Patent Application
20250079513
This application claims priority, under applicable law, to Canadian provisional patent application No. 3,145,591 filed on Jan. 14, 2022, the content of which is incorporated herein by reference in its entirety and for all purposes.
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), irreversibly consuming lithium, which reduces the coulombic efficiency of the battery. In addition, lithium anodes undergo significant morphological changes during battery cycling and lithium dendrites are formed. As these usually migrate through the electrolyte, they can eventually cause short circuits.
Safety concerns and the requirement for higher energy density have spurred research into the development of an all-solid-state rechargeable lithium battery with a polymer, ceramic or polymer-ceramic hybrid electrolyte, all three of which are more stable towards metallic lithium and reduce the growth of lithium dendrites.
However, the field of application of solid electrolytes is still limited. Indeed, solid electrolytes present problems related to their limited electrochemical stability, their limited interfacial stability, their relatively low ionic conductivity, loss of reactivity, poor contact between solid interfaces, etc.
Consequently, there is a need for the development of all-solid-state electrochemical systems that exclude one or more of the disadvantages of conventional all-solid-state electrochemical systems.
According to a first aspect, the present technology relates to a solid electrolyte comprising inorganic particles and an ionic bifunctional molecule of Formulae I or II:
More particularly, the present technology relates to a solid electrolyte comprising inorganic particles and an ionic bifunctional molecule of Formulae I or II:
According to an embodiment, the delocalized anion is selected from hexafluorophosphate (PF6−), bis(trifluoromethanesulfonyl)imide (TFSI−), bis(fluorosulfonyl)imide (FSI−), (fluorosulfonyl)(trifluoromethanesulfonyl)imide (FTFSI−), 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 (ClO4−), hexafluoroarsenate (AsF6−), trifluoromethanesulfonate (CF3SO3− or −OTf), fluoroalkylphosphate ([PF3(CF2CF3)3]− or FAP−), tetrakis(trifluoroacetoxy)borate ([B(OCOCF3)4]− or TFAB−), bis(1,2-benzenediolato(2-)-O,O′)borate ([B(C6O2)2]− or BBB−), difluoro(oxalato)borate (BF2(C6O4)− or FOB−), and an anion of formula C6O4Rx (Rx═C2-4alkyl).
According to an example, the delocalized anion is selected from hexafluorophosphate (PF6−), bis(trifluoromethanesulfonyl)imide (TFSI−), bis(fluorosulfonyl)imide (FSI−), (fluorosulfonyl)(trifluoromethanesulfonyl)imide (FTFSI−), tetrafluoroborate (BF4−), and trifluoromethanesulfonate (CF3SO3− or −OTf).
According to an example of interest, the delocalized anion is bis(trifluoromethanesulfonyl)imide (TFSI−).
According to some embodiments, R+ is an —N+(R1R2R3) group.
According to an example, R1, R2, and R3 are independently selected from substituted or unsubstituted linear or branched C1-12alkyl groups.
According to another example, R1, R2, and R3 are independently selected from linear or branched C1-12alkyl groups, or at least one of R1, R2, or R3 is substituted by a halogen atom or an alkoxyl, ether, ester, or siloxy group.
According to another example, R1 and R2 together with the nitrogen atom form a heterocycle having one or more rings and having from 3 to 12 members and R3 is as previously defined, preferably R3 is a C1-12 alkyl or a C1-4alkyl.
According to another example, R1, R2, and R3 together with the nitrogen atom form a partially unsaturated heterocycle or heteroaromatic having one or more rings and having 5 to 12 members.
According to another example, R+ is selected from:
wherein R3 is as previously defined, R4 is a substituted or unsubstituted linear or branched C1-12alkyl, C1-12alkenyl, or C1-12alkynyl group, R5 is a hydrogen atom, or a substituted or unsubstituted linear or branched C1-12alkyl, C1-12alkenyl, or C1-12 alkynyl group, and the heterocycle is optionally substituted.
According to an example, R4 is a C1-4alkyl group.
According to another example, R5 is a C1-4alkyl group.
According to another example, R3 is an unsubstituted C1-4alkyl group. According to an example of interest, R3 is selected from a methyl group, an ethyl group, an n- or i-propyl group, and an n-, i-, s-, or t-butyl group.
According to some other embodiments, R+ is a —P+(R1R2R3) group.
According to an example, R1, R2, and R3 are independently selected from substituted or unsubstituted linear or branched C1-12alkyl groups.
According to another example, R1, R2, and R3 are independently selected from linear or branched C1-12alkyl groups, or at least one of R1, R2, or R3 is substituted by a halogen atom or an alkoxyl, ether, ester, or siloxy group.
According to another embodiment, n is a number in the range from 2 to 10, or from 3 to 8, or from 4 to 6.
According to another embodiment, the ionic bifunctional molecule is 1,1′-(1,6-hexamethylene) bis(1-methylpyrrolidinium) bis(trifluoromethanesulfonyl)imide.
According to another embodiment, 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.
According to another embodiment, the ionic bifunctional molecule is 1,1′-(thiol bis(1,2-ethane)) bis(1-methylpyrrolidinum) bis(trifluoromethanesulfonyl)imide.
According to another embodiment, the ionic bifunctional molecule is 3,3′-(1,6-hexamethylene) bis(1,2-dimethylimidazolium) bis(trifluoromethanesulfonyl)imide.
According to another embodiment, the ionic bifunctional molecule is at a concentration of from about 0.5 wt. % to about 50 wt. %, or from about 2 wt. % to about 30 wt. %, or from about 4 wt. % to about 20 wt. %, or from about 5 wt. % to about 15 wt. % in the solid electrolyte.
According to another embodiment, the inorganic particles comprise a material selected from glasses, glass-ceramics, ceramics, nanoceramics, and a combination of at least two thereof.
According to some preferred embodiments, the inorganic particles comprise a fluoride-, phosphide-, sulfide-, oxysulfide- or oxide-based ceramic, glass, or glass-ceramic.
According to some preferred embodiments, the inorganic particles comprise a LISICON, thio-LISICON, argyrodite, garnet, NASICON, perovskite, oxide, sulfide, oxysulfide, phosphide, or fluoride compound in crystalline and/or amorphous form, or a combination of at least two thereof.
According to some preferred embodiments, the inorganic particles comprise a compound selected from inorganic compounds of formulae MLZO (for example, M7La3Zr2O12, M(7-a)La3Zr2AlbO12, M(7-a)La3Zr2GabO12, M(7-a)La3Zr(2-b)TabO12, and M(7-a)La3Zr(2-b)NbbO12); MLTaO (for example, M7La3Ta2O12, M5La3Ta2O12, and M6La3Ta1.5Y0.5O12); MLSnO (for example, M7La3Sn2O12); MAGP (for example, M1+aAlaGe2−a(PO4)3); MATP (for example, M1+aAlaTi2−a(PO4)3); MLTiO (for example, M3aLa(2/3−a)TiO3); MZP (for example, MaZrb(PO4)c); MCZP (for example, MaCabZrc(PO4)d); MGPS (for example, MaGebPcSd such as M10GeP2S12); MGPSO (for example, MaGebPcSdOe); MSiPS (for example, MaSibPcSd such as M10SiP2S12); MSiPSO (for example, MaSibPcSdOe); MSnPS (for example, MaSnbPcSd such as M10SnP2S12); MSnPSO (for example, MaSnbPcSdOe); MPS (for example, MaPbSc such as M7P3S11); MPSO (for example, MaPbScOd); MZPS (for example, MaZnbPcSd); MZPSO (for example, MaZnbPcSdOe); xM2S-yP2S5; xM2S-yP2S5-zMX; xM2S-yP2S5-zP2O5; xM2S-yP2S5-zP2O5-wMX; xM2S-yM2O-zP2S5; xM2S-yM2O-zP2S5-wMX; xM2S-yM2O-zP2S5-wP2O5; xM2S-yM2O-zP2S5-wP2O5-vMX; xM2S-ySiS2; MPSX (for example, MaPbScXd such as M7P3S11X, M7P2S8X, and M6PS5X); MPSOX (for example, MaPbScOdXe); MGPSX (MaGebPcSdXe); MGPSOX (MaGebPcSdOeXf); MSiPSX (MaSibPcSdXe); MSiPSOX (MaSibPcSdOeXf); MSnPSX (MaSnbPcSdXe); MSnPSOX (MaSnbPcSdOeXf); MZPSX (MaZnbPcSdXe); MZPSOX (MaZnbPcSdOeXf); M3OX; M2HOX; M3PO4; M3PS4; and MaPObNc (where a=2b+3c−5);
According to an example, M is selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, or a combination of at least two thereof. For example, M is Li.
According to another example, the inorganic particles comprise an inorganic compound of formula MATP.
According to another example, the inorganic particles comprise an argyrodite-type inorganic compound of formula Li6PS5X, wherein X is Cl, Br, I, or a combination of at least two thereof.
According to another example, the inorganic particles comprise an inorganic compound of formula Li6PS5Cl.
According to another embodiment, the inorganic particles are present at a concentration of from about 25 wt. % to about 95 wt. %, or from about 40 wt. % to about 90 wt. %, or from about 60 wt. % to about 90 wt. % in the solid electrolyte.
According to another embodiment, the ratio “inorganic particles:ionic bifunctional molecule” by weight is in the range from 2:1 to 30:1, or from 3:1 to 20:1, or from 5:1 to 15:1.
According to another embodiment, the solid electrolyte also comprises a polymer.
According to an example, the polymer is a linear or branched polymer selected from polyethers, polythioethers, polyesters, polythioesters, poly(dimethylsiloxanes), poly(alkylene carbonate), poly(alkylene thiocarbonate), poly(alkylene sulfones), poly(alkylene sulfamides), polyimides, polyamides, polyphosphazenes, polyurethanes, poly(vinyl alcohols), polyacrylonitriles, polyethacrylates, polymethacrylates, and copolymers thereof.
According to an example, the polyether is poly(ethylene oxide) (PEO), poly(propylene oxide) (POP), or a copolymer (EO/PO).
According to another example, the crosslinkable functional group is selected from acrylate, methacrylate, vinyl, glycidyl, and mercapto functional groups.
According to another example, the polymer is the reaction product of at least one monomer comprising at least one polymerizable or crosslinkable function and a compound comprising at least one SH functional group.
According to another embodiment, the polymer is present at a concentration of from about 0.1 wt. % to about 20 wt. %, or from about 1 wt. % to about 15 wt. %, or from about 2 wt. % to about 10 wt. % in the solid electrolyte.
According to another embodiment, the solid electrolyte also comprises an additive.
According to an example, the additive is a fluorinated compound comprising an amide function. For example, the fluorinated compound is of formula R6X6C(O)N(H)X7R7, where R6 and R7 are independently alkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl groups, X6 is O, NH, or is absent, and X7 is absent or is a C(O), S(O)2, or Si(R8R9) group, where R8 and R9 are alkyl groups, and where at least one of R6, R7, R8, and R9 is a group substituted by one or more fluorine atoms. According to an example of interest, R6 is a perfluorinated group and X6 is absent.
According to another example, the additive is present at a concentration of from about 5 wt. % to about 40 wt. %, or from about 10 wt. % to about 35 wt. %, or from about 15 wt. % to about 30 wt. % in the solid electrolyte.
According to another aspect, the present technology relates to an electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte, wherein the electrolyte is as herein defined.
According to an embodiment, the positive electrode comprises a positive electrode material comprising a positive electrode electrochemically active material.
According to an example, the positive electrode material is on a current collector.
According to another example, the positive electrode electrochemically active material is selected from metal phosphates, lithiated metal phosphates, metal oxides, and lithiated metal oxides.
According to another example, the positive electrode electrochemically active material is LiM′PO4 where M′ is Fe, Ni, Mn, Co, or a combination of at least two thereof, LiV3O8, V2O5F, LiV2O5, LiMn2O4, LiM″O2, where M″ is Mn, Co, Ni, or a combination of at least two thereof (such as NMC, LiMnxCoyNizO2 with x+y+z=1), Li(NiM′″)O2 (where M″′ is Mn, Co, Al, Fe, Cr, Ti, Zr, or a combination of at least two thereof), sulfur, elemental selenium, elemental iodine, iron(III) fluoride, copper(II) fluoride, lithium iodide, carbon-based active materials such as graphite, organic cathode active materials, or a combination of at least two thereof, when compatible with each other.
According to another embodiment, the positive electrode material further comprises an electronically conductive material, a binder, a salt, an ionic bifunctional molecule, and/or inorganic particles.
According to another embodiment, the negative electrode comprises a negative electrode material comprising a negative electrode electrochemically active material.
According to an example, the negative electrode material is on a current collector.
According to some preferred embodiments, the negative electrode electrochemically active material comprises a metal film comprising an alkali or alkaline earth metal or an alloy comprising an alkali or alkaline earth metal. According to an example, the alkali metal is selected from lithium and sodium.
According to further preferred embodiments, the negative electrode electrochemically active material comprises an intermetallic compound (for example, SnSb, TiSnSb, Cu2Sb, AlSb, FeSb2, FeSn2, and CoSn2), metal oxide, metal nitride, metal phosphide, metal phosphate (for example, LiTi2(PO4)3), metal halide (for example, metal fluoride), metal sulfide, metal oxysulfide, carbon (for example, graphite, graphene, reduced graphene oxide, hard carbon, soft carbon, exfoliated graphite, and amorphous carbon), silicon (Si), a silicon-carbon composite (Si—C), a silicon oxide (SiOx), a silicon oxide-carbon composite (SiOx—C), tin (Sn), a tin-carbon composite (Sn—C), a tin oxide (SnOx), a tin oxide-carbon composite (SnOx—C), and combinations thereof, when compatible. According to an example, the metal oxide is selected from compounds of formulae 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 ratio c:b is in the range from 2 to 3) (for example, MoO3, MoO2, MoS2, V2O5, and TiNb2O7), spinel oxides (for example, NiCo2O4, ZnCo2O4, MnCo2O4, CuCo2O4, and CoFe2O4) and LiM′″″O (where M′″″ is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination thereof) (for example, lithium titanate (such as Li4Ti5O12) or lithium molybdenum oxide (such as Li2Mo4O13)). According to an example of interest, the negative electrode material further comprises an electronically conductive material, a binder, a salt, an ionic bifunctional molecule, and/or inorganic particles.
According to another aspect, the present technology relates to a battery comprising at least one electrochemical cell as herein defined.
According to an embodiment, said battery is selected 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. According to an example of interest, said battery is a lithium battery. According to another example of interest, said battery is a lithium-ion battery.
), 5 (▴), 6 (●), and 7 (★), as described in Example 6(b).
), 9 (●), 10 (▴), and 11 (▾), as described in Example 6(b).
All technical and scientific terms and expressions used herein have the same definitions as those generally understood by the person skilled in the art of the present technology. The definition of some terms and expressions used is nevertheless provided below.
When the term “about” is used herein, it means approximately, in the region of, or around. For example, when the term “about” is used in relation to a numerical value, it modifies it by a variation of 10% above and below its nominal value. This term can also take into account, for example, the experimental error of a measuring device or rounding.
When a range of values is mentioned in the present application, the lower and upper limits of the range are, unless otherwise indicated, always included in the definition. When a range of values is mentioned in the present application, then all intermediate ranges and subranges, as well as the individual values included in the ranges of values, are included in the definition.
When the article “a” is used to introduce an element in the present application, it does not have the meaning of “only one”, but rather of “one or more”. Of course, where the description states that a particular step, component, element, or feature “may” or “could” be included, that particular step, component, element, or feature is not required to be included in each embodiment.
The chemical structures described herein are drawn according to the conventions of the field. Also, when an atom, such as a carbon atom, as drawn seems to include an incomplete valence, then it is assumed that the valence is satisfied by one or more hydrogen atoms even if they are not explicitly drawn.
The term “alkyl” as used herein refers to saturated hydrocarbons having from 1 to 12 carbon atoms, including linear or branched alkyl groups. Non-limiting examples of alkyl groups can include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, tert-butyl, sec-butyl, isobutyl, and so on. When the alkyl group is located between two functional groups, then the term alkyl also includes alkylene groups such as methylene, ethylene, propylene, and so on. The terms “Cm-Cnalkyl” and “Cm-Cnalkylene” respectively refer to an alkyl or alkylene group having from the indicated number “m” to the indicated number “n” of carbon atoms.
The term “cycloalkyl” as used herein refers to 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 system, including spiro (sharing an atom), fused (sharing at least one bond), or bridged carbocycles and can be optionally substituted. Examples of cycloalkyl groups include, without limitation, cyclopropyl, cyclobutyl, cyclopentyl, cyclopenten-1-yl, cyclopenten-2-yl, cyclopenten-3-yl, cyclohexyl, cyclohexen-1-yl, cyclohexen-2-yl, cyclohexen-3-yl, cycloheptyl, and so on. When the cycloalkyl group is located between two functional groups, the term cycloalkylene can also be used.
The term “heterocycloalkyl” as used herein refers to a group comprising a saturated or partially unsaturated (non-aromatic) carbocyclic ring comprising from 3 to 15 members in a monocyclic or polycyclic system, including spiro (sharing an atom), fused (sharing at least one bond), or bridged and can 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, NRx (Rx is an alkyl, acyl, aryl, heteroaryl, or cycloalkyl group), PO2, SO, SO2, and other similar groups). Heterocycloalkyl groups can be bonded to a carbon atom or a heteroatom (for example via a nitrogen atom) where possible. The term heterocycloalkyl includes both unsubstituted heterocycloalkyl groups and substituted heterocycloalkyl groups. When the heterocycloalkyl group is located between two functional groups, the term heterocycloalkylene can also be used.
The terms “aryl” or “aromatic” refer to an aromatic group having 4n+2 conjugated π(pi) electrons in which n is a number from 1 to 3, in a monocyclic group, or a fused bicyclic or tricyclic system having a total of from 6 to 15 ring members, in which at least one of the rings of a system is aromatic. The terms “aryl” or “aromatic” refer to both conjugated monocyclic and polycyclic systems. The terms “aryl” or “aromatic” also include substituted or unsubstituted groups. Examples of 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.
The terms “heteroaryl”, “heteroarylene”, or “heteroaromatic” refer to an aromatic group having 4n+2 conjugated π(pi) electrons in which n is a number from 1 to 3, for example having from 5 to 18 ring atoms, preferably 5, 6, or 9 ring atoms in a conjugated monocyclic or 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 (for example, NH and NRx (Rx is alkyl, acyl, aryl, heteroaryl, or cycloalkyl group), SO, and other similar groups). A polycyclic ring system comprises at least one heteroaromatic ring. Heteroaryls can be directly attached, or linked via a C1-C3alkyl group (also called heteroarylalkyl or heteroaralkyl). Heteroaryl groups can be linked to a carbon atom or a heteroatom (for example, via a nitrogen atom), where possible.
In general, the term “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 the present description are those resulting in the formation of a chemically stable compound. Examples of substituents include halogen atoms (such as fluorine) and hydroxyl, oxo, alkyl, alkoxyl, alkoxyalkyl, nitrile, azido, carboxylate, alkoxycarbonyl, alkylcarbonyl, primary, secondary, or tertiary amine, amide, nitro, silane, siloxane, thiocarboxylate, sulfonyl, sulfonate, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocycloalkyl groups, or a combination thereof.
The present technology generally relates to a solid electrolyte and its use in electrochemical applications. For example, the solid electrolyte can be a primarily inorganic solid electrolyte or a polymer-ceramic hybrid solid electrolyte.
The present technology relates more particularly to a solid electrolyte comprising inorganic particles and an ionic bifunctional molecule of Formulae I or II:
The delocalized anion can be selected from the group consisting of hexafluorophosphate (PF6−), bis(trifluoromethanesulfonyl)imide (TFSI−), bis(fluorosulfonyl)imide (FSI−), (fluorosulfonyl)(trifluoromethanesulfonyl)imide (FTFSI−), 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 (ClO4−), hexafluoroarsenate (AsF6−), trifluoromethanesulfonate (CF3SO3− or −OTf), fluoroalkylphosphate ([PF3(CF2CF3)3]− or FAP−), tetrakis(trifluoroacetoxy)borate ([B(OCOCF3)4]− or TFAB−), bis(1,2-benzenediolato(2-)-O,O′)borate ([B(C6O2)2]− or BBB−), difluoro(oxalato)borate (BF2(C6O4)− or FOB−), and an anion of formula C6O4Rx (Rx═C2-4alkyl). For example, the delocalized anion is selected from the group consisting of hexafluorophosphate (PF6−), bis(trifluoromethanesulfonyl)imide (TFSI−), bis(fluorosulfonyl)imide (FSI−), (fluorosulfonyl)(trifluoromethanesulfonyl)imide (FTFSI−), tetrafluoroborate (BF4−), and trifluoromethanesulfonate (CF3SO3− or −OTf).
According to an example, R+ is a group of formula —N+(R1R2R3), wherein R1, R2, and R3 are independently selected from substituted or unsubstituted linear or branched C1-12alkyl groups.
According to another example, R+ is a group of formula —N+(R1R2R3), wherein R1, R2, and R3 are independently selected from linear or branched C1-12alkyl groups, or at least one of R1, R2, or R3 is substituted by a halogen atom or an alkoxyl, ether, ester, or siloxy group.
According to another example, R+ is a group of formula —N+(R1R2R3), wherein R1 and R2 together with the nitrogen atom form a heterocycle having 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. According to an example of interest, 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.
According to another example, R+ is a group of formula —N+(R1R2R3), wherein R1, R2, and R3 together with the nitrogen atom form a partially unsaturated heterocycle or heteroaromatic having one or more rings and having from 5 to 12 members.
According to another example, R+ is selected from:
According to another example, R+ is a group of formula —P+(R1R2R3), wherein R1, R2, and R3 are independently selected from substituted or unsubstituted linear or branched C1-12alkyl groups.
According to another example, R+ is a group of formula —P+(R1R2R3), wherein R1, R2, and R3 are independently selected from linear or branched C1-12alkyl groups, or at least one of R1, R2, or R3 is substituted by a halogen atom or an alkoxyl, ether, ester, or siloxy group.
According to some examples, 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 limits included.
According to some examples, the ionic bifunctional molecule is selected from 1,1′-(1,6-hexamethylene) bis(1-methylpyrrolidinium) bis(trifluoromethanesulfonyl)imide, 1,1′-(1,12-dodecamethylene) bis(1-methylpyrrolidinium) bis(trifluoromethanesulfonyl)imide, 1,1′-(2,2′-(ethylenedioxy)diethane) bis(1-methylpyrrolidinium) bis(trifluoromethanesulfonyl)imide, 1,1′-(thiol bis(1,2-ethane)) bis(1-methylpyrrolidinum), and 3,3′-(1,6-hexamethylene) bis(1,2-dimethylimidazolium) bis(trifluoromethanesulfonyl)imide. According to an example of interest, the ionic bifunctional molecule is 1,1′-(1,6-hexamethylene) bis(1-methylpyrrolidinium) bis(trifluoromethanesulfonyl)imide.
The ionic bifunctional molecule can be present in the electrolyte at a concentration in the range from about 0.5 wt. % to about 50 wt. %, upper and lower limits included. For example, the ionic bifunctional molecule can be present in the electrolyte at a concentration in the range from about 2 wt. % to about 30 wt. %, or from about 4 wt. % to about 20 wt. %, or from about 5 wt. % to about 15 wt. %, upper and lower limits included.
The inorganic particles can be selected from any known inorganic solid electrolyte material particles and can be selected according to their compatibility with the various elements of an electrochemical cell. For example, the inorganic particles can comprise a material selected from glasses, glass-ceramics, ceramics, nanoceramics, and a combination of at least two thereof.
According to an example, the inorganic particles can comprise a fluoride-, phosphide-, sulfide-, oxysulfide- or oxide-based ceramic, glass, or glass-ceramic.
According to another example, the inorganic particles can comprise a LISICON, thio-LISICON, argyrodite, garnet, NASICON, perovskite, oxide, sulfide, oxysulfide, phosphide or fluoride compound in crystalline and/or amorphous form, or a combination of at least two thereof.
According to another example, the inorganic particles comprise a compound selected from the inorganic compounds of formulae:
For example, M can be selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, or a combination of at least two thereof. According to a variant of interest, M is Li.
According to a variant of interest, the inorganic particles comprise an inorganic compound of formula MATP as herein defined.
According to another variant of interest, the inorganic particles comprise an argyrodite-type inorganic compound of formula Li6PS5X, wherein X is Cl, Br, I, or a combination of at least two thereof. For example, the inorganic particles can comprise an inorganic compound of formula Li6PS5Cl.
The inorganic particles can be present in the solid electrolyte at a concentration in the range from about 25 wt. % to about 95 wt. %, upper and lower limits included. For example, the inorganic particles can be present in the solid electrolyte at a concentration in the range from about 40 wt. % to about 90 wt. %, or from about 60 wt. % to about 90 wt. %, upper and lower limits included.
The mass ratio of “inorganic particles:ionic bifunctional molecule” can be in the range from 2:1 to 30:1, upper and lower limits included. For example, the mass ratio of “inorganic particles:ionic bifunctional molecule” can be in the range from 3:1 to 20:1, or from 5:1 to 15:1, upper and lower limits included.
The solid electrolyte as herein defined can further include a polymer. For example, the polymer may be selected for its compatibility with the various components of an electrochemical cell. Any known compatible polymer is contemplated. The polymer can be selected from linear or branched polymers. Non-limiting examples of polymers include polyethers (for example, a polyether based on poly(ethylene oxide) (PEO), poly(propylene oxide) (POP) or a combination of the two (such as an EO/PO copolymer)), polythioethers, polyesters, polythioesters, poly(dimethylsiloxanes), poly(alkylene carbonates), poly(alkylene thiocarbonates), poly(alkylene sulfones), poly(alkylene sulfamides), polyimides, polyamides, polyphosphazenes, polyurethanes, poly(vinyl alcohols), polyacrylonitriles, polyethacrylates and polymethacrylates, and copolymers thereof, optionally comprising crosslinked units derived from crosslinkable functional groups (such as acrylate, methacrylate, vinyl, glycidyl, mercapto functions, etc.) or crosslinked equivalents thereof.
According to an example, the polymer, if present in the electrolyte, can be the product of the reaction between at least one monomer comprising at least one polymerizable or crosslinkable functional group and a compound comprising at least one SH functional group.
According to another example, the polymer can be present in the solid electrolyte at a concentration in the range from about 0.1 wt. % to about 20 wt. %, upper and lower limits included. For example, the polymer can be present in the solid electrolyte at a concentration in the range from about 1 wt. % to about 15 wt. %, or from about 2 wt. % to about 10 wt. %, upper and lower limits included.
For example, 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 can also further comprise the polymer as herein defined.
The solid electrolyte as herein defined can also optionally include an additive.
According to an example, the additive, if present in the electrolyte, can be a fluorinated compound comprising an amide function. The fluorinated compound can be of formula R6X6C(O)N(H)X7R7, where R6 and R7 are independently alkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl groups, X6 is O, NH, or is absent, and X7 is absent or is a C(O), S(O)2, or Si(R8R9) group, where R8 and R9 are alkyl groups, and where at least one of R6, R7, R8, and R9 is a group substituted by one or more fluorine atoms. For example, R6 is a perfluorinated group and X6 is absent.
According to an example, the additive, if present in the electrolyte, can be present in the solid electrolyte at a concentration in the range from about 5 wt. % to about 40 wt. %, upper and lower limits included. For example, the additive can be present in the solid electrolyte at a concentration in the range from about 10 wt. % to about 35 wt. %, or from about 15 wt. % to about 30 wt. %, upper and lower limits included.
The present technology also relates to an electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte, wherein the electrolyte is as herein defined.
The positive electrode comprises a positive electrode material optionally on a current collector. The positive electrode material comprises a positive electrode electrochemically active material. Non-limiting examples of positive electrode electrochemically active materials include metal phosphates, lithiated metal phosphates, metal oxides, and lithiated metal oxides.
For example, the metal of the electrochemically active material can be selected 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 at least two thereof, when compatible. According to a variant of interest, the metal of the electrochemically active material can be selected from titanium (Ti), iron (Fe), magnesium (Mg), manganese (Mn), vanadium (V), nickel (Ni), cobalt (Co), aluminum (Al), and a combination of at least two thereof, when compatible.
Non-limiting examples of positive electrode electrochemically active materials generally include metal phosphates and lithiated metal phosphates (for example, LiM′PO4 and M′PO4, where M′ is selected from Fe, Ni, Mn, Co, and a combination of at least two thereof), vanadium oxides and lithium vanadium oxides (for example, LiV3O8, V2O5, LiV2O5, and similar vanadium oxides and lithium vanadium oxides), and lithium metal oxides of formulae LiMn2O4, LiM″O2 (where M″ is selected from Mn, Co, Ni, and a combination of at least two thereof) (such as NMC, LiMnxCoyNizO2 with x+y+z=1), Li(NiM′″)O2 (where M″′ is selected from Mn, Co, Al, Fe, Cr, Ti, Zr, another similar metal, and a combination of at least two thereof), sulfur, elemental selenium, elemental iodine, iron(III) fluoride, copper(II) fluoride, lithium iodide, carbon-based active materials such as graphite, organic cathode active materials, or a combination of at least two of these electrochemically active materials, when compatible with each other.
The positive electrode material as herein defined can further include an electronically conductive material, a binder, a salt, an ionic bifunctional molecule (for example, an ionic bifunctional molecule as previously defined), and/or inorganic particles.
The negative electrode comprises a negative electrode electrochemically active material which is optionally on a current collector.
According to an example, 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. For example, the alkali metal can be selected from lithium and sodium.
According to another example, the negative electrode electrochemically active material can include an intermetallic compound (for example, SnSb, TiSnSb, Cu2Sb, AlSb, FeSb2, FeSn2, and CoSn2), a metal oxide, a metal nitride, a metal phosphide, a metal phosphate (for example, LiTi2(PO4)3), a metal halide (for example, a metal fluoride), a metal sulfide, a metal oxysulfide, carbon (for example, graphite, graphene, reduced graphene oxide, hard carbon, soft carbon, exfoliated graphite, and amorphous carbon), silicon (Si), a silicon-carbon composite (Si—C), a silicon oxide (SiOx), a silicon oxide-carbon composite (SiOx—C), tin (Sn), a tin oxide-carbon composite (Sn—C), a tin oxide (SnOx), a tin oxide-carbon composite (SnOx—C), and a combination of at least two thereof, when compatible. For example, the metal oxide can be selected from compounds of formulae 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 ratio c:b is in the range from 2 to 3) for example, MoO3, MoO2, MoS2, V2O5, and TiNb2O7), spinel oxides (for example, NiCo2O4, ZnCo2O4, MnCo2O4, CuCo2O4, and CoFe2O4) and LiM′″″O (where M′″″ is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination thereof) (for example, lithium titanate (such as Li4Ti5O12) or lithium molybdenum oxide (such as Li2Mo4O13)).
According to another example, the negative electrode material can further comprise an electronically conductive material, a binder, a salt, an ionic bifunctional molecule (for example, an ionic bifunctional molecule as previously defined), and/or inorganic particles.
The present technology also relates to a battery comprising at least one electrochemical cell as herein defined. For example, said battery is selected 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. According to a variant of interest, said battery is a lithium battery or a lithium-ion battery.
The presence of the ionic bifunctional molecule as herein defined 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.
According to an example, 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 creep. According to another example, the presence of the ionic bifunctional molecule can substantially improve the ionic conductivity and/or electrochemical stability of the solid electrolyte film. In some cases, the presence of the ionic bifunctional molecule can also substantially improve the flammability safety of the solid electrolyte film.
The following examples are for illustrative purposes and should not be construed as further limiting the scope of the invention as contemplated. These examples will be better understood by referring to the accompanying figures.
8 g of 1-methylpyrrolidine (94.1 mmol), 10.4 g of 1,6-dibromohexane (42.8 mmol) and 20 ml of tetrahydrofuran (THF) were introduced into a 100 ml single-neck flask. The solution was heated at a temperature of about 50° C. for about 12 hours. The precipitate formed during the reaction was then recovered by filtration and washed three times with THF. The product thus obtained was dried under vacuum at a temperature of about 50° C. for about 24 hours.
1,1′-(1,6-hexamethylene) bis(1-methylpyrrolidinium) bis(trifluoromethanesulfonyl)imide (Salt 1) was prepared by anionic exchange from lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and the 1,1′-(1,6-hexamethylene) bis(1-methylpyrrolidinium) dibromide prepared in Example 1(a). The anionic exchange was carried out in water at a temperature of about 40° C. for about 3 hours.
8 g of 1-methylpyrrolidine (94.1 mmol), 10.3 g of 1,12-dibromododecane (31.4 mmol) and 20 ml of THF were introduced into a 100 ml single-neck flask. The solution was heated to about 50° C. for about 12 hours. The precipitate formed during the reaction was then recovered by filtration and washed three times with diethyl ether. The product thus obtained was dried under vacuum at a temperature of about 50° C. for about 24 hours.
1,1′-(1,12-dodecamethylene) bis(1-methylpyrrolidinium) bis(trifluoromethanesulfonyl)imide (Salt 2) was prepared by anionic exchange from LiTFSI and the 1,1′-(1,12-dodecamethylene) bis(1-methylpyrrolidinium) dibromide prepared in Example 1(c). The anionic exchange was carried out in water at a temperature of about 40° C. for about 3 hours.
4 g of 1-methylpyrrolidine (46.6 mmol), 2.9 g of 1,2-bis(2-chloroethoxy)ethane (15.6 mmol) and 10 ml of THF were introduced into a 50 ml single-neck flask. The solution was heated at a temperature of about 50° C. for about 48 hours. The precipitate formed during the reaction was then recovered by filtration and washed three times with diethyl ether. The product thus obtained was dried under vacuum at a temperature of about 50° C. for about 24 hours.
1,1′-(2,2′-(ethylenedioxy)diethane) bis(1-methylpyrrolidinium) bis(trifluoromethanesulfonyl)imide (Salt 3) was prepared by anionic exchange from LiTFSI and the 1,1′-(2,2′-(ethylenedioxy)diethane) bis(1-methylpyrrolidinium) dichloride prepared in Example 1(e). The anionic exchange was carried out in water at a temperature of about 40° C. for about 3 hours.
5.75 g of 1-(2-hydroxyethyl)pyrrolidine (50 mmol), 8.52 g of iodomethane (60 mmol) and 10 ml of THF were introduced into a 50 ml single-neck flask. The solution was heated at a temperature of about 50° C. for about 12 hours. The precipitate formed during the reaction was then recovered by filtration and washed three times with diethyl ether. The product thus obtained was dried under vacuum at a temperature of about 50° C. for about 24 hours.
5.14 g of the 1-(2-hydroxyethyl)-1-methylpyrrolidinium iodide prepared in Example 1(g) (20 mmol), 23.8 g of thionyl dichloride (0.2 mol) were introduced into a 50 ml single-neck flask. The solution was heated to a temperature of about 70° C. for about 24 hours. The product was precipitated in 100 ml diethyl ether. The precipitate was then recovered by filtration and washed three times with diethyl ether. The product thus obtained was dried under vacuum at a temperature of about 50° C. for about 24 hours.
3 g of the 1-(2-chloroxyethyl)-1-methylpyrrolidinium prepared in Example 1(h) (11 mmol), 0.43 g sodium sulfide (5.5 mmol), 0.04 g of sodium hydroxide (1 mmol), 40 ml of deionized water and 60 ml of methanol were introduced into a 250 ml single-neck flask. The solution was heated at a temperature of about 50° C. for about 24 hours. The precipitate formed during the reaction was then recovered by filtration and washed three times with diethyl ether. The product thus obtained was dried under vacuum at a temperature of about 50° C. for about 24 hours.
1,1′-(thiol bis(1,2-ethane)) bis(1-methylpyrrolidinum) bis(trifluoromethanesulfonyl)imide (Salt 4) was prepared by anionic exchange from LiTFSI and the 1,1′-(thiol bis(1,2-ethane)) bis(1-methylpyrrolidinum) iodide prepared in Example 1(i). The anionic exchange was carried out in a water:methanol mixture (2:8 by volume) at a temperature of about 40° C. for about 3 hours.
5.77 g of 1,2-dimethylimidazole (60 mmol), 4.88 g of 1,6-dibromohexane (20 mmol) and 10 ml of THF were introduced into a 50 ml single-neck flask. The solution was heated to a temperature of about 50° C. for about 12 hours. The precipitate formed during the reaction was then recovered by filtration and washed three times with diethyl ether. The product thus obtained was dried under vacuum at a temperature of about 50° C. for about 24 hours.
3,3′-(1,6-hexamethylene) bis(1,2-dimethylimidazolium) bis(trifluoromethanesulfonyl)imide (Sel 5) was prepared by anionic exchange from LiTFSI and the 3,3′-(1,6-hexamethylene) bis(1,2-dimethylimidazolium) dibromide prepared in Example 1(k). The anionic exchange was carried out in water at a temperature of about 40° C. for about 3 hours.
Salts 1 to 5 prepared in Example 1 were characterized by proton nuclear magnetic resonance (1H NMR).
a) NMR characterization of Salt 1 prepared in Example 1(b)
The 1H NMR spectrum of Salt 1 prepared in Example 1(b) was obtained in methanol-d4 (deuterated methanol or CD3OD) as the solvent and the results obtained are shown in Table 1.
1H NMR results for Salt 1
The 1H NMR spectrum of Salt 2 prepared in Example 1(d) was obtained in chloroform-d (deuterated chloroform or CDCl3) as the solvent and the results obtained are presented in Table 2.
1H NMR results for Salt 2
The 1H NMR spectrum of Salt 3 prepared in Example 1(f) was obtained in CDCl3 as the solvent and the results obtained are presented in Table 3.
1H NMR results for Salt 3
The 1H NMR spectrum of Salt 4 prepared in Example 1(j) was obtained in dimethyl sulfoxide-d6 (deuterated dimethyl sulfoxide or DMSO-d6) as the solvent and the results obtained are presented in Table 4.
1H NMR results for Salt 4
e) 1H NMR characterization of Salt 5 prepared in Example 1(l)
The 1H NMR spectrum of Salt 5 prepared in Example 1(l) was obtained in DMSO-d6 as the solvent and the results obtained are presented in Table 5.
1H NMR results for Salt 5
The results of the thermal and thermogravimetric analyses are presented in Table 6.
The electrochemical stability of a liquid electrolyte comprising Salt 1 prepared in Example 1(b) was characterized by linear sweep voltammetry (LSV) and cyclic voltammetry (CV).
A liquid electrolyte comprising LiTFSI, TEGDME as the solvent and Salt 1 prepared in Example 1(b) was prepared. A liquid electrolyte comprising LiTFSI and TEGDME and a liquid electrolyte comprising LiTFSI, TEGDME and [PYR1,4]TFSI were also prepared for comparison. The composition of the liquid electrolytes used for electrochemical stability analyses is presented in Table 7.
Celgard™ 2325 separators made of a three-layer microporous polypropylene-polyethylene-polypropylene (PP/PE/PP) membrane with a thickness of about 25 μm were impregnated with the above liquid electrolytes. Discs with a diameter of 16 mm were then cut from the membranes impregnated with liquid electrolyte.
Cells for electrochemical stability analyses were assembled according to the following procedure. The cells were assembled in a button cell configuration. The disks impregnated with liquid electrolyte prepared in the present example were placed and pressed between an aluminum and a lithium electrode for the oxidation process (Al/electrolyte/Li) and between a copper and a lithium electrode for the reduction process (Cu/electrolyte/Li).
The configuration of each cell is presented below:
Electrochemical stability measurements for Cells 1 to 3 assembled in Example 4(a) were carried out by LSV. Electrochemical stability measurements for cells comprising electrolytes E2 and E3 were also carried out by CV. Measurements were performed with a Bio-Logic™ VMP-300 system at a scan rate of 0.1 mV/s.
The chemical stability of TEGDME, a solution comprising [PYR1,4]TFSI in TEGDME and a solution comprising Salt 1 prepared in Example 1(b) in TEGDME towards lithium metal was analyzed.
0.294 g of Li1.3Al0.3Ti1.7(PO4)3 (LATP, Toshima™), 0.126 g of N-methyltrifluoroacetamide (NMTFAm) and 0.06 g of Salt 1 prepared in Example 1(b) were thoroughly mixed and ground in a mortar at room temperature to obtain a solid electrolyte powder. Round pellets with a diameter of about 16 mm and a thickness of about 900 μm were obtained by compressing the solid electrolyte powder under a pressure of 120 psi.
The ionic conductivity of the inorganic solid electrolyte pellets prepared in Example 5(a) was characterized by electrochemical impedance spectroscopy.
To achieve this, the inorganic solid electrolyte pellets prepared in Example 5(a) were placed and pressed between two stainless steel electrodes.
Electrochemical impedance spectroscopy measurements were carried out using a Bio-Logic™ VMP-300 system with an amplitude of 100 mV 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.
The crosslinkable polymer used in the following example is a multi-branched polyether comprising crosslinkable units as described in U.S. Pat. No. 7,897,674 (hereinafter referred to as the “U.S. '674 polymer”).
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 PCT patent application published under number WO 2022/165598 (hereinafter referred to as the “WO '598 plastic crystal”).
Composite solid electrolyte films comprising a sulfide-based ceramic and 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 purposes.
All manipulations were carried out in a glovebox under an argon atmosphere (0.1 ppm H2O; 0.1 ppm O2).
Two sizes (about 3 μm and less than 1 μm) of sulfide-based ceramic inorganic solid electrolyte particles (Li6PS5Cl) were mixed in a mass ratio of 90:10 or 75:25 using a vortex. The binder used comprises a 40:60 by weight mixture of the U.S. '674 polymer with 0.5 wt. % of UV crosslinker and the WO '598 plastic crystal or one of Salts 1 to 5 was dissolved in dichloromethane (DCM). For binders comprising Salts 4 and 5, a small amount of acetone was added in order to achieve good dissolution of the salt.
The mass ratio of sulfide to binder was 90:10 by weight. The amount of DCM or DCM and acetone was adjusted to obtain a mixture with an appropriate viscosity. The mixture thus obtained was coated onto a previously degreased aluminum foil. The film thus obtained was dried in a glovebox. After drying, UV curing was carried out for about 15 seconds.
The composition of the ceramic-ionic plastic composite solid electrolyte films is presented in Table 8.
Pellets of 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 10 mm diameter mold and compressed under a pressure of 2.8 tons using a press. The pellets were then placed in a conductivity cell at a pressure of 5 MPa closed under an inert argon atmosphere. The configuration of each cell is presented below:
The ionic conductivity measurements of the cells assembled in the present example were carried out with a VMP-300 multi-channel potentiostat (Bio-Logic™). Measurements were carried out over a frequency range from 7 MHz to 200 mHz at an amplitude of 50 mV over a temperature range from −10° C. to 70° C. (in increase every 10° C.) and over a temperature range from 70° C. to 20° C. (in decrease every 10° C.).
Impedance measurements were obtained after a stabilization period of about one hour. Two impedance measurements were recorded at each temperature with 15 minutes between each measurement. ), 5 (▴), 6 (●), and 7 (★).
), 9 (●), 10 (▴), and 11 (▾).
It is possible to observe in
At a temperature of 20° C., the ionic conductivity results for Cells 6 and 7 are slightly lower than those obtained for sulfide-based ceramic type inorganic solid electrolyte particles (Li6PS5Cl) compressed alone and without an aluminum support, but measured under the same conditions.
It is possible to observe in
All manipulations were carried out in a glovebox under an argon atmosphere (0.1 ppm H2O; 0.1 ppm O2).
Two sizes (about 3 μm and less than 1 μm) of sulfide-based ceramic type inorganic solid electrolyte particles (Li6PS5Cl) were mixed in a mass ratio of 90:10 using a vortex.
The binder used comprises a 40:60 by weight mixture of the U.S. '674 polymer with 4.0 wt. % TBT and Salt 1 prepared in Example 1(b) dissolved in DCM.
The mass ratio of sulfide to binder was 90:10 by weight. The amount of DCM was adjusted to obtain a mixture with an appropriate viscosity. The mixture thus obtained was coated onto a previously degreased aluminum foil. The film thus obtained was dried in a glove box.
The composition of the ceramic-ionic plastic salt composite solid electrolyte films is presented in Table 9.
Pellets of 10 mm in diameter were taken from the ceramic-ionic plastic salt composite solid electrolyte films prepared in Example 7(a). The pellets were placed in a 10 mm diameter mold and compressed under a pressure of 2.8 tons using a press. The pellets were then placed in a conductivity cell at a pressure of 5 MPa closed under an inert argon atmosphere.
The configuration of each cell is presented below:
The ionic conductivity measurements of the cells assembled in the present example were carried out with a VMP-300 multi-channel potentiostat (Bio-Logic™). The measurements were carried out over a frequency range from 7 MHz to 200 mHz at an amplitude of 50 mV over a temperature range from −10° C. to 70° C. (in increase every 10° C.) and over a temperature range from 70° C. to 20° C. (in decrease every 10° C.).
Impedance measurements were obtained after a stabilization period of about one hour. Two impedance measurements were recorded at each temperature with 15 minutes between each measurement.
The crosslinking of the U.S. '674 polymer via the insertion of TBT between the chains of the U.S. '674 polymer allows inhibiting the ionic conduction of lithium ions through the U.S. '674 polymer, and therefore makes it possible to significantly increase the ionic conduction of ceramic-ionic plastic salt composite solid electrolyte films, particularly after the creep of Salt 1. This allows confirming the interaction between ionic plastic salt and sulfide-based ceramics (such as Li6PS5Cl), as well as the positive effect of the creep of the ionic plastic salt on the density of the resulting film and on its ionic conductivity. The ionic conductivity of the ceramic-ionic plastic salt-TBT composite solid electrolyte film is substantially identical to that obtained for a sulfide-based ceramic type inorganic solid electrolyte film (Li6PS5Cl).
Several modifications could be made to any of the above-described embodiments without departing from the scope of the present invention as contemplated. The references, patents or documents of scientific literature referred to in the present application are incorporated herein by reference in their entirety and for all purposes.
| Number | Date | Country | Kind |
|---|---|---|---|
| 3145591 | Jan 2022 | CA | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CA2023/050037 | 1/13/2023 | WO |
