinium) bis(trifluoromethanesulfonyl)imide.
• the ionic bifunctional molecule is bis(trifluoromethanesulfonyl)imide of 1,1′-(thiol bis(1,2-ethane))bis(1-methylpyrrolidinum).
• the ionic bifunctional molecule is 3,3′-(1,6-hexamethylene)bis(1,2-dimethylimidazolium) bis(trifluoromethanesulfonyl)imide.
• the ionic bifunctional molecule is at a concentration of from about 0.5% to about 50%, or from about 2% to about 30%, or from about 4% to about 20%, or from about 5% to about 15%, by weight in the solid electrolyte.
• the inorganic particles comprise a material chosen from among glasses, glass-ceramics, ceramics, nano-ceramics and a combination of at least two of these.
• the inorganic particles comprise a fluoride, phosphide, sulphide, oxysulphide or oxide based ceramic, glass or glass-ceramic.
• the inorganic particles comprise a compound of LISICON, thio-LISICON, argyrodite, garnet, NASICON, perovskite, oxide, sulphide, oxysulphide, phosphide, fluoride type in crystalline and/or amorphous form, or a combination at least two of these.
• the inorganic particles comprise a compound chosen from the inorganic compounds of formulas MLZO
• M is an alkali metal ion, an alkaline earth metal ion, or a combination of two or more thereof, and wherein when M comprises an alkaline earth metal ion, then the number of M is adjusted to achieve electroneutrality;
• X is selected from F, Cl, Br, I or a combination of at least two of these; a, b, c, d, e and f are numbers other than zero and are independently in each formula selected to achieve electroneutrality; and v, w, x, y and z are non-zero numbers and are independently in each formula selected to yield a stable compound.
• M is chosen from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba or a combination of at least two of these.
• M is Li.
• the inorganic particles comprise an inorganic compound of formula MATP.
• the inorganic particles comprise an inorganic argyrodite compound of the formula Li6PS5X, in which X is Cl, Br, I or a combination of at least two of these.
• the inorganic particles comprise an inorganic compound of formula Li 6 PS5CI.
• the inorganic particles are present at a concentration of about 25% to about 95%, or about 40% to about 90%, or about 60% to about 90%, by weight in the solid electrolyte.
• the "inorganic particles: ionic bifunctional molecule" ratio by weight is in the range of 2: 1 to 30: 1, or 3: 1 to 20: 1, or 5: 1 to 15:1.
• the solid electrolyte further comprises a polymer.
• the polymer is a linear or branched polymer chosen from polyethers, polythioethers, polyesters, polythioesters, poly(dimethylsiloxanes), poly(alkylene carbonates), poly(alkylene thiocarbonates), poly(alkylenesulfones), poly(alkylenesulfonamides), polyimides, polyamides, polyphosphazenes, polyurethanes, poly(vinyl alcohol), polyacrylonitriles, polyethacrylates and polymethacrylates, and their copolymers.
• polyethers polythioethers, polyesters, polythioesters, poly(dimethylsiloxanes), poly(alkylene carbonates), poly(alkylene thiocarbonates), poly(alkylenesulfones), poly(alkylenesulfonamides), polyimides, polyamides, polyphosphazenes, polyurethanes, poly(vinyl alcohol), polyacrylonitriles, polyeth
• the polyether is poly(ethylene oxide) (POE), poly(propylene oxide) (POP), or a copolymer (EO/PO).
• the crosslinkable functional group is chosen from acrylate, methacrylate, vinyl, glycidyl and mercapto functional groups.
• the polymer is the reaction product of at least one monomer comprising at least one polymerizable or crosslinkable function and of a compound comprising at least one SH functional group.
• the polymer is present at a concentration of about 0.1% to about 20%, or about 1% to about 15%, or about 2% to about 10%, by weight in the solid electrolyte.
• the solid electrolyte further comprises an additive.
• the additive is a fluorinated compound comprising an amide function.
• the fluorinated compound is of formula R 6 X 6 C(O)N(H)X 7 R 7 , where R 6 and R 7 are independently alkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl groups, X 6 is O, NH or absent, and X 7 is absent or is a C(O), S(O)2 group, or Si(R 8 R 9 ), where R 8 and R 9 are alkyl groups, and where at least one of R 6 , R 7 , R 8 and R 9 is a group substituted by one or more atom(s) of fluorine.
• R 6 is a perfluorinated group and X 6 is absent.
• the additive is present at a concentration of about 5% to about 40%, or about 10% to about 35%, or about 15% to about 30%, by weight in the solid electrolyte.
• the present technology relates to an electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, in which the electrolyte is as defined herein.
• the positive electrode comprises a positive electrode material comprising an electrochemically active positive electrode material.
• the positive electrode material is on a current collector.
• the positive electrode electrochemically active material is chosen from metal phosphates, lithiated metal phosphates, metal oxides, and lithiated metal oxides.
• M'PO4 where M' is Fe, Ni, Mn, Co,
• the positive electrode material further comprises an electronically conductive material, a binder, a salt, an ionic bifunctional molecule, and/or inorganic particles.
• the negative electrode comprises a negative electrode material comprising an electrochemically active negative electrode material.
• the negative electrode material is on a current collector.
• the electrochemically active negative electrode material comprises a metallic film comprising an alkali or alkaline earth metal or an alloy comprising an alkali or alkaline earth metal.
• the alkali metal is chosen from lithium and sodium.
• the electrochemically active negative electrode material comprises an intermetallic compound (eg, SnSb, TiSnSb, Cu2Sb, AlSb, FeSb2, FeSn2 and CoSn2), a metal oxide, a metal nitride, a metal phosphide, metal phosphate (e.g. LiTi2(PC>4)3), metal halide (e.g. metal fluoride), metal sulfide, metal oxysulfide, carbon (e.g.
• an intermetallic compound eg, SnSb, TiSnSb, Cu2Sb, AlSb, FeSb2, FeSn2 and CoSn2
• a metal oxide e.g. LiTi2(PC>4)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), oxide silicon (SiO x ), a silicon oxide-carbon composite (SiO x -C), tin (Sn), a tin-carbon composite (Sn-C), a tin oxide (SnO x ), a tin oxide-carbon composite (SnO x -C), and combinations thereof, when compatible.
• the metal oxide is chosen from compounds of formula M””bO c (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 lies in the interval from 2 to 3) (for example, a titanate (such as Li4Ti5O12) or lithium molybdenum oxide (such as Li2MO4O13)).
• the negative electrode material further comprises an electronically conductive material, a binder, a salt, an ionic bifunctional molecule, and/or inorganic particles.
• the present technology relates to a battery comprising at least one electrochemical cell as defined here.
• said battery is chosen from the group consisting of a lithium battery, a lithium-ion battery, a sodium battery, a sodium-ion battery, a potassium battery , a potassium-ion battery, a magnesium battery, and a magnesium-ion battery.
• said battery is a lithium battery.
• said battery is a lithium-ion battery.
• Figure 1 presents the results of the analysis by differential scanning calorimetry obtained for Salts 1, 2, 4 and 5, as described in Example 3.
• Figure 2 presents the results of the thermogravimetric analysis obtained for Salts 1 to 5, as described in Example 3.
• Figure 3 is a graph showing the line-scanning voltammetry curves obtained for cells comprising electrolytes E1 to E3, as described in Example 4(b).
• Figure 4 is a graph showing the cyclic voltammetry curves obtained for cells comprising electrolytes E2 and E3, as described in Example 4(b).
• Figure 5 presents images of a lithium foil dipped respectively in (A) in tetraethylene glycol dimethyl ether (TEGDME), in (B) in a solution of bis(trifluoromethanesulfonyl)imide of 1-butyl-1-methylpyrrolidinium ([ PYR1,4]TFSI) in TEGDME, and in (C) in a solution of Salt 1 in TEGDME, as described in Example 4(c).
• TEGDME tetraethylene glycol dimethyl ether
• B a solution of bis(trifluoromethanesulfonyl)imide of 1-butyl-1-methylpyrrolidinium ([ PYR1,4]TFSI) in TEGDME
• PYR1,4]TFSI 1-butyl-1-methylpyrrolidinium
• Figure 6 shows images of a solid electrolyte pellet, as described in Example 5(a).
• Figure 7 is a graph showing the results of ionic conductivity versus temperature for Cells as described in Example 6(b).
• Figure 8 is a graph showing the results of ionic conductivity versus temperature for Cells as described in Example 6(b).
• Figure 9 presents images of the ceramic-ionic plastic salt composite solid electrolyte film E6 obtained by scanning electron microscopy (SEM) in (A) before creep, and in (B) and (C) after creep at a temperature of 70°C, as described in Example 6(c).
• Figure 10 is a graph showing the ionic conductivity versus temperature results for Cells as described in Example 7(b).
• alkyl refers to saturated hydrocarbons having 1 to 12 carbon atoms, including linear or branched alkyl groups.
• alkyl groups can include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, tert-butyl, sec-butyl, isobutyl, and so on.
• alkyl group is located between two functional groups, then the term alkyl also includes alkylene groups such as methylene, ethylene, propylene groups, and so on.
• the terms "C m -C n alkyl” and "C m -C n alkylene” respectively refer to an alkyl or alkylene group having the indicated number "m” to the indicated number "n” of carbon atoms.
• cycloalkyl as used herein means a group comprising one or more saturated or partially unsaturated (non-aromatic) carbocyclic rings comprising from 3 to 15 members in a monocyclic or polycyclic ring system, including spiro carbocycles (sharing a atom), fused (sharing at least one bond), or bridged and may be optionally substituted.
• cycloalkyl groups include, without limitation, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentene-1-yl, cyclopentene-2-yl, cyclopentene-3-yl, cyclohexyl, cyclohexene-1-yl, cyclohexene-2-yl, cyclohexene-3-yl, cycloheptyl and so on.
• the term cycloalkylene can also be used.
• heterocycloalkyl refers to a moiety comprising a saturated or partially unsaturated (non-aromatic) carbocyclic ring comprising from 3 to 15 members in a monocyclic or polycyclic ring system, including spiro carbocycles (sharing one atom) , fused (sharing at least one bond), or bridged and may be optionally substituted, and having, carbon atoms and from 1 to 4 heteroatoms (for example, N, O, S or P) or groups containing such heteroatoms (for example, NH, NR X (R x is an alkyl, acyl, aryl, heteroaryl or cycloalkyl group), PO2, SO, SO2 , and other similar groupings).
• Heterocycloalkyl groups can be bonded to a carbon atom or to a heteroatom (e.g. via a nitrogen atom) where possible.
• the term heterocycloalkyl includes both unsubstituted heterocycloalkyl groups and substituted heterocycloalkyl groups.
• the term heterocycloalkylene can also be used.
• aryl or “aromatic” refer to an aromatic moiety having 4n+2 conjugated Tr(pi) electrons where n is a number from 1 to 3, in a monocyclic group, or a fused bicyclic or tricyclic system having a total from 6 to 15 ring members, in which at least one of the rings of a system is aromatic.
• aryl or “aromatic” refer to both monocyclic and conjugated polycyclic systems.
• aryl or “aromatic” also include substituted or unsubstituted groups.
• aryl groups include, without limitation, phenyl, benzyl, phenethyl, 1-phenylethyl, tolyl, naphthyl, biphenyl, terphenyl, indenyl, benzocyclooctenyl, benzocycloheptenyl, azulenyl, acenaphthylenyl, fluorenyl, phenanthrenyl, anthracenyl, perylenyl, and so on. .
• heteroaryl designate an aromatic group having 4n+2 conjugated electrons Tr(pi) in which n is a number from 1 to 3, for example having from 5 to 18 ring atoms ( s), preferably 5, 6, or 9 ring atoms in a monocyclic or conjugated polycyclic system (fused or not); and having, in addition to carbon atoms, from 1 to 6 heteroatoms selected from oxygen, nitrogen and sulfur or groups containing such heteroatoms or groups containing such heteroatoms (for example, NH and NR X ( R x is an alkyl, acyl, aryl, heteroaryl or cycloalkyl group, SO, and other similar groups).
• a polycyclic ring system includes at least one heteroaromatic ring.
• Heteroaryls can be directly attached, or joined by a C1-C3alkyl group (also called heteroarylalkyl or heteroaralkyl).
• Heteroaryl groups can be bonded to a carbon atom or to a heteroatom (eg, via a nitrogen atom), where possible.
• substituted means that one or more hydrogen atom(s) on the designated group is replaced by a suitable substituent.
• the substituents or combinations of substituents contemplated in this description are those resulting in the formation of a chemically stable compound.
• substituents include halogen atoms (such as fluorine) and hydroxyl, oxo, alkyl, alkoxy, alkoxyalkyl, nitrile, azido, carboxylate, alkoxycarbonyl, alkylcarbonyl, primary, secondary or tertiary amine, amide, nitro, silane , siloxane, thiocarboxylate, sulfonyl, sulfonate, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocycloalkyl, or a combination thereof.
• halogen atoms such as fluorine
• the present technology generally relates to a solid electrolyte and its use in electrochemical applications.
• the solid electrolyte can be a predominantly inorganic solid electrolyte or a hybrid polymer-ceramic solid electrolyte.
• the present technology relates more particularly to a solid electrolyte comprising inorganic particles and an ionic bifunctional molecule of Formulas I or II:
• A- is a delocalized anion
• R + is chosen from the groups -N + (R1R2R3) and -P + (R1R2R3) excluding the cations derived from amidine, guanidine and phosphazene superbases;
• R1, R2, and R3 are independently selected from a linear or branched, substituted or unsubstituted C1-12alkyl group; or R1 and R2 with the nitrogen or phosphorus atom together form a heterocycle with one or more rings and having from 3 to 12 members and R3 is as previously defined; or Ri, R2, and R3 with the nitrogen or phosphorus atom together form a heteroaromatic or partially unsaturated heterocycle with one or more rings and having 5 to 12 members;
• L is linear or branched C2-4alkylene
• the delocalized anion may be selected from the group consisting of hexafluorophosphate (PF6-), bis(trifluoromethanesulfonyl)imide (TFSF), bis(fluorosulfonyl)imide (FSI-), (flurosulfonyl)(trifluoromethanesulfonyl)imide ( 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 (NO3'), perchlorate (CIO 4 -), hexafluoroarsenate (AsF6-), trifluoromethanesulfonate (
• the delocalized anion is selected from the group consisting of hexafluorophosphate (PF6-), bis(trifluoromethanesulfonyl)imide (TFSI'), bis(fluorosulfonyl)imide (FSI), (flurosulfonyl)(trifluoromethanesulfonyl) imide (FTFSI'), tetrafluoroborate (BF4'), and trifluoromethanesulfonate (CF3SO3- or -OT.f)
• PF6- hexafluorophosphate
• TFSI' bis(trifluoromethanesulfonyl)imide
• FSI bis(fluorosulfonyl)imide
• FTFSI' flurosulfonyl)(trifluoromethanesulfonyl) imide
• BF4' tetrafluoroborate
• CF3SO3- or -OT.f triflu
• R + is a group of formula -NXR1R2R3), in which R1, R2, and R3 are independently chosen from linear or branched, substituted or unsubstituted C1-12alkyl groups.
• R + is a group of formula -N + (RIR2R3), in which Ri, R 2 , and R 3 are independently chosen from linear or branched C1-12alkyl groups, or at least one of Ri , R2, or R3 is substituted by a halogen atom or an alkoxy, ether, ester or siloxy group.
• R + is a group of formula -N + (RIR2R3), in which Ri and R 2 with the nitrogen atom together form a heterocycle with one or more rings and having from 3 to 12 members and R3 is as previously defined, preferably R3 is a C1-12alkyl group or a C1-4alkyl group.
• R3 is an unsubstituted C1-4alkyl group (such as methyl, ethyl, n- or i-propyl, n-, i-, s-, and t-butyl), and preferably R3 is a methyl group.
• R + is a group of formula -N+(R1R2R3), in which Ri, R2, and R3 with the nitrogen atom together form a partially unsaturated heteroaromatic or heterocycle with one or more rings and having 5 to 12 members.
• R + is chosen from: wherein,
• R3 is as previously defined, R4 is chosen from a C1-12alkyl, C1-12alkenyl and C1-12alkynyl linear or branched, substituted or unsubstituted, preferably C1-4alkyl group, R5 is a hydrogen atom or a C1 group -12alkyl, C1-12alkenyl or C1-12alkynyl linear or branched, substituted or unsubstituted, preferably C1-4alkyl, preferably R3 is an unsubstituted C1-4alkyl group (such as methyl, ethyl, n- or i-propyl, n-, i-, s-, and t-butyl, preferably methyl); and the heterocycle is optionally substituted.
• R4 is chosen from a C1-12alkyl, C1-12alkenyl and C1-12alkynyl linear or branched, substituted or unsubstituted, preferably C1-4alkyl group
• R + is a group of formula -P+(R1R2R3), in which R1, R2, and R3 are independently chosen from linear or branched, substituted or unsubstituted C1-12alkyl groups.
• R + is a group of formula -P + (RIR2R3), in which Ri, R2, and R3 are independently chosen from linear or branched C1-12alkyl groups, or at least one of Ri, R2 , or R3 is substituted by a halogen atom or an alkoxy, ether, ester or siloxy group.
• n can be a number in the range from 2 to 10, or from 3 to 8, or from 4 to 6, upper and lower bounds included.
• the ionic bifunctional molecule is chosen from bis(trifluoromethanesulfonyl)imide of 1,T-(1,6-hexamethylene)bis(1-methylpyrrolidinium), bis(trifluoromethanesulfonyl)imide of 1,1'-(1 ,12-dodecamethylene) bis(l-methylpyrrolidinium), bis(trifluoromethanesulfonyl)imide of 1,1'-(2,2'-(ethylenedioxy)diethane)bis(1-methylpyrrolidinium), bis(trifluoromethanesulfonyl)imide of 1,1'-(thiol bis(1,2-ethane))bis(1-methylpyrrolidinum) and 3,3'-(1,6-hexamethylene)bis(1,2-dimethylimidazolium) bis(trifluoromethanesulfonyl)imide .
• the ionic bifunctional molecule is chosen from bis(triflu
• the ionic bifunctional molecule may be present in the electrolyte at a concentration ranging from about 0.5% by weight to about 50% by weight, upper and lower limits inclusive.
• the ionic bifunctional molecule may be present in the electrolyte at a concentration ranging from about 2% by weight to about 30% by weight, or from about 4% by weight to about 20% by weight. by weight, or ranging from about 5% by weight to about 15% by weight, upper and lower limits included.
• the inorganic particles can be chosen from all known inorganic solid electrolyte material particles and can be selected according to their compatibility with the various elements of an electrochemical cell.
• the inorganic particles can comprise a material chosen from glasses, glass ceramics, ceramics, nano ceramics and a combination of at least two of these.
• the inorganic particles may include a fluoride, phosphide, sulfide, oxysulfide, or oxide ceramic, glass, or glass-ceramic.
• the inorganic particles can comprise a compound of LISICON, thio-LISICON, argyrodite, garnet, NASICON, perovskite, oxide, sulphide, oxysulfide, phosphide, fluoride in crystalline and/or amorphous form, or a combination of at least two of these.
• the inorganic particles comprise a compound chosen from the inorganic compounds of formulas:
• M is an alkali metal ion, an alkaline earth metal ion or a combination thereof, and wherein when M comprises an alkaline earth metal ion, then the number of M is adjusted to achieve electroneutrality;
• X is selected from F, Cl, Br, I or a combination of at least two of these; a, b, c, d, e and f are numbers other than zero and are independently in each formula selected to achieve electroneutrality; and v, w, x, y and z are non-zero numbers and are independently in each formula selected to yield a stable compound.
• M can be chosen from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba or a combination of at least two of these. According to a variant of interest, M is Li.
• the inorganic particles comprise an inorganic compound of formula MATP as defined here.
• the inorganic particles comprise an inorganic compound of argyrodite type of formula Li6PS5X, in which X is Cl, Br, I or a combination of at least two of these.
• the inorganic particles can comprise an inorganic compound of formula Li6PS5CI.
• the inorganic particles can be present in the solid electrolyte at a concentration ranging from about 25% by weight to about 95% by weight, upper and lower limits inclusive.
• the inorganic particles may be present in the solid electrolyte at a concentration ranging from about 40% by weight to about 90% by weight, or from about 60% by weight to about 90% by weight. by weight, upper and lower bounds included.
• the ratio "inorganic particles: ionic bifunctional molecule” by weight can be in the range of 2: 1 to 30: 1, upper and lower limits included.
• the ratio "inorganic particles: ionic bifunctional molecule” by weight can be in the range from 3: 1 to 20: 1, or from 5: 1 to 15: 1, upper and lower bounds inclusive.
• the solid electrolyte as herein defined may further include a polymer.
• the polymer can be chosen for its compatibility with the different elements of an electrochemical cell. Any known compatible polymer is contemplated.
• the polymer can be chosen from linear or branched polymers.
• Non-limiting examples of polymers include polyethers (e.g., a polyether based on poly(ethylene oxide) (POE), poly(propylene oxide) (POP) or a combination of the two (such as an EO copolymer /PO)), polythioethers, polyesters, polythioesters, poly(dimethylsiloxanes), poly(alkylene carbonates), poly(alkylene thiocarbonates), poly(alkylenesulfones), poly(alkylenesulfonamides), polyimides, polyamides, polyphosphazenes, polyurethanes, poly(vinyl alcohol), polyacrylonitriles, polyethacrylates and polymethacrylates, and their copolymers, optionally comprising crosslinked units originating from crosslinkable functional groups (such as acrylate, methacrylate, vinyl , glycidyls, mercapto, etc.) or their cross-linked equivalents.
• POE poly(ethylene oxide)
• the polymer if it is present in the electrolyte, can be the product of the reaction between at least one monomer comprising at least one functional group polymerizable or crosslinkable and a compound comprising at least one SH functional group.
• the polymer can be present in the solid electrolyte at a concentration ranging from about 0.1% by weight to about 20% by weight, upper and lower limits included.
• the polymer may be present in the solid electrolyte at a concentration ranging from about 1% by weight to about 15% by weight, or from about 2% by weight to about 10% by weight. weight, upper and lower bounds included.
• the ionic bifunctional molecule as herein defined acts as a binder between the inorganic particles in the solid electrolyte as herein defined, whereby the binder may thus also further comprise the polymer as herein defined.
• the solid electrolyte as defined here may also optionally include an additive.
• the additive if it is present in the electrolyte, can be a fluorinated compound comprising an amide function.
• the fluorinated compound may be of formula R 6 X 6 C(O)N(H)X 7 R 7 , where R 6 and R 7 are independently alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl groups, X 6 is O, NH or absent, and X 7 is absent or is a C(O), S(O)2, or Si(R 8 R 9 ) group, where R 8 and R 9 are alkyl groups, and where at least the one of R 6 , R 7 , R 8 and R 9 is a group substituted by one or more fluorine atoms.
• R 6 is a perfluorinated group and X 6 is absent.
• the additive if it is present in the electrolyte, can be present in the solid electrolyte at a concentration comprised within the interval going from about 5% by weight to about 40% by weight, limits upper and lower included.
• the additive may be present in the solid electrolyte at a concentration ranging from about 10% by weight to about 35% by weight, or from about 15% by weight to about 30% by weight. by weight, upper and lower bounds included.
• the present technology also relates to an electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, in which the electrolyte is as defined herein.
• the positive electrode includes positive electrode material optionally on a current collector.
• the positive electrode material includes a material electrochemically active positive electrode.
• positive electrode electrochemically active materials include metal phosphates, lithiated metal phosphates, metal oxides, and lithiated metal oxides.
• the metal of the electrochemically active material can be chosen from titanium (Ti), iron (Fe), magnesium (Mg), manganese (Mn), vanadium (V), nickel (Ni), cobalt (Co), aluminum (Al), chromium (Cr), copper (Cu), antimony (Sb) and a combination of two or more of these, when compatible.
• the metal of the electrochemically active material can be chosen from titanium (Ti), iron (Fe), magnesium (Mg), manganese (Mn), vanadium (V), nickel ( Ni), cobalt (Co), aluminum (Al) and a combination of two or more of these, when compatible.
• the positive electrode material as defined herein may further include an electronically conductive material, a binder, a salt, an ionic bifunctional molecule (for example, an ionic bifunctional molecule as defined previously), and/or inorganic particles .
• the negative electrode comprises a negative electrode electrochemically active material which is optionally on a current collector.
• the negative electrode electrochemically active material can comprise a metal film comprising an alkali or alkaline-earth metal or an alloy comprising an alkali or alkaline-earth metal.
• the alkali metal can be chosen from lithium and sodium.
• the negative electrode electrochemically active material can comprise an intermetallic compound (for example, SnSb, TiSnSb, Cu2Sb, AlSb, FeSb2, FeSn2 and CoSn2), a metal oxide, a metal nitride, a phosphide of metal, metal phosphate (eg, LiTi2(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 (SiO x ), silicon oxide-carbon composite (SiOx-C), tin (Sn), tin-carbon composite (Sn-C), tin oxide (SnO x ), tin oxide composite tin-carbon (SnO x -C), and
• the metal oxide can be chosen from the compounds of formulas 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., MoO3, MoO2, MoS2, V2O5, and TiNb2O7), spinel oxides or a combination thereof) (for example, a lithium titanate (such as Li4Ti5O12) or a lithium molybdenum oxide (such as Li2MO4O13)).
• a lithium titanate such as Li4Ti5O12
• Li2MO4O13 lithium molybdenum oxide
• the negative electrode material may also comprise an electronically conductive material, a binder, a salt, an ionic bifunctional molecule (for example, an ionic bifunctional molecule as defined previously), and/or inorganic particles .
• the present technology also relates to a battery comprising at least one electrochemical cell as defined here.
• said battery is selected from the group consisting of lithium battery, lithium-ion battery, sodium battery, sodium-ion battery, potassium battery, a potassium-ion battery, a magnesium battery, and a magnesium-ion battery.
• said battery is a lithium battery or a lithium-ion battery.
• the presence of the ionic bifunctional molecule as defined here in a solid electrolyte, for example, in an inorganic solid electrolyte or a polymer-ceramic hybrid solid electrolyte can significantly improve some of its physical and/or electrochemical properties.
• the presence of the ionic bifunctional molecule can, for example, substantially improve the mechanical strength of a solid electrolyte film and/or the densification of said solid electrolyte film after flow.
• the presence of the ionic bifunctional molecule can substantially improve the ionic conductivity and/or electrochemical stability of the solid electrolyte film.
• the presence of the ionic bifunctional molecule can also substantially improve the flammability safety of the solid electrolyte film.
• 1,1'-(1,6-hexamethylene) bis(1-methylpyrrolidinium) bis(trifluoromethanesulfonyl)imide (Salt 1) was prepared by anion exchange from lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and 1,1'-(1,6-hexamethylene)bis(1-methylpyrrolidinium) dibromide prepared in Example 1(a). The anion exchange was carried out in water at a temperature of about 40°C for about 3 hours. c) Preparation of 1,1'-(1,12-dodecamethylene) bis(1-methylpyrrolidinium) dibromide
• 1,1'-(1,12-dodecamethylene) bis(1-methylpyrrolidinium) bis(trifluoromethanesulfonyl)imide (Salt 2) was prepared by anion exchange from LiTFSI and 1,1'-(1 ,12-dodecamethylene) bis(1-methylpyrrolidinium) prepared in Example 1(c). The anion exchange was carried out in water at a temperature of about 40°C for about 3 hours. e) Preparation of 1,1'-(2,2'-(ethylenedioxy)diethane) bis(1-methylpyrrolidinium) dichloride
• 1,1'-(2,2'-(ethylenedioxy)diethane)bis(1-methylpyrrolidinium) bis(trifluoromethanesulfonyl)imide (Salt 3) was prepared by anion exchange from LiTFSI and 1,1 dichloride '-(2,2'-(ethylenedioxy)diethane)bis(1-methylpyrrolidinium) prepared in Example 1(e). The anion exchange was carried out in water at a temperature of about 40°C for about 3 hours. g) Preparation of 1-(2-hydroxyethyl)-1-methylpyrrolidinium iodide
• 3,3'-(1,6-hexamethylene) bis(1,2-dimethylimidazolium) bis(trifluoromethanesulfonyl)imide (Salt 5) was prepared by anion exchange from LiTFSI and 3,3'-dibromide (1,6-hexamethylene)bis(1,2-dimethylimidazolium) prepared in Example 1(k). The anion exchange was carried out in water at a temperature of about 40°C for about 3 hours.
• Figure 1 presents the results of the analysis by Differential Scanning Calorimetry (DSC) obtained for Salts 1, 2, 4 and 5 prepared respectively in Examples 1(b), 1(d). ) and 1(1). DSC analysis was performed over a temperature range of approximately -20°C to approximately 148°C at a heating rate (or rate) of 10°C/min. As shown in Figure 1, Salt 1 has a crystallization temperature of -11°C and a melting temperature of 63°C.
• Figure 2 presents the results of the thermogravimetric analysis ("thermogravimetric analysis (TGA)" in English) obtained for Salts 1 to 5 prepared respectively in Examples 1(b), 1(d), 1(f), 1( j) and 1(1).
• TGA thermogravimetric analysis
• thermogravimetric analysis was carried out in a temperature range ranging from about 40°C to about 600°C. As shown in Figure 2, Salt 1 has a decomposition point around 295°C. The results of the thermal and thermogravimetric analyzes are presented in Table 6.
• Example 4 Chemical and Electrochemical Stability
• the electrochemical stability of a liquid electrolyte comprising Salt 1 prepared in Example 1 (b) was characterized by linear sweep voltammetry (“Linear sweep voltammetry (LSV)” in English) and by cyclic voltammetry (“cyclic voltammetry ( Resume in English).
• LSV Linear sweep voltammetry
• cyclic voltammetry Resume in English
• a liquid electrolyte comprising LiTFSI, TEGDME as solvent and Salt 1 prepared in Example 1(b) was prepared.
• a liquid electrolyte comprising LiTFSI and TEGDME as well as a liquid electrolyte comprising LiTFSI, TEGDME and [PYR1,4]TFSI were also prepared for comparison.
• the composition of liquid electrolytes for electrochemical stability analyzes is presented in Table 7.
• Celgard MC 2325 separators made of a microporous polypropylene-polyethylene-polypropylene (PP/PE/PP) trilayer membrane with a thickness of about 25 ⁇ m were impregnated with the above liquid electrolytes. Disks having a diameter of 16 mm were then cut out of the membranes impregnated with liquid electrolyte.
• PP/PE/PP polypropylene-polyethylene-polypropylene
• Cells for electrochemical stability analyzes were assembled according to the following procedure. Cells were assembled in a button cell configuration. The discs impregnated with liquid electrolyte prepared in the present example were placed and pressed between an aluminum electrode and a lithium electrode for the oxidation process (Al/electrolyte/Li) and between a copper electrode and a lithium for the reduction process (Cu/electrolyte/Li).
• Electrochemical stability measurements for Cells 1-3 assembled in Example 4(a) were performed by LSV. Electrochemical stability measurements for cells comprising E2 and E3 electrolytes were also performed by CV. The measurements were performed with a Bio-Logic MC VMP-300 system at a scan rate of 0.1 mV/s.
• Figures 3 and 4 show the results of the analysis by LSV and CV, respectively.
• Cell 3 comprising the liquid electrolyte comprising LiTFSI, TEGDME and Salt 1 prepared in Example 1(b) has superior electrochemical stability than Cell 2 comprising the liquid electrolyte comprising LiTFSI, TEGDME and [PYR1,4]TFSI c)
• Figure 5 shows images of lithium foils soaked respectively in (A) in TEGDME, in (B) in a solution comprising [PYRI,4]TFSI in TEGDME in a ratio TEGDME: [PYRI,4]TFSI ( 40:60 by weight), and in (C) in a solution comprising Salt 1 prepared in Example 1(b) in TEGDME in a ratio TEGDME:Salt 1 (41:59 by weight).
• the lithium sheets were submerged in the three different solutions for about a week.
• only the solution comprising [PYRI,4]TFSI in TEGDME changed color from transparent to black (Figure 5(B)). This indicates that the chemical stability of TEGDME and the solution comprising Salt 1 in TEGDME is superior to that of the solution comprising [PYRI,4]TFSI in TEGDME.
• Example 5 Preparation and characterization of an inorganic solid electrolyte a) Preparation of an inorganic solid electrolyte pellet
• Lii.3Alo.3Tii.7(PO4)3 Lii.3Alo.3Tii.7(PO4)3 (LATP, Toshima MC ), 0.126 g /V-methyltrifluoroacetamide
• Example 1(b) 0.06 g of Salt 1 prepared in Example 1(b) were mixed well and ground in a mortar at room temperature to obtain a solid electrolyte powder. Round pellets having a diameter of about 16 mm and a thickness of about 900 ⁇ m were obtained by compressing the solid electrolyte powder under a pressure of 120 psi.
• Figure 6 presents images of a solid electrolyte pellet showing respectively in (A) its diameter (approximately 16 mm), and in (B) its thickness (approximately 900 ⁇ m).
• Example 5(a) The ionic conductivity of the inorganic solid electrolyte pellets prepared in Example 5(a) was characterized by electrochemical impedance spectroscopy.
• Example 5(a) the inorganic solid electrolyte pellets prepared in Example 5(a) were placed and pressed between two stainless steel electrodes.
• the electrochemical impedance spectroscopy measurements were performed using a Bio-Logic MC VMP-300 system with an amplitude of 100 mV and over a frequency range from 1 MHz to 200 mHz. An ionic conductivity of 2.5 mS/cm was measured at a temperature of 60°C.
• crosslinkable polymer used in the example that follows is a multi-branched polyether comprising crosslinkable units, as described in United States Patent No. 7,897,674 (referred to below as the "polymer US'674").
• the ionic plastic crystal used in the following example is an ionic plastic crystal including a delocalized bis(trifluoromethanesulfonyl)imide [TFSI]' anion paired with a cation derived from 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), as described in the PCT patent application published under the number WO 2022/165598 (referred to below as the "plastic crystal WO'598").
• DBU 1,8-diazabicyclo[5.4.0]undec-7-ene
• a) Preparation of ceramic-ionic plastic salt composite solid electrolyte films Composite solid electrolyte films comprising a sulfide-based ceramic and the Salt 1 prepared in Example 1(b) were prepared. Composite solid electrolyte films comprising a sulfide-based ceramic and the WO'598 plastic crystal were also prepared for comparison.
• LiePSsCI sulfide-based ceramic-like inorganic solid electrolyte
• the binder used comprises a 40:60 mixture by mass of the polymer US'674 at 0.5% by weight of UV crosslinker and the plastic crystal WO'598 or one of Salts 1 to 5 has been dissolved in dichloromethane (DCM ).
• DCM dichloromethane
• a small amount of acetone was added in order to obtain a good dissolution of the salt.
• the ratio by weight between sulphide and binder was 90:10 by mass.
• the amount of DCM or DCM and acetone was adjusted to obtain a mixture with an appropriate viscosity.
• the mixture thus obtained was coated on a previously degreased aluminum foil.
• the film thus obtained was dried in a glove box. After drying, UV curing was carried out for about 15 seconds.
• composition of the ceramic-ionic plastic salt composite solid electrolyte films is shown in Table 8.
• Pellets 10 mm in diameter were taken from the ceramic-ionic plastic salt composite solid electrolyte films prepared in Example 6(a). The pellets were placed in a mold 10 mm in diameter and compressed under a pressure of 2.8 tons using a press. The pellets were then placed in a closed conductivity cell at a pressure of 5 MPa under an inert argon atmosphere. The configuration of each cell is presented as follows:
• Cell 11 Electrode/E11/Electrode
• the ionic conductivity measurements of the cells assembled in the present example were carried out with a VMP-300 multichannel potentiostat (Bio-Logic TM ). The measurements were carried out over a frequency range from 7 MHz to 200 mHz under an amplitude of 50 mV in a temperature interval ranging from -10°C to 70°C (uphill every 10°C) and in an interval temperatures ranging from 70°C to 20°C (downhill every 10°C).
• Figure 7 shows that the ionic conductivity of Cells 6 and 7 is substantially higher than that of Cells 4 and 5 comprising ceramic-ionic plastic salt composite solid electrolyte films including Salt 1 and the plastic crystal WO’598, respectively. This indicates a better interaction of the lithium ions of the sulfide-based ceramic type inorganic solid electrolytes with the bifunctional ionic salt.
• Figure 7 also shows that the ionic conductivity of Cell 7 (mass proportion of Li6PSsCI (3 pm: ⁇ 1 pm) of 75:25) including Salt 1 is similar to that of Cell 4 (mass proportion of LiePSsCI (3 pm: ⁇ 1 pm) of 90:10) with the plastic crystal WO'598.
• the bifunctional ionic salt makes it possible to increase the addition of smaller size LiePSsCI particles ( ⁇ 1 ⁇ m) and thus to obtain under compression a better compactness of the composite solid electrolyte film ceramic-ionic plastic salt while maintaining substantially high performance.
• the ionic conductivity results for Cells 6 and 7 are slightly lower than those obtained for sulfide-based ceramic-like inorganic solid electrolyte particles (Li6PSsCI) compressed alone and without an aluminum support. , but measured under the same conditions.
• Figure 9 shows SEM images obtained in (A) before creep, and in (B) and (C) after creep at a temperature of about 70°C for the ceramic-ionic plastic salt composite solid electrolyte film E6 prepared in Example 6(a).
• Figure 9(A) shows that after compression, but before flow, the ceramic-ionic plastic salt composite solid electrolyte film is substantially dense and has a thickness of about 40 ⁇ m. It is possible to distinguish the different particles and/or agglomerates of sulfide-based ceramics.
• Figures 9(B) and (C) show the effect of creep at a temperature of 70°C (above the melting temperature of Salt 1) and down to room temperature. It is possible to observe that after creep, the ceramic-ionic plastic salt composite solid electrolyte film is substantially denser and no longer presents any agglomerate. This can be useful in the so-called “all-solid” configuration, especially in the lithium metal configuration in order to resist lithium dendrites.
• Example 7 Preparation and characterization of ceramic-ionic plastic salt composite solid electrolyte films (4,4'-thiobisbenzenethiol (TBT) crosslinking) a) Preparation of ceramic-ionic plastic salt composite solid electrolyte films and crosslinking of TBT
• Li6PS5CI sulfide-based ceramic-like inorganic solid electrolyte particles
• the binder used comprised a 40:60 by weight mixture of the 4.0 wt% TBT US'674 polymer and Salt 1 prepared in Example 1(b) dissolved in DCM.
• the ratio by weight between sulphide and binder was 90:10 by mass.
• the amount of DCM was adjusted in order to obtain a mixture with an appropriate viscosity.
• the mixture thus obtained was coated on a previously degreased aluminum foil.
• the film thus obtained was dried in a glove box.
• composition of the ceramic-ionic plastic salt composite solid electrolyte films is shown in Table 9. Table 9. Composition of ionic plastic ceramic-salt composite solid electrolyte films b) Ionic conductivity of polymer-ceramic hybrid solid electrolyte films
• Pellets 10 mm in diameter were taken from the composite ceramic-ionic plastic salt solid electrolyte films prepared in Example 7(a). The pellets were placed in a mold 10 mm in diameter and compressed under a pressure of 2.8 tons using a press. The pellets were then placed in a closed conductivity cell at a pressure of 5 MPa under an inert argon atmosphere. The configuration of each cell is presented as follows:
• the ionic conductivity measurements of the cells assembled in the present example were carried out with a VMP-300 multichannel potentiostat (Bio-Logic TM ). The measurements were carried out over a frequency range from 7 MHz to 200 mHz under an amplitude of 50 mV in a temperature interval ranging from -10°C to 70°C (uphill every 10°C) and in an interval temperatures ranging from 70°C to 20°C (downhill every 10°C).
• Impedance measurements were obtained after stabilization for approximately one hour. Two impedance measurements were recorded at each temperature with 15 minutes between each measurement.
• Figure 10 presents the results of measured ionic conductivity as a function of temperature for Cells 12 (•) and 13 ( ⁇ ).
• the crosslinking of the US'674 polymer via the insertion of TBT between the chains of the US'674 polymer makes it possible to inhibit the ionic conduction of lithium ions through the US'674 polymer and therefore makes it possible to significantly increase the ionic conduction of the films ceramic-ionic plastic salt composite solid electrolyte, especially after creep Salt 1.
• the ionic conductivity of the ceramic-ionic plastic salt-TBT composite solid electrolyte film is substantially the same as that obtained for a sulfide-based ceramic-type inorganic solid electrolyte film (Li6PSsCI).

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