Solid electrolytes containing ionic bifunctional molecules and their use in electrochemistry - Patents.com

Abstract

The present technology relates to a solid electrolyte comprising inorganic particles and ionic bifunctional molecules for use in electrochemical applications. Also described are electrochemical cells and batteries comprising said solid electrolyte. The present application relates to the field of hybrid solid electrolytes comprising ceramics and their use in electrochemical applications. More particularly, the present application relates to ionic compounds, their manufacturing methods, and their use in electrochemical cells, in particular so-called all-solid-state batteries.

Description

[Technical field]

[0001] Related Applications This application claims priority under applicable law to Canadian Provisional Patent Application No. 3,145,591, filed January 14, 2022, the contents of which are incorporated herein by reference in their entirety for all purposes.

[0002] Technical Field The present application relates to the field of hybrid solid electrolytes, including ceramics, and their use in electrochemical applications. More particularly, the present application relates to ionic compounds, their preparation methods, and their use in electrochemical cells, in particular so-called all-solid-state batteries. [Background technology]

[0003] background The liquid electrolytes used in lithium-ion batteries are flammable and slowly decompose to form a passivation layer on the surface of the lithium film or at the solid electrolyte interface (SEI), irreversibly consuming lithium, thereby reducing the coulombic efficiency of the battery. Furthermore, the lithium anode undergoes significant morphological changes during battery cycling, resulting in the formation of lithium dendrites. These typically migrate through the electrolyte and can eventually cause short circuits.

[0004] Safety concerns and requirements for higher energy density have driven research towards the development of all-solid-state rechargeable lithium batteries containing polymer, ceramic or polymer-ceramic hybrid electrolytes, all three of which are more stable relative to metallic lithium and reduce the growth of lithium dendrites.

[0005] However, the application fields of solid electrolytes are still limited: in fact, solid electrolytes exhibit problems related to their limited electrochemical stability, their limited interfacial stability, their relatively low ionic conductivity, reactivity losses, poor contact between solid interfaces, etc.

[0006] As a result, a need exists to develop an all-solid-state electrochemical system that eliminates one or more of the disadvantages of conventional all-solid-state electrochemical systems. Summary of the Invention [Means for solving the problem]

[0007] overview According to a first aspect, the present technology provides a method for preparing a granular material comprising: [ka] (In the formula, A - is a delocalized anion, R + -N + (R1R2R3) and -P + (R1R2R3) groups, R1, R2 and R3 are independently substituted or unsubstituted, linear or branched C 1~12 alkyl groups, or R1 and R2 together with the nitrogen or phosphorus atom have one or more rings and form a heterocyclic ring having 3 to 12 members, and R3 is as previously defined, or R1, R2 and R3 together with the nitrogen or phosphorus atom have one or more rings and form a partially unsaturated heterocyclic ring or heteroaromatic ring having 5 to 12 members, L is a linear or branched C 2~4 is alkylene, X is O or S; m is a number ranging from 1 to 6; n is a number ranging from 1 to 11. The present invention relates to a solid electrolyte comprising an ionic bifunctional molecule of the formula:

[0008] More specifically, the present technology relates to a method for producing a polymeric nanoparticle comprising the steps of: [ka] (In the formula, A - is a delocalized anion, R+ -N excluding cations derived from amidine, guanidine, and phosphazene superbases + (R1R2R3) and -P + (R1R2R3) groups, R1, R2 and R3 are independently substituted or unsubstituted, linear or branched C 1~12 alkyl groups, or R1 and R2 together with the nitrogen or phosphorus atom have one or more rings and form a heterocyclic ring having 3 to 12 members, and R3 is as previously defined, or R1, R2 and R3 together with the nitrogen or phosphorus atom have one or more rings and form a partially unsaturated heterocyclic ring or heteroaromatic ring having 5 to 12 members, L is a linear or branched C 2~4 is alkylene, X is O or S; m is a number ranging from 1 to 6; n is a number ranging from 1 to 11. The present invention relates to a solid electrolyte comprising an ionic bifunctional molecule of the formula:

[0009] According to one embodiment, the delocalized anion is 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), fluoroalkyl phosphate ([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(C2O4) - or F.O.B. - ), and the formula BF2O4R x (R x =C 2~4 The anion is selected from the group consisting of alkyl, aryl ...

[0010] In one example, the delocalized anion is hexafluorophosphate (PF6 - ), bis(trifluoromethanesulfonyl)imide (TFSI - ), bis(fluorosulfonyl)imide (FSI - ), (fluorosulfonyl)(trifluoromethanesulfonyl)imide (FTFSI - ), tetrafluoroborate (BF4 - ), and trifluoromethanesulfonate (CF3SO3 - or - OTf).

[0011] According to one example of interest, the delocalized anion is bis(trifluoromethanesulfonyl)imide (TFSI - ).

[0012] According to some embodiments, R + -N + (R1R2R3) group.

[0013] According to one example, R1, R2 and R3 are independently substituted or unsubstituted, linear or branched C 1~12 The alkyl group is selected from the group consisting of aryl, ... and alkyl groups.

[0014] According to another example, R1, R2 and R3 can be independently selected from linear or branched C 1~12 alkyl groups or at least one of R1, R2 or R3 is substituted by a halogen atom, or an alkoxyl, ether, ester or siloxy group.

[0015] According to another example, R1 and R2 together with the nitrogen atom form a heterocycle having one or more rings and 3 to 12 members, R3 is as previously defined, preferably R3 is C 1~12 Alkyl or C 1~4 It is an alkyl.

[0016] According to another example, R1, R2 and R3 together with the nitrogen atom form a partially unsaturated heterocyclic or heteroaromatic ring having one or more rings and having 5 to 12 members.

[0017] According to another example, R + teeth, [ka] (wherein R3 is as previously defined, and R4 is a substituted or unsubstituted, linear or branched C 1~12 Alkyl, C 1~12 Alkenyl, or C 1~12 R5 is a hydrogen atom or a substituted or unsubstituted, linear or branched C 1~12 Alkyl, C 1~12 Alkenyl or C 1~12 alkynyl group, the heterocycle being optionally substituted is selected from.

[0018] In one example, R4 is C 1~4 It is an alkyl group.

[0019] Another example is R5, C 1~4 It is an alkyl group.

[0020] According to another example, R3 is an unsubstituted C 1~4 According to the examples of interest, R3 is selected from the group consisting of a methyl group, an ethyl group, an n- or i-propyl group, and an n-, i-, s- or t-butyl group.

[0021] According to some other embodiments, R + -P + (R1R2R3) group.

[0022] According to one example, R1, R2 and R3 are independently substituted or unsubstituted, linear or branched C 1~12 The alkyl group is selected from the group consisting of aryl, ... and alkyl groups.

[0023] According to another example, R1, R2 and R3 can be independently selected from linear or branched C 1~12 alkyl groups or at least one of R1, R2 or R3 is substituted by a halogen atom, or an alkoxyl, ether, ester or siloxy group.

[0024] According to another embodiment, n is a number ranging from 2 to 10, or from 3 to 8, or from 4 to 6.

[0025] According to another embodiment, the ionic bifunctional molecule is 1,1'-(1,6-hexamethylene)bis(1-methylpyrrolidinium)bis(trifluoromethanesulfonyl)imide.

[0026] According to another embodiment, the ionic bifunctional molecule is 1,1'-(1,12-dodecamethylene)bis(1-methylpyrrolidinium)bis(trifluoromethanesulfonyl)imide.

[0027] According to another embodiment, the ionic bifunctional molecule is 1,1'-(2,2'-(ethylenedioxy)diethane)bis(1-methylpyrrolidinium)bis(trifluoromethanesulfonyl)imide.

[0028] According to another embodiment, the ionic bifunctional molecule is 1,1'-(thiolbis(1,2-ethane))bis(1-methylpyrrolidinum)bis(trifluoromethanesulfonyl)imide.

[0029] According to another embodiment, the ionic bifunctional molecule is 3,3'-(1,6-hexamethylene)bis(1,2-dimethylimidazolium)bis(trifluoromethanesulfonyl)imide.

[0030] According to another embodiment, the ionic bifunctional molecule is present in the solid electrolyte at a concentration of about 0.5% to about 50% by weight, or about 2% to about 30% by weight, or about 4% to about 20% by weight, or about 5% to about 15% by weight.

[0031] According to another embodiment, the inorganic particles comprise a material selected from a glass, a glass-ceramic, a ceramic, a nanoceramic, and a combination of at least two thereof.

[0032] According to some preferred embodiments, the inorganic particles comprise fluoride, phosphide, sulfide, oxysulfide or oxide based ceramics, glasses, or glass-ceramics.

[0033] According to some preferred embodiments, the inorganic particles comprise crystalline and / or amorphous forms of LISICON, thio-LISICON, argyrodite, garnet, NASICON, perovskite, oxide, sulfide, oxysulfide, phosphide or fluoride compounds, or a combination of at least two thereof.

[0034] According to some preferred embodiments, the inorganic particles are of the formula MLZO (e.g., M7La3Zr2O 12 , M(7-a) La3Zr2Al b O 12 , M (7-a) La3Zr2Ga b O 12 , M (7-a) La3Zr (2-b) Ta b O 12 , and M. (7-a) La3Zr (2-b) Nb b O 12 ), MLTaO (e.g., M7La3Ta2O 12 , M5La3Ta2O 12 , and M6La3Ta 1.5 Y 0.5 O 12 ), MLSnO (e.g., M7La3Sn2O 12 ), MAGP (e.g., M 1+a Al a Ge 2-a (PO4)3), MATP (e.g., M 1+a Al a Ti 2-a (PO4)3), MLTiO (e.g., M 3a La (2 / 3-a) TiO3), MZP (e.g., M a Zr b (PO4) c ), MCZP (e.g., M a Ca b Zr c (PO4) d ), MGPS (e.g., M a Ge b P c S d , e.g., M 10 GeP2S 12 ), MGPSO (e.g., M a Ge b P c S d O e ), MSiPS (e.g., M a S b P c S d , e.g., M 10 SiP2S 12 ), MSiPSO (e.g., M a S b Pc S d O e ), MSnPS (e.g., M a Sn b P c S d , e.g., M 10 SnP2S 12 ), MSnPSO (e.g., M a Sn b P c S d O e ), MPS (e.g., M a P b S c For example, M7P3S 11 ), MPSO (e.g., M a P b S c O d ), MZPS (e.g., M a Zinc b P c S d ), MZPSO (e.g., M a Zinc b P c S d O e ), xM2S-yP2S5, xM2S-yP2S5-zMX, xM2S-yP2S5-zP2O5, xM2S-yP2S5-zP2O5-wMX, xM2S-yM2O-zP2S5, xM2 S-yM2O-zP2S5-wMX, xM2S-yM2O-zP2S5-wP2O5, xM2S-yM2O-zP2S5-wP2O5-vMX, xM2S-ySiS2, MPSX (for example, M a P b S c X d For example, M7P3S 11 X, M7P2S8X, and M6PS5X), MPSOX (e.g., M a P b S c O d X e ), MGPSX(M a Ge b P c S d X e ), MGPSOX(M a Ge b P cS d O e X f ), MSiPSX(M a S b P c S d X e ), MSiPSOX(M a S b P c S d O e X f ), MSnPSX(M a Sn b P c S d X e ), MSnPSOX(M a Sn b P c S d O e X f ), MZPSX(M a Zinc b P c S d X e ), MZPSOX(M a Zinc b P c S d O e X f ), M3OX, M2HOX, M3PO4, M3PS4, and M a PO b N c (In the formula, a=2b+3c-5) (In the formula, M is an alkali metal ion, an alkaline earth metal ion, or a combination of at least two thereof, and when M comprises an alkaline earth metal ion, the number of M is adjusted to achieve electroneutrality; X is selected from F, Cl, Br, I, or a combination of at least two thereof; a, b, c, d, e and f are non-zero numbers and are independently selected in each formula to achieve electroneutrality; v, w, x, y and z are non-zero numbers and are independently selected in each formula to provide a stable compound. The compound includes a compound selected from the inorganic compounds of the formula:

[0035] According to one 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.

[0036] According to another example, the inorganic particles include an inorganic compound of the formula MATP.

[0037] According to another example, the inorganic particles include an argyrodite-type inorganic compound of formula Li6PS5X, where X is Cl, Br, I, or a combination of at least two thereof.

[0038] According to another example, the inorganic particles include an inorganic compound of the formula Li6PS5Cl.

[0039] According to another embodiment, the inorganic particles are present in the solid electrolyte at a concentration of about 25% to about 95% by weight, or about 40% to about 90% by weight, or about 60% to about 90% by weight.

[0040] According to another embodiment, the weight ratio of "inorganic particles:ionic bifunctional molecules" ranges from 2:1 to 30:1, or from 3:1 to 20:1, or from 5:1 to 15:1.

[0041] According to another embodiment, the solid electrolyte also includes a polymer.

[0042] According to one example, the polymer is a linear or branched polymer selected from polyethers, 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, polymethacrylates, and copolymers thereof.

[0043] According to one example, the polyether is poly(ethylene oxide) (PEO), poly(propylene oxide) (POP), or a copolymer (EO / PO).

[0044] According to another example, the crosslinkable functional groups are selected from acrylate, methacrylate, vinyl, glycidyl, and mercapto functional groups.

[0045] According to another example, a polymer is the reaction product of at least one monomer containing at least one polymerizable or crosslinkable functional group and a compound containing at least one SH functional group.

[0046] According to another embodiment, the polymer is present in the solid electrolyte at a concentration of about 0.1% to about 20% by weight, or about 1% to about 15% by weight, or about 2% to about 10% by weight.

[0047] According to another embodiment, the solid electrolyte also includes an additive.

[0048] According to one example, the additive is a fluorinated compound containing an amide functional group. For example, the fluorinated compound may be represented by the formula R 6 X 6 C(O)N(H)X 7 R 7 (In the formula, R 6 and R 7 is independently an alkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl group; X 6 is O, NH or absent, and X 7 is absent or is C(O), S(O)2 or Si(R 8 R 9 ) group, R 8 and R 9 is an alkyl group, R 6 , R 7 , R 8 and R 9 At least one of R is a group substituted with one or more fluorine atoms. 6 is a perfluorinated group, and X6 does not exist.

[0049] According to another example, the additive is present in the solid electrolyte at a concentration of about 5% to about 40% by weight, or about 10% to about 35% by weight, or about 15% to about 30% by weight.

[0050] According to another aspect, the present technology relates to an electrochemical cell including a negative electrode, a positive electrode, and an electrolyte, wherein the electrolyte is as defined herein.

[0051] According to one embodiment, the positive electrode comprises a positive electrode material that includes a positive electrode electrochemically active material.

[0052] According to one example, the positive electrode material is on the current collector.

[0053] According to another example, the positive electrode electrochemically active material is selected from metal phosphates, lithiated metal phosphates, metal oxides, and lithiated metal oxides.

[0054] According to another example, the positive electrode electrochemically active material may be LiM'PO4 (wherein M' is Fe, Ni, Mn, Co, or a combination of at least two thereof), LiV3O8, V2O5F, LiV2O5, LiMn2O4, LiM''O2 (wherein M'' is Mn, Co, Ni, or a combination of at least two thereof) (e.g., NMC, LiMn x Co y Ni z O2, where 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, e.g., graphite, organic cathode active materials, or a combination of at least two thereof, if compatible with each other.

[0055] According to another embodiment, the positive electrode material further comprises an electrically conductive material, a binder, a salt, an ionic bifunctional molecule, and / or an inorganic particle.

[0056] According to another embodiment, the negative electrode comprises a negative electrode material that includes a negative electrode electrochemically active material.

[0057] According to one example, the negative electrode material is on the current collector.

[0058] 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 containing an alkali or alkaline earth metal. According to one example, the alkali metal is selected from lithium and sodium.

[0059] According to further preferred embodiments, the negative electrode electrochemically active material is selected from the group consisting of intermetallic compounds (e.g., SnSb, TiSnSb, CuSb, AlSb, FeSb2, FeSn2, and CoSn2), metal oxides, metal nitrides, metal phosphides, metal phosphates (e.g., LiTi2(PO4)3), metal halides (e.g., metal fluorides), metal sulfides, metal oxysulfides, carbon (e.g., graphite, graphene, reduced graphene oxide, hard carbon, soft carbon, exfoliated graphite, and amorphous carbon), silicon (Si), silicon-carbon composites (Si-C), silicon oxides (SiO x ), silicon oxide-carbon composite (SiO x -C), tin (Sn), tin-carbon composite (Sn-C), tin oxide (SnO x ), tin oxide-carbon composite (SnO x -C), and combinations thereof, where compatible. According to one example, the metal oxide is of the formula M"" b O cCompounds of the formula (wherein M'''' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or combinations thereof, and b and c are numbers such that the ratio of c:b ranges from 2 to 3 (e.g., MoO3, MoO2, MoS2, V2O5, and TiNb2O7), oxide spinels (e.g., NiCo2O4, ZnCo2O4, MnCo2O4, CuCo2O4, and CoFe2O4), and LiM''''O (wherein M'''''' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or combinations thereof) (e.g., lithium titanates (e.g., Li4Ti5O 12 ), or lithium molybdate (e.g., Li2Mo4O 13 According to one example of interest, the negative electrode material further comprises an electrically conductive material, a binder, a salt, an ionic bifunctional molecule, and / or inorganic particles.

[0060] According to another aspect, the present technology relates to a battery comprising at least one electrochemical cell as defined herein.

[0061] In one embodiment, the 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. In one example of the object, the battery is a lithium battery. In another example of the object, the battery is a lithium ion battery. [Brief description of the drawings]

[0062] [Figure 1] FIG. 1 shows the results of differential scanning calorimetry obtained for salts 1, 2, 4 and 5 as described in Example 3.

[0063] [Diagram 2] FIG. 2 shows the results of the thermogravimetric analysis obtained for salts 1-5 as described in Example 3.

[0064] [Diagram 3]FIG. 3 is a graph showing linear sweep voltammetry curves obtained for cells containing electrolytes E1-E3 as described in Example 4(b).

[0065] [Figure 4] FIG. 4 is a graph showing cyclic voltammetry curves obtained for cells containing electrolytes E2 and E3 as described in Example 4(b).

[0066] [Diagram 5] FIG. 5 shows images of lithium foil immersed in (A) tetraethylene glycol dimethyl ether (TEGDME), (B) a solution of 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([PYR1,4]TFSI) in TEGDME, and (C) a solution of salt 1 in TEGDME, respectively, as described in Example 4(c).

[0067] [Figure 6] FIG. 6 shows an image of a solid electrolyte pellet as described in Example 5(a).

[0068] [Figure 7] FIG. 7 is a graph showing ionic conductivity results as a function of temperature for cells 4 (■), 5 (▲), 6 (●), and 7 (★) as described in Example 6(b).

[0069] [Figure 8] FIG. 8 is a graph showing ionic conductivity results as a function of temperature for cells 8 (■), 9 (●), 10 (▲), and 11 (▼) as described in Example 6(b).

[0070] [Figure 9] FIG. 9 shows scanning electron microscope (SEM) images of the ceramic-ion plastic salt composite solid electrolyte film E6 (A) before sweep, and (B) and (C) after sweep at a temperature of 70° C., as described in Example 6(c).

[0071] [Figure 10] FIG. 10 is a graph showing ionic conductivity results as a function of temperature for cells 12 (●) and 13 (▼) as described in Example 7(b). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0072] Detailed Description All scientific and technical terms and expressions used herein have the same definitions as commonly understood by those skilled in the art. Nevertheless, definitions of some of the terms and expressions used are provided below.

[0073] When the term "about" is used herein, it means approximately, in the range of, or around. For example, when the term "about" is used in connection with a numerical value, it modifies the numerical value by a variance of 10% above or below the numerical value. This term can also take into account, for example, experimental error or rounding of a measuring device.

[0074] When a range of values ​​is mentioned in this application, the upper and lower limits of the range are always included in this definition, unless otherwise indicated. When a range of values ​​is mentioned in this application, all intermediate ranges and subranges, as well as individual values, contained within the range of values ​​are included in this definition.

[0075] When the article "a" is used to introduce elements of the present application, it has the meaning of "one or more" and not "only one." It should be understood that when the description states that a particular step, component, element, or feature "may" be included or "can be included," that particular step, component, element, or feature need not be included in every embodiment.

[0076] The chemical structures described herein are drawn according to conventions in the art. Also, when a drawn atom, such as a carbon atom, appears to contain incomplete valences, it is assumed that the valences are satisfied by one or more hydrogen atoms, even if not explicitly described.

[0077] As used herein, the term "alkyl" refers to a saturated hydrocarbon having 1 to 12 carbon atoms, including straight-chain or branched alkyl groups. Non-limiting examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, tert-butyl, sec-butyl, and isobutyl. When an alkyl group is located between two functional groups, the term alkyl also includes alkylene groups, such as methylene, ethylene, and propylene. m ~C n Alkyl" and "C m ~C n The term "alkylene" refers to an alkyl or alkylene group having, respectively, a designated number "m" to a designated number "n" of carbon atoms.

[0078] As used herein, the term "cycloalkyl" refers to a group containing one or more saturated or partially unsaturated (non-aromatic) carbocyclic rings containing 3-15 members in a monocyclic or polycyclic system, including spiro (sharing atoms), fused (sharing at least one bond), or bridged carbocyclic rings, which may 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, and cycloheptyl. When a cycloalkyl group is located between two functional groups, the term cycloalkylene can also be used.

[0079] As used herein, the term "heterocycloalkyl" refers to a spiro (sharing atoms), fused (sharing at least one bond), or bridged, optionally substituted, mono- or polycyclic ring system containing 3-15 members and containing carbon atoms and 1-4 heteroatoms (e.g., N, O, S, or P), or groups containing such heteroatoms (e.g., NH, NR x (R x refers to groups containing saturated or partially unsaturated (non-aromatic) carbocyclic rings with a cyclic group (which may be an alkyl, acyl, aryl, heteroaryl, or cycloalkyl group), PO2, SO, SO2, and other similar groups). Heterocycloalkyl groups may be attached to a carbon atom or, where possible, to a heteroatom (e.g., via a nitrogen atom). The term heterocycloalkyl includes both unsubstituted and substituted heterocycloalkyl groups. When a heterocycloalkyl group is located between two functional groups, the term heterocycloalkylene can also be used.

[0080] The term "aryl" or "aromatic" refers to a monocyclic group having a total of 6 to 15 ring members, with at least one of the rings of the system being aromatic, or an aromatic group having 4n+2 conjugated π (pi) electrons (n ​​is a number from 1 to 3) in a fused bicyclic or tricyclic system. The term "aryl" or "aromatic" refers to both conjugated monocyclic and polycyclic systems. The term "aryl" or "aromatic" also includes 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, and perylenyl.

[0081] The terms "heteroaryl", "heteroarylene", or "heteroaromatic" refer to heterocyclic rings having 4n+2 conjugated π (pi) electrons (n ​​is a number from 1 to 3), e.g., 5 to 18 ring atoms, preferably 5, 6 or 9 ring atoms, in a conjugated monocyclic or polycyclic system (fused or not), and which, in addition to carbon atoms, contain 1 to 6 heteroatoms selected from oxygen, nitrogen and sulfur, or groups containing such heteroatoms (e.g., NH and NR x (R x refers to an aromatic group having an alkyl, acyl, aryl, heteroaryl, or cycloalkyl group), SO, and other similar groups. Polycyclic ring systems contain at least one heteroaromatic ring. Heteroaryls may be directly bonded or bonded via a C1-C3 alkyl group (also called heteroarylalkyl or heteroaralkyl). Heteroaryl groups may be bonded to a carbon atom or, where possible, to a heteroatom (e.g., via a nitrogen atom).

[0082] In general, the term "substituted" means that one or more hydrogen atoms of the indicated group are replaced by a suitable substituent. The substituents or combinations of substituents contemplated in this description are those that result in the formation of chemically stable compounds. Examples of substituents include halogen atoms (e.g., fluorine), and hydroxyl, oxo, alkyl, alkoxyl, alkoxyalkyl, nitrile, azide, carboxylate, alkoxycarbonyl, alkylcarbonyl, primary, secondary or tertiary amine, amide, nitro, silane, siloxane, thiocarboxylate, sulfonyl, sulfonate, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocycloalkyl groups, or combinations thereof.

[0083] The present technology generally relates to solid electrolytes and their use in electrochemical applications. For example, the solid electrolyte can be a primary inorganic solid electrolyte or a polymer-ceramic hybrid solid electrolyte.

[0084] The present technology more particularly relates to a method for producing a polymer comprising: [ka] (In the formula, A - is a delocalized anion, R + -N excluding cations derived from amidine, guanidine, and phosphazene superbases + (R1R2R3) and -P + (R1R2R3) groups, R1, R2 and R3 are independently substituted or unsubstituted, linear or branched C 1~12 alkyl groups, or R1 and R2 together with the nitrogen or phosphorus atom have one or more rings and form a heterocyclic ring having 3 to 12 members, and R3 is as previously defined, or R1, R2 and R3 together with the nitrogen or phosphorus atom have one or more rings and form a partially unsaturated heterocyclic ring or heteroaromatic ring having 5 to 12 members, L is a linear or branched C 2~4 is alkylene, X is O or S; m is a number ranging from 1 to 6; n is a number ranging from 1 to 11. The present invention relates to a solid electrolyte comprising an ionic bifunctional molecule of the formula:

[0085] The delocalized anion is 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), fluoroalkyl phosphate ([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(C2O4) - or F.O.B. - ), and the formula BF2O4R x (R x =C 2~4 For example, the delocalized anion may be 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).

[0086] According to one example, R + is the formula -N + (R1R2R3), where R1, R2 and R3 are independently substituted or unsubstituted, linear or branched C 1~12alkyl group).

[0087] According to another example, R + is the formula -N + (R1R2R3) (wherein R1, R2 and R3 are independently linear or branched C 1~12 or at least one of R1, R2 or R3 is substituted by a halogen atom, or an alkoxyl, ether, ester or siloxy group.

[0088] According to another example, R + is the formula -N + (R1R2R3) in which R1 and R2 together with the nitrogen atom form a heterocycle having one or more rings and 3 to 12 members, and R3 is as previously defined, preferably R3 is C 1~12 Alkyl group or C 1~4 According to the preferred embodiment, R3 is an unsubstituted C 1~4 An alkyl group (eg, methyl, ethyl, n- or i-propyl, n-, i-, s- and t-butyl), preferably R3 is a methyl group.

[0089] According to another example, R + is the formula -N + (R1R2R3) where R1, R2 and R3 together with the nitrogen atom form a partially unsaturated heterocyclic or heteroaromatic ring having one or more rings and having 5 to 12 members.

[0090] According to another example, R + teeth, [ka] (In the formula, R3 is as previously defined, and R4 is a substituted or unsubstituted, linear or branched C 1~12 Alkyl, C 1~12 Alkenyl, and C 1~12 Alkynyl groups, preferably C 1~4alkyl, R5 is a hydrogen atom, or C 1~12 Alkyl groups, substituted or unsubstituted, linear or branched, C 1~12 Alkenyl or C 1~12 Alkynyl, preferably C 1~4 alkyl, preferably R3 is unsubstituted C 1~4 an alkyl group (e.g. methyl, ethyl, n- or i-propyl, n-, i-, s- and t-butyl, preferably methyl); The heterocycle is optionally substituted. is selected from.

[0091] According to another example, R + is the formula -P + (R1R2R3), where R1, R2 and R3 are independently substituted or unsubstituted, linear or branched C 1~12 alkyl group).

[0092] According to another example, R + is the formula -P + (R1R2R3) (wherein R1, R2 and R3 are independently linear or branched C 1~12 or at least one of R1, R2 or R3 is substituted by a halogen atom, or an alkoxyl, ether, ester or siloxy group.

[0093] According to some examples, n can be a number ranging from 2 to 10, or 3 to 8, or 4 to 6, inclusive.

[0094] 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'-(thiolbis(1,2-ethane))bis(1-methylpyrrolidinium), 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.

[0095] The ionic bifunctional molecule may be present in the electrolyte at a concentration ranging from about 0.5% to about 50% by weight, inclusive. For example, the ionic bifunctional molecule may be present in the electrolyte at a concentration ranging from about 2% to about 30% by weight, inclusive, or from about 4% to about 20% by weight, inclusive, or from about 5% to about 15% by weight, inclusive.

[0096] 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 components of the electrochemical cell. For example, the inorganic particles can include a material selected from glass, glass-ceramic, ceramic, nanoceramic, and combinations of at least two thereof.

[0097] According to one example, the inorganic particles may include fluoride, phosphide, sulfide, oxysulfide or oxide based ceramics, glasses, or glass-ceramics.

[0098] According to another example, the inorganic particles may include crystalline and / or amorphous forms of LISICON, thio-LISICON, argyrodite, garnet, NASICON, perovskite, oxide, sulfide, oxysulfide, phosphide or fluoride compounds, or a combination of at least two thereof.

[0099] According to another example, the inorganic particles may have the formula: - MLZO (e.g. M7La3Zr2O 12 , M (7-a) La3Zr2Al b O 12 , M (7-a) La3Zr2Ga b O 12 , M (7-a) La3Zr (2-b) Ta b O 12 , and M. (7-a) La3Zr (2-b) Nb b O 12 ), - MLTaO (e.g., M7La3Ta2O 12 , M5La3Ta2O 12 , and M6La3Ta 1.5 Y 0.5 O 12 ), - MLSnO (e.g., M7La3Sn2O 12 ), - MAGP (e.g., M 1+a Al a Ge 2-a (PO4)3), - MATP (e.g., M 1+a Al a Ti 2-a (PO4)3), - MLTiO (e.g., M 3a La (2 / 3-a) TiO3), - MZP (e.g., M a Zr b (PO4) c ), - MCZP (e.g., M a Ca b Zr c (PO4)d ), - MGPS (e.g., M a Ge b P c S d , e.g., M 10 GeP2S 12 ), - MGPSO (e.g., M a Ge b P c S d O e ), - MSiPS (e.g., M a S b P c S d , e.g., M 10 SiP2S 12 ), - MSiPSO (e.g., M a S b P c S d O e ), - MSnPS (e.g., M a Sn b P c S d , e.g., M 10 SnP2S 12 ), - MSnPSO (e.g., M a Sn b P c S d O e ), - MPS (e.g., M a P b S c For example, M7P3S 11 ), - MPSO (e.g., M a P b S c O d ), - MZPS (e.g., M a Zinc b P c S d ), - MZPSO (e.g., M a Zinc b P c Sd O e ), - 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 (e.g. M a P b S c X d For example, M7P3S 11 X, M7P2S8X, and M6PS5X), - MPSOX (e.g. M a P b S c O d X e ), - MGPSX (e.g., M a Ge b P c S d X e ), - MGPSOX (e.g., M a Ge b P c S d O e X f ), - MSiPSX (e.g. M a S b P c S d X e ), - MSiPSOX (e.g., M a S b P c S d O e X f ), - MSnPSX (e.g., Ma Sn b P c S d X e ), - MSnPSOX (e.g., M a Sn b P c S d O e X f ), - MZPSX (e.g. M a Zinc b P c S d X e ), - MZPSOX (e.g., M a Zinc b P c S d O e X f ), - M3OX, - M2HOX, - M3PO4, - M3PS4, and - M a PO b N c (In the formula, a=2b+3c-5) (In the formula, M is an alkali metal ion, an alkaline earth metal ion, or a combination thereof, and when M comprises an alkaline earth metal ion, the number of M's is adjusted to achieve electroneutrality; X is selected from F, Cl, Br, I, or a combination of at least two thereof; a, b, c, d, e and f are non-zero numbers and are independently selected in each formula to achieve electroneutrality; v, w, x, y and z are non-zero numbers and are independently selected in each formula to provide a stable compound. The compound includes a compound selected from the inorganic compounds of the formula:

[0100] For example, M may 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.

[0101] According to a variant of interest, the inorganic particles comprise an inorganic compound of formula MATP as defined herein.

[0102] According to another variant of the object, the inorganic particles comprise an argyrodite-type inorganic compound of formula Li6PS5X, where X is Cl, Br, I, or a combination of at least two thereof. For example, the inorganic particles may comprise an inorganic compound of formula Li6PS5Cl.

[0103] The inorganic particles may be present in the solid electrolyte at a concentration ranging from about 25% to about 95% by weight, inclusive. For example, the inorganic particles may be present in the solid electrolyte at a concentration ranging from about 40% to about 90% by weight, inclusive, or from about 60% to about 90% by weight, inclusive.

[0104] The mass ratio of "inorganic particles:ionic bifunctional molecules" can be in the range of 2:1 to 30:1, inclusive. For example, the mass ratio of "inorganic particles:ionic bifunctional molecules" can be in the range of 3:1 to 20:1, inclusive, or 5:1 to 15:1, inclusive.

[0105] The solid electrolyte as defined herein may further comprise a polymer. For example, the polymer may be selected for its compatibility with various components of the electrochemical cell. Any known compatible polymer is contemplated. The polymer may be selected from linear or branched polymers. Non-limiting examples of polymers include polyethers (e.g., polyethers based on poly(ethylene oxide) (PEO), poly(propylene oxide) (POP), or combinations of the two (e.g., EO / PO copolymers)), 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, as well as copolymers thereof optionally containing crosslinking units derived from crosslinkable functional groups (e.g., acrylate, methacrylate, vinyl, glycidyl, mercapto functional groups, and the like) or crosslinked equivalents thereof.

[0106] According to one example, the polymer, when present in the electrolyte, can be the reaction product of at least one monomer containing at least one polymerizable or crosslinkable functional group and a compound containing at least one SH functional group.

[0107] According to another example, the polymer may be present in the solid electrolyte at a concentration ranging from about 0.1% to about 20% by weight, inclusive. For example, the polymer may be present in the solid electrolyte at a concentration ranging from about 1% to about 15% by weight, inclusive, or from about 2% to about 10% by weight, inclusive.

[0108] For example, an ionic bifunctional molecule as defined herein acts as a binder between inorganic particles in a solid electrolyte as defined herein, where the binder may also further comprise a polymer as defined herein.

[0109] A solid electrolyte as defined herein may also optionally contain additives.

[0110] According to one example, the additive, when present in the electrolyte, can be a fluorinated compound containing an amide functional group. The fluorinated compound has the formula R 6 X 6 C(O)N(H)X 7 R 7 (In the formula, R 6 and R 7 is independently an alkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl group; X 6 is O, NH or absent, and X 7 is absent or is C(O), S(O)2 or Si(R 8 R 9 ) group, R 8 and R 9 is an alkyl group, R 6 , R 7 , R 8 and R 9 At least one of R is a group substituted with one or more fluorine atoms. For example, 6 is a perfluorinated group, and X 6 does not exist.

[0111] According to one example, the additive, when present in the electrolyte, may be present in the solid electrolyte at a concentration ranging from about 5% to about 40% by weight, inclusive. For example, the additive may be present in the solid electrolyte at a concentration ranging from about 10% to about 35% by weight, inclusive, or from about 15% to about 30% by weight, inclusive.

[0112] The present technology also relates to an electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte, wherein the electrolyte is as defined herein.

[0113] 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.

[0114] For example, the metal of the electrochemically active material may 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, where appropriate, a combination of at least two thereof. According to a variant of interest, the metal of the electrochemically active material may be selected from titanium (Ti), iron (Fe), magnesium (Mg), manganese (Mn), vanadium (V), nickel (Ni), cobalt (Co), aluminum (Al), and, where appropriate, a combination of at least two thereof.

[0115] Non-limiting examples of positive electrode electrochemically active materials generally include metal phosphates and lithiated metal phosphates (e.g., LiM'PO4 and M'PO4, where M' is selected from Fe, Ni, Mn, Co, and combinations of at least two thereof), vanadium oxides and lithium vanadium oxides (e.g., LiV3O8, VO5, LiV2O5, and similar vanadium oxides and lithium vanadium oxides), and lithium metal oxides (e.g., NMC, LiMn2O4, LiM''O2, where M'' is selected from Mn, Co, Ni, and combinations of at least two thereof) of the formula. x Co y Ni z O2, where x+y+z=1), Li(NiM''')O2, where M''' is selected from Mn, Co, Al, Fe, Cr, Ti, Zr, another like metal, and combinations of at least two thereof, sulfur, elemental selenium, elemental iodine, iron(III) fluoride, copper(II) fluoride, lithium iodide, carbon-based active materials, e.g., graphite, organic cathode active materials, or combinations of at least two of these electrochemically active materials, if compatible with each other.

[0116] Positive electrode materials as defined herein may further comprise electrically conductive materials, binders, salts, ionic bifunctional molecules (e.g., ionic bifunctional molecules as previously defined), and / or inorganic particles.

[0117] The negative electrode comprises a negative electrode electrochemically active material optionally on a current collector.

[0118] According to one example, the negative electrode electrochemically active material may include a metal film comprising an alkali or alkaline earth metal, or an alloy including an alkali or alkaline earth metal. For example, the alkali metal may be selected from lithium and sodium.

[0119] According to another example, the negative electrode electrochemically active material can be an intermetallic compound (e.g., SnSb, TiSnSb, CuSb, AlSb, FeSb2, FeSn2, and CoSn2), a metal oxide, a metal nitride, a metal phosphide, a metal phosphate (e.g., LiTi2(PO4)3), a metal halide (e.g., a metal fluoride), a metal sulfide, a metal oxysulfide, carbon (e.g., graphite, graphene, reduced graphene oxide, hard carbon, soft carbon, exfoliated graphite, and amorphous carbon), silicon (Si), silicon-carbon composites (Si-C), silicon oxide (SiO x ), silicon oxide-carbon composite (SiO x -C), tin (Sn), tin oxide-carbon composite (Sn-C), tin oxide (SnO x ), tin oxide-carbon composite (SnO x -C), and, where compatible, a combination of at least two thereof. For example, the metal oxide may be of the formula M"" b O cCompounds of the formula (wherein M'''' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or combinations thereof, and b and c are numbers such that the ratio of c:b ranges from 2 to 3 (e.g., MoO3, MoO2, MoS2, V2O5, and TiNb2O7), oxide spinels (e.g., NiCo2O4, ZnCo2O4, MnCo2O4, CuCo2O4, and CoFe2O4), and LiM''''O (wherein M'''''' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or combinations thereof) (e.g., lithium titanates (e.g., Li4Ti5O 12 ), or lithium molybdate (e.g., Li2Mo4O 13 )) may be selected from.

[0120] According to another example, the negative electrode material may further include an electrically conductive material, a binder, a salt, an ionic bifunctional molecule (e.g., an ionic bifunctional molecule as previously defined), and / or inorganic particles.

[0121] The present technology also relates to a battery comprising at least one electrochemical cell as defined herein. For example, said battery is selected from the group consisting of lithium battery, lithium ion battery, sodium battery, sodium ion battery, potassium battery, potassium ion battery, magnesium battery, and magnesium ion battery. According to a variant of the object, said battery is a lithium battery or a lithium ion battery.

[0122] The presence of ionic bifunctional molecules as defined herein in a solid electrolyte, for example an inorganic solid electrolyte or a polymer-ceramic hybrid solid electrolyte, may significantly improve some of its physical and / or electrochemical properties.

[0123] According to one example, the presence of ionic bifunctional molecules can substantially improve, for example, the mechanical strength of the solid electrolyte film and / or the densification of said solid electrolyte film after sweeping. According to another example, the presence of ionic bifunctional molecules can substantially improve the ionic conductivity and / or electrochemical stability of the solid electrolyte film. In some examples, the presence of ionic bifunctional molecules can also substantially improve the flammability safety of the solid electrolyte film. EXAMPLES

[0124] The following examples are for illustrative purposes and should not be construed to further limit the scope of the invention as contemplated. These examples are better understood with reference to the accompanying drawings.

[0125] Example 1 Preparation and characterization of bifunctional ionic salts

[0126] a) Preparation of 1,1'-(1,6-hexamethylene)bis(1-methylpyrrolidinium) dibromide

[0127] 8 g (94.1 mmol) of 1-methylpyrrolidine, 10.4 g (42.8 mmol) of 1,6-dibromohexane, and 20 ml of tetrahydrofuran (THF) were introduced into a 100 ml one-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 collected 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.

[0128] b) Preparation of 1,1'-(1,6-hexamethylene)bis(1-methylpyrrolidinium)bis(trifluoromethanesulfonyl)imide (salt 1) [ka]

[0129] 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.

[0130] c) Preparation of 1,1'-(1,12-dodecamethylene)bis(1-methylpyrrolidinium) dibromide

[0131] 8 g (94.1 mmol) of 1-methylpyrrolidine, 10.3 g (31.4 mmol) of 1,12-dibromododecane, and 20 ml of THF were introduced into a 100 ml one-neck flask. The solution was heated to about 50° C. for about 12 hours. The precipitate formed during the reaction was then collected 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.

[0132] d) Preparation of 1,1'-(1,12-dodecamethylene)bis(1-methylpyrrolidinium)bis(trifluoromethanesulfonyl)imide (salt 2) [ka]

[0133] 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)dibromide prepared in Example 1(c). The anion exchange was carried out in water at a temperature of about 40° C. for about 3 hours.

[0134] e) Preparation of 1,1'-(2,2'-(ethylenedioxy)diethane)bis(1-methylpyrrolidinium) dichloride

[0135] 4 g (46.6 mmol) of 1-methylpyrrolidine, 2.9 g (15.6 mmol) of 1,2-bis(2-chloroethoxy)ethane, and 10 ml of THF were introduced into a 50 ml one-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 collected 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.

[0136] f) Preparation of 1,1'-(2,2'-(ethylenedioxy)diethane)bis(1-methylpyrrolidinium)bis(trifluoromethanesulfonyl)imide (salt 3) [ka]

[0137] 1,1'-(2,2'-(ethylenedioxy)diethane)bis(1-methylpyrrolidinium)bis(trifluoromethanesulfonyl)imide (salt 3) was prepared by anion exchange from LiTFSI and 1,1'-(2,2'-(ethylenedioxy)diethane)bis(1-methylpyrrolidinium)dichloride prepared in Example 1(e). The anion exchange was carried out in water at a temperature of about 40° C. for about 3 hours.

[0138] g) Preparation of 1-(2-hydroxyethyl)-1-methylpyrrolidinium iodide

[0139] 5.75 g (50 mmol) of 1-(2-hydroxyethyl)pyrrolidine, 8.52 g (60 mmol) of iodomethane, and 10 ml of THF were introduced into a 50 ml one-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 collected 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.

[0140] h) Preparation of 1-(2-chloroxyethyl)-1-methylpyrrolidinium iodide

[0141] 5.14 g (20 mmol) of 1-(2-hydroxyethyl)-1-methylpyrrolidinium iodide prepared in Example 1(g) and 23.8 g (0.2 mol) of thionyl dichloride were introduced into a 50 ml one-neck flask. The solution was heated to a temperature of about 70° C. for about 24 hours. The product was precipitated in 100 ml of diethyl ether. The precipitate was then collected 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.

[0142] i) Preparation of 1,1'-(thiolbis(1,2-ethane))bis(1-methylpyrrolidinium) iodide

[0143] 3 g (11 mmol) of 1-(2-chloroxyethyl)-1-methylpyrrolidinium prepared in Example 1(h), 0.43 g (5.5 mmol) of sodium sulfide, 0.04 g (1 mmol) of sodium hydroxide, 40 ml of deionized water, and 60 ml of methanol were introduced into a 250 ml one-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 collected 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.

[0144] j) Preparation of 1,1'-(thiolbis(1,2-ethane))bis(1-methylpyrrolidium)bis(trifluoromethanesulfonyl)imide (salt 4) [ka]

[0145] 1,1'-(thiolbis(1,2-ethane))bis(1-methylpyrrolidium)bis(trifluoromethanesulfonyl)imide (salt 4) was prepared by anion exchange from LiTFSI and 1,1'-(thiolbis(1,2-ethane))bis(1-methylpyrrolidium)iodide prepared in Example 1(i). The anion exchange was carried out in a water:methanol mixture (2:8 by volume) at a temperature of about 40° C. for about 3 hours.

[0146] k) Preparation of 3,3'-(1,6-hexamethylene)bis(1,2-dimethylimidazolium) dibromide

[0147] 5.77 g (60 mmol) of 1,2-dimethylimidazole, 4.88 g (20 mmol) of 1,6-dibromohexane, and 10 ml of THF were introduced into a 50 ml one-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 collected 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.

[0148] l) Preparation of 3,3'-(1,6-hexamethylene)bis(1,2-dimethylimidazolium)bis(trifluoromethanesulfonyl)imide (salt 5) [ka]

[0149] 3,3'-(1,6-hexamethylene)bis(1,2-dimethylimidazolium)bis(trifluoromethanesulfonyl)imide (Sel5) was prepared by anion exchange from LiTFSI and 3,3'-(1,6-hexamethylene)bis(1,2-dimethylimidazolium)dibromide prepared in Example 1(k). The anion exchange was carried out in water at a temperature of about 40°C for about 3 hours.

[0150] Example 2 Nuclear magnetic resonance (NMR) characterization

[0151] The salts 1 to 5 prepared in Example 1 were analyzed by proton nuclear magnetic resonance ( 1 The compound was characterized by 1 H NMR.

[0152] a) NMR characterization of salt 1 prepared in Example 1(b)

[0153] Salt 1 prepared in Example 1(b) 1H NMR spectra were obtained in methanol-d4 (deuterated methanol or CD3OD) as the solvent, and the results are shown in Table 1. [Table 1]

[0154] b) of salt 2 prepared in Example 1(d) 1 H NMR characterization

[0155] Salt 2 prepared in Example 1(d) 1 H NMR spectra were obtained in chloroform-d (deuterated chloroform or CDCl3) as the solvent, and the results are shown in Table 2. [Table 2]

[0156] c) of salt 3 prepared in Example 1(f) 1 H NMR characterization

[0157] Salt 3 prepared in Example 1(f) 1 H NMR spectra were obtained in CDCl3 as the solvent, and the results are shown in Table 3. [Table 3]

[0158] d) of salt 4 prepared in Example 1(j) 1 H NMR characterization

[0159] Salt 4 prepared in Example 1(j) 1 H NMR spectra were obtained in dimethylsulfoxide-d6 (deuterated dimethylsulfoxide or DMSO-d6) as the solvent, and the results are shown in Table 4. [Table 4]

[0160] e) of salt 5 prepared in Example 1(l) 1 H NMR characterization

[0161] Salt 5 prepared in Example 1(l) 1 H NMR spectra were obtained in DMSO-d6 as the solvent, and the results are shown in Table 5. [Table 5]

[0162] Example 3 Thermal and Thermogravimetric Analysis

[0163] Figure 1 shows the differential scanning calorimetry (DSC) analysis results obtained for salts 1, 2, 4 and 5 prepared in Examples 1(b), 1(d) and 1(l), respectively. The DSC analyses were carried out over a temperature range of about -20°C to about 148°C at a heating rate (or speed) 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.

[0164] Figure 2 shows the thermogravimetric analysis (TGA) results obtained for salts 1-5 prepared in Examples 1(b), 1(d), 1(f), 1(j) and 1(l), respectively. The thermogravimetric analyses were carried out over a temperature range of about 40°C to about 600°C. As shown in Figure 2, salt 1 has a decomposition point of approximately 295°C.

[0165] The results of the thermal analysis and thermogravimetric analysis are shown in Table 6. [Table 6]

[0166] Example 4 Chemical and electrochemical stability

[0167] The electrochemical stability of the liquid electrolyte containing salt 1 prepared in Example 1(b) was characterized by linear sweep voltammetry (LSV) and cyclic voltammetry (CV).

[0168] a) Cell configuration for electrochemical stability analysis

[0169] A liquid electrolyte was prepared containing LiTFSI, TEGDME as a solvent, and the salt 1 prepared in Example 1(b). 1,4 A liquid electrolyte containing TFSI was also prepared for comparison. The composition of the liquid electrolyte used for the electrochemical stability analysis is shown in Table 7. [Table 7]

[0170] A Celgard™ 2325 separator made of a three-layer microporous polypropylene-polyethylene-polypropylene (PP / PE / PP) membrane approximately 25 μm thick was impregnated with the liquid electrolyte. A disk with a diameter of 16 mm was then cut from the membrane impregnated with the liquid electrolyte.

[0171] The cells for electrochemical stability analysis were assembled according to the following procedure: The cells were assembled in a button cell configuration: a disk impregnated with the liquid electrolyte prepared in this example was placed and pressed between aluminum and lithium electrodes (Al / electrolyte / Li) for the oxidation process, and between copper and lithium electrodes (Cu / electrolyte / Li) for the reduction process.

[0172] The configuration of each cell is shown below. Cell 1: Electrode / E1 / Electrode Cell 2: Electrode / E2 / Electrode Cell 3: Electrode / E3 / Electrode

[0173] b) Electrochemical stability analysis

[0174] Electrochemical stability measurements for cells 1-3 assembled in Example 4(a) were carried out by LSV. Electrochemical stability measurements for cells containing electrolytes E2 and E3 were also carried out by CV. Measurements were carried out using a Bio-Logic™ VMP-300 system at a scan rate of 0.1 mV / s.

[0175] 3 and 4 show the results of the LSV and CV analysis, respectively. As shown in FIG. 3 and 4, cell 3 containing a liquid electrolyte containing LiTFSI, TEGDME, and salt 1 prepared in Example 1(b) showed a high electrochemical conductivity of LiTFSI, TEGDME, and [PYR 1,4 ] Cells containing liquid electrolytes containing TFSI have electrochemical stability exceeding that of cells 2.

[0176] c) Chemical stability analysis

[0177] TEGDME, [PYR 1,4 ] The chemical stability of a TEGDME solution containing TFSI and a TEGDME solution containing salt 1 prepared in Example 1(b) against lithium metal was analyzed.

[0178] Figure 5 shows (A) TEGDME and (B) TEGDME:[PYR 1,4 ]TFSI (40:60 depending on weight) ratio of [PYR 1,4 5 shows images of lithium foil immersed in (A) a TEGDME solution containing TFSI, (B) a TEGDME solution containing salt 1 as prepared in Example 1(b) in a ratio of TEGDME:salt 1 (41:59 by weight). The lithium foil was left in the three different solutions for about one week. As shown in FIG. 5, the [PYR 1,4 Only the TEGDME solution containing TFSI changed color from transparent to black (Figure 5(B)). This indicates that the chemical stability of TEGDME and the TEGDME solution containing salt 1 is improved by the addition of [PYR 1,4 ] shows that the chemical stability is higher than that of a TEGDME solution containing TFSI.

[0179] Example 5 Preparation and characterization of inorganic solid electrolytes

[0180] a) Preparation of inorganic solid electrolyte pellets

[0181] Li 1.3 Al 0.3 Ti 1.7 0.294 g of (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. The solid electrolyte powder was compressed under a pressure of 120 psi to obtain a round pellet with a diameter of about 16 mm and a thickness of about 900 μm.

[0182] FIG. 6 shows images of a solid electrolyte pellet showing (A) its diameter (about 16 mm), and (B) its thickness (about 900 μm), respectively.

[0183] b) Ionic conductivity

[0184] The ionic conductivity of the inorganic solid electrolyte pellets prepared in Example 5(a) was characterized by electrochemical impedance spectroscopy.

[0185] To achieve this, the inorganic solid electrolyte pellets prepared in Example 5(a) were placed between two stainless steel electrodes and pressed.

[0186] Electrochemical impedance spectroscopy measurements were performed using a Bio-Logic™ VMP-300 system at an amplitude of 100 mV over the frequency range of 1 MHz to 200 mHz. An ionic conductivity of 2.5 mS / cm was measured at a temperature of 60° C.

[0187] Example 6 Preparation and characterization of ceramic-ionic plastic salt composite solid electrolyte films

[0188] The crosslinkable polymer used in the following examples is a hyperbranched polyether containing crosslinkable units as described in US Pat. No. 7,897,674 (hereinafter referred to as the "US '674 polymer").

[0189] The ionic plastic crystals used in the following examples are delocalized bis(trifluoromethanesulfonyl)imide [TFSI] 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 WO2022 / 165598. - They are ionic plastic crystals containing anions (hereinafter referred to as "WO'598 plastic crystals").

[0190] a) Preparation of ionic ceramic-salt composite solid electrolyte films

[0191] A composite solid electrolyte film was prepared comprising a sulfide-based ceramic and salt 1 prepared in Example 1(b). A composite solid electrolyte film comprising a sulfide-based ceramic and WO'598 plastic crystal was also prepared for comparison purposes.

[0192] All manipulations were carried out in a glove box under an argon atmosphere (0.1 ppm H2O; 0.1 ppm O2).

[0193] Sulfide-based ceramic inorganic solid electrolyte particles (Li6PS5Cl) of two sizes (approximately 3 μm and less than 1 μm) were mixed in a mass ratio of 90:10 or 75:25 using a vortex.

[0194] The binders used included a mixture of 40:60 by weight US'674 polymer and 0.5 wt% UV crosslinker, WO'598 plastic crystals or one of salts 1-5 dissolved in dichloromethane (DCM). For binders containing salts 4 and 5, a small amount of acetone was added to achieve good dissolution of the salt.

[0195] 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 of suitable viscosity. The mixture thus obtained was coated onto a pre-degreased aluminum foil. The film thus obtained was dried in a glove box. After drying, UV curing was performed for about 15 seconds.

[0196] The composition of the ceramic-ion plastic composite solid electrolyte film is shown in Table 8. [Table 8]

[0197] b) Ionic conductivity of ceramic-ionic plastic salt composite solid electrolyte film

[0198] A pellet with a diameter of 10 mm was taken from the ceramic-ion plastic salt composite solid electrolyte film prepared in Example 6(a). The pellet was placed in a mold with a diameter of 10 mm and compressed under a pressure of 2.8 tons using a press. The pellet was then placed in a conduction cell at a pressure of 5 MPa and sealed under an inert argon atmosphere. The configuration of each cell is shown below. Cell 4: electrode / E4 / electrode Cell 5: electrode / E5 / electrode Cell 6: Electrode / E6 / Electrode Cell 7: Electrode / E7 / Electrode Cell 8: Electrode / E8 / Electrode Cell 9: Electrode / E9 / Electrode Cell 10: Electrode / E10 / Electrode Cell 11: Electrode / E11 / Electrode

[0199] Ionic conductivity measurements of the cells assembled in this example were performed on a VMP-300 multichannel potentiostat (Bio-Logic™). Measurements were performed at an amplitude of 50 mV over a frequency range of 7 MHz to 200 mHz, over a temperature range of -10°C to 70°C (in 10°C increments) and over a temperature range of 70°C to 20°C (in 10°C decrements).

[0200] Impedance measurements were taken after a stabilization time of approximately 1 hour. At each temperature, two impedance measurements were recorded at each measurement interval of 15 minutes. Figure 7 shows the ionic conductivity measurements as a function of temperature for cells 4 (■), 5 (▲), 6 (●), and 7 (★). Figure 8 shows the ionic conductivity measurements as a function of temperature for cells 8 (■), 9 (●), 10 (▲), and 11 (▼).

[0201] It can be observed in FIG. 7 that the ionic conductivities of cells 5 and 7 are lower than those of cells 4 and 6, which contain Li6PS5Cl (3 μm:<1 μm) in mass ratios of 75:25 and 90:10, respectively.

[0202] FIG. 7 shows that the ionic conductivity of cells 6 and 7 is substantially higher than that of cells 4 and 5, which contain ceramic-ionic plastic salt composite solid electrolyte films with salt 1 and WO'598 plastic crystal, respectively, indicating a better interaction of lithium ions from sulfide-based ceramic-type inorganic solid electrolytes with bifunctional ionic salts.

[0203] FIG. 7 also shows that the ionic conductivity of cell 7 containing salt 1 (75:25 Li6PS5Cl mass ratio (3 μm:<1 μm)) is similar to that of cell 4 containing WO'598 plastic crystal (90:10 Li6PS5Cl mass ratio (3 μm:<1 μm)). This indicates that with bifunctional ionic salts it is possible to increase the loading of smaller size (<1 μm) Li6PS5Cl particles and thus obtain better compactness of the ceramic-ionic plastic salt composite solid electrolyte film under compression while maintaining substantially high performance.

[0204] At a temperature of 20° C., the ionic conductivity results for cells 6 and 7 are slightly lower than the ionic conductivity obtained for sulfide-based ceramic type inorganic solid electrolyte particles (Li6PS5Cl) compressed alone and without an aluminum support but measured under the same conditions.

[0205] In FIG. 8 it can be observed that the ionic conductivities obtained for cells 8, 9 and 11 containing ceramic-ionic plastic salt composite solid electrolyte films with salts 2, 3 and 5, respectively, are higher than the ionic conductivities obtained for cell 10 containing ceramic-ionic plastic salt composite solid electrolyte film with salt 4.

[0206] c) Scanning Electron Microscopy (SEM) characterization of ceramic-ionic plastic salt composite solid electrolyte films

[0207] FIG. 9 shows SEM images of the E6 ceramic-ion plastic salt composite solid electrolyte film prepared in Example 6(a) taken (A) before sweep, and (B) and (C) after sweep at a temperature of about 70° C.

[0208] Figure 9(A) shows that the ceramic-ion plastic salt composite solid electrolyte film after compression but before sweeping is substantially dense and has a thickness of about 40 μm. Individual grains and / or agglomerates of the sulfide-based ceramic are distinguishable.

[0209] 9(B) and (C) show the effect of temperature sweeping at 70° C. (above the melting temperature of salt 1) and down to room temperature. After the sweep, it can be observed that the ceramic-ion plastic salt composite solid electrolyte film is substantially denser and no longer shows agglomeration. This can be useful for lithium dendrite resistance in so-called "all solid" configurations, especially in lithium metal configurations.

[0210] Example 7 Preparation and characterization of ceramic-ionic plastic salt composite solid electrolyte films crosslinked with 4,4'-thiobisbenzenethiol (TBT)

[0211] a) Preparation of ceramic-ion-plastic salt composite solid electrolyte film and TBT cross-linking

[0212] All manipulations were carried out in a glove box under an argon atmosphere (0.1 ppm H2O; 0.1 ppm O2).

[0213] Sulfide-based ceramic-type inorganic solid electrolyte particles (Li6PS5Cl) of two sizes (approximately 3 μm and less than 1 μm) were mixed in a mass ratio of 90:10 using a vortex.

[0214] The binder used included a 40:60 by weight mixture of US'674 polymer and 4.0 wt % TBT, and salt 1 prepared in Example 1(b) dissolved in DCM.

[0215] The mass ratio of sulfide to binder was 90:10 by weight. The amount of DCM was adjusted to obtain a mixture of suitable viscosity. The mixture thus obtained was coated onto a pre-degreased aluminum foil. The film thus obtained was dried in a glove box.

[0216] The composition of the ceramic-ion plastic salt composite solid electrolyte film is shown in Table 9. [Table 9]

[0217] b) Ionic conductivity of polymer-ceramic hybrid solid electrolyte film

[0218] A pellet with a diameter of 10 mm was taken from the ceramic-ion plastic salt composite solid electrolyte film prepared in Example 7(a). The pellet was placed in a mold with a diameter of 10 mm and compressed under a pressure of 2.8 tons using a press. The pellet was then placed in a conduction cell at a pressure of 5 MPa and sealed under an inert argon atmosphere. The configuration of each cell is shown below. Cell 12: Electrode / E12 / Electrode Cell 13: Electrode / E13 / Electrode

[0219] Ionic conductivity measurements of the cells assembled in this example were performed on a VMP-300 multichannel potentiostat (Bio-Logic™). Measurements were performed at an amplitude of 50 mV over a frequency range of 7 MHz to 200 mHz, over a temperature range of -10°C to 70°C (in 10°C increments) and over a temperature range of 70°C to 20°C (in 10°C decrements).

[0220] Impedance measurements were obtained after a stabilization time of approximately 1 hour. At each temperature, two impedance measurements were recorded at each measurement interval of 15 minutes. Figure 10 shows the ionic conductivity measurements as a function of temperature for cells 12 (●) and 13 (▼).

[0221] The cross-linking of the US'674 polymer through the insertion of TBT between the US'674 polymer chains makes it possible to inhibit the ionic conduction of lithium ions by the US'674 polymer and therefore to significantly increase the ionic conduction of the ceramic-ionic plastic salt composite solid electrolyte film, especially after the sweep of salt 1. This makes it possible to confirm the interaction between the ionic plastic salt and the sulfide-based ceramic (for example Li6PS5Cl) and the positive effect of the sweep of the ionic plastic salt on the density of the obtained film and its ionic conductivity. The ionic conductivity of the ceramic-ionic plastic salt-TBT composite solid electrolyte film is practically identical to that obtained for the sulfide-based ceramic type inorganic solid electrolyte film (Li6PS5Cl).

[0222] Several modifications can be made to any of the above embodiments without departing from the scope of the invention as contemplated. All references, patents or scientific literature articles mentioned in this application are incorporated herein by reference in their entirety for all purposes.

Claims

1. Inorganic particles and Formula I or II: 【Chemistry 11】 (In the formula, A － is a delocalized anion, R ＋ -N excluding cations derived from amidine, guanidine, and phosphazene superbases ＋ (R １ R ２ R ３ ) and -P ＋ (R １ R ２ R ３ ) group, R １ , R ２ and R ３ are independently substituted or unsubstituted, linear or branched C １～１２ alkyl groups, or R １ and R ２ together with the nitrogen or phosphorus atom, form a heterocyclic ring having one or more rings and 3 to 12 members, and R ３ is as previously defined, or R １ , R ２ and R ３ together with the nitrogen or phosphorus atom form a partially unsaturated heterocyclic or heteroaromatic ring having one or more rings and 5 to 12 members, L is a linear or branched C ２～４ is alkylene, X is O or S; m is a number ranging from 1 to 6; n is a number ranging from 1 to 11. A solid electrolyte comprising an ionic bifunctional molecule of the formula:

2. The delocalized anion is hexafluorophosphate (PF ６ － ), bis(trifluoromethanesulfonyl)imide (TFSI － ), bis(fluorosulfonyl)imide (FSI － ), (fluorosulfonyl)(trifluoromethanesulfonyl)imide (FTFSI) － ), 2-trifluoromethyl-4,5-dicyanoimidazol- ate (TDI － ), 4,5-dicyano-1,2,3-triazolate (DCTA － ), bis(pentafluoroethylsulfonyl)imide (BETI － ), difluorophosphate (DFP － ), tetrafluoroborate (BF ４ － ), bis(oxalato)borate (BOB － ), nitrate (NO ３ － ), perchlorate (ClO ４ － ), hexafluoroarsenate (AsF ６ － ), trifluoromethanesulfonate (CF ３ SO ３ － or － OTf), fluoroalkyl phosphate ([PF ３ (CF ２ CF ３ ) ３ ] － or FAP － ), tetrakis(trifluoroacetoxy)borate ([B(OCOCF ３ ) ４ ] － or TFAB － ), bis(1,2-benzenediolato(2-)-O,O')borate ([B(C ６ O ２ ) ２ ] － or BBB － ), difluoro(oxalato)borate (BF ２ (C ２ O ４ ) － or FOB － ), and formula BF ２ O ４ R ｘ (R ｘ =C ２～４ 2. The solid electrolyte of claim 1, wherein the delocalized anion is selected from the group consisting of hexafluorophosphate (PF 6 − ), bis(trifluoromethanesulfonyl)imide (TFSI − ), bis(fluorosulfonyl)imide (FSI − ), (fluorosulfonyl)(trifluoromethanesulfonyl)imide (FTFSI − ), tetrafluoroborate (BF 4 − ), and trifluoromethanesulfonate (CF 3 SO 3 − or − OTf), and more preferably the delocalized anion is bis(trifluoromethanesulfonyl)imide (TFSI − ).

3. R ＋ But, -N ＋ (R １ R ２ R ３ 2. The solid electrolyte according to claim 1, wherein the cation is a cation group.

4. (i) R １ , R ２ and R ３ are independently substituted or unsubstituted, linear or branched C １～１２ alkyl groups, (ii) R 1 , R 2 and R 3 are independently selected from linear or branched C 1-12 alkyl groups, or at least one of R 1 , R 2 or R 3 is substituted by a halogen atom, or an alkoxyl, ether, ester or siloxy group; (iii) R 1 and R 2 together with the nitrogen atom form a heterocycle having one or more rings and 3 to 12 members, and R 3 is as defined in claim 1, preferably R 3 is C 1-12 alkyl or C 1-4 alkyl, or (iv) R 1 , R 2 and R 3 together with the nitrogen atom form a partially unsaturated heterocyclic or heteroaromatic ring having one or more rings and 5 to 12 members; The solid electrolyte according to claim 3.

5. R ＋ but, 【Chemistry 12】 (In the formula, R ３ is as defined in claim 1, preferably R 3 is an unsubstituted C 1-4 alkyl group, preferably selected from methyl, ethyl, n- or i-propyl, and n-, i-, s- or t-butyl; R ４ is a substituted or unsubstituted, linear or branched C １～１２ Alkyl, C １～１２ alkenyl, or C １～１２ an alkynyl group, preferably R 4 is a C 1-4 alkyl group; R ５ represents a hydrogen atom or a substituted or unsubstituted, linear or branched C １～１２ Alkyl, C １～１２ Alkenyl or C １～１２ alkynyl group, preferably R 5 is a C 1-4 alkyl group; The heterocycle is optionally substituted. The solid electrolyte according to claim 3, wherein the solid electrolyte is selected from the group consisting of:

6. R ＋ But, -P ＋ (R １ R ２ R ３ 2. The solid electrolyte according to claim 1, wherein the cation is a cation group.

7. (i) R １ , R ２ and R ３ are independently substituted or unsubstituted, linear or branched C １～１２ alkyl groups, or (ii) R 1 , R 2 and R 3 are independently selected from linear or branched C 1-12 alkyl groups, or at least one of R 1 , R 2 or R 3 is substituted by a halogen atom, or an alkoxyl, ether, ester or siloxy group; The solid electrolyte according to claim 6.

8. 2. The solid electrolyte of claim 1, wherein n is a number in the range of 2 to 10, or 3 to 8, or 4 to 6.

9. 2. The solid electrolyte of claim 1, wherein the ionic bifunctional molecule is selected from the group consisting of 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'-(thiolbis(1,2-ethane))bis(1-methylpyrrolidinium)bis(trifluoromethanesulfonyl)imide, and 3,3'-(1,6-hexamethylene)bis(1,2-dimethylimidazolium)bis(trifluoromethanesulfonyl)imide.

10. 10. The solid electrolyte of claim 1, wherein the ionic bifunctional molecule is present in the solid electrolyte 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 %.

11. 10. The solid electrolyte of claim 1, wherein the inorganic particles comprise a material selected from glass, glass-ceramic, ceramic, nanoceramic, and combinations of at least two thereof.

12. The inorganic particles are (i) ceramics, glasses, or glass-ceramics based on fluorides, phosphides, sulfides, oxysulfides, or oxides; (ii) crystalline and / or amorphous forms of LISICON, thio-LISICON, argyrodite, garnet, NASICON, perovskite, oxide, sulfide, oxysulfide, phosphide or fluoride compounds, or combinations of at least two thereof; (iii) Formula MLZO (e.g., M ７ La ３ Zr ２ O １２ , M （７－ａ） La ３ Zr ２ Al ｂ O １２ , M （７－ａ） La ３ Zr ２ Ga ｂ O １２ , M （７－ａ） La ３ Zr （２－ｂ） Ta ｂ O １２ , and M （７－ａ） La ３ Zr （２－ｂ） Nb ｂ O １２ ), MLTaO (e.g., M ７ La ３ Ta ２ O １２ , M ５ La ３ Ta ２ O １２ , and M ６ La ３ Ta １．５ Y ０．５ O １２ ), MLSnO (e.g., M ７ La ３ Sn ２ O １２ ), MAGP (e.g., M １＋ａ Al ａ Ge ２－ａ (P.O. ４ ) ３ ), MATP (e.g., M １＋ａ Al ａ Ti ２－ａ (P.O. ４ ) ３ ), MLTiO (e.g., M ３ａ La （２／３－ａ） TiO ３ ), MZP (e.g., M ａ Zr ｂ (P.O. ４ ) ｃ ), MCZP (e.g., M ａ Ca ｂ Zr ｃ (P.O. ４ ) ｄ ), MGPS (e.g., M ａ Ge ｂ P ｃ S ｄ , for example, M １０ GeP ２ S １２ ), MGPSO (e.g., M ａ Ge ｂ P ｃ S ｄ O ｅ ), MSiPS (e.g., M ａ Si ｂ P ｃ S ｄ , for example, M １０ SiP ２ S １２ ), MSiPSO (e.g., M ａ Si ｂ P ｃ S ｄ O ｅ ), MSnPS (e.g., M ａ Sn ｂ P ｃ S ｄ , for example, M １０ SnP ２ S １２ ), MSnPSO (e.g., M ａ Sn ｂ P ｃ S ｄ O ｅ ), MPS (e.g., M ａ P ｂ S ｃ , for example, M ７ P ３ S １１ ), MPSO (e.g., M ａ P ｂ S ｃ O ｄ ), MZPS (e.g., M ａ Zn ｂ P ｃ S ｄ ), MZPSO (e.g., M ａ Zn ｂ P ｃ S ｄ O ｅ ), xM ２ S-yP ２ S ５ , xM ２ S-yP ２ S ５ -zMX, xM ２ S-yP ２ S ５ -zP ２ O ５ , xM ２ S-yP ２ S ５ -zP ２ O ５ -wMX, xM ２ S-yM ２ O-zP ２ S ５ , xM ２ S-yM ２ O-zP ２ S ５ -wMX, xM ２ S-yM ２ O-zP ２ S ５ -wP ２ O ５ , xM ２ S-yM ２ O-zP ２ S ５ -wP ２ O ５ -vMX, xM ２ S-ySiS ２ , MPSX (e.g., M ａ P ｂ S ｃ X ｄ , for example, M ７ P ３ S １１ X, M ７ P ２ S ８ X, and M ６ P.S. ５ X), MPSOX (e.g., M ａ P ｂ S ｃ O ｄ X ｅ ), MGPSX (M ａ Ge ｂ P ｃ S ｄ X ｅ ), MGPSOX (M ａ Ge ｂ P ｃ S ｄ O ｅ X ｆ ), MSiPSX (M ａ Si ｂ P ｃ S ｄ X ｅ ), MSiPSOX (M ａ Si ｂ P ｃ S ｄ O ｅ X ｆ ), MSnPSX (M ａ Sn ｂ P ｃ S ｄ X ｅ ), MSnPSOX (M ａ Sn ｂ P ｃ S ｄ O ｅ X ｆ ), MZPSX (M ａ Zn ｂ P ｃ S ｄ X ｅ ), MZPSOX (M ａ Zn ｂ P ｃ S ｄ O ｅ X ｆ ), M ３ OX, M ２ HOX, M ３ PO ４ , M ３ PS ４ , and M ａ PO ｂ N ｃ (where a = 2b + 3c - 5) (In the formula, M is an alkali metal ion, an alkaline earth metal ion, or a combination of at least two thereof, and when M comprises an alkaline earth metal ion, the number of M is adjusted to achieve electroneutrality, preferably M is selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, or a combination of at least two thereof, more preferably M is Li; X is selected from F, Cl, Br, I, or a combination of at least two thereof; a, b, c, d, e, and f are non-zero numbers and are independently selected in each formula to achieve electroneutrality; v, w, x, y, and z are non-zero numbers and are independently selected in each formula to provide a stable compound. a compound selected from the group consisting of inorganic compounds of (iv) an inorganic compound of formula MATP; (v) argyrodite-type inorganic compounds of the formula Li 6 PS 5 X, where X is Cl, Br, I, or a combination of at least two thereof; or (vi) inorganic compounds of formula Li 6 PS 5 Cl 12. The solid electrolyte of claim 11, comprising:

13. 10. The solid electrolyte of claim 1, wherein the inorganic particles are present in the solid electrolyte at a concentration of about 25% to about 95% by weight, or about 40% to about 90% by weight, or about 60% to about 90% by weight.

14. 2. The solid electrolyte of claim 1, wherein the weight ratio of "inorganic particles:ionic bifunctional molecules" is in the range of 2:1 to 30:1, or 3:1 to 20:1, or 5:1 to 15:

1.

15. The solid electrolyte of claim 1 further comprising a polymer.

16. The polymer (i) is the reaction product of at least one monomer containing at least one polymerizable or crosslinkable functional group and a compound containing at least one SH functional group; or (ii) linear or branched polymers selected from polyethers, 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, preferably wherein the polyether is poly(ethylene oxide) (PEO), poly(propylene oxide) (POP), or a copolymer (EO / PO); or wherein the polymer comprises crosslinking units or crosslinking equivalents derived from crosslinkable functional groups, the crosslinkable functional groups being preferably selected from acrylate, methacrylate, vinyl, glycidyl, and mercapto functional groups; The solid electrolyte according to claim 15.

17. 16. The solid electrolyte of claim 15, wherein the polymer is present in the solid electrolyte 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 %.

18. The solid electrolyte of claim 1 further comprising an additive.

19. 19. The solid electrolyte of claim 18, wherein the additive is a fluorinated compound containing an amide functional group, preferably of the formula R6X6C(O)N(H)X7R7, wherein R6 and R7 are independently alkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl groups; X6 is O, NH, or absent; X7 is absent or a C(O), S(O)2, or Si(R8R9) group; R8 and R9 are alkyl groups; at least one of R6, R7, R8, and R9 is a group substituted with one or more fluorine atoms; and R6 is a perfluorinated group; and X6 is absent.

20. 20. The solid electrolyte of claim 18, wherein the additive is present in the solid electrolyte 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 %.

21. An electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte, wherein the electrolyte is as claimed in any one of claims 1 to 20.

22. 22. The electrochemical cell of claim 21, wherein the positive electrode comprises a positive electrode material including a positive electrode electrochemically active material, the positive electrode material preferably on a current collector.

23. The positive electrode electrochemically active material is (i) selected from metal phosphates, lithiated metal phosphates, metal oxides, and lithiated metal oxides; or (ii) LiM'PO 4 (wherein M' is Fe, Ni, Mn, Co, or a combination of at least two thereof), LiV 3 O 8 , V 2 O 5 F, LiV 2 O 5 , LiMn 2 O 4 , LiM''O 2 (wherein M'' is Mn, Co, Ni, or a combination of at least two thereof) (e.g., NMC, LiMn x Co y Ni z O 2 , where x + y + z = 1), Li(NiM''')O 2 wherein 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, a carbon-based active material, e.g., graphite, an organic cathode active material, or a combination of at least two thereof, if compatible with each other; 23. The electrochemical cell of claim 22.

24. 23. The electrochemical cell of claim 22, wherein the positive electrode material further comprises an electrically conductive material, a binder, a salt, an ionic bifunctional molecule, and / or an inorganic particle.

25. 22. The electrochemical cell of claim 21, wherein the negative electrode comprises a negative electrode material including a negative electrode electrochemically active material, the negative electrode material preferably on a current collector.

26. 26. The electrochemical cell of claim 25, wherein 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, preferably wherein the alkali metal is selected from lithium and sodium.

27. The negative electrode electrochemically active material is an intermetallic compound (e.g., SnSb, TiSnSb, Cu ２ Sb, AlSb, FeSb ２ , FeSn ２ , and CoSn ２ ), metal oxides, metal nitrides, metal phosphides, metal phosphates (e.g., LiTi ２ (P.O. ４ ) ３ ), metal halides (e.g., metal fluorides), metal sulfides, metal oxysulfides, carbon (e.g., graphite, graphene, reduced graphene oxide, hard carbon, soft carbon, exfoliated graphite, and amorphous carbon), silicon (Si), silicon-carbon composites (Si—C), silicon oxide (SiO ｘ ), silicon oxide-carbon composite (SiO ｘ -C), tin (Sn), tin-carbon composite (Sn-C), tin oxide (SnO ｘ ), tin oxide-carbon composite (SnO ｘ -C), and, where appropriate, combinations thereof, Preferably, (i) the metal oxide is a compound of the formula M''''bOc (wherein M'''' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination thereof, and b and c are numbers such that the c:b ratio is in the range of 2 to 3) (e.g., MoO3, MoO2, MoS2, V2O5, and TiNb2O7), an oxide spinel (e.g., NiCo2O4, ZnCo2O4, MnCo2O4, CuCo2O4, and CoFe2O4), ), and LiM'''O, where M''''' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination thereof (e.g., lithium titanate (e.g., Li 4 Ti 5 O 12 ), or lithium molybdate (e.g., Li 2 Mo 4 O 13 )); or (ii) the negative electrode material further comprises an electrically conductive material, a binder, a salt, an ionic bifunctional molecule, and / or an inorganic particle; 26. The electrochemical cell of claim 25.

28. 22. A battery comprising at least one electrochemical cell according to claim 21, wherein the battery is preferably selected from the group consisting of lithium batteries, lithium ion batteries, sodium batteries, sodium ion batteries, potassium batteries, potassium ion batteries, magnesium batteries, and magnesium ion batteries, and is more preferably a lithium battery or a lithium ion battery.

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